阅读说明：本技术 一种高膨胀系数的封接微晶玻璃及低熔点加工方法 (High-expansion-coefficient sealing glass ceramic and low-melting-point processing method ) 是由 赵祥 齐圣卫 于 2020-06-19 设计创作，主要内容包括：本发明公开了一种高膨胀系数的封接微晶玻璃及低熔点加工方法,其特征在于所述高膨胀系数的封接微晶玻璃按重量份包括以下原料：SiO<Sub>2</Sub>:35-45份、ZnO:2.5-12份、Bi<Sub>2</Sub>O<Sub>3</Sub>:5.0-15.0份、Al<Sub>2</Sub>O<Sub>3</Sub>:5.5-7.5份、B<Sub>2</Sub>O<Sub>3</Sub>:7.0-15.0份、Na<Sub>2</Sub>CO<Sub>3</Sub>:2.0-3.5份、C<Sub>U</Sub>O:0.5-5.5份、TiO<Sub>2</Sub>:0.5-2.5份、P<Sub>2</Sub>O<Sub>5</Sub>:1.0-3.0份和石墨烯,低熔点加工方法晶化工序的养晶为450-480℃,本发明的有益效果是:用适量B203、Zn0和Bi2O3代替微晶玻璃中部分组分,使微晶玻璃的熔炼温度和晶化温度得到较大幅度下降,并创造性地在晶化工序中添加石墨烯,能够将无定型分子态氧化硼向晶体态氧化硼转换,且该结构对于膨胀系数具积极效果。(The invention discloses a high-expansion-coefficient sealing glass-ceramic and a low-melting-point processing method, which are characterized in that the high-expansion-coefficient sealing glass-ceramic comprises the following raw materials in parts by weight: SiO 2 2 35 to 45 portions of ZnO, 2.5 to 12 portions of Bi 2 O 3 5.0 to 15.0 portions of Al 2 O 3 5.5-7.5 parts of B 2 O 3 7.0 to 15.0 portions of Na 2 CO 3 2.0-3.5 parts of C U 0.5-5.5 parts of O and TiO 2 0.5-2.5 parts of P 2 O 5 1.0 to 3.0 portions of graphene, and the crystallization in the crystallization process of the low melting point processing method is 450-480 ℃, the invention has the advantages that a proper amount of B203, Zn0 and Bi2O3 are used for replacing partial components in the microcrystalline glass, so that the melting temperature and the crystallization temperature of the microcrystalline glass are greatly reduced, and the graphene is creatively added in the crystallization process, so that amorphous molecular boron oxide can be converted into crystalline boron oxideIn addition, the structure has positive effect on the expansion coefficient.)

1. The sealing glass ceramics with high expansion coefficient is characterized by comprising the following raw materials in parts by weight: SiO 2₂35 to 45 portions of ZnO, 2.5 to 12 portions of Bi₂O₃5.0 to 15.0 portions of Al₂O₃5.5-7.5 parts of B₂O₃7.0 to 15.0 portions of Na₂CO₃2.0-3.5 parts of C_U0.5-5.5 parts of O and TiO₂0.5-2.5 parts of P₂O₅1.0 to 3.0 portions.

2. A sealing glass-ceramic with high expansion coefficient according to claim 1, characterized in that the raw material further comprises graphene.

3. A sealing glass-ceramic with high expansion coefficient according to claim 2, characterized in that in the raw material B₂O₃The mass ratio of the graphene to the graphene is 1: 0.2-0.9.

4. A low-melting-point processing method of a sealing glass-ceramic with high expansion coefficient, which is used for preparing the sealing glass-ceramic with high expansion coefficient as claimed in any one of claims 2-3, and is characterized in that the processing method specifically comprises the following steps:

(1) a smelting process: mixing the raw material components except the graphene, adding the raw material components into a glass melting furnace, melting at 1150-1220 ℃ for 2-3 hours, and then cooling to 1020-1100 ℃ for clarification for 1.6-2 hours to prepare glass liquid;

(2) a cold quenching process: directly adding the glass liquid with the clarified surface into water, performing cold quenching to obtain a glass body, adding the glass body into a ball mill, performing ball milling to obtain glass powder with the fineness of 0.05-0.07mm, and drying;

(3) a crystallization process: putting the green body into a high-temperature box-type resistance furnace, and heating to 300-340 ℃ at the rate of 7-8 ℃/min at room temperature; heating to 750 plus 820 ℃ at the speed of 3-5 ℃/min, adding graphene, cooling to 450 plus 480 ℃ at the speed of 1-3 ℃/min, and carrying out heat preservation and crystal growth for 3-3.5 h;

(5) and (3) annealing: cooling the crystallized glass at the speed of 5-7 ℃/min, naturally cooling and rolling when the temperature is reduced to 250-300 ℃, and then grinding into glass powder;

(6) and (5) adding a binder into the glass powder obtained in the step (5) for granulation, and then preparing a glass blank.

5. A low-melting-point processing method for sealing glass ceramics according to claim 4, characterized in that the binder is PVA or PEG, and the amount of the binder is 1-3% by mass of the glass powder obtained in the step (5).

6. A low-melting-point processing method for sealing glass ceramics according to claim 4, characterized in that the sealing glass ceramics is used for sealing metal shells of electronic components or titanium alloy or aluminum alloy.

The technical field is as follows:

the invention belongs to the technical field of glass processing, and particularly relates to sealing glass ceramics with high expansion coefficient and a low-melting-point processing method.

Background art:

the traditional commercial sealing glass contains lead, and PbO-SiO and PbO-B are often selected₂0₃，PbO-B₂0-SiO₂And ZnO-PbO-SiO₂(ii) a The content of PbO is high, the pollution of lead to the environment causes attention in various aspects, and related policies or related measures are taken in many countries to limit or prohibit the use of lead-containing glass sealing materials for household electrical products, so that the microcrystalline glass for sealingLead-free treatment of (2) is indispensable.

According to the diagonal line and the adjacent principle of the periodic table of elements, elements which can replace lead are indium, tin, bismuth, indium, simple substances of ingots and oxides thereof are toxic; SnO-containing glass has poor insulating property, bismuth and other metal elements exist in the form of oxides in glass although bismuth is toxic, BiO is non-toxic, the electronic structures and atomic weights of bismuth and lead are extremely similar, and the bismuth and lead have many similar properties; therefore, in recent years, the preparation of lead-free sealing glass using bismuth instead of lead has been gaining more and more attention.

Bismuth-containing glasses currently under investigation are mainly Bi₂0₃-B₂0₃-SiO₂And Bi₂0₃-B₂0₃The glass system has a relatively low glass expansion coefficient, so that the glass crystal structure is relatively hard and fragile, is not beneficial to sealing, and cannot be suitable for sealing metal shells of electronic components or titanium alloy or aluminum alloy.

The search for a sealing microcrystalline glass which has better insulating property and is suitable for sealing the metal shell of an electronic component or the sealing of a titanium alloy or the sealing of an aluminum alloy is a hotspot of current research.

The invention content is as follows:

in order to solve the problems and overcome the defects of the prior art, the invention provides the sealing glass ceramics with high expansion coefficient and the processing method with low melting point, which can effectively solve the problem that the performances of the expansion coefficient and the insulativity are difficult to be coordinated.

The specific technical scheme for solving the technical problems comprises the following steps: the sealing microcrystalline glass with high expansion coefficient is characterized by comprising the following raw materials in parts by weight: SiO 2₂35 to 45 portions of ZnO, 2.5 to 12 portions of Bi₂O₃5.0 to 15.0 portions of Al₂O₃5.5-7.5 parts of B₂O₃7.0 to 15.0 portions of Na₂CO₃2.0-3.5 parts of C_U0.5-5.5 parts of O and TiO₂0.5-2.5 parts of P₂O₅1.0 to 3.0 portions.

Further, the raw material also comprises graphene.

Further, B in the raw materials₂O₃The mass ratio of the graphene to the graphene is 1: 0.2-0.9.

The low-melting-point processing method of the sealing glass-ceramic with high expansion coefficient is used for preparing the sealing glass-ceramic with high expansion coefficient, and is characterized by comprising the following steps:

(1) a smelting process: mixing the raw material components except the graphene, adding the raw material components into a glass melting furnace, melting at 1150-1220 ℃ for 2-3 hours, and then cooling to 1020-1100 ℃ for clarification for 1.6-2 hours to prepare glass liquid;

(2) a cold quenching process: directly adding the glass liquid with the clarified surface into water, performing cold quenching to obtain a glass body, adding the glass body into a ball mill, performing ball milling to obtain glass powder with the fineness of 0.05-0.07mm, and drying;

(3) a crystallization process: putting the green body into a high-temperature box-type resistance furnace, and heating to 300-340 ℃ at the rate of 7-8 ℃/min at room temperature; heating to 750 plus 820 ℃ at the speed of 3-5 ℃/min, adding graphene, cooling to 450 plus 480 ℃ at the speed of 1-3 ℃/min, and carrying out heat preservation and crystal growth for 3-3.5 h;

(5) and (3) annealing: cooling the crystallized glass at the speed of 5-7 ℃/min, naturally cooling and rolling when the temperature is reduced to 250-300 ℃, and then grinding into glass powder;

(6) and (5) adding a binder into the glass powder obtained in the step (5) for granulation, and then preparing a glass blank.

Further, the binder is PVA or PEG, and the using amount of the binder is 1-3% by mass of the glass powder obtained in the step (5).

Furthermore, the sealing glass ceramics are used for sealing metal shells of electronic components or titanium alloy or aluminum alloy;

the invention has the beneficial effects that:

SiO-ZnO-Bi of the invention₂O₃-Al₂O₃-B₂O₃System glass with appropriate amount of B₂0₃Zn0 and Bi₂O₃Replaces part of components in the microcrystalline glass, so that the melting temperature and the crystallization temperature of the microcrystalline glass are greatly reduced, and a crystal is obtainedThe processing method of the sealing microcrystalline glass with lower melting temperature reduces energy consumption and is beneficial to industrial application;

SiO-ZnO-Bi₂O₃-Al₂O₃-B₂O₃the system glass changes the components and the dosage of common glass ceramics, has higher expansion coefficient, obtains the glass ceramics with excellent sealing performance, and has good thermal expansion matching after sealing;

the original insulating property of a glass system can be kept by creatively adding the graphene in the crystallization process, and the fact that the graphene can convert amorphous molecular boron oxide into crystalline boron oxide under the condition of low-temperature crystallization is surprisingly found, the structure has a positive effect on the expansion coefficient, and the technical problem that the crystalline boron oxide is obtained by slowly cooling glassy boron oxide is solved,

the method for improving the expansion coefficient of the glass system by adding the graphene is realized, so that the glass system has a higher expansion coefficient, and the glass system with better insulating property and higher expansion coefficient is finally obtained.

Description of the drawings:

FIG. 1 is an electron microscope scanning image of molecular boron oxide in the prior art:

fig. 2 is a scanning electron microscope image of graphene in the prior art:

FIG. 3 is an electron microscope scanning image of crystalline boron oxide in graphene according to the present invention:

the specific implementation mode is as follows:

in the description of the invention, specific details are given only to enable a full understanding of the embodiments of the invention, but it should be understood by those skilled in the art that the invention is not limited to these details for the implementation. In other instances, well-known structures and functions have not been described or shown in detail to avoid obscuring the points of the embodiments of the invention. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.

The specific implementation mode of the invention is as follows: