阅读说明：本技术 一种消除介质浆料用高铋玻璃粉中气泡的方法 (Method for eliminating air bubbles in high-bismuth glass powder for dielectric paste ) 是由 张豪 周碧 雷莉君 王要东 艾志远 于 2021-10-19 设计创作，主要内容包括：本发明公开了一种消除介质浆料用高铋玻璃粉中气泡的方法,该方法是按高铋玻璃粉的配方组成配料后进行混料、熔炼,待所有原材料熔融完成,玻璃液表面出现大量气泡或“气盖”后,使用鼓风机通过耐高温空心陶瓷管向玻璃液中通入二氧化碳气体消除气泡。本发明通过往熔融玻璃液中通二氧化碳,可使玻璃液中气泡含量大幅度降低,操作简单,成本较低,且二氧化碳的热稳定性极好,基本不溶于高温状态的熔融玻璃液,可以有效消除玻璃气泡且不影响玻璃本身性能。(The invention discloses a method for eliminating bubbles in high-bismuth glass powder for dielectric paste, which comprises the steps of mixing materials according to the formula of the high-bismuth glass powder, smelting, and introducing carbon dioxide gas into glass liquid through a high-temperature resistant hollow ceramic tube by using an air blower to eliminate bubbles after a large number of bubbles or 'gas caps' appear on the surface of the glass liquid after all raw materials are melted. The invention can greatly reduce the bubble content in the molten glass by introducing carbon dioxide into the molten glass, has simple operation, lower cost and excellent thermal stability of the carbon dioxide, is basically insoluble in the molten glass in a high-temperature state, can effectively eliminate the glass bubbles and does not influence the performance of the glass.)

1. A method for eliminating air bubbles in high-bismuth glass powder for dielectric paste is characterized by comprising the following steps: mixing materials according to the formula of the high-bismuth glass powder, then mixing the materials, smelting the materials after the materials are uniformly mixed, introducing carbon dioxide gas into the glass liquid through a high-temperature resistant hollow ceramic tube by using an air blower to eliminate bubbles after all raw materials are melted and a large number of bubbles or 'gas caps' appear on the surface of the glass liquid, then quenching the glass liquid with water, and drying, ball-milling and sieving the obtained glass slag.

2. The method for eliminating bubbles in a high bismuth glass powder for dielectric paste as claimed in claim 1, wherein: the flow velocity of the carbon dioxide gas is 2-5 cubic meters per hour, and the introduction time is 10-40 minutes.

3. The method for eliminating bubbles in a high bismuth glass frit for dielectric paste as claimed in claim 1 or 2, wherein: any one of the high bismuth glass powder Bi-B-Si-Al system glass powder, Bi-B-Si system glass powder and Bi-Zn-Si-Al system glass powder.

4. The method for eliminating bubbles in the high bismuth glass powder for dielectric paste as claimed in claim 3, wherein: the Bi-B-Si-Al system glass powder comprises the following components in percentage by weight: 45-61% of bismuth oxide, 4-9% of boron oxide, 23-36% of silicon dioxide, 1-7% of aluminum oxide, 1-6% of zinc oxide and 1-7% of sodium carbonate.

5. The method for eliminating bubbles in the high bismuth glass powder for dielectric paste as claimed in claim 4, wherein: the melting temperature of the Bi-B-Si-Al system glass powder is 1100-1250 ℃, and the heat preservation time is 60-90 minutes.

6. The method for eliminating bubbles in the high bismuth glass powder for dielectric paste as claimed in claim 3, wherein: the Bi-B-Si system glass powder comprises the following components in percentage by weight: 35-50% of bismuth oxide, 15-28% of boron oxide and 25-40% of silicon dioxide.

7. The method for eliminating bubbles in the high bismuth glass powder for dielectric paste as claimed in claim 6, wherein: the melting temperature of the Bi-B-Si system glass powder is 1200-1350 ℃, and the heat preservation time is 60-90 minutes.

8. The method for eliminating bubbles in the high bismuth glass powder for dielectric paste as claimed in claim 3, wherein: the Bi-Zn-Si-Al system glass powder comprises the following components in percentage by weight: 33-50% of bismuth oxide, 14-28% of silicon dioxide, 10-22% of aluminum oxide and 15-26% of zinc oxide.

9. The method for eliminating bubbles in a high bismuth glass powder for dielectric paste as claimed in claim 8, wherein: the melting temperature of the Bi-Zn-Si-Al system glass powder is 1350-1500 ℃, and the heat preservation time is 60-120 minutes.

Technical Field

The invention belongs to the technical field of dielectric paste glass powder, in particular relates to a glass smelting preparation process, and relates to a method for eliminating bubbles in high-bismuth glass powder for dielectric paste, so as to improve the performance defect of the glass powder.

Background

The high bismuth glass powder is always the first choice of the glass powder in the dielectric paste, and has the advantages of realizing lead-free materials, lower softening point of the high bismuth glass, higher chemical stability, being capable of being used in more complex environment, and good performance of sintering film, acid resistance and electrical property of the paste; however, with the development of the times, the requirements of people on electronic materials are higher and higher, the problems of the dielectric paste prepared from the high-bismuth glass powder are gradually increased, and the performance of the glass powder serving as the dielectric paste with the weight ratio of more than 50% directly influences the performance condition of the subsequent paste; for example, the Bi-B-Si-Al system high bismuth glass powder is used as the largest high bismuth glass powder for the dielectric paste, so that a large amount of bubbles can be generated in the glass smelting process of the system, even a 'gas cap' is formed due to excessive bubbles, huge defects are caused to glass, the subsequent performance of the glass is seriously influenced, the bubbles are difficult to remove by a traditional method or the glass characteristics are changed due to the removal of the bubbles, and a method for effectively eliminating the glass bubbles without influencing the performance of the glass needs to be found.

Disclosure of Invention

The invention aims to provide a method for eliminating air bubbles in high-bismuth glass powder for dielectric paste.

Aiming at the purposes, the technical scheme adopted by the invention is as follows: mixing materials according to the formula of the high-bismuth glass powder, then mixing the materials, smelting the materials after the materials are uniformly mixed, introducing carbon dioxide gas into the glass liquid through a high-temperature resistant hollow ceramic tube by using an air blower to eliminate bubbles after all raw materials are melted and a large number of bubbles or 'gas caps' appear on the surface of the glass liquid, then quenching the glass liquid with water, and drying, ball-milling and sieving the obtained glass slag.

Preferably, the flow velocity of the carbon dioxide gas is 2-5 cubic meters per hour, and the time of the carbon dioxide gas is 10-40 minutes.

Any one of the high bismuth glass powder Bi-B-Si-Al bulk glass powder, Bi-B-Si bulk glass powder, Bi-Zn-Si-Al bulk glass powder and the like.

The Bi-B-Si-Al system glass powder comprises the following components in percentage by weight: 45-61% of bismuth oxide, 4-9% of boron oxide, 23-36% of silicon dioxide, 1-7% of aluminum oxide, 1-6% of zinc oxide and 1-7% of sodium carbonate, wherein the smelting temperature is 1100-1250 ℃, and the heat preservation time is 60-90 minutes.

The Bi-B-Si system glass powder comprises the following components in percentage by weight: 35-50% of bismuth oxide, 15-28% of boron oxide and 25-40% of silicon dioxide, wherein the smelting temperature is 1200-1350 ℃, and the heat preservation time is 60-90 minutes.

The Bi-Zn-Si-Al system glass powder comprises the following components in percentage by weight: 33-50% of bismuth oxide, 14-28% of silicon dioxide, 10-22% of aluminum oxide and 15-26% of zinc oxide, wherein the smelting temperature is 1350-1500 ℃, and the heat preservation time is 60-120 minutes.

The invention has the following beneficial effects:

the invention can greatly reduce the bubble content in the molten glass by introducing carbon dioxide into the molten glass. Compared with the traditional method for eliminating bubbles, the method is more effective for the high-bismuth glass powder; compared with the temperature rise, the over-high temperature can lead bismuth oxide in the glass melt to be over oxidized, thereby losing the performance of the glass melt; compared with the method that a stirring device is added, the stirring rod which extends into the molten liquid can not stir all bubbles, especially the 'gas cap', into the molten glass liquid to form backflow, and the effect is not ideal; compared with the addition of the defoaming agent, the addition of the defoaming agent can introduce new impurities or destroy the original glass system, thereby causing great unstable factors; the method is simple, has low cost and excellent thermal stability of the carbon dioxide, is basically insoluble in molten glass in a high-temperature state, can effectively eliminate glass bubbles and does not influence the performance of the glass.

Detailed Description

The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.

The grinding tool used in the following examples is made of high temperature resistant ceramic and has a cubic structure, an inner side length of 0.1 m, a thickness of 0.01 m, and an upper opening. The test method of the relative density comprises the following steps: the weight of the mold is M1, the weight of the mold after the molten glass liquid is filled and naturally cooled to the room temperature is M2, the volume of the glass is the volume of the mold (0.001 cubic meter), and the relative density of the glass is (M2-M1)/0.001; the higher the relative density, the less bubbles are contained in the glass, and conversely, the more bubbles are contained.

Example 1

The glass powder comprises the following components in percentage by weight: mixing 54% of bismuth oxide, 6% of boron oxide, 28% of silicon dioxide, 3% of aluminum oxide, 5% of zinc oxide and 4% of sodium carbonate for 2kg, pouring the mixture into a 5L turnover barrel, tightly covering the barrel cover, putting the turnover barrel into an eight-roller ball mill, and mixing the raw materials until the raw materials are uniform and have no color difference. And pouring the obtained mixture into a 2L quartz crucible, and putting the quartz crucible into a semi-closed silicon carbide rod resistance furnace for smelting at 1250 ℃ for 60 minutes. After the heat preservation is finished, introducing carbon dioxide gas into the molten glass liquid through a high-temperature resistant hollow ceramic tube by using an air blower at the flow speed of 2 cubic meters per hour for 15 minutes; pouring part of molten glass into a mold until the glass liquid is full, naturally cooling, weighing after the mold is cooled to room temperature, calculating the relative density of the obtained glass, and judging the quantity of bubbles according to the relative density; the rest glass liquid is poured into deionized water at normal temperature for quenching, the glass slag is put into a blast oven for drying for 10 hours at the drying temperature of 120 ℃, and then the softening point of the glass is tested, and the results are shown in table 1.

Comparative example 1

In example 1, the molten glass after the completion of the heat preservation was poured into a mold without introducing carbon dioxide gas, and the other steps were the same as in example 1. The relative density of the resulting glass was calculated and the softening point of the glass was tested and the results are shown in table 1.

Example 2

In example 1, the composition in terms of weight percent of the Bi-B-Si-Al bulk glass powder was: 60% of bismuth oxide, 4% of boron oxide, 23% of silicon dioxide, 7% of aluminum oxide, 3% of zinc oxide and 3% of sodium carbonate are mixed for 2kg, the melting temperature is 1100 ℃, and other steps are the same as those in the embodiment 1. The relative density of the resulting glass was calculated and the softening point of the glass was tested and the results are shown in table 1.

Comparative example 2

In example 2, the molten glass after the completion of the heat preservation was poured into a mold without introducing carbon dioxide gas, and the other steps were the same as in example 2. The relative density of the resulting glass was calculated and the softening point of the glass was tested and the results are shown in table 1.

Example 3

In example 1, the carbon dioxide gas was introduced for 40 minutes, and the other steps were the same as in example 1. The relative density of the resulting glass was calculated and the softening point of the glass was tested and the results are shown in table 1.

Example 4

In example 2, the carbon dioxide gas was introduced for 40 minutes, and the other steps were the same as in example 2. The relative density of the resulting glass was calculated and the softening point of the glass was tested and the results are shown in table 1.

TABLE 1

As can be seen from the data in Table 1, the bubble content of the Bi-B-Si-Al system glass can be effectively reduced by introducing carbon dioxide into the molten glass; however, the softening point of the glass is basically unchanged after the carbon dioxide gas is introduced, which shows that the essential performance of the Bi-B-Si-Al system glass is not influenced by the introduction of the carbon dioxide gas.

Example 5

The glass powder comprises the following components in percentage by weight: mixing 40% of bismuth oxide, 25% of boron oxide and 35% of silicon dioxide by 2kg, pouring the mixture into a 5L turnover barrel, covering a barrel cover tightly, putting the turnover barrel on an eight-roller ball mill, and mixing the raw materials until the raw materials are uniform and have no color difference. And pouring the obtained mixture into a 2L quartz crucible, and putting the quartz crucible into a semi-closed silicon carbide rod resistance furnace for smelting at 1250 ℃ for 60 minutes. After the heat preservation is finished, introducing carbon dioxide gas into the molten glass liquid through a high-temperature-resistant hollow ceramic tube by using an air blower at the flow speed of 3 cubic meters per hour for 15 minutes; pouring part of molten glass into a mold until the glass liquid is full, naturally cooling, weighing after the mold is cooled to room temperature, calculating the relative density of the obtained glass, and judging the quantity of bubbles according to the relative density; the remaining glass liquid was poured into normal temperature deionized water for quenching, the glass slag was dried in a forced air oven for 10 hours at a drying temperature of 120 c, and then the softening point of the glass was tested, the results are shown in table 2.

Comparative example 3

In example 5, the molten glass after completion of the heat preservation was poured into a mold without introducing carbon dioxide gas, and the other steps were the same as in example 5. The relative density of the resulting glass was calculated and the softening point of the glass was tested and the results are shown in table 2.

Example 6

In example 5, the composition in terms of weight percent of the Bi-B-Si bulk glass powder was: the preparation method comprises mixing bismuth oxide 45%, boron oxide 15% and silicon dioxide 40% at 1350 deg.C for 2kg, and the other steps are the same as those in example 5. The relative density of the resulting glass was calculated and the softening point of the glass was tested and the results are shown in table 2.

Comparative example 4

In example 6, the molten glass after completion of the heat preservation was poured into a mold without introducing carbon dioxide gas, and the other steps were the same as in example 6. The relative density of the resulting glass was calculated and the softening point of the glass was tested and the results are shown in table 2.

Example 7

In example 5, the carbon dioxide gas was introduced for 40 minutes, and the other steps were the same as in example 5. The relative density of the resulting glass was calculated and the softening point of the glass was tested and the results are shown in table 2.

Example 8

In example 6, the carbon dioxide gas was introduced for 40 minutes, and the other steps were the same as in example 6. The relative density of the resulting glass was calculated and the softening point of the glass was tested and the results are shown in table 2.

TABLE 2

The data in Table 2 show that the bubble content of the Bi-B-Si system glass can be effectively reduced by introducing carbon dioxide into the molten glass; however, the softening point of the glass is basically unchanged after the carbon dioxide gas is introduced, which shows that the essential performance of the Bi-B-Si system glass is not influenced by the introduction of the carbon dioxide gas.

Example 9

The glass powder comprises the following components in percentage by weight: preparing 2kg of bismuth oxide 35%, silicon dioxide 28%, aluminum oxide 22% and zinc oxide 15%, pouring the mixture into a 5L turnover barrel, covering a barrel cover tightly, putting the turnover barrel into an eight-roller ball mill, and mixing the raw materials until the raw materials are uniform and have no color difference. And pouring the obtained mixture into a 2L quartz crucible, and putting the quartz crucible into a semi-closed silicon carbide rod resistance furnace for smelting at the smelting temperature of 1500 ℃ for 90 minutes. After the heat preservation is finished, introducing carbon dioxide gas into the molten glass liquid through a high-temperature-resistant hollow ceramic tube by using an air blower at the flow speed of 5 cubic meters per hour for 15 minutes; pouring part of molten glass into a mold until the glass liquid is full, naturally cooling, weighing after the mold is cooled to room temperature, calculating the relative density of the obtained glass, and judging the quantity of bubbles according to the relative density; the remaining glass liquid was quenched in normal temperature deionized water, and the glass residue was dried in a forced air oven for 10 hours at 120 ℃ and then tested for softening point, the results are shown in table 3.

Comparative example 5

In example 9, the molten glass after completion of the heat preservation was poured into a mold without introducing carbon dioxide gas, and the other steps were the same as in example 9. The relative density of the resulting glass was calculated and the softening point of the glass was tested and the results are shown in table 3.

Example 10

In example 9, the composition in terms of weight percent of the Bi-Zn-Si-Al bulk glass powder was: the preparation method comprises the following steps of preparing 2kg of materials including 45% of bismuth oxide, 20% of silicon dioxide, 10% of aluminum oxide and 25% of zinc oxide, wherein the smelting temperature is 1350 ℃, and the other steps are the same as those in example 9. The relative density of the resulting glass was calculated and the softening point of the glass was tested and the results are shown in table 3.

Comparative example 6

In example 10, the molten glass after completion of the heat preservation was poured into a mold without introducing carbon dioxide gas, and the other steps were the same as in example 10. The relative density of the resulting glass was calculated and the softening point of the glass was tested and the results are shown in table 3.

Example 11

In example 9, the carbon dioxide gas was introduced for 40 minutes, and the other steps were the same as in example 9. The relative density of the resulting glass was calculated and the softening point of the glass was tested and the results are shown in table 3.

Example 12

In example 10, the carbon dioxide gas was introduced for 40 minutes, and the other steps were the same as in example 10. The relative density of the resulting glass was calculated and the softening point of the glass was tested and the results are shown in table 3.

TABLE 3

The data in Table 3 show that the bubble content of the Bi-Zn-Si-Al system glass can be effectively reduced by introducing carbon dioxide into the molten glass; however, the softening point of the glass is basically unchanged after the carbon dioxide gas is introduced, which shows that the essential performance of the Bi-B-Si-Al system glass is not influenced by the introduction of the carbon dioxide gas.