CA1074955A - Decoration for ceramics having the appearance of gold - Google Patents
Decoration for ceramics having the appearance of goldInfo
- Publication number
- CA1074955A CA1074955A CA260,952A CA260952A CA1074955A CA 1074955 A CA1074955 A CA 1074955A CA 260952 A CA260952 A CA 260952A CA 1074955 A CA1074955 A CA 1074955A
- Authority
- CA
- Canada
- Prior art keywords
- palladium
- silver
- gold
- composition
- appearance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
- C04B41/5111—Ag, Au, Pd, Pt or Cu
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/88—Metals
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/28—Other inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/17—Deposition methods from a solid phase
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Surface Treatment Of Glass (AREA)
- Powder Metallurgy (AREA)
- Ceramic Products (AREA)
Abstract
Abstract A decorative coating for application to ceramics is dis-closed, which although it contains no metallic gold, has the appearance of gold after firing. The coating is formed by mixing soluble metallo-organic compounds of palladium, silver, and a fluxing agent in a vehicle. When applied to opaque or translucent ceramic bodies and fired in the usual manner for such decorations, the appearance obtained previously with decorations containing substantial amounts of metallic gold is simulated. Compositions containing ratios of palladium to silver between 1:1 and 12:1 may be used. For most applications as by screen printing, rolling machine lining, stamping, spray-ing, brushing, etc. the total content of palladium and silver in the as applied coating will range between 1 and 12 weight percent, the balance being fluxing agents and vehicle.
Description
~ .
t ~, .
~ ~ ¦Background of the Invention ;?' The invention relates generally to the field of precious metal decorations for ceramics and in particular to a decora-¦
~; tive composition producing the appearance of gold after fir-ing, but which actually contains no metallic gold.
Decorative compositions for ceramics to achieve a gold appearance have heretofore contained substantial quantities of metallic gold, often of the order of 10-15 weight percent j , with the balance being fluxing agents and vehicle. Such prio~
I art decorations are disclosed in such patents as U.S. Patent Nos. 2,994,61~ and 3,092,504 which disclose and claim specifi~
.~ , gold compounds and compositions which were found useful for i decorations having a gold appearance. The maximum gold I
. . .
Ij 107~955 content is determined primarily by the cost of the gold and the fact that increasing the gold content does not indefinitel improve the appearance. The minimum gold content of such decorations is determined primarily by the poorer adherence and durability of low gold content films and the deterioration in their appearance. It will be appreciated that until recent , ~ years gold, although a precious metal, was less expensive than¦
some of the other precious metals. As the price of gold has risen, it has become of interest to reduce the quantity of gold used in decorations since at 4 to 5 times the previous cost the use of gold in decorating compositions becomes pro-hibitive, except for the most expensive articles.
~ Palladium has also been used in decorative compositions.
.~ In some compositions, it produces a white metal appearance when used in combination with gold, and simulates the hereto-fore more expensive platinum compositions. In other applica-ions, it has been used to produce a brown color. Examples ay be found in U. S. patent 3,216,834, which is principally , l irected to a new compound of palladium for use in decorative pplications. In one example of the patent, a composition ontaining 1.5 percent palladium, 3 percent silver, and much ~, maller amounts of rhodium and chromium is shown to produce '~ chocolate brown color useful for decoration. In other xamples, bright palladium decorating compositions are shown o contain large quantities of gold and smaller amounts of alladium. Other patents disclosing palladium compounds seful for decorative applications include U. S. Patents Nos.
,718,488 and 770,785.
t ~, .
~ ~ ¦Background of the Invention ;?' The invention relates generally to the field of precious metal decorations for ceramics and in particular to a decora-¦
~; tive composition producing the appearance of gold after fir-ing, but which actually contains no metallic gold.
Decorative compositions for ceramics to achieve a gold appearance have heretofore contained substantial quantities of metallic gold, often of the order of 10-15 weight percent j , with the balance being fluxing agents and vehicle. Such prio~
I art decorations are disclosed in such patents as U.S. Patent Nos. 2,994,61~ and 3,092,504 which disclose and claim specifi~
.~ , gold compounds and compositions which were found useful for i decorations having a gold appearance. The maximum gold I
. . .
Ij 107~955 content is determined primarily by the cost of the gold and the fact that increasing the gold content does not indefinitel improve the appearance. The minimum gold content of such decorations is determined primarily by the poorer adherence and durability of low gold content films and the deterioration in their appearance. It will be appreciated that until recent , ~ years gold, although a precious metal, was less expensive than¦
some of the other precious metals. As the price of gold has risen, it has become of interest to reduce the quantity of gold used in decorations since at 4 to 5 times the previous cost the use of gold in decorating compositions becomes pro-hibitive, except for the most expensive articles.
~ Palladium has also been used in decorative compositions.
.~ In some compositions, it produces a white metal appearance when used in combination with gold, and simulates the hereto-fore more expensive platinum compositions. In other applica-ions, it has been used to produce a brown color. Examples ay be found in U. S. patent 3,216,834, which is principally , l irected to a new compound of palladium for use in decorative pplications. In one example of the patent, a composition ontaining 1.5 percent palladium, 3 percent silver, and much ~, maller amounts of rhodium and chromium is shown to produce '~ chocolate brown color useful for decoration. In other xamples, bright palladium decorating compositions are shown o contain large quantities of gold and smaller amounts of alladium. Other patents disclosing palladium compounds seful for decorative applications include U. S. Patents Nos.
,718,488 and 770,785.
-2-,' ,. . . I _,_ Palladium has also been used with silver in a film which has the ability to separate gaseous mixtures by hydrogen diffusion through the film. U.S. Patent No.
3,413,777 discloses such a film which contains an alloy of 5-40 weight percent silver and the remainder palladium, the alloy being mixed with a glaze in the method of forming ¦
lthe desired film.
;What has been desired since the cost of gold has , increased many-fold is a decoration for ceramics which, while giving the appearance of gold after firing, does not ~,contain substantial quantities of that metal, in order that the cost may be kept at reasonable levels. This objective has been accomplished by the composition and the method of the present invention, in which no metallic gold is used.
Summary of the Invention ,;~
In one aspect, the invention consists of a composition which, when applied to ceramics and fired, produces a decoration having a gold appearance. This composition contains as its principal metallic constituents, minor amounts of palladium and sufficient silver to produce a gold appearance in combination with palladium. Typically, ~,~weight ratios of palladium to silver in compositions of the invention range between about 1:1 and about 12:1, with preferred ratios between about 2.3:1 and about 9:1. The total content of palladium and silver for most applications will be between 1 and 12 weight percent. Within the stated ranges, a gold color is produced in the fired decoration.
Outside these ranges, the color no longer satisfactorily simulates gold-containing decorations and in addition, the _3_ .~
~ !
s film has reduced reflectance or adherence. The gold appearance is particularly enhanced when applied as relatively narrow lines.
In another aspect, the invention comprises a method for decorating ceramics to produce a gold appearance using the composition discussed above. Suitable amounts of palladium and silver in the form of soluble metallo-organic compounds and within the described composition ranges are combined with a flux and vehicles to produce a mixture having an appropriate viscosity. The usual techniques for applying decorative compositions, such as screen printing, rolling, dipping, stamping, spraying, or brushing may be used.
Conditions under which the applied coating is fired for removing the vehicles and fusing the remaining residue are determined by the temperature which the substrate will ` accept, generally between 500 and 650C for glass and 650 to 800C for other ceramic materials, such as china.
i Description of the Preferred Embodiments In the prior art, palladium has been used to produce a ¦
white color in combination with large amounts of gold, as disclosed in U.S. Patent No, 3,216,834. It also has been ~1 used to produce a brown color when no gold is present.
Silver, when used alone, produces a film having an amber appearance. It has now been found that a combination of palladium with a sufficient amount of silver and within certain narrow ranges of composition produces a decorative composition having the appearance of metallic gold after firing. Outside those ranges, the simulation of gold is unsatisfactory, and the decorative film has reduced reflectance or poorer adherence. The following table ,i~
.. ..
10749S~
illustrates the sensitivity of the film color, reflectance, and adherence to the relative proportions of palladium and s silver.
Characteristics of the decorations after firing onto ' 5 the ceramic surface are not typically measured by a test method standardized within the industry, but are related by experience with what color, reflectance, and adherence are acceptable to purchasers of such decorative compositions.
s It should be understood that,in particular,evaluation of i 10 color and reflectance, although somewhat subjective, can be made when comparing side-by-side samples of various `} decorations and that those experienced in the art would be expected to concur in such evaluations. Adherence is a more !
objective quality and is usually judged by rubbing the ~, 15 decoration with a rubber eraser containing abrasive since it is known from experience that such a test correlates well with actual service life.
s All of the compositions shown were identical (and similar to the example given hereinafter) except for the 20 adjustment of the ratio of palladium to silver. Each composition contained a total of 5 weight percent palladium .' and silver since this amount gives particularly good i results with a minimum use of these expensive metals. Each ¦
was applied by roller topping to the rim of a translucent 25 opal glass saucer and fired at 600C before comparison of s the film properties was made. It can be seen from the table ~ that palladium alone, without silver, produces a brown :J' '. colored film with poor adherence. The addition of small quanti.ties of silver are insufficient to change the brown 30 ~ ~ color to gol but at the composition of 4.5 weight percent ¦
., '~, ~, .
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~ O O O O O O O O O d O 0 5 ','.. ~ . Q~ ~
.,. P K ~: h ~I h , ~ ~ ~1 3 ~ ~ A
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l 10749S5 palladium and 0.5 weight percent silver, a strong gold color film is produced with good reflectance and adherence.
This effect also occurs with a composition containing 4 weight percent palladium and 1 weight percent sllver. The color is weakened toward amber when the ratio of palladium to silver is reduced to about 1.5:1, although the reflectance and adherence are still good. At a 1:1 ratio of palladium to silver, the gold appearance has been ; weakened and the reflectance has been significantly reduced.
A- ~atio of 1 weight percent palladium to 4 weight percent silver produces a green-gray color which is dull and no longer reflective. Also, tarnishing of the film may limit the amount of silver which can be used. Thus, it can be seen that only over a narrow range of compositions can the desire~
gold appearance be obtained. For a total palladium and silver content of 5 weight percent this range may be more ~` broadly expressed as including compositions between 2.5 and ~- 4.6 weight percent palladium and 0.5 to 2 weight percent silver. The preferred ranges are 3.5 to 4.5 weight percent palladium and 0.5 to 1.5 weight percent silver. Expressed as weight ratios of palladium to silver the broad range is about 1:1 to about 12:1 and the preferred range about 2.3:1 to about 9:1.
Although a total of 5 weight percent palladium plus silver is preferred for rolling application, it has been found that a satisfactory golden appearance can be achieved using both higher and lower total metal contents. Although compositions containing larger metal contents would be more expensive to produce, if such are desired, a golden appearanc~
~' I I .
.
."' , i ll can be obtained by uslng palladium/silver weight ratios between 1:1 and 12:1. Metal contents below five percent total of palladium and silver can also be used for roller applications, although a metal content of 4 weight percent i5 is a practical minimum, as limited by reduced abrasion resistance and weakening of the reflective gold appearance.
The foregoing data and discussion is based on compositions suitable for such applications as machine banding and stamping which require a high viscosity mixture, which typically will contain a total of between 4 and 12 weight percent palladium and silver. For other applications ,~which require lower viscosity mixtures, as are typically used for silk screening and brushing, thetotal content of palladium and silver would be about 2-4 weight percent, and ,15 for spraying about 1-2 weight percent. The ratios of palladium to silver would be maintained between 1:1 and 12:1 in such other applications as in the principal examples.
If corresponding compositions were to be prepared from ithe prior art using metallic gold, the gold content of such compositions would be about 4-5 weight percent for sprayingus~, about 8-10 weight percent for brushing and silk screening, 12-15 weight percent for machine banding, and 15-20 weight percent for stamping. Thus, it is clear that in the present invention the total valuable metal content is distinctly lower and the cost of the metals used is less than metallic gold in the present market.
"Another important component of the composition of the invention is the flux material, which is typically a soluble `metallo-oxganic compound of a metal as typically used in the 30¦¦prior art to flu palladium and silver. Specifically, such ~!
..~
~ 1074955 metals include bismuth, chromium, lead, cadmium, uranium, tin copper, cobalt, antimony, and rhenium. Such flux materials are well known in the prior art. Reference may be made to U.S. 3,216,834 previously mentioned. Those experienced in th~
art will appreciate that such fluxes are useful to improve the adherence of the metal film and its abrasion resistance.
~ The fluxes have the property of softening or melting at thefiring temperature which, in general, the metallic components ~! do not. They react with the substrate and create an adhesive 10 vitreous layer for the metallic film and at the same time binc the metallic particles in the decorative film. All prior art fluxes, however, are not equally useful in the gold appearing decoration of the present invention. They may affect the color, the reflectance, and the adherence of the resultant 15 film and so be more or less useful.
In a preferred embodiment, a metallo-organic bismuth s~ compound is used. In the typical decorative compositions for roller topping, the bismuth content is preferably about 0.5 weight percent. Expressed more generally, the weight ratio 20 of bismuth to the combined palladium and sllver would typically be in the range of about 0.02:1 to 0.2:1, with a preferred ratio of Bi (Pd + Ag) of about 0.1:1 ~based on metal content).
A ~ A typical decorative composition of the invention , 25 formulated for machine roller topping is given in the ¦~following exampl ~''sr~ 1, ,s' :, i, , Weight Percent Resin in essential oil 47.17 Pd neodecanoate in solution 26.42 (15% Pd) Resin ester (plasticizer) 7.55 Balsam (tackifier) 5.66 Ag neodecanoate in solution 3.77 (25% Ag) Organic hydrocarbon solvent 7.55 ~! 10 (diluent for viscosity adjustment) Bi neodecanoate in solution 1.89 (26~ Bi) -100.00 As will be observed, the metallic constituents in compositionC
of the invention are present as soluble metallo-organic compounds. The neodecanoates shown in the examples were selected for ease of availability and low cost. Other . soluble organo-metallic compounds may also be used. For example, the following: sulfonates, sulfo-resinates, ~ 20 mercaptides, thio-ethers, chelates, and carboxylates can be .r substituted for neodecanoates.
~ ~ The solvent and resins serve to form a paste or ink- j ; like material and they are added as required to adjust the viscosity needed for particular applications. Generally, it is known in the art that compositions in the range of 50-100 poise are suitable for screen printing, machine lining, rolling, and stamping applications. On the other hand, for spraying or brushing more dilute solutions are applied.
Typically, these may have a viscosity of the order of 1 centi-poise. The relative proportion of the metallic constituents remain the same but they are diluted in the ,~ formulation in order to adjust the handling qualities of the resulting solution.
~, ~:' -10-I
", ~ I
After being applied to a ceramic article, they are : fired at temperatures typical of those of the prior art, . glass being fired typically between 500 and 650C and china, between 650 and 800C. During firing, the organic materials are substantially decomposed and removed, leaving behind a composition which consists essentially of finely divided . particles of palladium and silver in a base metal oxide . binder.
The resulting fired film gives a gold appearance when . 10 t~e proportions of palladium and silver are properly selected Owing to its relatively low cost, the decorative composition of the invention can be applied to many inexpensive applications where gold decorations using the traditional high gold content compositions would be too costly.
The gold appearance of films formed according to the invention is particularly pronounced with narrower lines;
.~ however, the decoration always gives a golden color. The highly reflectance property of such films appear to enhance the appearance of bright metallic gold when applied in ~, 20 narrower widths.
.~. The foregoing description of the preferred embodiments .,~. is for illustration of the invention only and not to limit 7~ the scope of the invention which is defined by the claims , ¦¦which Eollow.
'~ 1, ;j ~'''
lthe desired film.
;What has been desired since the cost of gold has , increased many-fold is a decoration for ceramics which, while giving the appearance of gold after firing, does not ~,contain substantial quantities of that metal, in order that the cost may be kept at reasonable levels. This objective has been accomplished by the composition and the method of the present invention, in which no metallic gold is used.
Summary of the Invention ,;~
In one aspect, the invention consists of a composition which, when applied to ceramics and fired, produces a decoration having a gold appearance. This composition contains as its principal metallic constituents, minor amounts of palladium and sufficient silver to produce a gold appearance in combination with palladium. Typically, ~,~weight ratios of palladium to silver in compositions of the invention range between about 1:1 and about 12:1, with preferred ratios between about 2.3:1 and about 9:1. The total content of palladium and silver for most applications will be between 1 and 12 weight percent. Within the stated ranges, a gold color is produced in the fired decoration.
Outside these ranges, the color no longer satisfactorily simulates gold-containing decorations and in addition, the _3_ .~
~ !
s film has reduced reflectance or adherence. The gold appearance is particularly enhanced when applied as relatively narrow lines.
In another aspect, the invention comprises a method for decorating ceramics to produce a gold appearance using the composition discussed above. Suitable amounts of palladium and silver in the form of soluble metallo-organic compounds and within the described composition ranges are combined with a flux and vehicles to produce a mixture having an appropriate viscosity. The usual techniques for applying decorative compositions, such as screen printing, rolling, dipping, stamping, spraying, or brushing may be used.
Conditions under which the applied coating is fired for removing the vehicles and fusing the remaining residue are determined by the temperature which the substrate will ` accept, generally between 500 and 650C for glass and 650 to 800C for other ceramic materials, such as china.
i Description of the Preferred Embodiments In the prior art, palladium has been used to produce a ¦
white color in combination with large amounts of gold, as disclosed in U.S. Patent No, 3,216,834. It also has been ~1 used to produce a brown color when no gold is present.
Silver, when used alone, produces a film having an amber appearance. It has now been found that a combination of palladium with a sufficient amount of silver and within certain narrow ranges of composition produces a decorative composition having the appearance of metallic gold after firing. Outside those ranges, the simulation of gold is unsatisfactory, and the decorative film has reduced reflectance or poorer adherence. The following table ,i~
.. ..
10749S~
illustrates the sensitivity of the film color, reflectance, and adherence to the relative proportions of palladium and s silver.
Characteristics of the decorations after firing onto ' 5 the ceramic surface are not typically measured by a test method standardized within the industry, but are related by experience with what color, reflectance, and adherence are acceptable to purchasers of such decorative compositions.
s It should be understood that,in particular,evaluation of i 10 color and reflectance, although somewhat subjective, can be made when comparing side-by-side samples of various `} decorations and that those experienced in the art would be expected to concur in such evaluations. Adherence is a more !
objective quality and is usually judged by rubbing the ~, 15 decoration with a rubber eraser containing abrasive since it is known from experience that such a test correlates well with actual service life.
s All of the compositions shown were identical (and similar to the example given hereinafter) except for the 20 adjustment of the ratio of palladium to silver. Each composition contained a total of 5 weight percent palladium .' and silver since this amount gives particularly good i results with a minimum use of these expensive metals. Each ¦
was applied by roller topping to the rim of a translucent 25 opal glass saucer and fired at 600C before comparison of s the film properties was made. It can be seen from the table ~ that palladium alone, without silver, produces a brown :J' '. colored film with poor adherence. The addition of small quanti.ties of silver are insufficient to change the brown 30 ~ ~ color to gol but at the composition of 4.5 weight percent ¦
., '~, ~, .
h h ~a. ~ ~ 'a ~a ~ ~ 'a ~ ~
h O O -i 0 0 0 0 0 0 0 0 0 0 a) oo~)ooooooooo o , '~:- a~
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, ~ ~ ,1 .. ~ .. . . .. .. . . .. . . .
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.. ~ d~ ~ ~ ~ Ul O U~
r 3 O O O O O ~ ~~~1 t~l ~I t~
~' ., ~1 ~D In O
¦ ~ l N ~ O
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`. I
l 10749S5 palladium and 0.5 weight percent silver, a strong gold color film is produced with good reflectance and adherence.
This effect also occurs with a composition containing 4 weight percent palladium and 1 weight percent sllver. The color is weakened toward amber when the ratio of palladium to silver is reduced to about 1.5:1, although the reflectance and adherence are still good. At a 1:1 ratio of palladium to silver, the gold appearance has been ; weakened and the reflectance has been significantly reduced.
A- ~atio of 1 weight percent palladium to 4 weight percent silver produces a green-gray color which is dull and no longer reflective. Also, tarnishing of the film may limit the amount of silver which can be used. Thus, it can be seen that only over a narrow range of compositions can the desire~
gold appearance be obtained. For a total palladium and silver content of 5 weight percent this range may be more ~` broadly expressed as including compositions between 2.5 and ~- 4.6 weight percent palladium and 0.5 to 2 weight percent silver. The preferred ranges are 3.5 to 4.5 weight percent palladium and 0.5 to 1.5 weight percent silver. Expressed as weight ratios of palladium to silver the broad range is about 1:1 to about 12:1 and the preferred range about 2.3:1 to about 9:1.
Although a total of 5 weight percent palladium plus silver is preferred for rolling application, it has been found that a satisfactory golden appearance can be achieved using both higher and lower total metal contents. Although compositions containing larger metal contents would be more expensive to produce, if such are desired, a golden appearanc~
~' I I .
.
."' , i ll can be obtained by uslng palladium/silver weight ratios between 1:1 and 12:1. Metal contents below five percent total of palladium and silver can also be used for roller applications, although a metal content of 4 weight percent i5 is a practical minimum, as limited by reduced abrasion resistance and weakening of the reflective gold appearance.
The foregoing data and discussion is based on compositions suitable for such applications as machine banding and stamping which require a high viscosity mixture, which typically will contain a total of between 4 and 12 weight percent palladium and silver. For other applications ,~which require lower viscosity mixtures, as are typically used for silk screening and brushing, thetotal content of palladium and silver would be about 2-4 weight percent, and ,15 for spraying about 1-2 weight percent. The ratios of palladium to silver would be maintained between 1:1 and 12:1 in such other applications as in the principal examples.
If corresponding compositions were to be prepared from ithe prior art using metallic gold, the gold content of such compositions would be about 4-5 weight percent for sprayingus~, about 8-10 weight percent for brushing and silk screening, 12-15 weight percent for machine banding, and 15-20 weight percent for stamping. Thus, it is clear that in the present invention the total valuable metal content is distinctly lower and the cost of the metals used is less than metallic gold in the present market.
"Another important component of the composition of the invention is the flux material, which is typically a soluble `metallo-oxganic compound of a metal as typically used in the 30¦¦prior art to flu palladium and silver. Specifically, such ~!
..~
~ 1074955 metals include bismuth, chromium, lead, cadmium, uranium, tin copper, cobalt, antimony, and rhenium. Such flux materials are well known in the prior art. Reference may be made to U.S. 3,216,834 previously mentioned. Those experienced in th~
art will appreciate that such fluxes are useful to improve the adherence of the metal film and its abrasion resistance.
~ The fluxes have the property of softening or melting at thefiring temperature which, in general, the metallic components ~! do not. They react with the substrate and create an adhesive 10 vitreous layer for the metallic film and at the same time binc the metallic particles in the decorative film. All prior art fluxes, however, are not equally useful in the gold appearing decoration of the present invention. They may affect the color, the reflectance, and the adherence of the resultant 15 film and so be more or less useful.
In a preferred embodiment, a metallo-organic bismuth s~ compound is used. In the typical decorative compositions for roller topping, the bismuth content is preferably about 0.5 weight percent. Expressed more generally, the weight ratio 20 of bismuth to the combined palladium and sllver would typically be in the range of about 0.02:1 to 0.2:1, with a preferred ratio of Bi (Pd + Ag) of about 0.1:1 ~based on metal content).
A ~ A typical decorative composition of the invention , 25 formulated for machine roller topping is given in the ¦~following exampl ~''sr~ 1, ,s' :, i, , Weight Percent Resin in essential oil 47.17 Pd neodecanoate in solution 26.42 (15% Pd) Resin ester (plasticizer) 7.55 Balsam (tackifier) 5.66 Ag neodecanoate in solution 3.77 (25% Ag) Organic hydrocarbon solvent 7.55 ~! 10 (diluent for viscosity adjustment) Bi neodecanoate in solution 1.89 (26~ Bi) -100.00 As will be observed, the metallic constituents in compositionC
of the invention are present as soluble metallo-organic compounds. The neodecanoates shown in the examples were selected for ease of availability and low cost. Other . soluble organo-metallic compounds may also be used. For example, the following: sulfonates, sulfo-resinates, ~ 20 mercaptides, thio-ethers, chelates, and carboxylates can be .r substituted for neodecanoates.
~ ~ The solvent and resins serve to form a paste or ink- j ; like material and they are added as required to adjust the viscosity needed for particular applications. Generally, it is known in the art that compositions in the range of 50-100 poise are suitable for screen printing, machine lining, rolling, and stamping applications. On the other hand, for spraying or brushing more dilute solutions are applied.
Typically, these may have a viscosity of the order of 1 centi-poise. The relative proportion of the metallic constituents remain the same but they are diluted in the ,~ formulation in order to adjust the handling qualities of the resulting solution.
~, ~:' -10-I
", ~ I
After being applied to a ceramic article, they are : fired at temperatures typical of those of the prior art, . glass being fired typically between 500 and 650C and china, between 650 and 800C. During firing, the organic materials are substantially decomposed and removed, leaving behind a composition which consists essentially of finely divided . particles of palladium and silver in a base metal oxide . binder.
The resulting fired film gives a gold appearance when . 10 t~e proportions of palladium and silver are properly selected Owing to its relatively low cost, the decorative composition of the invention can be applied to many inexpensive applications where gold decorations using the traditional high gold content compositions would be too costly.
The gold appearance of films formed according to the invention is particularly pronounced with narrower lines;
.~ however, the decoration always gives a golden color. The highly reflectance property of such films appear to enhance the appearance of bright metallic gold when applied in ~, 20 narrower widths.
.~. The foregoing description of the preferred embodiments .,~. is for illustration of the invention only and not to limit 7~ the scope of the invention which is defined by the claims , ¦¦which Eollow.
'~ 1, ;j ~'''
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A decorating composition for producing a gold appearance after being fired on ceramics comprising a vehicle and a metal content which, in addition to trace impurities, consists essentially of:
(a) a soluble metallo-organic compound of palladium;
(b) a soluble metallo-organic compound of silver in an amount sufficient to produce a gold appearing decoration in combination with said compound of palladium; and (c) a soluble metallo-organic flux compound for palladium and silver;
the weight ratio as metal of palladium to silver being in the range of 1:1 to 12:1 and said palladium and silver together com-prising at least about one percent by weight of said composition.
(a) a soluble metallo-organic compound of palladium;
(b) a soluble metallo-organic compound of silver in an amount sufficient to produce a gold appearing decoration in combination with said compound of palladium; and (c) a soluble metallo-organic flux compound for palladium and silver;
the weight ratio as metal of palladium to silver being in the range of 1:1 to 12:1 and said palladium and silver together com-prising at least about one percent by weight of said composition.
2. The decorating composition of claim 1 wherein said palladium and silver together comprise from about one to twelve weight percent of said composition.
3. The decorating composition of claim 1 wherein the weight ratio of palladium to silver is in the range of 2.3:1 to 9:1.
4. The decorating composition of claim 1 wherein the weight ratio of the metal portion of said flux compound to the combined palladium and silver is in the range of about 0.02:1 to 0.2:1.
5. A method of producing a decoration on ceramics having a gold appearance after firing comprising the steps of:
(a) preparing a decorating composition comprising a suitable vehicle and having a metal content which, in addition to trace impurities, consists essentially of:
(1) a soluble metallo-organic compound of palladium;
(2) a soluble metallo-organic compound of silver the weight ratio as metal of said palladium to said silver being in the range of 1:1 to 12:1, said palladium and silver together comprising at least about one percent by weight of said composition; and (3) a soluble metallo-organic flux compound for palladium and silver;
(b) applying said composition of (a) to a ceramic surface to be decorated by the selected application technique;
(c) firing the ceramic surface of (b) after applying the composition of (a) to remove the organic components thereof and to produce a gold appearing film on the ceramic surface.
(a) preparing a decorating composition comprising a suitable vehicle and having a metal content which, in addition to trace impurities, consists essentially of:
(1) a soluble metallo-organic compound of palladium;
(2) a soluble metallo-organic compound of silver the weight ratio as metal of said palladium to said silver being in the range of 1:1 to 12:1, said palladium and silver together comprising at least about one percent by weight of said composition; and (3) a soluble metallo-organic flux compound for palladium and silver;
(b) applying said composition of (a) to a ceramic surface to be decorated by the selected application technique;
(c) firing the ceramic surface of (b) after applying the composition of (a) to remove the organic components thereof and to produce a gold appearing film on the ceramic surface.
6. The method of claim 5 wherein said palladium and silver together comprise about one to twelve percent by weight of said composition.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US61349575A | 1975-09-15 | 1975-09-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1074955A true CA1074955A (en) | 1980-04-08 |
Family
ID=24457543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA260,952A Expired CA1074955A (en) | 1975-09-15 | 1976-09-10 | Decoration for ceramics having the appearance of gold |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS52148513A (en) |
| AU (1) | AU502816B2 (en) |
| CA (1) | CA1074955A (en) |
| DE (1) | DE2641321A1 (en) |
| FR (1) | FR2323657A1 (en) |
| GB (1) | GB1533628A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH076067B2 (en) * | 1990-09-14 | 1995-01-25 | 日本金液株式会社 | Liquid or paste precious metal composition for painting |
| US5281635A (en) * | 1991-05-17 | 1994-01-25 | Johnson Matthey Public Limited Company | Precious metal composition |
| GB9203394D0 (en) * | 1992-02-18 | 1992-04-01 | Johnson Matthey Plc | Coated article |
| DE4425815C1 (en) * | 1994-07-21 | 1995-08-17 | Demetron Gmbh | Precious metal-contg. resinate paste |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1240979A (en) * | 1959-11-20 | 1960-09-09 | Du Pont | Composition of vitreous enamel and ceramic object |
| FR1390983A (en) * | 1962-11-27 | 1965-03-05 | Engelhard Ind Inc | Decorative compositions and method of decorating with these compositions |
| FR1410324A (en) * | 1963-08-16 | 1965-09-10 | Engelhard Ind | Decorative composition and method for decorating using this composition |
| US3554796A (en) * | 1968-05-20 | 1971-01-12 | Rca Corp | Metallization of titanate wafers |
-
1976
- 1976-09-10 CA CA260,952A patent/CA1074955A/en not_active Expired
- 1976-09-13 FR FR7627465A patent/FR2323657A1/en active Granted
- 1976-09-13 GB GB3780476A patent/GB1533628A/en not_active Expired
- 1976-09-14 AU AU17708/76A patent/AU502816B2/en not_active Expired
- 1976-09-14 JP JP10950976A patent/JPS52148513A/en active Granted
- 1976-09-14 DE DE19762641321 patent/DE2641321A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61320B2 (en) | 1986-01-07 |
| DE2641321A1 (en) | 1977-03-24 |
| AU502816B2 (en) | 1979-08-09 |
| JPS52148513A (en) | 1977-12-09 |
| FR2323657B1 (en) | 1983-06-24 |
| AU1770876A (en) | 1978-03-23 |
| GB1533628A (en) | 1978-11-29 |
| FR2323657A1 (en) | 1977-04-08 |
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| MKEX | Expiry |