Glass composition and method for producing the same

文档序号：1307423 发布日期：2020-08-11 浏览：12次中文

阅读说明：本技术 玻璃组合物及其制备方法 (Glass composition and method for producing the same ) 是由原保平于天来苏学剑莫大洪于 2016-12-23 设计创作，主要内容包括：本发明提供一种颜色均匀、耐高温、硬度高的环保玻璃组合物,其组成含有：SiO2 35-70％；Al2O3 10-35％；MgO 0-25％；ZnO 0-25％；Al2O3/(MgO+ZnO)为1-2；NiO 0.1-4％；和/或Ni2O3 0.1-4％；和/或CoO 0.05-2％；和/或Co2O3 0.05-2％；和/或Fe2O3 0.2-3％；和/或MnO2 0.1-4％；和/或Er2O3 0.4-8％；和/或Nd2O3 0.4-8％；和/或Cu2O 0.5-4％；和/或Pr2O3 0.4-8％；和/或CeO2 0.5-4％。本发明通过在基质玻璃组合物中添加能够调节玻璃颜色的着色剂,使本发明玻璃可表现出各种颜色。(The invention provides a color-uniform, high-temperature-resistant,An environmentally friendly glass composition having high hardness, comprising: SiO2 2 35‑70％；Al 2 O 3 10‑35％；MgO 0‑25％；ZnO 0‑25％；Al 2 O 3 (MgO + ZnO) is 1 to 2; NiO 0.1-4%; and/or Ni 2 O 3 0.1-4%; and/or CoO 0.05-2%; and/or Co 2 O 3 0.05-2%; and/or Fe 2 O 3 0.2 to 3 percent; and/or MnO 2 0.1-4%; and/or Er 2 O 3 0.4-8%; and/or Nd 2 O 3 0.4-8%; and/or Cu 2 0.5 to 4 percent of O; and/or Pr 2 O 3 0.4-8%; and/or CeO 2 0.5 to 4 percent. The glass of the present invention can exhibit various colors by adding a colorant capable of adjusting the color of the glass to the base glass composition.)

1. Glass composition, characterized in that it comprises a matrix glass composition and a colouring agent, said matrix glass composition comprising, in percentages by weight: SiO2₂35-70％；Al₂O₃10-35％；MgO 0-25％；ZnO 0-25％；Al₂O₃(MgO + ZnO) is 1 to 2;

the colorant comprises the following components in percentage by weight: NiO 0.1-4%; and/or Ni₂O₃0.1-4%; and/or CoO 0.05-2%; and/or Co₂O₃0.05-2%; and/or Fe₂O₃0.2 to 3 percent; and/or MnO₂0.1-4%; and/or Er₂O₃0.4-8%; and/or Nd₂O₃0.4-8%; and/or Cu₂0.5 to 4 percent of O; and/or Pr₂O₃0.4-8%; and/or CeO₂0.5-4％。

2. The glass composition of claim 1, wherein the matrix glass composition further comprises: TiO2₂0-10％；ZrO₂0-6％；P₂O₅0-5％；Sb₂O₃0-1.5％；Na₂O 0-4％；K₂O 0-4％；Y₂O₃0-10％；La₂O₃0-10％。

3. The glass composition of claim 2, wherein: na (Na)₂O+K₂O is not more than 4 percent.

4. The glass composition of any one of claims 1-3, wherein: SiO2₂40-60 percent; and/or Al₂O₃15 to 30 percent; and/or 5-20% of MgO; and/or ZnO 5-20%.

5. The glass composition of any one of claims 1-3, wherein: NiO 0.1-3%; and/or Ni₂O₃0.1-3%; and/or CoO 0.05-1.8%; and/or Co₂O₃0.05 to 1.8 percent; and/or Fe₂O₃0.2-2%; and/or MnO₂0.1-3%; and/or Er₂O₃0.4-6%; and/or Nd₂O₃0.4-6%; and/or Cu₂0.5 to 3 percent of O; and/or Pr₂O₃0.4-6%; and/or CeO₂0.5-3％。

6. The glass composition according to any one of claims 1-3, wherein the colorants are, as expressed in weight percent: NiO 0.1-3%; and/or Ni₂O₃0.1-3％。

7. The glass composition according to any one of claims 1-3, wherein the colorants are, as expressed in weight percent: 0.05 to 1.8 percent of CoO; and/or Co₂O₃0.05-1.8％。

8. The glass composition according to any one of claims 1-3, wherein the colorants are, as expressed in weight percent: cu₂0.5 to 3 percent of O; and/or CeO₂0.5-3％。

9. The glass composition according to any one of claims 1-3, wherein the colorants are, as expressed in weight percent: fe₂O₃0.2-2% and 0.05-0.3% of CoO; or Fe₂O₃0.2-2％、Co₂O₃0.05 to 0.3 percent; or Fe₂O₃0.2-2%, CoO 0.05-0.3%, NiO 0.1-1%; or Fe₂O₃0.2-2％、Co₂O₃0.05-0.3％、NiO0.1-1％。

10. The glass composition according to any one of claims 1-3, wherein the colorants are, as expressed in weight percent: pr (Pr) of₂O₃0.4-6%; or Fe₂O₃0.2-2%; or MnO₂0.1-3%; or Er₂O₃0.4-6%; or Nd₂O₃0.4-6％。

11. The glass composition according to any one of claims 1-3, wherein the colorants are, as expressed in weight percent: er₂O₃0.4-6％、Nd₂O₃0.4-4％、MnO₂0.1-2％。

12. A method of making a glass composition, comprising the steps of:

(a) ingredients

Weighing the raw materials according to the weight proportion, and pouring the raw materials into a mixer to be uniformly mixed;

(b) melting

Putting the uniformly mixed glass raw materials into a smelting furnace, melting and clarifying the glass raw materials at high temperature to melt the glass raw materials into high-temperature glass stock solution, and removing bubbles and foreign matters in the high-temperature glass stock solution;

Molding the molten high-temperature glass stock solution at a certain tapping temperature;

(d) high temperature annealing

The formed glass is annealed for 1-3 times at the temperature of 600-1000 ℃ for color development.

13. The method of claim 12, wherein step (a) comprises providing the starting materials as MgO and Na₂O、K₂O is introduced in the form of a carbonate, nitrate or sulfate, and the other components are introduced in the form of oxides.

14. The method of claim 12, wherein said melting in step (b) is at a temperature of 1400 ℃ and 1600 ℃ for a period of 2 to 20 hours; the clarification is carried out at the temperature of 1500-1700 ℃ for 2-20 h.

15. The method of claim 12, wherein the tapping temperature of step (c) is 1450-1650 ℃.

16. The method of making a glass composition according to claim 12, wherein the high temperature annealing of step (d) is for a time period of 0.5 to 8 hours.

Technical Field

The invention relates to a glass composition, in particular to a colored glass composition and a preparation method thereof.

Background

With the continuous progress of science and technology, the living standard of people is continuously improved, the requirements of green, environmental protection and health are provided for color decorative articles, and especially the requirements of environmental protection, high hardness and high temperature resistance are provided for the decorative articles prepared from color glass.

The Mohs hardness of common color glass is 5H, the Mohs hardness of a commonly used cutter is 5.5-6H, and the Mohs hardness of silicon dioxide contained in gravel or dust is 7H, so that the glass surface of the existing decoration can be scratched or abraded, and the decoration effect and the service life of the glass are influenced; meanwhile, the common color glass can not resist high temperature, starts to soften at the temperature of 500-800 ℃, and can not be further processed and used at high temperature; some common color glass is colored by heavy metal, such as green glass, most of which is colored by Cr ions, and some common color glass contains PbO as a basic component, which violates the requirement of environmental protection and influences the use.

Disclosure of Invention

The invention aims to solve the technical problem of providing an environment-friendly glass composition with uniform color, high temperature resistance and high hardness.

The invention also provides a preparation method of the glass composition.

The technical scheme adopted by the invention for solving the technical problem is as follows: a glass composition comprising a matrix glass composition and a colorant, the matrix glass composition having a composition comprising, in weight percent: SiO2₂35-70％；Al₂O₃10-35％；MgO 0-25％；ZnO 0-25％；Al₂O₃(MgO + ZnO) is 1 to 2; the colorant comprises the following components in percentage by weight: NiO 0.1-4%; and/or Ni₂O₃0.1-4%; and/or CoO 0.05-2%; and/or Co₂O₃0.05-2%; and/or Fe₂O₃0.2 to 3 percent; and/or MnO₂0.1-4%; and/or Er₂O₃0.4-8%; and/or Nd₂O₃0.4-8%; and/or Cu₂0.5 to 4 percent of O; and/or Pr₂O₃0.4-8%; and/or CeO₂0.5-4％。

Further, the matrix glass composition further contains: TiO2₂0-10％；ZrO₂0-6％；P₂O₅0-5％；Sb₂O₃0-1.5％；Na₂O 0-4％；K₂O 0-4％；Y₂O₃0-10％；La₂O₃0-10％。

Further, wherein: na (Na)₂O+K₂O is not more than 4 percent.

Further, wherein: SiO2₂40-60 percent; and/or Al₂O₃15 to 30 percent; and/or 5-20% of MgO; and/or ZnO 5-20%.

Further, wherein: NiO 0.1-3%; and/or Ni₂O₃0.1-3%; and/or CoO 0.05-1.8%; and/or Co₂O₃0.05 to 1.8 percent; and/or Fe₂O₃0.2-2%; and/or MnO₂0.1-3%; and/or Er₂O₃0.4-6%; and/or Nd₂O₃0.4-6%; and/or Cu₂0.5 to 3 percent of O; andor Pr₂O₃0.4-6%; and/or CeO₂0.5-3％。

Further, the colorant is expressed by weight percentage as: NiO 0.1-3%; and/or Ni₂O₃0.1-3％。

Further, the colorant is expressed by weight percentage as: 0.05 to 1.8 percent of CoO; and/or Co₂O₃0.05-1.8％。

Further, the colorant is expressed by weight percentage as: cu₂0.5 to 3 percent of O; and/or CeO₂0.5-3％。

Further, the colorant is expressed by weight percentage as: fe₂O₃0.2-2% and 0.05-0.3% of CoO; or Fe₂O₃0.2-2％、Co₂O₃0.05 to 0.3 percent; or Fe₂O₃0.2-2%, CoO 0.05-0.3%, NiO 0.1-1%; or Fe₂O₃0.2-2％、Co₂O₃0.05-0.3％、NiO 0.1-1％。

Further, the colorant is expressed by weight percentage as: pr (Pr) of₂O₃0.4-6%; or Fe₂O₃0.2-2%; or MnO₂0.1-3%; or Er₂O₃0.4-6%; or Nd₂O₃0.4-6％。

Further, the colorant is expressed by weight percentage as: er₂O₃0.4-6％、Nd₂O₃0.4-4％、MnO₂0.1-2％。

A method of making a glass composition, the method comprising the steps of:

(a) ingredients

Weighing the raw materials according to the weight proportion, and pouring the raw materials into a mixer to be uniformly mixed;

(b) melting

Molding the molten high-temperature glass stock solution at a certain tapping temperature;

(d) high temperature annealing

The formed glass is annealed for 1-3 times at the temperature of 600-1000 ℃ for color development.

Further, the raw material of step (a), wherein MgO, Na₂O、K₂O is introduced in the form of a carbonate, nitrate or sulfate, and the other components are introduced in the form of oxides.

Further, the melting in the step (b) is carried out at the temperature of 1400 ℃ and 1600 ℃ for 2-20 h; the clarification is carried out at the temperature of 1500-1700 ℃ for 2-20 h.

Further, the tapping temperature in the step (c) is 1450-.

Further, the duration time of the high-temperature annealing in the step (d) is 0.5 to 8 hours.

The invention has the beneficial effects that: the invention can lead the glass of the invention to show various colors by adding the colorant capable of adjusting the color of the glass into the matrix glass composition; the color glass composition prepared by the invention has high hardness, the Mohs hardness is more than 7, the color glass composition can be applied to decorative materials and ornaments, the scratch problem of common color glass is solved, and the service life is prolonged; the color glass composition prepared by the invention has extremely high softening temperature, the softening point temperature is more than 1000 ℃, and the color glass composition can be further processed and used at high temperature; the glass composition with uniform color is prepared by adopting a one-time melting method, the preparation method is simple, the cost is low, and the glass composition is suitable for large-scale production; the color glass composition prepared by the invention is environment-friendly glass without harmful substances such as lead, arsenic, chromium and the like, and can be used for decorative materials in large scale.

Detailed Description

The glass composition of the present invention comprises a matrix glass composition and a colorant, both expressed as a percentage of the total weight, wherein the matrix glass composition is present in the following weight percentage ranges and functions as follows:

SiO₂is a formed body of matrix glass, canTo improve the hardness, mechanical properties and chemical stability of the glass, if SiO₂The content exceeds 70 percent, and the glass is difficult to melt; if SiO₂The content is less than 35%, the glass is easy to crystallize, and is difficult to form stable glass and difficult to mold. Thus, the SiO of the invention₂The content is limited to 35 to 70%, preferably 40 to 60%.

Al₂O₃Can improve the hardness, mechanical properties and chemical stability of the matrix glass if Al₂O₃The content exceeds 35 percent, and the glass is difficult to melt; if Al is present₂O₃The content is less than 10%, and the performance of high hardness cannot be achieved. Thus, Al₂O₃The content of (B) is 10-35%, preferably 15-30%.

MgO is used as a cosolvent to reduce the high-temperature viscosity of the glass and improve the chemical stability and mechanical strength of the glass, and when the MgO is used alone, if the content of MgO exceeds 25%, the glass is easy to crystallize. The MgO content is therefore not more than 25%, preferably 5-20%.

ZnO is taken as a cosolvent, so that the high-temperature viscosity and the expansion coefficient of the glass can be reduced, the luster of the colored glass composition can be improved, the chemical stability and the mechanical strength of the glass are improved, and when the ZnO is singly used, if the content of ZnO exceeds 25 percent, the glass is easy to phase separate and devitrify. The content of ZnO is therefore not more than 25%, preferably 5-20%.

The inventor finds that Al is the most common Al after a great deal of experimental research₂O₃Ratio Al to the sum of MgO and ZnO₂O₃When the ratio of MgO + ZnO is less than 1, the glass becomes difficult to melt and inclusions are liable to occur; when Al is present₂O₃When the ratio of MgO + ZnO is more than 2, the hardness of the glass is drastically reduced and the glass is easily devitrified. Thus, in the glass composition of the present invention, Al₂O₃preferably,/(MgO + ZnO) is 1 to 2.

TiO₂Can increase the stability of the glass, reduce the high-temperature viscosity of the glass, improve the refractive index and dispersion of the glass and ensure that the colored glass has good luster₂If the content exceeds 10%, the phase of the glass tends to be separated. Thus, the TiO of the present invention₂The content is controlled below 10%.

ZrO₂The hardness, chemical stability, mechanical properties, devitrification properties and refractive index of the glass can be improved, and the expansion coefficient of the glass can be reduced, but when the content exceeds 6%, the melting difficulty of the glass is increased, so that the content is below 6%.

P₂O₅Can improve the transmittance of the glass and reduce the melting temperature of the glass, and the invention introduces P of not more than 5 percent₂O₅Otherwise, the hardness and softening point of the glass are reduced.

Sb₂O₃The content of the clarifying agent is not more than 1.5%, and the clarifying effect cannot be achieved too much.

Na₂O and K₂O lowers the melting and fining temperatures of the glass, increases the transparency of the glass, and increases the gloss, but Na₂O、K₂When the content of O exceeds 4%, the hardness of the glass is lowered, so that Na₂O、K₂The content of O is 4% or less. In order to obtain glass of suitable hardness and gloss, Na in the present invention₂O、K₂Total amount of O (Na)₂O+K₂O) is preferably not more than 4%.

Y₂O₃And La₂O₃The additive is added, so that the melting temperature of the glass can be reduced, the refractive index of the glass, the chemical stability of the glass color and the glass forming capability can be improved, and the Y is₂O₃And La₂O₃The respective contents are not more than 10%, and if they are too large, the devitrification property of the glass is deteriorated.

The invention prepares the colored glass composition through a melting process, and the coloring agent comprises the following components in percentage by weight:

NiO and Ni are used in the brown or green glass composition prepared by the invention₂O₃Or Pr₂O₅Is a colorant. NiO and Ni₂O₃As colorants for the preparation of brown or green glass compositions, the two components can be used individually or in mixtures, in each case in amounts of generally not more than 4%, preferably not more than 3%, if the amounts are exceeded4% too much, the colorant does not dissolve well in the glass, the lower limit of the content of each is more than 0.1%, e.g., less than 0.1%, and the color of the glass is not noticeable, e.g., NiO and Ni when mixed₂O₃The total amount is usually not more than 4% and the lower limit of the total amount is not less than 0.1%. Using Pr₂O₅As a colorant for green glass compositions, it is used alone, and is generally contained in an amount of not more than 8%, preferably not more than 6%, with the lower limit of the content being 0.4% or more, e.g., less than 0.4%, and the color of the glass being not conspicuous.

The blue glass composition prepared by the invention uses CoO or Co₂O₃As the colorant, two colorant components may be used singly or in combination, and both of them are contained in an amount of not more than 2%, preferably not more than 1.8%, respectively, and if the content exceeds 2%, the colorant is not well soluble in the glass, and the lower limit of the content of each is not less than 0.05%, for example, less than 0.05%, and the color of the glass is not conspicuous. CoO and Co, if used in admixture₂O₃The total amount is not more than 2%, and the lower limit of the total amount is not less than 0.05%.

The yellow glass composition prepared by the invention uses Cu₂O or CeO₂The two colorant components are used alone or in combination as colorant, and have a lower limit of 0.5% or more, e.g., less than 0.5%, and no significant glass color, and Cu is used alone₂O is not more than 4%, preferably not more than 3%, and if the content exceeds 4%, the glass is easily devitrified; using CeO alone₂The content is generally not more than 4%, preferably not more than 3%, for example, the content exceeds 4%, and the glass gloss is not good. When two kinds of colorants are used in combination, the total amount thereof is usually not more than 4% and the lower limit of the total amount is not less than 0.5%.

The black or gray glass compositions prepared according to the invention use Fe alone₂O₃Is a colorant; or using Fe₂O₃And CoO; or using Fe₂O₃And Co₂O₃Two colorants used in combination; or using Fe₂O₃Three colorants mixed together, CoO and NiO; or using Fe₂O₃、Co₂O₃And NiO. Colorants for the production of black and smoky grey glasses have predominantly used Fe₂O₃Coloring, the content is not more than 3%, preferably not more than 2%, and the lower limit of the content is not less than 0.2%. CoO and Co₂O₃Can increase the blackness of the glass by absorbing visible light, and is generally matched with Fe₂O₃When used in combination, the content of each component is not more than 0.3%, and the lower limit of the total amount is not less than 0.2%. NiO absorbs visible light and can increase the blackness of the glass, and the content of NiO is not more than 1% and the lower limit of the total amount is 0.2% or more when it is used in a mixture.

The purple glass composition prepared by the invention uses MnO₂As a coloring agent, it is used in an amount of not more than 4%, preferably within 3%, and its lower limit is 0.1% or more, e.g., less than 0.1%, and the color of the glass is not conspicuous.

Er is used in the pink glass composition prepared by the invention₂O₃As a colorant, it is generally used in an amount of not more than 8%, preferably within 6%. Because of rare earth element Er₂O₃The coloring efficiency is low, when the content exceeds 8 percent, the color of the glass cannot be further deepened, but the cost of the glass is increased, and the lower limit of the content is more than 0.4 percent, such as less than 0.4 percent, and the color of the glass is not obvious.

The purple red glass composition prepared by the invention uses Nd₂O₃As a colorant, it is generally used in an amount of not more than 8%, preferably within 6%. Due to rare earth element Nd₂O₃The coloring efficiency is low, the use content exceeds 8 percent, the color of the glass cannot be further deepened, the cost of the glass is increased, the lower limit of the content is more than 0.4 percent, such as less than 0.4 percent, and the color of the glass is not obvious.

Er is used in the red glass composition prepared by the invention₂O₃、Nd₂O₃And MnO₂The red glass composition can be prepared by mixing the three substances, namely the mixed colorant, Er ions in the glass have absorption at 400-500nm, Mn ions mainly have absorption at 500nm, Nd ions mainly have strong absorption at 580nm, and the Er ions are mixed with the mixed colorant₂O₃And Nd₂O₃Coloring rare earth, relatively weak coloring ability, Er₂O₃The usage amount is less than 6 percent, Nd₂O₃The amount of Mn ion is within 4%, the coloring is strong, the amount is within 2%, and the lower limit of the total amount of the mixed colorant is above 0.9%.

The preparation method of the colored glass composition comprises the following steps:

(a) ingredients

Weighing the raw materials according to the weight ratio, pouring the raw materials into a mixer, and uniformly mixing the raw materials to obtain a glass raw material;

(b) melting

Putting the glass raw materials into a smelting furnace, melting and clarifying the glass raw materials at high temperature, dissolving the glass raw materials into high-temperature glass stock solution, and removing bubbles and foreign matters in the high-temperature glass stock solution;

Molding the molten high-temperature glass stock solution at a certain tapping temperature;

(d) high temperature annealing

And annealing the formed glass at high temperature to develop color.

The raw material of the step (a), wherein MgO and Na₂O、K₂O is introduced in the form of a carbonate, nitrate or sulfate, and the other components are introduced in the form of oxides. The melting in the step (b) is carried out, wherein the melting temperature is 1400-1600 ℃, and the melting time is 2-20 h; the clarification temperature is 1500-. The tapping temperature in the step (c) is 1450-1650 ℃, the high-temperature annealing in the step (d) is 600-1000 ℃, the duration time is 0.5-8h, and the high-temperature annealing is carried out for 1-3 times.

The glass composition with uniform color is prepared by adopting a one-step melting method, has the advantages of high hardness, good thermal stability, good chemical stability, good wear resistance, environmental protection and the like, and can be used for high-grade decoration projects such as decorative materials, building inner and outer walls, floors, pillars and the like.

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