阅读说明：本技术 玻璃材料、玻璃粉、玻璃粉的制备方法及其应用 (Glass material, glass powder, preparation method of glass powder and application of glass powder ) 是由 于洪林 秦国斌 卢克军 张宁 于 2021-10-18 设计创作，主要内容包括：本申请提供一种玻璃材料、玻璃粉、玻璃粉的制备方法及其应用,属于封接材料技术领域。玻璃材料包括玻璃成分和陶瓷类填料,陶瓷类填料的质量百分比为0％～20％。玻璃成分按质量百分比计包括：30～55％P-(2)O-(5)、10～30％V-(2)O-(5)、3～15％CaF-(2)、5～10％Bi-(2)O-(3)、1～10％Al-(2)O-(3)、1～9％ZnO及1～5％La-(2)O-(3)。玻璃粉的原料包括该玻璃材料,膨胀系数CTE为(30～79)×10～(-7)/℃；玻璃化转变温度Tg为280℃～390℃；压制成轴向高度15mm的圆柱状烧结1h后轴向高度≤14mm。该玻璃不含铅镉,Bi-(2)O-(3)添加少,玻璃化转变温度低、膨胀系数低、化学稳定性良好且烧结流动性良好。(The application provides a glass material, glass powder, a preparation method of the glass powder and application of the glass powder, and belongs to the technical field of sealing materials. The glass material comprises a glass component and a ceramic filler, wherein the ceramic filler accounts for 0-20% of the mass percentage. The glass comprises the following components in percentage by mass: 30-55% P 2 O 5 、10～30％V 2 O 5 、3～15％CaF 2 、5～10％Bi 2 O 3 、1～10％Al 2 O 3 1-9% ZnO and 1-5% La 2 O 3 . The raw material of the glass powder comprises the glass material, and the coefficient of expansion CTE is (30-79) x 10 ‑7 /° c; the glass transition temperature Tg is 280-390 ℃; press and pressThe cylindrical sintered product with the axial height of 15mm is made into a cylinder with the axial height of less than or equal to 14mm after 1 hour of sintering. The glass does not contain lead, cadmium and Bi 2 O 3 Less addition, low glass transition temperature, low expansion coefficient, good chemical stability and good sintering fluidity.)

1. A glass material comprising a glass component and a ceramic-based filler;

the mass percentage of the ceramic filler in the glass material is 0-20%;

the glass composition comprises the following components in percentage by mass: 30 to 55 percent of P₂O₅10% -30% of V₂O₅3 to 15 percent of CaF₂5 to 10 percent of Bi₂O₃1 to 10 percent of Al₂O₃1 to 9 percent of ZnO and 1 to 5 percent of La₂O₃。

2. The glass material according to claim 1, wherein the glass composition comprises, in mass percent: 40 to 50% of said P₂O₅25% to 30% of the V₂O₅3% -6% of CaF₂8 to 10% of the Bi₂O₃1 to 3% of the Al₂O₃5 to 7 percent of ZnO and 2 to 4 percent of La₂O₃。

3. The glass material according to claim 1 or 2, wherein the ceramic-based filler comprises one or at least two of zirconium tungstate, cordierite, β -spodumene, zircon, aluminum trioxide, silica sand, willemite, and niobium pentoxide.

4. A glass frit comprising the glass material according to any one of claims 1 to 3 as a raw material;

the coefficient of expansion CTE of the glass powder is 30 multiplied by 10^-7/℃～79×10^-7/℃；

The glass transition temperature Tg of the glass powder is 280-390 ℃;

when the glass powder is pressed into a cylinder with the axial height of 15mm, the axial height after sintering for 1h is less than or equal to 14 mm.

5. The glass frit according to claim 4, wherein at least one of the following conditions (a) to (c) is satisfied:

(a) of the glass powderCoefficient of expansion CTE of 40 x 10^-7/℃～75×10^-7/℃；

(b) The glass transition temperature Tg of the glass powder is 330-370 ℃;

(c) when the glass powder is pressed into a cylinder with the axial height of 15mm, the axial height after sintering for 1h is less than or equal to 13.5 mm.

6. The glass frit according to claim 4 or 5, wherein the particle size of the glass frit satisfies d50 ═ 1 to 3 μm.

7. A method for producing the glass frit according to any one of claims 4 to 6, comprising:

the glass component is heated to melt and cooled, and then mixed with the ceramic-based filler and pulverized.

8. The manufacturing method according to claim 7, wherein in the step of heating and melting, the glass material is melted at a temperature of 800 ℃ to 1000 ℃ for 0.5h to 2 h.

9. Use of the glass frit according to any one of claims 4 to 6 for sealing an electronic component.

10. Use according to claim 9, wherein the electronic component is a high power tube or a relay socket.

Technical Field

The application relates to the technical field of sealing materials, in particular to a glass material, glass powder, a preparation method of the glass powder and application of the glass material.

Background

The manufacture and use of electronic components have strict requirements on temperature, and particularly, the risk of damage to the electronic components can be reduced by reducing the sealing temperature as much as possible in the manufacturing process. At present, the sealing glass which plays roles of connection, sealing, coating, sealing and the like in electronic components is required to be used at the temperature of 400-600 ℃ and not more than 700 ℃ at most.

Most of the low-temperature sealing glass which is commercially used at present is lead-containing glass, and lead has great harm to human bodies and the environment. Therefore, the successful development of the pollution-free low-melting-point sealing glass without lead, cadmium and the like has very important strategic significance for the industries relating to electronic component products, such as household appliances, computers, precision parts, communication, consumer electronic products and the like.

Lead-free low-temperature sealing glasses have been proposed in the prior art, the composition of which contains at least 20% Bi₂O₃In some cases Bi₂O₃Even up to 50%. Addition of Bi in large amounts₂O₃The cost of raw materials is obviously increased, and particularly, the applicability is poor for some electronic products with small additional value.

Disclosure of Invention

The purpose of the application is to provide a glass material, glass powder and glass powderThe preparation method and the application thereof can reduce Bi under the condition that lead and cadmium are not used in the glass₂O₃The addition amount of the additive is low, and the characteristics of low glass transition temperature, low expansion coefficient, good chemical stability, good sintering fluidity and the like are considered.

The embodiment of the application is realized as follows:

in a first aspect, embodiments of the present application provide a glass material comprising a glass component and a ceramic-based filler;

the mass percentage of the ceramic filler in the glass material is 0-20 percent;

the glass comprises the following components in percentage by mass: 30 to 55 percent of P₂O₅10% -30% of V₂O₅3 to 15 percent of CaF₂5 to 10 percent of Bi₂O₃1 to 10 percent of Al₂O₃1 to 9 percent of ZnO and 1 to 5 percent of La₂O₃。

In a second aspect, embodiments of the present application provide a glass frit, which includes a glass material as provided in the first aspect;

the coefficient of expansion CTE of the glass frit is 30X 10^-7/℃～79×10^-7/℃；

The glass transition temperature Tg of the glass powder is 280-390 ℃;

when the glass powder is pressed into a cylinder with the axial height of 15mm, the axial height after sintering for 1h is less than or equal to 14 mm.

In a third aspect, embodiments of the present application provide a method for preparing glass frit as provided in the second aspect, including:

the glass component is heated to melt and cooled, and then mixed with a ceramic-based filler and pulverized.

In a fourth aspect, embodiments of the present application provide a use of the glass frit as provided in the second aspect for sealing an electronic component.

The glass material, the glass powder, the preparation method of the glass powder and the application of the glass material have the advantages that:

the application provides a glass materialWithout using lead or cadmium, and Bi₂O₃The amount of (A) is low. The glass components are mixed according to specific types and dosage, and the characteristics of low glass transition temperature, low expansion coefficient, good chemical stability, good sintering fluidity and the like can be better considered under the condition of adding a small amount of or even not adding ceramic fillers for reducing the expansion coefficient.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

It should be noted that "and/or" in the present application, such as "feature 1 and/or feature 2" refers to "feature 1" alone, "feature 2" alone, and "feature 1" plus "feature 2" alone.

In addition, in the description of the present application, unless otherwise specified, the range of "a numerical value to" b numerical value "includes both the values" a "and" b ".

The following specifically describes the glass material, glass frit, and methods for producing glass frit and their applications in the examples of the present application.

In a first aspect, embodiments herein provide a glass material comprising a glass component and a ceramic-based filler.

The mass percentage of the ceramic filler in the glass material is 0-20%, wherein the mass percentage of the ceramic filler in the glass material can be 0%. By way of example, the mass percentage of the ceramic-based filler in the glass material is, for example, but not limited to, any one or a range of values between any two of 0%, 5%, 10%, 15%, and 20%.

Among them, the ceramic-based filler is used to reduce the expansion coefficient of glass. If the content of the ceramic filler is too high, the glossiness of the glass is affected, the sintering fluidity of the glass is reduced, the sintering sealing effect is affected, and phase separation between the glass component and the ceramic filler is easily caused, so that the stability of the glass is affected.

The glass comprises the following components in percentage by mass:

30 to 55 percent of P₂O₅Of the P₂O₅The mass percentage in the glass composition is, for example, but not limited to, any one of 30%, 35%, 40%, 45%, 50%, and 55% or a range between any two.

10% -30% of V₂O₅The V is₂O₅The mass percentage in the glass composition is, for example, but not limited to, any one of 10%, 15%, 20%, 25%, and 30% or a range between any two.

3 to 15 percent of CaF₂The CaF₂The mass percentage in the glass composition is, for example, but not limited to, any one of 3%, 5%, 8%, 10%, 12%, and 15% or a range between any two.

5 to 10 percent of Bi₂O₃The Bi₂O₃The mass percentage in the glass composition is, for example, but not limited to, any one of 5%, 6%, 7%, 8%, 9%, and 10% or a range between any two.

1 to 10 percent of Al₂O₃Of the Al₂O₃The mass percentage in the glass composition is, for example, but not limited to, any one of 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, and 10% or a range value between any two.

1 to 9% of ZnO, wherein the mass percentage of ZnO in the glass composition is, for example, but not limited to, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% and 9%, or any value or range between any two values.

1% -5% of La₂O₃The La₂O₃The mass percentage in the glass composition is, for example, but not limited to, any one of 1%, 2%, 3%, 4%, and 5% or a range between any two.

Wherein:

P₂O₅when the content of the glass former is low, the glass former is not easily formed into a glass state; if the content is higher, the surface of the glass powder is easy to crystallize at the pre-sintering temperature.

V₂O₅The compound takes a proper proportion, and can effectively play a role in improving the chemical stability of the product.

CaF₂The refining agent component can play a role in refining homogenized glass liquid to improve the fluidity and can also reduce the glass transition temperature.

Bi₂O₃The glass powder occupies a proper proportion, and can effectively play a role in reducing the softening temperature of the glass.

Al₂O₃The glass takes up a proper proportion, on one hand, the chemical stability of the glass is improved, and on the other hand, the glass body can be stabilized within the sealing temperature range to avoid the occurrence of crystallization. If Al is present₂O₃Higher contents result in higher glass transition temperatures of the glass.

ZnO occupies a proper proportion, and can keep the sealing glass to have better fluidity and lower glass transition temperature. If the content of ZnO is lower, the effect of improving the related performance of the glass cannot be effectively exerted; if the content of ZnO is higher, the surface of the glass powder is easy to crystallize at the pre-sintering temperature.

La₂O₃The glass is used for making the glass structure compact, occupies a proper proportion, and can effectively play a role in improving the thermal stability and the weather resistance of the low-temperature glass. If La₂O₃The higher content of the glass causes the fluidity of the glass to be reduced, thereby affecting the sintering and sealing effect.

As an example, the glass composition comprises, in mass percent: 40 to 50 percent of P₂O₅25% -30% of V₂O₅3 to 6 percent of CaF₂8 to 10 percent of Bi₂O₃1 to 3 percent of Al₂O₃5 to 7 percent of ZnO and 2 to 4 percent of La₂O₃。

The glass material provided by the application does not use lead and cadmium, and is high in safety; bi₂O₃The addition amount of the sealing compound is low, and the cost of raw materials can be reduced, so that the sealing compound is more widely applied to sealing of electronic products.

The glass components are mixed according to specific types and dosage, and the characteristics of low glass transition temperature, low expansion coefficient, good chemical stability, good sintering fluidity and the like can be better considered under the condition of adding a small amount of or even not adding ceramic fillers for reducing the expansion coefficient.

The inventor researches and discovers that on the basis of the glass material provided by the application, particularly La is added₂O₃When the glass is replaced with another metal oxide, at least one of the properties of the glass in terms of expansion coefficient, glass transition temperature, sintering fluidity, etc. is significantly affected.

For example, La₂O₃Replaced by equal amounts of TeO₂When the glass is used, the coefficient of expansion of the glass is remarkably increased. La₂O₃Replaced with an equal amount of CeO₂In this case, the glass transition temperature of the glass is remarkably increased.

In the present application, the type of the ceramic filler is not limited as long as the ceramic filler can reduce the coefficient of expansion of the glass.

As an example, the ceramic-based filler includes one or at least two of zirconium tungstate, cordierite, β -spodumene, zircon, aluminum trioxide, quartz sand, willemite, and niobium pentoxide, and is, for example, cordierite.

In addition, the form of the glass material provided in the present application is not limited, and the glass component may be a raw material powder mixture obtained by mixing the above raw materials, or may be a glass frit obtained by mixing and sintering the above raw materials.

Considering that the glass component exists in the form of raw powder mixture, it needs to be melted for subsequent use, and does not need to be treated together with the ceramic-based filler during melting.

In view of the above considerations, when the glass component is present in the form of a raw powder mixture, the glass component is optionally packaged or stored separately from the ceramic-based filler, in order to facilitate subsequent processing applications of the glass material; when the glass component is present in the form of a glass frit, the glass component and the ceramic-based filler may be mixed or separated.

In a second aspect, embodiments of the present application provide a glass frit, which includes a glass material as provided in the first aspect. Illustratively, the raw material of the glass frit is a glass material as provided in the embodiment of the first aspect.

The glass powder provided by the application does not contain lead, cadmium and Bi₂O₃The addition amount is low, and the characteristics of low glass transition temperature, low expansion coefficient, good chemical stability, good sintering fluidity and the like are considered.

Wherein:

the coefficient of expansion CTE of the glass frit is 30X 10^-7/℃～79×10^-7/. degree.C, for example, 40X 10^-7/℃～75×10^-7V. C. The glass powder has a low expansion coefficient, is well matched with electronic components, and can be well used for sealing the electronic components.

The glass transition temperature Tg of the glass frit is from 280 ℃ to 390 ℃, for example from 330 ℃ to 370 ℃. The glass powder has lower glass transition temperature Tg, and can effectively reduce the risk of damage of electronic components when being applied to sealing of the electronic components.

When the glass powder is pressed into a cylindrical shape with an axial height of 15mm, the axial height after sintering for 1 hour is less than or equal to 14mm, for example, the axial height after sintering for 1 hour is less than or equal to 13.5 mm. The axial height of the glass powder after sintering is larger, which shows that the glass powder has better sintering fluidity, and the glass component can be well sintered with the ceramic filler during sealing, so that a good sealing structure can be formed.

According to the standard of GB 9622.11-88 test method for testing the water-resistant chemical stability of electronic glass, when the water-resistant weather resistance of the glass powder is tested, the water-resistant chemical stability can reach II-III level, and the glass powder shows better chemical stability.

To better meet the sealing application requirements, in some exemplary embodiments, the glass frit has a suitable particle size requirement, wherein the particle size of the glass frit satisfies the requirement that d50 be equal to (1 μm to 3 μm), such as but not limited to any one of 1 μm, 1.5 μm, 2 μm, 2.5 μm, and 3 μm or a range between any two.

In a third aspect, embodiments of the present application provide a method for preparing glass frit, which is used to implement the preparation of the glass frit provided in the embodiments of the second aspect.

The preparation method of the glass powder comprises the following steps: the glass component is heated to melt and cooled, and then mixed with a ceramic-based filler and pulverized.

It is noted that in the present application, the manner and parameter requirements for the heating melting, cooling and pulverization can be performed in a manner well known in the art without further explanation.

In order to better achieve the processing of the glass materials provided herein, some exemplary embodiments are presented below with respect to the steps of heating to melt, cooling, and pulverizing.

Regarding the heating and melting step, the glass material is optionally melted at a temperature of 800 to 1000 ℃ for 0.5 to 2 hours. Wherein the melting temperature is, for example, but not limited to, 800 ℃, 850 ℃, 900 ℃, 950 ℃ and 1000 ℃ or a range value between any two, and the melting time is, for example, but not limited to, 0.5h, 1h, 1.5h and 2h or a range value between any two.

With respect to the cooling step, the molten material obtained in the heating and melting step is optionally treated by water quenching or sheet rolling.

As for the pulverization step, alternatively, the glass obtained by cooling is first ground into matrix glass powder, and then the matrix glass powder is mixed with a filler in proportion and then ground into ultrafine powder by a planetary ball mill or the like.

In a fourth aspect, embodiments of the present application provide a use of the glass frit as provided in the second aspect for sealing an electronic component.

As an example, the electronic component is a high-power tube or a relay socket, and the electronic component has better matching performance with the glass powder provided by the application, and can be better sealed.

The features and properties of the present application are described in further detail below with reference to examples.

In each of examples and comparative examples, the glass frit was prepared as follows:

s1, weighing raw materials according to a glass material formula, and fully mixing to prepare a mixture.

S2, melting the mixture made of the glass material for 1 hour at the temperature of 1000 ℃ to obtain a molten liquid material.

And S3, cooling the molten liquid material obtained in the step S2 by a rolling mill in a sheet rolling mode to obtain glass sheets, and then ball-milling and sieving the glass sheets to prepare the matrix glass powder.

And S4, mixing the matrix glass powder obtained in the step S3 with a ceramic filler (the ceramic filler can be not added), and grinding the mixture into ultrafine powder with d50 ═ 1-3 mu m by a planetary ball mill.

(II) in each of examples and comparative examples, the compositions of glass materials are shown in Table 1.

Wherein the compositions in the glass components and the mass percentages of the compositions in the glass components are shown; the kind of the ceramic filler is also shown, and the parts by mass of the ceramic filler are shown on a standard where the mass of the glass material is 100 parts.

TABLE 1 compositions of glass materials

(III) test example

The glass transition temperature Tg, the coefficient of expansion CTE, the water chemical resistance stability, and the sintering property of the glass frits of the respective examples and comparative examples were examined. Among them, the sintering property includes appearance after sintering and sintering fluidity.

The detection criteria are as follows:

detection of glass transition temperature Tg: the glass transition temperature Tg was measured according to the standard of GB/T19466.2-2004 determination of glass transition temperature.

Measurement of coefficient of expansion CTE: the glass powder was pressed into a cylindrical shape with an axial height of 15mm and then sintered for 1 hour. And testing the average linear expansion coefficient of the fired glass column at 25-300 ℃ according to the standard of QB/T1321-2012 ceramic material average linear expansion coefficient determination method.

And (3) detecting the water-resistant chemical stability: the water resistance and weather resistance of the glass powder are tested according to the standard of GB 9622.11-88 test method for the chemical stability of electronic glass against water. Wherein, the water-resistant chemical stability of the I grade is superior to that of the II grade, and so on.

And (3) detection of sintering performance: the glass powder was pressed into a cylindrical shape with an axial height of 15mm and then sintered for 1 hour. The appearance after sintering is reflected by the glossiness of the glass after sintering, and the sintering fluidity is reflected by the axial height of the glass column after sintering.

The results of the performance test of the glass frit are shown in table 2.

TABLE 2 Performance test results of glass frit

Combining tables 1 and 2, it can be seen that:

(1) the expansion coefficient of the glass powder provided by the embodiment of the application can be effectively controlled to be 30 multiplied by 10^-7/℃～79×10^-7/° c even 40 × 10^-7/℃～75×10^-7In the range of/° c; the glass transition temperature Tg can be effectively controlled within the range of 280-390 ℃ and even 330-370 ℃; the sintered glass glaze has at least certain luster; the axial height of the sintered 15mm glass column can reach the standard of less than or equal to 14mm and even less than or equal to 13.5 mm; the water-resistant chemical stability is effectively controlled in IIGrade I and above.

(2) As can be seen from the comparison of examples 1 and 2 with comparative example 1, as the amount of the ceramic-based filler increases, the gloss of the glass decreases; the axial height of the sintered glass is increased, which shows that the sintering fluidity of the glass is reduced; and the water-chemical resistance of the glass is reduced.

The ceramic filler in the comparative example 1 has the advantages of overproof use level, lusterless glaze surface after sintering, poor sintering fluidity and poor water-resistant chemical stability.

(3) Comparative example 2 and example 2 comparison of La₂O₃Replaced by equal amounts of TeO₂The expansion coefficient is remarkably increased, and the expansion coefficient of the glass is too high, so that the packaging requirement of the electronic component cannot be well met.

(4) Comparative example 3 and example 2 comparison of La₂O₃Replaced with an equal amount of CeO₂The glass transition temperature is obviously increased and is too high, so that the packaging requirement of electronic components cannot be well met.

(5) Comparative example 4 and example 3 have the same ratio of the other components, and the main difference is that no La is added₂O₃The stability against the aqueous chemistry is lowered.

(6) Comparative example 5 compared with example 3, the proportion of the other components is equivalent, and the main difference is that La₂O₃The addition amount of (A) is too high, and the axial height of the sintered glass is large, which indicates that the sintering fluidity is poor.

The embodiments described above are some, but not all embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.