NEW L U S T E R

COLORS

FOR GLASS

AND PORCELAIN

(UDC 666.291.5 + 661.872.7)

Cand,

Tech.

Sci.

P, A.

Levin

Dulev Color Works

Translated from Steklo i Keramika, Vol. 23, No. 1,
pp. 26-29, January, 1966

Luster c e r a m i c colors are distinguished by high transparency and brilliance. By altering the thickness and
technique of application and using diluents it is possible to vary the intensity and tone of the colors of each luster
and to obtain peculiar decorative effects [1] and to reduce the cost of the de6oration. In addition to the traditional
use of preparations involving lusters, use is also being found for these materials in the production of building c e r a m ics and in architecture [2].
Lusters used for glass require special properties. They should be homogeneous, have satisfactory viscosity and
fluidity, optimum drying rates, and other qualities, tn contrast to lusters used for porcelain, glass lusters after firing
"work" in transmitted and not in reflected light, and a l l defects (streakiness, dots, irregularity of color, etc.) b e c o m e noticeable. Pottery lusters as a rule are unsuitable for decorating glass because of their technical properties
and poor coloring intensity. At the same t i m e most glass lusters are universal (~r
the use of the appropriate flux).
The development of lusters for glass in our factory started in 1958-59 when a purple luster was obtained on
the basis of liquid gold, phenyl siloxane resin, stable c a d m i u m resinate, and the appropriate solvents,
Before firing, the lusters consist of liquids similar to ordinary lacquers. The f i l m - f o r m i n g agents in t h e m are
organic compounds of metals and silicon which are decomposed in the process of firing on the glass and porcelain
with the formation of a stained layer of oxides and metals. In selecting solvents we do not always use methods of
l a c q u e r - p a i n t production [3] where aliphatic compounds and resfnates of many metals have not found extensive use
as f i l m - f o r m i n g agents, and their behavior during solution and their state in solution has been inadequately investigated. Furthermore, lusters possessing good lacquer properties after firing often prove to be unsatisfactory in terms
of decorative and t e c h n i c a l properties.
The properties of lusters depend on the external conditions, the m e t a t l i c compounds used in the composition
of the lusters (and silicon),and the solvents. To obtain brightly colored lusters we need to introduce the m a x i m u m
amount of coloring compounds - metals and their oxides. The content of the latter in the resinates and soaps used
for lusters is normally not high. At the same t i m e the introduction into the recipe of a large amount of h i g h - m o lecular soaps increases the viscosity of the composition. The lusters flow poorly, produce streakiness on the d e c o rative film, or form a thick layer which during firing often cracks. Upon storage these lusters produce a lot of
deposit and sometimes g e l a t i n i z e .
Investigations on the development of orange lusters* were carried in the following directions: producing c o m pounds of iron s o h b l e in organic solvents, the choice of the basic (incombustible) components, o p t i m i z a t i o n of the
lacquer properties of the luster colors.
The following were tested in various quantities and combinations: FezO 3 (1-3%), TiO z, PbO, ZnO, SnO 2, CdO
(about 1~
SiO 2 (up to 3~
BzOa (up to 0.5~
M e t a l l i c resinates, silicone lacquer FG-9,and boroisoamyl ester
were used as the carrier for these oxides.
The purely iron oxide lusters after firing had a satisfactory brilliance, bonding power, and brightness of color,
proportional to the percentage of F%O a. With an iron oxide content of less than 1.5~ the lusters were weak in color.
By adding BzOa or TiO 2 i t was possible to improve the color and shine of the luster. The remaining oxides
gave the lusters dirty yellow (ZnO), pale straw,and brown shades, impairing their decorative attraction. In the
* Z. I. Pokutaeva assisted in this work.

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~0

i _.2V~

/,5

J-!7,
r T-y ;

1\\ \

---

x\
0,5

Fig.

es0

....

___
\\

....L ~

-'---I

500
550 600
~/~56,
Wavelength in m/~

1. Spectral transmission curves for

purple luster colors. 1) No. 26; 2) English
product No. 405-C

..

'--3

20
0 ......

_~___~

OOO

500

600-

Wavelength in mp
Fig. 2. Spectral transmission of lusters. 1) Orange
No. 316; 2) dove-blue No,
73; 3) smoky gray No. 56.

system FezOs-SiOz-BzO3 (Fe20 a 1.6%),the amount of SiO z in one series of tests was varied from 0.18 to 1.8 moles
with a constant content of 0.38 moles B20 3 per 1 mole of FezO 3. The composition of the luster film (without taking
into account its reaction with the substratum) gradually altered from basic to neutral. In other experiments we varied
the content in the lusters both of the SiO 2 and the B20 3 and the composition of the luster gradually changed from a
strong basic to a weakly basic composition. In the third series the BzO3 was excluded and the molecular ratio
Fe20 3 : SiO 2 was varied from 4 : 1 to 2 : 3. With change in the composition of the basic silicates to acid we noted a
deterioration and then a complete loss of brilliance. Upon substitution of B2Osfor equivalent amounts of SiO 2 there
was a marked deterioration in color and in the basic brilliance of the lusters.
In the orange lusters we tested various quantitative ratios of benzene, xylene, chloroform, turpentine, nitrobenzene, cyclohexanol, tetraHn, and ester oils, and from these selected chloroform, turpentine, and tetralin.
For the production of orange lusters we use benzoate, precipitated iron resinate, and more often iron soap [4]
from which in our plant we obtain a light orange luster for porcelain which is of poor stability for storing and also
in terms of tone. The naphthenates, aliphatic salts, and other organic s o h b l e compounds of iron in the composition
of the lusters are generally not used; therefore we carried out work aimed at synthesizing fusible and precipitated
iron resinates, commercial iron soap, oleates, naphthenates, and benzoate of iron. We investigated their solubility
and certain other properties. All the compounds obtained were tested as components of luster colors.
The m e c h a n i c a l impurities in the h]sters tended to form a matte or heterogeneous decorative finish. This
cause atso produced only partly soluble fused resinate and certain oleates and naphthenates of iron which are not
suitable for lusters.
From the c o m m e r c i a l iron soap, precipitated resinates of iron, and benzoate we obtained lusters of inadequate
fluidity with a tendency to gelatinization and precipitation of deposits during standing. With a reduction in the
concentration of these substances, the lusters proved to be of weak color and unsuitable for decorating glass.
Lusters made from soluble oleates having excellent lacquer properties before firing did not possess brilliance
typical of lusters and had an unacceptable brown color after the firing process.
The poor quality of the lusters tested is due apparently to the substantial aggregation of the molecules in the
soap and the solution connected with the presence in many of them of free oxy groups. In connection with this, we
synthesized and tested highly soluble mixed b e n z o i c - a l i p h a t i c compound (soap) of iron which does not have free
oxy groups in the structure. Determination of the molecular weight of the substance showed that its particles in
benzene solution consist only of two molecules.
The use of this compound with additions of 0.8% B20s permitted us to develop a stable, intensely colored
orange luster No. 316 of the following composition (%): 27.2 b e n z o i c - a l i p h a t i c compound of iron (10.9% strength),
4.6 boroisoamyl ester (11% strength), 45-50 turpentine, 20-22 tetralin, and 0 chloroform.
The luster is stable during firing and resistant to temperatures of 550-900~
It possesses good adhesionto glass,
porcelain, and earthenware and can be used on each of these materials. In a very short time the output of this luster
will reach the level of production of the most popular luster colors.

32

Smoky (neutral) lusters and silver preparations can be obtained on the basis of the turpene sulfide of platinum
or 12% preparation of this agent; however, simple dilution of the preparation to a content of 1 . 4 5 Pt gives lusters
which are not well bonded to the glass and unsatisfactory in terms of other t e c h n i c a l properties.
The tone and bonding c a p a c i t y of platinum lusters made from metals and oxides are affected in the following manner.
Au in amounts of 2-2.5 times the weight of the Pt increases their optical density and makes it possible to reduce the content of Pt in the solution to 0.5-0.6%. Under these conditions, the lusters after firing remain smoky in
transmitted light or "silvery" in reflected light.
PbO slightly affects the adhesion of the fired lusters to the glass. The resistance of the luster to abrasion does
not change in the range 0 . 4 - 1 . 5 5 PbO in solution.
Bi203 substantially improves the adhesion. The o p t i m u m amount of Bi oxide in the luster is 0.7%.
content of more than 1-1.5% Bi there is a reduction in the m e t a l l i c shine or it disappears.

With a

Mn20 a gives the lusters an u n a c c e p t a b l e brown shade.

B203 improves the shine and tone of the lusters, and contributes to the formation of a uniform color. The opt~mum addition is 11% strength boric ester in amounts of 1.8%.
SiO 2 with a content of more than 0.05% gives the luster a brown shade and impairs its brilliance.
To improve the tone of the lusters we tested resinates of cobalt, tin, chromium, vanadium, and nickel,and
additions of various lusters of blue and green shades. The lusters are favorably affected by small amounts of chrom i u m and rhodium. Therefore, we should introduce gold into smoky lusters in the form of preparations of liquid
gold containing these elements.
The optimum composition for glass (out of 56 tests) was smoky luster composition containing (%): 0.6 Pt,
1.6 Au, 0.7 Bi2Oa, 0.2 BzO3, 0.008 Cr2Oa, 0.007 Rh. Dilution weakens the color and reduces the m e t a l l i c shine. With
an increase in the content of platinum (up to 1-1.2%) and gold the m e t a l l i c effect begins to be predominant in the
decorative properties. This luster, despite the lower (by a factor of 3-3.5) content of noble metals compared to
liquid gold, has the form and properties (stability, resistance to corrosive agents, adhesion to porcelain) of the latter
preparation but gives a silvery mirror film instead of the gold effect which is not always desirable. The "silvery"
preparations can be used in the decoration of porcelain and glass instead of the more expensive liquid gold, e s p e c i a l ly in combination with black and certain other colors.
Another interesting feature of the silver preparation is the high e l e c t r i c a l conductivity (R units in tenths of
one ohm/cruZ). Purple luster No. 26 containing a large amount of Au only (4.2%) compared with 1% Pt and 2.6%
Au has an e l e c t r i c a l conductivity like other lusters close to zero. The e l e c t r o - t e c h n i c a l properties of the film can
vary in wide limits as a result of dilution, concentration, or changing the thickness of the application. It is possible
to use platinum lusters for obtaining thin current conducting coatings, contacts, etc. on glass and ceramics.
As a solvent supplementary f i l m - f o r m i n g agent and thickening agent for lusters we used ethyl benzoate,
turpentine, chloroform, nitrobenzene and rosin.
Our factory is making an intense purple luster No. 26 (4.2% Au, 2.3 CdO, 3.7 SiO~) for finishing and decorative work, No. 190 purple-rose (2.5% Au) for surface coloring, and No. 191 ( 3 . 7 9 Au) possessing i n t e r m e d i a t e properties. In terms of t e c h n i c a l quality and spectral characteristics lusters No. 26 are as good as the best specimens (Fig. 1).
A start has been m a d e on the production of a d o v e - b l u e luster for glass (0.5% An). Work is being done on the
preparation of iridescent lusters.
The spectral properties of the lusters are shown in Fig. 2.
LITERATURE
1.
2.

3.
4.

CITED

P. A. Levin, Steklo i Keramika, No. 4 (1961).

R. Miller, Glass Industry, Vol. 45 (1964), p. 609; G. Allison, J. Canad. Ceram. Soc. (196Z), p. a6.
K. Weinmann, Farbe und Lack, Vol. 65 (1959), p. 450.
E. I. Orlov, Glazes, Enamels, C e r a m i c Colors, and Bodies [in Russian], Part I, 3rd Edition, Narkommestprom,
RSFSR (1987); F. Viehweger, Rezepthnch fur Glasurben-Farben (1959).

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