CN102173578B - Alkali-free phosphate glass and preparation method thereof - Google Patents
Alkali-free phosphate glass and preparation method thereof Download PDFInfo
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- CN102173578B CN102173578B CN 201110046007 CN201110046007A CN102173578B CN 102173578 B CN102173578 B CN 102173578B CN 201110046007 CN201110046007 CN 201110046007 CN 201110046007 A CN201110046007 A CN 201110046007A CN 102173578 B CN102173578 B CN 102173578B
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- glass
- alkali
- free phosphate
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Abstract
The invention relates to alkali-free phosphate glass and a preparation method thereof. The glass comprises the following components in percentage by weight: 30-57% of P2O5, 8-30% of ZnO, 15-45% of SnO, 15-40% of B2O3, 1-4% of SiO2 and 1-8% of Al2O3. The preparation method comprises the following steps of: (1) uniformly mixing all components, and melting the mixture in a silicon carbide rod furnace to obtain a glass liquid; (2) forming the molten glass liquid in a preheated die, annealing and cooling the die, and finally machining and forming to obtain the alkali-free phosphate glass. The alkali-free phosphate glass does not contain alkali or lead, so that the electrical insulating property of electronic devices is ensured, and the glass is friendly to the environment. The hermetical sealing temperature and the thermal expansion coefficient of the glass meet the low-temperature sealing-in requirement on electronic parts and components, the chemical stability is good, and the glass can be applied to the sealing-in and sealing of electronic components such as diodes, silicon controlled components, and the like. The preparation method has the advantages of simple process, low cost and good application prospect.
Description
Technical field
The invention belongs to the field of the phosphate glass of electronic devices and components, particularly a kind of alkali-free phosphate glass and preparation method thereof.
Background technology
Because having other, lead glass forms the unexistent character of glass, thus can make crystal glass, opticglass, the electric glass of use protects ray glass, and electronics is with glass for bonding etc.Lead glass is suitable for the mechanical-moulded of electricbulb with in the glass electric, and is core with the Dumet wire of copper sheath as lead-in wire in order to iron-nickel alloy, it can with the stable sealing-in of lead glass.Lead glass also is used for electric light, fluorescence etc., the sealing-in of cathode tube (CRT) and various electron tubes simultaneously.In addition also for the neck of the electron beam gun that holds cathode tube and the manufacturing of colour picture tube cone.Use PbO-B
2O
3-SiO
2The solder glass that glass frit end and stupalith are composited is used for the sealing of unicircuit ceramic package.Use PbO-Al
2O
3-SiO
2The glass frit end is coated in the groove of silicon chip then sintering, plays passivation, and the PN junction that protection is exposed improves its physical strength, so that more stable electric.Its application of lead glass is very widely.But it but has fatal shortcoming, and it is plumbous that lead glass contains a large amount of toxic metal! Therefore develop the alternative flint glass of Unlead low-smelting point glass and become one of vital task of present material scholar work.
More promising in the barium crown sealed glass system is Bi
2O
3-B
2O
3-SiO
2And ZnO-B
2O
3-SiO
2, the system such as vanadate, phosphoric acid salt, but the above two sealing temperatures are higher, and bismuthate and vanadate system cost are high.Phosphate system low temperature and unleaded aspect occupy very large advantage, most of performances all can compare favourably with the leaded seal glass of tradition, and remarkable environmental contamination reduction.Lead-free phosphate sealed glass will be the most potential substituent of traditional leaded seal glass.
The molecular fraction that H7-69672 number disclosed glass of Japanese Patent forms is: P
2O
525～50%, SnO 30～70%, and ZnO 0～25%, add on this basis an amount of B
2O
3, WO
3, Li
2O etc.SnO/ZnO during the glass of this system forms was greater than 5: 1, and the use temperature of glass is 350～450 ℃, and thermal expansivity is greater than 120 * 10
-7/ ℃, the method for employing weighting agent reduces the coefficient of expansion, the flowability the when adding of weighting agent has influence on glass sealing and the resistance to air loss of sealing device of glass in the patent.
The molecular fraction that No. 6306783 disclosed glass of United States Patent (USP) forms is: SnO 30～80%, B
2O
35～60%, P
2O
55～24%, ZnO 0～25%, WO
33～20%, MoO
33～5%, TiO
20～15%, ZrO
20～15%, CuO 0～10%, R
2O 2～35%.The transition temperature of the glass of this system is 280～380 ℃, and thermal expansivity is 90～110 * 10
-7/ ℃, the melt temperature of glass is 450～500 ℃, mobile radius is 22～26mm.Contain alkalimetal oxide R in this patent
2O, and thermal expansivity is very high.Owing to containing alkalimetal oxide R in the glass
2O can be so that the insulating property of glass decline to a great extent, and leakage current rises, can be so that electron device is breakdown, such as devices such as diode, silicon controlled rectifiers when serious.
Contain P
2O
5-B
2O
3-SiO
2Phase-splitting or crystallization very easily occur in the system of glass when founding, because they all are glass-formers, fight for mutually during high temperature that oxonium ion causes, in order to suppress this tendency, often add alkalimetal oxide in glass, on the one hand the resistivity of glass is declined to a great extent but add alkalimetal oxide, the insulating property of glass worsen, on the other hand also can so that the thermal expansivity of glass rise so that this base material that contains can only use with the part metals coupling.
Summary of the invention
Technical problem to be solved by this invention provides a kind of alkali-free phosphate glass and preparation method thereof, this glass alkali-free is not leaded, electrical insulation capability and the environmental friendliness of electron device have been guaranteed, the melting temperature sealing of glass and thermal expansivity satisfy the low-temperature sealing requirement of electronic devices and components, and chemical stability is good; Preparation method's technique is simple, and cost is low, has a good application prospect.
A kind of alkali-free phosphate glass of the present invention, its component comprises: by weight percentage, 30～57%P
2O
5, 8～30%ZnO, 15～45%SnO, 15～40%B
2O
3, 1～4%SiO
2With 1～8%Al
2O
3
Described alkali-free phosphate glass group comprises, by weight percentage, and 42～57%P
2O
5, 8～15%ZnO, 15～22%SnO, 15～22%B
2O
3, 2～3%SiO
2With 1～2.5%Al
2O
3
P in the described alkali-free phosphate glass component
2O
5And B
2O
3Total weight percent be 45～75%, and P
2O
5Content greater than B
2O
3Content.
The total weight percent of ZnO and SnO is that the weight ratio of 23～50%, ZnO and SnO is 1: 1～1: 2 in the described alkali-free phosphate glass component.
SiO in the described alkali-free phosphate glass component
2And Al
2O
3Total weight percent be 2～9%, and Al
2O
3Content greater than SiO
2Content.
Described alkali-free phosphate glass thermal expansivity is 60～85 * 10
-7/ ℃.
Described alkali-free phosphate glass transition temperature is 400～450 ℃, and softening temperature is 440～500 ℃.
The preparation method of a kind of alkali-free phosphate glass of the present invention comprises:
(1) by weight percentage, with 30～55%P
2O
5, 8～30%ZnO, 15～45%SnO, 15～40%B
2O
3, 1～4%SiO
2With 1～8%Al
2O
3Mix, be melted into glass metal in the globars electric furnace, glass melting temperature is 1050～1220 ℃, is incubated 0.5～1.5 hour; In 200～500 ℃, heat-up rate is 2～3 ℃/min, and the heat-up rate that all the other temperature ranges (25～200 ℃, 500～1220 ℃) adopt is 5～10 ℃/min;
(2) with the die for molding of the above-mentioned glass metal that melts in the process preheating, then annealing, annealing temperature is 350～400 ℃, is incubated cooling after 1 hour, last machine-shaping gets alkali-free phosphate glass.
P in the described step (1)
2O
5Raw material is ammonium phosphate, B
2O
3Raw material is boric acid, Al
2O
3Raw material is aluminium hydroxide.
Principle of the present invention is: in order to regulate the coefficient of expansion of seal glass, improve the chemical stability of glass, add silicon oxide and aluminum oxide in glass, still, a large amount of experiments show, SiO
2With Al
2O
3The content sum should not surpass 9%, SiO
2Optimum Contents be 2～3%, Al
2O
3Optimum Contents be 3～5%, otherwise the phase-splitting of glass or the tendency of crystallization can increase, the transition temperature of glass and melting temperature sealing all can obviously improve.
Equally, for phase-splitting or the tendency towards devitrification that reduces glass, P
2O
5+ B
2O
3Content is 45～70%, P
2O
5Optimum Contents is 40～50%, B
2O
3Optimum Contents is that 20～30%, ZnO+SnO content is that 23～50%, ZnO Optimum Contents is that 10～20%, SnO Optimum Contents is 20～30%.
Beneficial effect
(1) alkali-free of the present invention is not leaded, electrical insulation capability and the environmental friendliness of electron device have been guaranteed, the melting temperature sealing of glass and thermal expansivity satisfy the low-temperature sealing requirement of electronic devices and components, and chemical stability is good, can be used for sealing-in, the sealing of the electronic components such as diode, silicon controlled rectifier;
(2) preparation method's technique is simple, and cost is low, has a good application prospect.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
57%P by weight percentage
2O
5, 8%ZnO, 15%SnO, 15%B
2O
3, 3%SiO
2And 2%Al
2O
3Prepare burden, glass mixture is placed in the quartz crucible, heat in the globars electric furnace and found, in 200～500 ℃, the heat-up rate of employing is 2～3 ℃/min; All the other temperature ranges (25～200 ℃, 500～1100 ℃) adopt being rapidly heated of 5～10 ℃/min, to 1100 ℃ of insulation 30min.
The glass metal that melts is through the die for molding of preheating, and puts into fast retort furnace and anneal, and annealing temperature is 370 ℃, is incubated furnace cooling after 1 hour.
Sample after the annealing carries out performance analysis after attrition process, test result sees Table 1.
Embodiment 2
42%P by weight percentage
2O
5, 11%ZnO, 22%SnO, 22%B
2O
3, 2%SiO
2And 1%Al
2O
3Prepare burden, glass mixture is placed in the quartz crucible, heat in the globars electric furnace and found, in 200～500 ℃, the heat-up rate of employing is 2～3 ℃/min; All the other temperature ranges (25～200 ℃, 500～1150 ℃) adopt being rapidly heated of 5～10 ℃/min, to 1150 ℃ of insulation 30min.
The glass metal that melts is through the die for molding of preheating, and puts into fast retort furnace and anneal, and annealing temperature is 370 ℃, is incubated furnace cooling after 1 hour.
Sample after the annealing carries out performance analysis after attrition process, test result sees Table 1.
Embodiment 3
45%P by weight percentage
2O
5, 15%ZnO, 15%SnO, 20%B
2O
3, 3%SiO
2And 2%Al
2O
3Prepare burden, glass mixture is placed in the quartz crucible, heat in the globars electric furnace and found, in 200～500 ℃, the heat-up rate of employing is 2～3 ℃/min; All the other temperature ranges (25～200 ℃, 500～1200 ℃) adopted being rapidly heated of 5～10 ℃/min, to 1200 ℃ of insulations 1 hour.
The glass metal that melts is through the die for molding of preheating, and puts into fast retort furnace and anneal, and annealing temperature is 380 ℃, is incubated furnace cooling after 1 hour.
Sample after the annealing carries out performance analysis after attrition process, test result sees Table 1.
Embodiment 4
42.5%P by weight percentage
2O
5, 12%ZnO, 18%SnO, 22%B
2O
3, 3%SiO
2And 2.5%Al
2O
3Prepare burden, glass mixture is placed in the quartz crucible, heat in the globars electric furnace and found, in 200～500 ℃, the heat-up rate of employing is 2～3 ℃/min; All the other temperature ranges (25～200 ℃, 500～1200 ℃) adopt being rapidly heated of 5～10 ℃/min, to 1200 ℃ of insulation 40min.
The glass metal that melts is through the die for molding of preheating, and puts into fast retort furnace and anneal, and annealing temperature is 380 ℃, is incubated furnace cooling after 1 hour.
Sample after the annealing carries out performance analysis after attrition process, test result sees Table 1.
The performance of table 1 alkali-free phosphate glass
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| α(×10 -7/℃) | 80.6 | 73.6 | 73.1 | 62.2 |
| Transition temperature Tg ℃) | 418 | 429 | 437 | 432 |
| Softening temperature Tf (℃) | 449 | 457 | 475 | 467 |
Claims (3)
1. alkali-free phosphate glass, its component comprises: by weight percentage, 42.5%P
2O
5, 12%ZnO, 18%SnO, 22%B
2O
3, 3%SiO
2And 2.5%Al
2O
3, thermal expansivity is 62.2 * 10
-7/ ℃, transition temperature is 432 ℃, softening temperature is 467 ℃.
2. the preparation method of an alkali-free phosphate glass as claimed in claim 1 comprises:
(1) 42.5%P by weight percentage
2O
5, 12%ZnO, 18%SnO, 22%B
2O
3, 3%SiO
2And 2.5%Al
2O
3Prepare burden, glass mixture is placed in the quartz crucible, heat in the globars electric furnace and found, in 200～500 ℃, the heat-up rate of employing is 2～3 ℃/min; All the other temperature ranges adopt being rapidly heated of 5～10 ℃/min, to 1200 ℃ of insulation 40min;
(2) glass metal that melts is through the die for molding of preheating, and puts into fast retort furnace and anneal, and annealing temperature is 380 ℃, is incubated furnace cooling after 1 hour.
3. the preparation method of a kind of alkali-free phosphate glass according to claim 2 is characterized in that: P in the described step (1)
2O
5Raw material is ammonium phosphate, B
2O
3Raw material is boric acid, Al
2O
3Raw material is aluminium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110046007 CN102173578B (en) | 2011-02-25 | 2011-02-25 | Alkali-free phosphate glass and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110046007 CN102173578B (en) | 2011-02-25 | 2011-02-25 | Alkali-free phosphate glass and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102173578A CN102173578A (en) | 2011-09-07 |
| CN102173578B true CN102173578B (en) | 2013-04-03 |
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ID=44516878
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|---|---|---|---|
| CN 201110046007 Expired - Fee Related CN102173578B (en) | 2011-02-25 | 2011-02-25 | Alkali-free phosphate glass and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105502950B (en) * | 2016-01-15 | 2018-08-03 | 东华大学 | A kind of transitional glass stick and preparation method thereof |
| CN106535379B (en) * | 2016-10-19 | 2020-09-11 | 周智 | Automobile safety glass and production process thereof |
| CN108164150B (en) * | 2016-12-07 | 2022-04-29 | 辽宁省轻工科学研究院有限公司 | Preparation method and application of aluminum alloy sealing glass powder with high resistivity and high expansion coefficient |
| CN108164144A (en) * | 2016-12-07 | 2018-06-15 | 辽宁法库陶瓷工程技术研究中心 | A kind of low temperature high expansion coefficient titanium alloy seal glass and its preparation method and application |
| CN110372215A (en) * | 2019-08-07 | 2019-10-25 | 北京北旭电子材料有限公司 | A kind of sealing glass material and preparation method thereof, connection component |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1774405A (en) * | 2003-02-25 | 2006-05-17 | 肖特股份公司 | Antimicrobial phosphate glass |
| CN1830856A (en) * | 2006-03-17 | 2006-09-13 | 东华大学 | Leadless phosphate seal glass and its preparation method |
-
2011
- 2011-02-25 CN CN 201110046007 patent/CN102173578B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1774405A (en) * | 2003-02-25 | 2006-05-17 | 肖特股份公司 | Antimicrobial phosphate glass |
| CN1830856A (en) * | 2006-03-17 | 2006-09-13 | 东华大学 | Leadless phosphate seal glass and its preparation method |
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|---|---|
| CN102173578A (en) | 2011-09-07 |
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Granted publication date: 20130403 Termination date: 20160225 |