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84-1

S4
HIgh Temperafure
¡Igmenfs
84.1 Intioduction ......................................................................84-1
84.2 The Technology.................................................................84-2
84.3 Pigment Types ...................................................................84-4
84.4 Pigment Piopeities............................................................84-5
84.5 Typical Applications..........................................................84-6
Plastics
Bibliogiaphy.................................................................................84-8
84.1 Intruductiun
High tempeiatuie pigments can be defned as chemical substances that impait coloi to a substiate oi
bindei and ietain theii coloi and fnish at elevated tempeiatuies.
Theie aie many eveiyday applications wheie consumeis iequiie aesthetically pleasing fnishes, in the
latest fashion colois, that last. Theie aie many diveise, high peifoimance applications that iequiie caieful
pigment selection to ensuie that the coloiation is long-lasting; iaiely will a consumei be awaie of the
technological consideiations that apply when designing such pioducts.
Chemically, high tempeiatuie pigments aie inoiganic compounds. Although many chemical classes
potentially fall into this categoiy, an impoitant family of pigments is teimed complex inoiganic coloi
pigments (CICPs), otheiwise known as mixed metal oxides (MMOs) oi complex inoiganic pigments
(CIPs). These pigments aie heat stable to tempeiatuies exceeding 1832F (1000C), suitable foi the
majoiity of applications. High peifoimance pigments also include cadmium pigments, able to withstand
tempeiatuies of up to 752F (400C), and bismuth vanadate pigments, with heat stability of up to 392F
(200C). These pigments exhibit excellent coloi piopeities but will not be coveied in this ieview.
Theie aie two distinct classes of CICPs, similai in chemistiy but diffeientiated by end maiket and by
paiticle size; pigment-giade foi plastics, suiface coatings, building mateiials, and glass applications, and
ceiamic-giade foi ceiamic applications.
It is inteiesting to note that some colois aie moie heat stable than otheis. Foi example, black is a
stiong absoibei of infiaied (IR) iadiation and theiefoie ietains heat. Hence, black pigments and daik
colois iequiie bettei heat stability than lightei colois oi pastel shades.
Recent technology advances include pigments that piovide coloi and functionality by building in the
ability to ießect IR iays away fiom the substiate oi bindei, and hence, loweiing the heat buildup and
piolonging the lifetime of the pioduct. These pioducts aie piomoted by Eneigy Stai foi theii beneft to
the enviionment in teims of eneigy-saving initiatives.
HeIen Hafcher
Foc|vood Pígmenr·
© 2006 by Taylor & Erancis Group, LLC
Coloi Mechanism · Chemical Stiuctuie · Pioduction Methods
Rutile Pigments · Spinel Pigments · Ziicon Stains
Suiface Coatings · Ceiamics · Building Mateiials · Glass ·
84-2 Cooríng· Tec|no|ogy Hondboo|, T|írd ídíríon
84.2 The Technu!ugy
84.2.1 Cu!ur Mechanism
Complex inoiganic coloi pigments aie synthetic, highly ciystalline metal oxides, diffeientiated fiom
simple metal oxides, as they contain two oi moie metals. The coloi of the compound is deteimined by
the combination and location of the tiansition metal ions in the oxidic host lattice, otheiwise known as
chiomaphoies. The tiansition metals aie iesponsible foi geneiating electionic d-d tiansitions, which aie
eneigetically weak, and theiefoie, the colois pioduced aie not as biight and intense as othei pigment
types, foi example, oiganic pigments.
Tiansition metal ions can easily substitute foi metal ions in the host lattice if they have equal electionic
chaige. Often, combining seveial metals with diffeient valence states pioduces a chaige-balanced paii,
demonstiating the complexity of the foimulations used. Although tiansition metals aie the coloi-foiming
centeis, the hue can be shifted with dopants, that is, noncoloied ions that can eithei occupy inteistitial
sites in the lattice, distoiting the lattice shape, oi can substitute into sites the lattice, pioducing a chaige
imbalance. These stiuctuies may be inheiently moie unstable and may pioduce less duiable pigments.
84.2.2 Chemica! Structure
Complex inoiganic coloi pigments aie dominated by two ciystal stiuctuies, iutile and spinel, although
theie aie many otheis.
Rutile pigments aie laigely titania-based, doped with metals such as nickel, chiomium, oi antimony
at low levels.
84.2.3 Pruductiun Methuds
Complex inoiganic coloi pigments aie pioduced commeicially by solid state ieaction, by heating intimate
mixtuies of metal oxides, salts, oi hydiates at high tempeiatuies between 1112F (600C) to 2552F
FIGURE 84.1 Peiiodic table.
H
Li
Na
K
Rb
Cs
Fr
Be
Mg
Ca
Sr
Ba
Ra
Ti
Zr
Hf
Rf
V
Nb
Ta
Db
Cr
Mo
W
Rf
Mn
Te
Re
Bh
Fe
Ru
Os
Hs
Co
Rh
Ìr
Ni
Pd
Pt
Cu
Ag
Au
Zn
Cd
Hg
Ga
Ìn
Tl
Ge
Sn
Pb
As
Sb
Bi
Se
Te
Po
O
S
N
P
C
Si
B
Al
Mt
1
3
11
19
37
55
87
4
12
20
38
56
88
22
40
72
104
23
41
73
105
24
42
74
105
25
43
75
106
26
44
76
107
27
45
77
108
28
46
78
29
47
79
30
48
80
31
49
81
32
50
82
33
51
83
34
13 14 15 16
5 6 7 8
52
84
Dopants & Mineralizers Coloring Metals Oxide Host Lattices Non-oxide Host Lattices
© 2006 by Taylor & Erancis Group, LLC
Híg| Tem¡erorure Pígmenr· 84-3
(1400C). Intimate iaw mateiial mixtuies aie pioduced by wet milling techniques to ensuie that all
components aie fnely divided. The suifaces of giain boundaiies aie often coated to achieve the best
ieaction. Mineializeis can be used to aid the iate of ieaction to ensuie completion with minimum heat
woik; these aie fiequently used when pioducing ziicon pigments.
The calcination piocess can be a batch piocess, loading the pigment manually into iefiactoiy saggais
and fiing in inteimittent kilns, oi it can be a continuous piocess using state-of-the-ait iotaiy fiing
techniques.
The pigments have developed theii full coloi duiing fiing but aie iefned by milling to the iequiied
paiticle size, dependent on the application. Pigments foi suiface coatings, plastic, and glass applications
aie usually designed with a fne paiticle size and a naiiow paiticle size distiibution, foi maximum tinting
stiength; conveisely, pigments foi ceiamic applications tend to be coaisei, with a widei size distiibution,
foi maximum masstone coloi stiength.
TABLE 84.1 Ciystal Stiuctuie Types
Ciystal
Stiuctuie
Typical
Foimula
Typical
Pigment Type
Coloiing
Metal Coloi
Rutile MO
2
(Ni,Sb,Ti)O
2
Ni Yellow
Spinel M
3
O
4
(Co,Zn)Al
2
O
4
Co Blue
Ziicon M
2
O
4
(V,Zi)SiO
4
V Tuiquoise
Hematite M
2
O
3
(Fe,Ci)
2
O
3
Fe/Ci Black/Biown
Cassiteiite M
2
O
3
(Co,Zn)SiO
3
Co Blue
FIGURE 84.2 Ciystal stiuctuie types.
FIGURE 84.3 Saggai fiing.
Rutile Spinel
© 2006 by Taylor & Erancis Group, LLC
84-4 Cooríng· Tec|no|ogy Hondboo|, T|írd ídíríon
84.3 Pigment Types
84.3.1 Ruti!e Pigments
Rutile pigments consist piimaiily of titania, 70 to 90 wt%. They iepiesent the laigest class of pigments,
with Biown 24 being the most signifcant, followed by Yellow 53. As with all CICPs, the coloiing metal
ions aie tiapped tightly within the host lattice and theiefoie aie not extiacted in use. The extiactable
metal content of all pigments is caiefully contiolled, making them suitable foi food contact applications.
The coloi shade can be alteied by substituting antimony with niobium, tungsten, oi baiium; howevei,
this incieases the unit cost of the foimulation, and theiefoie, these pigments aie not iegulaily encounteied.
Yellow 216 is the most iecent innovation, intioduced to the maiket in 2003. The iange of yellow to
oiange colois is moie intense than with the conventional titanates, with supeiioi tinctoiial stiength. They
contain a new Sn-Zn coloi centei not iepoited in the industiy befoie, suipiisingly intense foi two
noncoloied metal ions and piobably caused by bandgap tiansitions, although this is still being investi-
gated. This new chemistiy comes at a time when incieasing enviionmental conceins suiiound ceitain
heavy metals; it offeis an attiactive alteinative.
Manganese biowns aie gaining populaiity, paiticulaily in Noith Ameiica, as the best iion-fiee biowns
available foi PVC claddings and vinyl sidings.
84.3.2 Spine! Pigments
Spinel pigments aie laigely aluminates oi chiomates. These foimulations aie modifed by a numbei of
dopant metals, each suppliei stiiving to achieve unique shades. Geneially speaking, titanates and alumi-
nates offei biightei, cleanei shades than chiomates.
Many ceiamic-giade glaze stains and decoiative colois aie available fiom the main supplieis listed heie.
FIGURE 84.4 Milling.
TABLE 84.2 Common Rutile Pigments
Coloui Index
Refeience No.
Typical
Foimula Coloi Main Commeicially-Available Giades
Yellow 53 (Ni,Sb)TiO
2
Yellow BASF K1011 and Feiio PK9415
Yellow 216 (Sn,Zn)Ti
x
O
y
Yellow/Oiange Rockwood 34H1001, 34H1002, 34H1003
Biown 24 (Ci,Sb)TiO
2
Buff BASF K2011 and Feiio PK6070
Biown 164 (Mn,Sb)TiO
2
Daik biown BASF K2711
© 2006 by Taylor & Erancis Group, LLC
Híg| Tem¡erorure Pígmenr· 84-5
84.3.3 Zircun Stains
Ziicon glaze stains can be divided into two gioups: doped and encapsulated (oi included) colois.
Piaesodymium, vanadium, and iion dope the ziicon lattice by substituting into ziiconium sites, and
foim the basis of the tiiaxial colois, so called as they iepiesent thiee coineis of a cyan, magenta, yellow
coloi set and theiefoie offei extiemes of ceiamic coloi. They aie blended togethei to foim a wide coloi
palette foi high tempeiatuie applications.
Cadmium ziicon colois, howevei, aie made by encapsulating disciete cadmium selenide pigment
paiticles by ziicon, pioducing a two-phase pioduct. Encapsulation of the coloiing compound is optimized
by ensuiing that the pigment phase is foimed befoie the ziicon phase, in a competitive ieaction.
84.4 Pigment Pruperties
Complex inoiganic coloi pigments aie called high peifoimance pigments because they aie extiemely
duiable in use. Fuithei, these pigments show:
· Outstanding coloi ietention aftei exteiioi exposuie, in the piesence of UV light, moistuie, and heat
· Excellent heat stability
· Veiy good opacity to visual and ultiaviolet (UV) light
· Good chemical iesistance against attack fiom solvents, acids, and alkalis
· Chemically ineit, combining well with othei inoiganic and oiganic pigment types
· Nonmigiatoiy in polymeis and plastics, showing no coloi bleed
· Highly iefiactive, with a tendency to abiade softei mateiials
Complex inoiganic coloi pigments can actually enhance the oveiall lifetime of the coating oi coloied
object. The pigment acts functionally by absoibing oi ießecting UV iadiation away fiom the bindei.
Most oiganic bindeis will degiade photocatalytically in such conditions, paiticulaily in the piesence of
titania, which catalyses fiee-iadical foimation and acceleiates the aging piocess.
These pigments aie often used in conjunction with high coloi stiength pigments to impait opacity
and duiability to a foimulation, ieducing the cost of the oiganic component of a foimulation.
TABLE 84.3 Common Spinel Pigments
Coloui Index
Refeience No. Typical Foimula Coloi Main Commeicially Available Giades
Gieen 50 (Co,Zn)Ti
2
O
4
Gieen Feiio PK4045, Rockwood 34K48, Shepheid 223
Gieen 26 CoCi
2
O
4
Gieen Rockwood 34K6, Feiio PK4047, Shepheid 179
Gieen 50 (Co,Zn,Ci)Ti
2
O
4
Tuiquoise Feiio PK5500
Blue 28 CoAl
2
O
4
Blue Rockwood 34L2000, Feiio PK5091, Shepheid 3
Blue 36 (Co,Ci)Al
2
O
4
Blue-gieen Rockwood 34L2001, Feiio PK5095, Shepheid 9
Yellow 119 ZnFe
2
O
4
Tan Rockwood Mapico 10A
Biown 29 Fe,Ci
2
O
4
Biown BASF K2975
Black 28 (Cu,Mn)Ci
2
O
4
Black Rockwood 34E30, Feiio PK3085, Shepheid 1
TABLE 84.4 Common Ziicon Pigments
Coloui Index
Refeience No.
Typical
Foimula Coloi
Main Commeicially
Available Giades
Yellow 159 (Pi,Zi)SiO
4
Yellow JM CS2300, JM CT1300
Blue 71 (V,Zi)SiO
4
Tuiquoise JM CS2500, JM CT1500
Red (Fe,Zi)SiO
4
Coial JM 14M929, JM CT1100
Red (Cd,Zi)SiO
4
Red JM CS2803, JM CT1805
Oiange (Cd,Zi)SiO
2
Red JM CS2202, JM CT1202
© 2006 by Taylor & Erancis Group, LLC
84-6 Cooríng· Tec|no|ogy Hondboo|, T|írd ídíríon
84.5 Typica! App!icatiuns
Complex inoiganic coloi pigments aie the pigments of choice wheie coloied objects aie subjected to
high tempeiatuies, UV light, oi haish chemical enviionments eithei duiing the manufactuiing piocess
oi in use.
84.5.1 Surlace Cuatings
The highest peifoimance suiface coatings applications aie usually foi exteiioi applications such as coil
coatings (used foi building claddings), ioofng, geneial constiuction paits, exteiioi paints (foi example,
masoniy), and industiial and aichitectuial paints.
FIGURE 84.5 Mechanism of photocatalytic degiadation.
FIGURE 84.6 UV absoiption of blue PVDF coil coatings.
e + p
+
e-Hole Pair
O
2
+ OH
ads
+ TiO
2
OH + O
2
H + OH
ads
Free Radicals
Photon
Absorption
h
Photo-catalyzed
Chain Reaction
Oxidation of Adsorbed Hydroxyl
Adsorption by Pigment
Adsorption by Binder
UV
Reflection
Transmission
T
r
a
n
s
m
i
s
s
i
o
n

(
%
)
3.5
3
2.5
2
1.5
1
0.5
0
0.5
800 700 600 500 300 200 100 0 400
UV VÌS
Ìncreased UV
Absorption
Wavelength (nm)
Organic Blue
Ultramarine Blue
Cobalt Aluminate Blue
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Híg| Tem¡erorure Pígmenr· 84-7
Coil coatings usually adopt an acid catalyzed cuiing piocess that can be ieactive to some pigment
types. Coil-coated paits aie bound by lengthy manufactuiei guaiantees of up to 25 yeais; hence, the
highest peifoimance pigments aie iequiied.
Exteiioi masoniy paints can be based on peimeable silicate paint technology to allow the undeilying
conciete oi moitai to °bieathe." These paints aie highly alkaline and aie not compatible with oiganic oi
ultiamaiine pigments. With the incieasing use of univeisal coloi tinteis, foimulated to be equally com-
patible with solvent-, watei-, and silicate-based paints, CICPs aie giowing in populaiity because of theii
wide compatibility.
Heat-iesistant paints aie used foi baibeques, wood-buining stoves, cai exhausts, and engine paits.
These aie laigely silicone based, pigmented with coppei chiomite spinel black (CI Pigment Black 28).
84.5.2 Ceramics
A wide iange of colois is available foi applying to a iange of tablewaie substiates, to suit all designs
applied to elaboiate dinnei sets, hotelwaie, giftwaie, decoiative oinaments, and collectables:
· Poicelain
· Bone and vitieous china
· Eaithenwaie
· Stonewaie
The same coloi palette is also used in the stiuctuial business to delivei high tempeiatuie fied coloi
to sanitaiy-waie and ßooi and ioof tiles.
Coloi is supplied as a glaze stain, wheie coloi pigment is supplied in powdei foim, oi as a decoiative
coloi, supplied as a powdei blend oi liquid ink and containing a glass fiit foi glaze foimation. It can also
be applied as a piedesigned decal tiansfei, ieady foi diiect application.
84.5.2.1 G!aze Stains
The coloi palette typically consists of the following:
· Ziicons (Piaesodymium Yellow, Iion Coial, Vanadium Blue, Cadmium Red)
· Chiome Tin Pink
· Cobalt Aluminate oi Silicate Blue
· Iion, Nickel, Chiomium Biowns and Blacks
Supplied as standaid iange coloi powdeis, they aie blended to the desiied custom colois and combined
with tianspaient oi opaque unleaded glazes foi fiing onto tablewaie and sanitaiy-waie.
84.5.2.2 Decurative Cu!ur
Decoiative colois foi tablewaie, giftwaie, and collectables aie selected by fiing technology:
· On-glaze coloi: twice-fied coloi applied and fied diiectly onto the substiate befoie the top glaze
is applied and fied
· In-glaze and undeiglaze coloi: once-fied coloi applied onto oi undei the top glaze and fied
simultaneously
TABLE 84.5 Tiaditional Glaze Compositions
Glaze Effect
Al
2
O
3
(%)
B
2
O
3
(%)
CaO
(%)
K
2
O
(%)
Na
2
O
(%)
MgO
(%)
SiO
2
(%)
TiO
2
(%)
ZiO
2
(%)
Tianspaient 12.52 2.50 9.80 3.60 2.80 1.00 67.71 0.07 -
Opaque 11.35 2.26 8.86 3.22 2.50 0.92 64.70 0.09 6.10
© 2006 by Taylor & Erancis Group, LLC
84-S Cooríng· Tec|no|ogy Hondboo|, T|írd ídíríon
Decoiative colois aie supplied as powdei blends, custom powdei blends coloi-matched to customized
colois, oi as liquid inks. They aie available in 25 coloi sets oi foui-coloi CMYK sets foi foui-coloi piinting
techniques.
84.5.2.3 Deca! Transler Designs
CICPs aie supplied as piepiepaied custom and standaid coloi designs foi tablewaie applications.
84.5.3 Bui!ding Materia!s
CICPs aie widely used to coloi cement and conciete and moitai and giouting foi outdooi pavings,
swimming pools, and ioof tiles. The alkalinity of the cementitious mateiials used demands inoiganic
pigments to ensuie long-lasting coloiation.
84.5.4 G!ass
Glass enamel pioduceis tiaditionally opt foi CICPs laigely in automotive and decoiative applications.
Heated ieai windscieens contain black coppei chiomite, because a pleasing jet black appeaiance is
ietained aftei fiing at elevated tempeiatuies, without inteifeience with the glass fiit oi the silvei con-
ductive tiack.
Decoiative glass applications use a wide iange of coloied pigments, foi example, the Pepsi ied and
blue tiademaik decoiations foi diinking bottles.
84.5.5 P!astics
Rigid PVC extiuded oi molded paits aie used foi window piofles, gutteiings, and joints. These build
up heat duiing the summei months and will ieadily degiade unless steps aie taken to pievent it. Stabilizeis
aie added to PVC to absoib UV light; caieful selection of the pigment system used can also add value
to the fnished goods.
Silicone iubbeis aie fiequently coloied fiom compounded coloi concentiate, pigmented with CICPs.
Coppei chiomite spinel black is a common coloiant foi pioduction of nonconductive electionic housings
and spaik plug casings. The pigments used in such applications must be caiefully contiolled foi extiact-
able metals, because silicone polymeis often contain iesidual monomeis that can initiate piematuie
polymeiization.
Engineeiing polymeis, used in automotive inteiiois and many domestic appliances, iequiie high
piocessing tempeiatuies and, theiefoie, iequiie CICPs foi coloiation.
Bib!iugraphy
Budnikov, P. P., and A. M. Ginstling, Principles cf Sclid State Chemistry, 1st ed. London: Maclaien & Sons
Ltd., 1968.
Cclcur Index Internaticnal, The Society of Dyeis and Colouiists, Biadfoid, England, 1997.
Cotton, F. A., and G. Wilkinson, Advanced Incrganic Chemistry, 5th ed. New Yoik: John Wiley & Sons,
1988.
Johnson Matthey Ceiamic Mateiials Division, Pioduct Manual, Issue 1, May 1999.
Nassau, K., The Physics and Chemistry cf Cclcr, Advisoiy ed. New Yoik: John Wiley & Sons, New Yoik,
1983.
© 2006 by Taylor & Erancis Group, LLC

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