CN110015844B

CN110015844B - Insulating glass and preparation method and application thereof

Info

Publication number: CN110015844B
Application number: CN201910242810.0A
Authority: CN
Inventors: 李志祥; 孙爱华; 张海青; 段雷; 张建飞; 许高杰; 郭建军; 程昱川; 刘丰华
Original assignee: Ningbo Institute of Material Technology and Engineering of CAS
Current assignee: Ningbo Institute of Material Technology and Engineering of CAS
Priority date: 2019-03-28
Filing date: 2019-03-28
Publication date: 2021-10-29
Anticipated expiration: 2039-03-28
Also published as: CN110015844A

Abstract

The invention belongs to the field of glass manufacturing, and particularly discloses insulating glass, which comprises the following components in an expression formula: (Bi)₂O₂)²⁺(A_m‑ ₁B_mO_3m+1)^2‑Wherein m has a value range of 1<m is less than or equal to 10, A comprises Bi, and optionally comprises any one or more of Al, Ln or Y; b comprises Si, the mole fraction of Si element in the metal element is 10 mol% -50 mol%, and B also comprises any one or more of Ti, Zr or Sn. The invention also provides a preparation method of the insulating glass. The formula of the invention does not contain alkali metal, alkali metal and boron, not only improves the insulativity and stability of the glass, but also improves the hardness and scratch resistance of the glass, is suitable for industrial large-scale production, and the produced insulating glass can be applied to the fields of preparing art glass and sealing.

Description

Insulating glass and preparation method and application thereof

Technical Field

The invention belongs to the field of glass manufacturing, and particularly relates to insulating glass and a preparation method and application thereof.

Background

Glass is a material with a plurality of excellent properties, and is widely applied to the fields of daily utensils, architectural decoration, automobiles, food packaging, medical treatment, chemical industry, optical devices, electronic equipment and the like. With the development of science and technology, the requirements on the performance of electronic components and the working environment thereof are higher and higher, for example, in the field of aerospace, the adoption of high-performance sealing glass can ensure that the electronic components still maintain a low leakage rate under the vacuum and high-temperature difference environment; in the field of heating of stainless steel thick films, a glass insulating film with the thickness of about 0.1 millimeter is adopted, so that the insulating and heat conducting effects can be achieved, and compared with other traditional heating modes, the heating device is higher in heat conductivity, higher in heat efficiency and better in safety.

At present, in the field of low-temperature lead-free sealing glass, a boron-bismuth-silicon system or an alkaline earth metal-aluminosilicate glass ceramics system is generally adopted. The boron-containing glass has a loose structure, a large thermal expansion coefficient and poor insulation, and is rarely used in the field of insulating glass; the alkali earth metal-aluminosilicate glass ceramics system has better insulating property because the thermal expansion coefficient can be adjusted, and is commonly used for systems which need electric insulation, such as stainless steel thick film heating and the like.

For example, the Chinese patent application with publication No. CN102482139A discloses a composition comprising mica and glass comprising 10-30 mol% SiO₂，5-40mol％BaO，15-30mol％B₂O₃The total content of zinc oxide, alkali metal oxide and alkaline earth oxide in the glass is 15-65 mol%. Such compositions are useful for molding at temperatures above the Tg of glass to form composite parts that can be used as electrical insulators.

However, the alkaline earth metal in the glass system has certain moisture absorption, and particularly when the content of the alkaline earth metal is high, non-bridge oxygen in the glass is increased, a silica network is broken, the structure is loose, the insulation performance is poor, the leakage current is obviously increased in a humid environment, and the requirement of safe power utilization is not met. Particularly in the field of packaging of voltage dependent resistor arresters, because the arresters are outdoors for a long time, and are blown by wind, rain and subjected to ultrahigh voltage, a new glass system with stable structure and good insulating property needs to be found.

Disclosure of Invention

The invention aims to provide the insulating glass with a specific formula, and the formula does not contain alkali metal, alkali metal and boron, so that the insulativity and stability of the glass are improved, the hardness and scratch resistance of the glass are improved, and the insulating glass is suitable for industrial large-scale production.

The invention discloses insulating glass, which comprises the following components in an expression formula:

(Bi₂O₂)²⁺(A_m-1B_mO_3m+1)^2-；

in the formula, the value range of m is 1< m < 10, A comprises Bi, and the selection comprises any one or more of Al, Ln or Y; b comprises Si and any one or more of Ti, Zr or Sn, wherein the Si accounts for 10-50 mol% of the metal element.

Generally, glass is an amorphous structure, a disordered structure is formed on a crystal structure, the invention can form some ordered bismuth layer-shaped perovskite structure ceramics locally by strictly limiting the proportion of 3-valent metal ions and 4-valent metal ions, so as to form a glass-ceramic system (also called microcrystalline glass), and because the layer structure has obvious anisotropy, conductive electrons and ions can be obviously scattered on the normal plane of the layer, so that the glass-ceramic system has high insulating strength.

In addition, the layered structure not only has poor light transmission, but also has a scattering effect on light, and when the glass reaches a certain thickness, the glass displays black due to weak intensity of reflected light, so that the effect of developing color without coloring ions can be achieved. In addition, because the formula does not contain elements such as alkali metal, alkaline earth metal, boron and the like, ion conductivity can not be formed under a high-voltage electric field, and the insulating property is good; furthermore, since the insulating film does not contain an oxide which is liable to absorb moisture, the insulating property can be maintained at a high level even in a humid environment. Moreover, because the titanium oxygen octahedron and the silicon oxygen octahedron are stable in structure, the glass of the system has high hardness and good scratch resistance.

Preferably, m is in the range of 1< m.ltoreq.5, and more preferably 2. ltoreq. m.ltoreq.3.

The proportion value of the 3-valence metal element and the 4-valence metal element in the formula composition is not continuously adjustable, but is limited to be near a plurality of specific values according to different m values, so that the range of the m value is strictly limited, the content ratio of the glass and the ceramic of a glass system is more suitable when m is more than or equal to 2 and less than or equal to 3, and the obtained glass has the best comprehensive performances such as insulation, gloss and the like. Too large a value of m results in too high a ceramic content and poor gloss, while too small a value of m results in unstable glass structure and poor insulating properties.

The molar fraction of the Si element in the metal element is preferably 15 mol% to 35 mol%, and more preferably 20 mol% to 30 mol%. When the Si content is too low, glass formation is not easy, and when the Si content is too high, the content of the ceramic phase is reduced and the insulating property is not high, so that it is necessary to control the Si content in a suitable range.

The insulating glass prepared according to the expression has the insulating strength of more than 50kv/mm and very high insulating strength.

The invention also discloses a preparation method of the insulating glass, which comprises the following steps: based on the component expression, uniformly mixing reaction raw materials, smelting for 0.5-96 hours at the temperature of 600-1600 ℃, and cooling to obtain the insulating glass.

Preferably, the temperature is 1100-1300 ℃, the smelting is carried out for 0.5-2 hours, and the glass product with stable structure and excellent insulating property can be obtained under the smelting condition.

After the clear molten glass is obtained by smelting, a glassware is prepared by adopting the modes of pouring, blowing, stretching and the like, or a water quenching mode is adopted, glass slag is directly obtained from the molten glass, and the glass slag is prepared into glass powder after being crushed for the use of the electronic and packaging industries.

The invention also discloses the application of the insulating glass in the sealing field, the softening sealing temperature range of the glass is 300-1000 ℃ by adjusting the formula, the low-temperature sealing glass and the high-temperature sealing glass are covered, and the application range is wider.

The invention also discloses the application of the insulating glass in the preparation of art glass, and the glass of the invention does not need CuO or MnO₂CoO and Fe₃O₄The coloring agent can realize the change among transparency, translucency, opaqueness, gold, yellow and black only by finely adjusting the formula, has bright color, can be used for manufacturing the artistic glass by utilizing simple formula change, and has strong application prospect.

Compared with the prior art, the invention has the following beneficial effects:

(1) the glass component does not contain boron which is a carcinogenic substance, so that the production process is safer; the glass prepared by the formula has the characteristics of low ionic conductivity, no moisture absorption, good and stable insulating property and the like.

(2) The raw material sources used by the glass of the invention are wider, the adjustable range of the glass is wider, in the traditional glass, the content of elements such as Ti, Zr, Sn and the like is lower, otherwise, the elements can be crystallized, in the glass prepared by adopting the formula, the content of the elements can reach 10mol percent or more, more elements can enter a glass grid, and many properties of the glass have the characteristic of number average addition, so the glass is more free in the aspect of glass performance regulation.

(3) The glass provided by the invention has the advantages that through formula adjustment, the softening temperature can cover 300-1000 ℃, the low-temperature sealing glass and the high-temperature sealing glass are covered, and the application range is wider.

(4) The system glass does not contain boron, alkali metal and alkaline earth metal, the glass liquid has weaker corrosivity to the crucible at high temperature, the adopted crucible material has wider source, the noble metal platinum crucible can be effectively avoided being used, and the noble metal resource is saved.

(5) The glass of the system does not contain CuO and MnO₂CoO and Fe₃O₄The coloring agent is mixed only by micro-blendingThe glass can realize the change among transparency, translucency, opacity, gold, yellow and black, has bright color, can be used for manufacturing art glass, and has wide application range.

(6) The insulating glass has the advantages of few preparation processes, simple process, low requirement on equipment and easy industrial large-scale production and application.

Drawings

FIG. 1: an optical photograph of the product of example 1, wherein x in fig. 1(a), (b), (c), and (d) is 0.6, 1.2, 1.8, and 2.4, respectively;

FIG. 2: an optical photograph of the product obtained when x is 1.8 in example 1;

FIG. 3: SEM photograph of the product obtained when x is 1.2 in example 1;

FIG. 4: an X-ray diffraction pattern of the product obtained when X is 1.2 in example 1;

FIG. 5: an elemental Analysis (AFS) spectrum detection chart of a product obtained when x is 1.2 in example 1;

FIG. 6: the withstand voltage measurement results of the product obtained when x is 1.2 in example 1;

FIG. 7: a nanoindentation measurement chart of the product obtained when x is 1.2 in example 1;

FIG. 8: optical photographs of the product of example 2;

FIG. 9: x-ray diffraction pattern of the product of example 2;

FIG. 10: optical photograph of the product of example 3.

Detailed Description

The invention is described in further detail below with reference to the accompanying examples.

Example 1

When m is 3, A is Bi, B is Si and Ti, and the specific expression is (Bi)₂O₂)²⁺(Bi₂Ti_3-xSi_xO₁₀)^2-Then x is respectively taken from 0.6, 1.2, 1.8 and 2.4, and Bi with specific molar ratio is weighed according to the molar ratio among the metal elements₂O₃、TiO₂And SiO₂Mixing, smelting at 1250 deg.C for 1.5 hr, and mixingPouring into a corundum crucible at room temperature, the product obtained is shown in FIG. 1. The background with characters in the photo is mainly used for explaining the light transmission of the glass, and from left to right, the larger the value of x, the better the light transmission, and the clearer the handwriting.

When x is 0.6, the glass obtained is as shown in fig. 1(a), and the molar fraction of silicon element in the glass to the metal element is 8.57 mol%, and a yellow translucent glass cannot be obtained. When x is 1.2, 1.8, 2.4, the obtained glass can obtain yellow translucent glass as shown in fig. 1(b), (c), and (d) in sequence, and the transparency of the glass gradually increases as the background writing becomes clearer with the increase of the content of silicon oxide. Fig. 2 shows the monolithic glass product obtained when x is 1.8, which is 25.7 mol% in terms of mole fraction.

When x is 1.2, the expression of the obtained product is (Bi)₂O₂)²⁺(Bi₂Ti_0.6Si_2.4O₁₀)^2-The microscopic scanning photograph is shown in fig. 3, and from SEM, the product is a glassy substance with continuity and no distinct grain boundaries; the X-ray diffraction pattern of the product is shown in figure 4, and as can be seen from the test result, no obvious crystallization peak is found, the whole pattern is an amorphous substance with a bulge structure, and the obtained product is proved to be glass; the results of the elemental analysis of the product are shown in FIG. 5, from which it can be seen that the product contained only Bi₂O₃、TiO₂And SiO₂And other trace elements which are negligible and do not contain B, which is common in conventional glasses₂O₃Alkali metals and alkaline earth metals, further demonstrating that the formulations provided by the present invention are novel glass systems.

Will be expressed as (Bi)₂O₂)²⁺(Bi₂Ti_0.6Si_2.4O₁₀)^2-The product glass was ground into a sheet of 0.5mm thickness, and silver electrodes having a diameter of about 5mm were coated on the surface of the sheet, and the IV curve was measured using a high voltage power supply, a voltmeter, and an ammeter, and the test results are shown in fig. 6. Through the IV curve, the resistance of the glass can be calculated to be in the order of 100G ohm, and the withstand voltage is more than 10⁵V/mm higher than that of common glassEdge strength (1.0-2.5) × 10⁴Level of V/mm.

The expression is (Bi)₂O₂)²⁺(Bi₂Ti_0.6Si_2.4O₁₀)^2-The nanoindenter test result of the product is shown in fig. 7, and the average hardness of the glass is 10Gpa, and the young modulus is 120Gpa on average, which is higher than that of the ordinary glass, namely 55 Gpa.

Example 2

When m is 3, A is Al and Bi, B is Si and Ti, and the specific expression is (Bi)₂O₂)²⁺(BiAlTiSi₂O₁₀)^2-Weighing a certain amount of Bi according to the molar ratio among the metal elements₂O₃、Al₂O₃、TiO₂And SiO₂After being mixed uniformly, the mixture was melted at 1250 ℃ for 1.5 hours, and then the resultant was poured into a corundum crucible in a room temperature state, and the resultant was obtained as shown in FIG. 8.

The obtained product is a black opaque glass-like substance, and the energy spectrum test result of the obtained product is shown in fig. 9, and it can be seen from the figure that the product is a glassy substance which is continuous and has no obvious grain boundary. The product only contains Bi₂O₃、Al₂O₃、TiO₂And SiO₂And other trace elements which are negligible and do not contain B, which is common in conventional glasses₂O₃Alkali metals and alkaline earth metals, further demonstrating that the formulation provided by the present invention is a new glass system.

Example 3

To verify the compositional expression of the present invention (Bi)₂O₂)²⁺(A_m-1B_mO_3m+1)^2-Effectiveness of the method, specially introducing Ca commonly used in the traditional soda-lime-silica glass²⁺According to the expression (Bi)₂O₂)²⁺(CaAlTiSi₂O_8.5)^2-Weighing certain amount of CaO and Bi₂O₃、Al₂O₃、TiO₂And SiO₂Mixing, melting at 1250 deg.C for 1.5 hr, and pouring the obtained product into corundum crucible at room temperatureThe product obtained is shown in figure 10.

As can be seen from fig. 10, the obtained product is yellow on the outside, flesh on the center, no glass luster, obvious granular boundaries and ceramic-like substance, and further proves that the formula provided by the invention does not contain alkaline earth metals common in the traditional glass and is a new glass system.

Claims

1. An insulating glass, characterized in that the composition expression of the insulating glass is:

(Bi₂O₂)²⁺(A_m-1B_mO_3m+1)^2-；

in the formula, m is 3, A comprises Bi, and any one or more of Al, Ln or Y is selected; b comprises Si and any one or more of Ti, Zr or Sn, wherein the Si accounts for 10-50 mol% of the metal element.

2. The insulating glass according to claim 1, wherein the Si element accounts for 15 mol% to 35 mol% of the molar fraction of the metal element.

3. The insulating glass according to claim 2, wherein the Si element accounts for 20 mol% to 30 mol% of the molar fraction of the metal element.

4. The insulating glass of claim 1, wherein the insulating glass has an insulating strength greater than 50 kv/mm.

5. A method for producing an insulating glass according to any one of claims 1 to 4, comprising: based on the component expression, uniformly mixing reaction raw materials, smelting for 0.5-96 hours at the temperature of 600-1600 ℃, and cooling to obtain the insulating glass.

6. The method for preparing insulating glass according to claim 5, wherein the temperature is 1100 to 1300 ℃ and the melting is performed for 0.5 to 2 hours.

7. Use of an insulating glass according to any of claims 1 to 4 in the sealing field, wherein the sealing temperature of the insulating glass is 300 to 1000 ℃.

8. Use of an insulating glass according to any one of claims 1 to 4 in the manufacture of an art glass.