IL104438A - Decorative multicolored glass and method of its manufacture - Google Patents

Description

DECORATIVE MULTICOLORED GLASS AND METHOD OF ITS MANUFACTURE V> (3 ' .JIG 'Z / DECORATIVE MULTICOLORED GLASS AND METHOD OF ITS MANUFACTURE Inventors : Friedrikh D. Kaminsky , Ninel L. Kaminsky Harav Kaniel str. 11/94 33199, Haifa Israel.

Appl . No Filed : Int. CI. C03C 3/ U.S. CI. 501 /32 Filed of Search : 501 /32, 501 /3, 501 /9, 501 /86 References Cited : U.S. PATENT DOCUMENT 4311529 6/1980 Danielson et al. 501/32 5070044 1/1991 Linda R. , Pinckney 501/3 S.U. PATENT DOCUMENT 874686 6/1981 Kaminsky et al. C03C 3/20 1530587 Al 8/1989 Nazimova et al. ( 51 ) 4 C03C 3/102, 4/102 OTHER PUBLICATIONS Engineered Materials Hand book. V.4 Ceramics and Glasses. ASM International the Materials Inform.

Soc. (1990) .

A. Paul. Chemistry of Glasses . Chapman and Hall (1990) ABSTRACT Decorative glass, wherein microcrystals and colloidal particles constitute the multicolored opacifying pattern, which, after heat treatment, exhibits dense coloration ranging from violet through blue to tftn to ivory and / or from dark-brown through blood-red to beige-brown to yellow-greenish, consisting essentially, expressed in terms weight percent : Chart 1 Chemical composition ranges Components Amount (weight percent) - 58 A½ 03 1 - 6 4 - 21 - 2 0 - 5 P2os 0 - 2.5 - 2 02-5 0 - 2 0 - 2 - 0.5 Coa Oj 0 - 0.2 - 1 0 - 1 SnO 0 - 0.5 01-1.5 A method for making a decorative multicolored glass having a melting temperature below 1400 eC, an average coefficient of thermal expansion in the range from about 75*10*' per °C up to about 95*10"' per °C at a temperature between 20 °C and 400°C , compression strength more than 600 MPa, microhardness (Vickers) about 8 GPa, water absorption (by wt%) about 0.01 and acid resistance to IN HgSO^ (by wt.%) about 99.5 s is shown.

BACKGROUND OF THE INVENTION 1. Field of the Invention The invention relates to a glass suitable for use in manufacturing of decorative and jewel products and more particularly applies to a glass consisting essentially of silicon dioxide ( SiOA ), aluminum oxide ( A-jOj ), alkaline earth oxides ( MgO,CaO,SrO and BaO ), titanium and zirconium dioxides ( TiOa, Zr04 ) , alkali oxides ( Li30, NaaO, Kj ), lead and zinc oxide ( PbO,ZnO ), boron oxide ( Β4¾ ), devitrification and reducing agents, colorants, which after heat treatment exhibits an opaque colored phase. 2. Description of the Prior Art Glasses suitable for use in manufacturing of decorative and jewel articles are well known in the art. One example of such a glass is disclosed in U.S. Pat. 5070043 filed Oct. 26 1990. It is also known in the art to produce decorative glass materials for ornamental articles and jewellery. Examples of such processes and glass materials are disclosed in U.S. Pat.

Nos 4703020 and 5114883. U.S. Pat. Nos 4767725 and 5010042 disclosed crystallized glass molded and sintered products of different colors and methods of their manufacturing.

Commonly manufacture of decorative multicolored multilayer crystallized glasses sufficiently complicated and expensive as it is necessary to have simultaneously some glasses of different color and composition and to join them.

In U.S. Pat. 5089444 it was disclosed a method of fabrication of colored crystallized glass by adding coloring agents ( Fea θ3 , CoO , NiO , Cra O3 ) to a crystallized glass material, molding the resulting mixture under pressure from 500 up to 3000 kg/cm*" and calcining the molded mixture to perform crystallization heat treatment. This method is also difficult and expensive for production of decorative articles.

The use of silicon monoxide as a reducing agent to intensify red color of ruby glass was described in an article entitled Copper Ruby Glass Based on Lead Crystal by N. Kaminsky and L. Nevsky which appeared in the Glass and Ceramics (Steklo i Keramika) N 9, September, 1982, at pages 24 -25. 3. Summary of the present invention The glass composition of the present invention is a novel, unique and improved glass composition which can be utilized for manufacturing multicolored decorative tiles and plates for interior room and furniture decoration and souvenirs , artistic and jewel articles.

The glass composition consists essentially of the following components ( by weight percent ): SiOa - 58 AlaOA 1 - 6 - 21 - 22 - 2 - 14 - 10 - 2 B3O3 - 5 pa 05 - 2.5 .5 .2 - 1 - 0.5 01-1.5 The glass composition of the present invention has a combination of components which interact in such manner that they form continuous series of solid solutions.

Therefore , one of the advantages of the present invention is that variation of RaO - CaO - MgO - TiOa - SiOa melt composition , devitrification and reducing agents , colorants and their melting temperatures results in the formation of a multicolored glass crystalline material ( where R is Li,Na and K ).

Another advantage of the present invention is that at least one of the used reducing components is silicon monoxide.

Another advantage of the present invention is that the glass composition contains colorants and reducing agents in a definite molar ratio.

Another advantage of the present invention is that the said molar ratio is following: Fea03 + FeO ) / SiO CuO + CuaO ) / SiO Another advantage of the present invention that said above molar ratio is allowed to regulate the intensity of different colors in glass.

Another advantage of the present invention that variation of CaO - MgO - TiOa - SiO^ , devitrification and reducing agents, colorants and their molar ratio are allowed to create multicolored glass crystalline material of different degree of transparency and color ranging from violet through blue to ten to ivory and from dark-brown through blood-red to beige-brown to yellow-greenish.

Another advantage of the present invention is that the method for manufacture of decorative glass includes the steps of glass melting at a temperature below 1400 °C, forming glass articles at a temperature below 1300 °C, heat treatment of glass articles at a temperature below 850 ¾ during a time sufficient to produce formation and growth of microcrystals and colloidal particles, slow cooling of glass articles to room temperature in order to avoid formation of residual stresses therein.

Another advantage of the present invention is that the decorative multicolored crystallized glass has a melting temperature below 1400 °C, an average coefficient of thermal expansion in the range of about 75*10"' per ¾ up to about 95*10"? per % at a temperature between 20 °C and 400 °C, water absorption (by wt.%) about 0.01, acid resistance to IN HaSO^ (by wt%) about 99.5, compression strength more than 600 MPa and microhardness (Vickers) about 8 GPa. 4. Description of the preferred embodiment Glass materials used in manufacture of decorative and jewel products determine their artistic expressiveness and physical and chemical properties.

An advantage of the present invention is that multicolored decorative glasses having (in wt.%) silicon dioxide (SiOjj ) of 37 to 58, aluminum oxide (Aa03) of 1 to 6, calcium and magnesium oxides (CaO+MgO) of 4 to 21, titanium and zirconium dioxides (Ti03+Zr¾ ) of 8 to 22, alkali oxides (Lip +Na20+KaO) of 6 to 14, lead and zinc oxides (PbO+ZnO) of 0 to 10, barium and strontium oxides (BaO+SrO) of 0 to 2, boron oxide (B2 ) of 0 to 5, devitrification agents (F and Ρ^Οά) , reducing agents (SnO and SiO) and colorants (Fe203, CuO, Mn^C^ Cr¾ 03 , Co 203 , Se, Sb¾ 03 ) are characterized by improved physical and chemical properties.

A glass of present invention has an average coefficient of thermal expansion in the range of about 75*10"?per°C to about 95*10"? per eC at a temperature between 20 "C and 400°C, compression strength more than 600 MPa, microhardness (Vickers) about 8 GPa, water absorption (by wt%) about 0.01, acid resistance to IN HaSO¾(by wt%) about 99.5.

Examples of glass compositions for practicing the invention is set forth in Chart 1 A and B herein below: CHART 1 Examples of glass composition PART A 5 MgO - - - 1 0.

TiOa 8 11 12 14 15 ZrO¾ - 2 1 0.5 0.

Lij,0 1 - 0.5 0.5 - Na20 6 4 2 2 2.

KxO . 7 7 8 7 7 PbO 10 4.5 3 5 5 ZnO - - 2 1 1.

SrO - - - - - BaO - 2 - - - B403 1 2 2.5 1.8 - P40_> - 0.49 1 1.7 1.

F 0.48 - 2 - 1.

Fe2O^FeO 0.02 0.1 1 1.5 1 CuO+Cu20 2 - 0.5 - - MnaOj - 2 - - - CojOj - - - 0.2 - Se - - - - 1 Sb403 - - - - 1 SnO 0.5 - 0.25 - - SiO 1 0.01 0.25 0.3 0.

PART B Components Ex-6 Ex-7 Ex-8 Ex-9 SiOa 42 40 39 37 4 4.7 5 6 CaO 14 15 16 18 MgO 1.5 2 2 3 TiOz 16 17 18 21 ZrOa - 1 - 1 Lij.0 - 1 - - Na20 2 2 2 2 K20 7 6 5 4 PbO 6 - - - ZnO 2 - - - SrO - 0.8 - - BaO - 1.2 - - B203 1 2 5 - Ps.05 1.94 1 2.5 0.5 F - 1.5 - 1 Fe¾ ¾ +FeO 2 3 3.5. 5 CuO+CuaO - 1.5 1 - MntO¾ 0.5 - - - Cr2Os - - 0.5 - Co203 0.01 - - - SnO - 0.1 - - SiO 0.05 0.2 0.5 1.5 The glass compositions of the preferred embodiment of the invention are presented in the columns under Examples Ex-3 and Ex-6 in the above described Chart.

It ie envisioned that the decorative multicolored glass could be used in a wide variety of applications, such as for producing decorative ornamental objects useful for furniture, interior and exterior walls, corridors, columns, desks etc. and souvenirs, artistic and jewel articles.

Claims (6)

What is claimed is:

1. Decorative glass, wherein microcrystals and colloidal particles constitute the multicolored opacifying pattern which, after heat treatment, exhibits a dense coloration ranging from violet through blue to tan to ivory and/or from dark-brown through blood-red to beige-brown to yellow-greenish, consisting essentially, expressed in terms of weight percent, of: SiOa. 37 - 58 A1203 1 - 6 4 - 21 TiOa+Zr02.... .8 - 22 2rOz .0 - 2 Li20+Na20+K20 .6 - 14 .0 - 10 SrO+BaO .0 - 2 BaOj .0 - 5 Pa Os .0 - 2.5 F .0 - 2 Fe2<¾+FeO .0. 02 -5 CuO+CUgO .0 - 2 MnJ 03 .0 - 2 C 203 .0 - 0.5 Coa03 .0 - 0.2 Se .0 - 1 Sb20S .0 - 1 SnO .0 - 0.5 SiO .0. 01 -1.5

2. A decorative glass of Claim 1 containing silicon monoxide at least as one of reducing agents, wherein the molar ratios of colorants Fe^Oj +FeO and/or CuO+Cu^O to silicon monoxide comprise: (Fe^03+FeO)/SiO = 1 - 11 (CuO+Cu^O) /SiO = 1 - 4.5

3. A decorative glass of Claims 1 and 2 wherein the glass consists of approximately the following composition in weight percent : SiOa 51 Al2Oa 2 CaO 11 TiOj 12 Zr02 1 Li¾0 0.5 NaaO 2 K20 8 PbO 3 ZnO 2 Ba03 2.5 P2°5 1 F 2 Fe¾03+FeO 1 CuO+CuaO 0.5 SnO 0.25 SiO 0.25 Wherein the molar ratios of colorants Fe O +FeO and CuO+Cu O to silicon monoxide comprise: (Fe203+FeO)/SiO 1.1 (CUO+CU2.O) /SiO 1.1.

4. A decorative glass of Claims 1 and 2 wherein the glass consists of approximately the following composition in weight percent: SiO^ 42 Α1Ζ05 4 MgO 1.5 CaO 14 Tio≥. 16 Na20 2 KjO 7 PbO 6 ZnO 2 BaOa 1 p¾o5 1.94 FeA03+FeO 2 Mna03 0.5 Coa03 0.01 SiO 0.05 Wherein the molar ratio of colorants Fe^05+FeO to silicon monoxide comprises: (Fe203+FeO)/SiO 11

5. A method for manufacture of decorative glass of Claims 1, 2 , 3, 4 comprising the steps of glass melting at a temperature below 1400°C, forming of glass articles at a temperature below 1300°C, heat treatment of glass articles at a temperature below 850eC during time sufficient to produce formation and growth of microcrystals and colloidal particles, slow cooling of glass articles to room temperature in order to avoid formation of residual stresses therein.

6. A decorative glass with a composition substantially as herein before described. Inventors! (Friedrikh D. Kaminsky) (Ninel L . Kaminsky)