阅读说明：本技术 复合微晶玻璃及其制备方法 (Composite microcrystalline glass and preparation method thereof ) 是由 陈亚兵 李倩倩 许仁 王伟 于 2019-10-18 设计创作，主要内容包括：本发明涉及一种复合微晶玻璃及其制备方法。该复合微晶玻璃包括质量百分数分别为84％～94％的微晶玻璃基体、5％～15％的辅助玻璃基体以及1％～5％的粘结剂。微晶玻璃基体的膨胀系数与辅助玻璃基体的膨胀系数的差值的绝对值≤1×10<Sup>-6</Sup>/℃。采用适当配比的微晶玻璃基体、辅助玻璃基体和粘结剂,微晶玻璃基体与辅助玻璃基体相互填充,能够提高复合微晶玻璃的致密度。同时,微晶玻璃基体与辅助玻璃基体的膨胀系数的差值的绝对值≤1×10<Sup>-6</Sup>/℃,不会由于收缩差而产生内应力,使得复合微晶玻璃不易变形,能够有效保持玻璃的形状和性能的稳定性。(The invention relates to composite glass ceramics and a preparation method thereof. The composite glass ceramics comprises, by mass, 84% -94% of glass ceramics matrix, 5% -15% of auxiliary glass matrix and 1% -5% of binder. The absolute value of the difference between the expansion coefficient of the microcrystalline glass substrate and the expansion coefficient of the auxiliary glass substrate is less than or equal to 1 x 10 ‑6 V. C. The microcrystalline glass substrate, the auxiliary glass substrate and the binder are adopted in proper proportion, and the microcrystalline glass substrate and the auxiliary glass substrate are mutually filled, so that the density of the composite microcrystalline glass can be improved. Meanwhile, the absolute value of the difference value of the expansion coefficients of the microcrystalline glass substrate and the auxiliary glass substrate is less than or equal to 1 multiplied by 10 ‑6 The internal stress caused by poor shrinkage can not be generated, so that the composite glass ceramics are not easy to deform and the stability of the shape and the performance of the glass can be effectively kept.)

1. A composite glass-ceramic is characterized in that: the material comprises the following raw materials in percentage by mass:

84-94% of microcrystalline glass substrate, 5-15% of auxiliary glass substrate and 1-5% of binder;

the absolute value of the difference value between the expansion coefficient of the microcrystalline glass substrate and the expansion coefficient of the auxiliary glass substrate is less than or equal to 1 multiplied by 10^-6/℃。

2. The composite glass-ceramic according to claim 1, characterized in that: the auxiliary glass substrate is an aluminosilicate glass substrate; the glass transition temperature of the auxiliary glass matrix is less than the glass transition temperature of the microcrystalline glass matrix.

3. The composite glass-ceramic according to claim 1, wherein: the binder is polyvinyl alcohol.

4. The composite glass-ceramic according to any one of claims 1 to 3, wherein: the microcrystalline glass substrate is prepared from the following raw materials in percentage by mass: 45-65% of silicon dioxide, 10-30% of aluminum oxide, 5-15% of crystalline phase forming oxide component, 4-10% of alkali metal oxide, 2-5% of nucleating agent and 5-8% of first additive.

5. The composite glass-ceramic according to claim 4, wherein: the crystal phase forming oxide component is one or more of lithium oxide, calcium oxide and magnesium oxide; and/or the presence of a gas in the gas,

the nucleating agent is one or more of titanium dioxide, zirconium oxide and phosphorus pentoxide; and/or the presence of a gas in the gas,

the first additive is one or more of lithium oxide, lanthanum oxide, yttrium oxide, barium oxide, antimony oxide, sodium sulfate, sodium chloride and calcium fluoride.

6. The composite glass-ceramic according to any one of claims 1 to 3 and 5, wherein: the auxiliary glass substrate is prepared from the following raw materials in percentage by mass: 50-65% of silicon dioxide, 15-25% of aluminum oxide, 15-19% of alkali metal oxide and 5-10% of a second additive.

7. The composite glass-ceramic according to claim 6, wherein: the second additive is one or more of lanthanum oxide, magnesium oxide, boron oxide, antimony oxide, sodium sulfate, sodium chloride, calcium fluoride and barium oxide.

8. A method for preparing the composite glass-ceramic according to any one of claims 1 to 7, characterized in that: the method comprises the following steps:

mixing and molding the microcrystalline glass substrate, the auxiliary glass substrate and the binder to obtain a composite microcrystalline glass preform; and sintering the composite glass ceramic preform.

9. The method for producing a composite glass-ceramic according to claim 8, characterized in that: the sintering step of the composite microcrystalline glass preform comprises the following steps: sintering the composite glass-ceramic preform at 550-650 ℃ for 30-60 min, and then sintering at 740-850 ℃ for 30-120 min.

10. The method for producing a composite glass-ceramic according to any one of claims 8 to 9, characterized in that: the method also comprises the step of preserving the heat of the composite microcrystalline glass preform for 0.8-1.5 h at the temperature of 360-450 ℃ before sintering the composite microcrystalline glass preform.

Technical Field

The invention relates to the technical field of glass manufacturing, in particular to composite glass ceramics and a preparation method thereof.

Background

The microcrystalline glass has the characteristics of both common glass and ceramic. The atoms in the common glass are not regularly arranged, so the common glass is easy to break; the atoms in the interior of the ceramic are regularly arranged and have higher strength than that of the common glass, but the brightness of the ceramic is low, so that the ceramic product is greatly limited in use. The microcrystalline glass has the advantages of high brightness of common glass and good strength of ceramic, so that the microcrystalline glass is widely applied. However, the microcrystalline glass obtained by the traditional sintering method has the problems of low density, easy deformation and the like.

Disclosure of Invention

Therefore, it is necessary to provide a composite glass ceramic with high density and difficult deformation and a preparation method thereof.

The composite glass ceramics comprises the following raw materials in percentage by mass:

84-94% of microcrystalline glass substrate, 5-15% of auxiliary glass substrate and 1-5% of binder;

the absolute value of the difference value between the expansion coefficient of the microcrystalline glass substrate and the expansion coefficient of the auxiliary glass substrate is less than or equal to 1 multiplied by 10^-6/℃。

In one embodiment, the auxiliary glass substrate is an aluminosilicate glass substrate; the glass transition temperature of the auxiliary glass matrix is less than the glass transition temperature of the microcrystalline glass matrix.

In one embodiment, the binder is polyvinyl alcohol.

In one embodiment, the microcrystalline glass substrate is prepared from the following raw materials in percentage by mass: 45-65% of silicon dioxide, 10-30% of aluminum oxide, 5-15% of crystalline phase forming oxide component, 4-10% of alkali metal oxide, 2-5% of nucleating agent and 5-8% of first additive.

In one embodiment, the crystalline phase forming oxide component is one or more of lithium oxide, calcium oxide, and magnesium oxide; and/or the presence of a gas in the gas,

the nucleating agent is one or more of titanium dioxide, zirconium oxide and phosphorus pentoxide; and/or the presence of a gas in the gas,

the first additive is one or more of lithium oxide, lanthanum oxide, yttrium oxide, barium oxide, antimony oxide, sodium sulfate, sodium chloride and calcium fluoride.

In one embodiment, the auxiliary glass substrate is prepared from the following raw materials in percentage by mass: 50-65% of silicon dioxide, 15-25% of aluminum oxide, 15-19% of alkali metal oxide and 5-10% of a second additive.

In one embodiment, the second additive is one or more of lanthanum oxide, magnesium oxide, boron oxide, antimony oxide, sodium sulfate, sodium chloride, calcium fluoride and barium oxide.

A preparation method of the composite glass-ceramic in any one of the above embodiments comprises the following steps:

mixing and molding the microcrystalline glass substrate, the auxiliary glass substrate and the binder to obtain a composite microcrystalline glass preform; and sintering the composite glass ceramic preform.

In one embodiment, the step of sintering the composite glass-ceramic preform comprises: sintering the composite glass-ceramic preform at 550-650 ℃ for 30-60 min, and then sintering at 740-850 ℃ for 30-120 min.

In one embodiment, the preparation method of the composite glass-ceramic further comprises the step of preserving the temperature of the composite glass-ceramic preform at 360-450 ℃ for 0.8-1.5 h before sintering the composite glass-ceramic preform.

The composite glass ceramics comprises a glass ceramics matrix with the mass percentage of 84 percent to 94 percent, an auxiliary glass matrix with the mass percentage of 5 percent to 15 percent and a binder with the mass percentage of 1 percent to 5 percent, and the absolute value of the difference value between the expansion coefficient of the glass ceramics matrix and the expansion coefficient of the auxiliary glass matrix is less than or equal to 1 multiplied by 10^-6V. C. By adopting the microcrystalline glass matrix, the auxiliary glass matrix and the binder which are properly proportioned, the microcrystalline glass matrix and the auxiliary glass matrix are mutually filled, and the density of the composite microcrystalline glass can be improved. Meanwhile, the absolute value of the difference value of the expansion coefficients of the microcrystalline glass substrate and the auxiliary glass substrate is less than or equal to 1 multiplied by 10^-6The temperature is lower than the temperature, the microcrystalline glass substrate and the auxiliary glass substrate cannot generate internal stress due to poor shrinkage, so that the composite microcrystalline glass is not easy to deform and the shape and the performance of the glass can be effectively maintainedAnd (4) stability.

The preparation method of the composite microcrystalline glass comprises the steps of mixing and molding the microcrystalline glass substrate, the auxiliary glass substrate and the binder, and then sintering. In the sintering process, the microcrystalline glass substrate and the auxiliary glass substrate are mutually filled, and the microcrystalline glass substrate can be crystallized to increase the difference value of the glass transition temperatures of the auxiliary glass substrate and the microcrystalline glass substrate, so that the auxiliary substrate and the microcrystalline glass substrate are more fully filled, and the prepared composite microcrystalline glass has high density. Meanwhile, the microcrystalline glass matrix and the auxiliary glass matrix cannot generate stress among particles due to poor shrinkage, so that the composite microcrystalline glass is not easy to deform and has good stability.

Detailed Description

In order that the invention may be more fully understood, reference will now be made to the accompanying examples. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

An embodiment of the invention provides composite glass ceramics, which comprises the following raw materials in percentage by mass:

84-94% of microcrystalline glass substrate, 5-15% of auxiliary glass substrate and 1-5% of binder;

the absolute value of the difference value between the expansion coefficient of the microcrystalline glass substrate and the expansion coefficient of the auxiliary glass substrate is less than or equal to 1 multiplied by 10^-6/℃。

Preferably, the composite glass ceramics comprise the following raw materials in percentage by mass:

84-94% of microcrystalline glass substrate, 5-15% of auxiliary glass substrate and 1-5% of binder;

the absolute value of the difference value between the expansion coefficient of the microcrystalline glass substrate and the expansion coefficient of the auxiliary glass substrate is less than or equal to 1 multiplied by 10^-6/℃。

In a specific example, the composite glass ceramics comprise the following raw materials in percentage by mass:

86-90% of microcrystalline glass substrate, 8-12% of auxiliary glass substrate and 2-5% of binder;

the absolute value of the difference value between the expansion coefficient of the microcrystalline glass substrate and the expansion coefficient of the auxiliary glass substrate is less than or equal to 5 multiplied by 10^-7/℃。

Preferably, the composite glass ceramics comprise the following raw materials in percentage by mass:

86-90% of microcrystalline glass substrate, 8-12% of auxiliary glass substrate and 2-5% of binder;

the absolute value of the difference value between the expansion coefficient of the microcrystalline glass substrate and the expansion coefficient of the auxiliary glass substrate is less than or equal to 5 multiplied by 10^-7/℃。

Further preferably, the expansion coefficient of the microcrystalline glass substrate is equal to the expansion coefficient of the auxiliary glass substrate.

In the embodiment, the raw materials of the composite microcrystalline glass comprise a microcrystalline glass substrate, an auxiliary glass substrate and a binder, and the microcrystalline glass substrate, the auxiliary glass substrate and the binder are properly proportioned, so that the viscosity of the auxiliary glass substrate is low when the microcrystalline glass substrate and the auxiliary glass substrate are at a sintering temperature due to the difference of glass transition temperatures of the microcrystalline glass substrate and the auxiliary glass substrate, and the auxiliary glass substrate is easily filled in gaps of the microcrystalline glass substrate, so that the density of the composite microcrystalline glass is improved. Meanwhile, the absolute value of the difference value of the expansion coefficients of the microcrystalline glass substrate and the auxiliary glass substrate is less than or equal to 1 multiplied by 10^-6And at/DEG C, the microcrystalline glass substrate and the auxiliary glass substrate cannot generate internal stress due to poor shrinkage to cause the reduction of the overall strength of the composite microcrystalline glass. In addition, the glass transition temperature and the viscosity of the microcrystalline glass substrate are high in the sintering process, so that the glass-ceramic composite material is preparedThe synthetic microcrystalline glass is not easy to deform, and the stability of the shape and the performance of the glass can be effectively kept.

In one particular example, the binder is polyvinyl alcohol. Preferably, the binder is of an average molecular weight of 0.8X 10⁵～1×10⁵。

In one particular example, the auxiliary glass substrate is an aluminosilicate glass substrate; the glass transition temperature of the aluminosilicate glass matrix is less than the glass transition temperature of the microcrystalline glass matrix.

The aluminosilicate glass matrix has good chemical stability, and the chemical stability of the composite glass ceramics can be further improved by taking the aluminosilicate glass matrix and the glass ceramics matrix as raw materials. When the composite microcrystalline glass is prepared, for example, the composite microcrystalline glass is prepared by adopting a sintering method, an aluminosilicate glass substrate and a microcrystalline glass substrate exist in raw materials at the same time, the glass transition temperature of the aluminosilicate glass substrate is lower than that of the microcrystalline glass substrate, and in the sintering process, the aluminosilicate glass substrate has low viscosity, is easy to fill in gaps of the composite microcrystalline glass, reduces the porosity of the composite microcrystalline glass, and improves the density of the composite microcrystalline glass. Meanwhile, in the sintering process, the microcrystalline glass substrate can be crystallized, so that the glass transition temperature of the microcrystalline glass substrate is further increased, the difference value of the glass transition temperatures of the aluminosilicate glass substrate and the microcrystalline glass substrate can be increased, the aluminosilicate glass substrate and the microcrystalline glass substrate can be more fully filled, and the density of the composite microcrystalline glass can be further improved.

On the other hand, the absolute value of the difference between the expansion coefficient of the aluminosilicate glass matrix and that of the microcrystalline glass matrix is 1X 10 or less^-6The aluminum silicate glass substrate and the microcrystalline glass substrate do not have internal stress due to poor shrinkage, so that the composite glass is not easy to deform, the appearance of the composite microcrystalline glass can be well maintained, the deformation of the composite microcrystalline glass is reduced, the stability of the shape and the performance of the composite microcrystalline glass is maintained, and the defective rate is reduced.

In a specific example, the microcrystalline glass substrate is prepared from the following raw materials in percentage by mass: 45-65% of silicon dioxide, 10-30% of aluminum oxide, 5-15% of crystalline phase forming oxide component, 4-10% of alkali metal oxide, 2-5% of nucleating agent and 5-8% of first additive.

In a specific example, the crystal phase forming oxide component is one or more of lithium oxide, calcium oxide, and magnesium oxide.

In a specific example, one or more of titanium dioxide, zirconium oxide, and phosphorus pentoxide.

In a specific example, one or more of lithium oxide, lanthanum oxide, yttrium oxide, barium oxide, antimony oxide, sodium sulfate, sodium chloride, and calcium fluoride.

In a specific example, the auxiliary glass substrate is prepared from the following raw materials in percentage by mass: 50-65% of silicon dioxide, 15-25% of aluminum oxide, 15-19% of alkali metal oxide and 5-10% of a second additive.

In a specific example, the second additive is one or more of lanthanum oxide, magnesium oxide, boron oxide, antimony oxide, sodium sulfate, sodium chloride, calcium fluoride, and barium oxide.

An embodiment of the present invention further provides a preparation method of the above composite glass-ceramic, including the following steps:

mixing and molding the microcrystalline glass substrate, the auxiliary glass substrate and the binder to obtain a composite microcrystalline glass preform; and sintering the composite glass ceramic preform. In a specific example, the step of sintering the composite glass-ceramic preform comprises the following steps: sintering the composite glass-ceramic preform at 550-650 ℃ for 30-60 min, and then sintering at 740-850 ℃ for 30-120 min.

Preferably, the microcrystalline glass matrix is powder, and the grain size of the microcrystalline glass matrix is 1-10 μm. The microcrystalline glass substrate is powder and has the grain diameter of 1-10 mu m, which is beneficial to better mixing with the auxiliary glass substrate, so that the composite microcrystalline glass has more uniform internal structure and is easy to sinter.

Preferably, the auxiliary glass matrix is a powder, and the particle size of the auxiliary glass matrix is 1-10 μm. The auxiliary glass substrate is powder and has a particle size of 1-10 μm, which is beneficial to better mixing with the microcrystalline glass substrate, further improves the uniformity of the internal structure of the composite microcrystalline glass, and is easy to sinter.

In a specific example, the preparation method of the composite glass-ceramic further comprises the step of preserving the temperature of the composite glass-ceramic preform at 360-450 ℃ for 0.8-1.5 h before sintering the composite glass-ceramic preform. Before sintering, the composite microcrystalline glass preform is subjected to heat preservation for 0.8 h-1.5 h at the temperature of 360-450 ℃ so that the binder in the composite microcrystalline glass preform is fully decomposed to remove the binder components.

In this example, the microcrystalline glass substrate, the auxiliary glass substrate, and the binder were mixed and molded, and then sintered. In the sintering process, the microcrystalline glass substrate and the auxiliary glass substrate are mutually filled, the microcrystalline glass substrate can generate crystallization phenomenon to increase the difference value of the glass transition temperatures of the auxiliary substrate and the microcrystalline glass substrate, so that the auxiliary substrate and the microcrystalline glass substrate are more fully filled, and the prepared composite microcrystalline glass has high density. Meanwhile, the microcrystalline glass and the auxiliary glass cannot generate stress among particles due to poor shrinkage in the sintering process, so that the composite microcrystalline glass is not easy to deform and has good stability.

Preferably, in the preparation process of the composite glass ceramics, the raw materials of the glass ceramics matrix are mixed and melted into glass ceramics liquid, then the glass ceramics liquid is quenched by water to obtain glass ceramics fragments, and the glass ceramics fragments are rolled into particles with the particle size of 1-10 μm to obtain the glass ceramics particles for later use. Mixing and melting raw materials of the auxiliary glass matrix into auxiliary glass liquid, then quenching the auxiliary glass liquid with water to obtain auxiliary glass fragments, and rolling the auxiliary glass fragments into particles with the particle size of 1-10 mu m to obtain auxiliary glass particles for later use. The microcrystalline glass particles and the auxiliary glass particles are mixed and added with the binder, and then dried (such as centrifugal drying) to obtain mixed powder. And then filling the mixed powder into a mold, and performing pressure forming in a press, wherein the pressure of the pressure forming is preferably 21-50 MPa, so as to obtain the composite microcrystalline glass preform. And then preserving the heat of the composite microcrystalline glass preform at the temperature of 360-450 ℃ for 0.8-1.5 h, sintering the heat-preserved composite microcrystalline glass preform at the temperature of 550-650 ℃ for 30-60 min, and then sintering at the temperature of 740-850 ℃ for 30-120 min to obtain a composite microcrystalline glass crude product. And grinding and polishing the crude product of the composite microcrystalline glass to obtain the composite microcrystalline glass.

It can be understood that in the preparation process of the composite microcrystalline glass, the microcrystalline glass substrate and the auxiliary glass substrate can be selected from waste excess materials generated in the production and processing processes of glass, and the waste excess materials are correspondingly rolled to obtain excess material particles. And then mixing the residual material particles with a binder, and then drying, pressurizing, preserving heat, sintering, grinding and polishing to obtain the composite glass ceramics. Waste excess materials generated in the glass production and processing process are selected as raw materials, so that the method is green and environment-friendly, and can reduce the production cost.

The following are specific examples.