GB2024189A - Pyrolytic deposition of a cobalt/tin oxide spinel film - Google Patents
Pyrolytic deposition of a cobalt/tin oxide spinel film Download PDFInfo
- Publication number
- GB2024189A GB2024189A GB7923105A GB7923105A GB2024189A GB 2024189 A GB2024189 A GB 2024189A GB 7923105 A GB7923105 A GB 7923105A GB 7923105 A GB7923105 A GB 7923105A GB 2024189 A GB2024189 A GB 2024189A
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- GB
- United Kingdom
- Prior art keywords
- cobalt
- tin
- substrate
- percent
- solution
- 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.)
- Granted
Links
- 239000010941 cobalt Substances 0.000 title claims abstract description 27
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910000428 cobalt oxide Inorganic materials 0.000 title claims abstract description 19
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 14
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 230000008021 deposition Effects 0.000 title claims abstract description 10
- 229910052596 spinel Inorganic materials 0.000 title description 2
- 239000011029 spinel Substances 0.000 title description 2
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 19
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 238000000151 deposition Methods 0.000 claims abstract description 13
- 229910052718 tin Inorganic materials 0.000 claims abstract description 13
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 10
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 150000003606 tin compounds Chemical class 0.000 claims abstract description 9
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 5
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract 2
- 230000001590 oxidative effect Effects 0.000 claims abstract 2
- 229910052760 oxygen Inorganic materials 0.000 claims abstract 2
- 239000001301 oxygen Substances 0.000 claims abstract 2
- 239000011135 tin Substances 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 24
- 239000011521 glass Substances 0.000 claims description 18
- 229940011182 cobalt acetate Drugs 0.000 claims description 8
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 230000005284 excitation Effects 0.000 claims description 6
- 238000002834 transmittance Methods 0.000 claims description 3
- 150000001869 cobalt compounds Chemical class 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- BSUSEPIPTZNHMN-UHFFFAOYSA-L cobalt(2+);diperchlorate Chemical compound [Co+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O BSUSEPIPTZNHMN-UHFFFAOYSA-L 0.000 claims description 2
- 239000011819 refractory material Substances 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- CZRDZAGTSCUWNG-UHFFFAOYSA-M chloro(dimethyl)tin Chemical compound C[Sn](C)Cl CZRDZAGTSCUWNG-UHFFFAOYSA-M 0.000 claims 1
- 239000011248 coating agent Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000376 reactant Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- WDHWFGNRFMPTQS-UHFFFAOYSA-N cobalt tin Chemical compound [Co].[Sn] WDHWFGNRFMPTQS-UHFFFAOYSA-N 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- PLOWAKQTEHQOFB-UHFFFAOYSA-L di(propan-2-yl)tin(2+);dichloride Chemical compound CC(C)[Sn](Cl)(Cl)C(C)C PLOWAKQTEHQOFB-UHFFFAOYSA-L 0.000 description 1
- BXVLQFGQYHYURU-UHFFFAOYSA-N diethyltin Chemical compound CC[Sn]CC BXVLQFGQYHYURU-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- YFRLQYJXUZRYDN-UHFFFAOYSA-K trichloro(methyl)stannane Chemical compound C[Sn](Cl)(Cl)Cl YFRLQYJXUZRYDN-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
-
- 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
- C03C17/23—Oxides
- C03C17/25—Oxides by deposition from the liquid phase
- C03C17/253—Coating containing SnO2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
-
- 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
- C03C2217/21—Oxides
- C03C2217/23—Mixtures
-
- 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
- C03C2218/112—Deposition methods from solutions or suspensions by spraying
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Surface Treatment Of Glass (AREA)
- Chemically Coating (AREA)
- Laminated Bodies (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The invention provides an aqueous solution for the pyrolytic deposition of coatings comprising cobalt, tin, and oxygen which comprises a water-soluble cobalt salt and a water- soluble tin compound. It also provides a coated substrate prepared by contacting a substrate surface at a temperature sufficient to pyrolyze a metal compound to a metal oxide with the aqueous solution. It further provides a method for depositing a film comprising the oxides of cobalt and tin comprising the steps of: a. maintaining a substrate in an oxidizing atmosphere at a temperature sufficient to pyrolyze a metal compound to a metal oxide; and b. contacting the surface of the substrate at said temperature with an aqueous solution comprising a water- soluble cobalt salt and a water-soluble tin compound capable of thermal decomposition to cobalt oxide and tin oxide, thus forming a cobalt/tin oxide spine-type film. m
Description
SPECIFICATION
Pyrolytic deposition of a cobalt/tin oxide spinel film
The present invention relates generally to the art of pyrolytic deposition of metal oxide films and more particularly to the pyrolytic deposition of metal oxide films from aqueous solutions of coating reactants.
The pyrolytic deposition of metal oxides onto a glass surface is described in U.S. Patent No 3,660,061 to
Donley et al. Organometallic salts, preferably acetylacetonates, are dissolved in an organic vehicle such as methylene chloride. Other suitable solvents include aliphatic and olefinic halocarbons, halogenated hydrocarbons, alcohols and nonpolar aromatic compounds such as benzene and toluene. The organic solution is sprayed onto a hot glass surface where it thermally decomposes to form a metal oxide film which changes the refictance and transmittance of solar energy by the glass.
In U.S. Patent No.3,411,935 Englehart et al disclose that cobalt oxide is particlarly suited for use as a coating on glass because of its good solar heat shielding properties. However, cobalt oxide coatings are not as uniform and adherent as desired. Englehart et al teach that the adherence, durability and optical quality of cobalt oxide films are improved by providing the glass surface with a thin tin oxide undercoating and then overcoating with cobalt oxide by thermal pyrolysis of a cobalt compound such as cobalt acetylacetonate.
Preferably, the cobalt oxide coating also contains the oxides of iron and chromium since these oxides improve the scratch resistance of the coating without detracting from the slar heat shielding properties of the cobalt oxide. A preferred solvent system for the metal coating reactants comprises a polar organic compound and a nonpolar aromatic compound, particularly methanol combined with either benzene or toluene.
Current interest in eliminating the health and environmental hazards of using large volumes of organic solvents has encouraged the development of aqueous coating compositions. It is known from U.S. Patent
No. 2,688,565 to Raymond that light reflecting coatings of cobalt oxide may be deposited by contacting a hot glass surface with an aqueous solution of cobalt acetate. However, such films have a grainy, irregular texture and are highly porous resulting in poor acid resistance evidenced by debonding of the film.
The present invention involves the pyrolytic deposition of a spinel-type film containing cobalt and tin oxides by thermal decomposition of an aqueous solution of a water soluble cobalt salt and a water soluble tin compound. The resultant film is more uniform in appearance and less porous than a cobalt oxide film which does not contain tin oxide. The cobalt/tin oxide film is also more durable as evidenced by the fact that it withstands immersion in 0.5 percent hydrofluoric acid solution for 8 minutes with no film debonding while a cobalt oxide film fails this durability test.
The cobalt and tin coating reactants are dissolved in water. The aqueous solution is then applied to a substrate surface e.g. a glass surface at a sufficiently high temperature to pyrolyze the coating reactants to form a metal oxide film.
Aqueous solutions of a water soluble cobalt salt, preferably cobalt acetate, and a water soluble tin compound, preferably dimethyltin dichloride, are prepared with wide variation in the ratio of cobalt to tin.
The ratio of cobalt to tin is preferably about 2:1 to 20:1 by weight and more preferably about 5:1 to 12:1.The total metal concentration in the solution preferably ranges from about 1 to 12 percent by weight and more preferably from about 5 to 6 percent.
Preferred cobalt salts include cobalt nitrate and cobalt perchlorate as well as cobalt acetate. Preferred water soluble tin compounds include tin chlorides such as SnC 12 and SnC 14 and other alkyltin chlorides such as methyltin trichloride, trimethyltin chloride, diethyltin dichioride, diisopropyltin dichloride, stannic bisacetylacetone dichloride and stannic acetate.
The aqueous solution of cobalt and tin coating reactants is applied to a surface of a glass substrate which is maintained at a temperature sufficient to pyrolyze the coating reactants to form an oxide film, preferably at least about 500"F. (about 260"C.) and more preferably about 1000-1200"F. (about 538 to 650"C).
In a particularly preferred embodiment of the present invention, a stock solution of cobalt acetate containing 5.0 percent by weight cobalt is prepared by dissolving the cobalt acetate in water, preferably including about 5 percent by weight glacial acetic acid to provide long shelf life. The selected hydrolyzable tin compound is separately dissolved in water. Coating solutions have a variety of cobalt/tin ratios are prepared by mixing the two solutions in various proportiions.
A particularly preferred method for applying the above solution to a hot glass surface is to spray the aqueous solution onto the surface of a continuous glass ribbon formed on a bath of molten metal in a refractory tank after the ribbon has been lifted from the bath and conveyed beyond the reducing atmosphere which protects the bath. A detailed description of a preferred method for the pyrolytic deposition of metal oxide films on glass is found in U.S. Patent No. 3,660,061, commonly assigned, which description is incorporated herein by reference.
The present invention will be further understood from the descriptions of specific examples which follow.
Spectral properties of the glass coated according to these examples are shown in Table 1.
EXAMPLE 1
A stock cobalt acetate solution is prepared by combining 21.13 percent by weight cobalt acetate tetrahydrate, Co(C2H302)2 4H2O, 5.25 percent by weight glacial acetic acid, and 73.62 percent by weight water. This stock cobalt solution contains 5.0 percent by weight cobalt. A stock tin solution is prepared by dissolving 23.13 percent by weight dimethyltin dich loride, (CH3)2 SnC I2, in 76.87 percent by weight water.
This stock tin solution contains 12.5 percent by weight tin.
A coating solution for depositing a cobalt/tin oxide spinel-type film is prepared by combining 100 parts by volume of the stock cobalt solution with 11.08 parts by volume of the stock tin solution. The ratio of cobalt to tin is 3.5 to 1.0 and the total metal concentration is 5.85 percent by weight. The coating solution is sprayed onto a glass surface at a temperature of 1050 to 1 0700F. (about 566 to 5770C.). The coating reactants pyrolyze to form a durable, uniform cobalt/tin oxide spinel-type film on the glass surface.
EXAMPLES II THROUGH VIII
Cobalt Tin Metal
Solution Solution Concentration Cobalt/Tin
(parts by (parts by (percent by (weight
Example volume) volume) weight) ratio)
II 100 7.75 5.59 5.0/1.0 lil 100 5.96 5.44 6.5/1.0
IV 100 5.17 5.38 7.5/1.0
V 100 4.56 5.34 8.5/1.0
VI 100 4.08 5.31 9.5/1.0
VII 100 3.88 5.29 10.0/1.0
VIII 100 3.52 5.26 11.0/1.0 TABLE 1
Spectral Properties (Illuminant C) of Coblat/Tin Oxide Spinel-Type Films
Transmittance Reflectance (Coated Surface) Reflectance (Uncoated Surface)
Dominant Excitation Dominant Excitation Dominant Excitation
Luminous Wavelength Purity Luminous Wavelength Purity Luminous Wavelength Purity
Example (percent) (nonometers) (percent) (percent) (nanometers) (percent) (percent) (nanometers) (percent)
I 45.2 577.0 12.6 29.6 568.4 7.0 24.3 546.4 7.8
II 41.1 577.6 14.9 31.5 567.6 7.5 25.8 563.0 7.8
III 35.8 577.5 19.3 33.2 569.7 9.7 26.8 565.9 9.7
IV 38.6 578.7 17.2 33.5 557.2 4.5 26.3 555.7 5.3
V 36.0 577.5 20.0 33.9 567.7 8.7 27.0 564.5 9.8
VI 33.5 578.0 20.9 34.9 568.1 8.7 28.0 564.3 9.4
VII 32.6 577.6 21.5 35.0 570.0 10.3 28.4 566.2 10.4
VIII 32.4 578.0 21.2 35.7 567.8 8.6 28.6 563.3 8.9 The above examples are offered to illustrate the present invention. Various modifications apparent to ones skilled in the art are included within the scope of the present invention. Other water soluble metal compounds may be employed as well as ratios and concentrations of metals outside the range of the specific examples. Cobalt/tin oxide spinel-type coatings may be deposited in conjunction with other films and on a variety of substrates other than glass, particularly nonmetallic substrates such as ceramics and other refractory materials. The scope of the present invention is defined by the following claims.
Claims (19)
1. An aqueous solution for the pyrolytic deposition of coatings comprising cobalt, tin, and oxygen which comprises a water-solubie cobalt salt and a water-soluble tin compound.
2. A solution according to claim 1 wherein the tin compound is a tin chloride or an alkyltin chloride.
3. A solution according to claim 1 or 2, wherein the cobalt compound is cobalt acetate, cobalt nitrate or cobalt perchlorate.
4. A solution according to claim 1,2 or 3 wherein the solution comprises dimethyltin chloride and cobalt acetate.
5. A solution according to any of claims 1 to 4wherein the ratio of cobalt to tin ranges from 2:1 to 20:1 and the total metal concentration ranges from 1 to 12 percent by weight of the solution.
6. A solution according to claim 5 wherein the ratio of cobalt to tin is from 5:1 to 12:1 and the total concentration of metal in the solution ranges from 5 to 6 percent.
7. An aqueous solution for the pyrolytic deposition of coatings substantially as herein described with referene to and as illustrated in any of the Examples.
8. A coated substrate prepared by contacting a substrate surface at a temperature sufficient to pyrolyze a metal compound to a metal oxide with an aqueous solution as claimed in any of claims 1 to 7.
9. A coated substrate according to claim 8 in which the substrate is glass at a temperature of at least 500"F. (about 260"C.).
10. A coated substrate according to claim 9 wherein the glass surface is at a temperature of about 1000 to 1200"F. (about 538 to 650"C).
11. A coated substrate according to claim 9 or 10 which has the following properties with respect to
Illuminant C: luminous transmittance - 30 to 50 percent, dominant wavelength of transmitted light - 575 to 580 nanometers, excitation purity of transmitted light - 10 to 25 percent; from the coated surface: luminous reflectance - 25 to 40 percent, dominant wavelength of reflected light 555 to 575 nanometers, excitation purity of reflected light 4 to 12 percent; from the uncoated surface: luminous reflectance - 20 to 30 percent, dominant wavelength of reflected light - 550 to 570 nanometers, and excitation purity of reflected light - 4 to 12 percent.
12. A coated substrate according to claim 8 wherein the substrate is a non-metallic refractory material.
13. A coated substrate substantially as herein described with reference to and as illustrated in any of the
Examples.
14. A method for depositing a film comprising the oxides of cobalt and tin comprising the steps of:
a. maintaining a substrate in an oxidizing atmosphere at a temperature sufficient to pyrolyze a metal compound to a metal oxide; and
b. containing the surface of the substrate at said temperature with an aqueous solution comprising a water-soluble cobalt salt and a water-soluble tin compound capable of thermal decomposition to cobalt oxide and tin oxide, thus forming a cobalt/tin oxide spinal-type film.
15. A method according to claim 14 wherein the substrate is glass.
16. A method according to claim 15 wherein the substrate surface is at a temperature of at least 5000F.
(about 260"C.).
17. A method according to claim 16 wherein the substrate surface is at a temperature of about 10000F. to 1200 F. (about 538 to 6500C.).
18. A method for depositing a film comprising the oxides of cobalt and tin substantially as herein described with reference to and as illustrated in any of the Examples.
19. Substrate coated by a method according to any of claims 14to 18.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US92168678A | 1978-07-03 | 1978-07-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2024189A true GB2024189A (en) | 1980-01-09 |
| GB2024189B GB2024189B (en) | 1982-08-25 |
Family
ID=25445826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7923105A Expired GB2024189B (en) | 1978-07-03 | 1979-07-03 | Pyrolytic deposition of a cobalt/tin oxide spinel film |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS558495A (en) |
| AU (1) | AU525347B2 (en) |
| CA (1) | CA1146702A (en) |
| DE (1) | DE2926243A1 (en) |
| FR (1) | FR2434126A1 (en) |
| GB (1) | GB2024189B (en) |
| IT (1) | IT1192651B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5094882A (en) * | 1990-12-12 | 1992-03-10 | Ford Motor Company | Zinc oxide film growth rate accelerator |
| EP0524481A1 (en) * | 1991-07-20 | 1993-01-27 | Th. Goldschmidt AG | Process for the surface treatment of hollow glass articles |
| WO2024052668A1 (en) * | 2022-09-06 | 2024-03-14 | Pilkington Group Limited | Process for depositing a layer |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL105456C (en) * | 1958-12-24 | |||
| GB1153761A (en) * | 1966-01-24 | 1969-05-29 | Nippon Sheet Glass Co Ltd | Glass having a Coloured Zone whose Boundary has been Blurred and method of producing the same |
-
1979
- 1979-04-06 CA CA000325036A patent/CA1146702A/en not_active Expired
- 1979-04-24 FR FR7910308A patent/FR2434126A1/en not_active Withdrawn
- 1979-05-03 AU AU46726/79A patent/AU525347B2/en not_active Ceased
- 1979-05-31 JP JP6810079A patent/JPS558495A/en active Granted
- 1979-06-28 IT IT23944/79A patent/IT1192651B/en active
- 1979-06-29 DE DE19792926243 patent/DE2926243A1/en not_active Withdrawn
- 1979-07-03 GB GB7923105A patent/GB2024189B/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5094882A (en) * | 1990-12-12 | 1992-03-10 | Ford Motor Company | Zinc oxide film growth rate accelerator |
| EP0524481A1 (en) * | 1991-07-20 | 1993-01-27 | Th. Goldschmidt AG | Process for the surface treatment of hollow glass articles |
| WO2024052668A1 (en) * | 2022-09-06 | 2024-03-14 | Pilkington Group Limited | Process for depositing a layer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS558495A (en) | 1980-01-22 |
| DE2926243A1 (en) | 1980-01-17 |
| JPS6311300B2 (en) | 1988-03-14 |
| FR2434126A1 (en) | 1980-03-21 |
| CA1146702A (en) | 1983-05-24 |
| AU4672679A (en) | 1980-01-10 |
| GB2024189B (en) | 1982-08-25 |
| IT1192651B (en) | 1988-05-04 |
| IT7923944A0 (en) | 1979-06-28 |
| AU525347B2 (en) | 1982-11-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |