Combinatorial and High-Throughput Screening of Materials ...

ACS Combinatorial Science
REVIEW
Figure 24. Structural phase diagram produced using the weights of the
basis diffraction patterns found using non-negative matrix factorization
(NMF). Each pie chart corresponds to a composition for which XRD
was measured and each piece of the pie chart corresponds to the weight
of one of the basis patterns found using NMF. Possible matches to a
database of known patterns are presented at the top left. From 237.
Applied physics letters by AMERICAN INSTITUTE OF PHYSICS.
Reproduced with permission of AMERICAN INSTITUTE OF PHY-
SICS. in the format Journal via Copyright Clearance Center.
adhesion, 35,247,248 abrasion/scratch resistance, 34,247 viscosity, 249
surface energy, 249 251 weatherability, 252 pot-life, 253 corrosion
inhibition, 254 viscoelastic properties, 255 256 262
fouling-release,
antimicrobial properties, 263,264 scrub resistance, 265,266 hardness,
267 cross-link density, 268 and barrier properties. 269
3.3.1. Cross-Linkers for Polyurethane Dispersions. The application
of CHT methods to coating development is relatively new
with the first description of a full CHT workflow being reported
in 2002. 247 One of the first reports focused on the CHT production
and characterization of coating libraries using a CHT workflow
was that of Bach and co-workers. 270 This report pertained to
the use of a CHT workflow to assess the relative degree of crosslinking
for binders derived from polyurethane dispersions. The
cross-linkers studied were polyaziridine compounds with the
general structure shown in Figure 25. Polyazirdine cross-linkers
react with carboxylic acid groups of water-dispersible polyurethanes
to form an ester cross-link. The study involved variations
in polyurethane composition, cross-linker composition, cosolvent
composition, urethane dispersion pH, and the time period between
cross-linker addition and film formation. The cross-linked
networks were screened using a fluorescence assay that involved:
(1) dissolution of a chemically inert fluorescent dye in the coating
solution; (2) production of a cured film in a container using film
casting; (3) extraction of a portion of the dye from the coating by
the addition of a solvent to the container holding the cured film;
and (4) quantification of the amount of dye extracted using a
fluorescence intensity measurement. With this assay, it is assumed
that lower fluorescence intensity is indicative of higher cross-link
density. Several thousand coating films were screened in the study,
and it was found that polyurethane composition and cross-linker
concentration dominated the response. Polyaziridine cross-linker
composition resulted in relatively small differences in cross-link
density. A major observed second-order interaction was between
cross-linker concentration and pH of urethane dispersion.
3.3.2. Polyurethane-Siloxane Fouling-Release Coatings. A
large majority of the polymer-based coating libraries described
Figure 25. Chemical structure of the polyazirdine cross-linkers utilized
by Bach and co-workers. 270
in the literature pertain to coatings designed to combat biofouling,
primarily, marine biofouling. The Webster Research Group
at North Dakota State University has been investigating the
concept of producing tough, fouling-release coatings from crosslinked
polyurethanes modified with polysiloxane segments.
271 273
With this concept, the lower surface energy polysiloxane was
expected to self-segregate to the coating/air interface while the
majority of the coating bulk was expected to be the tough
polyurethane. With this morphology, good-fouling release properties
were anticipated based on the low surface energy, PDMS-rich
surface. Initial screening studies involved the production of coatings
based on either aminopropyl-terminated polydimethylsiloxane
(NH 2 PDMS NH 2 ) or hydroxyethyloxypropyl-terminated
polydimethylsiloxane (HOCH 2 CH 2 PDMS CH 2 CH 2 OH) as
the PDMS component and isocyanaurate trimers of isophorone
diisocyanate or hexamethylene diisocyanate as the isocyanate
component. 273 Numerous compositional variables were explored
using CHT methods including siloxane content, solvent composition,
and siloxane chemical composition. A total of 82 unique
coating compositions were screened. High-throughput measurements
of surface energy and pseudobarnacle adhesion were used to
characterize coating surface compositional stability after water
immersion and fouling-release properties, respectively. A key
observation was that solvent composition played an important
role in coating surface stability and fouling-release performance.
Follow-up efforts were focused on coatings derived from a
hydroxy-functional PDMS, a trifunctional polycarprolactone
polyol, and a polyfunctional isocyanate based on isophorone
diisocyanate. 271 With this coating system, segregation of PDMS
chain segments to the coating/air interface was demonstrated.
Interestingly, coating compositions derived from the lowest concentration
of hydroxy-functional PDMS, which was 10 wt %,
showed a microstructured surface comprised of dispersed domains
rich in PDMS with an average domain diameter of 1.4 μm and
height of 50 nm. Surface microstructure was found to be dependent
on solvent composition and mixing time after the addition of
604 dx.doi.org/10.1021/co200007w |ACS Comb. Sci. 2011, 13, 579–633