CN105016734B - The preparation method of the infrared heat rejection microsphere of hollow gradient - Google Patents
The preparation method of the infrared heat rejection microsphere of hollow gradient Download PDFInfo
- Publication number
- CN105016734B CN105016734B CN201510413260.6A CN201510413260A CN105016734B CN 105016734 B CN105016734 B CN 105016734B CN 201510413260 A CN201510413260 A CN 201510413260A CN 105016734 B CN105016734 B CN 105016734B
- Authority
- CN
- China
- Prior art keywords
- microsphere
- precursor
- hollow
- heat rejection
- polystyrene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention discloses the preparation method of hollow gradient infrared heat rejection microsphere, is combined with precursor pyrolysis and hot pressing using seed precipitation, step is：Sulfonation crosslinked polystyrene (SPS) microsphere first, using the sedimentation method, Polycarbosilane (PCS) and metal alkoxide mixed solution are added drop-wise in the SPS aqueous solution that stirred, the SPS solid microsphere of graded ceramicses precursor cladding is obtained after drying and ripening, again solid microsphere is sintered (1,000 1400 DEG C) in vacuum drying oven, obtain hollow graded ceramicses microsphere.The present invention has preparation process is simple, excellent performance, and product infrared heat rejection effect is good, and the advantages of applied widely, micro-sphere structure is hollow, by ZrO2, SiC two phase composition, each phase component content along radial direction be in continuous graded.
Description
The application is parent application " a kind of hollow gradient lightweight high IR heat rejection microsphere for high-temperature resistant coating "
Divisional application, the Application No. 2014100298608 of parent application, the applying date of parent application is on January 17th, 2014.
Technical field
The present invention relates to a kind of structure of lightweight high IR heat rejection microsphere and preparation method thereof, in particular, it is related to
A kind of structure of anti-infra-red radiation microsphere for high temperature thermal insulation coating and preparation method thereof, belongs to high temperature insulating material field.
Background technology
Do not endangered by hot environment inside hot-end component and extended its service life to protect, various high temperature in recent years
The research and development of coating increasingly attract widespread attention, especially super to having in the field such as space flight and aviation aircraft
The demand of strong high temperature insulating performance coating is more and more urgent.In recent years, people do not turn off and send new low Heat Conduction Material.But
Radiant heat transfer accounts for significant proportion in material internal heat transfer in high temperature environments, especially has the infrared spoke of a wavelength range
Penetrate.Therefore, add high-performance obstruct infrared radiant material in high temperature coating and be effectively reduced material internal radiant heat transfer, improve material
The high temperature resistant and heat-proof quality of material.
Conventional infrared barrier filler in high temperature thermal insulation coating has TiO at present2、ZrO2、SiC、Cr2O3Deng.But these
Powder body density itself is larger, in irregular shape, and easily disperses uneven in the coating, increases solid phase heat transfer, reduce high temperature every
Thermal effect.The obstruct infrared radiation property that recent some investigators are found through experiments material is relevant with the shape of material, when
When being shaped as spherical of material, counter infrared ray radiation effect is optimal.In addition, the radiation-inhibiting material counter infrared ray effect of unitary system has
Limit, if complex phase compact texture can be obtained by composition adjustment, is greatly improved its counter infrared ray radiance.
Content of the invention
It is an object of the invention to overcoming the deficiencies in the prior art, provide a kind of hollow gradient for high-temperature resistant coating light
Matter high IR heat rejection micro-sphere structure and preparation method thereof.First pass through and the structure intercepting infra-red radiation heat-barrier material is set
Meter, its structure is that hollow gradient is spherical.And adopt the seed sedimentation method and ceramic precursor method in situ conversion process, it is separated using it
Prepare hollow SiC-MO2(M=Ti, Zr) graded ceramicses microsphere, has the new counter infrared ray spoke of high temperature thermal control function for preparation
Penetrate material.The purpose of the present invention proposes a kind of low-density, the ceramic fine bead new structure of high counter infrared ray radiation and preparation method thereof.
The purpose of the present invention is achieved by following technical proposals：The present invention devises a kind of hollow gradient-structure, that is,
Ceramic microsphere is hollow and each constituent content of ceramic microsphere is in continuous graded along radial direction, MO2(M=Ti,
Zr content) is gradually increased from inside to outside along radial direction, and the content of SiC is gradually reduced from inside to outside along radial direction.
And hollow graded ceramicses microsphere of knowing clearly is prepared by seed precipitation and precursor pyrolysis and hot pressing, its step is：1. prepare
Solid microsphere：(1) make crosslinked polystyrene (SPS) microsphere；(2) SPS obtaining microsphere is carried out sulfonation；2. preparation gradient pottery
Porcelain precursor coats the solid microsphere of SPS；(1) SPS microsphere is scattered in deionized water；(2) by Polycarbosilane (PCS) and alcohol
Salt mixes, and is dissolved in oxolane (THF)；(3) using the sedimentation method, the mixed solution of (2) is dropwise added drop-wise to the SPS that stirred
In aqueous solution, obtain the SPS solid microsphere of graded ceramicses precursor cladding；3. prepare hollow graded ceramicses microsphere:Using pioneer
The solid microsphere that the graded ceramicses obtaining precursor coats SPS is sintered by body conversion method in vacuum drying oven, obtains hollow graded ceramicses
Microsphere.
When described ceramic precursor mixture coats SPS solid microsphere, by the mixed solution of ceramic precursor and alkoxide
Dropwise it is added drop-wise in the SPS microsphere aqueous solution that stirred, continuously stirred 1-2h.
Described alkoxide content is 30%-50%；Alkoxide is Butyl Phthalate and tetrabutyl zirconate, and Butyl Phthalate is metatitanic acid two fourth
Ester or butyl titanate, tetrabutyl zirconate is zirconic acid dibutyl ester or tetrabutyl zirconate.
Described after the sedimentation method obtain the SPS solid microsphere of ceramic precursor mixture cladding, filter and wash, wash
The precipitate washed dries ripening in vacuum 80-120 DEG C, 15-20h, and prepared graded ceramicses precursor coats the solid micro- of SPS
Ball.
When the solid microsphere of described graded ceramicses precursor cladding SPS sinters in vacuum drying oven, high-temperature atmosphere furnace temperature
For 1000-1400 DEG C, temperature retention time is 1-2h.
The principle of the present invention：
The principle of the present invention is selected low-molecular-weight additive to be added to the polymeric preceramic that can form pottery
In body or its solution, solid microsphere is obtained using the seed sedimentation method, this mixture is carried out with ripening heat treatment, low-molecular-weight is added
Thing just separates out (formed chemical composition gradient) from polymer body phase, then pass through precursor in situ conversion process Pintsch process,
Calcining, removes the SPS centre of sphere, forms the compact hollow graded ceramicses microsphere of stable elementss.
Advantages of the present invention and feature are：
1. because inorganic powder is difficult to Design and Machining, and precursor is macromolecular material, has good mouldability, utilizes
The excellent mouldability of precursor is obtained microsphere by depositing technology, recycles precursor to separate out in cracking process different
Phase, forms hollow gradient spherical structure.
2. hollow gradient spherical structure has the advantages that density low and high temperature obstruct infrared radiation property is excellent.
3. adopt the sedimentation method to obtain microballon, preparation method, process is simple, low cost.
4. range is wide, and construction method is simple, can be using the technique such as spraying or brushing.
Brief description
Fig. 1 is the SEM photograph of hollow graded ceramicses microsphere.
Fig. 2 is the TEM photo of hollow graded ceramicses microsphere.
Specific embodiment
For content of the invention, feature and effect of the present invention can be further appreciated that, hereby enumerate following examples, and describe in detail
As follows：
Embodiment 1
A kind of preparation method of hollow graded ceramicses microsphere, comprises the following steps that：SPS after 3g sulfonation is processed is micro-
Ball is scattered in deionized water and is placed in stirring on magnetic stirring apparatuss, 3gPCS and 2g butyl titanate is dissolved in oxolane, will
The mixed solution of precursor is dropwise added drop-wise in the SPS aqueous solution that stirred, and obtains mixture microsphere, put after centrifugation, washing
In 80 DEG C of vacuum drying oven, 20h drying, ripening, obtain graded ceramicses precursor microsphere, 1200 sintering 1h, obtains in vacuum drying oven
To hollow graded ceramicses microsphere, and survey its infrared extinction coefficient for 61.4m2/Kg.
Embodiment 2
A kind of preparation method of hollow graded ceramicses microsphere, comprises the following steps that：SPS after 3g sulfonation is processed is micro-
Ball is scattered in deionized water and is placed in stirring on magnetic stirring apparatuss, 3gPCS and 3g butyl titanate is dissolved in oxolane, will
The mixed solution of precursor is dropwise added drop-wise in the SPS aqueous solution that stirred, and obtains mixture microsphere, put after centrifugation, washing
In 100 DEG C of vacuum drying oven, 12h drying, ripening, obtain PCS/TiO2 graded ceramicses precursor microsphere, 1300 in vacuum drying oven
DEG C sintering 2h, obtain hollow SiC/TiO2 graded ceramicses microsphere, and survey its infrared extinction coefficient be 62.5m2/Kg.
Embodiment 3
A kind of preparation method of hollow graded ceramicses microsphere, comprises the following steps that：SPS after 3g sulfonation is processed is micro-
Ball is scattered in deionized water and is placed in stirring on magnetic stirring apparatuss, 3gPCS and 3g tetrabutyl zirconate is dissolved in oxolane, will
The mixed solution of precursor is dropwise added drop-wise in the SPS aqueous solution that stirred, and obtains mixture microsphere, put after centrifugation, washing
In 110 DEG C of vacuum drying oven, 15h drying, ripening, obtain PCS/ZrO2Graded ceramicses precursor microsphere, 1250 in vacuum drying oven
DEG C sintering 1h, obtain hollow SiC/ZrO2Graded ceramicses microsphere, and survey its infrared extinction coefficient for 63.1m2/Kg.
Embodiment 4
A kind of preparation method of hollow graded ceramicses microsphere, comprises the following steps that：SPS after 3g sulfonation is processed is micro-
Ball is scattered in deionized water and is placed in stirring on magnetic stirring apparatuss, 3gPCS and 2g tetrabutyl zirconate is dissolved in oxolane, will
The mixed solution of precursor is dropwise added drop-wise in the SPS aqueous solution that stirred, and obtains mixture microsphere, put after centrifugation, washing
In 120 DEG C of vacuum drying oven, 18h drying, ripening, obtain PCS/ZrO2Graded ceramicses precursor microsphere, 1400 in vacuum drying oven
DEG C sintering 1.5h, obtain hollow SiC/ZrO2Graded ceramicses microsphere, and survey its infrared extinction coefficient for 63.6m2/Kg.
Embodiment provided above is only presently preferred embodiments of the present invention, any pro forma the limit not present invention made
System, any simple modification that every technical spirit according to the present invention is made to above example, component are replaced, equivalent variations with
Modify the scope belonging to technical scheme protection.
Claims (4)
1. the preparation method of the infrared heat rejection microsphere of hollow gradient is it is characterised in that the system of hollow gradient infrared heat rejection microsphere
Preparation Method is seed precipitation and precursor pyrolysis and hot pressing, and seed is crosslinked polystyrene microsphere, and precursor is Polycarbosilane, and conversion exists
Carry out under vacuum condition, comprise the following steps that：
1) prepare solid microsphere
(1) make crosslinked polystyrene microsphere；
(2) polystyrene microsphere obtaining is carried out sulfonation；
2) prepare the solid microsphere that graded ceramicses precursor coats polystyrene
(1) polystyrene microsphere is scattered in deionized water；
(2) Polycarbosilane is mixed with alkoxide, be dissolved in oxolane；The content of alkoxide is 30%-50%；Alkoxide is zirconic acid two
Butyl ester or tetrabutyl zirconate；
(3) using the sedimentation method, the mixed solution of (2) is dropwise added drop-wise in the polystyrene aqueous solution that stirred, obtains gradient pottery
The polystyrene solid microsphere of porcelain precursor cladding；
3) prepare hollow gradient infrared heat rejection microsphere：Will be poly- for the graded ceramicses obtaining precursor cladding using precursor pyrolysis and hot pressing
Cinnamic solid microsphere sinters in vacuum drying oven, obtains hollow gradient infrared heat rejection microsphere；The infrared heat rejection of hollow gradient is micro-
Ball be hollow gradient-structure, that is, hollow gradient high IR heat rejection microsphere be hollow, and hollow gradient infrared heat rejection microsphere by
Two phase compositions, each constituent content is in continuous graded along radial direction, wherein ZrO2Content along radial direction by inner to
It is gradually increased outward, the content of SiC is gradually reduced from inside to outside along radial direction.
2. the preparation method of the infrared heat rejection microsphere of hollow gradient according to claim 1 is it is characterised in that ceramic setter
During body mixture cladding polystyrene solid microsphere, the mixed solution of ceramic precursor and alkoxide is dropwise added drop-wise to and stirreds
In polystyrene microsphere aqueous solution, continuously stirred 1-2h.
3. the preparation method of the infrared heat rejection microsphere of hollow gradient according to claim 1 is it is characterised in that by precipitation
After method obtains the polystyrene solid microsphere of ceramic precursor mixture cladding, filter and wash, washed precipitate vacuum
80-120 DEG C, 12-24h drying ripening, prepared graded ceramicses precursor coats the solid microsphere of polystyrene.
4. the preparation method of the infrared heat rejection microsphere of hollow gradient according to claim 1 is it is characterised in that graded ceramicses
When the solid microsphere of precursor cladding polystyrene sinters in vacuum drying oven, high-temperature vacuum furnace temperature is 1000-1400 DEG C, insulation
Time is 1-2h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510413260.6A CN105016734B (en) | 2014-01-17 | 2014-01-17 | The preparation method of the infrared heat rejection microsphere of hollow gradient |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
| CN201510413260.6A CN105016734B (en) | 2014-01-17 | 2014-01-17 | The preparation method of the infrared heat rejection microsphere of hollow gradient |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410029860.8A Division CN103755346B (en) | 2014-01-17 | 2014-01-17 | A kind of hollow gradient lightweight high IR heat rejection microballoon for high-temperature resistant coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105016734A CN105016734A (en) | 2015-11-04 |
| CN105016734B true CN105016734B (en) | 2017-03-01 |
Family
ID=50522711
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410029860.8A Expired - Fee Related CN103755346B (en) | 2014-01-17 | 2014-01-17 | A kind of hollow gradient lightweight high IR heat rejection microballoon for high-temperature resistant coating |
| CN201510413260.6A Expired - Fee Related CN105016734B (en) | 2014-01-17 | 2014-01-17 | The preparation method of the infrared heat rejection microsphere of hollow gradient |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410029860.8A Expired - Fee Related CN103755346B (en) | 2014-01-17 | 2014-01-17 | A kind of hollow gradient lightweight high IR heat rejection microballoon for high-temperature resistant coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN103755346B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108648833B (en) * | 2018-05-11 | 2019-05-17 | 哈尔滨工业大学 | A kind of device and operating method of achievable microballoon any angle overturning |
| 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 |
| 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 |
| 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 |
| CN115160901A (en) * | 2022-07-06 | 2022-10-11 | 海利得新材料研究(上海)有限公司 | Cigarette end burning resistant UV coating and preparation method thereof, cigarette end burning resistant UV coating and preparation method thereof |
Family Cites Families (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 |
| AU2008260162B2 (en) * | 2007-05-29 | 2013-06-20 | Tpk Holding Co., Ltd. | Surfaces having particles and related methods |
| CN101323528B (en) * | 2008-07-15 | 2011-11-16 | 南京工业大学 | Preparation of continuous hole graded ceramic tube |
| CN102167622B (en) * | 2011-01-21 | 2013-03-06 | 武汉科技大学 | Aluminum-silicon light heat insulation brick and preparation method thereof |
| CN103387395B (en) * | 2013-07-25 | 2014-11-05 | 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
- 2014-01-17 CN CN201510413260.6A patent/CN105016734B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103755346A (en) | 2014-04-30 |
| CN105016734A (en) | 2015-11-04 |
| CN103755346B (en) | 2016-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105016734B (en) | The preparation method of the infrared heat rejection microsphere of hollow gradient | |
| CN103880390B (en) | A kind of for SiO 2infrared high shielded nucleus shell structure opalizer of aerogel and preparation method thereof | |
| CN103387395B (en) | Hollow ceramic microsphere and preparation method of hollow ceramic microsphere | |
| CN113105237B (en) | AB2O6 type tantalate ceramic and preparation method thereof | |
| CN105198475A (en) | Method for producing complex-shaped porous silicon nitride ceramic product | |
| CN105129805A (en) | Preparation method of silicon oxide/tin antimony oxide/zinc oxide ternary composite material | |
| CN102674898A (en) | Cerium oxide/ aluminium oxide micro-nanostructure ceramic pigment and preparation method thereof | |
| CN104230369B (en) | A kind of high porosity ceramic with honeycomb and preparation method thereof | |
| CN109403054A (en) | The preparation method and applications of carbon-doped nanometer tube aeroge composites sandwich structures | |
| CN105669186B (en) | The preparation method of high relative density low-resistivity tin indium oxide target material | |
| CN103400976A (en) | Titanium nitride coated lithium titanate material preparation method | |
| CN108239737A (en) | Method for preparing heat barrier coating | |
| CN103542564A (en) | Nanocrystalline ceramic selective absorbing coating of solar energy | |
| CN103864423B (en) | A kind of preparation method of microwave dielectric ceramic materials | |
| CN108707237A (en) | A kind of universal method preparing hollow metal organic frame | |
| CN109554658A (en) | A kind of superhigh temperature resistant infrared radiation emitting powder, coating and preparation method thereof | |
| CN108585912B (en) | Preparation method of inorganic high-emissivity coating containing graphene oxide | |
| CN105565781B (en) | It is a kind of for the infrared radiation ceramic powdered and preparation method thereof of thermal spraying | |
| CN107244891B (en) | Production method of external wall tile capable of automatically repairing surface scratches | |
| CN115433007A (en) | Solar spectrum wide-frequency absorption material and preparation method thereof | |
| CN104451512A (en) | Granulation method of thermal spray powder | |
| KR101732244B1 (en) | Manufacturing method of IR cut-off metal oxide particles | |
| CN103951428A (en) | Moderate-temperature stable-sintering-temperature low-loss microwave dielectric ceramic material | |
| CN104528822B (en) | A kind of preparation method of cubic phase zircite nano-crystal film | |
| CN103342383A (en) | Preparation method of microwave dielectric ceramic material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170301 Termination date: 20210117 |