CN114213000A - Sealing glass blank for electric connector and preparation method thereof - Google Patents
Sealing glass blank for electric connector and preparation method thereof Download PDFInfo
- Publication number
- CN114213000A CN114213000A CN202111609265.8A CN202111609265A CN114213000A CN 114213000 A CN114213000 A CN 114213000A CN 202111609265 A CN202111609265 A CN 202111609265A CN 114213000 A CN114213000 A CN 114213000A
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- China
- Prior art keywords
- sealing
- glass
- sealing glass
- electric connector
- cao
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B15/00—Drawing glass upwardly from the melt
- C03B15/14—Drawing tubes, cylinders, or rods from the melt
Abstract
A sealing glass blank for an electric connector and a preparation method thereof are characterized in that: the composition and the mass percentage of each component comprise SiO2：66~75%，B2O3：16~25%，P2O5：0.1~2.0%，Al2O3：0.1~3.9%，CaO：1~6%，MgO：1~6%，CaO+MgO：2~8%，MnO2：0.1~2%，SrF2：0.1~2%，SnO2/Sb2O3：0.1~2%，B2O3/(SiO2+Al2 O3): 0.13 to 0.35. The sealing glass blank prepared by the oxide component ratio has the advantages of high size precision, less bubbles in the sealing part, high sealing strength, good electrical performance and the like, the relative dielectric constant is less than or equal to 4.5 at the frequency of 5GHz, and the dielectric loss is less than or equal to 3 multiplied by 10‑3The sealing temperature is as low as 880-900 ℃, and the sealing airtightness is less than or equal to 1.0 multiplied by 10‑7 Pa·cm3S, suitable for use as high frequencyThe accurate positioning sealing of the electric connector and the sealing glass with super-long size under the condition can reduce the impedance delay and the signal transmission loss of the electronic device.
Description
Technical Field
The invention belongs to the technical field of glass preparation, relates to the field of electronic glass, and particularly relates to a sealing glass blank for an electric connector and a preparation method thereof.
Background
With the rapid development of electronic industry technology, the role of electrical connectors is becoming more and more important. The electric connector is widely applied to the high-tech fields of electronic communication, aerospace, national defense, military industry and the like, and the precision degree and the working reliability of the electric connector directly influence the normal work of the circuit of the related electronic equipment. Therefore, the quality and reliability of the sealing glass of the electrical connector are required to be higher.
In recent years, the operating frequency ranges of radio frequency connectors, microwave devices and the like are greatly improved, in order to reduce impedance delay and power loss caused by the operating frequency ranges, low-resistivity metal and low-dielectric materials can be used as interconnection media to meet the use requirements, and low-dielectric sealing glass is an ideal candidate material. The frequency of electromagnetic waves used in the signal transmission process is above GHz, and the smaller the dielectric constant of the material is, the faster the signal propagation rate is; the smaller the dielectric loss of a material, the smaller its propagation loss at a fixed propagation frequency. Therefore, there is a need for a sealing glass for electrical connectors having a low dielectric constant and dielectric loss.
However, at present, the sealing glass for the domestic high-end electric connector is mainly monopolized by foreign manufacturers, becomes a technical bottleneck restricting the development of downstream industries, and affects the safety of related industrial chains in China. The problems of the sealing glass for the electric connector in China mainly comprise: 1. the sealing glass has high dielectric constant and dielectric loss, and is difficult to meet the use requirement of a high-end electric connector on dielectric performance; 2. the sealing glass exists in the form of granulated powder, so that a spray granulation process is required, but the production process has high energy consumption and low yield; 3. the traditional sealing granulation powder needs to use procedures of blank making, wax removal and the like in the subsequent use process, the sealing process is complex, and the problems of air bubbles, incomplete glue removal and the like are very easy to exist after sealing; 4. the sealing glass is easy to have the problem of poor interface compatibility with a sealed piece, and the sealing temperature is higher, which affects the sealing effect of the device.
Disclosure of Invention
Aiming at the practical problems of the sealing glass for the electric connector at present, the invention develops a sealing glass blank for the electric connector and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
seal for electric connectorThe glass-connecting blank is characterized by being prepared from the following oxides in percentage by mass, SiO2 66~75%，B2O3 16~25%，P2O5 0.1~2.0%，Al2O3 0.1~3.9%，CaO 1~6%，MgO 1~6%，CaO+MgO 2~8%，MnO2 0.1~2%，SrF2 0.1~2%，SnO2/Sb2O3 0.1~2%，B2O3/(SiO2+Al2 O3) 0.25~0.35。
The further optimized technical scheme is as follows: the sealing glass blank for the electric connector is made of oxides with the following mass percentage of SiO2 69~71%，B2O3 23~25%，P2O5 0.5~2.0%，Al2O3 0.5~2.0%，CaO 2~5%，MgO 1~5%，CaO+MgO 3~6%，MnO2 0.2~1.5%，SrF2 0.5~1.5%，SnO2/Sb2O3 0.2~1%，B2O3/(SiO2+Al2 O3) 0.3~0.34。
The invention also provides a preparation method of the sealing glass blank for the electric connector, which is characterized by comprising the following steps:
a. preparing a mixture: converting the oxides into introduced compound raw materials according to the formula, weighing the compound raw materials according to the mass percentage, fully and uniformly mixing the raw materials in a mixer added with zirconium balls, and mixing for 1-3 hours to prepare a mixture;
b. melting: loading a crucible in a high-temperature electric furnace, adding the mixture, raising the temperature to 1550-1600 ℃ according to a step temperature system, and preserving the heat for 90-180 minutes to obtain clarified molten glass;
c. and cooling the melted glass liquid by 200-300 ℃, then carrying out tube drawing and forming operation to prepare a long glass tube with the required diameter, and then cutting the long glass tube into glass blanks with the required length to finally obtain the sealing glass blanks for the electric connector.
The further technical proposal is that when the frequency of the prepared sealing glass blank is 5GHz, the relative dielectric constant is less than or equal to 4.5, and the dielectric loss is less than or equal to 3 multiplied by 10-3。
The further technical proposal is thatThe sealing temperature of the sealing glass blank is 880-900 ℃, and the sealing air tightness is less than or equal to 1.0 multiplied by 10-7 Pa·cm3/s。
In the invention, the reasons for selecting the functions and contents of the glass components in the formula and the technical principle on which the invention is based are as follows:
the dielectric constant is mainly related to the polarizability of ions, the polarizability of the ions is mainly determined by the electron displacement polarizability of the ions and the glass network structure, and the lower the electron displacement polarizability of the ions is, the higher the polymerization degree of the network structure is, the lower the dielectric constant is; the dielectric loss is mainly influenced by the compactness of the glass network structure, and the higher the compactness of the network is, the smaller the dielectric loss is.
SiO2Is a glass network forming body, the increase of the content is beneficial to reducing the dielectric constant, but the high content can cause large viscosity of glass liquid and difficult melting, and the SiO in the invention2The suitable range of (A) is 66-75%; b is2O3Ionic polarizability ratio of SiO2Low, [ BO ]3]Can be converted into [ BO4]To improve the compactness of the network, so that B is properly improved2O3The content of (A) can reduce the dielectric constant and dielectric loss of the glass. At the same time B2O3Has good fluxing effect and can effectively reduce the high-temperature viscosity of the glass. But B2O3The content of B in the invention is too high, which causes the problems of poor water resistance of sealing glass and the like and influences the sealing effect2O3The suitable range of (A) is 16-25%; p2O5Having a specific SiO ratio2Lower ionic polarizability, and P2O5The viscous activation energy of the melt is small, so that P is properly introduced2O5Is beneficial to reducing the dielectric constant and the melting temperature of the glass. But too much P is introduced into the glass2O5Can cause the deterioration of chemical stability and influence the sealing effect, and P in the invention2O5The suitable range of (A) is 0.1-2.0%; al (Al)2O3The introduction of aluminum enables the formation of aluminotetrahedra by the oxygen of the phosphorus-oxygen double bond, which has the effect of improving and strengthening the glass structure, but Al2O3Excessive use of Al in the present invention leads to an increase in the dielectric constant and dielectric loss of the glass2O3The suitable range of (A) is 0.1-3.9%; CaO and MgO are used for adjusting the high-temperature viscosity of the molten glass and promoting the melting and clarification of the molten glass, but the dielectric constant of the glass is increased due to excessive use amount, and the appropriate range of CaO and MgO is 2-15%; MnO2Can reduce the glass melting temperature, has lower ionic polarizability and plays a role in reducing the dielectric constant and dielectric loss. When the device is sealed, it contains MnO2The glass has better interface compatibility with metals such as iron and the like in a sealed piece, plays a role in enhancing the sealing effect, but the dielectric constant is greatly increased due to too much using amount, and MnO in the invention2The suitable range of (A) is 0.1-2%; SrF2Can accelerate the reaction of glass formation, reduce the viscosity and surface tension of molten glass, promote the clarification and homogenization of the molten glass, and reduce the surface tension to be beneficial to the formation of a glass drawing tube, and meanwhile, Sr2+Can also reduce the dielectric loss, the SrF in the invention2The suitable range of (A) is 0-2%; selection of SnO2/Sb2O3The composite clarifier is used as the clarifier of the invention, can achieve good clarification effect at lower temperature, the better the clarification effect of the sealing glass is, the more beneficial to the subsequent sealing effect, the SnO in the invention2/Sb2O3The suitable range of the composite clarifying agent is 0.1-2%.
Compared with the prior art, the invention has the following advantages:
has the advantages that: 1. the invention has simple raw material components and lower cost, and the prepared sealing glass has low dielectric constant and dielectric loss; 2. the preparation method is unique, the traditional spray granulation method is abandoned for preparing the glass powder, the sealing glass is directly prepared into the glass blank, the complex processes of glass powder granulation, blank preparation, glue discharge and the like are omitted, and the sealing process is greatly reduced; 3. the glass blank has good sealing effect, does not have the problems of bubbles, incomplete glue discharge and the like after heating and sealing, has the advantages of high size precision, less bubbles in the sealing piece, high sealing strength, good air tightness and the like, and is suitable for accurately positioning and sealing electronic devices and sealing ultra-long glass; 4. the high energy consumption procedures such as drying and granulating of the glass powder are avoided, the energy is greatly saved, and the preparation process conforms to the policies of carbon peak reaching and carbon neutralization.
Detailed Description
A sealing glass blank for an electric connector and a preparation method thereof are disclosed, the specific embodiment adopts the following operation steps:
1. preparing a mixture: converting the oxide into an introduced compound according to the formula, weighing compound raw materials according to the parts by weight, and fully and uniformly mixing the raw materials in a mixer added with zirconium balls for 1-3 hours to prepare a mixture;
2. melting: loading a crucible in a high-temperature electric furnace, feeding, and heating according to a step temperature system: heating from room temperature to 1000 ℃ at the heating rate of 8 ℃/min, heating to 1580 ℃ at the heating rate of 4 ℃/min, and preserving heat for 120min to obtain clear glass liquid;
3. the tube drawing forming method comprises a manual tube drawing method and a mechanical forming method, wherein the manual tube drawing method is to cool the melted glass liquid at 200-300 ℃, then carry out operations such as material picking, material rolling, material blowing, tube drawing and the like, and draw a long glass tube with a required diameter at a certain speed; the mechanical forming method comprises a horizontal pipe drawing method and a vertical drawing method, wherein the horizontal drawing method comprises a Danner method and a Vero method, and the vertical drawing method comprises a grooved method and a non-grooved method. And cutting the long glass tube formed by tube drawing into glass blanks with required lengths, and finally obtaining the sealing glass blanks for the electric connector. Whether manual pipe drawing or mechanical pipe drawing is the prior art!
4. The sealing glass blank is placed between a packaging shell and a metal leading-out end of the electric connector and is sintered together at high temperature, so that the base metal part of the electric connector and glass form good sealing, the sealing and insulating effects are achieved, and finally, the sealing performance, the sealing strength and other related electrical properties are detected.
TABLE 1
| Composition (I) | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| SiO2 | 69.5 | 69.3 | 69.1 | 69.3 | 69.0 | 69.1 |
| B2O3 | 24.0 | 24.0 | 24.0 | 24.0 | 24.0 | 24.0 |
| P2O5 | 1.8 | 1.5 | 1.5 | 1.0 | 0.5 | 0.5 |
| Al2O3 | 1.0 | 1.0 | 1.0 | 1.5 | 2.0 | 2.0 |
| CaO | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 |
| MgO | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| MnO2 | 0.3 | 0.7 | 0.7 | 0.5 | 0.3 | 0.2 |
| SrF2 | 0.2 | 0.3 | 0.5 | 0.5 | 1.0 | 1.0 |
| SnO2/Sb2O3 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Coefficient of thermal expansion (. times.10)-6/℃） | 4.01 | 3.82 | 3.64 | 3.75 | 3.92 | 4.06 |
| Dielectric constant @5GHz | 4.43 | 4.26 | 4.12 | 3.98 | 4.19 | 4.30 |
| Dielectric loss 10-3@5GHz | 2.56 | 2.42 | 2.13 | 2.25 | 2.38 | 2.46 |
| Melting temperature (10)2Pa·s)(℃) | 1306 | 1316 | 1322 | 1331 | 1320 | 1311 |
| Sealing temperature (. degree.C.) | 885 | 891 | 895 | 897 | 892 | 889 |
| Sealing airtightness (Pa. cm)3/s） | 6.8×10-9 | 9.2×10-9 | 1.4×10-8 | 4.7×10-8 | 4.2×10-8 | 2.1×10-8 |
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; those skilled in the art can make numerous possible variations and modifications to the present teachings, or modify equivalent embodiments to equivalent variations, without departing from the scope of the present teachings, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.
Claims (5)
1. A sealing glass blank for electric connector is prepared from SiO2 66~75%，B2O3 16~25%，P2O5 0.1~2.0%，Al2O3 0.1~3.9%，CaO 1~6%，MgO 1~6%，CaO+MgO 2~8%，MnO2 0.1~2%，SrF2 0.1~2%，SnO2/Sb2O3 0.1~2%，B2O3/(SiO2+Al2 O3) 0.25~0.35。
2. A sealing glass gob for an electrical connector as set forth in claim 1, characterized in that it is made of an oxide of SiO2 69~71%，B2O3 23~25%，P2O5 0.5~2.0%，Al2O3 0.5~2.0%，CaO 2~5%，MgO 1~5%，CaO+MgO 3~6%，MnO2 0.2~1.5%，SrF2 0.5~1.5%，SnO2/Sb2O3 0.2~1%，B2O3/(SiO2+Al2 O3) 0.3~0.34。
3. A method for producing a sealing glass gob for an electrical connector as set forth in claim 1 or 2, comprising the steps of:
a. preparing a mixture: converting the oxides into introduced compound raw materials according to the formula, weighing the compound raw materials according to the mass percentage, fully and uniformly mixing the raw materials in a mixer added with zirconium balls, and mixing for 1-3 hours to prepare a mixture;
b. melting: loading a crucible in a high-temperature electric furnace, adding the mixture, raising the temperature to 1550-1600 ℃ according to a step temperature system, and preserving the heat for 90-180 minutes to obtain clarified molten glass;
c. and cooling the melted glass liquid by 200-300 ℃, then carrying out tube drawing and forming operation to prepare a long glass tube with the required diameter, and then cutting the long glass tube into glass blanks with the required length to finally obtain the sealing glass blanks for the electric connector.
4. A method for producing a sealing glass gob for electric connectors as claimed in claim 3, wherein the sealing glass gob produced has a relative dielectric constant of 4.5 or less and a dielectric loss of 3X 10 or less at a frequency of 5GHz-3。
5. The method for preparing a sealing glass blank for an electric connector according to claim 3, wherein the sealing glass blank prepared has a sealing temperature of 880-900 ℃ and a sealing airtightness of not more than 1.0 x 10-7 Pa·cm3/s。
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111609265.8A CN114213000A (en) | 2021-12-27 | 2021-12-27 | Sealing glass blank for electric connector and preparation method thereof |
| PCT/CN2022/141488 WO2023125299A1 (en) | 2021-12-27 | 2022-12-23 | Sealing glass gob for electrical connector and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111609265.8A CN114213000A (en) | 2021-12-27 | 2021-12-27 | Sealing glass blank for electric connector and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114213000A true CN114213000A (en) | 2022-03-22 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111609265.8A Pending CN114213000A (en) | 2021-12-27 | 2021-12-27 | Sealing glass blank for electric connector and preparation method thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN114213000A (en) |
| WO (1) | WO2023125299A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023125299A1 (en) * | 2021-12-27 | 2023-07-06 | 中建材玻璃新材料研究院集团有限公司 | Sealing glass gob for electrical connector and preparation method therefor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5885915A (en) * | 1996-07-30 | 1999-03-23 | General Electric Company | Glass composition |
| JP2004083403A (en) * | 2002-08-24 | 2004-03-18 | Carl Zeiss:Fa | Borosilicate glass and utilization of the same |
| CN1868945A (en) * | 2005-05-23 | 2006-11-29 | 肖特股份有限公司 | Hydrolysis-resistant glass, a method of making said glass and uses of same |
| CN109399937A (en) * | 2018-12-27 | 2019-03-01 | 中建材蚌埠玻璃工业设计研究院有限公司 | A kind of glass with low dielectric constant powder and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1078294B (en) * | 1959-03-19 | 1960-03-24 | Jenaer Glaswerk Schott & Gen | Glass for fusion purposes |
| CN101031518B (en) * | 2004-09-29 | 2012-07-25 | 日本电气硝子株式会社 | Glass for semiconductor sealing, sheath tube for semiconductor sealing and semiconductor electronic part |
| CN101428966A (en) * | 2008-12-05 | 2009-05-13 | 北京工业大学 | Borosilicate glass suitable for electric light source |
| CN112456803A (en) * | 2020-11-05 | 2021-03-09 | 东南大学 | Preparation method of high-performance sealing glass for kovar alloy |
| CN114213000A (en) * | 2021-12-27 | 2022-03-22 | 中建材蚌埠玻璃工业设计研究院有限公司 | Sealing glass blank for electric connector and preparation method thereof |
-
2021
- 2021-12-27 CN CN202111609265.8A patent/CN114213000A/en active Pending
-
2022
- 2022-12-23 WO PCT/CN2022/141488 patent/WO2023125299A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5885915A (en) * | 1996-07-30 | 1999-03-23 | General Electric Company | Glass composition |
| JP2004083403A (en) * | 2002-08-24 | 2004-03-18 | Carl Zeiss:Fa | Borosilicate glass and utilization of the same |
| CN1868945A (en) * | 2005-05-23 | 2006-11-29 | 肖特股份有限公司 | Hydrolysis-resistant glass, a method of making said glass and uses of same |
| CN109399937A (en) * | 2018-12-27 | 2019-03-01 | 中建材蚌埠玻璃工业设计研究院有限公司 | A kind of glass with low dielectric constant powder and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023125299A1 (en) * | 2021-12-27 | 2023-07-06 | 中建材玻璃新材料研究院集团有限公司 | Sealing glass gob for electrical connector and preparation method therefor |
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| Publication number | Publication date |
|---|---|
| WO2023125299A1 (en) | 2023-07-06 |
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