CN106543446A - A kind of preceramic polymer microsphere and preparation method thereof - Google Patents
A kind of preceramic polymer microsphere and preparation method thereof Download PDFInfo
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- CN106543446A CN106543446A CN201611013228.XA CN201611013228A CN106543446A CN 106543446 A CN106543446 A CN 106543446A CN 201611013228 A CN201611013228 A CN 201611013228A CN 106543446 A CN106543446 A CN 106543446A
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- preceramic polymer
- microsphere
- polymer microsphere
- carborane
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/08—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing boron
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/563—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on boron carbide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2385/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers
- C08J2385/04—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers containing boron
Abstract
The invention provides a kind of preceramic polymer microsphere and preparation method thereof.The preceramic polymer microsphere is with poly- carborane precursor as spherical shell.The preceramic polymer method for preparing microsphere is using the emulsifying microencapsulation based on precursor pyrolysis and hot pressing, using poly- carborane precursor solution as mesophase, preceramic polymer milk particle is obtained using the coating function of oil-water interfaces, then by washing, solidification, dry acquisition preceramic polymer microsphere.Preceramic polymer microsphere of the present invention and preparation method thereof has process is simple, mild condition, good dispersion, microsphere yield and high yield rate, and can save boron source, reduces production cost, reaches energy-saving and environmental conservation effect.The preceramic polymer microsphere of the present invention can be as the precursor material for preparing boron carbide ceramics microsphere, while also can be applied in fields such as superhard coating, radiation proof material, laser inertial confinement fusion Physical Experiments.
Description
Technical field
The invention belongs to technical field of material, and in particular to a kind of preceramic polymer microsphere and preparation method thereof.
Background technology
Boron carbide has a series of noticeable advantages such as high temperature resistant, antioxidation, high intensity and low-density, in military state
There is important potential application in the fields such as anti-, nuclear industry, Aero-Space, can be used as high-temperature structural material, functional material, neutron-absorbing
The candidate materials of material and ICF targets.It should be noted that boron carbide ceramics microsphere can be not only used for ICF targets, due to micro-
The features such as distinctive physico-chemical property of ball, such as higher specific surface area, excellent monodispersity, controllable porosity and permeability,
Coupled the excellent thermomechanical property of boron carbide ceramics, chemical stability and excellent neutron absorption capability so as to aerospace,
The high-tech areas such as nuclear energy, electronics, living things catalysis and advanced weaponry also all show tempting application prospect.
At present, boron carbide ceramics material is typically prepared using carbothermic method or magnesium reduction process, and this kind of method is burnt
It is high into temperature, and be difficult to obtain the products such as thin film, fiber or microsphere.Even if needing production boron carbide ceramics microsphere to also tend to adopt
Coating technique carries out film forming using methods such as magnetron sputtering or chemical vapor depositions, then on polymer mandrel realizing
Boron carbide spherical shell material is obtained by removing mandrel.Requirement of this kind of method to experimental facilitiess is higher, the control to experiment condition
Require extremely strict, and the more difficult control of quality of gained coating, thus there is significant limitation, can't efficiently, high-quality
Production boron carbide ceramics microsphere.
Polymer pyrolysis technology fundamentally solves this difficult problem, the designability of the method set molecule, good work
Skill, preparation temperature be low and the advantages of achievable net molding in one, it is possible to obtain traditional handicraft is difficult to the advanced ceramics for preparing
Material, compared with traditional coating method, the chemical composition that can pass through to control monomer improves ceramic performance, and can be abundant
Using the good machinability of polymer, the molding difficulty of boron carbide ceramics is fundamentally improved, be expected to realize single dispersing carbon
The controllable standby of change boron microsphere, but at present for the preceramic polymer microsphere how prepared needed for boron carbide ceramics microsphere still
Without open report.
The content of the invention
A technical problem to be solved by this invention there is provided a kind of preceramic polymer microsphere, and the present invention will be solved
Another technical problem certainly there is provided a kind of preparation method of preceramic polymer microsphere.
The preceramic polymer microsphere of the present invention, is characterized in, described preceramic polymer microsphere is with poly- carborane elder generation
Drive body is spherical shell, and poly- carborane precursor, with thiazolinyl Decaboron tetradecahydride. as basic structural unit, is thiazolinyl Decaboron tetradecahydride. and monoene copolymerization
Preceramic polymer, described poly- carborane precursor is poly-（6- norbornene Decaboron tetradecahydride .-co- norborene）, it is poly-（Ring is pungent
Thiazolinyl Decaboron tetradecahydride .-co- norborene）, it is poly-（6- norbornene Decaboron tetradecahydride .-co- Decaboron tetradecahydride.）, it is poly-（6- norbornene last of the ten Heavenly stems boron
Alkane-co-1,5 hexadienes）In one kind, the weight average molecular weight of poly- carborane precursor（M w）More than or equal to 5000.
The chemical formula of described poly- carborane precursor is as follows：
It is poly-（6- norbornene Decaboron tetradecahydride .-co- norborene）：
（1）
It is poly-（Cyclo-octene base Decaboron tetradecahydride .-co- norborene）：
（2）
It is poly-（6- norbornene Decaboron tetradecahydride .-co- Decaboron tetradecahydride.）：
（3）
It is poly-（6- norbornene Decaboron tetradecahydride .-co-1,5 hexadienes）：
（4）
Wherein, m and n is the degree of polymerization.
The preparation method of the preceramic polymer microsphere of the present invention, comprises the following steps：
A. poly- carborane precursor solution is formed after fully dissolve poly- carborane precursor in organic solvent, while preparing
Polyvinyl alcohol water solution；
B. milk particle is produced using emulsifying microencapsulation：A kind of micro-injection pump point for being to inject by three scalable flow velocity
Deionized water, poly- carborane precursor solution and polyvinyl alcohol water solution the interior phase of microchannel template, centre are not respectively pressed into into
Phase and foreign minister, form water/oil/water（W1/O/W2）Double emulsion systems, prepare the preceramic polymer milk particle of Bao Shui；Another kind is
The micro-injection pump of flow velocity is injected respectively by poly- carborane precursor solution and polyvinyl alcohol water solution pressure by two scalable
Enter interior phase and the foreign minister of microchannel template, form oil/water（O/W）Single emulsion system, prepares solid preceramic polymer milk particle；
C. preceramic polymer milk particle is collected, isothermal curing in polyvinyl alcohol water solution is put into, in preceramic polymer milk particle
During isothermal curing, constantly diffusion is consumed organic solvent, makes the preceramic polymer microsphere and solid precursor of Bao Shui
Polymer microballoon；
D. filter, collect preceramic polymer microsphere, and using the deionized water repeated washing preceramic polymer microsphere of heat,
Subsequently preceramic polymer microsphere is put in baking oven, is dried in 25 C ~ 40 C, finally obtain hollow poly- carborane
Preceramic polymer microsphere and solid poly- carborane preceramic polymer microsphere.
Organic solvent described in step a is benzene, fluorobenzene, one or more in 1,2- dichloroethanes, poly- carborane pioneer
Body mass concentration in organic solvent is 10% ~ 30%；
The mass concentration of the polyvinyl alcohol water solution described in step a is 0.5% ~ 4%.
The coaxial loop passage that microchannel template described in step b is made up of the capillary tube of 2 ~ 3 kinds of different-diameters, foreign minister
Flow velocity keep maximum in preceramic polymer milk particle preparation process.
Solidification temperature described in step c is 10 C ~ 30 C, and polyvinyl alcohol water solution is stirred continuously in solidification process, is controlled
Dispersity of the preceramic polymer milk particle processed in foreign minister, it is to avoid preceramic polymer milk particle mutually collides, reunites and cause
Deformation, rupture.
Preceramic polymer microsphere of the present invention and preparation method thereof is using the emulsion micropackaging based on precursor pyrolysis and hot pressing
Technology, using poly- carborane precursor solution as mesophase, obtains preceramic polymer breast using the coating function of oil-water interfaces
Grain, then by washing, solidification, dry acquisition preceramic polymer microsphere.The preceramic polymer microsphere of the present invention and its preparation
Method has process is simple, mild condition, good dispersion, microsphere yield and high yield rate, and can save boron source, reduces life
Cost is produced, energy-saving and environmental conservation effect is reached.The preceramic polymer microsphere of the present invention can be used as preparing boron carbide
The precursor material of ceramic microsphere, while also can lead in superhard coating, radiation proof material, laser inertial confinement fusion Physical Experiment etc.
Domain is applied.
Description of the drawings
Fig. 1 is the optical microscope picture of the preceramic polymer microsphere of the present invention.
Specific embodiment
The present invention is specifically described below by embodiment.It is important to point out that following examples are served only for this
Invention is further described, it is impossible to be interpreted as limiting the scope of the invention, and the person skilled in the art in the field can be with
Some nonessential modifications and adaptations are made according to foregoing invention content to the present invention.
Embodiment 1
A. will be poly-（6- norbornene Decaboron tetradecahydride .-co- Decaboron tetradecahydride.）It is dissolved in fluorobenzene, the weight average molecular weight of preceramic polymer
（M w）For 68000, the mass percent of solution is 30%.It is foreign minister that configuration quality percentage ratio is 2% polyvinyl alcohol water solution；
B. deionized water, poly- carborane precursor solution and polyvinyl alcohol water solution are distinguished using three micro-injection pumps
Most interior phase, mesophase and the foreign minister of microchannel template are pressed into, make three-phase form water/oil/water（W1/O/W2）Double emulsion systems；
C. milk particle is collected in the revolving bottle equipped with outer water phase, be placed in milk particle rotation solidification instrument, solidification temperature 30oC, up time
Pin is rotated around trunnion axis with 25 rpm, solidifies 24 h；
D. pour liquid in revolving bottle into except sieve goes water phase, and put through hot deionized water repeated washing several times
Enter baking oven to be dried in 40 C, that is, obtain 500 μm or so poly- carborane preceramic polymers of diameter as shown in Figure 1 hollow micro-
Ball.
Embodiment 2
A. will be poly-（6- norbornene Decaboron tetradecahydride .-co-1,5 hexadienes）It is dissolved in benzene, the weight average molecular weight of preceramic polymer
（M w）For 5200, the mass percent of solution is 20%.It is foreign minister that configuration quality percentage ratio is 2% polyvinyl alcohol water solution；
B. deionized water, poly- carborane precursor solution and polyvinyl alcohol water solution are distinguished using three micro-injection pumps
Most interior phase, mesophase and the foreign minister of microchannel template are pressed into, make three-phase form water/oil/water（W1/O/W2）Double emulsion systems；
C. milk particle is collected in the revolving bottle equipped with outer water phase, be placed in milk particle rotation solidification instrument, solidification temperature 20oC, up time
Pin is rotated around trunnion axis with 25 rpm, solidifies 48 h；
D. pour liquid in revolving bottle into except sieve goes water phase, and put through hot deionized water repeated washing several times
Enter baking oven to be dried in 40 C, that is, obtain the poly- carborane preceramic polymer tiny balloon of 620 μm or so of diameter.
Embodiment 3
A. will be poly-（6- norbornene Decaboron tetradecahydride .-co- norborene）, benzene and 1,2- dichloroethanes are with 10: 45:45 mass
Fraction configures oil phase, the weight average molecular weight of preceramic polymer（M w）For 15000, the mass percent of solution is 10%.And configure
It is foreign minister that mass percent is 4% polyvinyl alcohol water solution；
B. deionized water, poly- carborane precursor solution and polyvinyl alcohol water solution are distinguished using three micro-injection pumps
Most interior phase, mesophase and the foreign minister of microchannel template are pressed into, make three-phase form water/oil/water（W1/O/W2）Double emulsion systems；
C. milk particle is collected in the revolving bottle equipped with outer water phase, be placed in milk particle rotation solidification instrument, solidification temperature 10 oC, up time
Pin is rotated around trunnion axis with 25 rpm, solidifies 72 h；
D. pour liquid in revolving bottle into except sieve goes water phase, and put through hot deionized water repeated washing several times
Enter baking oven to be dried in 25 C, that is, obtain the poly- carborane preceramic polymer tiny balloon of 500 μm or so of diameter.
Embodiment 4
A. will be poly-（Cyclo-octene base Decaboron tetradecahydride .-co- norborene）It is dissolved in fluorobenzene, the weight average molecular weight of preceramic polymer
（M w）For 13000, the mass percent of solution is 20%.It is foreign minister that configuration quality percentage ratio is 0.5% polyvinyl alcohol water solution；
B. two micro-injection pumps are adopted, different injection flow velocitys is adjusted, by poly- carborane precursor solution and polyvinyl alcohol
The interior phase of aqueous solution press-in microchannel template and foreign minister, make biphase formation water/oil（O/W）Single emulsion system；
C. milk particle is collected in the beaker equipped with outer water phase, and persistently 24 h of stirring solidification, solidification temperature 25oC；
D. pour liquid in beaker into except sieve goes water phase, and put it into through hot deionized water repeated washing several times
Baking oven is dried in 30 C, that is, obtain the poly- carborane preceramic polymer solid microsphere of 300 μm or so of diameter.
Claims (6)
1. a kind of preceramic polymer microsphere, it is characterised in that described preceramic polymer microsphere is with poly- carborane precursor
For spherical shell, poly- carborane precursor, with thiazolinyl Decaboron tetradecahydride. as basic structural unit, is the pioneer of thiazolinyl Decaboron tetradecahydride. and monoene copolymerization
Body polymer, described poly- carborane precursor is poly-（6- norbornene Decaboron tetradecahydride .-co- norborene）, it is poly-（Cyclo-octene base
Decaboron tetradecahydride .-co- norborene）, it is poly-（6- norbornene Decaboron tetradecahydride .-co- Decaboron tetradecahydride.）, it is poly-（6- norbornene Decaboron tetradecahydride .-
Co-1,5 hexadienes）In one kind, the weight average molecular weight of poly- carborane precursor（M w）More than or equal to 5000；
The chemical formula of described poly- carborane precursor is as follows：
It is poly-（6- norbornene Decaboron tetradecahydride .-co- norborene）：
It is poly-（Cyclo-octene base Decaboron tetradecahydride .-co- norborene）：
It is poly-（6- norbornene Decaboron tetradecahydride .-co- Decaboron tetradecahydride.）：
It is poly-（6- norbornene Decaboron tetradecahydride .-co-1,5 hexadienes）：
Wherein, m and n is the degree of polymerization.
2. a kind of preparation method of preceramic polymer microsphere, it is characterised in that comprise the following steps：
A. poly- carborane precursor solution is formed after fully dissolve poly- carborane precursor in organic solvent, while preparing
Polyvinyl alcohol water solution；
B. milk particle is produced using emulsifying microencapsulation：A kind of micro-injection pump point for being to inject by three scalable flow velocity
Deionized water, poly- carborane precursor solution and polyvinyl alcohol water solution the interior phase of microchannel template, centre are not respectively pressed into into
Phase and foreign minister, form water/oil/water（W1/O/W2）Double emulsion systems, prepare the preceramic polymer milk particle of Bao Shui；Another kind is
The micro-injection pump of flow velocity is injected respectively by poly- carborane precursor solution and polyvinyl alcohol water solution pressure by two scalable
Enter interior phase and the foreign minister of microchannel template, form oil/water（O/W）Single emulsion system, prepares solid preceramic polymer milk particle；
C. preceramic polymer milk particle is collected, isothermal curing in polyvinyl alcohol water solution is put into, in preceramic polymer milk particle
During isothermal curing, constantly diffusion is consumed organic solvent, makes the preceramic polymer microsphere and solid precursor of Bao Shui
Polymer microballoon；
D. filter, collect preceramic polymer microsphere, and using the deionized water repeated washing preceramic polymer microsphere of heat,
Subsequently preceramic polymer microsphere is put in baking oven, is dried in 25 C ~ 40 C, finally obtain hollow poly- carborane
Preceramic polymer microsphere and solid poly- carborane preceramic polymer microsphere.
3. the preparation method of preceramic polymer microsphere according to claim 2, it is characterised in that：Having described in step a
Machine solvent is benzene, fluorobenzene, one or more in 1,2- dichloroethanes, and poly- carborane precursor quality in organic solvent is dense
Spend for 10% ~ 30%.
4. the preparation method of preceramic polymer microsphere according to claim 2, it is characterised in that：It is poly- described in step a
The mass concentration of vinyl alcohol aqueous solution is 0.5% ~ 4%.
5. the preparation method of preceramic polymer microsphere according to claim 2, it is characterised in that：It is micro- described in step b
The coaxial loop passage that passage template is made up of the capillary tube of 2 ~ 3 kinds of different-diameters, the flow velocity of foreign minister is in preceramic polymer
Keep in milk particle preparation process maximum.
6. the preparation method of preceramic polymer microsphere according to claim 2, it is characterised in that：Consolidating described in step c
Change temperature is 10 C ~ 30 C, and polyvinyl alcohol water solution is stirred continuously in solidification process, and control preceramic polymer milk particle is outside
Dispersity in phase, it is to avoid preceramic polymer milk particle mutually collides, reunites and caused deformation, rupture.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106964304A (en) * | 2017-05-04 | 2017-07-21 | 中国人民解放军国防科学技术大学 | A kind of method that emulsifying microencapsulation prepares poly- carborane tiny balloon |
| CN108840966A (en) * | 2018-05-25 | 2018-11-20 | 北京航空航天大学 | A kind of high-content boron hydrogen olefin polymer and its application |
| CN109265690A (en) * | 2018-08-08 | 2019-01-25 | 厦门大学 | A kind of hollow polymer nanosphere and preparation method thereof |
| CN112390658A (en) * | 2020-10-29 | 2021-02-23 | 中国工程物理研究院激光聚变研究中心 | Mechanical processing and forming method for oxide foamed ceramic material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4871826A (en) * | 1987-06-22 | 1989-10-03 | Massachusetts Institute Of Technology | Lewis base adducts of decaborane for forming new preceramic polymers, using as binders, forming shaped bodies and forming fibers |
| JPH05310404A (en) * | 1992-05-07 | 1993-11-22 | Tokuyama Soda Co Ltd | Boron nitride precursor and production of boron nitride |
| CN104609423A (en) * | 2015-01-29 | 2015-05-13 | 中国人民解放军国防科学技术大学 | Preparation method of boron carbide hollow microspheres |
| CN104891494A (en) * | 2015-05-14 | 2015-09-09 | 中国人民解放军国防科学技术大学 | Preparation method of boron carbide precursor with high boron content |
| CN105622843A (en) * | 2016-03-29 | 2016-06-01 | 中国人民解放军国防科学技术大学 | Synthetic method for boron-containing precursor copolymer |
-
2016
- 2016-11-18 CN CN201611013228.XA patent/CN106543446A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4871826A (en) * | 1987-06-22 | 1989-10-03 | Massachusetts Institute Of Technology | Lewis base adducts of decaborane for forming new preceramic polymers, using as binders, forming shaped bodies and forming fibers |
| JPH05310404A (en) * | 1992-05-07 | 1993-11-22 | Tokuyama Soda Co Ltd | Boron nitride precursor and production of boron nitride |
| CN104609423A (en) * | 2015-01-29 | 2015-05-13 | 中国人民解放军国防科学技术大学 | Preparation method of boron carbide hollow microspheres |
| CN104891494A (en) * | 2015-05-14 | 2015-09-09 | 中国人民解放军国防科学技术大学 | Preparation method of boron carbide precursor with high boron content |
| CN105622843A (en) * | 2016-03-29 | 2016-06-01 | 中国人民解放军国防科学技术大学 | Synthetic method for boron-containing precursor copolymer |
Non-Patent Citations (1)
| Title |
|---|
| XIAOJUAN ZHANG,JING LI: "《Synthesis and characterization of B–C polymer hollow microspheres from a new organodecaborane preceramic polymer》", 《RSC ADVANCES》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106964304A (en) * | 2017-05-04 | 2017-07-21 | 中国人民解放军国防科学技术大学 | A kind of method that emulsifying microencapsulation prepares poly- carborane tiny balloon |
| CN108840966A (en) * | 2018-05-25 | 2018-11-20 | 北京航空航天大学 | A kind of high-content boron hydrogen olefin polymer and its application |
| CN109265690A (en) * | 2018-08-08 | 2019-01-25 | 厦门大学 | A kind of hollow polymer nanosphere and preparation method thereof |
| CN112390658A (en) * | 2020-10-29 | 2021-02-23 | 中国工程物理研究院激光聚变研究中心 | Mechanical processing and forming method for oxide foamed ceramic material |
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