CN105776868B - A kind of high temperature resistant height insulation seal glass and preparation method thereof - Google Patents

A kind of high temperature resistant height insulation seal glass and preparation method thereof Download PDF

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Publication number
CN105776868B
CN105776868B CN201610187641.1A CN201610187641A CN105776868B CN 105776868 B CN105776868 B CN 105776868B CN 201610187641 A CN201610187641 A CN 201610187641A CN 105776868 B CN105776868 B CN 105776868B
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glass
temperature
batch
seal glass
temperature resistant
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CN201610187641.1A
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Chinese (zh)
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CN105776868A (en
Inventor
任越锋
冯庆
赵红刚
华斯嘉
贾波
黄晋
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西安赛尔电子材料科技有限公司
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24Fusion 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

Abstract

The invention discloses a kind of preparation methods of high temperature resistant height insulation seal glass, using silica as skeleton structure, as the generation body of glass, the ingredient of BaO can reduce glass smelting temperature, adjusts the thermal expansion coefficient of glass and improve glass mobility, and Al is added2O3It can make to form AlPO in glass4Unit, network structure is become from straight chain, to make the structure of glass tend towards stability, chemical stability improves, in addition, the addition of ZrO2 is also beneficial to improve the chemical stability of glass, other bivalent metal oxides such as CaO substitutes part BaO and reduces glass smelting temperature and adjust the coefficient of expansion of glass, improves the chemical stability of glass, TiO2Addition is that glass has high dielectric constant and low dielectric constant, improves the electrical insulating property of glass, As2O5Participation forms glass structure, will not be precipitated from the network skeleton of glass;Wherein 1000~1050 DEG C of the sealing temperature of seal glass, thermal expansion coefficient are 70~100 × 10‑7/℃;There is good high temperature high voltage resistant, insulating properties is good after sealing-in.

Description

A kind of high temperature resistant height insulation seal glass and preparation method thereof

Technical field

The invention belongs to glass making techniques fields, more particularly to a kind of high temperature resistant height insulation seal glass and its preparation side Method.

Background technique

With the high speed development of modern industrial production, largely connected using thermocouple, thermal resistance, heating device and signal The various function elements such as part carry out the control and measurement of temperature, pressure, the parameters such as electromagnetism, this is allowed for encapsulating material and close The requirement of encapsulation technique is higher and higher, it is desirable that it is with high reliability, high temperature resistant, high pressure resistant, anti-oxidant, corrosion-resistant, high sealing, height The advantages that insulation, especially compared with fields such as harsh environments such as high temperature, high pressure, oil-gas mining.Most sealings are used at present Glass material cannot reach its required main performance index, such as high-insulativity, elevated-temperature seal, long-time stability and reliability Deng.Traditional packaging method carries out solidification sealing just like epoxy resin, silicon rubber and different high-temp glues, due to these high temperature Glue is organic material, is limited by self performance, cannot be used in high temperature or hyperbaric environment, while can send out during use Raw aging rice seed, leads to package failure, therefore be not able to satisfy needed for production.

Summary of the invention

The purpose of the present invention is to provide a kind of high temperature resistant height insulation seal glasses and preparation method thereof, to overcome existing skill The deficiency of art.

In order to achieve the above objectives, the present invention adopts the following technical scheme:

A kind of preparation method of high temperature resistant height insulation seal glass, specifically includes the following steps:

1), take raw material with molar percent,

2), raw material will be chosen in step 1) and be uniformly mixed into batch, then by batch in 200~300 DEG C of heat preservation 4h It is pre-processed;

3) pretreated batch, is put into platinum crucible, is then placed in silicon molybdenum high temperature furnace and is melted to obtain glass Glass liquid;

4), then required seal glass is can be obtained into according to requiring to pour into the glass metal melted in mold.

Further, each component oxide raw material is introduced in the form of following in step 1): with quartz sand introduce silica, It analyzes pure barium carbonate and introduces barium monoxide, the pure calcium carbonate introducing calcium oxide of analysis, aluminium hydroxide introducing aluminum oxide, remaining component It is introduced by each autoxidisable substance.

Further, batch is put into high temperature furnace in step 2) and is pre-processed in 200~300 DEG C of heat preservation 4h.

Further, melting process in step 3) specifically: 1400 are warming up to from room temperature with 5~8 DEG C/min speed~ 1550 DEG C, in 1400~1550 DEG C of heat preservation 30min~90min.

Further, required seal glass can be obtained in the glass metal natural cooling poured into mold in step 4).

Further, the grinding tool in step 4) is graphite jig.

Further, 1000~1050 DEG C of the sealing temperature of glass, thermal expansion coefficient are 70~100 × 10-7/℃。

Compared with prior art, the invention has the following beneficial technical effects:

A kind of preparation method of high temperature resistant height insulation seal glass of the present invention, using silica as skeleton structure, as The generation body of glass, the ingredient of BaO can reduce glass smelting temperature, adjust the thermal expansion coefficient of glass and improve glass flowing Property, Al is added2O3It can make to form AlPO in glass4Unit becomes network structure from straight chain, so that the structure of glass be made to tend to be steady Fixed, chemical stability improves, in addition, the addition of ZrO2 is also beneficial to improve the chemical stability of glass, other divalent metals Oxide such as CaO substitutes part BaO and reduces glass smelting temperature and adjust the coefficient of expansion of glass, improves the chemical stabilization of glass Property, TiO2Addition is that glass has high dielectric constant and low dielectric constant, improves the electrical insulating property of glass, As2O5Participate in shape At glass structure, will not be precipitated from the network skeleton of glass.

A kind of high temperature resistant height insulate seal glass, 1000~1050 DEG C of the sealing temperature of glass, and thermal expansion coefficient is 70~ 100×10-7/℃;Resulting seal glass is free of lead, has good high temperature high voltage resistant after sealing-in, and insulating properties is good.

Specific embodiment

The invention will be described in further detail below:

A kind of preparation method of high temperature resistant height insulation seal glass, the specific steps are as follows:

1), take raw material with molar percent,

2), raw material will be chosen in step 1) and be uniformly mixed into batch, then by batch in 200~300 DEG C of heat preservation 4h It is pre-processed;

3), pretreated batch is put into platinum crucible, then platinum crucible is put into silicon molybdenum high temperature furnace and is melted Fining glass liquid is made, wherein melting process specifically: 1400~1550 DEG C are warming up to from room temperature with 5~8 DEG C/min speed, In 1400~1550 DEG C of heat preservation 30min~90min;

4) glass metal melted then, is prepared into sample according to requiring to pour into mold, natural cooling can be obtained required Seal glass.

Wherein batch is put into high temperature furnace in step 2) and is pre-processed in 200~300 DEG C of heat preservation 4h.Wherein step 4) mold in is graphite jig.

Each component oxide raw material is introduced in the form of following in above-mentioned steps 1: pure with quartz sand introducing silica, analysis Barium carbonate introduces barium monoxide, the pure calcium carbonate of analysis introduces calcium oxide, aluminium hydroxide introduces aluminum oxide, remaining component by respective Oxide introduces.

Sample after processing is tested, test method are as follows: Tg, Tf, α of glass are using II double rod of ZNO-expansion system Number analyzer measurement, after glass sample to be made into the bar-shaped sample of 100mm or so, rises to 300 DEG C by room temperature, heating rate 3 ~5 DEG C/min.

High-temperature insulation resistance performance test after sealing-in: megger test insulation resistance instrument resistance meter measures its insulation Closure is heated to 210 DEG C of tests by resistance, and insulation resistance is greater than 1G Ω/1000VDC, that is, meets the high insulating requirements of product; (2) determination of gas tightness: being detected using helium mass spectrometer leak detector, and air-tightness No leakage meets product seal request.

A kind of high temperature resistant height insulation seal glass, the sealing temperature of glass are 1000~1050 DEG C, thermal expansion coefficient 70 ~100 × 10-7/℃。

Embodiment 1:

1) glass raw material, will be prepared and be mixed into batch according to following molar percentage, SiO2: BaO:CaO:TiO2: Bi2O3: Al2O3: ZrO2: As2O5: CeO2For 50:30:4:7:2:2:1:3:1,

2), raw material being chosen in step 1) and being uniformly mixed into batch, then batch is put into high temperature furnace 200 ~300 DEG C of heat preservation 4h are pre-processed;

3), pretreated batch is put into platinum crucible then platinum crucible is put into silicon molybdenum high temperature furnace and is melted Obtain fining glass liquid, specific melting process are as follows: 1434 DEG C are warming up to from room temperature with 5~8 DEG C/min speed, then at 1434 DEG C Keep the temperature 60min;

4) glass metal melted then, is prepared into sample according to requiring to pour into mold, natural cooling can be obtained required Seal glass.

By detection, obtained high temperature resistant height insulation seal glass, 1010 DEG C of the sealing temperature of glass, thermal expansion coefficient It is 93.88 × 10-7/℃。

Each component oxide raw material is introduced in the form of following in above-mentioned steps 1: pure with quartz sand introducing silica, analysis Barium carbonate introduces barium monoxide, the pure calcium carbonate of analysis introduces calcium oxide, aluminium hydroxide introduces aluminum oxide, remaining component by respective Oxide introduces.

Embodiment 2:

1) glass raw material, will be prepared and be mixed into batch according to following molar percentage, SiO2: BaO:CaO:TiO2: Bi2O3: Al2O3: ZrO2: As2O5: CeO2For 53:27:7:4:3:3:1:2:1,

2), raw material will be chosen in step 1) be uniformly mixed into batch, then batch is put into high temperature furnace 200~ 300 DEG C of heat preservation 4h are pre-processed;

3), pretreated batch is put into platinum crucible then platinum crucible is put into silicon molybdenum high temperature furnace and is melted Obtain fining glass liquid, specific melting process are as follows: be warming up to 1464 DEG C from room temperature with 5~8 DEG C/min speed, keep the temperature at 1464 DEG C 60min;

4) glass metal melted then, is prepared into sample according to requiring to pour into mold, natural cooling can be obtained required Seal glass.

By detection, obtained high temperature resistant height insulation seal glass, 1010 DEG C of the sealing temperature of glass, thermal expansion coefficient It is 87.5 × 10-7/℃。

Each component oxide raw material is introduced in the form of following in above-mentioned steps 1: pure with quartz sand introducing silica, analysis Barium carbonate introduces barium monoxide, the pure calcium carbonate of analysis introduces calcium oxide, aluminium hydroxide introduces aluminum oxide, remaining component by each Autoxidisable substance introduces.

Embodiment 3:

1) glass raw material, will be prepared and be mixed into batch according to following molar percentage, SiO2: BaO:CaO:TiO2: Bi2O3: Al2O3: ZrO2: As2O5: CeO2For 56:24:8:3:2:5:1.2:0:0.5,

2), raw material will be chosen in step 1) be uniformly mixed into batch, then batch is put into high temperature furnace 200~ 300 DEG C of heat preservation 4h are pre-processed;

3), pretreated batch is put into platinum crucible then platinum crucible is put into silicon molybdenum high temperature furnace and is melted Obtain fining glass liquid, specific melting process are as follows: be warming up to 1500 DEG C from room temperature with 5~8 DEG C/min speed, keep the temperature at 1500 DEG C 90min;

4) glass metal melted then, is prepared into sample according to requiring to pour into mold, natural cooling can be obtained required Seal glass.

By detection, obtained high temperature resistant height insulation seal glass, 1030 DEG C of the sealing temperature of glass, thermal expansion coefficient It is 79.75 × 10-7/℃。

Each component oxide raw material is introduced in the form of following in above-mentioned steps 1: pure with quartz sand introducing silica, analysis Barium carbonate introduces barium monoxide, the pure calcium carbonate of analysis introduces calcium oxide, aluminium hydroxide introduces aluminum oxide, remaining component by respective Oxide introduces.

Embodiment 4:

1) glass raw material, will be prepared and be mixed into batch according to following molar percentage, SiO2: BaO:CaO:TiO2: Bi2O3: Al2O3: ZrO2: As2O5: CeO2For 60:34:2:2:0:2:0:0:0,

2), raw material will be chosen in step 1) and is uniformly mixed into batch, then by batch 200 in being put into high temperature furnace~ 300 DEG C of heat preservation 4h are pre-processed;

3), pretreated batch is put into platinum crucible then platinum crucible is put into silicon molybdenum high temperature furnace and is melted Obtain fining glass liquid, specific melting process are as follows: be warming up to 1468 DEG C from room temperature with 5~8 DEG C/min speed, keep the temperature at 1468 DEG C 80min;

4) glass metal melted then, is prepared into sample according to requiring to pour into mold, natural cooling can be obtained required Seal glass.

By detection, obtained high temperature resistant height insulation seal glass, 1020 DEG C of the sealing temperature of glass, thermal expansion coefficient It is 92.4 × 10-7/℃。

Each component oxide raw material is introduced in the form of following in above-mentioned steps 1: pure with quartz sand introducing silica, analysis Barium carbonate introduces barium monoxide, the pure calcium carbonate of analysis introduces calcium oxide, aluminium hydroxide introduces aluminum oxide, remaining component by respective Oxide introduces.

Embodiment 5:

1) glass raw material, will be prepared and be mixed into batch according to following molar percentage, SiO2: BaO:CaO:TiO2: Bi2O3: Al2O3: ZrO2: As2O5: CeO2For 65:27:2:2:0:2:1:1:0,

2), raw material will be chosen in step 1) and is uniformly mixed into batch, then by batch 200 in being put into high temperature furnace~ 300 DEG C of heat preservation 4h are pre-processed;

3), pretreated batch is put into platinum crucible then platinum crucible is put into silicon molybdenum high temperature furnace and is melted Obtain fining glass liquid, specific melting process are as follows: be warming up to 1513 DEG C from room temperature with 5~8 DEG C/min speed, keep the temperature at 1513 DEG C 90min;

4) glass metal melted then, is prepared into sample according to requiring to pour into mold, natural cooling can be obtained required Seal glass.

By detection, obtained high temperature resistant height insulation seal glass, 1050 DEG C of the sealing temperature of glass, thermal expansion coefficient It is 78.27 × 10-7/℃。

Each component oxide raw material is introduced in the form of following in above-mentioned steps 1: pure with quartz sand introducing silica, analysis Barium carbonate introduces barium monoxide, the pure calcium carbonate of analysis introduces calcium oxide, aluminium hydroxide introduces aluminum oxide, remaining component by respective Oxide introduces.

Table 1 be prepare molar percentage between each oxide of glass and be made glass thermal expansion coefficient,

Glass melting temperature.

A kind of test method of high temperature resistant height insulation seal glass, specifically includes following steps are as follows: Tg, Tf, α of glass are adopted It is measured with II double rod coefficient of expansion analyzer of ZNO-, after glass sample to be made into the bar-shaped sample of 100mm or so, by room temperature liter To 300 DEG C, heating rate is 3~5 DEG C/min.

High-temperature insulation resistance performance test after sealing-in: megger test insulation resistance instrument resistance meter measures its insulation Closure is heated to 210 DEG C of tests by resistance, and insulation resistance is greater than 1G Ω/1000VDC, that is, meets the high insulating requirements of product; (2) determination of gas tightness: being detected using helium mass spectrometer leak detector, and air-tightness No leakage meets product seal request.

Claims (5)

1. a kind of preparation method of high temperature resistant height insulation seal glass, which is characterized in that specifically includes the following steps:
1), take raw material with molar percent:
2), raw material will be chosen in step 1) and be uniformly mixed into batch, then carry out batch in 200~300 DEG C of heat preservation 4h Pretreatment;Each component oxide raw material is introduced in the form of following: being introduced silica with quartz sand, is introduced oxidation with barium carbonate Barium is introduced calcium oxide with pure calcium carbonate, is introduced with aluminium hydroxide introducing aluminum oxide, remaining component by each autoxidisable substance;
3) pretreated batch, is put into platinum crucible, is then placed in silicon molybdenum high temperature furnace and is melted to obtain glass metal, 1400~1550 DEG C are warming up to from room temperature with 5~8 DEG C/min speed, in 1400~1550 DEG C of heat preservation 30min~90min;
4), then required seal glass is can be obtained into according to requiring to pour into the glass metal melted in mold.
2. a kind of preparation method of high temperature resistant height insulation seal glass according to claim 1, which is characterized in that step 2) Middle batch is put into high temperature furnace pre-processes in 200~300 DEG C of heat preservation 4h.
3. a kind of preparation method of high temperature resistant height insulation seal glass according to claim 1, which is characterized in that step 4) In the glass metal natural cooling poured into mold required seal glass can be obtained.
4. a kind of preparation method of high temperature resistant height insulation seal glass according to claim 1, which is characterized in that step 4) In mold be graphite jig.
A kind of seal glass 5. resulting high temperature resistant height of preparation method according to claim 1 insulate, which is characterized in that sealing-in 1000~1050 DEG C of the sealing temperature of glass, thermal expansion coefficient are 70~100 × 10-7/℃。
CN201610187641.1A 2016-03-29 2016-03-29 A kind of high temperature resistant height insulation seal glass and preparation method thereof CN105776868B (en)

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CN108328929A (en) * 2018-03-06 2018-07-27 厦门百嘉祥微晶材料科技股份有限公司 A kind of high-temperature high-insulation glass and preparation method thereof for electric heating pipe port sealing-in

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104692663A (en) * 2013-12-05 2015-06-10 辽宁法库陶瓷工程技术研究中心 High resistivity and high expansion coefficient glass powder for aluminum and aluminum alloy sealing and preparation method thereof
CN104961337A (en) * 2015-07-01 2015-10-07 京东方科技集团股份有限公司 Lead-free sealing glass and preparation method thereof

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DE102009038812A1 (en) * 2009-08-31 2011-03-10 Borsig Process Heat Exchanger Gmbh High temperature resistant crystallizing glass solders

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104692663A (en) * 2013-12-05 2015-06-10 辽宁法库陶瓷工程技术研究中心 High resistivity and high expansion coefficient glass powder for aluminum and aluminum alloy sealing and preparation method thereof
CN104961337A (en) * 2015-07-01 2015-10-07 京东方科技集团股份有限公司 Lead-free sealing glass and preparation method thereof

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