1 Study of new laboratory prepared periclase- Magnesium ...
1 Study of new laboratory prepared periclase- Magnesium ...
1 Study of new laboratory prepared periclase- Magnesium ...
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<strong>Study</strong> <strong>of</strong> <strong>new</strong> <strong>laboratory</strong> <strong>prepared</strong> <strong>periclase</strong>- <strong>Magnesium</strong> aluminate spinel<br />
refractories from sintered dead burned magnesite and various presynthesized<br />
spinel- based compositions (II):Compositional variation between coexisting<br />
spinel, <strong>periclase</strong>, Ca silicate and Ca-aluminate phases in magnesia spinel<br />
refractories and in their spinel- based precursors. .<br />
P.G. Lampropoulou*, C.G. Katagas, I. Iliopoulos<br />
Department <strong>of</strong> Geology, University <strong>of</strong> Patras, 26500 Patras, Greece<br />
*Corresponding author: P.G. Lampropoulou Tel: +30-2610997599, Fax: +30-<br />
2610997560, E-mail address: p.lampropoulou@upatras.gr<br />
Abstract<br />
The chemistry and distribution <strong>of</strong> phases formed in a set <strong>of</strong> six <strong>laboratory</strong> <strong>prepared</strong><br />
magnesia-magnesium aluminate spinel ceramics and in three <strong>of</strong> their precursor spinel<br />
based compositions, sintered at 1600 o C and 1760 o C respectively, are examined and<br />
compared.<br />
Despite the differences in stoichiometry <strong>of</strong> the spinel phases formed in each type <strong>of</strong><br />
the materials and in their firing temperatures, the spinels have a strong preference for<br />
normal structure. Microtextures and microanalyses <strong>of</strong> cracked and non cracked<br />
domains in <strong>periclase</strong> crystals from spinel based compositions suggest that the<br />
development <strong>of</strong> fractures is probably facilitated by differences in the thermal<br />
expansion coefficient <strong>of</strong> <strong>periclase</strong> crystals having domains differing in their Al 2 O 3<br />
contents. A comparison <strong>of</strong> coexisting phases from both types <strong>of</strong> materials indicate that<br />
heat treatment <strong>of</strong> <strong>periclase</strong> and spinel mixtures at lower temperatures (1600 o C)<br />
involved reactions leading to the formation <strong>of</strong> different <strong>periclase</strong> s.s and spinel s.s in<br />
the ceramics, which contrary to the theoretically predicted compositions, depart<br />
clearly from equilibrium assemblages.<br />
Minor amounts <strong>of</strong> stoichiometric Ca-silicate and Ca-aluminate phases were formed in<br />
both types <strong>of</strong> the materials and are encountered as small particles in the siliceous<br />
bonds; C 3 S 2 , the most abundant <strong>of</strong> the low melting metastable phases, occurs in<br />
microdomains <strong>of</strong> only few microns wide, and cannot be augmented with Ca-aluminate<br />
phases to a migrated liquid, which could result in extensive negative effects on the<br />
properties <strong>of</strong> the refractory ceramics.<br />
1
Introduction<br />
Most <strong>of</strong> the studies concerned with magnesia-spinel refractories focuse mainly to their<br />
physical and technological properties as related to their microstructures. Such studies<br />
on the physical properties <strong>of</strong> various Magnesia-spinel based compositions and their<br />
microstructures in relation to their densification parameters and refractory resistance<br />
as well as on different synthesis routes (1-5) and on the effects <strong>of</strong> different additives<br />
on the development <strong>of</strong> spinel based compositions with improved sintered properties<br />
have been published by many workers [e.g. 6-10].<br />
It is now well established that Magnesia-Spinel refractories derived from pure raw<br />
materials with a high degree <strong>of</strong> direct bonding <strong>of</strong> MgO-MgO and MgO-spinel grains,<br />
and with low amounts <strong>of</strong> low-melting silicate phases, exhibit high hot temperature<br />
strength, an improved resistance to slag attack, and dimensional stability at high<br />
temperatures [11, 12].<br />
Nowadays, the need for a detailed study <strong>of</strong> magnesia spinel materials is further<br />
triggered in order to promote their uses in many other fields such as in catalysis,<br />
optical ceramics, humidity sensors [13-17] under the framework <strong>of</strong> “green policies”<br />
which are widely sought for by organizations and governments. Newly developed<br />
magnesium-aluminate spinel ceramics, for instance, appear to meet the requirements<br />
for geological time-period disposal <strong>of</strong> high level nuclear and hazardous wastes [18,<br />
19]. In a companion paper to this study [20] we report details on the <strong>laboratory</strong><br />
synthesis, mineralogical composition, microstructure and property evaluation <strong>of</strong> a set<br />
<strong>of</strong> six rebonded magnesia-magnesium aluminate spinel refractories containing various<br />
amounts <strong>of</strong> Al 2 O 3 , synthesized from three previously <strong>prepared</strong> spinel-based<br />
compositions and high purity MgO. The objective was to contribute to the<br />
development <strong>of</strong> more environmentally friendly refractories, which could substitute for<br />
the magnesia-chromite bricks, or find applications to some advanced usage.<br />
Unfortunately, relatively few studies have presented detailed systematic data on the<br />
chemistry <strong>of</strong> coexisting phases in spinel based compositions and on their significance<br />
on the growth <strong>of</strong> refractory <strong>periclase</strong>-spinel bearing technological materials.<br />
However, understanding chemical and mineralogical compatibilities among<br />
coexisting <strong>periclase</strong>, magnesium aluminate spinel, Ca-silicate and Ca-aluminate<br />
phases in various bulk compositions and temperatures is an essential prerequisite for<br />
the experimental design <strong>of</strong> magnesia-spinel refractories and for the evaluation and<br />
characterization <strong>of</strong> these materials before their use as refractories or in other<br />
2
applications. In this article we present results <strong>of</strong> investigations on variations in the<br />
chemical composition <strong>of</strong> coexisting phases from the six <strong>laboratory</strong> synthesized<br />
magnesia spinel refractories <strong>of</strong> various compositions as well as from their respective<br />
spinel based precursors, and examine and compare the chemical mineralogy and some<br />
microstructural characteristics <strong>of</strong> these materials in relation to their bulk chemical<br />
composition and firing temperatures.<br />
Experimental procedures, materials and methods<br />
We present here only a brief account <strong>of</strong> the synthesis procedures and the analytical<br />
methods used for the chemical, mineralogical and microstructural characterization <strong>of</strong><br />
the materials. More detailed information on these issues is presented in the<br />
companion paper to this study. [20].<br />
Pure magnesia (MgO>96%), and Alumina (Al 2 O 3 >99.5%) powders, mixed in<br />
different proportions, were used as raw materials for the <strong>laboratory</strong> synthesis <strong>of</strong> three<br />
spinel based compositions. The compacted raw materials mixtures were initially<br />
calcined to 1760 o C, followed by regrinding to powder, recompaction and refiring at<br />
the same temperature. The spinel based materials were termed (a) Sp55z : made <strong>of</strong><br />
alumina and magnesia in about 1:1 ratio and 0.5 wt% zirconium silicate (ZrSiO 4 ) as<br />
additive; (b) Sp73z: made <strong>of</strong> alumina and magnesia in about 2.3:1 ratio and 1wt%<br />
ZrSiO 4 as additive; and (c) Sp73chr: made <strong>of</strong> alumina and magnesia in about 2.3:1<br />
ratio and 3wt% chromite (Mg 0.48 Fe 0.54 )(Cr 1.18 Al 0.57 Fe 0.22 )O 4 . as additive.<br />
Using mixtures <strong>of</strong> ground powders <strong>of</strong> the presynthesized spinel-based compositions<br />
and pure dead-burned magnesia, six <strong>new</strong> magnesia-magnesium aluminate spinel<br />
refractory materials, containing various amounts <strong>of</strong> Al 2 O 3 were <strong>laboratory</strong> <strong>prepared</strong><br />
(see 19, 20). After mixing, the powders <strong>of</strong> various grain sizes were pressed, dried and<br />
sintered up to 1600 o C, remained at this firing temperature for four hours and then the<br />
samples were furnaced-cooled for twelve hours. Three <strong>of</strong> the powder mixtures were<br />
selected to result to rebonded magnesia-magnesium aluminate spinel refractories (M-<br />
Sp-L) containing low (L) amounts <strong>of</strong> Al 2 O 3 (~8-11wt%) while the rest three samples<br />
(M-Sp-H) have a high (H) Al 2 O 3 content (~19-21wt%)<br />
ICP –MS bulk chemical analyses <strong>of</strong> the six <strong>new</strong> refractory materials and their three<br />
precursors are summarized in Table 1. Phase identification was performed through X-<br />
Ray powder diffraction, SEM imaging and SEM EDS-WDS microanalyses on<br />
polished, carbon coated thin sections <strong>of</strong> all samples. Micro-Raman spectroscopy has<br />
3
een tentatively used to study the degree <strong>of</strong> order in spinel crystals and for the<br />
identification <strong>of</strong> minor phases, in one <strong>of</strong> the samples employing a T6400 Jobin Yvon<br />
monochromator and Ar + laser tube<br />
Phase composition <strong>of</strong> the synthesized materials.<br />
Detailed results on the mineralogical composition and microstructure, <strong>of</strong> the<br />
synthesized materials were reported in the companion paper <strong>of</strong> this article[19];<br />
Periclase and various amounts <strong>of</strong> spinel, dependent on the Al 2 O 3 wt% contents <strong>of</strong> the<br />
starting materials, are major phases <strong>of</strong> the spinel based materials (20-21).<br />
Minor Ca-silicate and Ca-aluminate phases are confined to small domains <strong>of</strong> the<br />
microstructures and many <strong>of</strong> them are probably not equilibrium phases, because they<br />
were not expected to form on the basis <strong>of</strong> known phase equilibria for bricks <strong>of</strong> these<br />
compositions [22, 23].<br />
Back scattered electron images from the magnesia spinel bricks suggested the growth<br />
<strong>of</strong> spinel crystals with a characteristic shape, showing different micro-structural and<br />
possibly different compositional characteristics from those in their precursor materials<br />
as well as secondary spinel precipitates, visible along magnesia-magnesia or<br />
magnesia-spinel grain boundaries or as small exsolution blobs precipitates within<br />
periclace. Secondary Ca-aluminate and Ca-silicate phases are also present in low<br />
amounts in tiny domains <strong>of</strong> a few microns wide.<br />
Results and discussion<br />
Chemical compositions <strong>of</strong> phases<br />
Spinel<br />
Knowledge <strong>of</strong> the chemical composition <strong>of</strong> the spinel is <strong>of</strong> great importance because<br />
variations in lattice parameters, occurring as the stoichiometry <strong>of</strong> the spinel changes<br />
among spinel grains, must considerably affect the mechanical stability <strong>of</strong> the material.<br />
According to Nestola et al [24] and references therein, an excess <strong>of</strong> Al in the spinel<br />
structure, accompanied by the formation <strong>of</strong> cation vacancies mostly at the octahedral<br />
site, strongly affects its thermal expansion.<br />
Spinels with the general chemical formula AB 2 O 4 , have a unit cell capable <strong>of</strong> holding<br />
a large number <strong>of</strong> cations occupying octahedral and tetrahedral sites in different ways.<br />
The cation distribution is said to be normal if all the A cations (Mg, Fe 2+ , Zn, Mn) are<br />
4
on tetrahedral sites with all B cations (Al, Cr, Fe 3+ ) on octahedral sites or inverse if it<br />
is characterized by occupation <strong>of</strong> one <strong>of</strong> B-sites by a divalent cation with one trivalent<br />
cation taking its place on the A-site. Thus, normal spinel has a general formula<br />
A 2+ B 3+ 2 O 4 in which the A-cations exhibit 4-coordination and B-cations exhibit 6-<br />
coordination, and in inverse spinels, with the general formula B 3+ A 2+ B 3+ O 4 , the A<br />
cations are 6-coordinated and half <strong>of</strong> the B cations are 4-coordinated and half are 6-<br />
coordinated.<br />
The MgAl 2 O 4 spinel formed in the Periclase-spinel refractories and their precursor<br />
materials, is assumed to have a strong preference for the normal structure, since<br />
simple radius ratio arguments suggest that smaller cations would prefer to occupy<br />
tetrahedral sites and Mg +2 is the smallest (r=0.66Å). However, it is known that by heat<br />
treating natural or synthetic spinel to high temperatures, aluminum and magnesium<br />
ions start to change sites, giving rise to more random distributions <strong>of</strong> the cations<br />
leading to different degrees <strong>of</strong> inversion. This change in the distribution <strong>of</strong> the cations<br />
is accompanied by changes in the thermodynamic properties <strong>of</strong> the spinel and can be<br />
retained depending on the temperature <strong>of</strong> the heat treatment and cooling rate (25, 26,<br />
27). XRD and SEM/EDS-WDS analyses were used to examine the degree <strong>of</strong><br />
inversion and stoichiometry <strong>of</strong> the spinel phases formed at 1760 o C in the pre<strong>prepared</strong><br />
spinel-based compositions and <strong>of</strong> those formed at 1600 o C in the Periclasemagnesium<br />
aluminate spinel refractories. Raman spectroscopy has been applied on<br />
one <strong>of</strong> the nearly stoichiometric spinel based compositions to test the distribution <strong>of</strong><br />
the cations in the spinel structure.<br />
The spinel phase in spinel based compositions<br />
More than thirty spot microanalyses (spot size
usually accompanied by the formation <strong>of</strong> cation vacancies. Microanalyses <strong>of</strong> crystals<br />
from the sample with chromite additive (Sp73chr) show lower mean Αl 2 Ο 3 wt%<br />
values than those from samples with zirconium silicate additive. This is thought to be<br />
a result <strong>of</strong> mainly Cr and Fe 3+ ions substituting for Al in the spinel lattice. As Cr 2 O 3,<br />
Fe 2 O 3 and FeO enter the spinel by solid solution, its lattice parameter and crystal<br />
density increase as a function <strong>of</strong> the ionic radii <strong>of</strong> the divalent and trivalent ions (See<br />
Table 2a, Sp73chr sample) and the direct diffusion bonding should be stronger [18].<br />
The lattice parameters and the mean density values <strong>of</strong> spinel crystals from each<br />
sample have been calculated according to Cullity [28] and Deer et al [29] using the<br />
general empirical formula: ρ=1.66020*MW <strong>of</strong> the spinel/α 3 ;<br />
α(Å)=5.790+0.95R 2+ +2.79R 3+ . In the present study we see that the α cell parameter<br />
values <strong>of</strong> the spinels formed in the spinel based materials, as derived from their X-Ray<br />
diffraction patterns are much closer to the ideal lattice parameter values reported in<br />
the literature than those obtained using their chemical analyses and the above cited<br />
empirical formula. The latter α lattice parameter values <strong>of</strong> spinels from both types <strong>of</strong><br />
materials are always lower than the expected by about 3.0-3.3%. This discrepancy<br />
needs further investigation.<br />
It has been suggested that when a single crystal <strong>of</strong> Al 2 O 3 is converted to spinel<br />
through a reaction with <strong>periclase</strong>, a concentration gradient is developed by counter<br />
diffusion <strong>of</strong> Mg 2+ inward and Al 3+ outward, therefore compositional differences are<br />
expected to occur in various microdomains. In the backscattered - micrographs <strong>of</strong><br />
spinel based composition with chromite additive for instance, spinel exhibits very<br />
<strong>of</strong>ten different shades <strong>of</strong> gray. Line scan elemental pr<strong>of</strong>iles performed on such a<br />
spinel crystal demonstrated that such variations are common and reflect variations in<br />
the atomic distribution, especially <strong>of</strong> Cr and Fe 3+ , in micro domains <strong>of</strong> the spinel<br />
crystal (Fig 1). Recalculations <strong>of</strong> spot analyses from the sample sp73chr spinels<br />
(Table 2a), indicate that the spinels may differ slightly in their Fe 2+ and Fe 3+ contents,<br />
departing thus from the spinel-hercynite -chromite-magnesiochromite plane <strong>of</strong> the<br />
normal spinels, towards the magnesi<strong>of</strong>errite-magnetite (or ulvospinel) compositions.<br />
<strong>Study</strong> <strong>of</strong> the XRD patterns <strong>of</strong> the spinel crystals, however, indicate that there is not a<br />
significant degree <strong>of</strong> inversion since most <strong>of</strong> the stronger odd reflections like (311)<br />
etc, show higher intensities compared to the standard list <strong>of</strong> the fully ordered spinel<br />
peaks recorded in the ICDD 21-1152 pattern, while the stronger even reflections e.g.<br />
(400) do not show an increase but present lower, similar intensities or are absent [29].<br />
6
The use <strong>of</strong> Raman spectroscopy, which has not yet found a wide application in the<br />
study <strong>of</strong> the mineral phases, was experimentally tested on the Sp73z sample and a<br />
representative Raman spectrum for the MgOAl 2 O 3 is presented in Fig. 2. According<br />
to Barpanda et al [30] a peak near 723cm -1 indicates the occupancy <strong>of</strong> some Al ions in<br />
tetrahedral sites making it a disordered structure while the intensity <strong>of</strong> this peak<br />
decreases or entirely collapses with increasing calcination temperature. The absence<br />
<strong>of</strong> such a peak from the Raman spectrum obtained from the spinel <strong>of</strong> Sp73z suggests<br />
the formation <strong>of</strong> an ordered spinel structure, after sintering <strong>of</strong> the spinel based<br />
composition at 1760 o C.<br />
The spinel phase in Magnesia-<strong>Magnesium</strong> Aluminate spinel refractories.<br />
Though some original spinel crystals seem to have been inheritted, apparently<br />
unchanged, from the precursor spinel based compositions, careful examination by<br />
analytical scanning electron microscopy revealed that with MgO addition to<br />
presynthesized materials, and subsequent sintering most <strong>of</strong> the primary spinel reacted<br />
with <strong>periclase</strong> to form secondary spinels (and <strong>periclase</strong>) <strong>of</strong> different compositions. It<br />
is <strong>of</strong> interest that at the calcination temperature <strong>of</strong> 1600 o C used for their synthesis, a<br />
temperature lower than the firing temperature <strong>of</strong> the precursor spinel based<br />
compositions (1760 o C), there appear to be marked compositional (and<br />
microstructural) changes in the spinel particles <strong>of</strong> the six magnesia-magnesium<br />
aluminate spinel refractories, indicating thus that spinel is not an inert component in<br />
the system at this lower temperature. Secondary spinel is also found in the form <strong>of</strong><br />
exsolved precipitates which have been formed by exsolution from <strong>periclase</strong> solid<br />
solution on cooling, as particles with no characteristic euhedral shape, or as white<br />
streaks occurring mostly in <strong>periclase</strong> -<strong>periclase</strong> grain boundaries (Figs. 3, 4).<br />
The abundance <strong>of</strong> the secondary spinel in the various magnesia-magnesium aluminate<br />
spinel refractories is affected by the proportions <strong>of</strong> the raw materials in the mixtures<br />
and as expected, increases with increasing the proportions <strong>of</strong> the presynthesized spinel<br />
based material. The amount <strong>of</strong> the grain boundary spinel is negligible as compared<br />
with that <strong>of</strong> the large primary supposed spinels in the matrix <strong>of</strong> the refractories. The<br />
micrographs in Fig. 3 show various <strong>periclase</strong> and spinel particles.<br />
Representative combined SEM EDS-WDS analyses performed on primary supposed<br />
spinel crystals from magnesia-spinel refractory polished thin sections specimens are<br />
7
summarized in Table 2b. The stoichiometries <strong>of</strong> the spot analyses indicate that the<br />
spinels formed obey to the general formula A 2+ B 3+ 2O 4 <strong>of</strong> the normal spinel.<br />
There was a difficulty in identifying and obtaining fully quantitative chemical<br />
analyses <strong>of</strong> minute exsolved secondary spinels and <strong>of</strong> spinel streaks confined to small<br />
bond regions. Admissible analyses <strong>of</strong> these phases were accomplished only in the<br />
samples M-Sp55z-L, M-Sp73z-H and M-Sp73chr-H and were plotted in the Mg-<br />
Fe(tot)-Al+Cr ternary diagram (Fig. 5a) .<br />
The projection <strong>of</strong> the chemical composition <strong>of</strong> the spinel crystals from the six<br />
Magnesia-Spinel refractories and <strong>of</strong> those from their respective pre-synthesized spinel<br />
based compositions in the Mg-Fe(tot)-Al+Cr ternary diagram (Fig. 5a) revealed a Mg<br />
enrichment in the spinel crystals <strong>of</strong> the former in respect to those in their counterpart<br />
precursor compositions (with the exception <strong>of</strong> the M-Sp73chr-H sample).<br />
Moreover, as is illustrated in the same ternary diagram (Fig. 5a), the secondary spinel<br />
Type II in the refractory materials M-Sp55z-L and M-Sp73z-H (both involving<br />
primary spinel that was synthesized with zirconium silicate as additive) is enriched in<br />
Mg and Fe and impoverished in Al compared to the secondary spinel crystals <strong>of</strong> Type<br />
I. A similar trend has been recorded in the spinels <strong>of</strong> the refractory material M-<br />
Sp73chr-H, synthesized employing a pre-<strong>prepared</strong>, chromite added, magnesiumaluminate<br />
spinel based material. Such variations have been attributed to the<br />
combination <strong>of</strong> the eutectic iron-calcium-aluminate silicate solutions that formed at<br />
the sintering temperatures at the boundaries <strong>of</strong> the <strong>periclase</strong> and spinel grains [31],<br />
and to the vicinity <strong>of</strong> the precipitated secondary spinel <strong>of</strong> Type II with <strong>periclase</strong><br />
grains/crystals. A perforated texture has been occasionally observed in the bonding<br />
secondary spinel <strong>of</strong> the magnesia spinel refractories (Fig. 4) which could be attributed<br />
to the presence <strong>of</strong> limited amounts <strong>of</strong> spinel phase in these micro domains, in<br />
conjuction with the remoteness <strong>of</strong> the alterated silicate liquid during the cooling<br />
processes .<br />
Structural formulae recalculations <strong>of</strong> the spinel crystals (Table 2) provide evidence<br />
that iron ions (Fe +2 and Fe +3 ) may occupy both octahedral and/or tetrahedral sites in<br />
the spinel lattice <strong>of</strong> the spinel based compositions, whereas the majority <strong>of</strong> the spinel<br />
microanalyses from the Magnesia-Spinel refractories, indicate that iron is mainly<br />
octahedrally coordinated. According to the melting points <strong>of</strong> the MgFe 2 O 4 (1750 o C)<br />
and FeAl 2 O 4 (1440 o C) end members <strong>of</strong> spinel series, one can predict that the trivalent<br />
iron oxide in the MgOAl 2 O 3 lattice plays a more critical role under high temperatures.<br />
8
Periclase<br />
Representative combined EDS-WDS SEM analyses performed on <strong>periclase</strong> crystals<br />
from all specimens are summarized in Table 3a.<br />
The <strong>periclase</strong> in spinel based compositions<br />
The <strong>periclase</strong> crystals in spinel based compositions exhibit intra-individual variation<br />
in their FeO content within sample, as well as variation among the different samples.<br />
Although individual analyses reveal that <strong>periclase</strong> can contain up to 2.1wt% FeO in<br />
solid solution as wustite, the mean values <strong>of</strong> FeO wt% contents from each sample are<br />
significantly lower (1.32, 0.64 and 0.74wt% for samples Sp55z, Sp73z and Sp73chr,<br />
respectively).<br />
Periclase crystals from the chromite added sample (Sp73chr), incorporate small<br />
amounts <strong>of</strong> chromium (not exceeding 0.002 a.p.f.u.) in their structure as a solid<br />
solution, while in the case <strong>of</strong> the samples with zirconium silicate additive, <strong>periclase</strong><br />
crystals contain only trace amounts <strong>of</strong> ZrO 2 .<br />
The solid solubility <strong>of</strong> Al 2 O 3 in the <strong>periclase</strong> crystals is low; the maximum Al 2 O 3<br />
content recorded in the analyses was only 1.1wt% (max. mean value: 0.34wt% in<br />
Sp73z sample). Although, the <strong>periclase</strong> crystals <strong>of</strong> the raw pure magnesia can contain<br />
up to ~2.0%CaO in solid solution [32], the crystals <strong>of</strong> the spinel based compositions<br />
contain only trace amounts <strong>of</strong> CaO. The negligible CaO component <strong>of</strong> <strong>periclase</strong> in the<br />
spinel based compositions is probably due to longer cooling time compared to that <strong>of</strong><br />
the feeding material, leading to the destruction <strong>of</strong> the Cao-MgO solid solution.<br />
Periclase crystals in spinel based compositions <strong>of</strong>ten exhibit cracks (See in<br />
companion paper [20], Fig. 2a) that maybe attributed to their higher thermal<br />
coefficient factor compared to that <strong>of</strong> the surrounding spinel. The latter inhibits<br />
probably the maximum expansion <strong>of</strong> <strong>periclase</strong> crystals resulting to microcracks. It is<br />
worthy to note, that microanalyses <strong>of</strong> cracked and no cracked regions <strong>of</strong> <strong>periclase</strong> (Fig<br />
6) reveal higher Al 2 O 3 wt% contents in the fractured domains. It has been suggested<br />
that thermal expansion coefficient values are probably higher in <strong>periclase</strong> crystals<br />
having more appreciable Al 2 O 3 contents. Expansion <strong>of</strong> such <strong>periclase</strong> crystals may<br />
lead to the development <strong>of</strong> micro-fractures and the formation <strong>of</strong> smaller<br />
microdomains. Wilson et al [33] and Aksel et al [34] argued that microcracks in free<br />
<strong>periclase</strong> bearing spinel based compositions improve the resistance <strong>of</strong> the materials to<br />
thermal shocks. However, <strong>periclase</strong> hydration to brucite due to a long atmospheric<br />
9
exposure <strong>of</strong> the materials prior to their examination, could also lead to cracks<br />
manifestation in the microstructure.<br />
The <strong>periclase</strong> in Magnesia-Spinel refractory materials<br />
Micro analyses <strong>of</strong> <strong>periclase</strong> crystals from the magnesia-spinel refractory materials and<br />
their respective spinel based compositions (Table 3b), plotted in the Mg-Fe(tot)-<br />
Al+Cr ternary diagram (Fig. 5b) illustrate an Mg enrichment <strong>of</strong> the <strong>periclase</strong> formed<br />
in the former materials. Iron is found in <strong>periclase</strong> crystals in all samples as wustite,<br />
but it never exceeds 0.01 a.p.f.u and does not affect the melting point <strong>of</strong> this phase.<br />
The maximum mean values <strong>of</strong> aluminium and chromium, are recorded in <strong>periclase</strong><br />
crystals <strong>of</strong> the M-Sp73z-L (0.003 a.p.f.u) and M-Sp73chr-H (0.002 a.p.f.u)<br />
refractories, respectively.<br />
As noted earlier, an intracrystalline distribution <strong>of</strong> spherical shaped microscopic<br />
pockets (up to ca. 5μm in diameter) filled by exsolved spinel grains and a calciumaluminate<br />
phase has been recognised in the <strong>periclase</strong> crystals. Fig. 7 is a<br />
representative SEM/EDS elemental mapping <strong>of</strong> a <strong>periclase</strong> crystal from the M-<br />
Sp73z-H sample, illustrating the distribution <strong>of</strong> magnesium, iron, calcium, aluminium<br />
and silicon.<br />
Coexisting <strong>periclase</strong>-spinel pairs<br />
Various studies have established that <strong>periclase</strong> and spinel solid solutions can stably<br />
coexist at temperatures above 1500 o C.<br />
According to the phase diagram <strong>of</strong> the binary MgO-Al 2 O 3 system [35] and the<br />
compositional range <strong>of</strong> the studied materials, <strong>periclase</strong> is expected to shift to more<br />
Al 2 O 3 rich compositions whereas the coexisting magnesium aluminate spinel becomes<br />
slightly depleted in Al 2 O 3 and enriched in MgO, with increasing temperatures,<br />
following the solvus limbs.<br />
Contrary to the theoretically predicted compositions, our results indicate that coexisting<br />
<strong>periclase</strong> and spinel crystals from the magnesia-magnesium aluminate spinel<br />
refractories are both more MgO rich and Al 2 O 3 poor than <strong>periclase</strong>-spinel pairs from<br />
the precursor spinel based materials, despite the lower firing temperature (1600 o C) <strong>of</strong><br />
the former.<br />
Yet, whereas the chemical compositions <strong>of</strong> most <strong>of</strong> the coexisting <strong>periclase</strong>-spinel<br />
pairs from the pre-synthesized materials seem to have been equilibrated, though at<br />
10
temperatures lower than the expected (~1650 o C instead <strong>of</strong> 1760 o C), <strong>periclase</strong>-spinel<br />
pairs from the refractory materials depart clearly from equilibrium. As is evident from<br />
Fig. 8 (M-Sp73z), various MgO-rich spinel solid solution crystals in the refractories<br />
(for example in M-Sp73z) indicate temperatures higher than those actually prevailed<br />
during their formation, whereas a variety <strong>of</strong> coexisting <strong>periclase</strong> s.s. crystals indicate<br />
temperatures close to or only little higher than the theoretically predicted by the phase<br />
diagram.<br />
We have not an obvious explanation for the observed discrepancies however, several<br />
factors could conceivably account for the lack <strong>of</strong> equilibrium between coexisting<br />
<strong>periclase</strong> and spinel after the firing <strong>of</strong> the refractory mixtures at 1600 o C.<br />
Heating <strong>of</strong> <strong>periclase</strong> and spinel bearing mixtures at this subsolidus temperature could<br />
produce a more random distribution <strong>of</strong> aluminium and magnesium cations, which,<br />
depending on other components present in the system, may lead to the formation <strong>of</strong><br />
different MgO and spinel solid solutions. Compositional differences in various<br />
microdomains due to inhomogeneous distribution and differences in grain size <strong>of</strong> the<br />
precursor constituents, could also produce random distribution <strong>of</strong> the cations,<br />
principally on the basis <strong>of</strong> lack <strong>of</strong> short diffusion paths between spinel and magnesia<br />
particles [36]. The presence <strong>of</strong> other oxides as impurities (CaO, SiO 2 , Fe 2 O 3 , TiO 2 ) or<br />
additives (chromite, zirconium silicate) may contribute to the inhomogeneous<br />
distribution <strong>of</strong> the magnesium and aluminium atoms. For example, the addition <strong>of</strong><br />
chromite enchances the solid solution reaction <strong>of</strong> Al 2 O 3 in the spinel, as Cr +3<br />
substitute for Al +3 in the spinel lattice and spinel is therefore not a strictly MgO-Al 2 O 3<br />
solid solution phase. The <strong>periclase</strong> crystal structure permits also substantial solid<br />
solution <strong>of</strong> Cr 2 O 3, Al 2 O 3 and FeO/Fe 2 O 3 at this temperature. Furthermore, the soaking<br />
time <strong>of</strong> 4hr at 1600 o C might not be so effective as to permit a strong interaction<br />
between the larger spinel and <strong>periclase</strong> grains and a rapid attainment <strong>of</strong> equilibrium,<br />
while the after heating slow furnace cooling treatment <strong>of</strong> the samples could also<br />
contribute to the development <strong>of</strong> a variety <strong>of</strong> compositions, depending on the other<br />
matrix phases present. SEM observations suggest that <strong>periclase</strong>-spinel crystals in the<br />
spinel based compositions may have been cooled quickly enough to suppress<br />
exsolution textures, whereas in the refractory materials, in which the lower<br />
temperature along solvus limbs reactions are expected to be more sluggish, exsolution<br />
<strong>of</strong> various spinels in the exsolving host <strong>periclase</strong> crystals are developed.<br />
11
Ca-silicate and ca-aluminate bonding phases<br />
Small amounts <strong>of</strong> SiO 2 , CaO and iron oxides present in the starting materials are<br />
combined after heating with the major components <strong>of</strong> the system resulting in various<br />
calcium silicate and calcium aluminate phases, among others. According to Landy<br />
[37] the CaO/SiO 2 wt% ratio controls the kinds <strong>of</strong> the phases that will form and also<br />
affects the thermal, chemical and mechanical properties <strong>of</strong> the materials at high<br />
temperatures through the CAS liquid formation and the distribution <strong>of</strong> the low melting<br />
phases in the bond [38].<br />
Minor calcium-silicate and / or calcium-aluminate phases are usually found as small<br />
particles in the bonding regions <strong>of</strong> the examined samples impeding accurate<br />
quantitative analyses. Thus, only the few representative micro-analyses which either<br />
satisfy stoichiometric constraints <strong>of</strong> the phases occurring in the siliceous bond regions<br />
<strong>of</strong> the precursor and refractory materials or approximate them very closely, are<br />
presented in Tables 4.<br />
Occasionally the C 2 S crystals exhibit a relatively little replacement <strong>of</strong> Ca by Fe,<br />
reaching up to ~1wt% FeO (in Sp55z sample) and a more extended replacement <strong>of</strong> Ca<br />
by Mg up to ~2 wt% MgO (in M-Sp73z-H sample).<br />
A limited substitution <strong>of</strong> Ca by Mg in the lime structure seems to be possible,<br />
considering the data presented in Table 4. It is also worth noting that although Zr +4<br />
can be accommodated in the octahedrally coordinated sites <strong>of</strong> the MgAl 2 O 4 spinel<br />
forming a solid solution (16) (reference in the originally submitted) the stabilizing<br />
additive <strong>of</strong> zirconium silicate favoured the formation <strong>of</strong> the high melting point phase<br />
<strong>of</strong> CaZrO 3 in the relevant samples. An additional characteristic is the formation <strong>of</strong> the<br />
2CaOSiO 2 -3CaOP 2 O 5 solid solution phase due to the use <strong>of</strong> a low amount (0.5wt%)<br />
<strong>of</strong> hexaphosphate as stabilizer in the refractory materials. The presence <strong>of</strong> these s.s.<br />
phases was proved by a number <strong>of</strong> microanalyses in which, when they were<br />
recalculated on the basis <strong>of</strong> 12(O), the number <strong>of</strong> cations Ca:Si:P ratio remain stable<br />
to approximately 5:1:2<br />
The majority <strong>of</strong> the C 12 A 7 crystals analyses show an almost stoichiometric formula,<br />
although crystals with Si up to 0.98 a.p.f.u. (in Sp73chr sample ) or with Fe up to 0.04<br />
a.p.f.u. (in Sp55z sample ) have been analyzed.<br />
Electron microanalyses <strong>of</strong> C 3 S, C 3 S 2 and C 3 A exhibit approximately stoichiometric<br />
proportions and only traces <strong>of</strong> Mg and Fe or Si, participate in their structures<br />
respectively.<br />
12
The non equilibrium metastable phases C 12 A 7 and C 3 S 2 have melting points (1455 and<br />
1475 o C, respectively) lower than the temperature conditions usually prevailed during<br />
the use <strong>of</strong> their host as refractory materials. The presence <strong>of</strong> a liquid phase at<br />
temperatures lower than ~1500 o C is certainty a disadvantage for the stability <strong>of</strong> the<br />
refractory, however, these phases appear usually in low amounts. The most abundant<br />
<strong>of</strong> them, C 3 S 2 , occurs in microdomains <strong>of</strong> only a few microns wide, and does not<br />
coexist with other calcium-aluminate or calcium silicate phases, preventing in this<br />
way a liquid augmentation and extensive liquid migration [38].<br />
It is also worth noting that although Zr 4+ can be accommodated in the octahedrally<br />
coordinated sites <strong>of</strong> the MgAl 2 O 4 spinel cell forming a solid solution [23], in the<br />
ZrSiO 4 added samples M-Sp55z-L, M-Sp73z-L, M-Sp55z-H, M-Sp73z-H, the<br />
stabilizing additive <strong>of</strong> zirconium silicate favoured the formation <strong>of</strong> the high melting<br />
point phase CaZrO 3 by tying up Ca 2+ from the system.<br />
According to Perepelitsym and Sivash [39] satisfying high energy structure criteria<br />
(energy density and energy strength) among the secondary phases <strong>of</strong> the materials,<br />
CaZrO 3 and C 2 S could be theoretically predicted as high wear resistant compounds<br />
under extreme thermodynamic conditions (high temperature, high pressure, high<br />
concentrations <strong>of</strong> corrosive agents).<br />
Of particular interest are the results obtained from the application <strong>of</strong> Raman<br />
spectroscopy to sample Sp73z. The Raman spectra <strong>of</strong> Fig. 9a confirm the coexistence<br />
<strong>of</strong> the non equilibrium phase C 3 S 2 with spinel and Fig.9b affirms the presence <strong>of</strong> the<br />
C 2 S phase in equilibrium with spinel.<br />
Thus, despite <strong>of</strong> the difficulties that Raman spectroscopy encounters in detecting<br />
minor phases in such microstructures, the results obtained hitherto make its use<br />
advisable and advantageous for the identification <strong>of</strong> phases even when they occur in<br />
microdomains <strong>of</strong> up to 2 μm wide.<br />
Conclusions<br />
The study <strong>of</strong> spinel phases formed at 1760 o C in the pre-<strong>prepared</strong> spinel-based<br />
compositions and <strong>of</strong> those formed at 1600 o C in the <strong>periclase</strong>-magnesium<br />
aluminate spinel refractories revealed that there is not a significant degree <strong>of</strong><br />
inversion, it is therefore suggested that the observed differences in the<br />
stoichiometry <strong>of</strong> the spinel phases formed in each <strong>of</strong> the materials or among spinel<br />
13
grains <strong>of</strong> the same sample, could not considerably affect the mechanical stability<br />
<strong>of</strong> the refractories.<br />
Microanalyses <strong>of</strong> cracked and non cracked domains <strong>of</strong> <strong>periclase</strong> crystals from<br />
spinel based compositions revealed higher Al 2 O 3 wt% contents in the fractured<br />
domains, suggesting that the development <strong>of</strong> different thermal expansion<br />
coefficient values within a <strong>periclase</strong> crystal scale, is probably responsible for this<br />
fracturing.<br />
The study <strong>of</strong> the chemical composition <strong>of</strong> coexisting phases in magnesiamagnesium<br />
aluminate refractories indicate that heat treatment at 1600 o C <strong>of</strong><br />
compacted powder mixtures <strong>of</strong> presynthesized at 1760 o C magnesium aluminate<br />
spinel based compositions and <strong>periclase</strong>, involved reactions <strong>of</strong> primary spinels<br />
with <strong>periclase</strong> to form spinels and <strong>periclase</strong> <strong>of</strong> different compositions, indicating<br />
that spinel is not an inert component in the system when this is fired at lower<br />
temperatures. However, contrary to the theoretically predicted compositions, our<br />
results indicate that coexisting <strong>periclase</strong> s.s and spinel s.s crystals from the six<br />
synthesized refractories have compositions which depart clearly from equilibrium.<br />
Several factors have been considered which may all contribute to a random<br />
distribution <strong>of</strong> Al +3 and Mg +2 cations in microdomains <strong>of</strong> the refractories, leading<br />
thus to the development <strong>of</strong> a variety <strong>of</strong> coexisting <strong>periclase</strong> and spinel solid<br />
solutions which are not in fact equilibrium assemblages.<br />
The calcium silicate and calcium aluminate phases formed in the magnesia-spinel<br />
refractories are chemically fairly similar to those found in their counterpart spinel<br />
based compositions. Most <strong>of</strong> them are usually encountered as small particles in the<br />
siliceous bond. Microanalyses <strong>of</strong> the bonding phases C 3 S, C 3 S 2 and C 3 A are<br />
almost stoichiometric and reveal the presence <strong>of</strong> trace amounts <strong>of</strong> Mg, Fe or Si in<br />
their structures. Occasionally, the C 2 S crystals exhibit relatively little replacement<br />
<strong>of</strong> Ca by Fe and a more extended <strong>of</strong> Ca by Mg; appreciable substitution <strong>of</strong> Al by<br />
Si in the C 12 A 7 structure seems to be possible. C 3 S 2 , the most abundant <strong>of</strong> the low<br />
melting non-equilibrium metastable phases (C 3 S 2 and C 12 A 7 ) occurs in<br />
microdomains <strong>of</strong> only few microns wide and does not coexist with other calcium<br />
aluminate phases, preventing in this way a liquid augmentation which could result<br />
in extensive liquid migration and negative effects on the properties <strong>of</strong> the<br />
refractories.<br />
14
The results obtained from the application <strong>of</strong> Raman spectroscopy, (a method<br />
which has not yet had wide application in the study <strong>of</strong> mineral phases) to one <strong>of</strong><br />
the spinel based composition samples are promising for a wider implementation <strong>of</strong><br />
the method for the determination <strong>of</strong> the structural characteristics <strong>of</strong> spinel as well<br />
as for the identification <strong>of</strong> minor calcium/aluminate/silicate phases occurring in<br />
microdomains with a diameter <strong>of</strong> up to 2μm.<br />
Acknowledgments<br />
The authors wish to thank Mr. V. Kotsopoulos <strong>of</strong> the <strong>laboratory</strong> <strong>of</strong> Electron<br />
Microscopy and Microanalysis, University <strong>of</strong> Patras, for his help with the<br />
Microanalyses and SEM photomicrographs as well as to Mr G. Voyiatzis, Principal<br />
Researcher <strong>of</strong> Institute <strong>of</strong> Chemical Engineering and High Temperature Chemical<br />
Processes <strong>of</strong> University <strong>of</strong> Patras, for his assistance on carrying on Micro-Raman<br />
analyses. Special thanks are due to Pr<strong>of</strong>. P. Tsolis-Katagas and Dr. Ch.Rathossi for<br />
their precious comments on improving an early version <strong>of</strong> the manuscript.<br />
References<br />
1. Zawrah M.F.M, SERRY M.A. , ZUM GAHR K-Z.: Ceram. For. Intern. 76 (5),<br />
36 (1999).<br />
2. Singh V.K. ,Sinha R.K.: Mater. Lett.31, 281 (1997).<br />
3. Suyama Y., Kato A.: Ceram. Intern. 8 (1), 17 (1982) -1.<br />
4. Behera S.K., Barpanda P., Pratihar S.K., Bhattacharya S.: : Mater. Lett. 58,<br />
1451 (2004) -.<br />
5. Khalil N.M., Hassan M.B., Ewais E.M.M., Saleh F.A., : J. All. Comp. 496(1-<br />
2), 600 (2010). -<br />
6. Szczerba J.,Pedzich Z., Nikiel M., Kapuscinska D., : J.l Eur. Ceram. Soc. 27<br />
(2-3), 1683 (2007). -<br />
7. Aksel C., Rand B.,. Riley F. L, Warren P. D.: J. Eu. Ceram. Soc. 22, 745<br />
(2002) -.<br />
8. . komorovskaya L.A: Glass& Ceram. 50 (3-4), 165 (1993) -.<br />
9. Sarkar R.,. Das S.K, Bannerjee G.: Ceram. Intern. 29 (1), 55 (2003) -.<br />
10. Lampropoulou P.G., Katagas C.G., : Ceram. Intern. 34, 1247 (2008). -<br />
11. Goto K., Lee W.: J.l Am. Ceram. Soc., 78 (7), 1753 (1995) -.<br />
15
12. Serry M., Othman A.G.M., Girgis L.G., , J. Mater. S.e 31, 4913 (1996) -4.<br />
13. Zargar H.R., Fard F.G., Rezaie H.R., J.l Ceram. Proc. Res. 9[1], 46 (2008) -.<br />
14. Mukhopadhyay S., Pal P., Nag B., Jana P., Ceram.. Int. 33[2] 175 (2007) -.<br />
15. Li J.G., Ikegami T., Lee J.H., Mori T. Yajima Y., Ceram. Int. 27[4], 481<br />
(2001) .<br />
16. Jang S.W., Shin K.C. Lee S.M., J. Ceram. Proc. Res. 2[4], 189 (2001) -.<br />
17. Guo* J., Lou H., Zhao H., Wang X., Zheng X.: Mater. Lett. 58, 1920<br />
(2004).–<br />
18. Lumpkin C.R.,: Elem. 2[6], 365 (2006). -.<br />
19. Rokhvarger A., Adams, J., Cowgill M., Moskowitz P.: Brookhaven National<br />
Laboratory -67518. informal report (2001).<br />
20. Lampropoulou P.G., Katagas C.G., Iliopoulos I., Papoulis D.: J.Ceram Sil.,<br />
Part I companion paper, submitted.<br />
21. Lampropoulou P.: Ph.d Thesis, University <strong>of</strong> Patras, Greece, p. 208, 2003.<br />
22. White J., : High Temperature Oxides, Part I, Magnesia, Lime and Chrome<br />
Refractories, p. 77-139, Allen M. Alper, Academic Press, New York and<br />
London, 1970..<br />
23. Serry M., Hammad S.M., Zawrah M.F.M., , Brit. Ceram. Trans. 97, 275<br />
(1998) -.<br />
24. Nestola, Secco L., Prencipe M., Martignago F., Princivalle F., Dal Negro A., :,<br />
Min. Mag. 73[2], 301 (2009). -<br />
25. Hallstedt B.: J. Am. Ceram. Soc. 75[6], 1497 (1992) -.<br />
26. Wood B., Kirkpatrick R., Montez B.: Am. Min. 71[7,8], 999 (1986) -.<br />
27. Cormack A., Lewis G., Parker S., Catlow C., : J. Phys. Chem. Solids 49[1], 53<br />
(1988) -.<br />
28. Cullity B.DStock., S.R.:: Elements <strong>of</strong> X-Ray Diffraction, third edition p. 308-<br />
311, prentice Hall Upper Saddle River,, NJ, 07458, 2001.<br />
29. Deer W.A., Howie R.A., Zussman J., : An introduction to the Rock-Forming<br />
Minerals, 2 nd ed, . p560, Pearson, Prentice Hall, England, 1992,.<br />
30. Barpanda B., Behera S., Gupta P.K., Pratihar S.K., Bhattacharya S. : J. Europ.<br />
Ceram. Soc. 26[13], 2603 (2006) -.<br />
16
31. Roine A., Bjorklund P., Riikonen P.: HSC <strong>of</strong> OUTOCAMPU chemistry for<br />
windows, chemical reaction and equilibrium s<strong>of</strong>tware with extensive thermo<br />
chemical database,version 5.1, 2002.<br />
32. P. Lampropoulou. G, Katagas C. G., Papamantellos D. C., :J. Am. Ceram.<br />
Soc., 88 (6), 1568 (2005) -.<br />
33. Wilson D.R., Evans R.M., Wadsworth I., Cawley J., in: UniteCR 93, 749<br />
(1993) -.<br />
34. Aksel C., Rand B., Riley, L., WarrenP.D: J. Eur. Ceram. Soc., 22, 745 (2002)<br />
-.<br />
35. Alper A.M., McNally R.N., Ribbe P.G., Doman R.C.: J. Am. Ceram. Soc., 45<br />
[6], 264 (1962).<br />
36. Brauilio M.A.L., Bittencourtb L.R.M., Pandolfellia V.C.: J. Eur. Ceram.Soc.<br />
28[15], 2845 (2008.)<br />
37. Landy R.A.: Magnesia Refractories handbook, Marcell Dekker Inc. p109-<br />
1492004.<br />
38. Sarpolaky HZhang., S., Argent B., Lee W.: J. Am. Ceram. Soc. 84[2], 426<br />
(2001) -.<br />
39. Perepelitsyn V.A., Sivash V.G.: Refr. Ind. Ceram. , 44 (3), 165 2003. -<br />
17
Table 1: Chemical composition (ICP-MS) and bulk density <strong>of</strong> the spinel based compositions and the synthesized Magnesia-Spinel<br />
refractories.<br />
Sample Sp55z Sp73z Sp73chr M-Sp55z-L M-Sp55z-H M-Sp73z-L M-Sp73z-H M-Sp73chr-L M-Sp73chr-H<br />
%wt<br />
SiO 2<br />
Al 2 O 3<br />
Fe 2 O 3 (tot)<br />
MnO<br />
MgO<br />
CaO<br />
Na 2 O<br />
K 2 O<br />
TiO 2<br />
P 2 O 5<br />
Cr 2 O 3<br />
ZrO 2<br />
0.55<br />
46.28<br />
2.51<br />
0.03<br />
48.34<br />
1.76<br />
0.02<br />
0.06<br />
Table 2a: Representative microanalyses, lattice parameter and mean density <strong>of</strong> spinel crystals in spinel based compositions.<br />
samples Sp55z Sp73z Sp73chr<br />
wt% 1 2 Range<br />
Mean<br />
1 2 Range<br />
Mean<br />
1 2 Range<br />
Mean<br />
Al 2 O 3 70.85 69.76 69.76-71.74<br />
71.08<br />
70.47 70.56 69.36-71.25<br />
70.44<br />
70.91 68.50 68.20-70.91<br />
69.54<br />
TiO 2
Table 2b: Representative microanalyses and lattice parameters <strong>of</strong> spinel crystals in Magnesia-Spinel refractories.<br />
samples M-Sp55z-L M-Sp73z-L M-Sp73chr - -L<br />
wt% 1 2 Range<br />
Mean<br />
1 2 Range<br />
Mean<br />
1 2 Range<br />
Mean<br />
Al 2 O 3 69.62 71.06 69.61-71.33<br />
70.73<br />
69.81 69.88 69.07-70.22<br />
69.96<br />
69.33 68.34 67.34-69.33<br />
68.41<br />
TiO 2
Table 2b (cont.)<br />
samples M-Sp55z - -H M-Sp73z-H M-Sp73chr - H<br />
wt% 1 2 Range<br />
Mean<br />
1 2 Range<br />
Mean<br />
1 2 Range<br />
Mean<br />
Al 2 O 3 67.94 70.06 67.93-70.97<br />
69.77<br />
70.42 70.57 69.71-70.71<br />
70.40<br />
71.11 70.86 69.07-71.59<br />
70.88<br />
TiO 2
Table 3a: Representative microanalyses <strong>of</strong> <strong>periclase</strong> crystals in spinel based compositions<br />
samples Sp55z Sp73z Sp73chr<br />
wt% 1 2 Range<br />
Mean<br />
1 2 Range<br />
Mean<br />
1 2 Range<br />
Mean<br />
Al 2 O 3 0.25 0.13 0.11-1.01<br />
0.26<br />
0.18 0.09 0.09-1.10<br />
0.34<br />
0.18 0.18 0.11-0.18<br />
0.17<br />
TiO 2
Table 3b: Representative microanalyses <strong>of</strong> <strong>periclase</strong> crystals in Magnesia-Spinel refractories<br />
samples M-Sp55z-L M-Sp73z-L M-Sp73chr - L<br />
wt% 1 2 Range<br />
Mean<br />
1 2 Range<br />
Mean<br />
1 2 Range<br />
Mean<br />
Al 2 O 3 0.28 0.20 0.18-0.43<br />
0.25<br />
0.25 0.27 0.27-0.51<br />
0.33<br />
0.23 0.14 0.11-0.29<br />
0.20<br />
TiO 2
Table 3b (cont.)<br />
samples Magnesia-Sp 55z- H Magnesia-Sp 73z -H Magnesia-Sp 73chr- H<br />
wt% 1 2 Range<br />
Mean<br />
1 2 Range<br />
Mean<br />
1 2 Range<br />
Mean<br />
Al 2 O 3 0.24
Table 4: Microanalyses <strong>of</strong> C/A-silicates phases in spinel based compositions and Magnesia-Spinel refractories.<br />
phases C 2 S C 3 S C 3 S 2 C 3 A C C 2 S-C 3 P C 12 A 7 CZ<br />
samples M-Sp55z -L M-Sp73z-H M-Sp73chr- Sp55z M-Sp73z-l M-Sp73chr- M-Sp73chr-H Sp73z<br />
H<br />
L<br />
wt%<br />
Al 2 O 3
FIGURE CAPTIONS<br />
Figure 1: Line scan elemental pr<strong>of</strong>iles in a spinel crystal <strong>of</strong> the Sp 73chr spinel based<br />
composition.<br />
Figure 2: Raman spectrum <strong>of</strong> spinel in the Sp 73z sample.<br />
Figure 3: Periclase and spinel particles in M-Sp73chr-H. (M)= <strong>periclase</strong>; (PMA)=<br />
primary supposed spinel (SMA)= secondary spinel; (C/A-S)= Ca-silicate or<br />
aluminate;(P)= pore.<br />
Figure 4: Perforated texture <strong>of</strong> the secondary spinel in the magnesia spinel<br />
refractories.<br />
Figure 5: (a): Mg-Fe(tot)-Al+Cr ternary plot <strong>of</strong> the primary supposed spinel (PMA)<br />
in the Magnesia-Spinel refractories and in their respective raw spinel based<br />
compositions, and plot <strong>of</strong> the secondary spinel (SMA) in M-Sp55z-L, M-Sp73z-H and<br />
M-Sp73chr-H.<br />
(b):Mg-Fe-(Al+Cr) ternary plot <strong>of</strong> the <strong>periclase</strong> in the Magnesia-Spinel refractories<br />
and in their respective raw spinel based compositions.<br />
Figure 6: Histogram <strong>of</strong> Al 2 O 3 (wt%) contents in cracked and no cracked <strong>periclase</strong><br />
crystals in the spinel based compositions.<br />
Figure 7: Elemental mapping (SEM) in a <strong>periclase</strong> crystal <strong>of</strong> the M-Sp73z-H sample,<br />
using the distribution <strong>of</strong> magnesium, iron, calcium, aluminium and silicon and<br />
SEM/EDS spectra <strong>of</strong> the exsolved phases.<br />
Figure 8: Plots <strong>of</strong> coexisting spinel and periclace chemical compositions in the Sp73z<br />
and M-Sp73z-H samples on the MgO-Al 2 O 3 phase diagram [35].<br />
Figure 9a: Raman spectrum <strong>of</strong> spinel and C 3 S 2 in the Sp73z sample; b: Raman<br />
spectrum <strong>of</strong> spinel and C 2 S in the Sp73z sample.<br />
26
Fig. 1<br />
50<br />
spinel(=sp)<br />
sp(380cm -1 - )<br />
45<br />
Relative Intensity<br />
40<br />
35<br />
sp(650.02cm -1 )<br />
sp(702.5cm -1 )<br />
sp(822.5cm -1 - )<br />
30<br />
500 1000<br />
Raman Shift (cm -1 )<br />
Fig 2<br />
Fig 3<br />
28
Fig 4<br />
Fe2 + Fe3<br />
Mg<br />
b<br />
a<br />
Al + Cr<br />
Sp55z<br />
Sp73z<br />
Sp73chr<br />
M-Sp55z-L<br />
M-Sp73z-L<br />
M-Sp73chr-L<br />
M-Sp55z-H<br />
M-Sp73z-H<br />
M-Sp73chr-H<br />
b a<br />
M-Sp55z-L<br />
(SMA)<br />
M-Sp73z-H<br />
(SMA)<br />
M-Sp73chr-H<br />
(SMA)<br />
Mg<br />
Fig 5<br />
Al + Cr<br />
mean values <strong>of</strong> wt%Al 2<br />
O 3<br />
in cracked and no cracked <strong>periclase</strong> crystals<br />
0,8<br />
0,6<br />
0,4<br />
0,2<br />
0,0<br />
cracked <strong>periclase</strong><br />
no cracked <strong>periclase</strong><br />
1 2 3<br />
spinel based compositions*<br />
Fig 6<br />
*1:sp 55z ; 2:sp 73z ; 3:sp 73chr<br />
29
cps<br />
cps<br />
cps<br />
50 0<br />
Mg<br />
60 0<br />
Mg<br />
15 0<br />
Mg<br />
Al<br />
Ca<br />
30 0<br />
Al<br />
40 0<br />
10 0<br />
O<br />
O<br />
10 0 C<br />
0<br />
0<br />
20 0<br />
O<br />
C<br />
Ca<br />
Fe Fe<br />
0<br />
2 4 6 8 Energy (keV) 0<br />
C<br />
50<br />
Al<br />
Ca Fe Fe<br />
0<br />
2 4 6 8 Energy (keV) 0<br />
Ca<br />
Fe<br />
Fe<br />
2 4 6 8<br />
Energy (keV)<br />
Fig 7<br />
Temperature C<br />
o<br />
2800<br />
2400<br />
2000<br />
1600<br />
0<br />
1200<br />
0<br />
MgO<br />
Mole Al 2<br />
O 3<br />
0,2 0,4 0,6 0,8 1,0<br />
Periclase<br />
solid solution<br />
+<br />
Liquid<br />
Periclase<br />
solid solution<br />
Liquid<br />
Periclase<br />
solid solution<br />
+<br />
Spinel<br />
20 40 60 80 100<br />
Al 2<br />
O 3<br />
Wt (% )<br />
Spinel +<br />
Liquid<br />
Spinel<br />
B, b<br />
Spinel<br />
+<br />
Corundium<br />
a<br />
0<br />
Mole Al O<br />
0,2 0,4 0,6 0,8 1,0<br />
Temperature C<br />
o<br />
1600<br />
Periclase<br />
solid solution<br />
Periclase + Spinel<br />
Spinel<br />
2 3<br />
b<br />
Spinel +<br />
Corundium<br />
Fig 8<br />
1200<br />
0<br />
MgO<br />
20 40 60 80 100<br />
Wt (% )<br />
Al 2 O 3<br />
Spinel crystals in equilibrium with <strong>periclase</strong> crystals in Sp73z<br />
Spinel crystals in no equilibrium with <strong>periclase</strong> crystals in M-Sp73z-H<br />
30
70<br />
60<br />
50<br />
spinel+C 3<br />
S 2<br />
sp+C 3<br />
S 2<br />
(825cm -1 )<br />
Relative Intensity<br />
40<br />
30<br />
20<br />
10<br />
sp+C 3<br />
S 2<br />
(395.65cm -1 )<br />
0<br />
-10<br />
200 300 400 500 600 700 800 900 1000<br />
Raman Shift (cm -1 )<br />
Fig 9a<br />
Relative Intensity<br />
70<br />
65<br />
60<br />
55<br />
50<br />
spinel+C 2<br />
S<br />
sp<br />
C 2<br />
S(491.1cm -1 )<br />
C 2<br />
S(961.1cm -1 )<br />
C 2<br />
S(577.78cm -1 )<br />
sp C C 2<br />
S(1122.2cm -1 2<br />
S(855.56cm -1 )<br />
)<br />
45<br />
Fig 9b<br />
40<br />
300 400 500 600 700 800 900 1000 1100 1200<br />
Raman shift (cm -1 )<br />
31
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