second interim report - Eu-ARTECH

2 nd Year Interim Report
Eu-ARTECH
Access, Research and Technology for the conservation
of the European Cultural Heritage
Integrating Activity
implemented as
Integrated Infrastructure Initiative
Contract number: RII3-CT-2004-506171
Project Co-ordinator: Prof. Brunetto Giovanni Brunetti
Reporting period: from June 1 st 2005 to November 30 th 2005
Project funded by the European Community
under the “Structuring the European Research Area”
Specific ProgrammeResearch Infrastructures action
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1 ST YEAR INTERIM ACTIVITY REPORT
1. PROGRESS REPORT
1.1 Summary of activities ................................................................................................. 3
1.2 Management Activity ............................................................................................... 3
1.2.1 Management tasks .................................................................................................. 3
1.2.2 General meetings .................................................................................................... 4
1.3 Networking Activities ............................................................................................... 6
1.3.1 N1-Sharing knowledge and resources ............................................................... 6
1.3.1.1 Activity progress...................................................................................... 6
1.3.1.2 Meetings and workshops......................................................................... 8
1.3.2 N2- Materials and methods in conservation .................................................... 11
........ 1.3.2.1 Activity progress.................................................................................... 11
1.3.2.2 Meetings and workshops....................................................................... 12
1.4 Transnational Access Activities.............................................................................. 13
1.4.1 TA1: AGLAE ........................................................................................................ 13
1.4.1.1 Description of the publicity concerning the new opportunities
for access ............................................................................................. 13
1.4.1.2 Description of the selection procedures and access activity ............. 13
1.4.1.3 Meetings and workshops .................................................................... 15
1.4.2 TA2: MOLAB ..................................................................................................….15
1.4.2.1 Description of the publicity concerning the new opportunities
for access ........................................................................................... ..15
1.4.2.2 Description of the selection procedures and access activity............. .16
1.4.2.3 Meetings and workshops…………………………………………..17
1.5 Joint Research Activities.................................................................................... .. 18
........ 1.5.1 JRA1: Development and evaluation of new treatments for the
conservation-restoration of outdoor stone and bronze monuments............... 18
1.5.1.1 Activity progress.................................................................................... 18
1.5.1.2 Meetings and workshops....................................................................... 19
........ 1.5.2 JRA2: New methods in diagnostics: Imaging and spectroscopy ………………....19
1.5.2.1 Activity progress.................................................................................... 19
1.5.2.2 Meetings and workshops....................................................................... 21
…
2. LIST OF DELIVERABLES……………………………………………………………… 22
3. USE AND DISSEMINATION OF KNOWLEDGE……………………………………… 24
ANNEXES
.......Annex 1 – Summary Report of the Second Interim Meeting………………………………..26
.......Annex 2 – Composition of the Users Selection Panel……………………..…..…………….30
.......Annex 3 – List of AGLAE and MOLAB User-Projects …………………………………… 31
.......Annex 4 – Standardised format for analytical procedures…………….………….……..…..33
.......Annex 5 – Summary on the workshop on “Non-invasive NMR and Cultural Heritage…. ...36
.......Annex 6 – Summary on GUPIX course…………………………………….………….…….40
.......Annex 7 – Summary on AGLAE and MOLAB Users Meeting………………………..…....41
.......Annex 8 – Summary Report on JRA1………………………………………………….…....46
....... Annex 9 – Summary Report on JRA2………………………………………………………108

1. PROGRESS REPORT
1.1 – Summary of activities
The second year activities of Eu-ARTECH started on June 1 st 2005. All the various tasks of the planned
networking, access and joint research activities had their regular development, according to the
implementation plan of the second period and, after 18 months from the start-up of the project, significant
progresses have been done and all the planned milestones have been achieved.
The present interim report describes the activities that have been developed during the first six month of
the second year (June 1 st - November 30 th 2005), preparing the way towards the more articulated Second
Annual Report to be delivered at the end of May 2006.
1.2 – Management Activity
The Eu-ARTECH management activity of the period consisted mainly of the preparation of the First Annual
Report, of the dissemination of the Eu-ARTECH activities with emphasis to Transnational Access, of the
intensification and deepening of the relations with other I3 initiatives or other projects operating in the field
of conservation of cultural heritage. During this period, one meeting of the Governing Board was held. All
these activities are described in the following paragraphs.
1.2.1 – Management tasks
The main management task of the second year was the preparation of the First Annual Report. After the
Ormylia Meeting, a fruitful intense work was carried out by the Coordinator and the Consortium partners in
order to satisfy all the administrative requirements of the reporting. In particular, strong efforts were
dedicated to the preparation of all the documentation necessary for the signature of the Audit Certificates. At
the deadline (July 15 th ) all the partners were ready, apart one exception due to internal specific rules of the
institution. This difficulty lead to some delay in the presentation of the Annual Report, that was finally
delivered on September 2005. After the delivery, some integration of documents have been requested by EC.
The last documents were delivered in December 2005, that is during the days of preparation of this report.
Contacts were maintained with other organisations or infrastructures with the objective to promote crossfertilisations
in order to establish a common area of encounter and interchange of knowledge. Other contacts
were maintained with other I3 or other organisations or infrastructures in order to exchange administrative
experience in the perspective of future both managerial and programme aspects of FP7. The activities of
ESFRI to produce an infrastructure road map was also monitored. Specific contacts were maintained and
deepened with:
- I3 initiatives, such as LASERLAB, NMI3, and IA-SFS, developing work in the field of cultural
heritage;
- I3 Forum;
- infrastructures operating in the field of study and conservation of cultural heritage, such as the ICTP,
Abdus Salam International Centre for Theoretical Physics of Trieste, or the LABEC – INFN of
Florence;
- EC projects, such as COST G8, COST G7, CEN/TC 346 dedicated to the “Conservation of Cultural
Property, or with Marie-Curie actions such as ATHENA and EPISCON, dedicated to the formation
of young conservation scientists.
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-During the period, the Eu-ARTECH website (www.eu-artech.org) was continuosly adjourned, introducing
new pages and links in the effort to create an easily readable interface with users and institutions external to
the Consortium. The specific restricted area of the website was reserved to the exchange and diffusion of
working documents.
The Governing Board met one time during the period June 1 st - November 30 th 2005, in Paris in occasion of
the Second Interim meeting (November 21 st , 2005). A report on this meeting is in the following paragraph.
1.2.2 General Meetings
The Second Interim Meeting of Paris, held at C2RMF, Palais du Louvre, in November 2005, was the 4 th
General Meeting of Eu-ARTECH.
In Paris, the 4 th Governing Board Meeting was held. According to the Consortium Agreement, this meeting
was restricted to the Coordinator and one authorised representative for each participant infrastructure.
The following GB members were present: Coordinator: B.Brunetti; UNIPG: A. Sgamellotti; CNRS-C2RMF:
M.Menu; CNR-ICVBC: S.Bracci; NGL: A. Roy; OPD: D. Pinna; BLFD: M. Mach; OADC: S. Sotiropoulou;
ICN: M. Bommel; LNEC: J. Delgado; IRPA: J. Wouters; RWTH: B. Bluemich; UNIBO: R. Mazzeo; INOA:
L. Pezzati.
1- Amendments to the contract
The Coordinator announced that from June 1 st INOA formally merged into CNR, however it was authorised
to maintain its administrative rules, being entered in a transitory phase. The GB decided to ask to the EC
Research Infrastructure office if the change of model cost from AC (cost model of INOA in the contract) to
FC (the cost model of CNR) is obligatory or can be postponed up to the end of the transitory phase. In case
of obligation, the request of amendment of the contract is to be considered authorised by the GB.
B. Brunetti illustrated the content of the clause 39 that could be introduced in the contract. It allows
institutions having an annual budget lower than 150.000 euros to skip the audit.
The Coordinator presented and discussed advantages and possible inconvenients of the introduction of clause
39. After accurate evaluation by the Consortium representatives, it was decided to renounce to the clause 39
and accept the rule of presenting every year the Audit Certificate for each institution.
As a third point, the possible extension of the participation of RWTH to the Eu-ARTECH activities was
discussed. The original formulation of the contract includes the participation of RWTH limited to the first
two years. However, RWTH is developing a relevant work on new NMR methodologies for the laboratory
and in-situ studies of artworks; therefore, it would be important for Eu-ARTECH to extend its participation,
at least, for another year. All the partners agreed on this point. In order to allow RWTH to continue its
activity, the Coordinator proposed to shift part of the UNIPG budget (coordinator), corresponding to an
amount of 25.000 euros, to RWTH. Unanimously, the GB accepted the proposal of the Coordinator inviting
him to proceed to the request of amendment of the contract.
The Coordinator communicated that the Bank of UNIPG changed its coordinates. The change was due to the
merging of the Banca dell’Umbria into the largest UniCredit Banca. The new coordinates will be
communicated to the EC asking for the relative amendment of the contract. All GB members agreed with the
request of amendment. The new name of the Bank is: UniCredit Banca; the new IBAN:
IT58G0200803016000029489728.
2- Administrative notes
The Coordinator informed the Consortium member representatives that the procedure to close the First
Annual Report with the inclusion of the Audit Certificates of all the participating institutions was close to the
end.
Due to the strong foreseen delay in the pre-financing of the second year, the Coordinator announced to
reserve to himself the use of the residue of the budget of the First Year not yet distributed to the partners, for
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a pre- prefinancing of those institutions (only) that spended all or almost all their first year budget. The
assembly was favourable.
3- Next Meetings
At the end of the meeting the proposal of Munchen as location for the Third Year Annual Meeting was
advanced by M. Mach of BLFD. The proposal was unanimously accepted.
The National Gallery of London, as site for the Third Year Interim Meeting was also proposed and accepted.
Therefore the locations of the next Eu-ARTECH meetings is the following:
-Second Year Annual Meeting – Lisbon, LNEC, May 3-5 2006;
-Third Year Interim Meeting – London, NGL, date to be established;
-Third Year Annual Meeting, Munchen, BLFD, date to be established.
4- General notes
It has been proposed by LNEC and accepted by GB, to define and publish on the Eu-ARTECH website a list
of trainees & training opportunities “stock exchange” among the participating institutions. Such a simple and
flexible item will permit to increase and diversify the training possibilities in the areas of the project.
With this last decision, the Governing Board meeting was closed.
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1.3 – Networking activity
According to the contract, networking activity was continued, articulated in two lines, one regarding the
analysis and diagnostics on artwork materials (N1), the second regarding the materials and methods used in
conservation of cultural heritage (N2). Networking discussions on the rational use of analytical methods and
resources (N1) is considered of outmost importance to optimise research; the definition of best methods and
materials in conservation of artworks (N2) is recognised as the proper way to better guarantee the diffusion
of best practices for their preservation.
The two networking activities were accomplished through continuous interactions among the
responsibles of the networking tasks and participants, who took care of the work. Natural coordination
followed also from the Eu-ARTECH periodical meetings (every six months).
Participants are all the partners, apart INOA and RWTH.
Responsible for networking is UNI-BO.
1.3.1 – N1: Sharing knowledge and resources
N1 networking specific activities of the first six months of the second year consisted mainly in:
- continuation of Task 1 on Analytical resources, analytical procedures and investigation strategies,
especially referred to organic substance investigations;
- start of Task 2- Exchange knowledge and expertise.
In particular, it was planned:
-Task 1c (CNRS-C2RMF): Proposition of a standardised format for describing analytical procedures for
natural organic substances investigations, to allow these procedures to be readily compared and reproduced.
Continuation of interlaboratory comparison on dyestuffs investigation. with focus on complementary nondestructive
techniques available via MOLAB and AGLAE.
-Task 2 (ICN): Subtask 2a, Reference Materials Sharing, overview on possible sharing of reference materials
among infrastructures.
-Subtask 2b (C2RMF): Cooperation with CAMEO (MFA, Boston);
-Subtask 2c (UNIPG), Workshop on Non-invasive NMR and Cultural Heritage comprising educational
lectures and practical training exercises with mobile NMR equipment. Training course for PIXE users on
GUPIX data processing software.
Behind these tasks, other activities of dissemination were carried out.
Responsible for N1 is CNRS-C2RMF.
1.3.1.1 – Activity progress
The effort on establishing fruitful interactions among Eu-ARTECH and relevant infrastructures in the field
of cultural heritage had no stop. Information on Eu-ARTECH activities was currently distributed among
interested institutions and researchers. At the end of November 2005, 127 institutions of 27 countries, plus 3
international organisations, have manifested interest in the Eu-ARTECH project and have been registered in
the Eu-ARTECH mailing list. In the next future, other efforts will be done particularly towards libraries,
archives, historical buildings and archaeological institutions, restoration workshops, producers of cultural
heritage materials (pigments, dyes, paper, textiles, wood, stone, ceramics…).
Along this line, a list of conferences, seminars, training courses in the area of conservation of cultural
heritage was regularly updated, distributed to the institutions and researchers of the Eu-ARTECH mailing
list, and made available on the Eu-ARTECH website. A list of relevant websites of interest in the
conservation science and conservation/restoration of cultural heritage was also westablished and made
accessible through the Eu-ARTECH website. The list was regularly updated and enriched.
The database initiated during the previous European project LabS TECH related to the institutions (public
cultural heritage institutions, universities, research centres, museums, libraries, restoration workshops,
foundations, industrial technology research centres...) active in characterisation & analysis of cultural
heritage artefacts and their component materials has been continuously updated. New entries, via the interest
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manifested to Eu-ARTECH initiatives, have permitted the extension of the database from 106 to 126
institutions belonging to 28 different countries and working with 114 different investigation techniques.
It has been proposed and accepted to update regularly the database, and to link it to the Eu-ARTECH
website. Once this will be done, improvements (widening to new techniques and extension of the areas of
cultural heritage activity) will be introduced.
Task1 - Analytical resources, analytical procedures and investigation strategies (OADC, ICN, NGL, KIK-
IRPA, UNIPG, C2RMF)
Task 1c (CNRS-C2RMF): Proposition of a standardised format for describing analytical procedures for
natural organic substances investigations, to allow these procedures to be readily compared and reproduced.
A template format for documenting analytical protocols and data exchange has been set up (see Annex 4)
and distributed among the partners to be assessed for its relevance, completeness and applicability to real
cases. Discussion is in progress on the essential relevant analytical parameters to be adopted as common
reference for exchange of results
A future action in collaboration with MaSC users group is scheduled, focusing on the adaptation and
assessment of the existing JCAMP format (for MS data) for UV-Vis spectra linked with chromatographic
data.
Task 2 (ICN): Subtask 2a, Reference Materials Sharing, overview on possible sharing of reference materials
among infrastructures.
Interlaboratory comparison
In cooperation with the COST G8 action, “Non-destructive Analysis and Testing of Museum Objects”, and
within the framework of Irina Petroviciu’s short time scientific mission (COST-STSM-G8-01461) at KIK-
IRPA and NGL, well documented reference materials have been prepared to be shared for analysis and
interlaboratory comparison of results among the partners.
In continuation of the pilot study on Weld, five other well-characterised natural biological sources (plants
and animals) of interest have been selected, for the distribution of 22 dyed wool and silk fibres and fabrics
(prepared at KIK-IRPA) and 7 lake pigments (prepared at the NGL).
The following plants and insects have been selected:
-dyer’s broom (Genista tinctoria),
-sappanwood (Caesalpinia sappan),
-safflower (Carthamus tinctorius),
-Mexican cochineal (Dactylopius coccus) and
-indigo (Indigofera sp.).
Additionally, madder (Rubia sp.) and madder dyed wool provided by MODHT - Monitoring of Damage in
Historic Textiles - EU 5th FP (C. No EVK4-2001-00020) ended on June 2005 (from which several reference
materials are available to be shared) have been also used for the standards of madder lake pigments.
Laboratory recipes have been adopted, based on historic literature citations but adapted and established to be
controllable and reproducible. All procedures for the preparation of pigments and dying textiles are reported
in detail and documented with pictures to be distributed to all the partners who will participate to the
interlaboratory activities.
Well prepared and documented samples of reference materials are presently shared for interlaboratory
comparison among all the laboratories involved in the present task (NGL, KIK-IRPA, ICN, OADC, UNI-
PG) and some cooperating institutions external to the project (such as GCI, NMS/UoE). In occasion of the
ICOM-CC conference a proposal for the initiative NOPART was advanced, in the perspective of possible
future interaction with ICOM-CC (see Annex 4).
Results will be evaluated and discussed:
-first, during the 2nd Eu-ARTECH annual meeting in May 2006 in Lisbon,
-extensively, at the one day Eu-ARTECH Working meeting attached to the DHA25 in Romania, 21-23
September 2006.
Task 2b - Cooperation between Eu-ARTECH and MFA, Boston, for the improvement of CAMEO
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A plan for a possible co-operation between EU-ARTECH and MFA Boston, related to CAMEO, has been
adopted, setting a reasonable and workable contribution of the Consortium’s members.
A Memorandum of Agreement has been written, in order to propose to MFA Boston the conditions of the
contribution of Eu-ARTECH, the information on the CAMEO website and on the Eu-ARTECH website, the
intellectual property conditions and the interface with the “Conservation dictionary”.
A dedicated working group has discussed these aspects during the second intermediate meeting in Paris. It
has been proposed to organise a meeting with MFA, to finalise this co-operation, in Amsterdam or London,
in March or April 2006.
Subtask 2c (UNIPG), Dissemination: Workshop on Non-invasive NMR and Cultural Heritage comprising
educational lectures and practical training exercises with mobile NMR equipment. Training course for PIXE
users on GUPIX data processing software.
A double initiative has been developed at the University of Perugia in September 19-23 2005: a “Workshop
on non-invasive NMR and Cultural Heritage” and the “5th Colloquium in Mobile NMR”, organised by
RWTH Aachen (B. Blümich), SMAArt UNIPG (A. Sgamellotti) and CNR-IMC (A. Segre). The workshop
and the Colloquium had a large participation( 42 researchers at the workshop; 72 researchers at the
Colloquium). During both meetings, but in particular during the “Workshop on non-invasive NMR and
Cultural Heritage”, the general bases of the NMR technique and the design of the portable NMR-MOUSE
(Nuclear Magnetic Resonance – MObile Universal Surface Explorer) were fully described, both from the
theoretical and experimental point of view. In many presentations, attention was dedicated not only to the
applications already carried out, but also to the developments of the NMR-MOUSE and to the “depthprofile”
version of this instrument. A short report, including the agenda and list of participants to the
workshop, is reported in Annex 5.
The “Training course for PIXE users on GUPIX data processing software”, organised by C2RMF with the
co-operation of the University of Guelph (Canada), was held in the rooms of C2RMF – Paris, on october 5 th
–7 th 2005. The course included theoretical lectures and practical exercise in the AGLAE-PIXE laboratory
and was attended by AGLAE TA users.
A summary report of the training course, is reported in Annex 6.
1.3.1.2. Meetings and workshops
The following meetings and workshops were organised:
- “Workshop on Non-invasive NMR and Cultural Heritage”, 19th - 290th September 200 – Perugia,
comprising educational lectures and practical training exercises with mobile NMR equipment
(RWTH, UNIPG). (Annex 5).
- “Training course for PIXE users on GUPIX data processing software”, with the co-operation of the
University of Guelph (Canada), C2RMF – Paris, 5-7 October 2005. the workshop was held in Paris
at C2RMF and included practical exercise in the AGLAE-PIXE laboratory. (Annex 6).
In addition, Eu-ARTECH participated, with the active presence of several Consortium members, to relevant
conferences or workshops, such as:
- “COST and Cultural Heritage: crossing borders” – Florence – October 20-22 2005
(http://www.echn.net/cost-hig/florence2005) a European meeting where the COST activities of the
field have been discussed in the perspective of future developments. During this meeting, Eu-
ARTECH had a relevant evidence.
Information on Eu-ARTECH activities were largely diffused at:
- “3rd International conference on the application of Raman spectroscopy in art & archaeology”–
Paris - 31 August - 3 September 2005 (participation of C2RMF and UNIPG);
- “14th ICOM-CC Triennial Meeting” - The Hague - 12-16 September 2005. ICOM-CC is the largest
association of conservators of the world having more than 1400 members. It aims to promote the
conservation, investigation and analysis of culturally and historically significant works and to further
the goals of the conservation professions. At this conference Eu-ARTECH was present with a stand,
where brochures and other documentations on the Consortium activities (with emphasis to AGLAE
and MOLAB Transnational Access) were distributed to the interested conservators. In addition to a
general poster on Eu-ARTECH networking, another poster presented the concepts and content of the
interlaboratory comparison experiment on dyes’ analysis (illustrating the weld pilot study). On the
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day of 16th September, during the ICOM-CC conference, a short target meeting was held, presenting
the outline of the NOPART initiative and discussing possible future interaction with ICOM-CC, as
well as aims and topics of a future joint meeting which could be scheduled jointly as an ICOM-CC
working group meeting. (In Annex 4, an introduction sent to the Coordinators of the ICOM-CC
working groups, before the target meeting as well as a short report on the meeting itself are
included). A relevant detail is that, at the closure conference, Tim Whalen, the General Director of
the Getty Conservation Institute of Los Angeles, mentioned Eu-ARTECH as the most relevant
project in the field of conservation of cultural heritage in Europe. Also relevant, for the strengthening
of the relationships between Eu-ARTECH and ICOM-CC, was the election, as President of the
ICOM-CC for the next Triennium, of Jan Wouters, representative of IRPA within Eu-ARTECH.
The Eu-ARTECH’s approach and activity on organic substances’ analytical strategies have been diffused by
the partners participating in relevant European conferences or meetings, attracting the interest of
interdisciplinary researchers in the field. They are:
-“MODHT end-of-project meeting” on 20th-21st June. (Monitoring of Damage in Historic Textiles).
Eu-ARTECH partners present: Jan Wouters (KIK-IRPA), Ina Vanden Berghe (KIK-IRPA), Jo Kirby
(NGL). Possible ways of cooperation were discussed (e.g. sharing of reference materials, benefit
from the experiences of the MODHT project).
- “29 th International Symposium on High Performance Liquid Phase Separations and Related
Techniques”, 26-30 June 2005, Stockholm, Sweden. Eu-ARTECH partner present: Yannis
Karapanagiotis (OADC). Topics of the Eu-ARTECH networking initiatives related to Studies on
organic materials in artworks have been promoted.
-“MaSC Users Group”, 7-10 September 2005, Van Gogh Museum, Amsterdam. Eu-ARTECH
partners present: Catherine Higgitt (NGL), Maarten van Bommel(ICN). Presentation of the N1
networking activity and of planned collaboration with MaSC.
- “14th ICOM-CC triennial meeting”, in The Hague, 12-16 September 2005. Eu-ARTECH partners
who are leading the Organic Analyses topic in attendance: Jan Wouters (KIK-IRPA), Ina Vanden
Berghe (KIK-IRPA), Jo Kirby (NGL), Maarten van Bommel (ICN), Costanza Miliani (UNI-PG),
Sophia Sotiropoulou (OADC). This meeting has been already mentioned.
- “Dyes in History and Archaeology annual meeting, DHA 24”, in Liverpool, 3-5 November 2005.
Eu-ARTECH partners present: Jan Wouters (KIK-IRPA), Ina Vanden Berghe (KIK-IRPA), Jo Kirby
(NGL), Catherine Higgitt(NGL), Maarten van Bommel (ICN), Sophia Sotiropoulou (OADC), Catia
Clementi (UNI-PG). Dissemination of the concept, scope and results of the weld pilot study. Key
findings and perspectives, presented by M. van Bommel [.ppt on the website]. A Working Meeting
of Eu-ARTECH partners of OADC , ICN , IRPA , NGL and UNI-PG present at DHA 24 took place
in Liverpool on November 4th 2005, where the progress of the work on both topics of dyes and
natural polymers have been discussed.
Other N1 working meetings were held during the last semester:
-“Bilateral OADC-C2RMF meeting” held at C2RMF, 11-12 July 2005, Paris, France
Participants: Yannis Karapanagiotis (OADC), Martine Regert and Thibaut Devièse (C2RMF),
Key points regarding sample preparation procedures and analytical protocols with respect to the
utilization of chromatographic methods were discussed in detail. Major attention was focused on the
assessment of different analytical methodologies and complementary techniques to build a more
complete picture in the analysis of natural dyes. Utilization of HPLC-PDA and LC-MS techniques in
dyestuff analysis and evaluation of the various analytical protocols was a priority of the meeting.
C2RMF has recently acquired a new HPLC-PDA instrument and therefore has the intention to be
actively involved in the intercomparison experiments and networking actions on Organic substances
analyses issues, which are planned in the next period.
Similar issues, related to binding media identification were also discussed, to be developed under the
extension of Eu-ARTECH N1 activity on natural polymers analytical strategies. OADC and C2RMF
had the opportunity to share knowledge on these issues, based on the recent conclusions and
concerns of Networking activity N1.
-“Bilateral Meeting OADC-UNIPG” held in Ormylia, on 4-9 august, 2005. Participants:
S.Sotiropoulou and G.Karagiannis (OADC), B.G.Brunetti, A. Sgamellotti (UNIPG). During the
meeting, problens regarding intellectual property rights were clarified, as well as publications on
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joint research. Advances in JRA2 were also discussed and a plan for the activities at the Eu-
ARTECH stand at the ICOM was established (posters, ICOM-CC publication, flyers, ecc.). For the
documents produced see the Eu-ARTECH website.
-“Bilateral meeting ICN-NGL” held in London at the NGL (August 2005)
Participants: Maarten van Bommel (ICN), Jo Kirby and Catherine Higgitt (NGL). The progress on
the weld project and the content for the dissemination of first results of the presentation to be given
at DHA were discussed.
- A separate “NOPART discussion”, took place during the Paris interim meeting (November 22 nd
2005). Participants: Sophia Sotiropoulou (OADC), Costanza Miliani, (UNI-PG), Laura Cartechini
(UNI-PG), Jan Wouters (KIK-IRPA), Ina Vanden Berghe (KIK-IRPA), Maarten van Bommel (ICN).
To those who were not present during the discussion held at then ICOM-CC conference on 16
September 2005, a brief overview was prepared (see Appendix 4). The best strategy is to focus on a
single material. At this meeting it was decided that the focus should be on proteins. Contact will be
sought with both the Getty Conservation Institute and the coordinators of the working groups of
ICOM-CC which are related to proteins (a possible common area of interest could be defined, in
relation with GCI running project “The Organic Materials in Wall Paintings (OMWP)”,
http://www.getty.edu/conservation/publications/newsletters/19_2/gcinews1.html . The OMWP
project brings together an international group of conservation science laboratories — including the
GCI — with expertise in the study of wall paintings and in the use and evaluation of analytical
techniques. The workings groups which will be contacted are Scientific Research, Textiles,
Paintings, Leather and related materials, wet organic and archaeological materials. etc.
The aim is to organise a meeting, possibly prior to or directly after the annual Eu-ARTECH meeting
in May 2007, which will be held in Munich.
It is already established that for the next six months of the second year, the following meetings will be
organised by Eu-ARTECH:
– Workshop on Seventeenth Century Northern European paintings, National Gallery London – 12 December
2005. This workshop will be held within the task on “Examination of paintings” coordinated by NG. A
maximum number of 40 participants is planned. This number is kept deliberately relatively low, so that the
workshop will have a seminar-type format, and active discussions will be promoted. Participants include
conservation scientists, art historians, curators, and conservators, mainly from Europe (especially Britain, the
Netherlands and Belgium, as might be expected given the subject of the workshop), as well as from the
United States.
– International conference on “The painting technique of Matthias Grünewald and his contemporaries” –
Colmar, Musée d’Unterlinden in co-operation with C2RMF – January 24-26 2006 The first day will be
dedicated to the technique of Matthias Grünewald strictly speaking, the second day to the corpus of
Grünewald production and the third day to the painting technique of contemporary artists. Publication of the
proceedings is foreseen in Techné.
- Together with the second Eu-ARTECH annual meeting: International seminar on the theme “Theory and
practice in conservation – A tribute to Cesare Brandi” (May 4-5 2006 Lisbon - LNEC). The meeting will
coincide with the 100 th anniversary of Cesare Brandi’s birthday.
A suggestion has been made to invitate Christiane Maierhofer (BAM – Berlin, and also a member of the
ECTP-FACH) to make a presentation on the European Project “Onsiteformasonry”.
In the next six months, to disseminate Eu-ARTECH activities and establish fruitful contacts with other
European initiatives, Eu-ARTECH consortium members will also participate to meetings such as:
- “RICH (Research Infrastructures for Cultural Heritage) workshop” - Trieste - December 12-13 2005
(http://neutron.neutron-eu.net/n_nmi3/n_networking_activities/rich); in particular, it is planned that
Eu-ARTECH will contribute to the organisation of the workshop;
- “MIP 2006 (Metals in paper) final conference” - Newcastle upon Tyne – January 24-27 2006
(http://www.miponline.org/final.htm).
- “Synchrotron Radiation in Art and Archaeology, SR2A” – Berlin, end 2006
A special attention will be given to get in touch with the participants in the recently launched European
programme ECTP (European Construction Technology Platform) and especially its dedicated Focus Area
Cultural Heritage (FACH) (http://www.ectp.org/fa_cultural_heritage.asp). Potential interferences and/or cooperations
will be examined.
10

1.3.2 – N2: Materials and methods in conservation
The N2 networking planned work was concerned with the continuation of Task 1- Cleaning and
consolidation methods and materials already developed during the first year (resp. CNR-ICVBC). In
particular, during the period of this report, the development of Task 1d was foreseen: Survey on cleaning and
consolidation.
After the approval of the final revised version of the survey forms of the first year, a translation into Italian,
French, German, Dutch and Portuguese was planned. The formation of a list of curators and conservators
operating in different fields and different members’ countries was also planned (in cooperation with N1)
together with the preparation of database-forms for the storage and analysis of the collected survey data. A
relevant dissemination of the N2 activity was foreseen for the 14 th Triennial Meeting of ICOM-CC in The
Hague, on September 2005. All these tasks have been accomplished and their development is described in
the following.
1.3.2.1 – Activity progress
Multi language Forms
Following the decision during the first Eu-ARTECH Annual Meeting in Ormylia, the 9 FORMS in their
English version have been re-structured and compressed; at the end of the process, 4 survey “question
packages” have been prepared, according to the different materials: Stones, Metals, Paintings, Mural
Paintings.
- Package Stone: Cleaning, Consolidation, Treatment of biodeteriogens;
- Package Metals: Cleaning
- Package Painting: Cleaning, Treatment of biodeteriogens;
- Package Mural Paintings: Consolidation, Treatment of biodeteriogens;
Each package contains a special page for the identification of the Compiler and the grant to use personal
data.
With the help of the partners the English version of the packages are translated into other language for a
better diffusion: Italian, French, German, Dutch, Portuguese, Spanish, Rumanian.
Italian, French and Portuguese versions have been already completed, while the other versions are still in
progress.
The fact that not all the translations are completed is due to the long revision of the forms after the first
application among partners and their quality evaluation; the future application will imply probably a small
delay of the distribution of the forms to the compilers. Revised final version of the Forms are available in the
reserved area of the website.
Database for the analysis of results of the survey action
The structure of the database has been revised according to the completion of the packages. The database has
been set-up with the Microsoft Access software. The main file to be filled in, is: Eu-ARTECH_N2
survey.mdb It contains 5 pages: Stone, Metals, Paintings, Mural paintings, plus the Compiler page. Once
filled in, the database is blocked and can’t be modified. The data will be transferred from the compiled forms
by a single person authorised by the responsible of the Survey Action. A scheme of the database is delivered
through the Eu-ARTECH website (reserved area).
Report on the Survey action at ICOM-CC Meeting
The activity has been focused on the first appointment with the restorers and conservators, that is the launch
of the “exploring” survey action at 14 th Triennal Meeting ICOM-CC, 12-16 September, The Hague,
Netherlands.
There is a growing understanding that in order to preserve our Cultural Heritage successfully, it is necessary
to actively involve the public. If the public feels a sense of responsibility and understands the decision
processes involved, we can achieve a stronger basis for the conservation of Cultural Heritage. To promote
this dialogue, the theme for the ICOM-CC 2005 Congress has been: Our Cultural Past – Your Future! The
11

main task of N2 activity is completely in agreement with this idea and therefore the ICOM – CC Conference
has been chosen as the ideal first launch of the Survey Action in the framework of EU-Artech. To reach this
goal two different actions have been carried out:
• a mini-stand was reserved nad managed at the trade fair of the congress; the stand was completely
devoted to promote Eu-ARTECH activities; some posters have been exposed regarding the
Transanational Access (MOLAB and AGLAE) and regarding the Joint Research Activity (JRA1
and JRA2); a depliant regarding the Project and particularly the Networking N2 activity has been
distributed to the public (file Euartech_depliant 2005.pdf, see Eu-ARTECH website);
• at the mini-stand two young researcher of ICVBC have explained the general aims of the N2 Survey
action, collecting the opinion of international conservators about the Forms; at the mini-stand they
also established around 100 contacts with different professionals, that have been registered in the
List of Conservators. Many observations on the forms, their content, their feasibility and clarity
were collected and thereafter discussed.
• an editorial space was prepared and printed on the newspaper of the ICOM-CC Meeting (ICOM-
CC2005-Congress-Newspaper.pdf - pag.12/20); the space consisted of one page advertisement
explaining the three different activities of the Project (Networking, Access, Research); attention was
particularly dedicated to Transantional Access and N2 activity and tSurvey on “Cleaning and
consolidation methods and materials” (see the file ICOM-CC2005-Congress-Newspaper.pdf -
pag.12/20 and file Euartech_advert _ICOM CC.pdf on the Eu-ARTECH website).
• Set up of a List of conservators
This task was particularly onerous: all the partners contributed to send a list of conservators. The list is long
and consists of about 700 names, however, the list must not be considered as closed. A Microsoft Access
specific file has been set-up to collect the survey-data: Eu-ARTECH_N2 survey_Compiler.mdb.
Many countries revealed to have a poor organisation of the professionals of restoration of cultural heritage;
in addition, the survey proposal met some resistance among some associations of restorers. In any case, at
the end of the 18 th month, about 700 compilers’ data were collected, even if the distribution of contacts
among the European countries will be improved during the next months.
Inorder to have a very large basis of Compilers (better statistics) the launch of the survey action probably
will be delayed because, according to the partners’ opinion, great care and attention should be devoted to
prepare the action: it is critically important to try to assure the maximum participation.
1.3.2.2 – Meetings and workshops
The Networking activity has been promoted during other Conferences by presentation and participation of
the partners:
- “Scienza e Beni Culturali” XXI International Congress in Brixen (I), 12-15 Jul 2005;
- the 3 rd Congress of the Italian Group IIC “Lo Stato dell’Arte” Palermo, 22-24 Sept 2005;
- 9th Congress on Environment and Cultural Heritage Chemistry, Bologna-Rimini, Italy, 8-9 Sept
2005
- 14 th Triennial ICOM-CC Meeting, The Hague, NL, September 2005.
12

1.4 Transnational Access
Access was offered by AGLAE and MOLAB. In AGLAE non-destructive elemental composition studies
were carried out, in the unique environment of the laboratories operating in the basement of the Louvre
Museum; in MOLAB access was offered to the unique collection of portable instrumentations, that allowed
users to carry out in-situ non-destructive measurements.
The milestones of both AGLAE and MOLAB for the first six months of the second year were to ensure
continuity in offering access, according to the schedules indicated in previous reports and to the
implementation plan of the period.
During the first six months of the second year, both accesses have been operative and successful
measurements have been carried out.
1.4.1 AGLAE
1.4.1.1 Description of the publicity concerning the new opportunities for access.
The possibility for users to access the AGLAE facility was spread by poster contributions at the ICOM-CC at
The Hague, Nederland (12-16 September 2005) and the IBA 2005 in Seville, Spain (26 th June - 2 nd July
2005). For this occasion A0 Posters were made and printed at the C2RFM.
Furthermore, as a reminder, an informative email announcing the deadline for proposals was spread to all
people who have shown interest in this project.
The AGLAE Access program was publicised through presentations at various international meetings:
• On the ICOM-CC conference at The Hague, Nederlands (12th - 16thSeptember 2005) the program
was presented by Michel Menu (C2RMF).
• At a one day workshop held at the BAM (Federal Institute of Materials Research and Testing) on the
17th October 2005 in Berlin, Germany, the work of AGLAE and the Eu-ARTECH AGLAE Access
program were presented in an oral presentation by Stefan Röhrs (C2RMF). This workshop was
addressing the German ion beam analysis community to reflect about current and future fields of
application of this analytical method.
• On an international symposium in Gubbio, Italy (9th – 11th November) with the title “Mastro
Giorgio da Gubbio: Art, Science & Technology of Lustred Majolicas” results of the project from G.
Padeletti (ISMN) were orally presented by Marc Aucoutouier (C2RMF), who mentioned and
acknowledged the Eu-ARTECH AGLAE Access program.
• A international workshop took place in Lecce, Italy organized by the University of Lecce with the
tile: “Non Destructive Nuclear Techniques for Dating and Analysis” (16th-17th December 2005).
Joseph Salomon (C2RMF) was invited to give a talk about “AGLAE: past, present, future” in which
AGLAE and the Eu-ARTECH AGLAE Access program were presented.
1.4.1.2 Description of the selection procedures and access activities
Proposals and their selection. For the second semester of the second year (December 2005 to May 2006), 11
proposals were received, from 10 research teams, among which 4 teams come from Italy and each one team
from Austria, Belgium, Germany, Great Britain, Romania and Spain.
These projects were evaluated by the AGLAE Peer Review International Committee, namely: Pr. Annemie
Adriaens, Department of Analytical Chemistry, University of Ghent, Belgium; Pr. Aurelio Climent-Font,
Universidad Autónoma de Madrid; Dr. Patrick Trocellier, Research Center of Atomic Energy Commission
(CEA), Saclay, France. The project evaluation was carried out on December 8 th . 3 proposals were turned
down due to the lack of time available at AGLAE. The other 8 were positively evaluated. For the period
from December 2005 to May 2006 the Eu-ARTECH users will receive 25% of the beam time available.
Table 1 at the end of this document gives a summary of the received and accepted proposals.
Among these accepted users for the first half of 2006 are some who have already participated to the AGLAE
Access program and continue their work or have submitted a different project for this semester:
13

R. Bertoncello (December 2005) aimed to analyse glass samples coated with a sol-gel silica film after
artificial weathering in a climatic chamber. These samples were previously analyzed before weathering in the
first run performed in March 2005.
A. von Bohlen will come a second time. During the last project an idea was developed to try an internal
standard calibration for PIXE to overcome problems which occur by in air analysis of thick samples with
material that have a dark matrix (i.e. wood, parchment). The problem stems from the lack of a sufficient
charge measurement by in air IBA with isolating samples.
B. Constantinescu is continuing his work on the Visigothic ‘Pietroasa’ gold hoard , based on µ-PIXE
analysis.
B. Colston continues her work on the hazardous organic and inorganic residues applied to dried botanical
collections, indeed the large number of samples involved in this study (over 300) necessitates a second run.
R. Golser will come a second time for further tests and damage evaluation on sensible parchment samples.
A. Polvorinos del Rio is coming a third time analysing lustred ceramic. He will analyse a new set of
archaeological objects from another region.
Access activity results - In the second period of 2005 (June to November) 9 research teams came to AGLAE
via the Eu-ARTECH program. The names of the group leaders, their institutes and the subjects can be found
in Table 2 at the end of this document.
The first project in June was concerned with the analysis of gold foils and objects coming from the tomb of
Akrotiki in Greece. 18 objects were analyzed by PIXE and PIGE, further more 6 objects were analyzed by
PIXE-XRF method to obtain a better limit of detection for Pt.
The second project in June dealt with the study of glass chandeliers from the Nostetangen Glassworks
factory in Norway by PIXE and PIGE. A. Björke has brought the objects to AGLAE, 110 Spectra were
acquired in this run.
Another project used the PIXE and RBS techniques to analyse the lustred ceramics from Triana/Seville,
Spain. In this project specific techniques of the ceramic workshops of Triana were identified through the
study of archaeological objects. Since the luster layer was inhomogeneous beside punctual analysis also
mappings were made. Results of this and earlier runs were submitted and excepted for the proceedings of the
IBA 2005 Conference, Seville :
A. Polvorinos, J. Castaing, M. Aucouturier, Metallic nano-particles distribution in lustre glazed ceramic
from the 15 th century in Seville. Submitted to NIM-B.
A project concerning violin varnishes was carried out with A. von Bohlen. On small wood/varnish samples
µPIXE mappings were done to find different elemental contributions for the various varnish layers. PIXE
mappings were made. Publication of this results is in preparation.
To insure the security of curators dealing with dried botanical collections the contend of hazardous inorganic
elements of an herbarium was analyzed. V. Purewal and B. Colston have brought herbarium samples from
the National Museum of Wales which were analyzed by PIXE (points and mapping). The aim of this study is
to find a easy and for every museum accessible way to estimate the hazardous potential of this collections
e.g. utilizing UV-light.
Continuing the work on the ceramic workshop of Mastro Giorgio G. Padeletti has analysed two objects from
the Town Museum from Gubbio, Italy and two objects from the Louvre. PIXE and RBS was used to enrich
the data concerning the Gubbio lustred ceramics production. The results of this run and the previous one lead
to the following publication:
G. Padeletti, G.M. Ingo, A. Bouquillon, S. Pages-Camagna, M. Aucouturier, S. Roehrs, P. Fermo, First-time
observation of Mastro Giorgio masterpieces by means of non-destructive techniques. Submitted and
accepted by Applied Physics A.
Another project dealt with the analyses of excavated glasses from the site of San Martino di Ovaro (northeastern
Italy). The samples belong to different periods of this site, a paleo-christian church (5 th – 10 th
centuries) and a market place (12 th - 16 th centuries), were brought by A. Zucchiatti. 142 points were
measured by PIXE to attribute this glass to different production periods.
In a study on corrosion of historical glasses a feasibility test was made with altered glass samples. Nonvacuum
ERDA was used to estimate the thickness of the hydrated layer on the surface of a standard glass.
The samples were provided by M. Maeder and were also analysed by other methods like 15 N-NRA in another
laboratory.
The last experiment carried out in this period concerns ion beam induced luminescence and its application in
the field of cultural heritage. A wide range of pigments and varnish materials were analyzed by A. Quaranta
14

to gain a better understanding of the processes and to find the best experimental parameter for ion beam
induced luminescence spectroscopy.
1.4.1.3 Meetings and workshops
In November 2005 a meeting of the Eu-ARTECH AGLAE users took place at the C2RMF in Paris. On this
occasion, M. Menu and J. Salomon presented respectively an overview of the C2RMF activities and of the
AGLAE facility. Five oral presentations were given by AGLAE users illustrating the work carried out in the
last six month. The given talks and authors were the following:
• Polvorinos Del Rio (University of Seville, Spain) “Analysis of lustred ceramics from the Triana
workshop in Seville”
• G. Padeletti (ISMN-CNR, Roma, Italy) “First-time observation of Mastro Giorgio masterpieces by
means of non-destructive techniques.”
• A. Von Bohlen (Institute for Analytical Sciences, Dortmund, Germany) “Violin varnishes – material
analysis using µPIXE”
• R. Bertoncello (University Padova, Italy) “Lead silicate glasses protected by silica coatings”
• M. F. Guerra (C2RMF, Paris, France) “Etruscan gold work from the Campana’s collection (Louvre
Museum): manufacture techniques and identification of 19 th century restorations and pastiches”
74 People from 11 European countries have registered to this user meeting, the participants were coming
from Italy, France, UK, Portugal, Netherlands, Czech Republic, Germany, Belgium, Spain, Greece, and
Malta. A more detailed report on the Users’ Meeting is reported in Annex 7.
1.4.2 MOLAB
1.4.2.1 Description of the publicity concerning the MOLAB access.
The diffusion of information regarding MOLAB access continued regularly through the website fo Eu-
ARTECH (www.eu-artech.org) where a prominent relevance was given to the Transnational Acces activities.
In particular, through the list of institutions and researchers collected by the networking activity N1 (see this
Report) information on MOLAB work and accessibility was capillarly diffused. The website was
continuously updated and explanations on eligibility and information on compilation of proposal forms were
improved. The website was enriched with the list of projects, carried out from the beginning of the project,
with pictures and Users Reports.
A particular advertisement on MOLAB was carried out at the ICOM-CC Triennial Meeting in The Hague
(September 2005). At the Eu-ARTECH stand, MOLAB (as well as AGLAE) had a large prominence. A
poster and a brochure were prepared and rendered avilable to potential users. The proposal preparation forms
were also available and presentation procedures were explained to interested people. Apart this diffusion, at
the end of the meeting, during the closure plenary lecture, the Director of the GCI (USA), Tim Whalen,
mentioned AGLAE and MOLAB as the most relevant opportunity offered to European conservators in the
last years. More specifically, the results obtained by MOLAB on the Vergin of the Rocks by Leonardo, at the
National Gallery of London, and on the Lamentation on the Dead Christ by Bronzino, at the Museum of Fine
Arts and Archaeology in Besancon, were described as exemplary cases of non-invasive in-situ measurements
(see ICOM-CC newspaper in the Eu-ARTECH website).
Diffusion of information on MOLAB activity was carried out also at other relevant conferences of the field.
For example, at the conference “COST and cultural heritage: crossing borders”, held in Florence on october
20 th -21 st 2005 (http://www.echn.net/cost-hig/florence2005/) , the Coordinator B.Brunetti (UNIPG) was
invited to talk on “Transnational Access in cultural heritage: the case of Eu-ARTECH”, where the focus was
centred on AGLAE and MOLAB activities. The talk was certainly successful and attracted the attention of
researchers and public.
The positive impact of MOLAB in the field is also well witnessed by the invited lecture to the LACONA VI
Meeting (6 th International Congress on Lasers in the Conservation of Artworks, Wien
http://www.lacona6.at”) that was held in Vienna on the 21 st - 25 th september 2005. The invited lecture was
entitled “MOLAB: a mobile laboratory for in-situ non-invasive studies in arts and archaeology” and was
presented by L.Pezzati (INOA).
15

1.4.2.2 Description of the selection procedures and access activities
As reported in the First Annual Report, at the Ormylia meeting of the Peer Review Committee, held in May
2005, 8 new proposals were received by researchers from Germany (1 proposal), Romania ( 1 proposal), UK
(3 proposals), Macedonia (1 proposal), Poland (1 proposal), and Spain (1 proposal). Six were approved
while two applicants were invited to present again the proposals after modifications.
At the beginning of the second year activities the list of proposals approved by the PR Committee and still to
be worked out was the following:
1- Study of the painting technique of Johann Baptist Lampi, father and son, at the Moravian Gallery in
Brno (CZ). Acronym: LAMPI. Project leader: D. Hradil.
2- Romanian illuminated medieval manuscripts in Putna: materials and techniques
Acronym: PUTNA. Project leader: M. Lupu
3- Non-invasive analysis of materials from paintings by Paul Cezanne in the Courtauld Institute
Gallery, London. Acronym: CEZANNE. Project leader: Aviva Burnstock.
4- Study of gemstones in historical jewellery at the Victoria and Albert Museum, by non-destructive
techniques. Acronym: GEM. Project leader: Lucia Burgio.
5- The Macclesfield Psalter & Metz Pontifical at the Fitzwilliam in Cambridge. Acronym: M&M.
Project leader: Spike Bucklow.
6- Analysis of polychromies and of the effects of consolidation in the stones of the façades of the
Cathedral and Provincial Museum of Huesca (Spain). Acronym: SPASTONE. Project leader: Rosa
Maria Esbert.
7- Paint on Early Meissen Stoneware in Dresden Museum. Acronym: POEM. Project leader: Anette
Loesch.
During the first six months of the second year two of these projects were carried out: the study of the
painting technique of Lampi, father and son, in Brno (Czek Republic), and the study of materials of the
Romanian illuminated medieval manuscripts in Putna (Romania). The works were carried out in june and
september 2005. Of these two works is reported in the website of Eu-ARTECH. In both cases the results
permitted to achieve significant conclusions on the execution techniques of the examined artworks. The work
on the painters Lampi (father and son) was presented by D. Hradil at the First MOLAB Users Meeting in
Paris at C2RMF the 23 rd november 2005. For a report on the meeting see Annex 7.
At the moment of writing the present report (december 2005) another of the planned MOLAB intervention
was carried out: the project CEZANNE at the Courtauld Institute of Art Gallery in London.
Further interventions will be carried out in january 2006 in London, at the V&A Museum (GEM) and at the
Fitzwilliam Museum in Cambridge, UK (M&M). Other interventions have been planned during the spring
2006 in Huesca, E (SPASTONE), and possibly Dresden, D (POEM).
The deadline for new proposals, relative to the second semester of the second year (december 2005-may
2006), was november 1 st . Nine new proposals were received. Their evaluation was carried out during the
Second Interim Meeting in Paris on november 23 rd , 2005. At the PR meeting six of the presented proposals
were approved. One was not recognised as eligible for MOLAB because the movement of the laboratory was
not justified; the second was recognised as interesting but the planned measurements could be not adequate
to solve the specific conservation problems; the third proposal was extremely interesting and very well
presented but the location of the work (a site in China) requires a specific preparation and difficulties in
logistics, therefore the proposers were invited to present again the proposals at the next deadline, leaving
time to the PR committee and MOLAB office to evaluate the feasibility of the intervention.
At the Interim Meeting in Paris, the Steering Committee evaluated as positive the activities developed.
Milestones were all respected.
Table: A2 - Summary of selection Panel activities during the reporting period (MOLAB PRC)
Date
Selection
meetings
Location
Projects
N° & Countries
Submitted Selected
Nov 2005
4 rth MOLAB-PRC
Meeting
Paris 9
Germany[1], United Kingdom
[2], Bulgaria [1], Portugal [2],
Greece [1], Turkey [1], Italy [1]
6
16

1.4.2.3 Meetings and workshops
A joint meeting INOA-UNIPG-OPD and CNR-ICVBC was held in Florence during the “COST and Cultural
Heritage” meeting (october 2005). The logistic organisation of the planned MOLAB interventions was
discussed among partners and a defined calendar was established, according to the decisions of the MOLAB
PR Committee.
At the Florence COST meeting, B.Brunetti presented as invited speaker the talk “Transnational Access in
Cultural Heritage: the case of Eu-ARTECH”, where both MOLAB and AGLAE TA activities were
presented.
L. Pezzati (INOA) participated, as invited speaker, to the conference LACONA VI in Vienna, presenting the
talk “MOLAB: a mobile laboratory for in-situ non-invasive studies in arts and archaeology”.
The First AGLAE and MOLAB Users Meeting was organised by Eu-ARTECH in May 2005 and held in
Paris, at the Louvre Pavilion (C2RMF). The morning was dedicated to the presentations of the work
developed by AGLAE users, while the afternoon was dedicated to the MOLAB Users. The meeting had a
large participation, including potential users (see Annex 7 ). After a general presentation of C. Miliani on the
more recent acquisitions and improvement of performances of MOLAB, Luke Syson (National Gallery,
London), Bruno Mottin (C2RMF, Paris), Lucia Burgio (V&A Museum, London), D. Hradil (Academy of
Science, Prague – Moravian Gallery, Brno), and Sophia Sotiropoulou (as substitute of Demetra Papanikola-
Bakirtzis) presented the work developed through the MOLAB facility. The meeting was also the occasion for
the users to meet each other and to discuss not only the scientific aspects of the work, but also to evaluate the
MOLAB intervention together with the users.
Suggestions about the improvement of the website were done, especially regarding the communication of the
evaluations of the PR Committee. All the users declared their satisfaction for the opportunities offered by
MOLAB, expressing the intention to present further proposals in the future.
17

1.5 Joint research activities
The continuation of both the two Eu-ARTECH JR activities was foreseen. As explained in the previous
reports, JRA1-Development and evaluation of new treatments for the conservation-restoration of outdoor
stone and bronze monuments has the objective to clarify and define advantages and limits of new
conservative treatments on outdoor monuments, comparing new and traditional methods. The second joint
research activity, JRA2-New methods in diagnostics: Imaging and spectroscopy is dedicated to the
development of new methodologies in diagnostics and monitoring, setting-up innovative instrumentation for
in-situ non-invasive and non-contact measurements.
1.5.1 JRA1- Development and evaluation of new treatments for the conservation-restoration
of outdoor stone and bronze monuments
The planned work for the first six month of the second year was concerned with the partial development of
Task2-Development of new treatments and procedures-chemical process and application prococols (resp.
UNIPG) and Task3-Accelerated ageing of samples-stone and bronzes (resp. LNEC). The work was developed
according to the planned schedule and milestones were all achieved. A Report on the developed activities is
in Annex 8.
Participants are CNR-ICVBC, UNI-PG, UNI-BO, BLFD, LNEC and OPD.
1.5.1.1 Activity progress
The definition of the drilling parameters for testing Ançã and Lecce stones was set within the scope of Task
1, finished in the middle of the 1st year. However, during the reporting period, some complementary work
was carried aiming at improving the drilling conditions, taking advantage of new innovative developments
introduced in this testing tool. The conditions addressed were: drying of specimens; drilling speed; use of a
pilot-hole and dust extraction. The new results pointed out the importance of using dried specimens and the
benefit of using the pilot hole drilling technique with dust suction. Although the hole-over-hole drilling
technique significantly lowered the range of forces in Ançã and Lecce stones, the discrimination of any
subtle differences (such as a consolidation action) is assured by the increased reliability and precision of the
data obtained with the new technique. The new drilling conditions adopted on the basis of the results are
reported in the Summary report of Annex 8.
Task 2- For the study of the chemical processes and identification of the critical parameters of the treatment,
a study was carried out by UNI-PG on the kinectic aspects of artificial oxalate formation on carbonatic
stones and sandstones, compared to ethylsilicate in two treatments (TEOS and TEOS + coupling). For the
applied conditions, the kinetic study indicated that a plateau in quantity of oxalate is obtained after 48 hours.
Among the various stones, marble is producing the highest quantity, followed by limestones and sandstones.
The same comparisons of oxalate treatments with TEOS and TEOS+coupling treatments were carried out on
limestones by LNEC. Two different types of treatments (immersion and poulticing) with ammonium oxalate
were tested, monitoring relevant parameters such as colour variation, water absorption, and drilling
resistance.
ICVBC, studied treatments by Ba(OH)2 in different conditions, monitoring performances, in terms of colour,
quantity of product, water absorption, etc. Finally, OPD carried out a study on the influence of salt
contamination in the treatments.
Task 3- Tests on ageing procedures of marble by thermal shock (ICVBC) and of sandstone either with
thermal shock and salt contamintaion ( LNEC) were also carried out.
The results of all these studies are reported in Annex 8.
Analogous advances of the work were carried out on T2 and T3 for bronzes by UNIBO, BLFD, and LNEC.
Details on this activity are again in Annex 8.
18

1.5.1.2 Meetings and workshops
A general working meeting has been held, with all the participating researchers (representatives from CNR-
ICVBC, LNEC, UNIPG, OPD, BLFD, UNIBO), during the Eu-ARTECH meeting in Paris, November 22 nd
2005. During the meeting the developed activities have ben discussed and coordination plans on future
activities established.
The developed work has been presented at the following conferences:
- “Scienza e Beni Culturali” XXI International Congress in Brixen (I), 12-15 Jul 2005;
- 14 th Triennial ICOM-CC Meeting, The Hague, NL, September 2005.
- 9th Congress on Environment and Cultural Heritage Chemistry, Bologna-Rimini, Italy, 8-9 Sept
2005
- the 3 rd Congress of the Italian Group IIC “Lo Stato dell’Arte” Palermo, 22-24 Sept 2005;
1.5.2 JRA2- New methods in diagnostics: Imaging and spectroscopy
By this activity, four different new analytical methodologies for artwork studies are developed, assembling
in parallel four new portable equipments for in-situ non destructive measurements.
In Task1, new applications of NMR techniques to artwork studies are foreseen, included the application of
the portable NMR-MOUSE; in Task2, two different and complementary methods for imaging spectroscopy
in the near IR are set-up: high resolution imaging at various fixed wavelengths, with low wavelength
resolution, and low resolution imaging at continuous wavelengths, with high wavelength resolution; in
Task3, a new method is developed and experimented for in-situ X-ray diffraction (XRD) and X-ray
fluorescence measurements (XRF); in Task4, an existing portable micro-Raman technique is joint with the
VIS micro-fluorescence technique for the identification of organic colorants.
1.5.2.1 Activity progress
Task 1 -Application and development of laboratory analytical NMR methods and of protable NMR-MOUSE.
Subtask 1.1 (UNIPG, RWTH) The study of the behaviour of clay as a function of temperature continued
with the writing of a paper that has been published on Journal of Physical Chemistry. Further measurements
have been carried out on new clay samples. Measurements are in progress.
Subtask 1.2 (UNIPG, RWTH) A study has been started on the NMR determination of water content in stones
measuring spin-lattice (T1) and spin-spin (T2) relaxation times with the objective to establish correlations of
T1 and T2 with stone porosity, pore size distribution, permeability, etc. Three Umbrian stones have been
chosen for the first approach: San Presto, Pianello, and Palombina Turri. Through Hahn Echo experiments
the moisture content of these stones, in equilibrium with the environment, have been determined. It was
found that the highest water content in normal conditions is in San Presto stone. Regarding the T1
measurements, it was found that San Presto stones show the shortest T1 values. For T2 the values are
comparables. Subsequent measurements were carried out on San Presto stones wetted by water capillary
absorption. A clear increase in the Hahn Echo was found. In addition, an increase of T2 spin-spin relaxation
time have been observed due to the increased water in the pores. (See Annex 9)
Subtask 1.3 (RWTH, UNIPG) Towards the perspective of realisation of a device for the 3 D non-invasive
study of painting layers an NMR sensor has been developed placed on a table that can be micrometrically
moved to probe layers with a depth resolution of about 20 micrometers. No contact is necessary with the
painting: once the panting and probe are aligned, the sensor is able to “explore” the material in depth.
Through this new device it has been possible to carry out measurements where the thickness of paint layers,
preparation, and canvas have been measured in several historical panel paintings at The National Gallery of
Umbria. Among the studied painters are Gentile da Fabriano, Pietro Perugino, and Piero della Francesca.
Data are in Annex 9.
19

Task2-New devices for multispectral imaging of painted surfaces in the near infrared.
Subtask 2.1. and 2.2 (OPD, OADC) The reference panel (standards) prepared during the first year have been
characterised microscopically, through SEM picture recordings and EDS, Energy Dispersive X-ray
Spectroscopy. Samples were taken out from the standards and cross sections were appropriately prepared for
the study.For each examined sample, a BSE image of the cross section and EDS spectra of the various paint
layers have been recorded.
Other special reference samples have been prepared and spectroscopically characterised in the IR range.
They have been prepared with gradually higher paint layer thickness in order to study the transmission and
reflection of the IR radiation through them. These samples are painted on a common white ground and with
the same binding medium in order to minimise the uncertainty of the applied algorithm during the tests.
Examples of cross section images, EDS spectra at differenth depth, and IR analyses are given in Annex 9.
Subtask 2.3 (OADC, INOA) Advances in the assembling of the two nIR imaging equipments have been
done. In particular, in OADC a golden integration sphere has been assembled in order to permit the study of
reflection and integration of the IR radiation from 800 nm up to 4500 nm. Details of the design of the
integration sphere are in the Annex 9.
On the other side, INOA provided to better establish a new set of cost-effective IR detectors, to design and
realise the filter holders, the sub-rack unit, and the first proptotype of 16 fiber bundle. In this case, 14 Vis-
NIR and 2 UV-Vis multi-mode optical fibers were used, with a cladding diameter of 230 microns. In order to
properly align the 16 fibers in a square-shaped bundle, a 1 mm grove was dig.
Task 3. A new device for in-situ XRD and XRF measurements.
Continuing the task for the determination of the optimal conditions for XRF and XRD in-situ measurements,
the Energy Dispersive X-ray Diffraction (ED-XRD) was already ruled out based on literature survey.
However, during this period diffraction experiments were carreied ou to verify performances of ED-XRD
with the traditional angular detection. Few different specimen were analysed: polycristalline silicon, quartz,
calcite, and calcite covered by a thin layer of goethite. The measurements were carried out at 2 or 3 different
2-Theta angles for each sample (this resulted in a shift of the energy peak positions). A significant case was
that of polycristalline Si, because its fluorescence peaks are in the low energy range, in this way the
diffraction peaks interfer only with the Cu signal due to the anode of the X-ray tube. For the other samples,
the overlapping of fuorescence and diffraction can represent a strong difficulty in the spectra interpretation.
Due to this overlap, the technique was confirmed not suitable for mineral identification with a portable
instrument. Moreover fluorescence peaks are usually much more intense than diffraction ones. Another
problem is that the diffraction peak intensity is not only weak, but also is quite large, due to the detector
energy resolution and to the superposition of different diffractions. In principle these problems could be
overcome by systematically doing measurements at several different angles. This could be done in a
relatively quick measurement time by using a multi-element detector or some single detectors located at
different 2θ angles. Indeed this solution could be appropriate, but it requires a complex and heavy equipment
(not easily portable!) and also a non-trivial data analysis.
In conclusion, the initial idea, based on the literature, to rule out the ED-XRD for the planned portable
system was widely confirmed.
In a second phase, X-ray diffraction using an “imaging plate” detection was experimented. Test
measurements have been performed at the Laboratoire de Cristallographie (CNRS UPR 5031) in Grenoble.
The source used was a Philips C-Tech type x-ray tube, with Cu anode and a maximum power of 2200 W (60
kV). The x-ray beam was monochromatic by means of two mirrors: only Kα1, Kα2 and Kβ appear in the
spectrum (with approximately the following ratio between intensities Kα/Kβ≈10 -3 ÷10 -4 ). The divergence of
the beam was approximately 0.05° and its dimension was around 1.5mm x 1mm in the centre of the
goniometer, with a flux of around 10 7 ph/s. The tube was biased at 50 kV and 40 mA.
For each investigated sample two XRD detector systems have been used:
- a conventional scintillator detector, with a monochromator in front of it, in a θ-2θ configuration
- an Imaging Plate (IP) perpendicular to the incident X-ray beam at distance of around 20 cm from
sample.
The Imaging Plate detector proved to be a valid alternative to the one-dimensional scintillator detector: the
measurement times are comparable (around 20÷30 minutes for both), even if Imaging Plate seems to be more
efficient. Imaging Plates have the big advantage of being a two-dimensional low-noise system, with a
flexible and wireless mounting, and they allow to collect data in a parallel detection configuration. On the
20

other hand the scanner system requires around 3 minutes to read the recorded image (it is not an online
measurement; the result is visible only at the end of the process) and Imaging Plates are light sensitive
(Annex 9).
Task 4 – A joint micro-Raman and micro-fluorimeter new portable apparatus.
The vibrational and electronic characterisation of dyestuffs and lakes was continued largely increasing the
microRaman and UV-VIS fluorescence database of solid powder standard dyes and lakes.
Standard materials have been examined employing micro-Raman in the lab set-up using two excitation
wavelength 532 nm and 785 nm. The portable set-up has been experience as micro-Raman using the 532nm
excitation and as fluorimeter using again the 532nm excitation, but conveniently moving the polychromator.
MicroRaman and fluorescence spectra are reported in the database format in Annex 9. Interestingly, the
portable equipment has been proven to be well set-up for the study of red anthraquinone dyes, in fact in this
case using the 532 nm excitation it is observed a resonance enhancement and a relatively low fluorescence
background thanks to a large Stoke shift.
1.5.2.2 Meetings and workshops
A general working meeting has been held with all the participating researchers (representatives of UNIPG,
RWTH, INOA, OADC, and C2RMF) during the Eu-ARTECH meeting in Paris, november 2005.
A bilateral meting RWTH and UNIPG was held in Perugia, from July 17 th to 22 nd (J.Perlo, RWTH;
F.Presciutti, B.Brunetti, A.Sgamellotti, UNIPG). The meeting was dedicated to discuss details of the portable
NMR depth-profile device. Improvements were introduced and measurements were carried out at the
National Gallery of Umbria. A report on these measurements is in the Annex 9.
Another working meeting on the NMR depth-profile was held in Perugia, in the evening of july 20 th , at the
end of the NMR School on portable NMR in Cultural Heritage. Participants were: B. Bluemich, F.Casanova,
and J.Perlo, RWTH, and F.Presciutti, B.Brunetti , and A.Sgamellotti, UNIPG. During these meeting the
results obtained in the lab-study on water content in Umbrian stones were examined and discussed. A plan of
new measurements was also done.
21

2. LIST OF DELIVERABLES
Activity
N1
Deliv
No
Deliverable Name Task No Delivered by
Contractor
1 REPORT ON THE STANDARDISED FORMAT
FOR DESCRIBING ANALYTICAL
PROCEDURES.
2 REPORT ON INTERLABORATORY
COMPARISON
3 REPORT ON OVERVIEW ON POSSIBLE
SHARING OF REFERENCE MATERIALS
4 REPORT ON THE NMR WORKSHOP (CD
ON PRESENTATIONS)
Task 1c
Task 1b
OADC, ICN, NGL,
IRPA,OPD,ICVBC,
UNIPG,UNIBO,
C2RMF, LNEC,
BLFD
OADC, ICN, NGL,
IRPA,OPD,ICVBC,
UNIPG, C2RMF,
LNEC, BLFD,
UNIBO
Task 2a ICN, NGL, IRPA,
OADC, UNIPG,
Task 2c UNIPG, RWRTH,
NGL, OPD
OADC
Plan
ned
(imon
ths)
Achieved
(months)
18 18
[Annex 4 ]
18 18
[this report
and Annex 4]
18 18
[this report,
pages 7-8]
18 18
[Annex 5 ]
5 REPORT ON THE GUPIX COURSE Task 2c C2RMF 18 18
[Annex 6 ]
N2 6 MULTI LANGUAGE FORMS
Task 1d CNR-ICVBC, OPD,
IRPA,ICN,LNEC,
UNIPG, C2RMF,
BLFD,NGL, UNIBO,
OADC
18 18
[see website;
res.area]
7 DATABASE FOR THE ANALYSIS OF
RESULTS OF THE SURVEY ACTION
Task 1d CNR-ICVBC, OPD 18 18
[see website;
res.area]
8 REPORT ON THE SURVEY ACTION AT
ICOM-CC
Task 1d CNR-ICVBC, ICN,
UNIPG, C2RMF
IRPA, OPD, OADC
18 18
[this report
and website]
9 SET UP OF A LIST OF CONSERVATORS Task 1d CNR-ICVBC, OPD, 18 18
IRPA,ICN,LNEC,
UNIPG, C2RMF,
BLFD,NGL, UNIBO,
[for the list,
see website;
res.area]
TA1 10 SUMMARY REPORT ON AGLAE
11 1 ST
USERS’ MEETING REPORT C2RMF,
UNIPG,INOA,CNR-
TA2 12 SUMMARY REPORT ON MOLAB
C2RMF 18 18
[this report,
ICVBC,OPD
UNI-PG, INOA,
CNR-ICVBC, OPD
13 1 ST
USERS’ MEETING REPORT C2RMF,
UNIPG,INOA,CNR-
JRA1 14 PROGRESS REPORT ON THE
PROCEDURES TO BE ADOPTED FOR EACH
TREATMENT UNDER STUDY
15 PROGRESS REPORT ON THE
CHARACTERISTICS OF THE SAMPLES
JRA2 16
(STONE AND BRONZE) DURING AGEING
PROCEDURES
PROGRESS REPORT ON LAB NMR AND
METHODOLOGY FOR IN-SITU STUDY OF
WATER-RELATED PROPERTIES OF STONE
Task 2
ICVBC,OPD
CNR-ICVBC,UNIPG,
BLFD,OPD, and
participating partners
pages 13-15]
18 18
[Annex 7 ]
18 18
[this report,
pages 15-17]
18 18
[Annex 7]
18 18
[Annex 8]
Task 3 UNIBO, BLFD,LNEC 18 18
[Annex 8]
Task1-
Subtask
1.1
UNI-PG,RWTH 18 18
[Annex 9]
22

17 PROGRESS REPORT ON NMR MOUSE
3D
18 PROGRESS REPORT ON MICRO- AND
SPECTROSCOPIC CHARACTERISATION OF
STANDARDS.
19 REPORT ON OPTIMAL CONDITIONS FOR
ARTWORK XRD STUDIES AND ON
XRD&XRF SYSTEM DESIGN AND
ASSEMBLING.
20 REPORT ON THE SPECTROSCOPIC
CHARACTERISATION OF THE PREPARED
SAMPLES.
Task 1-
Subtask
1.3
RWTH , UNIPG 18 18
[Annex 9]
Task2- INOA, OADC 18 18
[Annex 9]
Task3-
Subtask
1
Task4-
Subtask
1
CNRS-C2RMF 18 18
[Annex 9]
UNIPG 18 18
[Annex 9]
23

3. USE AND DISSEMINATION OF KNOWLEDGE
Dissemination has been carried out through all the media that are commonly available to contact potential
users (that are identified as conservation scientists, conservator, restorers, libraries, museums, schools on
conservation, cultural institutions, etc.) but also public. Indeed, conservation of cultural heritage has strong
societal implications and it is of general interest for the public and policy makers. Used media have been:
internet, e-mail, conferences, contacts with other organisations, and, in some cases, press.
The Eu-ARTECH website (www.eu-artech.org) was continuosly adjourned, introducing new pages and links
in the effort to create an easily readable interface with institutions internal and external to the Consortium,
potential users, and public. A specific restricted area, accessible only by password, was reserved to the
exchange and diffusion of working documents.
A list of relevant websites of interest in the conservation science and conservation/restoration of cultural
heritage was also established and made accessible in the website.
A specific relevance was given to the AGLAE and MOLAB Transational Access starting from the home
page. Information is also available on the projects already developed, through the Users Report on-line e
picture documentation.
Relevance is also given to the events, open to potential users and public, organised or promoted by Eu-
ARTECH such as workshops, schools, conferences and meetings.
The website has been built as the more friendly interface between the Consortium and the community of
conservation scientists, conservators, restorers, scholars, as well as funding agencies and policy makers.
The effort on establishing fruitful interactions among Eu-ARTECH and relevant infrastructures in the field
of cultural heritage had no stop. On this type of dissemination of knowledge has been given large space ib
the networking N1 section of this report.
Other diffusion or dissemination of knowledge was carried out through plenary lectures, invited conferences,
seminars, or presentations of Eu-ARTECH programs and initiatives in relevant international and national
congresses and meetings, such as:
- “COST and Cultural Heritage: crossing borders” – Florence – October 20-22 2005
(http://www.echn.net/cost-hig/florence2005) a European meeting where the COST activities of the field have
been discussed in the perspective of future developments. During this meeting, Eu-ARTECH had a large
evidence. The Coordinator gave the lecture: “Transnational Access in Cultural heritage: the case of Eu-
ARTECH”.
- “3rd International conference on the application of Raman spectroscopy in art & archaeology”– Paris - 31
August - 3 September 2005
-“MODHT end-of-project meeting” on 20th-21st June. (Monitoring of Damage in Historic Textiles).
- “29 th International Symposium on High Performance Liquid Phase Separations and Related Techniques”,
26-30 June 2005, Stockholm, Sweden
-“MaSC Users Group”, 7-10 September 2005, Van Gogh Museum, Amsterdam.
-“Dyes in History and Archaeology annual meeting, DHA 24”, in Liverpool, 3-5 November 2005.
- “14th ICOM-CC Triennial Meeting” - The Hague - 12-16 September 2005.
Contacts have been consolidated with organisations developing activities in the same field or of interest in
the field, such as:
- I3 initiatives, such as LASERLAB (http://www.laserlab-europe.net/index.html) , NMI3
(http://neutron.neutron-eu.net/n_nmi3), and IA-SFS (http://www.elettra.trieste.it/i3/), also working in the
field of cultural heritage;
- infrastructures operating in the field, such as the ICTP (Abdus Salam International Centre for Theoretical
Physics of Trieste, http://www.ictp.it/ ) or the LABEC – INFN of Florence (http://labec.fi.infn.it/index.html);
- EC projects, such as COST G8 (http://srs.dl.ac.uk/arch/cost-g8/index.htm), COST G7
(http://alpha1.infim.ro/cost/pagini/home.html), CEN/TC 346 (http://www.cenorm.be/CENORM/index.htm)
dedicated to the “Conservation of Cultural Property;
24

- ICOM-CC (http://icom-cc.icom.museum/) or IIC (http://www.iiconservation.org/index.php);
- Marie-Curie actions, such as ATHENA and EPISCON
(http://www.scienze.unibo.it/Scienze+Matematiche/Post+Laurea/Altri+corsi+post+laurea/episcon.htm), a
European PhD in Science for Conservation.
Regarding the press, Eu-ARTECH activities were disseminated in occasion of the press release, organised by
the National Gallery of London on the work developed, through MOLAB, on the “Vergin of the Rocks” of
Leonardo. The new had a European relevance.
25

Annex 1
ANNEXES
Summary Report of the Second Interim Meeting
Paris, november 21 st -22 nd 2005 – Pavilion du Louvre- C2RMF
The meeting was helsd in the rooms of the C2RMF with participants from all the Consortium institutions.
The following people was present:
Nathalie Balcar C2RMF, Bernhard Blümich RWTH, Eliane Bohnert C2RMF, David Bourgarit C2RMF, Jean
Louis Boutaine C2RMF, Susanna Bracci CNR-ICVBC, Brunetto Giovanni Brunetti UNIPG, Laura
Cartechini UNIPG, Jacques Castaing C2RMF, Nathalie Collain CNRS, José Delgado Rodrigues LNEC,
Maria Douka CEE, Ana Paula Ferreira Pinto Instituto Superior Técnico (IST), Alessandra Gianoncelli
C2RMF, Ineke Joosten ICN, Mathias Kocher BLFD, Christian Lahanier C2RMF, Anne-Solenn Le Hô
C2RMF, Martin Mach BLFD, Francine Mariani-Ducray Direction des Musées de France, Vincent Mazel
C2RMF, Rocco Mazzeo UNIBO, Michel Menu C2RMF, Costanza Miliani UNIPG, João Mimoso LNEC,
Christiane Naffah C2RMF, Cristiana Nunes LNEC, Sandrine Pagès C2RMF, Juan Perlo RWTH, Luca
Pezzati INOA, Daniela Pinna OPD, Martine Regert C2RMF, Pascale Richardin C2RMF, Dominique Robcis
C2RMF, Stefan Röhrs C2RMF, Ashok Roy NGL, Barbara Sacchi CNR – ICVBC, Barbara Salvadori OPD,
Manfred Schreiner Academy of Fine Arts Wien, Antonio Sgamellotti UNIPG, Sophia Sotiropoulou OADC,
Marika Spring NGL, Olivier Tavoso C2RMF, Lucia Toniolo CNR – ICVBC, Stéphane Vaiedelich Musée de
la musique de Paris, Maarten Van Bommel ICN, Elsa Van Elslande C2RMF, Ina Vanden Berghe KIK –
IRPA, Jan Wouters KIK – IRPA.
The meeting started with the introductory notes of the new Director of C2RMF, Dr. Christiane Naffah, who
presented herself to the Consortium and welcomed all participants.
After a general review by M. Menu (C2RMF) of the planned two days work, the Coordinator B.G. Brunetti
opened the formal meeting presenting the main line of the Eu-ARTECH dissemination of knowledge during
the period June-November 2005. He mentioned the Schools and Meetings sponsored or directly organized by
Eu-ARTECH, such as
-the “3 rd International Conference on the application of Raman spectroscopy in Art and Archaeology” (Paris
F, Aug 31-Sept 3,2005);
-the Workshop on Non-invasive NMR in Cultural Heritage and NMR Colloqium (Perugia, I, Sept 19-23,
2005);
-the GUPIX School (Paris, Oct 6-7, 2005).
B.Brunetti dedicated particular attention to the description of the presence of Eu-ARTECH at the Triennial
Meeting of ICOM-CC (The Hague, NL, September 2005).
Dr. Maria Douka of the R.I. Office of the EC, presented the perspectives of evolution of Research
Infrastructures towards the 7 th Framework Programme. Great attention of the odeon was achieved during the
discussion of the activities of ESFRI and the perspectives of creation of the ERA in the field.
I - Consortium Governing Board n. 4
After a short break, the fourth Eu-ARTECH Consortium Governing Board was held. According to the
Consortium Agreement, this meeting was restricted to the Coordinator and one authorised representative for
each participant infrastructure.
The following representatives were present: Coordinator: B.Brunetti; UNIPG: A. Sgamellotti; CNRS-
C2RMF: M.Menu; CNR-ICVBC: S.Bracci; NGL: A. Roy; OPD: D. Pinna; BLFD: M. Mach; OADC: S.
26

Sotiropoulou; ICN: M. Bommel; LNEC: J. Delgado; IRPA: J. Wouters; RWTH: B. Bluemich; UNIBO: R.
Mazzeo; INOA: L. Pezzati.
1- Amendments to the contract
The Coordinator announced that from June 1 st INOA formally merged into CNR, however it was authorised
to maintain its administrative rules, being entered in a transitory phase. The GB decided to ask to the EC R.I.
office if the change of model cost from AC (cost model of INOA in the contract) to FC (the cost model of
CNR) is obligatory or can be postponed up to the end of the transitory phase. In case of obligation, the
request of amendment of the contract is to be considered authorised by the GB.
B. Brunetti illustrated the content of the clause 39 that could be introduced in the contract. It allows
institutions having an annual budget lower than 150.000 euros to skip the audit. Specifically, clause 39 says:
“Nothwithstanding the provision of article 7.2 of this contract, contracors requesting a EC financial
contribution for one or more reporting periods of less than 150.000 euros, need not to submit an audit
certificate, until the comulative request for EC financialcontribution is equal or exceeds 150.000 euros for
the reportingperiods for which an audit certificate has not yet been submitted.In all cases an audit certificate
shall be submitted at the latest 45days after the final reporting period. This final audit will cover all the
periods for which an audit certificate has not been previously submitted.”
The Coordinator presented and discussed advantages and possible inconvenients of the introduction of clause
39. After accurate evaluation by the Consortium representatives, it was decided to renounce to clause 39 and
accept the rule of presenting every year the Audit Certificate for each institution.
As a third point, the possible extension of RWTH participation to Eu-ARTECH was discussed. The original
formulation of the contract includes a participation of RWTH limited to the first two years. However, RWTH
is developing a relevant work on new NMR methodologies for the laboratory and in-situ studies of artworks;
therefore, it would be important for Eu-ARTECH to extend its participation, at least, for another year. All the
partners agreed on this point. In order to allow RWTH to continue its activity, the Coordinator proposed to
shift part of the UNIPG budget (corresponding to an amount of 25.000 euros) to RWTH. Unanimously, the
GB accepted the proposal of the Coordinator inviting him to proceed to the request of amendment of the
contract.
The Coordinator communicated that the Bank of UNIPG changed its coordinates. The change was due to the
merging of the Banca dell’Umbria into the largest UniCredit Banca. The new coordinates will be
communicated to the EC asking for the relative amendment of the contract. All GB members agreed with the
request of amendment. The new name of the Bank is: UniCredit Banca; the new IBAN:
IT58G0200803016000029489728.
2- Administrative notes
The Coordinator informed the Consortium member representatives that the procedure to close the First
Annual Report with the inclusion of the Audit Certificates of all the participating institutions was not yet
ended. However, all the documentation should be ready in few days.
In any case, due to the strong foreseen delay in the pre-financing of the second year, the Coordinator
announced to reserve to himself the use of the residue of the budget of the First Year, not yet distributed to
the partners, for a pre- prefinancing of those institutions (only) that spended all (or almost all) their first year
budget.
The assembly was favourable.
3- Next Annual Meetings
At the end of the GB meeting the proposal of Munchen as location for the Third Year Annual Meeting was
advanced by M. Mach of BLFD. The proposal was unanimously accepted.
The National Gallery of London, as possible site for the Third Year Interim Meeting was also proposed and
accepted.
Therefore the locations of the next Eu-ARTECH meetings is the following:
-Second Year Annual Meeting – Lisbon, LNEC, May 3-5 2006;
-Third Year Interim Meeting – London, NGL, date to be established;
-Third Year Annual Meeting, Munchen, BLFD, date to be established.
27

4- Note
It has been proposed by LNEC and accepted by GB, to define and publish on the Eu-ARTECH website a list
of trainees & training opportunities “stock exchange” among the participating institutions. Such a simple and
flexible item will permit to increase and diversify the training possibilities in the areas of the project. No Eu-
ARTECH funding will be involved. Institutions and/or trainees will manage by themselves to find the
necessary financing.
With this last decision, the Governing Board meeting was closed.
II- Networking N1 and N2 Joint Activities.
After the lunch break, the meeting continued with the discussion of the networking activities N1 and N2.
Rocco Mazzeo (UNIBO) briefly presented the project EPISCON (European PhD in Science for
Conservation), a Marie Curie Early Stage Training fellowships of the 6th Framework Programme, recently
approved.
J.L.Boutaine, the Convenor of N1 introduced the discussion of N1 activities.
N1 networking specific activities of the first six months of the second year consisted mainly in the
continuation of Task 1 on Analytical resources, analytical procedures and investigation strategies,
especially referred to organic substance investigations and the start of Task 2- Exchange knowledge and
expertise. Within Task 1 the continuation of dissemination of Eu-ARTECH activities on analytical
investigations of artwork materials was also planned (with particular reference to examination of paintings).
Discussions followed where all the activities developed in the various tasks and subtasks were presented.
Lucia Toniolo introduced then the discussion on N2. The problems related to the translation of the survey
forms were discussed and the data base structure for the analysis of results of the survey was presented. It
was also presented the diffusion of the survey action at the ICOM-CC meeting (a specific association of
conservators and conservation scientists), where it was started the set-up of a list of conservators interested to
participate to the survey.
III- Transnational Access Activities
M.Menu, C2RMF, shortly presented the AGLAE access activity of the first six months of the second year.
Immediately after, C.Miliani, , UNIPG, did the same for the MOLAB activities. The presentation was limited
to few information on the proposals received (10 for AGLAE and 9 for MOLAB) because a wider
discussion on Transantional Access is forseen for the day of November 23 rd , where the First Users Meeting
of AGLAE and MOLAB will be held.
At the end of the first day, a social dinner was held at the Restaurat “Gran Louvre” inside the Museum.
According to the Agenda, the morning of tuesday 22 nd , the meeting started with the presentation of the Joint
Research activities.
IV – Joint Research Activities.
Regarding JRA1, under the coordination of S. Bracci, ICVBC, kinectic aspects of artificial oxalate formation
on carbonatic stones and sandstones compared to ethylsilicate in two treatments (TEOS and TEOS +
coupling) were presented by C. Miliani, UNIPG. The same comparisons of oxalate treatments with TEOS
and TEOS+coupling was carried out on limestones by LNEC (J. Delgado). S. Bracci, ICVBC, described
results obtained in treatments by Ba(OH)2 in different conditions (verification of performances, in terms of
colour, quantity of product, water absorption, etc).
Tests on ageing procedures of marble by thermal shock and of sandstone either with thermal shock and salt
contamintaion were also presented. Finally, OPD (D.Pinna) presented results on treatments by oxalate and
procedures for contamination by salts.
28

Analogous advances of the work were discussed for bronzes by R.Mazzeo, UNIBO, M. Mach, BLFD, and
J.Mimoso, LNEC.
In the afternoon, after the lunch break, first the results obtained on JRA2 laboratory NMR studies were
presented by UNIPG. These studies led to a publication that will appear on Journal of Physical Chemistry A.
The paper will concern with the structural aluminosilicate modifications during the firing of clays. The more
recent results on portable NMR were also presented, regarding the performances of the NMR profilometer
developed under the coordination of RWTH. Then the recent advances on the systems for IR imaging were
presented by L.Pezzati, INOA, and S.Sotiropoulou, OADC. A. Gianoncelli presented the advancement in the
work carried out by C2RMF in setting a new XRF and XRD equipment and, finally, A.Sgamellotti presented
the more recent results for the system to carry out micro-Raman and micro-fluorescence measurements.
At the end of all the presentations, the Coordinator and the Steering Committee verified that in all cases, the
work had a regular development and milestones were achieved, according to the contract.
Before the closure, the Coordinator briefly synthetised the work carried out during the two days of the
meeting and traced the general lines of development of the work to be carried out during the following six
months. Final thanks were addressed to C. Naffah, M.Menu and all C2RMF members, who took care of the
excellent organisation.
29

Annex 2
Components of the Peer Review International Committees
AGLAE
MOLAB
Components of the Peer Review Committee
Annemie Adriaens Department of Analytical Chemistry, University of Ghent,
Belgium
Aurelio Climent-Font Departmento de Física Aplicada, Universidad Autónoma de
Madrid, Cantoblanco, Madrid, Spain
Patrick Trocellier Research Centre of Atomic Energy Commission (CEA), Saclay
France
Jean Claude Dran AGLAE representative
Manfred Schreiner Institute of Chemistry, Academy Fine Arts, Vienna , Austria
Modesto Montoto Dept. of Geology, Group of Petrophysics, University of
Oviedo, Spain
Marisa Tabasso Former Director of Laboratories of Istituto Centrale del
Restauro and ICCROM, Rome, Italy
Brunetto Giovanni MOLAB representative
Brunetti
30

Annex 3
List of new AGLAE and MOLAB User-Projects presented and evaluated
during the first six-months of the second year.
AGLAE
Applicant Institution Project title/number Time
requested
(days)
R. Bertoncello University of
Padova (I)
A. Von Bohlen
C. Luglie
Study of protective sol-gel layers for
ancient glass
ISAS
Internal standard method µPIXE to
Dortmund/Germa
analyze paper, parchment and wood
ny
University
Cagliati/Italy
IFIN-HH
B. Constantinescu Bucarest/Romani
B. Colston
a
Lincoln
University
Lincoln/UK
A. Zucchiatti INFN Genoa/Italy
R. Golser
R. Bertoncello
A. Polvorinos del
Rio
D. Strivay
University
Vienna/Austria
University
Padova/Italy
University
Sevilla/Spain
European Centre
of Archaeometry
Liège/Belgium
Neolithisation and obsidian circulation in
western Mediteranean Sea
early periode of Sardinian neolithic
Micro-PIXE studies on Visigothic
“Pietroasa”gold hoard objects
Analysis of hazardous organic and
inorganic residues applied to dried
botanical collections
PIXE study of Morocco zelliges and
mortars from the XIVth to XVIIIth
centuries
Damage evaluation for Micro-PIXE used
for the analysis of metal point drawings
Study of sol-gel protectives for ancient
glass
Analyses of lustered ceramics from
Andalusia
9
Time
allocated
(days)
Planned
month
5 December
5 5 March
4 5 February
3 3 January
2 2 March
3 0
2 2 March
6 0
4 4 April
Study of patinas of antique bronzes 6 5 May
Sum of days 47 31
% total time available 38% 25%
Total days available 125
31

MOLAB
Applicant Institution Project title/Acronym Techniques Approval
Kitan
Kitanov
Ines Abreu
Correia
Bulgarian
Ministry of
Culture
National
Archives
Institute- Torre
do Tombo, P
Isabel Ribeiro Portuguese
Institute for
Conservation
and Restoration
Nicola
Spinosa
Noni
Maravelaki
Soprintendenza
Speciale per il
Polo Museale di
Napoli
25th Ephorate of
Prehistoric and
Classical
Antiquities,
Ministry of
In-situ analysis of the early
Hellenistic wall painting in
the Thracian tomb near the
village of Alexandrovo,
Bulgaria (HELLEN)
Comparative
characterization of two
illuminated medieval codex
of the 12 th century and
damage assessment of the
parchment support.
(MEDI-COD)
Casas Pintadas de Évora.
(EVORACAP)
Drawing and colour in
designing a painting:
Polidoro artwork in
Capodimonte.
(CAPODIMONTE)
In-situ identification of the
penetration depth of
consolidants on bioclastic
limestones through microdrilling
measurements
XRF, FT-IR, Vis-NIR,
micro-Raman, UV-Vis
fluorescence,
fluorescence imaging,
micro-drilling
XRF, FTIR, micro-
Raman, UV-Vis
fluorescence,
fluorescence imaging,
NMR-MOUSE
FT-IR, Vis-NIR, micro-
Raman, IR-colour
scanner, laser microprofilometry,UV-Vis
fluorescence,
fluorescence imaging
XRF, IR-colour
scanner, fluorescence
imaging
Notes
-- Measurements
could be not
adequate to
solve the
specific
conservation
problems
yes
yes
yes
Micro-drilling yes
Culture (KRETE)
Fusun Okyar Tubitak Study of archaeological XRF, Vis-NIR, micro- -- Project not
Marmara materials from Iznik: Glazes Raman
Research center and colour of original Iznik
materials ware. (IZNIK)
institute
pertinent for
in-situ studies
David English Heritage Investigation of Silver XRF, FTIR, Vis-NIR yes
Thickett
Tarnish Risk and Remaining
Protection Afforded by
Lacquers.(SILVER)
Sharon Courtauld Non-Invasive Analysis of XRF, FT-IR, Vis-NIR, -- To be
Cather Institute of Art,
University of
London
Mural Paintings.
(NIAM)
micro-Raman, IRcolour
scanner, UV-Vis
fluorescence,
fluorescence imaging,
NMR-MOUSE
presented at
the next
deadline
Roberto Gemäldegalerie - A Technical Study of the XRF, FTIR, Vis-NIR, yes
Contini Staatliche Paintings: Amor Vincit IR-Colour scanner,
Museen zu Omnia by Caravaggio, laser microprofilometry,
Berlin Portrait of a Lady (Dorotea) NMR-MOUSE
and Reclining nude of a
woman in a landscape
(Cerere) by Sebastiano del
Piombo (CARAVAGGIO)
32

Annex 4
I-Report on the standardised format for describing analytical procedures
DELIVERABLE N.1
Proposed format analytical protocol
- Aim of the protocol, short description
- Name of the Author
- Date of latest version
- Chemicals
o Reagent, grade, concentration, supplier, product number
- Materials (below some examples when dealing with HPLC protocols)
o Column
Dimension column
Nature of particle
Monomeric or polymeric column
Particle size
Particle distribution and deviation
Pore diameter
Surface area
Total carbon %
Surface coverage
End capped
Supplier, product number
Add reference if available: What did we want with this?
o Guard column → type, dimension, supplier, product number
o Filters→ type, dimension, supplier, product number
Reagent preparation
Equipment (below some examples when dealing with HPLC protocols)
o Pump
o Degasser
o Autosampler / injector
o Column oven
o Post column derivatisation system
o Detector
Pre-examination
Sample pre-treatment
Analysis
- Blank analysis, what serves as a blank and how often is it done
- Standards, what is used as a standard, with which purpose and how often
- Detection parameters
- Data evaluation
- Additional field for specific comments
- Show example of analysis of a standard
- Add relevant literature about the analysis (if available)
33

II- Interlaboratory Comparison
Analytical investigation strategies on organic materials
DELIVERABLE N. 3
NOPART meeting, 16 September 2005, Brainstorm about Networking on Natural Organic Polymer:
Identification and Alteration
Present:
Jo Kirby National Gallery London, UK
David Saunders British Museum, UK dsaunders@thebritishmuseum.ac.uk
Chris Maines National Gallery, Washington,
USA
c-maines@nga.gov
Patrick Dieterman Bayerisches Landesamt für
Denkmalpflege, Germany
Patrick.dietemann@blfd.bayern.de
Marianne Odlyha Birkbeck College, UK m.odlyha@bbk.ac.uk
Rene Larssen School of Conservation,
Denmark
rl@kons.dk
Anne-Laurance Dupont CRCDG, France
aldupont@mnhn.fr
Sophia Sotiropoulou OADC, Greece
Ina Vanden Berghe KIK/IRPA, Belgium
Maarten van Bommel ICN, The Netherlands
Introduction by Jan Wouters:
Natural organic polymers are among the main constituents of materials such as textiles, leather,
parchment, paper, photographs, bone, horn, antlers, natural adhesives and binding media of paint. They are
composed of cellulose and protein mainly. Their presence in cultural heritage artefacts of such diversity has
resulted in the existence of object-specific research lines, as clearly expressed in a series of past and present
European research projects (Leather Project CT90-0105; Leather Project EV5V-CT94-0514; ENVIART on
artificial marble; MAP and IDAP on parchment; InkCor, Papylum, ServeNIR, PaperTreat and MIP on paper;
MODHT on textiles), many of them based on national research efforts. It is the main objective of this
initiative to provide appropriate bridging of these.
Joint meetings of researchers will focus on sample preparation, analysis procedures and parameters
to calculate, in order to contribute to the material’s and the object’s damage assessment. Balances of
invasiveness/destruction on the one hand and detail and wealth of analytical information on the other will be
critically evaluated. Investigating how the properties of a natural organic polymer change as a function of
materials added may help formulating jeopardizing conservation or treatment conditions. For example may
be compared the way cellulose degrades, in paper written with corrosive iron-gall ink or in a cotton fabric
mordanted with an iron mordant and dyed with a natural organic dye. The changes brought about in collagen
may be compared, in parchment where stability is provided by drying animal hide under tension or in leather
where hide collagen is chemically reacted with tannins for it’s stabilisation.
The ways by which a critical selection of parameters which indicate early changes in the polymer’s
composition may lead to the description of early warning systems, will be investigated. On their turn may
such investigations contribute to the development of models for improving ageing studies of such polymers
(cf. COST G7) and of organic polymer degradation dedicated sensors (cf. MIMIC, MASTER, LIDO).
The formulation of suitable analytical pathways must look for universality with respect to damage
assessment and archaeometry.
34

Summary of the meeting
Further networking will be sought with Eu-ARTECH (networking activities, MOLAB Access) and the
MaSC group (on mass spectrometry and chromatography) and through international and multidisciplinary
platforms such as the conservation committee of ICOM (ICOM-CC) and the International Institute for
Conservation of Historic and Artistic Works (IIC).The participants showed many different interests with
quite some overlap. One can describe this in a matrix such as:
Application Material Problems
Paper Polysaccharides identification,
mechanism of ink corrosion
Textiles Proteins monitoring degradation
Polysaccharides identification: monitoring degradation
Leather Resins effects on physical, mechanical properties
Proteins monitoring degradation
Parchment Oils ink corrosion
Proteins monitoring degradation
Binding media lipids etc
Etc etc
The list above is not complete of course. Usually, the described problems are object-related and
discussed in separate workgroups of ICOM-CC. Between the different disciplines; there is not so much
exchange of information. However, there is a general feeling among the participants that such an exchange
can be of benefit for us all. The consortium of Eu-ARTECH can organise a joint meeting, together with
ICOM-CC (or at least some of the related working groups from ICOM-CC) on one of the topics mentioned
above.
So far we are considering a meeting about polysaccharides only, or polysaccharides and proteins, for
all applications mentioned above. There is some discussion if we want to focus on one specific problem or if
we want to leave that open. At present, no specific problem has been chosen. An option is to organise the
meeting with different themes which can have the focus of interdisciplinary discussion. We have to think
about and define more clearly the different topics of interest and their possible inter-relationships. In
addition, we need to identify those who can actively contribute to these topics.
All participants feel that the meeting should be mainly a discussion meeting, rather then a series of
presentations. So short presentations will be requested (5 – 10 min) followed by brainstorming sessions.
Although, this could in itself be a single fruitful event, it may be that from this first meeting a core
group can take over and organise more of these interdisciplinary meetings.
35

Annex 5
Report on the “Workshop on non-invasive NMR and Cultural Heritage” (19 th -
20 th ) and on the “5th Colloquium in Mobile NMR” (21 st -23 rd ) – Perugia,
September 2005.
(UNIPG-RWTH)
DELIVERABLE N. 4
Within the Eu-ARTECH project, two initiatives have been developed out at the University of Perugia in the
period, September 19-23, 2005: the “Workshop on non-invasive NMR and Cultural Heritage” and the “5th
Colloquium in Mobile NMR”, organized by RWTH Aachen (B. Blümich), SMAArt Perugia (A. Sgamellotti)
and CNR-IMC (A. Segre).
During both meetings, but in particular during the “Workshop on non-invasive NMR and Cultural Heritage”,
the general bases of the NMR technique and the design of the portable NMR-MOUSE (Nuclear Magnetic
Resonance – MObile Universal Surface Explorer) were fully described, both from the theoretical and
experimental point of view. In many presentations, attention was dedicated not only to the applications
already carried out, but also to the developments of the NMR-MOUSE and to the “depth-profile” version of
this instrument (see JRA2, Task1 – this report).
The main features of the portable NMR device are the following:
-two permanent magnets, are mounted on an iron yoke with anti-parallel polarization to form the classical
horseshoe geometry;
-the main direction of the polarisation field B0 is across the gap;
-the rf field B1 is generated by a surface coil which is mounted in the gap;
-by the use of “NMR echoes” relaxation rates 1/T2 are accessible which are characteristic of material
hardness.
Almost all studies are performed using 1 H-NMR, due to high sensitivity and the natural abundance of
protons. Nevertheless, during the meeting some communications reported some preliminary results to extend
the investigations to nuclei other than 1 H.
Several applications in the field of cultural heritage were discussed and presented. Among them, two relevant
applications regarded: the study of presence of humidity in frescoes of the Vasari’s house in Florence and the
study of the humidity on an ancient Roman fresco, as well as the bricks, of the walls at the Colle Oppio
Cryptoporticus in Rome. In these works, the signal of the water in the pores was measured approaching the
fresco up to one millimetre distance, without touching it. The echo envelope was then analyzed by inverse
Laplace transformation for a distribution of relaxation times. Although some signal loss has to be accounted
for by translational self diffusion in the highly inhomogeneous magnetic field of the NMR-MOUSE the
signal amplitude at short T2 can nevertheless be attributed to water in small pores, and the signal at large T2
to water in large pores. The wet fresco showed signal at both small and large T2. So small and large pores
were filled with water. The brick wall supporting the fresco gave similar results, in particular when
considering that the bricks have a pore size distribution different from the fresco material.
On the other hand the bricks, in another dryer part of a different wall of the Cryptoporticus, showed low
signal at high T2. This is in line with laboratory drying studies, which show that during drying the NMR
signal vanishes first from the large pores and only later from the small pores. By calibration with laboratory
samples, including established mercury porosimetry studies on test samples, the non-destructive
measurements by the NMR-MOUSE can be used to quantify the pore-size distribution and the water
distribution within the pores. This technology can also be used for inspection of stone conservation
procedures, which reduce the pore sizes in the outer stone layers by impregnation with polymers.
In the field of nuclear magnetic resonance, a new portable device has been recently developed, presented and
tested at the Workshop: the “profile NMR-MOUSE”, which aims to obtain microscopic resolution depthprofiles
in paintings or other artworks, with a single-sided sensor.
The common single-sided NMR sensors combine open magnets and surface rf coils to generate a sensitive
volume external to the sensor and inside the object. The shape of the sensitive volume, which is fully
determined by the geometry of the magnet system, defines the best spatial resolution attainable with the
36

sensor. A novel magnet was developed by the Aachen group, the main characteristic is that the resolution is
improved by almost three orders of magnitude. The depth-profiling procedure requires repositioning of the
sensor with respect to the sample. For this purpose a high-precision lift was illustrated in one of the
communications. It has an acrylic plate, where to place the sample and a movable plate to control the
position of the sensor. To quantify the improvement in the spatial resolution, an experiment was reported
where the point spread functions for the new sensor was measured to be 2.3 µm, instead of 1 mm, typical
value for a common sensor.
An application of the profile NMR-MOUSE to the field of cultural heritage was presented, with special
reference to the study of panel paintings.
In laboratory experiments, different models of a paintings, with progressive degrees of complexity, were
investigated: containing different binders (egg. tempera, linseed oil and casein), varnishes (amber, chios and
dammar), organic colorants (lakes) and pigments. The preliminary results were analyzed in order to have
reliable information on the painting technique and on the stratigraphy.
Furthermore, in-situ measurements, performed at the National Gallery of Umbria on the Renaissance
paintings on the “Adorazione dei Magi” of Perugino and on the “Triptych of Sant’Antonio” of Piero della
Francesca were presented. For the first time, it has been possible to measure, by a non-invasive technique,
the thickness of the painting layers, including the painting, the preparation, and the “incamottatura”.
New results were also reported on the use of the spin-lattice decay, as screening indicator, to obtain
information on the painting technique.
During the workshop, practical sessions were held, during which the participants had the possibility to carry
on measurements on paintings, on stone materials, and on paper artworks: the results were then analyzed and
discussed in full detail.
The workshop was followed by the “5th Colloquium on Mobile NMR”. The colloquium had a large
participation and several topics regarding theory and applications of mobile NMR were presented and
discussed. Among these topics a relevant role had the applications to the study of cultural heritage that
attracted the attention and the interest of several scientists.
The participants to the workshop and to the Colloquium were, respectively, 42 and 70, coming mainly from
European countries, but also from Canada, United States, Japan and New Zeland.
NOTE: Due to the necessity to preserve intellectual property rights, it has been not possible to produce the
planned CD with the various presentations to the “Workshop on non-invasive NMR and Cultural Heritage”.
In substitution, however, the Book of Abstracts of the “5th Colloquium in Mobile NMR” is available and
will be published in the website.
The Agenda of both meetings is available at: http://www.nmr-mouse.de/5mnmr/
____________________________________
List of participants to the “Workshop on non-invasive NMR and Cultural Heritage”:
Participant Institution e-mail address
1
Adams Buda, Alina
ITMC, RWTH
Aachen
abuda@mc.rwth-aachen.de
2
Adams, Michael
ITMC, RWTH
Aachen
madams@mc.rwth-aachen.de
3
Bluemich, Bernhard
ITMC, RWTH
Aachen
bbluemich@mc.rwth-aachen.de
4
Blumler, Peter
Institut ICG-III,
Julich
p.bluenler@fz-juelich.de
5
Bortolotti, Villiam
University of Bologna,
Bologna
villiam.bortolotti@unibo.it
6 Brunetti, Brunetto
Giovanni
Centre SMAArt, University
of Perugia, Perugia
bruno@dyn.unipg.it
7
Cagnini, Andrea
Opificio delle Pietre Dure,
Firenze
micindri@supereva.it
8
Camaiti, Mara
CNR-ICVBC,
Firenze
m.camaiti@icvbc.cnr.it
9 Capitani, Donatella Istituto di Metodologie donatella.capitani@imc.cnr.it
37

10
11
12
13
14
15
Cartechini, Laura
Chimiche, CNR, Roma
ISTM, CNR, Dep. of
Chemistry, Perugia
laura@thch.unipg.it
Casanova, Federico ITMC, RWTH Aachen fcasanova@mc.rwth-aachen.de
Cozzolino, Sara
Del Federico, Eleonora
Galeotti, Monica
Gehlen, Christa
16 Herrmann, Volker
Centre S.M.A.Art,
University of Perugia,
Perugia
Pratt Institute, Science and
Mathemathics, USA
Opificio delle Pietre Dure,
Firenze
ITMC, RWTH
Aachen
sara.cozzolino@imc.cnr.it
edelfede@pratt.edu
cgehlen@mc.rwth-aachen.de
Degussa AG, Koln, Germany volker.herrmann@degussa.com
17
Higgit, Catherine
The National Gallery,
London
Cathrine.higgit@ng-london.org.uk
18 Kolz, Jurgen ITMC, RWTH
Aachen
jkolz@mc.rwth.aachen.de
19 Kremer, Kai ACT GmbH,
Roetgen, D
kai.kremer@sct-aachen.com
20 Maddinelli, Giuseppe CHIF – Physical Chemistry
Dept, Milano
gmaddinelli@enitecnologie.eni.it
21 Marble, Andrew MRI Research Centre,
University of New
Brunswick, Canada
andrew.marble@unb.ca
22 Masic Admir
University of Torino, Torino admir.masic@unito.it
23 Megens, Luc Netherland Institut of
Cultural Heritage,
Amsterdam
luc.megens@icn.nl
24 Miliani, Costanza ISTM, CNR, Dep. of
Chemistry, Perugia
miliani@tchch.unipg.it
25 Nestle, Nikolau
nikolaus.nestle@physik.tudarmstadt.de
26 Neevel, Han Netherlands Institute for
Cultural Heritage
han.neevel@icn.nl
27 Perlo, Juan
ITMC, RWTH Aachen jperlo@mc.rwth.aachen.de
28 Pirazzoli, Ilaria University of Rome“La
Sapienza”
29 Presciutti, Federica University of Perugia,
Perugia
30 Rossi, Enrico
31 Roy, Ashok
32 Ruffolo, Silvestro Antonio
ilaria.pirazzoli@roma1.infn.it
federica@thch.unipg.it
enrico.rossi@imc.cnr.it
National Gallery, London Ashok.roy@ng-london.org.uk
University of Calabria Silvio.ruffolo@libero.it
33 Segre, Annalaura Institute of Chemical
Methodologies of CNR,
Rome
segre@imc.cnr.it
34 Sgamellotti, Antonio University of Perugia,
Perugia
sgam@thch.unipg.it
35 Spring, Marika
National Gallery, London Marika.spring@ng-london.org.uk
36 Stork, Holger
Holger.stork@physik.tu-darmstadt.de
37 Tabasso, Marisa m.tabasso@agora.it
38

38 Tedoldi, Fabio
39 Utsuzawa, Shin
Bruker, Italy fabio.tedoldi@bruker.it
University of Tsukuba utsuzawa@mrlab.bk.tsukuba.ac.jp
40 Voda, Alexandra Freudenberg
Forschungsdienste KG,
Weinheim
alexandra.voda@freudenberg.de
41 Weglarz, Wladyslaw Unilever Wladyslaw.Werglarz@unilever.com
42 Yiming, Zhang Chinese Academy of
Science, Beijing, China
ymzhang@mail.iee.ac.cn
39

Annex 6
Summary Report on GUPIX Course
C2RMF
DELIVERABLE N. 5
The first edition of the “GUPIX School” was organised at the C2RMF from the 6 th to 7 th October 2005.
The aim of this small workshop was to improve user's expertise in running GUPIX, the most popular
program used to process PIXE spectra, which is also used at AGLAE.
The school was given by Prof. J.L. Campbell, professor at the Guelph University, Canada, one of the most
renowned expert in PIXE and co-designer of the GUPIX program. The 6 th and 7 th October were dedicated to
the presentation of the new GUPIXWIN windows version (release 1.1)
On October 5 th , one day before the school, the operation of AGLAE was dedicated to participants wishing to
collect fresh PIXE spectra of their own samples in order to use them as sample spectra during the workshop.
24 users and owners of the GUPIX program from seven western European countries were gathered. Five
participants were directly connected with the AGLAE transnational access program (names underlined in the
list of participants, below).
The first day of the school Prof. J.L. Campbell presented a detailed review of the capabilities of this new
version of GUPIX, which has a completely redesigned interface running under windows. The second day
was dedicated to practising GUPIX on various sample spectra with increasing complexity (hidden elements,
layers, etc.). Finally, in the last afternoon the participants had the occasion to submit remarks and
suggestions to J.L. Campbell, to help the improvement of the next version of GUPIXWin.
List of Participants
Nr Name Surname E-mail Institute Town
1 Dr Janusz LEKKI Janusz.Lekki@ifj.edu.pl INP Cracow Po
2 Dr Wojciech KWIATEK Wojciech.Kwiatek@ifj.edu.pl INP Cracow Po
3 Prf Iain CAMPBELL Guelph
University
CAN
4 Dr Richard THOMPSON r.l.thompson@durham.ac.uk University of
Durham
UK
5 Dr Christian NEELMEIJER c.neelmeijer@fz-rossendorf.de FZW Rossend D
6 Dr Thomas CALLIGARO Thomas.Calligaro@culture.fr C2RMF Paris F
7 Dr Jacques CASTAING Jacques.castaing@culture.fr C2RMF Paris F
8 Mr David BOURGARIT David.Bourgarit@culture.fr C2RMF Paris F
9 Dr Stefan ROEHRS Stefan.Roehrs@culture.fr C2RMF Paris F
10 Mr Laurent PICHON Laurent.Pichon@culture.fr C2RMF Paris F
11 Dr Isabelle BIRON Isabelle.Biron@culture.fr C2RMF Paris F
12 Dr Joseph SALOMON Joseph.Salomon@culture.fr C2RMF Paris F
13 Dr Lucile BECK Lucile.beck@culture.fr C2RMF Paris F
14 Dr Inés ORTEGA iofeliu@us.es CNA Seville E
15 Dr Petra KROEPFL Petra.Kroepfl@ap.univie.ac.at VERA Vienna A
16 Dr Barbara WUNSCHEK Barbara.Wunschek@ap.univie.ac.at VERA Vienna A
19 Dr Stéphane LUCAS Stephane.Lucas@fundp.ac.be LARN - Namur B
20 Dr Claire RAMBOZ cramboz@cnrs-orleans.fr ISTO Orleans F
21 Dr Olivier ROUER orouer@ cnrs-orleans.fr ISTO Orleans F
22 Dr Caroline RAEPSAET caroline.raepsaet@cea.fr CEA
DRECAM
Saclay F
23 Dr Hélène BUREAU hbureau@drecam.cea.fr CEA
DRECAM
Saclay F
24 Dr Mohammad ROUMIÉ mroumie@cnrs.edu.lb CNRS LEB
orf
40

Annex 7
Report on the First AGLAE and MOLAB Users Meeting - (Paris, 23 rd November 2005)
C2RMF, Palais du Louvre, Porte des Lions, 14 - quai François Mitterrand.
C2RMF, UNIPG, INOA, CNR-ICVBC, OPD
DELIVERABLES N.11, 13
The meeting was opened by M. Menu, as Eu-ARTECH responsible for T.A. activities. He briefly described
the Access activities developed during the first 18 months of the project by both AGLAE and MOLAB
infrastructures.
J.Salomon presented a lecture on the general characteristics of AGLAE, introducing the main new technical
AGLAE solutions for obtaining the highest performances in PIXE, PIGE, RBS, ERDA measurements.
A.Polvorinos Del Rio and G.Padeletti presented the results obtained in the study of “lustre” ceramics of the
“Hispano-Islamic” and “Italian Renaissance” periods. In particular, while Polvorinos presented results
obtained on several shards from the excavation of the Triana (Sevilla) workshop, Padeletti presented an
extended study carried out on several plates by Mastro Giorgio da Gubbio. Both studies were carried out in
AGLAE, through PIXE and RBS measurements.
In the case of the lustre shards from Triana (Sevilla), small amounts of Cu and Ag, the species known to be
at the origin of the lustre effects, were detected by PIXE. It was found that Cu concentration increases with
the Pb content of the glaze. Ag was not always present. RBS analyses led to the detailed characterisation of
the distribution of elements in the surface layers of the decorations. It was confirmed the occurrence of thin
layers (less than 300 nm) containing metallic silver and/or copper, very likely as nanoparticles, embedded in
the glassy matrix of the glaze. A correlation was attempted between the copper and/silver content of the
upper layers and the surface colour aspect.
In the case of the Renaissance lustre, two campaigns of measurements were carried out. In each case, the
available beamtime has been used for PIXE analyses under 3 MeV protons, and to RBS acquisitions under a
3 MeV beam. The examined objects included several original Renaissance plates such as “Caduta di
Fetonte”, “Pico, Circe e Canente” "Dedalus", "The cup of riders and infantrymen", "The birth of Adonis",
and others, from the Museo Comunale di Gubbio and Museums of Sevres and Ecouen. In the majority of
cases, the glazes have been precisely characterised and the nature of different pigments, blue, green, black,
yellow, etc. have been identified. RBS analyses gave information on the metal content of the lustered layers,
as well as on their in-depth distribution. Results indicated that the layers containing copper and/or silver are
of the order of a few hundred nanometres thick and contain a relatively low amount of metals (few percent
weight). The comparison of the data obtained on the different objects provided parameters useful to identify
markers of the technological evolution of the workshops all along the considered period, such as, for
example, the use of a cobalt mineral containing a relatively high impurity of arsenic.
A. Von Bohlen, from the Institute for Analytical Sciences, in Dortmund, Germany, presented relevant results
in the study of varnishes in ancient musical instruments, such as violins. The study was carried out through
micro-PIXE an lead to interesting results part of which are under processing.
R. Bertoncello, from the University of Padova, Italy, presented the results he obtained in a study of sol-gel
silica coatings, deposited on different kinds of glass substrate, in order to test their activity in glass
protection. An interesting aspect of this study was the analysis of ion-interdiffusion between glass and
coating.
Different types of glass samples, coming from the Corning Museum, have been used in order to test the
mobility of lead. The results showed that the protective coatings experience a low lead migration when they
are in contact with G glass (content of lead in the protective coating: 0.030 atom %) and in C glass (content
of lead in the protective coating: 0.006 atom %). In particular, lead catalysed coatings showed an
homogeneous amount of lead in the sol-gel silica layer (owing to the homogeneous migration of Pb 2+ from
the glass substrate) while the non-catalysed layers showed an in-homogeneous composition, with at least two
indexes of ion migration (on glass C): a first layer with a lower amount of lead (0.010 atom %) and a second
layer with a larger amount of lead (0.019 atom %). This behaviour could be related to the fact that, in the
non-catalysed coating, lead diffusing from the substrate, acts by itself as a non-homogeneously dispersed
polymerising catalyst, causing a non-homogeneous growing of the silica coating, while in the case of lead
catalysed coatings the migration reaches its equilibrium and does not evolve any more. This consideration
41

would be coherent with a better protective action of lead catalysed sol-gel silica with respect to the noncatalysed
one.
In conclusion of the session dedicated to the AGLAE users, M.Guerra presented relevant results in a study of
Etruscan gold work from the Campana’s collection (Louvre Museum). The study was able to put well in
evidence many details of the manufacture techniques and allowed for the identification of 19 th century
restorations and pastiches.
In the afternoon, C. Miliani, from the University of Perugia, introduced the session dedicated to MOLAB
presenting several unpublished results obtained through MOLAB national access. The presentation had the
objective to show new case studies of MOLAB to the public of actual and potential users.
After this introduction, B. Mottin (C2RMF) presented the work developed in-situ on the Lamentation on the
dead Christ altarpiece, located in the Museum of Fine Arts and Archaeology of Besançon. The painting was
executed for the Chapel of Eleonora of Toledo, the wife of Cosimo I de' Medici and daughter of the Viceroy
of Naples, in Palazzo Vecchio in Florence. It was finished in 1545 and, in the same year, it was sent to
Besançon to the private secretary of the Emperor Charles V with whom Cosimo had important negotiations.
The Lamentation on the dead Christ in Besançon was studied, through the following techniques: fiber-optic
FT-IR; fiber-optic Vis-NIR; fiber-optic fluorescence; fluorescence imaging; IR-colour scanner
reflectography; laser micro-prophilometry. XRF measurements and X-ray radiographies were carried out
separately by C2RMF. The IR-colour reflectogram put in light several pentimenti of Bronzino with
modification of the position of the various figures or even their substitutions. The false-coulour image gave a
clear idea of the distribution of different materials allover the painted surface. The almost complete set of
used pigments was identified by the combination of XRF and mid-FTIR. Repaintings by cobalt-blue were
also evidenced. Two different types of lakes were identified by wavelength resolved Vis-fluorescence.
Within the mixtures of lakes and oil (as binder) the presence of glass powder was found. The study shed light
on the general painting techniques of Florentine painters of the period.
D. Hradil, from the Academy of Science of the Czek Republic, presented his work on the painting techniques
of J. B. Lampi, father and son, from the 19 th century collection of the Moravian Gallery in Brno. Within this
project, five paintings of two authors, Johann Baptist Lampi elder and Johann Baptist Lampi younger were
studied. In some of their paintings the authorship was uncertain, because the son adapted the style of his
father very markedly. For this reason, the finding of material features distinguishing between the two authors
seemed to be extremely difficult, although not impossible. As a reference, a painting of a different author,
probably Friedrich Amerling, was used. The results were positive. Although the mobile instrumental
techniques did not provide a definite answer to the question of the authorship, it yielded very quick and
objective confirmation of the originally proposed assignment. Several measurement were carried out that led
to a wide characterisation of the materials used by the painters. The most important distinguishing feature
seemed to be the presence of really uncommon lead-tin-antimony yellow, which could indicate some
preferences in the pigment selection. In particular, the results showed that this pigment was preferred by the
younger authors – J.B. Lampi junior and F. Amerling.
The results of non-destructive IR spectroscopy and XRF focused the attention to the need of more detailed
analysis of yellows and greens (mixed from yellows and blues in all paintings). This conclusion is vital to
guide microsampling of painting layers for further developments of the study through stratigraphic analyses.
L. Syson, from the National Gallery of London, presented his technical study of Leonardo’s Vergin of the
Rocks and associated Leonardesque paintings by the IR-colour scanner of INOA. Two distinct compositional
underdrawings were seen under the surface of the Virgin of the Rocks. The first of these, drawn directly on
the gesso ground using a fluid medium, does not correspond at all to the image that we know so well today.
The second underdrawing, drawn over a priming layer, is for the Virgin of the Rocks as it was finally
executed, but here too there is evidence of several substantial changes of mind and of a complicated working
procedure.
The study have radically altered the understanding of Leonardo’s working methods, particularly with regard
to his use of cartoons, and allowed L.Syson to distinguish between his underdrawing style and method and
those of his collaborators.
L.Burgio from the Victoria and Albert Museum of London presented her study of 11 majolicas by Mastro
Giorgio Andreoli, conserved in the V&A .Three techniques were used in the study: energy dispersive X-ray
fluorescence (EDXRF), Raman spectroscopy and visible and near-infrared spectroscopy (Vis-NIR). The use
of a portable EDXRF spectrometer allowed for the detection of copper and silver, which can be related to the
colour of the decoration. Portable fibre-optic Vis-NIR spectroscopy allowed the quantification of colours
42

and, at the same time, the qualitative detection of copper and silver nanoparticles. The identification was
carried out by measuring the surface plasmon resonances, specific absorption peaks typical of nanoparticles
dispersed in a transparent medium. The resonances appear at different wavelength, according to the nature,
dimension and concentration of the nanoparticles and on the refractive index of the hosting medium. Finally,
the glassy network of the glaze was studied by micro-Raman spectroscopy. Raman spectra from many
different areas of the lustre decoration were recorded, making it possible to compare spectra taken from
different decorations of the same plate or analogous decorations in different plates. In particular, a specific
yellow-orange decoratioon showed the typical spectrum of lead antimonate with some specific features to be
attributed to the presence of zinc (also detected by XRF).
As a final presentation, S.Sotiropoulou from Ormylia, presented the main features of the study carried out by
MOLAB on the St. Euthimios Chapel wall paintings (XIV century) at St. Demetrios in Thessaloniki.
Information was collected on the use of various pigments, combining XRF with mid- and near-FTIR
spectroscopic results. The information strongly contributed to shed light on the Byzanthine painting
technique of the time. The results are currently compared with those obtained in a previous study of
Panselinos mural paintings in the Protaton church in Mount Athos.
At the end of the day, M.Menu and B.Brunetti together underlined the relevance and the high interest of the
study presented. The positive results confirmed the constructive role of transantional access to promote the
highest level of research, to strenghten the international cooperation among scientist, conservators and
scholars on cultural heritage, and, therefore, to contribute to the creation of European area of research in the
field of artwork studies and conservation.
The Agenda of the Meeting is available on the website.
Being open to the community of researchers external to the Consortium, the meeting was publicised and
more than 70 participants were present.
List of participants:
First Name Family name Institution Country Email Telephone
1 Marc Aucouturier C2RMF F marc.aucourturier@culture.gouv.fr 01 40 20 57 49
2 Nathalie Balcar C2RMF F nathalie.balcar@culture.fr 01 40 20 56 79
3 Gilles Bastian C2RMF F gilles.bastian@culture.fr
4
5
Lucile Beck C2RMF F lucile.beck@culture.fr 01 40 20 24 82
Ludovic Bellot-Gurlet
6 Renzo Bertoncello
CNRS -
Université P.
F
et M. Curie,
Paris IV
bellot-gurlet@glvt-cnrs.fr 01 49 78 11 14
University of
I renzo.beroncello@unipd.it 3904 98 27 52 04
Padova
7 Anne Bouquillon C2RMF F anne.bouquillon@culture.fr 01 40 20 68 58
8 David Bourgarit C2RMF F david.bourgarit@culture.fr 01 40 20 56 39
9 Jean-Louis Boutaine C2RMF F jean-louis.boutaine@wanadoo.fr
10 Susanna Bracci ICVBC-CNR I s.bracci@icvbc.cnr.it 39-055-5225413
11 Brunetto
Giovanni
Brunetti
Universita’ di
I bruno@impact.dyn.unipg.it
Perugia
12 Emilien Burger C2RMF F emilien.burger@culture.gouv.fr 06 16 08 29 38
13 Lucia Burgio V&A Museum UK l.burgio@vam.ac.uk
14 Laura Cartechini
Universita’ di
I laura@thch.unipg.it 390 755 855 526
Perugia
15 Jacques Castaing C2RMF F jacques.castaing@culture.gouv.fr 01 40 20 56 69
16 Christian Degrigny
Heritage
Malta
Malta cdegrigny@mcr.edu.mt
43

17 José
18
Delgado
Rodrigues
Françoise Douau
LNEC P delgado@lnec.pt 351 218 443 699
Musée
d'Archélogie
Nationale
F francoise.douau@culture.gouv.fr 01 39 01 12 13
19 Marie-Pierre Etcheverry LRMH F marie-pierre.etcheverry@culture.fr 01 60 37 77 86
20 Paola Fermo
21
Ana Paula Ferreira Pinto
University of
I paola.fermo@unimi.it 0039-02 50314425
Milan
Instituto
Superior
Técnico (IST)
P anapinto@civil.ist.utl.pt 351 218 418 363
22 Eva Goetz ICN NL eva.goetz@icn.nl 0031 20 3054 733
23 Maria Filomena Guerra C2RMF F maria.guerra@culture.gouv.fr 01 40 20 24 58
24 Rosemarie Heulin
25
26
David Hradil
Janka Hradilova
Musée du
F rosemarie.heulin@quaibranly.fr
Quai Branly
Academy of
Sciences of
the CZ Rep.
Academy of
Fine Arts in
Prague
06 16 74 65 21 /
01 56 61 71 59
CZ hradil@iic.cas.cz 420-266172187
CZ hradilovaj@volny.cz 420-233015334
27 Ineke Joosten ICN NL ineke.joosten@icn.n 31(0)20 3054728
28 Ildiko Katona C2RMF F ildiko.katona@culture.fr
29 Mathias Kocher BLFD D mathias.kocher@blfd.bayern.de 00 49 89 21 14 323
30
Christian Lahanier C2RMF F christian.lahannier@culture.gouv.fr 01 40 20 58 71
31 Anne-Solenn Le Hô C2RMF F anne-solenn.leho@culture.gouv.fr 01 40 20 54 78
32 Marie-Anne Loeper-Attia Restorer F philattia@wanadoo.fr 01 46 07 87 97
33 Claudine Loisel LRMH F claudine.loisel@culture.fr 01 60 37 77 80
34 Martin Mach BLFD D martin.mach@blfd.bayern.de 0049 089/2114-323
35
François Mathis
Université de
Liège
B francois.mathis@ulg.ac.be
36 Vincent Mazel C2RMF F vincent.mazel@culture.gouv.fr
37 Anna Maria Mecchi CNR ICVBC I a.mecchi@icvbc.cnr.it 39 3485221116
38 Michel Menu C2RMF F michel.menu@culture.gouv.fr 01 40 20 56 59
39 Costanza Miliani
Universita’ di
Perugia
I miliani@thch.unipg.it
40 João Mimoso LNEC P lmimoso@lnec.pt 351,218,443,553
41 Jean-Pierre Mohen
Musée du
Quai Branly
F jmo@quaibranly.fr 01 56 61 53 09
42 Bruno Mottin C2RMF F bruno.mottin@culture.fr 01 40 20 56 61
43 Christiane Naffah C2RMF F christiane.naffah@culture.gouv.fr 01 40 20 56 50
44 Cristiana Nunes LNEC P clpn@lnec.pt 351,218,443,979
45 Giuseppina Padeletti CNR - ISMN I pad@mlib.cnr.it 39-06-90672346
46 Sandrine Pagès C2RMF F sandrine.pages@culture.gouv.fr 01 40 20 54 78
47
Silvia Païn
Service
archéologique
départemental
des Yvelines
F spain@cg78.fr 01 61 37 36 90
44

48 Juan Perlo
RWTH-
Aachen
D jperlo@mc.rwth-aachen.de 49 241/8026-430
49
Luca Pezzati INOA I luca@ino.it
39 055 23 08 221
50
Laurent Pichon C2RMF F laurent.pichon@culture.gouv.fr 01 40 20 24 62
51 Daniela Pinna
52 Angel Polvorinos
53 Stéphanie
Rabourdin-
Auffret
Opificio delle
Pietre Dure
Seville
University
Université
Paris I
I daniela.pinna@unibo.it 051.4209428
E polvorin@us.es 95 455 71 40
F srabourdin.auffret@free.fr 01 53 19 97 37
54 Elisabeth Ravaud C2RMF F elisabeth.ravaud@culture.gouv.fr 01 40 20 56 57
55 Martine Regert C2RMF F martine.regert@culture.fr
56 Pascale Richardin C2RMF F pascale.richardin@culture.fr
57 Ashok Roy NGL UK ashok.roy@ng-london.org.uk 44 (0) 207 747 2823
58 Barbara Sacchi ICVBC-CNR I b.sacchi@icvbc.cnr.it 39-055-5225413
59 Joseph Salomon C2RMF F joseph.salomon@culture.gouv.fr
60
Barbara Salvadori
61 Antonio Sgamellotti
62
63
Jacek Sobczyk
Joanna Sobczyk
Opificio delle
Pietre Dure
Universita’ di
Perugia
Polish
Academy of
Sciences
National
Museum in
Krakow
I salvadori@csgo.unifi.it 055-4625488
I sgam@thch.unipg.it 390,755,855,516
Pol sobczyk@img-pan.krakow.pl 48 12 637 62 00
Pol
jsobczyk@muz-nar.krakow.pl,
lanboz@op.pl
48 12422 26 35
64 Sophia Sotiropoulou OADC Gr s.sotiropoulou@artdiagnosis.gr 302,371,098,400
65
Marika Spring NGL UK marika.spring@ng-london.org.uk 44 20 7747 2827
66 Luke Syson NGL UK
67 Olivier Tavoso C2RMF F
68 Annick Texier LRMH F annick.texier@culture.fr 01.60.37.77.80
69 Lucia Toniolo CNR - ICVBC I lucia.toniolo@polimi.it 39 02 2399 3935
70 Maarten Van Bommel ICN NL maarten.ven.bommel@icn.nl 31-(0)20-3054780
71 Elsa Van Elslande C2RMF F elsa.van-elslande@culture.fr
72
Ina
Van den
Berghe
KIK - IRPA B ina.vendenberghe@kikirpa.be 0032 2 7396846
73
Philippe Walter C2RMF F philippe.walter@culture.gouv.fr
74 Eléonore Welcomme C2RMF F eleonore.welcomme@culture.gouv.fr 01 40 20 68 54
45

Annex 8
Progress report on JRA1- DEVELOPMENT AND EVALUATION OF TREATMENTS
FOR THE CONSERVATION-RESTORATION OF OUTDOOR STONE AND BRONZE MONUMENTS
(ICVBC-CNR, LNEC, UNI-PG, OPD)
(DELIVERABLE N.14) Progress report on the procedures to be adopted for each treatment under study
(DELIVERABLE N.15) Progress report on the characteristics of the samples during ageing procedures
Prepared by:
ICVBC-CNR – S. Bracci, B. Sacchi;
LNEC - J. Delgado Rodrigues, A. Ferreira Pinto, C. Paulos Nunes;
OPD - D. Pinna, S. Porcinai, B. Salvadori;
UNI-PG – C. Miliani, B. Doherty
Summary
1. TASK 1 - REPORT ON IDENTIFICATION, SELECTION AND CHARACTERIZATION
OF STONE SPECIMENS FOR TESTING
1.1 NEW DRILLING CONDITIONS
2. TASK 2 - PROGRESS REPORT ON THE DEVELOPMENT OF NEW TREATMENTS
AND PROCEDURES (Chemical processes and application protocols)
2.1 CHEMICAL PROCESSES AND INDIVIDUATION OF CRITICAL PARAMETERS
FOR TREATMENTS
2.1.1 Kinetic study of Calcium oxalate
2.1.2 Experimental
2.1.3 Results
2.2 TREATMENTS UNDER EVALUATION
2.2.1 Tests of consolidation treatments on Gioia Marble, Firenzuola and Santafiora
stones
2.2.2 Tests of drilling on Gioia Marble
2.2.3 Tests of consolidation treatments on Ançã and Lecce stones
2.2.3.1 Treatment T2
2.2.3.2 Treatment T3 and T4
2.2.4. Tests of protective treatments
2.2.4.1 Definition of further steps
3. TASK 3 - PROGRESS REPORT ON ACCELERATED AGEING TESTS
3.1 ACCELERATED AGEING TESTS UNDER EVALUATION
3.2 THERMAL SHOCK
3.3 SALT CRYSTALLISATION
46

1. TASK 1 - REPORT ON THE IDENTIFICATION, SELECTION AND CHARACTERIZATION OF
STONE SPECIMENS FOR TESTING
1.1 New drilling conditions
(LNEC)
The definition of the drilling parameters for testing Ançã and Lecce stones was set within the scope of
Task 1 finished in the middle of the 1 st year. However, during the reporting period, complementary work was
carried aiming at improving the drilling conditions, taking advantage of new innovative developments
introduced in this testing tool. The conditions addressed were:
• drying of specimens;
• drilling speed;
• introduction of a pilot-hole and dust extraction.
• Drying of specimens
In order to investigate the influence of the humidity content in the stone specimens conditioned at the
laboratory (20-25ºC, 45-65%), the specimens were drilled after being dried at 60ºC during 24h. The results
obtained are shown in Fig. 1. These results illustrate the need of drying the specimens before testing to
avoid the occurrence of abnormal results.
Force [N
12
10
• New drilling conditions
8
6
4
2
400rpm 15mm/min
After drying(5holes)
Before drying (2holes)
Ançã
0
0
Fisher drill bit
5 10 15
Depth [mm]
20 25 30
Fig. 1 - Graphic showing the drilling resistance of Ançã stone
before and after drying
The drilling conditions set in the first report were 400r.p.m. of rotation speed and 15mm/min of
penetration rate. Both Ançã and Lecce stones were characterised by a low force range with these testing
parameters (Fig. 2). In order to increase it some tests were carried out with different drilling parameters,
namely 100 and 200r.p.m. of rotation speed and 20mm/min of penetration rate (Fig. 3).
The range of forces obtained with 100r.p.m and 20mm/min for both limestones were considered the
ones which better fit for comparison testing.
47

Force [N
25
20
15
10
5
0
Force [N
0 10 20
5
4
3
2
1
Ançã
Lecce
0
0 5 10 15 20 25 30
Depth [mm] Diamond Drill Bit
Fig. 2 - Drilling resistance profiles for Ançã and Lecce stones
with the first testing parameters
20mm/min Ançã
100 r.p.m. (3holes)
200 r.p.m.(3holes)
Depth [mm]
Diamond drill bit
30
Force [N
25
20
15
10
5
0
20mm/min
100 r.p.m.(7holes)
200 r.p.m.(3holes)
Lecce
Diamond drill bit
0 5 10 15 20 25
Depth [mm]
Fig. 3 - Drilling resistance profiles for Ançã and Lecce stones using 100 and 200 r.p.m. at 20mm/min
• Use of a pilot hole and dust suction
A new drilling technique proposed by Mimoso and Costa 1 was tested in order to avoid the
occurrence of dust packing. This is a highly important aspect when analysing the drilling resistance of
stones in depth, since packing occurs predominantly in soft stones at low rotational speeds and when a
consolidating treatment aggregates the stone cuttings.
The technique consists of drilling holes in stone over previously made pilot holes (hole-overhole
method). In the present case a 5mm diameter diamond drill bit was used to drill over a pilot hole of
3mm diameter.
The use of a pilot hole practically avoids packing phenomenon. However packing situations may
still occur. In the case of Ançã and Lecce stones this aspect proved to be important. Slight packing
occurred when drilling the stones at 100r.p.m. and 20mm/min. over a pilot hole of 3mm diameter. The
phenomenon proved to be effectively controlled by means of dust suction during the drilling run (Figs.
1 Mimoso, J. M. and Costa, D. – “A new DRMS drilling technique with pilot holes”. (communication to be presented to
the Conference Heritage, weathering & Conservation, Madrid, 2006)
48

Force [N
4, 5 and 6). Since the specimens selected for this research are slabs with 3cm thick, this technique is easy
to implement since the drill bit is able to cross completely the slab thickness.
25
20
15
10
5
without guide-hole(3holes)
with guide-hole(3holes)
Diamond drill bit
0
0 5 10 15 20 25
Force [N
25
20
15
10
5
0
Dust suction
Fig. 4 - Scheme of the hole-over-hole drilling technique applied with a
3mm pilot hole and a 5mm drill bit (Mimoso and Costa)
Depth [mm]
Ançã
100rpm 20mm/min
without guide-hole(7holes)
with guide-hole(4holes)
0 5 10 15 20 25
Depth [mm]
Lecce
Diamond drill bit
100rpm 20mm/min
Fig. 5 - Drilling resistance profiles for Ançã and Lecce stones with and without the hole-over-hole drilling technique
applied with a 5mm drill bit over a 3mm pilot hole
Force [N
8
6
4
2
0
without dust suction
0 5 10 15 20 25
Depth [mm]
with dust suction
Ançã
Force [N
8
6
4
2
0
without dust suction
with dust suction
0 5 10 15 20 25
Depth [mm]
Lecce
Fig. 6 - Drilling resistance profiles for Ançã and Lecce stones obtained with the hole-over-hole drilling technique
(100r.p.m. and 20mm/min.) with and without dust suction
49

• Final remarks
These new results point out the importance of using dried specimens and the benefit of using the
pilot hole drilling technique with dust suction, namely in the case of Ançã and Lecce stones.
Although the hole-over-hole drilling technique significantly lowered the range of forces in Ançã and
Lecce stones, the discrimination of any subtle differences (such as a consolidation action) is assured by the
increased reliability and precision of the results obtained with this technique.
1.
The new drilling conditions adopted on the basis of the results here reported are summarised in Table
Stone specimen Drill bit
Dried for at least
24h at 60ºC
Table 1 : New drilling conditions defined for Ançã and Lecce stones
Diamond - φ5mm
with dust suction
Pilot hole
Rotational speed
[r.p.m.]
Penetration rate
[mm/min]
φ3mm 100 20
50

2. TASK 2 – PROGRESS REPORT ON THE DEVELOPMENT OF NEW TREATMENTS AND
PROCEDURES (Chemical processes and application protocols)
2.1 CHEMICAL PROCESSES AND INDIVIDUATION OF CRITICAL PARAMETERS FOR
TRATMENTS
(UNI-PG)
2.1.1 Kinetic study of calcium oxalate artificial deposition
This report outlines the results of the laboratory study, carried out in the first semester of the
second year, of artificial treatment on powdered substrates in an attempt to understand the kinetics and
mechanisms involved in the method.
2.1.2 Experimental
Separate kinetic reactions were controlled for differing contact times (hours) between reagents
namely: 0.5, 1, 3, 6, 18, 24, 48, 72, 120, and 168 hours, that were conducted in sealed 50ml flasks
placed on a magnetic stirrer, which allowed the constant agitation of the solution, at room
temperature (20-27°C). In order to block the reactions at the different times, filtration of the
solution is followed by passing through deionized water (200 ml). The product was then dried in an
oven at 40°C - 60°C for two to tree days and then quantitatively weighed and measured by means of
a Jasco FT/IR-400Plus Fourier Transform Infrared laboratory Spectrometer. All spectra
measurements have been gathered in absorption mode with a measurement range of 4000 cm -1 to
400 cm -1 , a resolution of 2cm -1 and 100 scans using a pressed potassium bromide pellet as
background. All powdered samples were weighed (1.4 x 10 -3 g) and prepared using KBr (0.4g) in
the die method with a manual hydraulic press.
2.1.3 Results
Fourier transform Infrared spectroscopy is used for a quantitative evaluation of the kinetic reaction
of calcium oxalate in the different work conditions. Spectra were analyzed in terms of the
absorbance of the calcium oxalate product which was previously compared to each stone under
study (figure 7). The 3 main characteristic oxalate frequencies are observed at 1622cm -1 relative to
the ν (C=O), at 1320cm -1 assigned as the νs (C-O) + δ (O-C=O) and 782 cm -1 given by the δ (O-
C=O) + ν (M-O). In comparison to the calcium carbonate reagents, the frequency at 1320cm -1 may
be influenced by the broad band at 1424cm -1 , the ν3 fundamental stretching vibration of the CO3 2-
ion. Similarly the characteristic bending of water ≈1620cm -1 may disturb the signal at 1618cm -1 .
Hence the band at 782cm -1 has been chosen as representative of the presence of the calcium oxalate
product. Each spectrum was subjected to an identical baseline treatment to render the results
coherent and comparable.
Absorbance
3,0
2,5
2,0
1,5
1,0
0,5
0,0
1624
1318
1800 1600 1400 1200 1000 800 600
Wavenumber (cm -1 )
Ança limestone
Gioia marble
Santafiora sandstone
Firenzuola sandstone
Lecce marble
CALCIUM OXALATE STD
Fig. 7 - FTIR spectra of the five stone matrices with the oxalate product
782
51

The absorbance of δ (O-C=O) + ν (M-O) given by the band at 782cm -1 in function with the number
of contact hours was used to convert the chosen relative absorbance characteristic frequency into relative
concentration/weight percentage using the representative linear fit equation (y = 0.037+0.019x) that was
previously calculated from a series of standard spectra based on known quantities of calcium oxalate
dispersed in a matrix of calcium carbonate substrate. Kinetic curves have been plotted for each of the five
different stone matrices (figure 8),
% Oxalate product formed
30
25
20
15
10
5
0
Gioia marble
Firenzuola sandstone
Santafiora sandstone
Lecce limestone
Ança limestone
-20 0 20 40 60 80 100 120 140 160 180
Time (hours)
Fig. 8 - Scatter plots of relative absorbance with converted oxalate concentration versus time for
each stone matrix, Gioia marble, Lecce limestone, Ança limestone, Santafiora sandstone
and Firenzuola sandstone .
Analytical interpretation of the kinetic curves graphics has been carried out for all the reactions
utilizing the plateau value absorbance at 48 hours used to calculate the percentage oxalate formed giving the
characteristic features expressed in Table 2.
Table 2 : Characteristic features of reactions conducted with 2.5% (NH4)2C2O4.
Substrate
Time
(h)
Plateau value
(Abs)
CaC2O4
formed
(weight %)
Gioia marble 48 0.490 23.85 0.052 2.212
Lecce limestone 48 0.402 19.19 0.136 1.765
Ança limestone 48 0.430 20.69 0.110 2.287
Santafiora sandstone 48 0.370 17.54 0.066 0.219
Firenzuola sandstone 48 0.219 9.60 0.265 0.195
It may be noted that all of the stone types were subjected to the artificial protective, even though
research has suggested that this treatment is normally most adapt to limestone and marble as they are mostly
constituted by calcium carbonate, the main reagent in the oxalate protective method. However, as the
sandstones contain a non negligible quantity of carbonate, the ammonium oxalate was also applied in order
to understand any eventual response.
The kinetic curves resulting, indicates that maximum quantity of oxalate product is generated given
by the trends reaching a plateau after a an approximate 48 hours reaction. The behaviour of the stone groups
marble, limestone and sandstone, each observing the same granulometry (160microns), may be an indicator
as to the response of each lithotype to the artificial oxalate treatment. On the whole, the trend of the kinetic
curves indicates three groups given by the quantity of oxalate formed, marble produces the most, followed
by limestone and lastly sandstone. The available surface area of reaction of each stone is the same, yet the
chemical composition and petrophysical properties of the carbonate stones seem to have an important role on
k1
k2
52

the rate of reaction between Ca 2+ and C2O4 2- , as it may be seen through the division in time of reaction
required by each stone to achieve plateau.
2.2 TREATMENTS UNDER EVALUATION
2.2.1 Tests of consolidation treatments on Gioia Marble, Firenzuola and Santafiora stones
(ICVBC)
In the first year of the project, ICVBC-CNR started the study in the framework of Task 2 with a first
series of samples as planned on not aged samples. In the first semester of the second year, ICVBC continued
the study, varying some of the parameters in the procedures.
The measurements done up to now on the treated stones are the following:
amount of products applied;
colour determination;
absorption by sponge method.
- T1 treatment [Ba(OH)2, immersion, on Marble]
The procedure followed was exactly the same used in the first experiment (see Report @ 12 months)
for immersion application, except for the time of immersion, which was changed after the first experiment.
The samples dimensions were 10x5x3 cm.
For the treatment carried out in the first experiments, time of immersion was 30 days.
For the new treatments:
a) time immersion = 3 hours;
b) time immersion = 5 days;
c) time immersion = 15 days.
The differences in weight (g), colour changes and water absorption for T1 treatment are reported in
Figure 9, Figure 10 and Figure 11.
Amount of product
(g)
1,200
1,000
0,800
0,600
0,400
0,200
0,000
T1 - Barium Hydroxide
3 hours 5 days 15 days 30 days
Fig. 9 - Amount of product applied for T1 treatment
Marble
53

Amount of water
absorbed (g/(cm 2 *min)
)
∆E
7
6
5
4
3
2
1
0
8,0
6,0
4,0
2,0
0,0
T1 - Barium Hydroxide
Marble
3 hours 5 days 15 days 30 days
Fig. 10 - Colour changes for T1 treatment
Untreated Ba(OH)2
hours
Marble - T1
Water absorption by sponge method
Ba(OH)2
days
Ba(OH)2
days
Ba(OH)2
days
Ba(OH)2
Immersion - 3 Immersion - 5 Immersion - 15 Immersion - 30 Poultice - 3
hours
1 minute
2 minutes
5 minutes
Fig. 11 - Water absorption by sponge method before and after T1 treatment
- T3 and T4 treatment [TEOS+APS and TEOS]
The procedure followed was exactly the same used in the first test T3 and T4 (see Report @ 12
months). The only difference was that TEOS and modified TEOS were diluted in acetone (50:50 w/w). The
samples dimensions were 10x5x3 cm.
The volumes are reported in Table 3: Vmax was the maximum volume applied in the first tests, VDmax
is the maximum (diluted) volume applied in the tests of this second year.
54

Table 3 : Determination of maximum volume on different stones
volume/sample (ml)
surface 10x 5 cm 2
Vmax
VDmax
Gioia Marble 0.70 1.45
Firenzuola
Sandstone
Santafiora
Sandstone
0.80 1.50
1.65 2.50
Measurements done up to now on the treated stones are the following:
amount of products applied;
colour determination;
absorption by sponge method.
The differences in weight (g), colour changes and water absorption for T3 and T4 treatment are reported
in Table 4 and Table 5 and Figures 12 - 15.
Table 4 : Weight increase and colour changes after T3 and T4 treatments
Gioia Marble
Firenzuola Sandstone
Santafiora Sandstone
Vmax
Weight increase (g)
Vmax/2
Vmax/2+
Vmax/2
T4 0.270 0.074 0.208
T3 0.195 0.060 0.165
T4 0.254 0.130 0.262
T3 0.212 0.103 0.254
T4 0.556 0.291 0.531
T3 0.425 0.292 0.508
55

Table 5 : Weight increase and colour changes after T3 and T4 treatments (diluted 50% w/w with acetone)
Gioia Marble
Firenzuola Sandstone
Santafiora Sandstone
∆E
∆E
8,0
6,0
4,0
2,0
0,0
8,0
6,0
4,0
2,0
0,0
Weight increase (g)
VDmax VDmax/2 VDmax/2+
VDmax/2
T4 n.d. n.d. n.d.
T3 0.147 0.100 0.134
T4 0.153 0.063 0.127
T3 0.156 0.089 0.225
T4 0.297 0.153 0.260
T3 0.239 0.206 0.308
T4 - TEOS
T4 - Vmax
T4 - Vmax/2
T4 - Vmax/2+Vmax/2
M F S
T4 - TEOS Diluted Solution
T4 dil. - VDmax
T4 dil. - VDmax/2
T4 dil. - VDmax/2 + VDmax/2
M F S
Fig. 12 - Colour changes for T4 and diluted T4 treatments
56

∆E
∆E
8,0
6,0
4,0
2,0
0,0
8,0
6,0
4,0
2,0
0,0
T3 - TEOS + APS
T3 - Vmax
T3 - Vmax/2
T3 - Vmax/2+Vmax/2
M F S
T3 - (TEOS + APS) Diluted Solution
T3 dil. - VDmax
T3 dil. - VDmax/2
T3 dil. - VDmax/2 + VDmax/2
M F S
Fig. 13 - Colour changes for T3 and diluted T3 treatments
57

1,50
1,00
0,50
0,00
Gioia Marble - T4
Water absorption by sponge method - Time of contact
2,00
1,00
0,00
TEOS Vmax TEOS Vmax/2 +
2 minutes TEOS
Vmax/2
Santafiora Sandstone - T4
TEOS Vmax TEOS Vmax/2 +
Vmax/2
TEOS Vmax/2
Water absorption by sponge method - Time of contact
3,00
2,00
1,00
0,00
2 minutes
Firenzuola Sandstone - T4
TEOS Vmax/2
Water absorption by sponge method - Time of contact
TEOS Vmax TEOS Vmax/2 +
Vmax/2
TEOS Vmax/2
Dil. Sol.
TEOS
Dil. Sol.
2 minutes TEOS
Fig. 14 - Water absorption by sponge method for T4 and diluted T4 treatments (time of contact = 2 minutes)
Dil. Sol.
58

1,50
1,00
0,50
0,00
Gioia Marble - T3
Water absorption by sponge method - Time of contact
1,50
1,00
0,50
0,00
2 minutes
TEOS + APS Vmax TEOS + APS
Vmax/2 + Vmax/2
Santafiora Sandstone - T3
TEOS + APS Vmax TEOS + APS
Vmax/2 + Vmax/2
TEOS + APS
Vmax/2
TEOS + APS
Vmax/2
Mod. TEOS
Dil. Sol.
Water absorption by sponge method - Time of contact
3,00
2,00
1,00
0,00
2 minutes
Firenzuola Sandstone - T3
Water absorption - Time of contact 2 minutes
TEOS + APS Vmax TEOS + APS
Vmax/2 + Vmax/2
TEOS + APS
Vmax/2
Mod. TEOS
Dil. Sol.
Mod. TEOS
Fig. 15 - Water absorption by sponge method for T3 and diluted T3 treatments (time of contact = 2 minutes)
Dil. Sol.
59

2.2.2 Tests of drilling on Gioia Marble
First tests with Drilling Force Measurement Treatments were made on Gioia Marble. Drilling tests on
the Sandstones will be carried out in the next months, with a new method which should make up to the
problem of the abrasion of the drill bits with this kind of materials.
The drilling conditions were 600 rpm rotation speed and 10 mm/min of the penetration rate. The drill bit
used was a diamond drill bit Diaber.
Drilling Force profiles are reported in Figures 16- 21
F (N)
40
35
30
25
20
15
10
5
0
Gioia Marble - T1 - Immersion
Untreated
Immersion - 3 hours
Immersion - 5 days
Immersion - 15 days
Immersion - 30 days
0 2 4 6 8 10
Penetration depth (mm)
Fig. 16 - Drilling resistance graphs of Gioia Marble stone treated with Barium hydroxide (T1) by immersion
F (N)
35
30
25
20
15
10
5
0
Gioia Marble - T2
0 2 4 6 8 10
Penetration depth (mm)
Untreated
Immersion
Poultice
Fig. 17 - Drilling resistance graphs of Gioia Marble stone treated with Ammonium Oxalate (T2) by immersion and
poultice.
60

F (N)
Gioia Marble - T4 (TEOS)
50
40
30
20
10
0
Untreated
Vmax
Vmax/2
0 2 4 6 8 10
Penetration depth (mm)
Vmax/2 + Vmax/2
Fig. 18 - Drilling resistance graphs of Gioia Marble stone treated with TEOS (T4) by brush
F (N)
50
40
30
20
10
0
Gioia Marble - T4 (TEOS - Dil. sol.)
0 2 4 6 8 10
Penetration depth (mm)
Untreated
Vmax
Vmax/2
Vmax/2 +
Fig. 19 - Drilling resistance graphs of Gioia Marble stone treated with TEOS (T4 - Diluted Solution) by brush
61

F (N)
40
35
30
25
20
15
10
5
0
Gioia Marble - T3 (TEOS + APS)
0 2 4 6 8 10
Penetration depth (mm)
Untreated
Vmax
Vmax/2
Vmax/2 + Vmax/2
Fig. 20 - Drilling resistance graphs of Gioia Marble stone treated with modified TEOS (T3) by brush
F (N)
40
35
30
25
20
15
10
5
0
Gioia Marble - T3 (TEOS + APS Dil. sol.)
0 2 4 6 8 10
Penetration depth (mm)
Untreated
Vmax
Vmax/2
Vmax/2 + Vmax/2
Fig. 21 - Drilling resistance graphs of Gioia Marble stone treated with modified TEOS (T3 - Diluted Solution) by brush
2.2.3 Tests of consolidation treatments on Ançã and Lecce stones
(LNEC)
Consolidating treatments tested by LNEC on limestones:
• T2) Ammonium Oxalate [(NH4)2C2O4];
• T3) Modified Ethylsilicate (TEOS + APS);
• T4) Ethylsilicate (TEOS).
The ammonium oxalate treatment as consolidant (T2-C) was tested on Ançã and Lecce stones with two
different procedures:
i) by immersion of the stone specimens in the ammonium oxalate solution;
ii) by application of poultices with the ammonium oxalate solution on the stone surface.
The specimen’s dimensions for both treatment procedures were 10×5×3cm.
62

The T3 (BSOH100+APS) and T4 (BSOH100) treatments were applied by brushing on Ançã and
Lecce stones without any previous ageing.
2.3.1.1 Treatment T2) Ammonium Oxalate [(NH4)2C2O4]
Description of the immersion treatment procedure
Specimens were placed in a desiccator with CaCl2 for a 24h period and then weighted. Specimens
were then inserted in a desiccator by placing them on glass rods or glass spheres in order to have a high
portion of the lower surface in contact with the solution and the desiccator is evacuated applying a vacuum
pump for 1h. After that time a solution of Ammonium oxalate (2.5% w/w in water) was added in order to
completely fill the vessel.
The specimens were maintained immersed in the solution for 2 days (@ room temperature).
Afterwards the specimens were removed from the solution, immersed in water for surface cleaning and
gently dabbed with a soft cloth, weighted and left to dry by positioning them on glass rods or spheres in the
laboratory until constant weight.
Description of the poulticing treatment procedure
Specimens were sealed (with epoxy resin 2 ) on the lateral surfaces, leaving both the wider surfaces
free. After the resin was set, the specimens were placed in a desiccator with CaCl2 for 24h and weighted.
The Ammonium oxalate solution (2.5% w/w in water) was mixed to a cellulose powder (Arbocel) in
order to produce a poultice able to be applied on one of the two free surfaces without causing any leaching
problems.
The poultices were prepared by mixing 12% (w/w) of cellulose with 88% demineralised water, and a
portion of approximately 70g of this mixture, with a thickness of approximately 1cm, was applied over the
surface of each specimen. Between the poultice and the stone surface a foil of Japanese paper was interposed
in order to enable to weight the materials in separate.
The contact time was 5h for all the lithotypes, taking care to maintain humid the poultice by
supplying additional solution of ammonium oxalate. After the removal of the poultice the surfaces were
sprayed with water, cleaned and weighed.
Aluminium foil was applied over the exposed area of the poultice to prevent excessive evaporation.
The specimens were positioned with the treated surface on the top on glass rods and left to dry in the
laboratory environment until constant weight.
In the case of the treatment procedure by poulticing, the mass evolution during treatment was also
monitored. The procedure followed for the mass evolution monitoring was the same as described in 2.2.1.1.
Monitoring of colour variation
The Ammonium Oxalate treatments were responsible for some colour variation on Ançã and Lecce stone
(Figs. 22 and 23):
• For the treatment by poulticing:
• Ançã stones show a high colour variation after 15 days and important differences among the
treated specimen occurred. Lecce stone presents only slight yellowing that, as in Ançã stone, is
stronger near the edges.
• For the treatment by immersion:
• the top and lateral surfaces, i.e. those more exposed to drying, showed colour changes;
2 Sikadur 32N
63

• Ançã stone shows a very strong colour variation – the surface shows orange stains mainly
near the edges which possibly is linked with a stronger evaporation process in these areas.
Lecce stone only presents a slight yellow increment.
Fig. 22 - Colour variation on Ançã (P) and Lecce (L) treated with ammonium oxalate by poulticing (NT –
non treated)
Top face
Top face
Lateral face
Lateral face
Fig. 23 - Colour variation on Ançã (P) and Lecce (L) treated by immersion with ammonium oxalate (NT –
non treated)
Monitoring of water absorption by the contact sponge method
The results obtained by the contact sponge method on Ançã and Lecce stones are presented on Fig.
24. A very high reduction of water absorption can be noticed in both lithotypes, but clearly higher in the
Ançã stone. When comparing the two treatment procedures on Ançã stone, the differences are very low.
Lecce stone shows small differences, with a slightly higher decrease produced by the immersion procedure.
64

Absorption [g. cm -2 . min -1 ]
0,25
0,2
0,15
0,1
0,05
0
Immersion
Poultice
Immersion
Poultice
Ançã Ançã Ançã Lecce Lecce Lecce
Absorption [g. cm
-2 . min -1 ]
0,05
0,04
0,03
0,02
0,01
0
Immersion Poultice Immersion Poultice
Ançã Ançã Lecce Lecce
Fig. 24 - Water absorption by the contact sponge method on Ançã and Lecce stone treated with ammonium oxalate by
immersion and by poulticing
Monitoring with drilling resistance
The effect of the ammonium oxalate treatment by immersion and poulticing on Ançã and Lecce
stones is shown in Fig. 25.
The results obtained on Ançã and Lecce stones are different. The drilling resistance increment of
Ançã stone is very low. Lecce stone shows a higher mechanical strength increment near the surface for both
poulticing and immersion procedures.
Depth [mm
10
8
6
4
2
0
NT
0 5 10 15 20 25 30
Force [N]
Ammonium Oxalate
Ançã
Immersion
Poultice
Depth [mm
10
8
6
4
2
0
NT
0 5 10 15 20 25 30
Force [N]
Ammonium Oxalate
Lecce
Fig. 25 - Drilling resistance of Lecce treated with ammonium oxalate by immersion and poulticing
Immersion
Poultice
Inside each stone type, the way how the ammonium oxalate is applied does not induce significant
differences in the mechanical strength properties.
65

2.2.3.2 Treatments T3) Modified Ethylsilicate (TEOS + APS) and T4) Ethylsilicate (TEOS)
Description of the immersion treatment procedure
The T3 (BSOH100+APS) and T4 (BSOH100) were applied by brushing on Ançã and Lecce stones
as without any previous ageing. The following tentative procedures were tested:
• Specimens were weighted before treatment;
• Consolidants were applied wet on wet by brush with three different procedures:
1) Until apparent refusal (refusal was considered to be reached when the treated surface remains
wet for at least 60 seconds) in order to individuate for each lithotype the volume which will
be considered a reference “maximum” absorbed volume (Vmax);
2) Application of half of the maximum absorbed volume (Vmax); and
3) Application of half of the maximum absorbed volume in two steps with a time interval of
two weeks (Vmax/2+ Vmax/2).
Specimens were then positioned on glass rods or spheres and left to evaporate the solvent and to
complete reaction in the laboratory conditions until constant weight is reached.
Ançã stone was also subject to treatment with another type of ethyl silicate – Tegovakon, referred as
TG – as supplied by the manufacturer and also mixed with APS.
Amount of product absorbed
Tables 6, 7 and 8 present the first results of the amount of consolidant absorbed ( M / S) by Ançã
and Lecce stones.
Table 6 : Test trials with Tegovakon+APS and Tegovakon treatments on Ançã stone
Lithotype Treatment Procedure ∆t / S
(brush) [×10 -2 min⋅cm -2 ∆M / S
] [kg⋅m -2 ]
Ançã TG+APS Vmax 27 2.54
TG
Vmax 27 2.70
Table 7 : Test trials with T3 (BSOH100) treatments on limestones
Lithotype Procedure ∆t / S
(brush) [×10 -2 min⋅cm -2 ∆M / S
] [kg⋅m -2 Fringe
] [mm]
Ançã Vmax 63.6 3.51 19
Vmax/2 33.4 1.90 9
Vmax/2
+
32.6 1.78
9
Vmax/2
155.6 1.71
(Σ=3.49)
9
Lecce Vmax 42.9 2.02 9-10
Vmax/2 16.3 1.10 6
Vmax/2
+
6 1.11
5-6
Vmax/2
15 1.01
(Σ=2.12)
5
66

Table 8 : Test trials with T4 (BSOH100+APS) treatments on limestones
Lithotype Procedure
∆t / S
(brush) [×10 -2 min⋅cm -2 ∆M / S
] [kg⋅m -2 Fringe
] [mm]
Ançã Vmax 80.7 3.51 15
Vmax/2 35.0 2.4 8-9
Vmax/2
+
34.2
1.77
8-9
Vmax/2
68.5
0.18
(Σ=1.97)
2
Lecce Vmax
64.4 1.99 6
Vmax/2 18.1 1.10 5-6
Vmax/2
+
22.5
1.02
5-6
Vmax/2
49.1
0.53
(Σ=1.55)
5
The BSOH100 consolidant (as received from the manufacturer) seems to “cure” so rapidly after the
addition of APS that curing on the surface inhibits penetration. This happened after about half an hour of the
products mixture. Fig. 26 shows the aspect of Ançã and Lecce treated surfaces with BS+APS after 7hours;
the part of the product applied that was not absorbed formed a film at the specimens surface that
subsequently cracked. To avoid this problem it was necessary to prepare the solution of BSOH100 and APS
and to apply it immediately after.
Fig. 26 - Aspect of the Ançã (left) and Lecce (right) treated surfaces with BS+APS after 7
hours (7×)
Monitoring with colour variation
The treatments T3) Modified Ethylsilicate (TEOS + APS) and T4) Ethylsilicate (TEOS) did not
induce relevant colour variations on Ançã and Lecce stones.
67

Monitoring with water absorption by the contact sponge method
The results obtained by the contact sponge method on Ançã and Lecce stones are presented on Fig.
27. It can be noticed that water reduction was sensitive to the treatment procedure and to the amount of
product applied.
Water absorption [10-3 g.cm-2 .min-1 Water absorption [10 ]
-3 g.cm-2 .min-1 ]
Water absorptio
[10 -3 g.cm - [10 2.min-1
-3 g.cm - 2.min-1
14
12
10
8
6
4
2
0
TG+APS
TG
V/2 V V/2 + V/2
Treatment
Ançã
BS+APS
BS
Water absorption [10-3 g.cm-2 .min-1 Water absorption [10 ]
-3 g.cm-2 .min-1 ]
Water absorption [ 10 -3 g. cm-2.
14
12
10
8
6
4
2
0
V/2 V V/2 + V/2
Treatment
Lecce
BS+APS
Fig. 27 - Water absorption by the contact sponge method on Ançã and Lecce stone treated with T3) Modified
Ethylsilicate (BS + APS) and T4) Ethylsilicate alone (BS). The ethylsilicate TG is added for comparison
Monitoring with drilling resistance
The drilling resistance evaluated on the stone specimens treated with T3) Modified Ethylsilicate (TEOS
+ APS) and T4) Ethylsilicate (TEOS) treatments show:
• visible differences between the two ethylsilicate products,
• scarce influence of the lithotype,
• identifiable APS action,
• influence of the amount of product in the depth of penetration,
• influence of the treatment procedure in the consolidation action.
-differences between the two ethylsilicate products
Tegovakon and BSOH100 consolidants show a high penetration capacity. However, TG seems to be more
homogeneously dispersed in the stone matrix since the drilling resistance is practically constant in depth.
BS
68

14
12
De 10
pt
h 8
[m
m] 6
Scarce influence of the lithotype
4
2
TG (2,7kg.m -2 )
Ançã - NT
BS (3,5 kg.m -2 )
Vmax
0
0 5
Diamond drill bit; guide hole
100rpm; 20mm/min
10
Force [N]
15 20
Fig. 28 - Drilling resistance of Ançã stone treated with two
ethylsilicate products (TG- Tegovakon; BS – BSOH100)
The drilling resistance in depth revealed a scarce influence of the lithotype on the consolidation action
obtained with BSOH100 (BS) and BSOH100 + APS (BS+APS), Fig.29.
Force [N]
Force [N]
14
12
10
14
12
10
8
6
4
2
8
6
4
2
0
Lecce - NT
BSOH100 (BS)
(2,0 kg.m -2 )
0 5 10 15 20 25
Depth [mm] Diamond drill bit; guide hole
100rpm; 20mm/min
-2
(1,9 kg.m )
Ançã - NT
0
0 5 10 15 20 25 30
Depth [mm]
BSOH100 (BS)
Diamond drill bit; guide
h l
100rpm; 20mm/min
Force [N]
14
12
10
8
6
4
2
Lecce - NT
(2,0 kg.m -2 )
BSOH100 (BS) +
0
0 5 10 15 20 25
Depth [mm]
Diamond drill bit; guide ho
100rpm; 20mm/min
0
0 5 10 15 20 25 30
Fig. 29 - Drilling resistance of Ançã and Lecce stone treated with BSOH100 (BS) and BSOH100 + APS
(BS+APS)
Force [N]
14
12
10
8
6
4
2
Depth[mm]
(2,0kg.m -2 )
Ançã - NT
BSOH100 (BS) + APS
Diamond drill bit; guide hole
100rpm; 20mm/min
69

APS action
The results point out that APS may be responsible for:
• a resistance increase near the treated surface, Fig.30;
• reducing the capability of ethylsilicate to penetrate inside the stone, Fig.31.
This behaviour may be assigned to the rapid gelification of the consolidant when mixed with APS as
mentioned above. In Fig. 32 the differences between the BSOH 100 with and without APS after 20h of
gelification can be observed.
Force e [N
14
12
10
8
6
4
Ançã - NT
BS + APS
BS
Vmax
2
(3,5 kg.m
0
0 5 10 15 20
Depth[mm] Diamond drill bit; guide hole
100rpm; 20mm/min
-2 )
Force [N
14
12
10
8
6
4
2
BS + APS
BS
Lecce - NT
Vmax
0
(2,0 kg.m
0 5 10 15 20
Depth [N] Diamond drill bit; guide hole
100rpm; 20mm/min
-2 )
Fig. 30 - APS action evaluated by the drilling resistance of Ançã and Lecce stone treated with BSOH100 (BS) and
BSOH100 + APS (BS+APS)
Force [N
10
8
6
4
2
0
Lecce - NT
15mm
BSOH100 (BS)
BSOH100 (BS) + APS
(1,1 kg.m -2 )
(1,1 kg.m -2 )
19mm
0 5 10 15 20 25
Depth [mm] Diamond drill bit; guide hole
100rpm; 20mm/min
Fig. 31 - APS may be responsible for reducing the capability of ethylsilicate
to penetrate inside the stone
BSOH
BSOH+APS
Fig. 32 : BSOH and
BSOH+APS after 20h of
gelification
BSOH100
70

the amount of product influences the depth of penetration
The comparison between the consolidation action obtained with the same procedure treatment but
with different amounts of consolidant on Ançã and Lecce stones show that the amount of product influences
the consolidated thickness, Fig.33.
Force [N
Fig. 33 - Influence of the amount of consolidant applied on the consolidation action
the treatment procedure influences the consolidation action
The comparison between the action of the treatments applied by the different procedures above mentioned
on Ançã and Lecce stones is shown in Fig.34. The results show the influence of the treatment procedure on
the consolidation action.
Force[N
14
12
10
8
6
4
2
14
12
10
8
6
4
2
Lecce - NT
Lecce - NT
(2,1 kg.m -2 )
0
0 5 10 15 20 25
Diamond drill bit; guide hole
100rpm; 20mm/min
Depth [mm]
2.2.4 Tests of protective treatments
(OPD)
BSOH100 (BS)
Vmax
Vmax/2
(2,0 kg.m -2 )
(1,1 kg.m -2 )
0
0 5 10 15 20 25
Depth [mm]
Diamond drill bit; guide hole
100rpm; 20mm/min
BSOH100 (BS)
Vmax
Vmax/2+Vmax/2
(2,0 kg.m -2 )
Fig. 34 - Influence of the treatment procedure on the consolidation action
(2,0 kg.m -2 )
(2,0 kg.m -2 )
Vmax
Vmax/2
0
0 5 10 15 20 25
Depth [mm]
Diamond drill bit; guide hole
100rpm; 20mm/min
The application of protective treatments on stone specimens contaminated by the planned tentative
procedure had produced some undesirable superficial effects: formation of a shiny, plastic layer on samples
treated with DMPS (Fig. 35) and strong re-crystallisation of NaCl on samples treated with ammonium
Force [N
Force [N
14
12
10
14
12
10
8
6
4
2
8
6
4
2
Lecce - NT
(1,8 kg.m -2 )
Lecce - NT
BSOH100 (BS) + APS
(1,1 kg.m -2 )
BSOH100 (BS) + APS
Vmax
Vmax/2+Vmax/2
0
0 5 10 15
Diamond drill bit; guide hole Depth [mm]
100rpm; 20mm/min
20 25
71

oxalate poultice. (Fig. 36) This effects meant that the strong conditions (10% w/w solution, long times of
imbibition) adopted for contamination had to be adjusted in order to both reduce the amount of salt and avoid
the formation of an impenetrable barrier of NaCl crystals.
Fig. 35 - Stereomicroscope image of the shiny coating of
protective on Lecce stone: the presence of a strong layer of
NaCl under the surface prevents the penetration of DMPS
treatment.
Fig. 36 - SEM image of NaCl efflorescence after treatment
of Ança stone with ammonium oxalate poultice.
Therefore, a different protocol of contamination was set up. The most important parameters to be
adjusted were:
• the concentration of salt
• the contact time with the solution
• the temperature of the oven
Satisfactory results were thus achieved by drastically reducing the soaking time of the specimens in the
saline bath and then immediately allowing them to dry in oven at 70°C.
By adopting this procedure, no covering effect of NaCl crystals was observed, and subsequent stages of
treatment could be undertaken.
2.2.4.1 Definition of further steps
In order to evaluate the performance of treatments at best, a procedure was established, based on the
comparison of color, contact angle and capillary rise measurements before and after the application of
protective. Also, some reference sets of samples (both contaminated but untreated and treated without any
previous contamination) were prepared in order to assess whether the presence of salt had any influence on
the capillary absorption measurements. A scheme of the different sets of samples is reported in Fig. 37.
72

The procedure was established as follows:
Fig. 37 - Scheme of the different sets of samples.
• Contamination of specimens of each lithotype, to be executed according to the new experimental
parameters;
• Introduction into oven at 70 °C until constant weight is reached;
• Color and contact angle tests on contaminated specimens, to be treated with protective;
• Capillary measurements on contaminated reference set;
• Application of protective on all the other samples according to the planned procedure (see §2.4 and first
application);
• Wait period until treatments have stabilized;
• Color and contact angle measurement on treated specimens;
• Capillary rise test on treated specimens.
The samples have been contaminated and treated, and the planned tests have been carried out before
treatments. After stabilization of the protective treatments, the measurements will be repeated; the data
collected before and after the treatments will be thus compared in order to evaluate the performance of each
protective product. Moreover, the amount of protective product applied will be evaluated.
73

3. TASK 3 - PROGRESS REPORT ON ACCELERATED AGEING TESTS AND RESULTS
3.1 ACCELERATED AGEING TESTS UNDER EVALUATION
(LNEC, ICVBC)
The accelerated ageing tests under evaluation by LNEC and ICVBC in the reporting period are:
• Thermal shock on Gioia marble, Firenzuola and Santafiora stones;
• Salt crystallisation on limestones and sandstones.
3.2 THERMAL SHOCK
(LNEC)
Thermal shock description
The 1 st annual activity report presented the tests carried out to define the experimental conditions to
induce degradation by temperature changes on some spare specimens of marbles and to select the experimental
protocol.
During the reporting period degradation on Gioia marble was induced by thermal shock by using the
selected experimental protocol. This condition was achieved by placing the specimens in contact with a heated
plate, at ~300ºC, for 5 minutes and, after that, allowed to cool at room temperature. Table 9 summarizes the
work conditions applied in the Gioia marble tests.
Table 9 : Thermal shock work conditions on Gioia marble
Specimen
Thickness
(mm)
Heated
plate
Temperature (ºC)
Face in contacted
with the heated plated
Opposite face
Number of
cycles
tested
G9 30 300 200-240 90-110 5
G12 30 300 200-220 90-100 3
G10 30 300 200 100 1
Ageing by thermal shock was monitored by the detection of eventual changes in water absorption
characteristics (microdrops absorption time, water absorption by sponge and water absorption by capillarity).
In order to minimize the variants of the measurement of the ageing action by the contact sponge
method and the microdrops absorption time the specimens were always manipulated with care in order to
avoid contamination with the grease from the hands. The water absorption by the contact sponge method was
performed as follows:
• the same sponge was always used for each specimen;
• at least three measurements were taken for each specimen;
• the sponges were always dried at room temperature for at least one day;
Results
The results of microdrops absorption time and water absorption by contact sponge are presented in
Tables 10 and 11. The microdrops absorption and water absorption (by sponge) tests revealed didn’t detect any
alteration due to ageing as can be observed in Fig. 38 for two different specimens, G9 and G12.
74

Table 10 : Water absorption by the contact sponge evaluated on the specimens heated faces
Specimen
Microdrops absorption time [%]
before ageing t1 t2 t3 t4 t5
G9 7 3 17 17 13 12
G12 9 5 3 6
G10 8 10
Table 11 : Water absorption by the contact sponge evaluated on the specimens heated faces
Microdrop Absorption [%] [%] [%]
Specimen
5
10
15
20
25
30
Water absorption by the contact sponge
[×10 -4 g⋅cm -2 ⋅min -1 ]
before ageing t1 t2 t3 t4
G9 112 132 47 37 38
G12 154 147 139 131
G10 122 112
Cycle number
0 1 2 3 4 5
0
180
150
120
90
60
30
0
Absorption Absorption by sponge by [10 Spon
[g.cm-2.min-1]
-4 .g.cm-2 .min-1 Absorption Absorption by sponge by [10 Spon
]
[g.cm-2.min-1]
-4 .g.cm-2 .min-1 ]
Fig. 38 - Thermal shock test on two Gioia specimens (G9 and G12).
Microdrops absorption time and water absorption with sponge
Experiments were taken in order to investigate the possible influence of the excessive dryness of the
specimens on the results of microdrops absorption time and water absorption by contact sponge. The
experiments consisted in humidifying the specimens before the water absorption evaluation and monitoring
before and after the wetting procedure by the microdrops absorption time and the contact sponge method.
The following procedures were adopted to wet the specimens:
1. Surface wetting with an humid sponge, Fig.39;
2. Specimens conditioning in an humid atmosphere (95-100% RH) at room temperature (20-25ºC)
during 4 days, Fig.40;
75

Microdrop absorption time
25
20
15
10
5
0
Before surface wetting After surface wetting
Wa [g/cm^2.m
0,005
0,004
0,003
0,002
0,001
0
Before surface wetting After surface wetting
Fig. 39 - Microdrops absorption time and water absorption by the contact sponge method before and after the
surface humidification with a humid sponge
Microdrops absorption time
20
15
10
5
0
Before surface wetting After surface wetting
Wa [g/cm^2.min^
0,015
0,01
0,005
0
Before surface wetting After surface wetting
Fig. 40 - Microdrops absorption time and water absorption by the contact sponge method before and after
specimens conditioning in humid atmosphere
The results point out that the state of dryness of the specimens is not a relevant factor. In fact, the
results show very low variations between each measurement that seem to reveal that the process of drying
doesn’t influence the results.
Since no improvement can be introduced in the measuring process, we may conclude that
microdrops absorption time and contact sponge methods are not adequate to monitor the ageing action on
Gioia marble.
Water absorption by capillarity was then tested to monitor the thermal shock on Gioia marble. This
method has shown to be sensitive.
When analysing each curve plotted in Fig. 41 it can be noticed that the first thermal shock is the
main responsible for the damaged produced and that the further cycles do not increase significantly the decay
intensity.
The results point out that the method is suitable to control the ageing action on Gioia marble and that
a unique thermal shock seems to be sufficient to produce damage.
76

-4 -2
g.mm-2 g.mm ]
∆M ∆M/S / S [x [10 10
5
4
3
2
1
0
Final remarks
G11
Cycle 0
Cycle 1
Cycle 2
Cycle 3
0 60 120 180
Tempo [s 1/2 ]
Water aborption -4 by capillarity -2
∆M/S [10 g.mm ] [10-4 g
Fig. 41 - Water absorption by capillarity evolution
5
4
3
2
1
0
G13
Cycle 0
Cycle1
Cycle 2
Cycle 3
0 60 120 180
Tempo [s 1/2 ]
The test results pointed out that the methods initially used to monitor the ageing action on Gioia marble
namely microdrops absorption time and water absorption by the contact sponge methods are not adequate.
The possible influence of the state of dryness of the specimens on the results obtained with these
methods was investigated and it was proved that the state of dryness is not the cause of it.
The water absorption by capillarity seems to be an adequate method to monitor the damage induced
by the thermal shock.
Table 12 summarises the final proposal for the ageing of Gioia marble.
Temperature of the
heated plate
[ºC]
Table 12 : Summary of the proposal conditions for the Gioia marble ageing
Contact Time
[min]
Cooling temperature
[ºC]
Ageing monitoring
~300 5 20-25 Water absorption by
capillarity
3.2 THERMAL SHOCK
(ICVBC)
The specimens were placed in contact with a heated plate, at ~200ºC, for 3 minutes and, after that, let to
cool at room temperature. The monitoring of the induced decay was carried out by measures of capillary water
absorption at short time and by sponge method. The parameters were measured after 5, 10 and 20 cycles.
Capillary water absorption at long times was measured at 0 and 20 cycles.
Experimental data are reported in Figures 42 - 47.
77

Amount of water absorbed
(g)
Amount of water absorbed (s)
0,200
0,150
0,100
0,050
0,000
Amount of water
absorbed (g)
0,9
0,9
0,8
0,8
0,7
0,7
0,200
0,150
0,100
0,050
0,000
Gioia Marble
M-A1 M-A2 M-A3 (control)
S-1 S-2
0 cycles
5 cycles
10 cycles
20 cycles
Sievec Marble 0 cycles
Carrara Marble
X 104 X105
5 cycles
10 cycles
20 cycles
0 cycles
5 cycles
10 cycles
20 cycles
Fig. 42 - Capillary water absorption at short time of Marble specimens treated with thermal shock
78

Amount of water
absorbed
(g)
0,7
0,6
0,5
0,4
0,3
0,2
0,1
0,0
Amount of
water
absorbed (g)
Firenzuola Sandstone
0,6
0,4
0,2
0,0
F-A1 F-A2 F-A3 (control)
Santafiora Sandstone
S-A1 S-A2 S-A3
(control)
Fig. 43 - Capillary water absorption at short time of Sandstone specimens treated with thermal shock
79

Water absorbed
(mg/(cm 2 *min))
Sievec Marble
2,00
1,50
1,00
0,50
0,00
Water absorbed
(mg/(cm 2 *min))
Gioia Marble
10,00
8,00
6,00
4,00
2,00
0,00
0 cycles
5 cycles
10 cycles
20 cycles
M-A1 M-A2 M-A3
Water absorbed
(mg/(cm 2 *min))
2,00
1,50
1,00
0,50
0,00
0 cycles
5 cycles
10 cycles
20 cycles
Carrara Marble
S-1 S-2 X 104 X 105
0 cycles
5 cycles
10 cycles
20 cycles
Fig. 44 - Capillary water absorption by sponge method (time of contact = 2 minutes) of Marble specimens treated with
thermal shock
Water absorbed
Firenzuola Sandstone
(mg/(cm 2 /min))
3,50
3,00
2,50
2,00
0 cycles
5 cycles
10 cycles
20 cycles
Santafiora Sandstone
Water absorbed
(mg/(cm2/min))
3,00
2,50
2,00
F-A1 F-A2 F-A3 S-A1 S-A2 S-A3
0 cycles
5 cycles
10 cycles
20 cycles
Fig. 45 - Capillary water absorption by sponge method (time of contact = 2 minutes) of Sandstone specimens treated
with thermal shock
80

4,000
3,500
3,000
2,500
2,000
1,500
1,000
0,500
0,000
5,000
4,000
3,000
2,000
1,000
0,000
F-A1
0 cycles
20 cycles
0 100 200 300 400 500 600 700 800
S-A1
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
0,500
0,000
0 100 200 300 400 500 600 700 800
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
0,500
0,000
4,000
3,000
2,000
1,000
0,000
F-A3 (control)
0 100 200 300 400 500 600 700 800
0 cycles
20 cycles
S-A3 (control)
4,500
3,500
2,500
1,500
0,500
F-A2
0 cycles
20 cycles
0 100 200 300 400 500 600 700 800
0 cycles
20 cycles
(not aged)
0 100 200 300 400 500 600 700 800
S-A2
0 cycles
20 cycles
-0,500
0 100 200 300 400 500 600 700 800
0 cycles
20 cycles (not aged)
Fig. 46 - Amount of water absorbed (g) by the samples treated with thermal shock
81

1,000
0,900
0,800
0,700
0,600
0,500
0,400
0,300
0,200
0,100
0,000
M-A1
0 cycles
20 cycles
0 100 200 300 400 500 600 700 800
1,000
0,900
0,800
0,700
0,600
0,500
0,400
0,300
0,200
0,100
0,000
1,000
0,900
0,800
0,700
0,600
0,500
0,400
0,300
0,200
0,100
0,000
M-A3 (control)
0 100 200 300 400 500 600 700 800
M-A2
0 cycles
20 cycles
0 100 200 300 400 500 600 700 800
0 cycles
20 cycles
(not aged)
Fig. 47 - Amount of water absorbed (g) by the Gioia Marble samples treated with thermal shock
3.3 SALT CRYSTALLISATION
(LNEC)
Salt crystallisation tests
LNEC took the responsibility of carrying out the tests on ageing with salt crystallisation aiming at
finding a suitable and quick way of producing artificially decayed surfaces in the selected stone types: limestones
(Ançã and Lecce stones) and sandstones (Santafiora and Firenzuola). The results of the first experiments carried
out on Ançã stone were presented in the 1 st annual activity report.
The preliminary tests on Ançã stone were further developed and extended to the other lithotypes in order to
obtain two distinct degradation patterns:
1. superficial degradation;
2. gradual degradation in depth.
In all the ageing procedures the study was focused on the crystallisation of mirabilite from a high
concentrated sulphate solution by means of a rapid temperature decrease. This sudden temperature change is
able to promote a fast precipitation of the heptahydrate and decahydrate forms of sodium sulphate without
water evaporation. The distinct patterns degradation abovementioned were tested in different conditions for
all stones.
Monitoring of the ageing tests was carried out by visual inspection and with a binocular microscope for all
the stone specimens. Drilling profiles were executed for the limestones aiming to provide information on salt
distribution within the stone and on the induced mechanical damage. The sandstone’s ageing was monitored
with water absorption by the contact sponge method.
During the reporting period the desalination procedure by immersion and with poultices was also studied.
Experimental protocol
82

Each specimen was initially dried at 40ºC and impregnated by capillarity in its individual glass Petri
dish with sodium sulphate solutions at 40ºC. After the impregnation, each specimen was immediately placed
in a climatic chamber between 5º and 10ºC during thirty minutes to promote mirabilite crystallization and
then oven dried at 40ºC for 24h, before starting a new salt impregnation.
Each specimen was individually tested and different procedures were adopted. The testing conditions
to carry out the degradation were different in what concerns:
• number of cycles,
• lateral surfaces: sealed and not sealed,
• concentration of the salt solution: 14% and 20%,
• desalination: immersion and poulticing,
• impregnation layer – achieved by controlling the time interval of salt solution absorption:
• to promote superficial degradation up to 2-3mm;
• to promote gradual degradation in depth in the range of 2-10mm.
After each test, specimens were desalinated by immersion in distilled water or with wet poultices. The
salt extraction was monitored by measuring the water conductivity.
Desalination
The desalination procedure is a very time consuming task. Trying to accelerate the desalination process,
experiments were made with wet poultices in order to compare its efficiency with the immersion procedure. In
both methods the desalination was tested at 40ºC and at room temperature.
Ançã stone specimens (5×5×3cm) with the lateral surfaces sealed and with approximately the same salt
content were used for the comparison.
In the case of the desalination performed at 40ºC, the specimens were salinated by the gradual procedure
(3 steps salination) with a salt solution of 20%-w sodium sulphate. In the case of the desalination at room
temperature, the specimens were also salinated by the gradual procedure with a salt solution of 20%-w sodium
sulphate but twice, i.e., 6 salt impregnations at different depths (10mm, 5mm, 2mm).
- Experimental protocols
Immersion procedure
-
1. The specimen is immersed in 1000ml demineralised water. The base of the specimen is put over
glass rods. The container is closed (Fig. 48).
2. The salt extraction is monitored by measuring the water electrical conductivity. The water is changed
periodically being the first time intervals smaller (1, 3, 5 days – continued at time intervals of 5
days) until the electrical conductivity falls bellow 100µS⋅cm -1 ) – and it generally lasts for 20 days.
Closed
1000 ml water
Sample
Glass rods
Fig. 48 - Scheme of desalination procedure by immersion
83

-Wet poultice procedure
1. A mixture of 20% cellulose (ARBOCEL BC 1000) and 40% demineralised water (w/w) is prepared
and applied over the top surface (the top surface of the specimen is the one that has been subjected to
salt impregnation. The thickness of the poultice is of approximately 1cm;
2. The specimen is immersed in water (a volume 500ml or less, depending on the container
dimensions) leaving approximately 5mm height of the specimen out of the water; the base of the
specimen is put over glass rods (Fig. 49);
3. Both poultice and desalination water is periodically changed being the first time intervals smaller.
The electrical conductivity of the poultice is measured by diluting it in 400ml water that is then
filtrated and washed with 100ml water obtaining 500ml of extraction water – the electrical
conductivity of the resulting solution is measured. The water extracted from the poultice and the
water of immersion are measured separately. The volume of the immersion water is quantified and,
if lower than 500ml, more demineralised water is added until 500ml volume is reached. Finally, the
water extracted from the poultice and the immersion water are mixed, resulting in a solution volume
of 1000ml and the electrical conductivity of the final solution is measured.
- Results
Opened
container
Cellulose poultice
10mm
5mm
Sample
Water
Glass rods
Fig. 49 - Scheme of desalination procedure with wet poultices
Fig. 50 shows the results obtained with the two desalination methods. It can be considered that the
desalination using poultices does not promote a relevant increase in the desalination efficiency. Regarding the
higher amount of experimental work involved in the desalination procedure by poulticing and the difficulties to
keep temperature at 40ºC, it is considered that the desalination process shall be carried out by immersion at room
temperature.
Conductivity [uS/c
3000
2400
1800
1200
600
Immersion - Troom
Poultice - Troom
Immersion - 40ºC
Poultice - 40ºC
0
0 7 14 21 28 35
Desalinisation Period [days]
Fig. 50 - Graphic showing the measured conductivity over time
by the immersion and wet poultice procedure
84

Superficial degradation
Table 13 summarizes the work in progress with the superficial ageing procedure.
Table 13 : Summary of the work in progress with the superficial ageing procedure
Lithotype Lateral [Na2SO4] Contact Impregnation Desalination
surfaces %, w/w time depth [mm] procedure
Ançã
Not sealed
14
20 ~2-5sec.
Immersion at 40ºC
Sealed 20 2-3 Poulticing at 40ºC
Lecce Sealed 20
Poulticing at 40ºC
Santafiora
Firenzuola
Sealed
Sealed
20
20
5min.
Poulticing at 40ºC
Poulticing at 40ºC
The contact time set for the limestones was of approximately 2-5 seconds. A larger period of time
was set for the sandstones because of its lower capillarity absorption coefficient. In order to reach 2-3mm
depth, the specimens were left in contact with the salt solution during 5minutes.
The results obtained with Ançã stone not sealed are shown in the present report. The experiments
with the other lithotypes are still in progress and will be presented in the next report.
Ançã results - Superficial degradation
The results here reported concern the Ançã stone tested on specimens with the lateral faces not sealed
and using salt solutions with 14% and 20% concentration.
The Ançã specimen tested with the salt solutions with 14% concentration was submitted to the following steps:
• 1º cycle
• four salt solution impregnation during 2-5 seconds . After each impregnation the
specimen was immediately placed in a climatic chamber at 5º or 10ºC during thirty minutes to
promote mirabilite crystallization and then oven dried at 40ºC before starting a new salt
impregnation,
• desalination by immersion at 40ºC.
• 2º cycle
• seven salt solution impregnations during 2-5 seconds. After each impregnation the
specimen was immediately placed in a climatic chamber at 5º or 10ºC during thirty minutes and
then oven dried at 40ºC before starting a new salt impregnation,
• desalination by immersion at 40ºC.
The results obtained with the drilling profiles taken after each cycle (Fig. 51) indicate that salt
concentrates near the surface.
Regarding the tests carried out with a 14% salt solution concentration, slight loss of material could
be observed at the top and at the sides (1mm height). However, the surfaces were pretty stable and only a
slight surface roughness increase could be noticed, Fig.52.
85

Force [N
25
20
15
10
5
0
before desalination
0 5 10 15
Depth [mm]
Fig. 51 - Drilling resistance of Ançã stone after the 7 salt
impregnations of the 2 nd cycle with a 14% salt solution
Fig. 52 - Salt degradation promoted on the Ançã
specimen tested with the salt solutions with 14%
concentration. Top face (photo above) and lateral
face
The Ançã specimen tested with the salt solutions with 20% concentration was submitted to the following steps:
• 1º cycle
• one salt solution impregnation during 2-5 seconds. After the impregnation the specimen
was immediately placed in a climatic chamber at 5º or 10ºC during thirty minutes to and then oven
dried at 40ºC,
• desalination by immersion at 40ºC;
• 2º cycle
• four salt solution impregnation during 2-5 seconds. After each impregnation the
specimen was immediately placed in a climatic chamber at 5º or 10ºC during thirty minutes and
then oven dried at 40ºC before starting a new salt impregnation,
• desalination by immersion at 40ºC
The experiments carried out with a 20% salt solution concentration promoted powdering and surface
delamination as presented in Fig. 53.
Fig. 53 - Aspect of the top surface of the specimen showing delamination and
powdering after 2 cycles with a 20%-w sodium sulphate solution
The results obtained showed that the salt is mainly concentrated at the surface submitted to salt
impregnation. The use of a 14% salt solution concentration resulted in surface powdering whereas the 20%
salt solution promoted powdering and delamination more rapidly.
86

Gradual
degradation in depth
The procedure carried out to promote the gradual degradation procedure was defined in order to avoid
plaque formation and to achieve a moderate and gradual degradation pattern in depth. The risks of this procedure
are the possibility of specimen destruction and to achieve a not-controlled degradation, Fig.54.
The adopted ageing method comprises 3 salt impregnation tests at different penetration depths (3-steps
salination), controlled with the contact time of each lithotype. Three different procedures were set
and applied in
all lithotypes. Table 14 presents the conditions defined for each test.
• avoid plaque formation
• achieve moderate and
gradual degradation
• non control gradual
degradation
• Sample destruction
Fig. 54 - Objectives and risks associated to the salt gradual degradation
procedure
Table 14 : Summary of the tests carried out to promote a gradual degradation
pattern
Test Lateral [Na2SO4] Impregnation Desalination procedure
surfaces
%, w/w depth
[mm]
A Not sealed
B Sealed
14
14
14
C Sealed 20
14
Water
Immersion
10
5
2 Poulticing
Two consecutive salt solution
impregnations followed by
desalination
2
Poulticing
5
10
Each cycle in Test A and B correspond to one salt solution impregnation (3-steps salination)
followed
by desalination.
Table 15 presents the adopted contact time necessary to reach the impregnation depth specified in Table 14.
87

Test [Na2SO4]
%, w/w
A and B
C
Table 15 : Adopted contact time with salt solution for each lithotype
14
14
14
20
14
Water
Impregnation depth
[mm]
10
5
2
2
5
10
Contact time
Limestones
[min]
5
2
1
1
2
5
Contact time
Sandstones
5 h
1 h
15 min
15 min
1 h
5 h
Results obtained with Test A are shown in the present report. Tests B and C are still in progress and
will be presented in the next report.
In order to obtain information about the salt distribution inside the specimens the stone cuttings
obtained during drilling were collected at each 5mm depth drilling run (in the same drilling hole) before its
desalination. The collected powder was dried until constant weight at 70ºC. Afterwards 0.15g of each
specimen were stirred in 50ml of demineralised water and filtrated. Finally, the electrical conductivity of the
resulting solution was measured.
The results of the drilling profiles taken on Ançã stone aged with Test A are presented in Fig. 31. It can
be noticed that salt concentrates not only close to the surface but also at 10-15mm depth. During desalination,
after 3 cycles the specimen split in two parts. Results point out that 3 cycles are excessive for ageing this
lithotype.
The results of the drilling profiles taken on Lecce stone aged with Test A are presented in Fig. 32. It can
be noticed that salt concentrates mainly near the surface and that a gradual degradation pattern in depth could be
achieved – the mechanical strength lowered more near the surface and reached approximately 1cm depth. During
the ageing procedure, the specimen lost material by powdering and scaling mainly at the top surface as shown in
Fig. 57.
This procedure seems to be adequate for Lecce stone since it shows a gradual degradation pattern in
depth, being more severe on the top face where salt concentrates. The decay intensity achieved with 3 ageing
cycles also seems to be adequate but further cycles will be carried out in order to achieve higher decay levels.
Force [N
15
10
5
0
200
150
100
0 5 10 15 20 25 30
Depth [mm]
Diamond drill bit; no guide-hole
50
0
400rpm/15mm.min -1
Fig. 55 - Drilling resistance on Ançã stone after 3 cycles before desalination
Conductivity [uS/c
88

Force [N
30
20
10
0
Force [N
400
300
200
100
0 5 10 15 20 25 30
Diamond drill bit; no guide-hole
Depth [mm] 400rpm/15mm.min-1
10
8
6
4
2
0
Lecce
Lecce aged
0 5 10 15 20 25
Depth [mm]
Diamond drill bit; guide-hole
100rpm/20mm.min-1
Fig. 56 - Drilling resistance of Lecce stone after 3 cycles
before (above) and after desalination
0
Conductivity [uS/c
Fig. 57 - Aspect of Lecce stone after 3
cycles. Top face showing superficial
scaling and powdering (above). Lateral
surface showing a gradual loss of
material in depth
The results of the ageing monitoring after 3 cycles by the water absorption with the contact sponge
method carried out on Santafiora stone aged with Test A are presented in Fig. 34. It can be noticed that there is
a slight gradual increase in the water absorption meaning that this testing procedure is promoting decay.
However, no significant loss of material was observed. The decay intensity achieved with three ageing cycles
does not seem to be sufficient for ageing the Santafiora sandstone since the surfaces resulted pretty stable (Fig.
59).
The contact sponge seems to be a suitable method to monitor the ageing action. A drilling profile will be
taken after achieving decay intensity detectable by visual inspection.
The results of the ageing monitoring with the water absorption by the contact sponge method carried out
on Firenzuola sandstone aged with Test A are presented in Fig. 60. As in the case of Santafiora sandstone, it can
be noticed that there is a slight gradual increase in the water absorption meaning that this testing procedure is
promoting decay. However, no loss of material was observed.
The decay intensity achieved with three ageing cycles does not seem to be sufficient for ageing the
Firenzuola sandstone since the surfaces resulted even more stable than those of Santafiora sandstone (Fig. 61).
At the binocular microscope a slight corrosion of the biotites could be noticed.
89

-2 -1
.min ]
-3
Wa Wa [x10 [x10 -3 g.cm g. cm -2.mi
15
10
5
0
0 1 2 3
Cycle
Fig. 58 - Water absorption by the contact sponge method after each
ageing cycle of Test A on Santafiora sandstone
Fig. 59 - Aspect of Santafiora
sandstone after 3 cycles: Lateral
surface (above) and top surface
90

-2 -1
.min ]
-3
Wa [x10 Wa [g/cm^2/m g. cm
15
10
5
0
0 1 Cycle 2 3
Fig. 60 - Water absorption by the contact sponge method after each
ageing cycle of Test A on Firenzuola sandstone
Fig. 61 - Aspect of Firenzuola sandstone
after 3 cycles: Lateral surface (above)
and top surface
Final remarks
The higher amount of experimental work involved in the desalination procedure by poulticing and
the difficulties associated with the temperature maintenance at 40ºC it is considered that the desalination
process shall be carried out by immersion at room temperature.
Salt crystallisation procedures adopted to promote a surface degradation pattern on Ançã stone
indicate that this degradation pattern can be achieved more rapidly with the use of 20% sodium sulphate
solution. These testing conditions for Ançã stone should be confirmed during the next period. The procedure
for superficial degradation of the other stones is not yet defined. The tests continue.
Decay obtained with the gradual degradation procedure of Test A in limestones and sandstones differ
in a clear way. The results pointed out that three cycles are excessive for ageing the Ançã stone. With this
testing procedure Ançã stone must be only submitted to two cycles. These testing condition and degradation
pattern will be confirmed in the next period on Ançã stone.
In the case of Lecce stone the method abovementioned seems to be adequate since it shows a gradual
degradation pattern in depth. The decay intensity achieved with three ageing cycles also seems to be adequate
but further cycles will be carried out in order to achieve higher decay levels.
The decay intensity achieved with three ageing cycles of Test A does not seem to be sufficient for
ageing the Santafiora and Firenzuola sandstones since the surfaces resulted stable. The contact sponge
method seems suitable for monitoring the ageing procedure. These tests will be continued during the next
period.
This task will be finely tuned when the degradation morphology and decay intensity exhibited by the
aged stones fulfil the requirements for the further consolidation study.
91

JRA1 - DEVELOPMENT AND EVALUATION OF NEW TREATMENTS FOR THE
CONSERVATION-RESTORATION OF OUTDOOR STONE AND BRONZE MONUMENTS
(LNEC, BLfD, UNI-BO)
Prepared by:
LNEC - J. Delgado Rodrigues, A. Ferreira Pinto, C. Paulos Nunes;
BLfD - M. Mach;
UNI-BO – R. Mazzeo, E. Joseph
BRONZE
1 TASK 2. ......................................................................................................................................................
A PROGRESS REPORT ON THE LABORATORY STUDIES ON NEW TREATMENTS ...........................
1.1 .......BRIEF DESCRIPTION OF THE TREATMENTS UNDER EVALUATION (UNI-BO, BLfD)
.............................................................................................................................................................................
1.2 DEVELOPMENT OF TREATMENTS AND FIRST RESULTS.....................................................
1.2.1.a Silanes, waxes, incralac treatments
1.2.1.b Chemical formation of artificial copper oxalate
1.2.1.c Formation of artificial copper oxalate by fungi
1.2.1.d Formation of thicker cuprite layer
B PROGRESS REPORT ON ACCELERATED TESTS AGEING AND FIRST RESULTS............................
1.3 AGEING PROCEDURES FOR ARTIFICIAL AND NATURAL URBAN PATINA
FORMATION (BLFD,UNI-BO,LNEC).........................................................................................................
1.4 AGEING PROCEDURES FOR ARTIFICIAL AND NATURAL MARINE PATINA
FORMATION (BLFD,UNI-BO,LNEC).........................................................................................................
1.4.1 accelerated ageing in laboratory chambers to simulate natural marine patinas formation
(MA)
1.4.2 Ageing of the bronze specimens for the formation of a natural marine patina (MN)
Tables index
Table 1 – treatments used for preliminary tests
Table 4 – SEM-EDX results on fungi growth and copper oxalates formation
Figure index
Figure 1 - Enhancement of the Cuprite layer
Figure 2 - a) copper roof sheets fixed on exposure support, b) schema indicating the different areas of
treatments
Figure 3 - a) sceptre of Colleoni treated with selected materials, b) schematic view (black arrow indicates the
application of wax R21 over tested material)
Figure 4 – Results of EIS measurements of different treatments on sceptre and copper roof sheets
Figure 5 – scanner (600 dpi) of various treatments after 8 months exposure where (a) no visual alterations are
visible and (b) chromatic alterations are visible
Figure 6 – SEM microphotogram showing Aspergillus niger covering on roof sheet
Figure 7 – SEM microphotogram of copper oxalate crystalline form
Figure 8 – Scanner 600dpi of roof sheet before and after fungi invasion
Figure 9 - Precipitation of Cuprite within the Cuprite layer
Figure 10 - Controlled precipitation of Cuprite on a microscope slide
Figure 11 - Cuprite crystals on a microscope slide
Figure 12 - Cuprite formation on a one Cent coin
Figure 13 - Artificial urban patina
Figure 14 - Natural urban patina
Figure 15 - Schematic layer sequence of bronze
Figure 16 - Layer sequence of Pichler’s sample
Figure 17 - Chemical composition of Pichler’s patina
Figure 18 - Microstructure of Pichler’s
Figure 19 - Microstructure of natural patina (SEM)
92

1. TASK 2 - A PROGRESS REPORT ON THE LABORATORY STUDIES ON NEW
TREATMENTS
• brief description of the treatments under evaluation
• Development of treatments and first results
1.1 BRIEF DESCRIPTION OF THE TREATMENTS UNDER EVALUATION
(UNI-BO, BLfD)
Four approaches were selected: 1) silane materials, 2) formation of artificial copper oxalate patinas, 3) formation
of artificial copper oxalate by fungi, 4) formation of a thicker cuprite layer.
1) New generation of silanes, which are commonly applied to protect stone monument, were chosen for
their ability to produce, after hydrolysis, chemical bonds with copper hydroxysulphates and/or
hydroxychlorides. They have been applied by a metal restorer following the procedures suggested by
the manufacturers.
2) As the copper oxalate patinas are known to be very protective (insoluble) an attempt is made to
transform existing copper hydroxysulphates and copper hydroxychlorides into copper oxalate by
chemical reaction with saturated solution of oxalate salts (sodium oxalate, Na2C2O4).
3) For the same reasons mentioned above in 2), fungi which produce oxalic acid have been used to
transform existing copper hydroxysulphates and copper hydroxychlorides into copper oxalate. Some
fungi species resistant to copper have been grown and applied to bronze samples in a microbiology
laboratory (Prof. Daniel Job and Gilles Farron, botany institute, university of Neuchâtel,
Switzerland).
4) The intention is to strengthen the Cuprite layer, as the best-preserved bronze memorials tend to have
a thick and dense Cuprite layer which is considered to be highly protective and markedly more
corrosion resistant than the bare metal (figure 1).
Layer with new Cuprite (Cu2O)
Cuprite layer
Bronze with inclusions
Fig. 1 - Enhancement of the Cuprite layer.
All treatments will be photographically documented and analysed with the use of colorimetry,
thickness measurements, corrosion tests (EIS, Rp), FTIR microscopy and cross-sections analysis with optical
microscopy and SEM-EDX.
93

1.2 DEVELOPMENT OF TREATMENTS AND FIRST RESULTS
1.2.1 Silanes, waxes, incralac treatments
Since copper roof samples (R) were already available, some of them were used for a preliminary
evaluation of the performances of the selected treatments. The same selected treatments were applied to s real
case: the sceptre of the equestrian bronze monument of Bartolomeo Colleoni located in Venice. The
monument is under restoration carried out by G. Morigi.
The different treatments (table 1) were applied on both the roof sheets (figure 2a) and on the Colleoni’s
sceptre (figure 3a). Each copper roof sample was divided in three areas: 1st) tested material + wax, 2 )
rd
tested material, 3 ) reference area without any treatment (see figure 2b and 3b). After application, the sheets
were fixed with a bolt on a wood support inclined 45 °C and exposed the 11th February together with the
sceptre outside in the restoration construction site, located in Venice (I).
Table 1 : treatments used for preliminary tests.
treatment product sheet sceptre
T1 Dynasylan F8263
R1 x
T2 SIVO clear R4 x
T3a Protectosil SC
R3 -
(1:1 in H20) T3b (1:2 in H20) Protectosil SC R8 x
T3c (1:8 in H20) Protectosil SC
R9 x
T3d (1:14 in H20) Protectosil SC
R10 -
T4 Dynasylan BSM 40 R2
x
T5 VP 5035 R5 x
T6 Incralac R6 x
T7 Microcrystalline wax R21 Applied on T1-T6
T9 Wax TeCe 3534F R15 x
a
R2
1 2 3
b
Fig. 2 - a) copper roof sheets fixed on exposure support, b) schema indicating the different areas of treatments
nd
94

a
b
Fig. 3 - a) sceptre of Colleoni treated with selected materials, b) schematic view (black arrow indicates the application
of wax R21 over tested material)
Both the sceptre and partially the copper roof sheets have been submitted to EIS measurement after 8
months exposure by the subcontractor ISMAR institute. The preliminary EIS results (table 2) showed how
the untreated brochantite patina on the sceptre have similar protective features in respect to the one present
on the copper roof plates. EIS measurements on treatments are summarized in figure 4. T1, T2 and T4 have
similar protective features as the reference treatments T6. T5 shows poor results and T3b seems to be less
protective the untreated patina. T9 shows the highest values which correspond to very protective feature.
Table 2 : Results of EIS measurements on sceptre and copper roof sheet patinas
sceptre
Copper roof
T1 T2 T3b T4 T5 T3c T6 T9
Sample |Z|10mHz Ω KΩ MΩ
TP1NC16
TP1NC21
TP2NC21
R6NC17
R6NC22
R10NC22
259477
203885
57410
155000
144000
493800
65095
60058
106000
251700
219400
221700
247300
232 ± 39
106 ± 69
63 ± 4
192 ± 77
235 ± 18
R15NC22 237800 238
R5NC22 71260 71
.
319 ± 247
Media sceptre
0,2 ± 0,2
Media sceptre
0,19 ± 0,05
Media copper roof
0,16 ± 0,09
Media copper roof
0,21 ± 0,05
95

Fig. 4 - Results of EIS measurements of different treatments on sceptre and copper roof sheets.
At the same time colorimetric measurements and microFTIR analyses have been performed in order
to make a first selection of those treatments to be further investigated. The evaluation of possible chromatic
alterations due to the application of treatments without the addition of R21 wax (3) and exposition has been
performed with colorimetric measurements. The results are expressed in term of euclidean distance. With the
visual appearance of samples it was possible to distinguish two groups (figure 5) which have been confirmed
with the colorimetry (table 3).
96

T1 T4
T2
T5
T3a T3b
T3d
a
b
Fig. 5 - Scanner (600 dpi) of various treatments after 8 months exposure where (a) no visual alterations are visible and
(b) chromatic alterations are visible.
T3c
T6 T9
3
97

Table 3 : Colorimetric results on silanes at interval of 8 months.
treatment Euclidean distance DE*
2 2 2
[√(DL*) +(Da*) + Db*) ]
February 2005
With the microFTIR spectroscopy it has been possible to chemically characterise the treatments on
the copper sheet samples. For technical reasons, it was not possible to perform the same analysis on sceptre
since it’s too large to be placed on the FTIR microscope stage. So far, it has been not possible to evaluate the
formation of the chemical bond which was supposed to be formed between the silanes and the copper
hydroxysulphates or hydroxychlorides . This issue will be further investigated during the next six months
research.
1.2.1.1 Chemical formation of artificial copper oxalate
A copper roof sheet with an existing copper hydroxysulphate surface was treated by immersion in a
saturated solution of sodium oxalate for different period of time (2 min, 10 min, 1 hour and 2 hours). The results
have been checked with the microFTIR combined with ATR and it seems that copper oxalate’s patina is still not
formed. Nevertheless alternative procedures will be performed by modifying the saturated sodium oxalate
solution pH.
1.2.1.2 Formation of artificial copper oxalate by fungi
DE*
October
2005
Two copper roof sheets with copper hydroxysulphate (brochantite) patina and one with a artificial
copper hydroxychloride patina were given to the microbiology laboratory to carry out tests with different fungi
species. Tests started on sheets with brochantite patina with Penicillium sp. (strain F75), Gloeophilum trabeum
and Aspergillus niger, strain 14 and strain 6 isolated from the grapevine. SEM-EDX morphological
investigations have been carry out to evaluate whether the copper oxalate is produced (table 4) and Aspergillus
niger seems to give the best results (figure 6 and 7). No colour modification were observed by visual
examination of the treated with Aspergillus niger and untreated samples as shown in figure 8.
Table 4 : SEM-EDX results on fungi growth and copper oxalates formation.
Colour difference
DE* ≤ 1 : unperceivable
DE* ≥ 2 : just perceivable
DE* ≥ 5 : clearly perceivable
T1 Dynasylan F8263 2 2-3 just perceivable
T2 SIVO clear 3.31

Fig. 6 - SEM microphotogram showing Aspergillus
niger covering on roof sheet.
original
Fig. 7 - SEM microphotogram of copper oxalate
crystalline form.
Fig. 8 - Scanner 600dpi of roof sheet before and after fungi invasion.
Since the first result seems to be very promising, further investigations will be carried out in order to
optimized the activity of the fungi on the brochantite patina. It has been decided to concentrate the research on
Aspergillus niger and tested it also on the copper sheet with a artificial copper hydroxychloride patina. A
subcontract will be established with the microbiology laboratory (Prof. Daniel Job and Gilles Farron, Magali
Kocher, botany institute, university of Neuchâtel, Switzerland) since this laboratory has longstanding
experience in the research on oxalates formation by fungi.
1.2.1.3 Formation of a more dense cuprite layer
treated
One experimental line was to test oxidants in aqueous solution. Those oxidants were thought to
penetrate into the Cuprite layer, in particular into the Cuprite layer defects. At the borderline between bronze
and Cuprite oxidants should react with the metallic bronze, forming new Cuprite and by this would heal the
Cuprite layer defects specifically in the faulty areas (figure 9).
99

Fig. 9 - Precipitation of Cuprite within the Cuprite layer.
For experimental purposes the Brochantite layer of the urban type substrates (see task 3) was
selectively removed. As has been shown by Mauro Matteini’s work on the Florence Baptistery Doors,
Rochelle salt can be used in order to selectively remove the sulphate layer. After treatment with Rochelle salt
a pure bronze/Cuprite system is left behind which can be inspected and controlled much easier than the full
patina layer system with Brochantite on top.
It was possible to create new Cuprite crystals on the bronze surface in experiments by means of 30%
aqueous hydrogen peroxide (H O ). But when going back to the complete patina systems it turned out that
2
hydrogen peroxide immediately reacted with the Brochantite, destroying the Brochantite, presumably by
forming CuO (Tenorite). First it was thought that this destructive reaction might have been caused by an
acid-base reaction, so carbonate buffered hydrogen peroxide was used instead in order to maintain neutral
pH values in the chemical reagents’ system. But when the buffered solutions showed the same destructive
reaction it was decided that the oxidation pathway with hydrogen peroxide had to be skipped.
The second experimental approach was to rinse the patina with a solution containing complexed
copper ions and then let the copper ions precipitate within the Cuprite layer defects as solid Cuprite. A series
of tentative experiments revealed that a reactive solution can be prepared easily, just by mixing the following
solutions:
Solution F1: 0.7 g CuSO * 5 H O in 10 ml H O
4 2 2
Solution F2: 3.5 g sodium potassium tartrate and 1 g NaOH in 10 mlH O
2
Solution G: 2 g glucose in 10 ml H20
2
Cuprite layer
Bronze
Equal volume parts of the solutions F1 and F2 are mixed, after some stirring a further volume part of
solution G is added, after stirring again the mixture is clear and ready for use. It is a pale-blue liquid, similar
in viscosity to pure water. The Cuprite precipitation can be triggered and speed-controlled by mild heating,
allowing a wide range of temperature-time variations, with a typical triggering temperature of around 40°C.
The reaction time can be in the range 60 of seconds or lower, a time period which minimises the risk
of unwanted secondary chemical reactions. In any case the remaining solution which is depleted of copper
due to the precipitation will have to be removed by thorough rinsing the patina. First experiments showed
that also a full patina system with Brochantite on top was not markedly affected by the precipitation solution
treatment.
When tested in vitro the precipitation can be studied on a microscope slide (figure 10). The Cuprite
particles appear as tiny globular, brown particles with typical sizes of about 1 micrometer down to 100 nm
(figure 11). Similar size particles can be formed on a Copper coin (figure 12). The Cuprite formed has an
enormous adherence towards any substrate, a fact which can easily be demonstrated by performing the
reaction on a microscope slide and then washing vividly under tap water: most of the precipitated Cuprite
will remain on the slide.
100

Fig. 10 - Controlled precipitation of Cuprite on a microscope slide.
Fig. 11 - Cuprite crystals on a REM carbon support slide.
101

Fig. 12 – Experimental Cuprite formation on a one Cent coin.
Planned steps: The precipitation behaviour of the Cuprite (grain size, particle density, effectiveness
of protection) will be evaluated by light microscope, scanning electron microscope and electrochemical
impedance spectroscopy (EIS). For this reason preliminary measurements of the Copper
Alloy/Cuprite/Brochantite system have been made. In the next six months further EIS measurements of
treated samples will be performed in order to evaluate the protective character of the treated Cuprite.
Furthermore, a new generation of copper complexing agents, the so-called TOMATS (i.e.
Trioctylmethylammoniumthiosalicylate) will be taken into account as reagents and will be checked for the
given application. Those modern complexing agents can be used in organic, e.g. alcoholic solution and
therefore might be an interesting alternative to water-based systems. There are fair chances that they will
react to a lesser extent with the patina than water based systems.
If necessary, the treatment might be enhanced by additional ingredients or a second step procedure, e.g. with
a polysiloxane based medium.
102

TASK 3 - B PROGRESS REPORT ON ACCELERATED TESTS AGEING AND FIRST RESULTS
1.3 AGEING PROCEDURES FOR ARTIFICIAL AND NATURAL URBAN PATINA FORMATION
(BLFD,UNI-BO,LNEC)
All urban type substrates, i.e. "urban type, artificial patina" and "urban type, natural patina (copper
roof)" are ready for treatment.
Bronze samples were sent to Prof. Pichler, Hochschule für Angewandte Kunst, Vienna, in order to
produce the set of “urban artificial” (UA) with his patented cuprite / brochantite surface layer. The urban
type artificial patina samples have been prepared by the so-called Pichler process. The Pichler type substrates
(figure 13) mimic the natural bronze patina perfectly as far as layer sequence (figures 15 and 16) and
chemical composition (figure 17) are concerned: Cross sections through the artificial Pichler patina revealed
a red Cuprite layer (ca. 10 - 15 µm) and above a green Brochantite layer (ca. 50 µm). The respective XRD
findings are Cuprite and Brochantite, nothing else. Nevertheless the visual appearance of the urban artificial
substrates is markedly different from the natural ones (figure 14). The artificial substrates show a darker,
more saturated green whereas the natural substrates have the colour of powdered synthetic Brochantite, i.e. a
light green. SEM investigations led to the conclusion that the colour difference has to be attributed to
different micro-crystallinity (figures 18 and 19). At magnifications of 100x and more Pichler type samples
show Brochantite crystals whereas it was not possible to detect a single Brochantite crystal on natural
substrates, even at the highest SEM resolutions available.
Fig. 13 - Artificial urban patina
(Pichler typ).
Fig. 14 - Natural urban patina
of a copper roof sheet.
103

Brochantite or
Atacamite layer
Cuprite layer
Bronze with inclusions
Fig. 15 - Schematic layer sequence of bronze.
Substrate: Urban Artificial
"Pichler type"
Top view of Brochantite layer
Fig. 18 - Microstructure of Pichler’s patina (SEM).
Fig. 17 - Chemical composition of Pichler’s patina.
Urban Artificial
cross section
Green: Brochantite layer,
ca. 50 µm
Red: Cuprite layer,
ca. 10-15 µm
Fig. 16 - Layer sequence of Pichler’s sample.
Substrate: Urban Natural
"Copper roof"
Top view of Brochantite layer
Fig. 19 - Microstructure of natural patina (SEM).

1.4 AGEING PROCEDURES FOR ARTIFICIAL AND NATURAL MARINE PATINA
FORMATION
(BLFD,UNI-BO,LNEC).
1.4.1 Accelerated ageing in laboratory chambers to simulate natural marine patinas formation
(MA)
On July was initiated the accelerated exposure of bronze specimens for the formation of a
patina in marine simulated conditions in lab. The accelerated exposure includes two phases. First
phase: 3 months in a climatic chamber (T= 50ºC and RH> 95%) and the Second phase: 6 months in
salt spray chamber ( 5% NaCl, T= 38ºC). At the initiation of the first phase the formation of powered
white corrosion products was observed. The white powder can be easily removed from the bronze
surface cleaning with a cloth. XRD identify the presence of cerussite. Later at the end of the first
phase, black and brown products begin to be formed under the cerussite powder. As was indicated by
XRD these corrosion products are a mix of cuprite and tenorite, Figure 20. After the first month of
exposure in the salt chamber ( Second Phase) green patina formation begin to be formed in some spots
of the surface. The second phase will be finished before 24 months of the project as planned.
H - Hidrocerussite Pb3(CO3)2(OH)2
C – Cuprite Cu2O
T – Tenorite CuO
Q – Quartzo SiO2
Fig. 20 - Aspect of the bronze surface after the first phase of accelerated exposure conditions and XRD analysis
of corrosion products
105

1.4.2 Ageing of the bronze specimens for the formation of a natural marine patina (MN)
The ageing of the bronze specimens in marine exposure at Cabo Raso station go on .The green
patina formed during the first six months of exposure , Figure 21, show a very powered aspect and a
very low adherence to the bronze surface, probably due to the polished initial state of bronze surface .
The XRD analysis of the patina products indicated that products are mainly amorphous and the
crystalline products are atacamite. After the first 6 months patina seems turn to more compact and
with a better adherence. Thickness is around 10 µm. Localized corrosion at the alloy Pb inclusions
was observed on SEM/BSE, Figure 22. The measurement of the environmental parameters at the
exposure site also goes on, since the beginning of the exposure. It is expected that marine exposure
can be finished also until the 24 months of the project.
Cl – Atacamite Cu2Cl(OH)3
Fig. 21 - Natural marine patina after six of exposure . XRD spectrum
106

SEM/BSE
SEM/BSE
a) b)
Fig. 22 - Natural marine patina at SEM/BSE. Corrosion of the bronze specimens at the Pb inclusions a). patina
with 10 µm of thickness b)
107

Annex 9
Progress report on JRA2
I- JRA2 Task 1- Progress report on Lab-NMR and methodology for in-situ study of
stones
Resp. UNIPG, RWTH
DELIVERABLE N. 16
Materials and Methods
Three stones, from Umbria, (Italy), have been characterized by Unilateral NMR.
They are:
1. San Presto (n° 20)
2. Pianello (n° 134)
3. Palombina Turri (n° 39)
All measurements have been carried out on dry stones, i.e., on stones in equilibrium with their
environment. The NMR signal is due to the moisture in the stone, exchanging with the environment.
The San Presto stone has also been studied after capillary water absorption for 24 hours.
All NMR measurements were performed with a commercial unilateral NMR “ProFiler” from Bruker
Biospin, Italy, with a probehead operating at 18.153 MHz with a penetration depth of about 1 mm.
Spin-lattice relaxation times T were measured with the a periodic saturation recovery pulse
sequence.
1
Spin-spin relaxation times T 2 were measured with the CPMG pulse sequence; the echo time 2τ
was 50 µs; 2048 echoes were collected in all cases.
Results
1) NMR Characterisation of dry stones
Hahn Echo Experiment
A single Hahn Echo has been collected for the three stones and the results are reported in Figure 1. A
major moisture content in San Presto stone on respect to Pianello and Palombina Turri stones has
been found.
I (%)
30
20
10
0
0,00 0,01 0,02 0,03 0,04 0,05
Figure 1
t (ms)
San Presto I(%) = 31
Pianello I (%) = 13
Palombina Turri I(%) = 9
108

T1 Experiment
In table 1, T1 spin-lattice relaxation
values of the three stones are reported. A
bi-exponential behavior has been found
for all stones.
In figure 2 T1 trends are shown. San
Presto stone shows the shortest T1 values
on respect to Pianello and Palombina
Turri stones.
T2 Experiment
Normalized Intensity
Table 1
1,2
1,0
0,8
0,6
0,4
0,2
0,0
0 500 1000 1500 2000 2500
t (ms)
Figure 2
San Presto
Pianella
Palombina Turri
best fit
San Presto Pianello Palombina Turri
Wa (%) 46 29 29
T1a (ms) 1.53±0.15 12.1±1.7 24±6
Wb (%) 54 71 71
T1b (ms) 188±9 279±16 329±37
In table 2, T2 spin-spin relaxation
values of the three stones are
reported. Three T2 values have been
found for San Presto and Pianello
stones whereas two values has been
obtained for Palombina Turri stone.
In figure 3 T2 trends are shown.
Normalized Intensity
1,0
0,8
0,6
0,4
0,2
0,0
0 1 2 3 4 5
t (ms)
San Presto
Pianello
Palombina Turri
best fit
6
109

Table 2
Figure 3
San Presto Pianello Palombina Turri
Wa (%) 55 57
T2a (ms) 0.121±0.004 0.122±0.006
Wb (%) 40 37 85
T2b (ms) 0.539±0.015 0.471±0.015 0.379±0.007
Wc (%) 5 6 15
T2a (ms) 4.35±0.16 7.29±0.26 3.31±0.13
2) NMR characterisation of San Presto stone wetted by water capillary absorption
Hahn Echo Experiment
In Figure 4 the single Hahn Echo for the dry and wet San Presto stone are shown. A clear increase of
intensity has been found for the wetted one.
Normalized Intensity
70
60
50
40
30
20
10
0
0, 00 0, 01 0, 02 0,03 0,04 0,05 0,06
t (ms)
Figure 4
dry I(%) = 31
wet I(%)= 60
110

T2 Experiment
In table 3, T2 spin-spin relaxation
values of dry and wet stones are
reported. In figure 5 T2 trends are
shown.
An increase of all T2 values are
observed due to water into the pores.
In particular a considerable increase
of the longest T2 component has been
found.
Table 3
Normalized Intensity
1.2
1.0
0.8
0.6
0.4
0.2
0.0
-0.2
0 5 10 15 20
t (ms)
Figure 5
San Presto dry San Presto wet
Wa (%) 55 39
T2a (ms) 0.121±0.004 0.477±0.032
Wb (%) 40 34
T2b (ms) 0.539±0.015 1.72±0.18
Wc (%) 5 27
T2a (ms) 4.35±0.16 8.0±0.6
dry
wet
best fit
111

II- JRA2 Task 1- Progress report on NMR-MOUSE, towards the 3D.
Resp. RWTH
DELIVERABLE N. 17
During the first year of the project the NMR-MOUSE as well as the methods (pulses sequences) were
improved based on the results obtained from reference samples. In July 2005 the first measurement on
ancient paintings were carried out at the Galleria Nazionale dell’Umbria in Perugia. It is important to
stress that the complete NMR instrumentation, including computer, spectrometer, NMR-MOUSE, and
the lift, can be packed in a suitcase and can be carried by one person (Portable NMR).
Several paintings have been studied, such as a panel by Maestro del Farneto, a Virgin with
Child by Gentile da Fabriano, the Adorazione dei Magi by Perugino, and the Tryptic of Sant’Antonio
by Piero della Francesca.
Figure 4a describes the typical configuration of the sensor required to perform the experiment.
The sensor is placed on a table that can be moved up and down on order to control the vertical
position, while the lateral position is controlled simply by displacing the sensor. Since the lateral
resolution is of about 1 cm in both direction (up-down and left-right) the mechanism results of good
precision. The direction that results more critical is along the depth where the space resolution goes
down to 20 micrometers. The proper alignment can be done by taking as reference the acrylic plate
and setting it parallel to the painting surface. The ratio between the sizes of the acrylic plate and the
sensitive region (30cm/1cm) is a demultiplication factor that allows one to precisely align the sensitive
volume. For example, an error of 0.5 mm at the border of the plate represents a deviation of only 16
µm across the sensitive volume.
Notice that there is no need to have any contact with the painting. Once the plate is aligned,
the sensor is moved respect to the plate by a high-precision lift. Figure. 4b shows two depth profiles
measured at two different positions on the Virgin with Child by Gentile da Fabriano. The NMR signal
amplitude is plotted as a function of the depth. The first peak (depth~0 mm) corresponds to the paint
layer which has a thickness of about 130 µm, this is followed by a flat region of about 800 µm that
corresponds to the preparation. The second peak at about 1 mm depth is assigned to canvas that is
glued at the interface between the preparation and the wood support.
1
130 µm
800 µm
300 µm
Fig 4. a) The NMR-MOUSE set up to measure depth profiles of the Virgin with Child by Gentile da Fabriano.
The acrylic plate is aligned parallel to the painting surface but does not touch the paint; a distance of about 1 mm
is left between them. b) NMR signal amplitude plotted as a function of the depth into the painting. The
multilayer structure of the painting can be observed, from left to right: paint, preparation, canvas, and wood.
112

The same structure, paint-preparation-canvas-wood, was observed in the panel by the Maestro del
Farneto, the Adorazione dei Magi from Perugino, and the Tryptic of Sant’Antonio by Piero della
Francesca, but the thickness of those layers were different from painting to painting. Interestingly, in
the case of the Adorazione dei Magi by Perugino (figure 5a), a region where the canvas layer is much
broader than normal was found. In region 1, the profile shows the preparation layer became thin while
the canvas reaches a thickness of about 1 mm. A possible explanation could be that the wood support
is composed by pieces that are joined together, and in the join line several canvas layers are used for
reinforcing. Close to the measured spot one of this joins can be seen.
2 1
Fig 5. a) Adorazione dei Magi from Perugino. b) NMR signal amplitude profiles.
113

III- JRA2- Task 2: Progress report on micro- and spectroscopic characterisation of
standards and technical advances
DELIVERABLE N. 18
JRA2 Task2, Ia- Characterisation of standards
Resp. OPD
Within the Joint Research Activity 2, Opificio delle Pietre Dure contributed to this activity by
providing multilayer painted standards for both Task1 (NMR methods) and Task2 (Multispectral
imaging). During the first year activity, some pictorial standards were prepared and a preliminary
characterisation had been carried out on microsample cross sections by means of optical microscopy
under both visible and UV light.
In order to have a complete stratigraphical characterisation of the standard samples in terms of
thickness and composition of the paint layers, the samples have been analysed by Scanning Electron
Microscopy – Energy Dispersive Spectroscopy (SEM-EDS), which measures the energy and intensity
distribution of X-ray signals generated by the electron beam striking the surface of the specimen.
Due to some troubles occurred to the EDS device, that is currently under repair, it was possible to
examine only samples A-D; the results so far achieved are reported in the following sections.
Preparation of samples to be investigated
SEM samples were prepared by mounting the cross sections on aluminium stubs (0.5” aluminium
stubs, purchased by AGAR Scientific LTD, Stansted, UK), by means of a double-stick carbon
tape (AGAR). An optimal contact between the sample and the metallic support was provided
by subsequently using a quick drying silver paint (AGAR). Embedded cross sections are nonconductors
of electricity, therefore when placed in the path of the electron beam the samples
would charge causing deviation of the beam, as well as discharging. The sample were thus
coated by a conductive material: carbon was the choice because of its low Z, minimal effect
on the X-Ray spectrum either in terms of producing X-ray lines or absorbing X-rays. The
carbon coat was applied using a vacuum evaporator at pressure of less than 10 -4 torr (AGAR
SEM Carbon Coater, Mod. 108C). The film thickness was around 100-150 nm.
Experimental Conditions
The samples were examined by a Cambridge Stereoscan 440i, coupled with an Oxford 5431
microprobe (Software LINK ISIS) which provided the microanalyses. The accelerating voltage was 20
kV, the beam current 120 pA. In order to better distinguish the different constituent phases and
elements in the various areas, a back-scattered electrons detector was used (BSE)
SEM-EDS examination
For each examined sample, a BSE image of the cross-section and EDS spectra of the various paint
layers were collected. The results are reported in the following figures.
Ground: EDS spectra were collected on the ground of the standards, which was the same for all
the samples and consisted of a mixture of gypsum and rabbit glue; as expected, calcium and
sulphur were found. A representative spectrum is shown in Figure 1. In the following
micrographs, the ground is always labelled as “1”.
114

Figure 1. EDS Spectrum of the ground of the standards (mixture of gypsum and rabbit glue).
Standard A (Figure 2): the sample consisted of indian yellow (3, outer layer) laid on lead and tin
yellow (2, intermediate layer). Due to the organic composition of indian yellow, no relevant peak was
detected on layer 3 (spectrum not reported).
a
cps
30
20
10
0
C
O
Ca
S
Ca
Ca
0 5 10 15 20
Energy (keV)
0 5 10 15 20
Energy (keV)
b
Figure 2. (a) Standard A, containing indian yellow (3, outer layer) and lead and tin yellow (2, inner layer);
(b) SEM-EDS of layer 2 (lead and tin yellow).
cps
60
40
20
0
C
O
Pb
Sn
Sn
Sn Sn
Pb
Pb
115

Standard B (Figure 3): the sample consisted of spincervino yellow (3, outer layer) laid on lead and
tin yellow (2, intermediate layer). The EDS spectrum of spincervino revealed presence of aluminium,
potassium and sulphur, possibly related to the use of alum as a supporting material for the organic
colorant.
cps
40
30
20
10
0
C
O
Na
Al
S
K
0 5 10 15 20
Energy (keV)
b
a
Figure 3. (a) Standard B, containing spincervino yellow (3, outer layer) and lead and tin yellow (2, inner
layer); (b) SEM-EDS of layer 3 (spincervino yellow); (c) SEM-EDS of layer 2 (lead and tin yellow).
cps
60
40
20
0
C
O
Si
Pb
Sn
Sn
Sn
0 5 10 15 20
Energy (keV)
c
Pb
Pb
116

Standard C (Figure 4): the sample consisted of saffron yellow (3, outer layer) laid on lead and tin
yellow (2, intermediate layer). Due to the organic composition of saffron yellow, no relevant peak was
detected on layer 3 (spectrum not reported).
a
Figure 4. (a) Standard C, containing saffron yellow (3, outer layer) and lead and tin yellow (2, inner layer);
(b) SEM-EDS of layer 2 (lead and tin yellow).
cps
80
60
40
20
0
C
O
Si
Pb
Sn
Sn
Sn
0 5 10 15 20
Energy (keV)
b
Pb
Pb
117

Standard D (Figure 5): the sample consisted of rubia lake (3, outer layer) laid on a mixture of
cinnabar and lead white (2, intermediate layer). The EDS spectrum of rubia lake revealed the presence
of aluminium, probably related to the use of alumina in the lake. In layer 2, the larger grains resulted
to be composed of cinnabar, whereas smaller grains consisted of lead white.
cps
150
100
50
0
C
O Al
Hg
a
Hg
0 5 10 15 20
Energy (keV)
Hg
c
d
Figure 5. (a) Standard D, containing rubia lake (3, outer layer) and cinnabar + lead white (2, inner layer) (b)
SEM-EDS of layer 3 (rubia lake); (c) SEM-EDS of layer 2 (cinnabar); (d) SEM-EDS of layer 2 (lead white).
JRA2 Task2, I b- Technical advances in design of INOA scanning systems
(Subtask 2.3).
Resp. INOA
cps
100
80
60
40
20
0
C
O
0 5 10 15 20
Energy (keV)
Pb
b
0 5 10 15 20
Energy (keV)
During the first semester of the second year of the project the following activities have been carried
out:
1. Further study and definition of a new set of cost-effective IR detectors
2. Design and realization of the filter holders
3. Design and realization of the sub-rack unit
cps
150
100
50
0
C
O
Al
Pb
Pb
118

4. Realization of the first bundle prototype
1. IR detectors
The detection system will be made of 14 photodiodes to cover the spectral region from 800 nm to
2400 nm. Each sensor is equipped with an interferential filter (see 12-monthly report). The first 3
channels will be equipped with Si photodiodes; from 4 to 11 channel InGaAs photodiodes will be used
and, finally for channels 12 to 14 pre-amplified thermoelettrically cooled photodiodes will be used.
The 14 identified photodiodes are resumed in Table 1, together with the central wavelength and
bandwidth of the corresponding filter.
Table 1. Sensors identified for the detection system.
CHANNEL PHOTOTDIODE λfilter [nm] ∆λfilter [nm]
1 Hamamatsu S2386 5K 800 10
2 Hamamatsu S2386 5K 850 67
3 Hamamatsu S2386 5K 952 67
4 Hamamatsu G8370-01 1030 55
5 Hamamatsu G8370-01 1112 66
6 Hamamatsu G8370-01 1200 66
7 Hamamatsu G8370-01 1300 90
8 Hamamatsu G8370-01 1400 90
9 Hamamatsu G8370-01 1500 90
10 Hamamatsu G8370-01 1600 90
11 Hamamatsu G8371-01 1700 90
12 Hamamatsu G6122 1820 100
13 Hamamatsu G6122 1930 112
14 Hamamatsu G6122-03 2265 590
119

2. Filter holders
A set of filter holders were designed to host the 14 filters and the photodiodes. Depending on filter
dimensions and detector shape, they were studied to have the best match between the fiber output and
the detector sensitive area. Three different types of holders were then designed, and they are shown in
figure 1.
3. Sub-rack unit
(a) (b) (c)
Figure 1. Filter holders for channels (a) I-III; (b) IV-XI and (c) XII-XIV
As the instrument is supposed to be used for in situ measurement campaigns, compactness is an
important requirement. A purpose-build sub-rack unit was then designed to keep all the detectors
together. It also comprehends a power supply unit and an interface whose output goes directly to ADC
by means of a flat cable. Figure 2 shows a sketch of the sub-rack unit, together with the Printed Circuit
Board of the interface.
P
o
w
e
r
S
u
p
p
l
y
(a) (b)
Figure 2. (a) Sub-rack unit; (b) PCB interface between the set of 14 sensors and the ADC.
120

4. Bundle
A first prototype of 16 fiber bundle was realized. 14 VIS-NIR and 2 UV-VIS multi-mode optical
fibers were used, with a cladding diameter of 230 micron. In order to properly align in a square-shaped
bundle the 16 fibers, a 1 mm groove was dig. The 16 fibers were then stick all together with a twocomponent
glue. The microscope image of the bundle section is shown in figure 3. The 16-fiber array
is not perfectly regular, as one of the lines is shifted with respect to the others. We are planning a new
technique for the bundle realization that makes use of a different glue, in order to stick separately the
four 4-fiber layers.
Figure 3. Microscope image of the bundle section.
121

JRA2 Task2, I c – Advances in preparation and characterisation of standards of layered
painting materials (Subtask 2.1) and in transmission and reflection of IR radiation on layered
standards (Subtask 2.2)
Resp. OADC
1.1.1 - Preparation of the reference samples in order to study the parameters of the models that will be
used for the identification/investigation of the stratigraphy (Reference panels with eight levels of
gradually higher thicknesses of the different 19 basic pigments).
Within the period between the 12 th and the 18 th month special reference samples were
developed on wooden panels of gradually higher paint layer thickness in order to study the
transmission and reflection of the IR radiation through them. The way that these reference
samples are created is displayed in figure 1.1a. Multi-spectral spectra of these samples will be
acquired in the visible, near infrared (nIR) and mid infrared (mIR) area of the spectrum (up to
4500nm).
Figure 1.1a: Reference sample (way of fabrication of gradually higher thickness )
The reference samples are painted on a common white ground and with the same binding
medium in order to minimize the uncertainty to our applied algorithms during the tests.
Ground : CaCO3 + animal glue
Binding Medium : Egg yolk
In appendix 1 all the first testing measurements on the panels are provided. For the time being
the Perkin ELMER Lambda 900 spectrophotometer was used in the wavelength range of
200nm-2400nm. These measurements will serve as a reference for the testing of the device
under development. Within the next months and after the first assembly of the device, the
measurements will be performed using the new device and the new developed method will be
tested in the extensive wavelength range between 800nm and 4500nm.
122

1.1.2. Materials and methodology of creation of the reference panels (standards)
(Samples of 17 pigments in paint layers of gradually higher thickness).
The panels with samples of different (gradually higher) thickness were prepared in successive steps, as
follows: first, all eight parts of one pigment sample were painted at once in 2 or 3 layers of paint, then
one part was masked out and the remaining seven layers were painted again in 2 or 3 layers. Then two
parts were masked and the remaining six were painted, and so forth. Between each step, the paint was
allowed to dry satisfactorily. The panels were set-aside for a month to dry well before the first
measurements are taken.
The panels for the samples of different thickness were prepared by lightly scoring rectangles,
separated in 8 parts each of 2x5cm. These were then split in two lengthwise, one half painted in 3
layers of carbon black with egg as a binding medium and the other scored in pencil with diagonal
lines, again on half of its area.
Figure 1.1.2a: Samples of 10 pigments in paint layers of gradually higher thickness.
123

Subtask 2.3: Assembling of nIR imaging equipments
(Integration sphere design and assembly).
A golden integration sphere is assembled in order to permit the reflection and integration of
the IR radiation from 800nm up to 4500nm. The design of the integration sphere is displayed
in Fig 1.2.1a.
Figure 1.2.1a: Integration sphere that will be used for diffused reflectance measurements from
800nm up to 4500nm the dimensions are in INCHES.
The description of the all the other parts of the equipment is in the 1 st year report of OADC
(JRA2).
124

APPENDIX 1
Vertical axis (Reflectivity R%) - Horizontal axis Wavelengths 200-2400nm)
Lead White
(over Black)
100
90
80
70
60
50
40
30
20
10
0
0 500 1000 1500 2000 2500
Yellow Ochre
(over Black)
60
50
40
30
20
10
0
0 500 1000 1500 2000 2500
Warm Ochre
(over Black)
50
45
40
35
30
25
20
15
10
5
0
0 500 1000 1500 2000 2500
(over White)
90
80
70
60
50
40
30
20
10
0 500 1000 1500 2000 2500
(over White)
70
60
50
40
30
20
10
0
0 500 1000 1500 2000 2500
80
70
60
50
40
30
20
10
(over White)
0
0 500 1000 1500 2000 2500

Red Ochre
(over Black)
35
30
25
20
15
10
5
0
0 500 1000 1500 2000 2500
Sienna Burnt
(over Black)
30
25
20
15
10
5
0
0 500 1000 1500 2000 2500
Hematite
(over Black)
70
60
50
40
30
20
10
(over White)
0
0 500 1000 1500 2000 2500
(over White)
70
60
50
40
30
20
10
0
0 500 1000 1500 2000 2500
(over White)
126

40
35
30
25
20
15
10
5
0
0 500 1000 1500 2000 2500
Caput Mortuum
(over Black)
70
60
50
40
30
20
10
0
0 500 1000 1500 2000 2500
Umber Raw(over Black)
50
45
40
35
30
25
20
15
10
5
0
0 500 1000 1500 2000 2500
Cinnabar
(over Black)
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
60
50
40
30
20
10
0
0 500 1000 1500 2000 2500
(over White)
0
0 500 1000 1500 2000 2500
(over White)
60
50
40
30
20
10
0
-10
0 500 1000 1500 2000 2500
(over White)
127

70
60
50
40
30
20
10
Minium
(over Black)
90
80
70
60
50
40
30
20
10
0
0 500 1000 1500 2000 2500
0
0 500 1000 1500 2000 2500
Green Earth
(over Black)
30
25
20
15
10
5
0
-5
-10
-15
0 500 1000 1500 2000 2500
Malachite
0.35
0.3
0.25
0.2
0.15
0.1
0.05
-0.05
-0.1
70
60
50
40
30
20
10
0
0 500 1000 1500 2000 2500
140
120
100
0
80
60
40
20
(over White)
0
0 500 1000 1500 2000 250
(over White)
-0.15
0 500 1000 1500 2000 2500
128

(over Black)
40
30
20
10
0
-10
-20
0 500 1000 1500 2000 2500
Azurite
(over Black)
40
35
30
25
20
15
10
5
Ultramarine
(over Black)
0
0 500 1000 1500 2000 2500
25
20
15
10
5
0
-5
Indigo
(over Black)
-10
0 500 1000 1500 2000 2500
60
50
40
30
20
10
0
-10
(over White)
-20
0 500 1000 1500 2000 2500
(over White)
80
70
60
50
40
30
20
10
0
-10
0 500 1000 1500 2000 2500
80
70
60
50
40
30
20
10
(over White)
0
0 500 1000 1500 2000 2500
(over White)
129

25
20
15
10
5
0
-5
0 500 1000 1500 2000 2500
Cobalt Blue(over Black)
60
50
40
30
20
10
0
-10
0 500 1000 1500 2000 2500
100
90
80
70
60
50
40
30
20
10
0
0 500 1000 1500 2000 2500
(over White)
70
60
50
40
30
20
10
0
0 500 1000 1500 2000 2500
130

JRA2 Task 3 - Report on optimal conditions for artwork XRD studies and XRD and
XRF assembling
Resp. C2RMF – A.Gianoncelli, J.Castaing)
DELIVERABLE N. 19
Introduction
The complete knowledge of materials characteristics requires the determination of the different
phases (chemical composition, crystal structure) that are present in an object and the description of
the microstructure (grain size, texture, lattice imperfections, etc.). The target of the project is to
obtain this information thanks to a new tool for in situ studies of the constitutive materials of
artworks by means of X ray fluorescence (XRF) and X ray diffraction (XRD). In the first twelve
months, an assessment of the possible geometries has been made and general specifications have
been established. We ruled out the energy dispersive X ray diffraction (ED-XRD) option based on
a literature survey. However, we performed diffraction experiments to compare the performance of
ED-XRD with traditional angular detection; we present the first results that confirm our initial
choice.
Another choice has been made concerning the detection of diffracted beams; we purchased an
imaging plate system and have started to test it for XRD recording.
Energy dispersive X-ray diffraction experiments
Energy Dispersive X-ray diffraction (ED-XRD) experiments have been carried out at the
Laboratoire de Cristallographie (CNRS UPR 5031) in Grenoble in order to test the performance of
this method for a portable XRD instrument.
X-ray diffraction occurs when there is constructive interference between incident and diffracted
waves; this means that the path difference between the two waves must be an integer number of
wavelengths.
This leads to the Bragg’s law:
2 d sinϑ
= nλ
= n (1.24 / E)
where d is the spacing between the planes in the atomic lattice
λ is the wavelength of the incoming x-ray of energy E (in keV for λ in nm)
n is an integer
θ is the angle between the incident beam and the scattering planes.
Angle dispersive methods rely on the identification of the angles θ corresponding to constructive
interference, once λ has been fixed.
Energy dispersive methods allow to recognise the crystal structure of the sample (d-spacing) by
analysing the energy of the peaks present in the spectra, acquired at a fixed angle θ.
The following instrumentation was used during the test:
- Cu anode X-ray tube biased at 40 kV and 40 mA;
- Si(Li) detector, 8 µs peaking time, nominal energy resolution of 180 eV @ Mn Kα line (5.898
eV).
- Goniometre to rotate detector and sample independently
A few different specimens have been analysed: polycrystalline silicon, quartz, calcite and calcite
covered by a thin layer of goethite.
The measurement have been taken at two or three different 2θ angles for each sample; this results
in a shift of the peak position (energy) by changing the angle.
131

We show the results obtained for polycrystalline silicon (figures 1 and 2). The position of the
peaks for Polycristalline Si is indicated in table 1, according to the crystalline plane and to the
angle between X-ray beam and detector axis (2θ).
Due to difficulties in the alignment of the system, the geometry of the experiment is not well
known, in fact the detected peaks correspond to the angles indicated 2θ=31° and 2θ=36°.
hkl
d-spacing
[Å]
Table 1.
position [keV]
@ 31°
position [keV]
@ 36°
111 3.1355 7,398 6,398
220 1.9201 12,081 10,448
311 1.6374 14,167 12,252
400 1.3567 17,098 14,787
331 1.2459 18,619 16,102
422 1.1085 20,927 18,097
This kind of sample is an ideal one because its fluorescence peaks are in the low energy range (Si
Kα is at 1.740 keV); in this way the diffraction peaks can only interfer with the Cu peaks due to the
anode of the X-ray tube. The Si peaks are not visible in the spectrum because of the absorption of
the air (the distance between sample and detector is around 15 cm).
For most complicate or multi-elemental samples, the overlapping of fluorescence and diffraction
peaks can make the peak identification more difficult.
Figures 1 and 2 show the spectra acquired at two different angles. Peaks have been identified as
diffraction peaks: the corresponding crystalline plane is indicated in the spectra.
- Figure 1. Spectrum of a polycristalline Si, acquired with the Si(Li) detector and 2θ1=30°;
measurement time (real time): 150 sec
132

- Figure 2. Spectrum of a polycristalline Si, acquired with the Si(Li) detector and 2θ1=35°;
measurement time (real time): 150 sec
As expected, by changing the 2θ angle, the diffraction peak energy changes. For instance, the
(111) peak is included in the fluorescence Cu-Kα in figure 1 and it is visible in figure 2, but it
coincides with the escape peak.
Similar observations were made on the other compounds. In these cases, the fluoresecnce of Ca
and Fe from the specimens add up to the fluorescence of copper that originates from the X ray
source.
Although the measurements showed that it is possible to identify the diffraction peaks by using
energy dispersive methods, this technique does not seem suitable for mineral identification with a
portable instrument. The diffraction peak intensity is quite weak and the peak width is quite large,
due to the detector energy resolution and to the superposition of different diffraction peaks.
Fluorescence peaks can strongly interfere with diffraction peaks making their identification more
difficult. Moreover fluorescence peaks are usually much more intense than diffraction ones.
In principle these problems could be overcome by systematically doing measurements at several
different angles. This could be done in a relatively quick measurement time by using a multielement
detector or some single detectors located at different 2θ angles. This solution would allow
to evaluate the geometry and to separate diffraction and fluorescence peaks. On the other hand this
requires a complex and heavy equipment, and also a non-trivial data analysis.
This supports our initial conclusion, based on the literature, to rule out the ED-XRD for the
planned portable system.
X-ray Diffraction experiments with Imaging Plate
The experiments have been performed at the Laboratoire de Cristallographie (CNRS UPR 5031) in
Grenoble. The source used is a Philips C-Tech type x-ray tube, with Cu anode and a maximum
power of 2200 W (60 kV). The x-ray beam is monochromatic by means of two mirrors: only Kα1,
Kα2 and Kβ appear in the spectrum (with approximately the following ratio between intensities
Kα/Kβ≈10 -3 ÷10 -4 ).
The divergence of the beam is approximately 0.05° and its dimension is around 1.5mm x 1mm in
the centre of the goniometer, with a flux of around 10 7 ph/s.
The tube is biased at 50 kV and 40 mA.
133

Different kinds of samples and different times of measurement have been taken into account in
order to test the system.
For each sample two XRD detector systems have been used:
- a conventional scintillator detector, with a monochromator in front of it, in a θ-2θ
configuration
- an Imaging Plate (IP) perpendicular to the incident X-ray beam at distance of around 20
cm from sample, with ω being the angle between x-ray beam and sample surface.
Here, we present the results obtained for quartz. For a measurement time less than 5 min the IP
scanner did not read anything.
Since the first image with the fixed sample showed some preferential orientation (punctuation on
the rings) of the crystals in the quartz, further measurements were taken with the sample turning
on itself in order to obtain a more uniform diagram (figure 3).
Figure 4 and 5 show a comparison between the diagram recorded by the scintillator detector (1h
and 6 minute measurement) and the diagram obtained from the fitting (Fit2D) of the image
recorded with the Image Plate (10 minutes), respectively. Considering the measurement times and
the intensity shown in the diagram, the efficiency of the imaging plate appears quite high.
Figure 3. Diagram recorded on the imaging place for a turning quartz sample irradiated for 10 min
with a monochromatic radiation (Cu Kα) and ω=15°, read at 16 bit.
Figure 4. θ-2θ XRD diagram for quartz, recorded with a scintillator detector over a 2θ range from
20° to 60° (0,05°/step with 5s/point) for a total measurement time of around 1h and 6 minutes.
134

Figure 5. Result of the fitting of an XRD diagram recorded with an imaging plate, for a quartz
sample irradiated for 10 min and ω =15° (16 reading bits).
The imaging plate detector proved to be a valid alternative to the one-dimensional scintillator
detector: the measurement times are comparable (around 20÷30 minutes for both), even if imaging
plate seems to be more efficient. Imaging plates have the big advantage of being a twodimensional
low-noise system, with a flexible mounting and wireless, and they allow to collect
data in a parallel detection configuration. On the other hand the scanner system requires around 3
minutes to read the recorded image (it is not an online measurement; the result is visible only at
the end of the process) and imaging plates are light sensitive.
Further tests are in progress in order to determine the needs for an analyzer for the diffracted
beams and the types of slits/diaphragms necessary for optimal XRD. This is will allow to choose
the optimal X ray source compatible for XRF and XRD.
135

JRA2 Task 4 - Report on the spectroscopic characterisation of the prepared
samples
Resp. UNIPG
DELIVERABLE N. 20
The JRA2 research activity of task 4 during the first semester of the second year has been focused
on the enlargement of the microRaman and UV-VIS fluorescence database of solid powder
standard dyes and lakes. Standard materials reported on table 1 have been examined employing
MicroRaman in the lab set-up using two excitation wavelength 532 nm and 785 nm. The portable
set-up has been experience as MicroRaman using the 532nm excitation and as fluorimeter using
again the 532nm excitation but conveniently moving the polychromator. MicroRaman and
fluorescence spectra are here reported in the database format, maxima of vibrational scatterings
and electronic emissions are labeled. Interestingly, the portable equipment resulted to be properly
set-up for the study of red anthraquinone dyes, in fact in this case using the 532 nm excitation we
can observe an resonance enhancement and a relatively low fluorescence background thanks to
their large Stock-Shift.
Table 1: Standard colorant and dye descriptions
Name and molecular formula
Natural red dyestuff
Origin
Anthraquinone
Source
Madder lake-(Alizarin & Purporin) Vegetable origin National Gallery
Alizarin
Purporin
Gum lake
Carminic acid
Carmine
Kermes lake
Lac lake
Dragon’s blood
dracorhodin
dracorubin
Brasilwood
brasilin
brasilein
Quercitin
Vegetable origin Aldrich
Vegetable origin Aldrich
Insect origin Zecchi
Insect origin Aldrich
Insect origin Aldrich
Insect origin National Gallery
Insect origin National Gallery
Natural resin Zecchi
Vegetable origin National Gallery
Natural yellow, yellow brown dyestuffs
Flavononid
Vegetable origin Riedel-de Haen AG
Fustic -(Morin & Fisetin) Vegetable origin Zecchi
Morin
Vegetable origin Aldrich
Fisetin Vegetable origin Fluka
136

Curcumin
Arzica
Luteolin
Stil De Grain
Saffron/crocetin
Apigenin
Natural blue dyestuff
indigo
Campeggio (logwood)
Orcein
Orcinol
Vegetable origin Zecchi
Vegetable origin Zecchi
Vegetable origin Zecchi
Vegetable origin Zecchi
Vegetable origin Zecchi
Natural violet dyestuff
Vegetable origin Zecchi
Vegetable origin Aldrich
Synthetic violet dyestuff
Man-made Aldrich
137

MicroRaman Spectroscopy: Laboratory instrument JASCO Ventuno.
1. Pure standard colorants and dyes
1.a Analyses carried out using 532nm excitation (no baseline effected)
Intensity (a.u)
Intensity (a.u)
Intensity (a.u)
11
10
9
8
7
6
5
4
3
20
15
10
5
15
12
9
6
3
0
1480
1420
1328
1276
Madder lake
1239
511
1079
1600 1400 1200 1000 800 600
989
Raman shift (cm -1 )
Porporin
915
839
4000 3000 2000 1000
Raman shift (cm -1 )
Carminic acid
5000 4000 3000 2000 1000
Raman shift (cm -1 )
659
Intensity (a.u)
Intensity (a.u)
Intensity (a.u)
80
60
40
15
1570
1590
1480
1458
1402
1332
Alizarin
1216
1192
1600 1400 1200 800 600 400
80
60
40
20
0
25
20
15
10
831
Raman shift (cm -1 )
Lacca di gomma
5000 4000 3000 2000 1000
5
0
819
Raman shift (cm -1 )
Carmine
680
627
4000 3000 2000 1000
Raman shift (cm -1 )
473
424
138

Intensity (a.u)
Intensity (a.u)
Intensity (a.u)
40
30
20
10
Brazilwood
5000 4000 3000 2000 1000
12
9
6
3
50
40
30
20
10
Raman shift (cm -1 )
Dragon's blood
4000 3000 2000 1000
Raman shift (cm -1 )
Fustetto
4000 3000 2000 1000
Raman shift (cm -1 )
Intensity (a.u)
Intensity (a.u)
Intensity (a.u)
50
40
30
20
60
40
20
20
15
10
5
Verzino
4000 2000
Raman shift (cm -1 )
Quercetin
1622
1563
1334
4000 3000 2000 1000
Raman Shift (cm -1 )
Morin
857
4000 3000 2000 1000
Raman shift (cm -1 )
607
529
139

Intensity (a.u)
Intensity (a.u)
Intensity (a.u)
25
20
15
10
5
Fisetin
1634
1570
5000 4000 3000 2000 1000
140
120
100
120
100
80
60
40
20
80
60
40
20
0
Raman shift (cm -1 )
Arzica
4000 3000 2000 1000
Raman shift (cm -1 )
Zafferano
4000 3000 2000 1000
Raman Shift (cm -1 )
1559
1185
1023
Intensity (a.u)
Intensity (a.u)
Intensity (a.u)
50
40
30
20
12
10
8
6
4
2
25
20
15
10
5
Curcumina
4000 3000 2000 1000
Raman shift (cm -1 )
Stil De Grain
4000 3000 2000 1000
Raman shift (cm -1 )
Tioindaco
4000 3000 2000 1000
Raman shift (cm -1 )
1648
1573
1350
1191
809
629
397
140

1.b Analyses carried out using 785nm excitation (no baseline effected)
Intensity (a.u)
Intensity (a.u)
Intensity (a.u)
90
60
30
1.2
Madder lake
1430
1496
1468
1339
1600 1200 800
Carminic acid
1465
1244
1180
Raman Shift (cm -1 )
Purpurin
654
448
509
1500 1000 500
Raman shift (cm -1 )
1300
1600 1400 1200 1000
1224
Raman Shift (cm -1 )
910
1098
1076
1007
552
585
Intensity (a.u)
Intensity (a.u)
Intensity (a.u)
80
40
0
50
40
30
20
785nm
Alizarin
3000 2000 1000
Gum lake
Carminio
Raman shift (cm -1 )
3000 2000 1000
Raman Shift (cm -1 )
60 977
1319
1263
1400 1200 1000
Raman Shift (cm -1 )
141

Intensity (a.u)
Intensity (a.u)
Intensity (a.u)
8
7
6
5
4
3
2
1
0
100
50
Dragon's blood
4000 3000 2000 1000
2.1
1.4
0.7
Kermes lake
Brazilwood
3000 2000 1000
Raman Shift (cm -1 )
Raman Shift (cm -1 )
1442
1324
1267
1127
1065
1016
904
1526
3000 2000 1000
Raman Shift (cm -1 )
Intensity (a.u)
Intensity (a.u)
Intensity (a.u)
80
40
0
6
4
2
0
30
20
10
0
Lac lake
Verzino
3000 2000 1000
Raman Shift (cm -1 )
3000 2000 1000
Fustic
Raman Shift (cm -1 )
3000 2000 1000
Raman Shift (cm -1 )
142

Intensity (a.u)
Intensity (a.u)
Intensity (a.u)
14
4
2
7
Morin
Curcumin
1.8 Stil de Grain
0.9
3000 2000 1000
Raman Shift (cm -1 )
3000 2000 1000
Raman Shift (cm -1 )
3000 2000 1000
Raman Shift (cm -1 )
Intensity (a.u)
Intensity (a.u)
Intensity (a.u)
25
20
15
10
4
2
5
0
Fisetin
4000 3000 2000 1000
6 Arzica
30
20
10
0
Saffron
Raman Shift (cm -1 )
3000 2000 1000
Raman Shift (cm -1 )
1541
1166
1216
1282
2000 1500 1000 500
Raman Shift (cm -1 )
143

Intensity (a.u)
Intensity (a.u)
0.9 Tioindigo
0.8
0.7
20
10
0
Orceine
3000 2000 1000
Raman Shift (cm -1 )
3000 2000 1000
Raman Shift (cm -1 )
Intensity (a.u)
Intensity (a.u)
40
30
20
10
3
2
1
0
Campeggio
Orcinol
3000 2000 1000
Raman Shift (cm -1 )
1615
1335
1384
1158
1004
975
595
518
556
2000 1500 1000 500
Raman Shift (cm -1 )
407
330
144

2. MicroRaman Spectroscopy: Portable spectrophotometer of UNIPG
Pure standard colorants and dyes
Analyses carried out using 532nm excitation (no baseline effected), monochromator :876nm
Intensity (a.u)
Intensity (a.u)
Intensity (a.u)
1.5x10 5
1.0x10 5
5.0x10 4
5x10 4
4x10 4
3x10 4
1.2x10 5
8.0x10 4
4.0x10 4
417
452
Madder lake
1327
1572
500 1000 1500 2000 2500
Purpurin
1048
956
Carmine
Raman shift (cm-1)
1329
1243
1466
900 1800 2700
Raman shift (cm-1)
1094
1308
1487
500 1000 1500 2000 2500
Raman shift (cm-1)
Intensity (a.u)
Intensity (a.u)
Intensity (a.u)
1.2x10 5
8.0x10 4
4.0x10 4
1.2x10 5
1.0x10 5
8.0x10 4
6.0x10 4
4.0x10 4
2.0x10 4
6x10 5
5x10 5
4x10 5
3x10 5
2x10 5
Alizarin
1185
1477
1325
1593
900 1800 2700
Carminic acid
Raman shift (cm-1)
1229
1466
500 1000 1500 2000 2500
Quercetin
486
521
594
1097
Raman shift (cm-1)
1318
1363
1397
1437
1550
1612
500 1000 1500 2000 2500
Raman shift (cm-1)
145

Intensity (a.u)
Intensity (a.u)
Intensity (a.u)
7x10 4
6x10 4
5x10 4
4x10 4
3x10 4
1.4x10 5
1.2x10 5
1.0x10 5
8.0x10 4
6.0x10 4
1.2x10 5
9.0x10 4
6.0x10 4
3.0x10 4
Fustic
500 1000 1500 2000 2500
562
512
Fisetin
778
Raman shift (cm-1)
1636
1575
500 1000 1500 2000 2500
Stil de Grain
Raman shift (cm-1)
1000 2000
Raman shift (cm-1)
Intensity (a.u)
Intensity (a.u)
Intensity (a.u)
2.0x10 5
1.5x10 5
1.0x10 5
2.0x10 5
1.5x10 5
1.0x10 5
5.0x10 4
2.0x10 5
1.5x10 5
1.0x10 5
5.0x10 4
Morin
800 1200 1600 2000 2400 2800
Arzica
Saffron
Raman shift (cm-1)
900 1800 2700
1160
Raman shift (cm-1)
1537
500 1000 1500 2000 2500
Raman shift (cm-1)
146

Intensity (a.u)
Intensity
(a.u)
2.4x10 5
1.6x10 5
8.0x10 4
3.6x10 5
2.7x10 5
1.8x10 5
Tioindigo
3. Microfluorimeter
500 1000 1500 2000 2500
Raman shift (cm-1)
Pure standard colorants and dyes
569
Arzica
595
540 550 560 570 580 590 600 610 620 630
Raman shift (cm-1)
Intensity
(a.u)
Intensity (a.u)
1.4x10 5
1.2x10 5
1.0x10 5
8.0x10 4
Analyses carried out using 532nm excitation (no baseline effected)
Intensity (a.u)
3x10 5
2x10 5
1x10 5
579
Tioindigo
550 560 570 580 590 600 610 620 630
Wavenumber (nm)
Intensity (a.u)
6.0x10 4
3.0x10 4
515
634
989
1337
1428
1502
1581
500 1000 1500 2000 2500
Raman shift (cm-1)
9.0x10 4 570
594
9.0x10 4
Stil de Grain
Orcinol
540 560 580 600 620
548
1.2x10 5 578
1873
Wavenumber (nm)
Orcinol
540 550 560 570 580 590 600 610 620 630
Wavenumber (nm)
147

Intensity (a.u)
Intensity (a.u)
Intensity (a.u)
240000
210000
180000
60000
55000
50000
45000
390000
360000
330000
595
Curcumina
580 600 620
624
Wavenumber (nm)
Madder lake
600 650 700 750 800
Wavenumber (nm)
619
Morin
590 600 610 620 630 640 650 660 670 680
Wavenumber (nm)
Intensity (a.u)
490000
420000
350000
547
Zafferano
540 630 720
Wavenumber (nm)
148

Intensity (a.u)
Intensity (a.u)
Intensity (a.u)
96000
90000
84000
150000
120000
90000
666
Campeggio
650 700
Wavenumber (nm)
620 640 660 680 700 720
240000 652
200000
160000
664
Gum lake
Wavenumber (nm)
Carminic acid
640 680 720
Wavenumber (nm)
Intensity (a.u)
Intensity (a.u)
180000
150000
12000
9000
6000
658
Dragon's blood
640 680 720
Wavenumber (nm)
667
Carmine
620 640 660 680 700 720
Wavenumber (nm)
149