CN105016734A - Preparation method of hollow gradient infrared heat-barrier microspheres - Google Patents
Preparation method of hollow gradient infrared heat-barrier microspheres Download PDFInfo
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- CN105016734A CN105016734A CN201510413260.6A CN201510413260A CN105016734A CN 105016734 A CN105016734 A CN 105016734A CN 201510413260 A CN201510413260 A CN 201510413260A CN 105016734 A CN105016734 A CN 105016734A
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Abstract
The invention discloses a preparation method of hollow gradient infrared heat-barrier microspheres. According to the preparation method, seed deposition and precursor conversion are combined. The preparation method comprises the following steps: crosslinked polystyrene (SPS) microspheres are sulfonated firstly; a polycarbosilane (PCS) and metal alkoxide mixed solution is dripped into the stirred SPS aqueous solution by a precipitation method; after drying and curing, a gradient ceramic precursor-coated SPS solid microspheres; and finally, the solid microspheres are sintered in a vacuum furnace (1000-1400 DEG C) so as to obtain the hollow gradient ceramic microspheres. The preparation method provided by the invention has advantages as follows: the technology is simple; and the product has excellent performance, good infrared heat barrier effect and wide application range. The microsphere structure is hollow and is composed of two phases, namely ZrO2 and SiC. Component contents of each phase show a continuous gradient change in the radial direction.
Description
The application is the divisional application of parent application " a kind of hollow gradient lightweight high IR heat rejection microballoon for high-temperature resistant coating ", and the application number of parent application is 2014100298608, and the applying date of parent application is on January 17th, 2014.
Technical field
The present invention relates to structure of a kind of lightweight high IR heat rejection microballoon and preparation method thereof, in particular, relate to structure of a kind of anti-ir radiation microballoon for high temperature thermal insulation coating and preparation method thereof, belong to high temperature insulating material field.
Background technology
In order to protect, hot-end component is inner not to be subject to the harm of hot environment and to extend its work-ing life; the research and development of various high temperature coating in recent years more and more attract widespread attention, especially more and more urgent to the demand with superpower high temperature insulating performance coating in the field such as space flight and aviation aircraft.In recent years, people continually develop out novel low thermally conductive material.But radiative transfer accounts for significant proportion in material internal heat transfer in high temperature environments, especially has the ir radiation of a wavelength range.Therefore, add high-performance obstruct infrared radiant material in high temperature coating and can effectively reduce material internal radiative transfer, improve the high temperature resistant and heat-proof quality of material.
Infrared barrier filler conventional in high temperature thermal insulation coating at present has TiO
2, ZrO
2, SiC, Cr
2o
3deng.But the density of these powders own is comparatively large, out-of-shape, and easily disperses inequality in the coating, increases solid phase heat transfer, reduce high temperature insulating effect.The obstruct infrared radiation property that recent some investigators found through experiments material is relevant with the shape of material, and when the shape of material is spherical, counter infrared ray radiation effect is best.In addition, the radiation-inhibiting material counter infrared ray limited efficiency of unitary system, if obtain complex phase dense structure by composition adjustment, can improve its counter infrared ray radiance greatly.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of hollow gradient lightweight high IR heat rejection micro-sphere structure for high-temperature resistant coating and preparation method thereof is provided.First by designing the structure intercepting ir radiation lagging material, its structure is that hollow gradient is spherical.And adopt the seed precipitator method and ceramic precursor method in situ conversion process, utilize its hollow SiC-MO of preparation that is separated
2(M=Ti, Zr) graded ceramics microballoon, for the preparation of the novel counter infrared ray radiative material with high temperature thermal control function.Object of the present invention proposes the ceramic fine bead novel texture and preparation method thereof of a kind of low density, high resistance ir radiation.
Object of the present invention is achieved by following technical proposals: the present invention devises a kind of hollow gradient-structure, and namely ceramic microsphere is hollow and each component concentration of ceramic microsphere is continuous print graded along radial direction, MO
2the content of (M=Ti, Zr) increases from inside to outside gradually along radial direction, and the content of SiC reduces from inside to outside gradually along radial direction.
And prepare by seed precipitation and precursor pyrolysis and hot pressing hollow graded ceramics microballoon of knowing clearly, the steps include: that 1. prepare solid microsphere: (1) makes crosslinked polystyrene (SPS) microballoon; (2) the SPS microballoon obtained is carried out sulfonation; 2. prepare the solid microsphere of the coated SPS of graded ceramics precursor; (1) SPS microballoon is scattered in deionized water; (2) Polycarbosilane (PCS) is mixed with alkoxide, be dissolved in tetrahydrofuran (THF) (THF); (3) utilize the precipitator method to be dropwise added drop-wise to by the mixing solutions of (2) in the SPS aqueous solution that stirred, obtain the SPS solid microsphere that graded ceramics precursor is coated; 3. prepare hollow graded ceramics microballoon: utilize precursor pyrolysis and hot pressing to be sintered in vacuum oven by the solid microsphere of the coated SPS of graded ceramics precursor obtained, obtain hollow graded ceramics microballoon.
During the coated SPS solid microsphere of described ceramic precursor mixture, the mixing solutions of ceramic precursor and alkoxide is dropwise added drop-wise in the SPS microballoon aqueous solution that stirred, Keep agitation 1-2h.
Described alkoxide content is 30%-50%; Alkoxide is Butyl Phthalate and tetrabutyl zirconate, and Butyl Phthalate is dibutyltitanate or tetrabutyl titanate, and tetrabutyl zirconate is zirconic acid dibutylester or tetrabutyl zirconate.
Described obtain the coated SPS solid microsphere of ceramic precursor mixture by the precipitator method after, filter and wash, washed throw out in vacuum 80-120 DEG C, 15-20h dries slaking, the solid microsphere of the obtained coated SPS of graded ceramics precursor.
When the solid microsphere of the described coated SPS of graded ceramics precursor sinters in vacuum oven, high-temperature atmosphere furnace temperature is 1000-1400 DEG C, and soaking time is 1-2h.
Principle of the present invention:
Principle of the present invention is that selected lower molecular weight additive is joined in the polymer precursor or its solution that can form pottery, the seed precipitator method are utilized to obtain solid microsphere, slaking thermal treatment is carried out to this mixture, lower molecular weight additive just from polymer body mutually separate out (formed chemical composition gradient), then by precursor in situ conversion process Pintsch process, calcining, the removing SPS centre of sphere, forms the compact hollow graded ceramics microballoon of stabilizing component.
Advantage and disadvantage of the present invention is:
1. because inorganic powder is difficult to Design and Machining, and precursor is macromolecular material, there is good formability, utilize the formability of the excellence of precursor to obtain microballoon by depositing technology, recycling precursor separates out different phases in cracking process, forms hollow gradient globosity.
2. hollow gradient globosity has the advantage that density low and high temperature intercepts infrared radiation property excellence.
3. adopt the precipitator method to obtain microballon, preparation method, technique are simple, and cost is low.
4. use range is wide, and constructional method is simple, can adopt the techniques such as spraying or brushing.
Accompanying drawing explanation
Fig. 1 is the SEM photo of hollow graded ceramics microballoon.
Fig. 2 is the TEM photo of hollow graded ceramics microballoon.
Embodiment
For summary of the invention of the present invention, Characteristic can be understood further, hereby exemplify following examples, and be described in detail as follows:
Embodiment 1
A kind of preparation method of hollow graded ceramics microballoon, comprise following processing step: be scattered in deionized water to be placed on magnetic stirring apparatus by the SPS microballoon after 3g sulfonation process and stir, 3gPCS and 2g tetrabutyl titanate is dissolved in tetrahydrofuran (THF), the mixing solutions of precursor is dropwise added drop-wise in the SPS aqueous solution that stirred, through centrifugal, mixture microballoon is obtained after washing, be placed in vacuum drying oven 80 DEG C, 20h is dried, slaking, obtain graded ceramics precursor microsphere, 1200 sintering 1h in vacuum oven again, obtain hollow graded ceramics microballoon, and to survey its infrared extinction coefficient be 61.4m
2/ Kg.
Embodiment 2
A kind of preparation method of hollow graded ceramics microballoon, comprise following processing step: be scattered in deionized water to be placed on magnetic stirring apparatus by the SPS microballoon after 3g sulfonation process and stir, 3gPCS and 3g tetrabutyl titanate is dissolved in tetrahydrofuran (THF), the mixing solutions of precursor is dropwise added drop-wise in the SPS aqueous solution that stirred, through centrifugal, mixture microballoon is obtained after washing, be placed in vacuum drying oven 100 DEG C, 12h is dried, slaking, obtain PCS/TiO2 graded ceramics precursor microsphere, 1300 DEG C of sintering 2h in vacuum oven again, obtain hollow SiC/TiO2 graded ceramics microballoon, and to survey its infrared extinction coefficient be 62.5m
2/ Kg.
Embodiment 3
A kind of preparation method of hollow graded ceramics microballoon, comprise following processing step: be scattered in deionized water to be placed on magnetic stirring apparatus by the SPS microballoon after 3g sulfonation process and stir, 3gPCS and 3g tetrabutyl zirconate is dissolved in tetrahydrofuran (THF), the mixing solutions of precursor is dropwise added drop-wise in the SPS aqueous solution that stirred, through centrifugal, washing after obtain mixture microballoon, be placed in vacuum drying oven 110 DEG C, 15h is dried, slaking, obtains PCS/ZrO
2graded ceramics precursor microsphere, then in vacuum oven 1250 DEG C sintering 1h, obtain hollow SiC/ZrO
2graded ceramics microballoon, and to survey its infrared extinction coefficient be 63.1m
2/ Kg.
Embodiment 4
A kind of preparation method of hollow graded ceramics microballoon, comprise following processing step: be scattered in deionized water to be placed on magnetic stirring apparatus by the SPS microballoon after 3g sulfonation process and stir, 3gPCS and 2g tetrabutyl zirconate is dissolved in tetrahydrofuran (THF), the mixing solutions of precursor is dropwise added drop-wise in the SPS aqueous solution that stirred, through centrifugal, washing after obtain mixture microballoon, be placed in vacuum drying oven 120 DEG C, 18h is dried, slaking, obtains PCS/ZrO
2graded ceramics precursor microsphere, then in vacuum oven 1400 DEG C sintering 1.5h, obtain hollow SiC/ZrO
2graded ceramics microballoon, and to survey its infrared extinction coefficient be 63.6m
2/ Kg.
Above illustrated embodiment is only preferred embodiment of the present invention; the any pro forma restriction not made the present invention, every any simple modification, component done above embodiment according to technical spirit of the present invention is replaced, equivalent variations and modification all belong to the scope that technical scheme of the present invention is protected.
Claims (4)
1. hollow gradient infra-red heat intercepts the preparation method of microballoon, it is characterized in that, the preparation method of hollow graded ceramics microballoon is seed precipitation and precursor pyrolysis and hot pressing, seed is crosslinked polystyrene (SPS) microballoon, precursor is Polycarbosilane (PCS), transform and carry out under vacuum, concrete steps are as follows:
1) solid microsphere is prepared
(1) crosslinked polystyrene (SPS) microballoon is made;
(2) the SPS microballoon obtained is carried out sulfonation;
2) solid microsphere of the coated SPS of graded ceramics precursor is prepared
(1) SPS microballoon is scattered in deionized water;
(2) Polycarbosilane (PCS) is mixed with alkoxide, be dissolved in tetrahydrofuran (THF) (THF); The content of alkoxide is 30%-50%; Alkoxide is zirconic acid dibutylester or tetrabutyl zirconate;
(3) utilize the precipitator method to be dropwise added drop-wise to by the mixing solutions of (2) in the SPS aqueous solution that stirred, obtain the SPS solid microsphere that graded ceramics precursor is coated;
3) hollow graded ceramics microballoon is prepared: utilize precursor pyrolysis and hot pressing to be sintered in vacuum oven by the solid microsphere of the coated SPS of graded ceramics precursor obtained, obtain hollow graded ceramics microballoon; Microballoon is hollow gradient-structure, and namely hollow gradient high IR heat rejection microballoon is hollow, and ceramic microsphere is by two phase composites, and each component concentration is continuous print graded, wherein ZrO along radial direction
2content increase gradually from inside to outside along radial direction, the content of SiC reduces from inside to outside gradually along radial direction.
2. hollow gradient infra-red heat according to claim 1 intercepts the preparation method of microballoon, it is characterized in that, during the coated SPS solid microsphere of ceramic precursor mixture, the mixing solutions of ceramic precursor and alkoxide is dropwise added drop-wise in the SPS microballoon aqueous solution that stirred, Keep agitation 1-2h.
3. hollow gradient infra-red heat according to claim 1 intercepts the preparation method of microballoon, it is characterized in that, after obtaining the coated SPS solid microsphere of ceramic precursor mixture by the precipitator method, filter and wash, washed throw out vacuum 80-120 DEG C, 12-24h dries slaking, the solid microsphere of the obtained coated SPS of graded ceramics precursor.
4. hollow gradient infra-red heat according to claim 1 intercepts the preparation method of microballoon, and it is characterized in that, when the solid microsphere of the coated SPS of graded ceramics precursor sinters in vacuum oven, high-temperature vacuum furnace temperature is 1000-1400 DEG C, and soaking time is 1-2h.
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| CN201510413260.6A CN105016734B (en) | 2014-01-17 | 2014-01-17 | The preparation method of the infrared heat rejection microsphere of hollow gradient |
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| CN201510413260.6A CN105016734B (en) | 2014-01-17 | 2014-01-17 | The preparation method of the infrared heat rejection microsphere of hollow gradient |
| CN201410029860.8A CN103755346B (en) | 2014-01-17 | 2014-01-17 | A kind of hollow gradient lightweight high IR heat rejection microballoon for high-temperature resistant coating |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108648833A (en) * | 2018-05-11 | 2018-10-12 | 哈尔滨工业大学 | A kind of device and operating method of achievable microballoon any angle overturning |
| CN112876913A (en) * | 2021-01-19 | 2021-06-01 | 宋玉强 | Water-based composite antifouling light coating and preparation method thereof |
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| CN106631112B (en) * | 2016-12-29 | 2019-07-30 | 中国科学院上海应用物理研究所 | A kind of preparation method of hollow ceramic microspheres |
| CN109513929B (en) * | 2018-12-24 | 2021-07-16 | 哈尔滨工程大学 | Batch preparation method of metal hollow spheres with uniform wall thickness |
| CN114085092A (en) * | 2021-11-23 | 2022-02-25 | 兆山科技（北京）有限公司 | Closed-cell ceramic microsphere filled gradient ceramic coating and preparation method thereof |
| CN115160901B (en) * | 2022-07-06 | 2024-06-21 | 海利得新材料研究(上海)有限公司 | Cigarette end scalding resistant UV coating and preparation method thereof, and cigarette end scalding resistant UV coating and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003433A (en) * | 2006-12-26 | 2007-07-25 | 毛海燕 | Ceramic bricks possessing function of heat insulation and preservation, and preparation method |
| CN101323528A (en) * | 2008-07-15 | 2008-12-17 | 南京工业大学 | Preparation of continuous hole graded ceramic tube |
| CN101910263A (en) * | 2007-05-29 | 2010-12-08 | 伊诺瓦材料有限责任公司 | Surfaces having particles and related methods |
| CN102167622A (en) * | 2011-01-21 | 2011-08-31 | 武汉科技大学 | Aluminum-silicon light heat insulation brick and preparation method thereof |
| CN103387395A (en) * | 2013-07-25 | 2013-11-13 | 天津城建大学 | Hollow ceramic microsphere and preparation method of hollow ceramic microsphere |
-
2014
- 2014-01-17 CN CN201410029860.8A patent/CN103755346B/en not_active Expired - Fee Related
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003433A (en) * | 2006-12-26 | 2007-07-25 | 毛海燕 | Ceramic bricks possessing function of heat insulation and preservation, and preparation method |
| CN101910263A (en) * | 2007-05-29 | 2010-12-08 | 伊诺瓦材料有限责任公司 | Surfaces having particles and related methods |
| CN101323528A (en) * | 2008-07-15 | 2008-12-17 | 南京工业大学 | Preparation of continuous hole graded ceramic tube |
| CN102167622A (en) * | 2011-01-21 | 2011-08-31 | 武汉科技大学 | Aluminum-silicon light heat insulation brick and preparation method thereof |
| CN103387395A (en) * | 2013-07-25 | 2013-11-13 | 天津城建大学 | Hollow ceramic microsphere and preparation method of hollow ceramic microsphere |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108648833A (en) * | 2018-05-11 | 2018-10-12 | 哈尔滨工业大学 | A kind of device and operating method of achievable microballoon any angle overturning |
| CN112876913A (en) * | 2021-01-19 | 2021-06-01 | 宋玉强 | Water-based composite antifouling light coating and preparation method thereof |
| CN112876913B (en) * | 2021-01-19 | 2021-12-14 | 广东安捷伦新材料科技有限公司 | Water-based composite antifouling light coating and preparation method thereof |
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| CN103755346B (en) | 2016-01-06 |
| CN105016734B (en) | 2017-03-01 |
| CN103755346A (en) | 2014-04-30 |
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