CN114195396A - Preparation method of borosilicate glass modified by hollow glass beads - Google Patents
Preparation method of borosilicate glass modified by hollow glass beads Download PDFInfo
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- CN114195396A CN114195396A CN202111512312.7A CN202111512312A CN114195396A CN 114195396 A CN114195396 A CN 114195396A CN 202111512312 A CN202111512312 A CN 202111512312A CN 114195396 A CN114195396 A CN 114195396A
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- glass
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- hollow glass
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- 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
- C03C12/00—Powdered glass; Bead compositions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B11/00—Pressing molten glass or performed glass reheated to equivalent low viscosity without blowing
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- 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
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
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- 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacturing & Machinery (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a preparation method of hollow glass bead modified borosilicate glass, which adopts borosilicate glass as a main body, 0-50% of micron-sized hollow glass beads are added in the process of preparing slurry, composite glass granulation powder is prepared by a spray drying method, corresponding glass blanks are manufactured by the granulation powder, and then glass-metal sintering is utilized to test the mechanical strength and the dielectric property of the glass. The test result shows that the comprehensive performance of the borosilicate glass can be effectively improved by adding the hollow glass beads, and the mechanical strength and the dielectric property of the corresponding glass-metal sealing piece are also improved along with the increase of the content of the hollow glass beads. The method has good effects on the preparation of the high-performance glass granulated powder and the improvement of the sealing performance.
Description
Technical Field
The invention relates to the technical field of electronic glass, in particular to a preparation method of borosilicate glass modified by hollow glass beads.
Background
In recent years, the integration level of integrated circuits is rapidly improved, the working frequency ranges of radio frequency connectors, microwave devices and the like are also greatly improved, and in order to reduce impedance delay and power loss caused by the working frequency ranges, it is important to reduce the parasitic capacitance of a dielectric layer besides low-resistivity metal. Because the capacitance C is in direct proportion to the dielectric constant epsilon, a low-dielectric-constant material can be used as an interconnection medium to reduce impedance delay, thereby meeting the development requirement of an integrated circuit.
The low dielectric glass is an ideal candidate material, is widely applied to the field of electronic packaging due to the outstanding performance characteristics, and plays roles in protecting circuits, isolating insulation, preventing signal distortion and the like. The low dielectric glass has the advantages of good heat resistance, good chemical stability, high mechanical strength, air tightness, electrical insulation performance and the like, can meet the requirements of severe working environments of electronic components, and also has low dielectric constant and dielectric loss, the low dielectric constant can reduce relaxation and cross interference of signals, the low dielectric loss can reduce excessive heat consumption under high frequency and high resistivity, and good heat dissipation effect is realized.
There are also some reports in the prior art on low dielectric constant glass compositions, such as disclosed in application No. CN202110688872.1, which discloses a low dielectric constant glass composition having a composition comprising, in mole percent: SiO 2264.8～68.2mol％；B2O323.9～28.8mol％；R2O2.5-6.51 mol%; wherein, R is2O is Li2O、Na2O and K2One or more of O, and the glass linear expansion coefficient alpha at 20-120 ℃ is 34.5-40 multiplied by 10-7K is the sum of the values of k and k. Further comprising: al (Al)2O3 0～3.1mol％；MO 0～5mol％；Sb2O30-0.1 mol%, wherein MO is one or two of BaO and SrO. Also, as disclosed in the invention application with application number CN202110446122.3, a low dielectric sealing glass powder for a micro radio frequency glass insulator is prepared from the following raw materials in mol percent: SiO 22：70.5～74.0％，B2O3：20.5～23.5％，Ga2O3：0.5～2.0％，P2O5：0.25～2.0％，Li2O：0.4～6.0％，K2O：0.1～1.5％，LaB6：0.05～1.0％，NaCl：0.03～0.3％。
The hollow glass bead has the characteristics of low impurity, low dielectric, low density, high strength and the like, and is a novel additive material in recent years.
Disclosure of Invention
Aiming at the problems of insufficient mechanical property and dielectric property and the like of the glass sealing material in the prior art, the invention aims to optimize the prior preparation technology of the glass sealing material, utilize the characteristics of low impurity, low dielectric, low density, high strength and the like of hollow glass beads, add the hollow glass beads into glass powder, and prepare a hollow glass bead/glass composite material by adopting a granulation technology, thereby improving the mechanical property and the dielectric property of glass. Experiments prove that the glass-metal sealing element has higher mechanical property and lower dielectric constant by using the composite glass material provided by the invention to seal with metal, and the performance of the original glass-metal sealing element is greatly improved.
The technical scheme adopted by the invention for solving the technical problem is as follows: a method of making borosilicate glass modified with hollow glass microspheres, said method comprising the steps of:
step 1), preparing raw materials according to a molar ratio, wherein the raw materials comprise the following components in parts by weight: SiO 22：60～70％；BaO：5～15％；Na2O：5～18％；K2O：6～18％；B2O3：0～8％；Li2O：0～6％；La2O3: 0-6%; adding the raw materials into a ball mill and uniformly mixing;
step 2), placing the glass raw material prepared in the step 1 in a high-temperature furnace, heating the glass raw material to be in a liquid state at 1600-1650 ℃, keeping the temperature for a certain time, taking out the glass raw material, pouring the glass raw material into water, and quenching the glass raw material to obtain glass slag;
step 3), crushing, grinding and vibrating screening the glass slag obtained in the step 2 to obtain glass powder with a certain granularity;
step 4), mixing glass powder, a dispersing agent, a binder and water according to a mass ratio of 90-110: 1-4: 8-15: mixing according to the proportion of 60-90, simultaneously adding a certain amount of hollow glass beads, and fully stirring the mixture in a ball mill to obtain slurry;
step 5), taking out the slurry prepared in the step 4, and introducing the slurry into a spray granulator to prepare granulated powder; then pouring the granulation powder into a briquetting machine to prepare a glass blank; placing the glass blank in a vitrification furnace for full reaction; assembling the glass blank and placing the glass blank in a sintering furnace to prepare a product.
Further, in the step 3, the particle size range of the glass powder obtained by screening is 1-20 μm.
Further, in the step 4, the amount of the hollow glass beads is 0-50% of the mass of the glass powder; the hollow glass beads have a particle size of 5-100 μm and a dielectric constant of 1-4 at 10 GHz.
Further, in the step 4, the solid content of the prepared slurry is 55-65%.
In step 4, both the dispersant and the binder are organic high molecular polymers.
Preferably, the dispersant is sodium tripolyphosphate or ammonium polyacrylate; the binder is polyvinyl alcohol, PVA and PVB.
Further, in the step 5, the aperture of a nozzle of the spray granulator is 0.5-1.0 mm during spray granulation; the spraying pressure is 10-20 kg/cm3(ii) a The inlet temperature is 215-265 ℃, and the outlet temperature is 90-115 ℃.
The invention has the beneficial effects that: compared with the prior art, the preparation method of the borosilicate glass modified by the hollow glass beads provided by the invention has the advantages that the hollow glass beads serving as an additive have good strength and low dielectric constant performance, and the hollow glass beads added into the glass can play a role in bridging, serve as a reinforcing agent in the glass and can also play a role in reducing the dielectric constant of the whole material. In addition, the surfaces of the hollow glass beads are fused with the glass components to form chemical bonds, so that the combination is firmer. Experiments prove that the glass-metal sealing element has higher mechanical strength and lower dielectric constant by utilizing the composite glass material provided by the invention to seal with metal, the performance of the original glass-metal sealing element is greatly improved, the problems of poor strength, good dielectric loss and the like of the existing glass sealing material are solved, and the level of large-scale industrial use can be reached.
Detailed Description
The invention is further illustrated by the following specific examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention.
Examples
Preparing materials: 500g of raw materials are prepared according to the following component molar ratio, 600g of agate balls are added and mixed evenly. SiO 22：65％；BaO：8％；Na2O：8％；K2O：8％；B2O3：5％；Li2O：3％；La2O3：3％。
Melting: and (3) placing the uniformly mixed glass powder into a high-temperature furnace, heating to 1600-1650 ℃, preserving heat for a certain time, taking out, pouring into water, and quenching to obtain the glass slag.
Milling: and melting the obtained glass slag according to a ball-to-feed ratio of 1.2: the glass powder with the granularity of 1-20 mu m is obtained by crushing and grinding the glass powder in a ball mill for 2-2.5 h and then vibrating and screening the crushed glass powder with a sieve.
Pulping: mixing glass powder, a dispersing agent, a binder and water according to the weight ratio of 100: 3: 12: 80, adding a certain content of hollow glass beads, and placing the mixture in a ball mill for fully stirring. The solid content of the slurry is controlled to be 60% in the whole process, and hollow glass bead powder with the mass content of 0%, 5%, 10%, 20%, 30%, 40% and 50% is respectively added.
And (3) granulation: taking out the prepared slurry and introducing into a centrifugal spray granulator to prepare granulated powder; wherein the spraying pressure is 15kg/cm3(ii) a The aperture of the nozzle is 1.0 mm; the inlet temperature was 250 ℃ and the outlet temperature was 110 ℃.
Blank preparation: and pouring the prepared granulation powder into a briquetting machine to prepare a glass blank.
Vitrification: and placing the prepared glass blank in a vitrification furnace for full reaction.
Sealing: assembling the glass blank and placing the glass blank in a sintering furnace to prepare a product.
And (3) carrying out performance test on the composite material prepared by the method:
1. and (3) dielectric constant test: the composite material prepared in each example was prepared into a wafer of phi 10 with a thickness of 5mm, and the wafer was placed in a dielectric constant tester for testing at a frequency of 10 GHz.
2. The composite sealing products obtained in the respective examples were tested for airtightness, insulation and breaking strength. The adopted product is a connector sintered part, the air tightness is tested by adopting a helium mass spectrometer leak detector, the insulativity is tested by adopting a resistance tester, and the destructive strength is tested by adopting a press machine.
The results of the performance testing for each example are shown in the following table:
the above embodiments are only for illustrating the invention and are not to be construed as limiting the invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention, therefore, all equivalent technical solutions also belong to the scope of the invention, and the scope of the invention is defined by the claims.
Claims (7)
1. A preparation method of borosilicate glass modified by hollow glass beads is characterized by comprising the following steps:
step 1), the molar ratio is measuredPreparing raw materials, wherein the raw materials comprise the following components in parts by weight: SiO 22：60～70％；BaO：5～15％；Na2O：5～18％；K2O：6～18％；B2O3：0～8％；Li2O：0～6％；La2O3: 0-6%; adding the raw materials into a ball mill and uniformly mixing;
step 2), placing the glass raw material prepared in the step 1 in a high-temperature furnace, heating the glass raw material to be in a liquid state at 1600-1650 ℃, keeping the temperature for a certain time, taking out the glass raw material, pouring the glass raw material into water, and quenching the glass raw material to obtain glass slag;
step 3), crushing, grinding and vibrating screening the glass slag obtained in the step 2 to obtain glass powder with a certain granularity;
step 4), mixing glass powder, a dispersing agent, a binder and water according to a mass ratio of 90-110: 1-4: 8-15: mixing according to the proportion of 60-90, simultaneously adding a certain amount of hollow glass beads, and fully stirring the mixture in a ball mill to obtain slurry;
step 5), taking out the slurry prepared in the step 4, and introducing the slurry into a spray granulator to prepare granulated powder; then pouring the granulation powder into a briquetting machine to prepare a glass blank; placing the glass blank in a vitrification furnace for full reaction; assembling the glass blank and placing the glass blank in a sintering furnace to prepare a product.
2. The method of claim 1, wherein the borosilicate glass is modified with hollow glass beads by: in the step 3, the granularity range of the glass powder obtained by screening is 1-20 μm.
3. The method of claim 1, wherein the borosilicate glass is modified with hollow glass beads by: in the step 4, the amount of the hollow glass beads is 0-50% of the mass of the glass powder; the hollow glass beads have a particle size of 5-100 μm and a dielectric constant of 1-4 at 10 GHz.
4. The method of claim 1, wherein the borosilicate glass is modified with hollow glass beads by: in the step 4, the solid content of the prepared slurry is 55-65%.
5. The method of claim 1, wherein the borosilicate glass is modified with hollow glass beads by: in the step 4, the dispersant and the binder are both organic high molecular polymers.
6. The method of claim 5, wherein the borosilicate glass is modified with hollow glass beads by: the dispersing agent is sodium tripolyphosphate and ammonium polyacrylate; the binder is polyvinyl alcohol, PVA and PVB.
7. The method of claim 1, wherein the borosilicate glass is modified with hollow glass beads by: in the step 5, the aperture of a nozzle of the spray granulator is 0.5-1.0 mm during spray granulation; the spraying pressure is 10-20 kg/cm3(ii) a The inlet temperature is 215-265 ℃, and the outlet temperature is 90-115 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111512312.7A CN114195396A (en) | 2021-12-08 | 2021-12-08 | Preparation method of borosilicate glass modified by hollow glass beads |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111512312.7A CN114195396A (en) | 2021-12-08 | 2021-12-08 | Preparation method of borosilicate glass modified by hollow glass beads |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4867935A (en) * | 1988-02-26 | 1989-09-19 | E. I. Du Pont De Nemours And Company | Method for preparing ceramic tape compositions |
| US5204289A (en) * | 1991-10-18 | 1993-04-20 | Minnesota Mining And Manufacturing Company | Glass-based and glass-ceramic-based composites |
| JPH05286785A (en) * | 1992-04-06 | 1993-11-02 | Fujitsu Ltd | Formation of insulating film |
| CN101167226A (en) * | 2005-04-28 | 2008-04-23 | 3M创新有限公司 | Sealant materials and methods of using thereof |
| CN111138081A (en) * | 2019-12-31 | 2020-05-12 | 西安赛尔电子材料科技有限公司 | Improved preparation method of glass sealing material |
-
2021
- 2021-12-08 CN CN202111512312.7A patent/CN114195396A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4867935A (en) * | 1988-02-26 | 1989-09-19 | E. I. Du Pont De Nemours And Company | Method for preparing ceramic tape compositions |
| US5204289A (en) * | 1991-10-18 | 1993-04-20 | Minnesota Mining And Manufacturing Company | Glass-based and glass-ceramic-based composites |
| JPH05286785A (en) * | 1992-04-06 | 1993-11-02 | Fujitsu Ltd | Formation of insulating film |
| CN101167226A (en) * | 2005-04-28 | 2008-04-23 | 3M创新有限公司 | Sealant materials and methods of using thereof |
| CN111138081A (en) * | 2019-12-31 | 2020-05-12 | 西安赛尔电子材料科技有限公司 | Improved preparation method of glass sealing material |
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