CN104803666A - LiAlSiO4 microspheres with negative thermal expansion coefficient and preparation method of LiAlSiO4 microspheres - Google Patents
LiAlSiO4 microspheres with negative thermal expansion coefficient and preparation method of LiAlSiO4 microspheres Download PDFInfo
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- CN104803666A CN104803666A CN201510182547.2A CN201510182547A CN104803666A CN 104803666 A CN104803666 A CN 104803666A CN 201510182547 A CN201510182547 A CN 201510182547A CN 104803666 A CN104803666 A CN 104803666A
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- lialsio
- expansion coefficient
- lialsio4
- microballoon
- negative expansion
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Abstract
The invention discloses LiAlSiO4 microspheres with a negative thermal expansion coefficient and a preparation method of the LiAlSiO4 microspheres. The LiAlSiO4 microspheres are prepared as follows: Li2Co3 powder, SiO2 powder and Al2O3 powder are uniformly mixed in a mortar, heated to 1,300 DEG C-1,400 DEG C to be melted, preserved at the temperature for over 5 hours and cooled in ice water, a LiAlSiO4 block is obtained and subjected to ball milling, LiAlSiO4 particles with different particle sizes are obtained, the LiAlSiO4 particles subjected to ball milling are dissolved with deionized water, and sol is obtained; finally, the sol is subjected to flame jet in an acetylene atmosphere, and the LiAlSiO4 microspheres with a negative thermal expansion coefficient are obtained. The negative thermal expansion coefficient material with controllable size, uniform distribution and good sphericity is prepared with a two-step method.
Description
Technical field
The present invention relates to a kind of LiAlSiO of negative expansion coefficient
4microballoon and preparation method thereof, belongs to negative expansion coefficient functional materials research field.
Background technology
Minus thermal-expansion coefficient is because himself having very low thermal expansivity, making material can keep dimensional stability when experiencing temperature variation, thus being paid close attention to widely in Electronic Packaging, optics, sensitive original paper and other exquisite systems and applying.But minus thermal-expansion coefficient also has many problem demanding prompt solutions.Conventional chemical methods prepares minus thermal-expansion coefficient, although can obtain lower thermal expansivity, be often faced with sintering time long, consumed energy is many, and the uneven first-class problem of grain diameter, limits its large-scale application.On the other hand, although the homogeneous particle of size distribution can be obtained through mechanical ball milling, mechanical milling process often energy charge time, material granule sphericity is also often lower, do not reach the exquisite system such as Electronic Packaging, optics encapsulation rigors.Therefore exploitation preparation technology efficiency is high, size distribution is homogeneous, the negative expansion material microballoon of good sphericity has become current focus and emphasis.
LiAlSiO
4thermal expansivity be about-6 × 10
-6k
-1, for matrix material, add the LiAlSiO with negative expansion coefficient
4after, significantly can reduce the thermal expansivity of matrix material, have significant effect to the performance improving material.(the China.Integrated.Circult 2014 such as En-bo zhu, 3,53 – 56) additive using preparing spherical SiO 2 as epoxy film material (EMC), effectively reduce the wear intensity of EMC filler to equipment, improve reliability and the operability of EMC, and then improve the reliability of package.But the coefficient of expansion of silicon dioxide microsphere does not reach desirable negative expansion coefficient requirement, have impact on electrical property and the stability of EMC.Bo Wang etc. (CERAMICS INTERNATIONAL 2014,40,2853-2856) utilize SiC and varigrained LiAlSiO
4the LAS/SiC porous ceramics of obtained negative expansion coefficient, and the negative expansion coefficient of porous ceramics is with LiAlSiO
4granularity increase and lower.But its negative expansion coefficient is far from reaching lower requirement, and the physical strength of LAS/SiC porous ceramics has to be reinforced.Wei Zhang etc. (Bulletin Of The Chinese Ceramic Society 2008,2,243-253), join Al by the eucryptite with negative expansion coefficient
2o
3in in, by non-pressure sintering technology, prepared aluminum oxide-eucryptite compound heatproof and shockproof ceramic, improve the heat-shock resistance of alumina-ceramic.But microstructure finds out that there are obvious corner angle at the edge of LAS/SiC porous ceramics crystal grain, though such pottery can alleviate certain thermal stresses, far do not reach higher anti-thermal shock requirement.
Summary of the invention
The object of the invention is to provide a kind of LiAlSiO of negative expansion coefficient
4microballoon and preparation method thereof.
The present invention's adopted technical scheme that solves the problem is: a kind of LiAlSiO of negative expansion coefficient
4microballoon, described LiAlSiO
4microspherulite diameter distributes between 1 to 30 micrometers, and negative expansion coefficient is-6.5 × 10
-6~ (-7) × 10
-6k
-1between.
A kind of LiAlSiO of negative expansion coefficient
4the preparation of microballoon, by Li
2cO
3, SiO
2, Al
2o
3powder mixes in mortar; Be warming up to 1300-1400 DEG C of scorification and be incubated more than 5h, and rapidly in frozen water quenching namely obtain LiAlSiO
4block; By block ball milling, obtain the LiAlSiO of different-grain diameter
4particulate; With the LiAlSiO that deionized water dissolving ball milling is crossed
4particulate, obtains colloidal sol; The LiAlSiO of negative expansion coefficient is obtained after colloidal sol is carried out flame spraying under acetylene atmosphere
4microballoon.
In above-mentioned steps, Li in raw material
2cO
3, SiO
2, Al
2o
3mol ratio be 1:1:2.
In above-mentioned steps, frozen water temperature is not higher than 5 DEG C.
In above-mentioned steps, LiAlSiO
4block Ball-milling Time is 2-12h.
Compared with prior art, tool of the present invention has the following advantages:
(1) LiAlSiO of negative expansion coefficient of the present invention
4microballoon negative expansion coefficient reaches as high as-7 × 10
-6k
-1.
(2) LiAlSiO of negative expansion coefficient of the present invention
4microsphere particle size is controlled between 1 to 30 micrometers, and even particle size distribution.
Accompanying drawing explanation
Fig. 1 is the LiAlSiO of negative expansion coefficient of the present invention
4method for preparing microsphere schema.
Fig. 2 is the LiAlSiO of the negative expansion coefficient of preparation
4the XRD figure of microballoon.
Fig. 3 is the LiAlSiO of the negative expansion coefficient of preparation
4the SEM figure of microballoon.
Fig. 4 is the LiAlSiO of the negative expansion coefficient of preparation
4the thermal expansion figure of microballoon.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
A kind of LiAlSiO of negative expansion coefficient
4the preparation method of microballoon, its flow process, as Fig. 1, includes following steps:
(1) Li is adopted
2cO
3, SiO
2, Al
2o
3powder is as raw material, and wherein mol ratio 1:1:2, mixes in mortar.
(2) particle mixed be warming up to 1300-1400 DEG C of scorification and be incubated more than 5h, and rapidly in frozen water quenching namely obtain LiAlSiO
4block.
(3) by the LiAlSiO of preparation
4block ball milling 2-12h, obtains the LiAlSiO of different-grain diameter
4particulate.With the LiAlSiO that deionized water dissolving ball milling is crossed
4particulate, obtains colloidal sol.
(4) flame spray gun is connected oxygen, acetylene and argon gas, light spray gun, adjustment oxyacetylene torch is neutral flame; The colloidal sol prepared is added in spray gun hopper, by argon jet negative pressure, colloidal sol is sucked in spray gun, spurt in the oxyacetylene torch of high temperature after shower nozzle atomization.Collect reacted particulate with cooling distilled water, after drying, obtain the LiAlSiO of negative expansion coefficient
4microballoon.
Embodiment 1
The LiAlSiO of negative expansion coefficient
4preparation method's (detailed process is as shown in Figure 1) of microballoon:
By 0.3mol Li
2cO
3powder, 0.3mol SiO
2powder, 0.6mol Al
2o
3powder, mixes in mortar, the particle mixed is warming up to 1300 DEG C of scorifications and is incubated more than 5h, and rapidly in frozen water quenching namely obtain LiAlSiO
4block.By the LiAlSiO of preparation
4block ball milling 2h, obtains LiAlSiO
4particulate.With the LiAlSiO that deionized water dissolving ball milling is crossed
4particulate, obtains colloidal sol.The LiAlSiO of negative expansion coefficient is obtained after colloidal sol is carried out flame spraying under acetylene atmosphere
4microballoon.
The LiAlSiO of the negative expansion coefficient of preparation in above-described embodiment 1
4the XRD figure of microballoon, as shown in Figure 2, can find out that principal crystalline phase is LiAlSiO synthesis temperature 1300 DEG C
4, illustrate and synthesize a large amount of eucryptite (LiAlSiO
4), inner also containing a little Li
2al
2si
2o
10.
The LiAlSiO of the negative expansion coefficient of preparation in above-described embodiment 1
4the SEM figure of microballoon, as shown in Figure 3, can find out synthesis temperature 1300 DEG C, and after ball milling 2h, LiAlSiO
4microspherulite diameter distribution 2-30um, sphericity is fine.
The LiAlSiO of the negative expansion coefficient of preparation in above-described embodiment 1
4the thermal expansion figure of microballoon, as shown in Figure 4, can draw synthesis temperature 1300 DEG C, and after ball milling 2h, LiAlSiO
4microballoon negative expansion coefficient reaches-6.5 × 10
-6k
-1.
Embodiment 2
By 0.3mol Li
2cO
3powder, 0.3mol SiO
2powder, 0.6mol Al
2o
3powder, mixes in mortar, the particle mixed is warming up to 1350 DEG C of scorifications and is incubated more than 5h, and rapidly in frozen water quenching namely obtain LiAlSiO
4block.By the LiAlSiO of preparation
4block ball milling 7h, obtains LiAlSiO
4particulate.With the LiAlSiO that deionized water dissolving ball milling is crossed
4particulate, obtains colloidal sol.The LiAlSiO of negative expansion coefficient is obtained after colloidal sol is carried out flame spraying under acetylene atmosphere
4microballoon.
The LiAlSiO of the negative expansion coefficient of preparation in above-described embodiment 2
4in the XRD figure of microballoon, can show that principal crystalline phase is still LiAlSiO synthesis temperature 1350 DEG C
4, illustrate and synthesize a large amount of eucryptite (LiAlSiO
4).
The LiAlSiO of the negative expansion coefficient of preparation in above-described embodiment 2
4in the SEM figure of microballoon, can draw synthesis temperature 1350 DEG C, and after ball milling 7h, LiAlSiO
4microspherulite diameter distribution 1-19um, sphericity is fine.
The LiAlSiO of the negative expansion coefficient of preparation in above-described embodiment 2
4in the thermal expansion figure of microballoon, can draw synthesis temperature 1350 DEG C, and after ball milling 7h, LiAlSiO
4microballoon negative expansion coefficient reaches-6.8 × 10
-6k
-1.
Embodiment 3
The LiAlSiO of negative expansion coefficient
4preparation method's (detailed process is as shown in Figure 1) of microballoon:
By 0.3mol Li
2cO
3powder, 0.3mol SiO
2powder, 0.6mol Al
2o
3powder, mixes in mortar, the particle mixed is warming up to 1400 DEG C of scorifications and is incubated more than 5h, and rapidly in frozen water quenching namely obtain LiAlSiO
4block.By the LiAlSiO of preparation
4block ball milling 12h, obtains LiAlSiO
4particulate.With the LiAlSiO that deionized water dissolving ball milling is crossed
4particulate, obtains colloidal sol.The LiAlSiO of negative expansion coefficient is obtained after colloidal sol is carried out flame spraying under acetylene atmosphere
4microballoon.
The LiAlSiO of the negative expansion coefficient of preparation in above-described embodiment 3
4in the XRD figure of microballoon, can show that principal crystalline phase is still LiAlSiO synthesis temperature 1400 DEG C
4, illustrate to there is a large amount of eucryptite (LiAlSiO
4).
The LiAlSiO of the negative expansion coefficient of preparation in above-described embodiment 3
4in the SEM figure of microballoon, can draw synthesis temperature 1400 DEG C, and after ball milling 12h, LiAlSiO
4microspherulite diameter distribution 1-13um, sphericity is fine.
The LiAlSiO of the negative expansion coefficient of preparation in above-described embodiment 3
4in the thermal expansion figure of microballoon, can draw synthesis temperature 1400 DEG C, and after ball milling 12h, LiAlSiO
4microballoon negative expansion coefficient reaches-7.0 × 10
-6k
-1.
Claims (5)
1. the LiAlSiO of a negative expansion coefficient
4microballoon, is characterized in that, described LiAlSiO
4microspherulite diameter distributes between 1 to 30 micrometers, and negative expansion coefficient is-6.5 × 10
-6~ (-7) × 10
-6k
-1.
2. the LiAlSiO of a negative expansion coefficient
4the preparation method of microballoon, is characterized in that, by Li
2cO
3, SiO
2, Al
2o
3powder mixes in mortar; Be warming up to 1300-1400 DEG C of scorification and be incubated more than 5h, and rapidly in frozen water quenching namely obtain LiAlSiO
4block; By block ball milling, obtain the LiAlSiO of different-grain diameter
4particulate; With the LiAlSiO that deionized water dissolving ball milling is crossed
4particulate, obtains colloidal sol; The LiAlSiO of negative expansion coefficient is obtained after colloidal sol is carried out flame spraying under acetylene atmosphere
4microballoon.
3. the LiAlSiO of negative expansion coefficient as claimed in claim 1
4the preparation method of microballoon, is characterized in that, Li in raw material
2cO
3, SiO
2, Al
2o
3mol ratio be 1:1:2.
4. the LiAlSiO of negative expansion coefficient as claimed in claim 1
4the preparation method of microballoon, is characterized in that, frozen water temperature is not higher than 5 DEG C.
5. the LiAlSiO of negative expansion coefficient as claimed in claim 1
4the preparation method of microballoon, is characterized in that, LiAlSiO
4block Ball-milling Time is 2-12h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510182547.2A CN104803666A (en) | 2015-04-16 | 2015-04-16 | LiAlSiO4 microspheres with negative thermal expansion coefficient and preparation method of LiAlSiO4 microspheres |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510182547.2A CN104803666A (en) | 2015-04-16 | 2015-04-16 | LiAlSiO4 microspheres with negative thermal expansion coefficient and preparation method of LiAlSiO4 microspheres |
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| Publication Number | Publication Date |
|---|---|
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Family
ID=53688926
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|---|---|---|---|
| CN201510182547.2A Pending CN104803666A (en) | 2015-04-16 | 2015-04-16 | LiAlSiO4 microspheres with negative thermal expansion coefficient and preparation method of LiAlSiO4 microspheres |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108557832A (en) * | 2018-05-23 | 2018-09-21 | 江苏联瑞新材料股份有限公司 | A kind of preparation method of negative expansion coefficient spherical powder |
| CN108584970A (en) * | 2018-05-11 | 2018-09-28 | 江苏联瑞新材料股份有限公司 | The preparation method of the high temperature negative expansion micro-nano rice flour of one type beta-eucryptite structure |
| CN108609629A (en) * | 2018-04-27 | 2018-10-02 | 江苏联瑞新材料股份有限公司 | A kind of preparation method of negative expansion silicon composite |
| CN109776086A (en) * | 2017-11-15 | 2019-05-21 | 中国科学院上海硅酸盐研究所 | A kind of glass and Ceramic Composite Zero-expansion material and preparation method thereof |
| CN111116185A (en) * | 2019-12-18 | 2020-05-08 | 智核环保科技股份有限公司 | Composite phase honeycomb ceramic and method for controlling expansion coefficient of ceramic |
| CN112250078A (en) * | 2020-10-29 | 2021-01-22 | 淄博辰东新材料有限公司 | Ultralow-expansion-coefficient eucryptite and preparation method thereof |
| CN114892037A (en) * | 2022-05-18 | 2022-08-12 | 重庆大学 | Magnesium-based composite material with nearly zero thermal expansion coefficient within 20-150 ℃, and preparation method and application thereof |
-
2015
- 2015-04-16 CN CN201510182547.2A patent/CN104803666A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776086A (en) * | 2017-11-15 | 2019-05-21 | 中国科学院上海硅酸盐研究所 | A kind of glass and Ceramic Composite Zero-expansion material and preparation method thereof |
| CN108609629A (en) * | 2018-04-27 | 2018-10-02 | 江苏联瑞新材料股份有限公司 | A kind of preparation method of negative expansion silicon composite |
| CN108584970A (en) * | 2018-05-11 | 2018-09-28 | 江苏联瑞新材料股份有限公司 | The preparation method of the high temperature negative expansion micro-nano rice flour of one type beta-eucryptite structure |
| CN108557832A (en) * | 2018-05-23 | 2018-09-21 | 江苏联瑞新材料股份有限公司 | A kind of preparation method of negative expansion coefficient spherical powder |
| CN111116185A (en) * | 2019-12-18 | 2020-05-08 | 智核环保科技股份有限公司 | Composite phase honeycomb ceramic and method for controlling expansion coefficient of ceramic |
| CN112250078A (en) * | 2020-10-29 | 2021-01-22 | 淄博辰东新材料有限公司 | Ultralow-expansion-coefficient eucryptite and preparation method thereof |
| CN112250078B (en) * | 2020-10-29 | 2023-01-31 | 淄博辰东新材料有限公司 | Ultralow-expansion-coefficient eucryptite and preparation method thereof |
| CN114892037A (en) * | 2022-05-18 | 2022-08-12 | 重庆大学 | Magnesium-based composite material with nearly zero thermal expansion coefficient within 20-150 ℃, and preparation method and application thereof |
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