CN105521745B - The preparation method of organic polymer-based heat conduction microballoon - Google Patents
The preparation method of organic polymer-based heat conduction microballoon Download PDFInfo
- Publication number
- CN105521745B CN105521745B CN201410564178.9A CN201410564178A CN105521745B CN 105521745 B CN105521745 B CN 105521745B CN 201410564178 A CN201410564178 A CN 201410564178A CN 105521745 B CN105521745 B CN 105521745B
- Authority
- CN
- China
- Prior art keywords
- organic polymer
- heat conduction
- organic
- polymeric microspheres
- added
- 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.)
- Active
Links
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses a kind of preparation methods of organic polymer-based heat conduction microballoon, include the following steps：Organic polymeric microspheres are provided；Surface activation process is carried out to the organic polymeric microspheres；And the organic polymeric microspheres for completing surface active are added in silver-colored ammonia complexing solution, mixing is simultaneously heated to 40~55 DEG C, it is subsequently added into reducing agent, filters and retain solid after reacting 30min~1h, the solid is the organic polymer-based heat conduction microballoon of electroplate.The preparation method of this organic polymer-based heat conduction microballoon, in the outer layer deposition of silver of organic polymer-based heat conduction microballoon, on the one hand the advantages that remaining good mechanical performance, thermal stability and the low-density of organic polymeric microspheres, on the other hand significantly increases the heat-conductive characteristic of organic polymer-based heat conduction microballoon.
Description
Technical field
The present invention relates to field of compound material, more particularly to a kind of preparation method of organic polymer-based heat conduction microballoon.
Background technology
Organic and inorganic core-shell material has become a hot spot of materials science field, such as magnetic material, ceramic material, amount
Sub- material, optical material etc..Especially formed as shell using polymer particle as core and metal or metal oxide
Composite material has attracted more and more concerns, because they are in chemical catalysis, biomaterial, senser element and heat conduction etc.
With great potential application.
Heat filling with high thermal conductivity, one kind is metal oxide, carbide and nitride etc., such as Al2O3、
MgO、ZnO、SiO2、BeO、BN、AlN、Si3N4, SiC and bortz powder etc.；It is another kind of for metal powder, graphite etc., as Ag, Ni,
Graphite etc..The various aspects such as comprehensive preparation technology, cost, heat conductivility compare, and silver is a kind of ideal heat conduction modified material.
Argent grain has high thermal coefficient, also has many advantages, such as very high thermal conductivity after inoxidizability, and oxidation,
It is a kind of highly desirable heat filling, but when as heat filling, one side cost is excessively high so that large-scale application
Feasibility greatly reduces, and on the other hand, since Argent grain has larger density, when being used in filler, process is the study found that meeting
There is a large amount of Argent grain and be deposited to bottom, conductive particle is caused to be unevenly distributed, influences its performance.
Organic polymer material has good mechanical performance, and thermal stability etc., more important is its low-density, Ke Yiyou
Avoid to effect the generation of sedimentation.But usually, the thermal conductivity of organic polymer material is very poor, and institute is for heat filling
On, it needs to carry out heat conduction modification.Current heat conduction study on the modification is concentrated mainly on polymeric inner addition heat filling, also seldom
Have and outer layer is modified and is modified.
Invention content
Based on this, it is necessary to provide a kind of organic polymer-based heat conduction that the outer layer to organic polymer material is modified
The preparation method of microballoon.
A kind of preparation method of organic polymer-based heat conduction microballoon, includes the following steps：
Organic polymeric microspheres are provided；
Surface activation process is carried out to the organic polymeric microspheres；And
The organic polymeric microspheres for completing surface active are added in silver-colored ammonia complexing solution, mixing is simultaneously heated to 40 DEG C
Between~55 DEG C, it is subsequently added into reducing agent, filters and retain solid after reacting 30min~1h, the solid is electroplate
The organic polymer-based heat conduction microballoon.
In one embodiment, the organic polymeric microspheres are prepared via a method which to obtain：By the organic polymer
Object microballoon is added to emulsifier solution and is emulsified to the organic polymeric microspheres, is subsequently added into initiator and is warming up to 82 DEG C
~85 DEG C, 78 DEG C~80 DEG C are cooled to until fully reaction, retains filter residue, institute after reaction solution filtering after keeping the temperature 20min~30min
It is the organic polymeric microspheres to state filter residue, wherein the mass ratio of the organic polymer monomer and the emulsifier is
11.5：1~14.5：1, the mass ratio of the organic polymer monomer and the initiator is 11.5：1~14.5：0.8.
In one embodiment, that the organic polymeric microspheres are added to emulsifier solution is micro- to the organic polymer
The operation that ball is emulsified is：The organic polymer monomer is added in the emulsifier solution that temperature is 55 DEG C~60 DEG C,
It is 78 DEG C~80 DEG C that temperature of reaction system is adjusted after mechanical agitation mixing, continues mechanical agitation until emulsification is completed.
In one embodiment, that the organic polymeric microspheres are added to emulsifier solution is micro- to the organic polymer
The operation that ball is emulsified is：The organic polymer monomer is added in emulsifier solution, then high speed shear mixing is straight
It is completed to emulsification.
In one embodiment, the organic polymer monomer is methyl methacrylate；
The emulsifier is neopelex；
The initiator is ammonium persulfate.
In one embodiment, it is to the operation of organic polymeric microspheres progress surface activation process：Have described
Machine polymer microballoon is dissolved in water, and ultrasound 10min~15min after colloid palladium is added, reservation solid and will be described solid after filtering
Body washs drying；
The colloid palladium is obtained by following operation preparation：It is protected under the conditions of by palladium bichloride and stannous chloride existing for hydrochloric acid
Temperature, you can obtain.
In one embodiment, the mass ratio of the organic polymeric microspheres and the colloid palladium is 0.5：0.05~2：
0.05。
In one embodiment, the mass ratio of the organic polymeric microspheres and content silver-colored in the silver-colored ammonia complexing solution
It is 0.5：1.07~2：1.07.
In one embodiment, the reducing agent is glucose, formaldehyde or tartaric acid, the reducing agent and the silver-colored ammino
The mass ratio for closing silver-colored content in solution is 1.6：1.07~1.6：1.
The preparation method of this organic polymer-based heat conduction microballoon is deposited in the outer layer of organic polymer-based heat conduction microballoon
Silver, the advantages that on the one hand remaining good mechanical performance, thermal stability and the low-density of organic polymeric microspheres, on the other hand
Significantly increase the heat-conductive characteristic of organic polymer-based heat conduction microballoon.The preparation side of this organic polymer-based heat conduction microballoon
Method is modified by the outer layer to organic polymer material, and it is micro- to have obtained the preferably organic polymer-based heat conduction of heat-conductive characteristic
Ball.
Description of the drawings
Fig. 1 is the flow chart of the preparation method of the organic polymer-based heat conduction microballoon of an embodiment；
Fig. 2 is the SEM photograph of organic polymer-based heat conduction microballoon prepared by embodiment 1；
Fig. 3 is the SEM photograph of organic polymer-based heat conduction microballoon prepared by embodiment 1；
Fig. 4 is the XRD curve graphs of organic polymer-based heat conduction microballoon prepared by embodiment 1.
Specific implementation mode
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, below in conjunction with the accompanying drawings to the present invention
Specific implementation mode be described in detail.Many details are elaborated in the following description in order to fully understand this hair
It is bright.But the invention can be embodied in many other ways as described herein, those skilled in the art can be not
Similar improvement is done in the case of violating intension of the present invention, therefore the present invention is not limited to the specific embodiments disclosed below.
The preparation method of the organic polymer-based heat conduction microballoon of an embodiment as shown in Figure 1, includes the following steps：
S10, organic polymeric microspheres are provided.
Organic polymeric microspheres can be prepared via a method which to obtain：It is molten that organic polymeric microspheres are added to emulsifier
Liquid emulsifies organic polymeric microspheres, is subsequently added into initiator and is warming up to 82 DEG C~85 DEG C, heat preservation 20min~30min
After be cooled to 78 DEG C~80 DEG C until fully reaction, reaction solution filtering after retain filter residue, filter residue is organic polymeric microspheres.
Wherein, the mass ratio of organic polymer monomer and emulsifier is 11.5：1~14.5：1, organic polymer monomer and
The mass ratio of initiator is 11.5：1~14.5：0.8.
In present embodiment, organic polymeric microspheres is added to emulsifier solution, organic polymeric microspheres are emulsified
Operation can be：The organic polymer monomer is added in the emulsifier solution that temperature is 55 DEG C~60 DEG C, machinery stirs
Adjusting temperature of reaction system is 78 DEG C~80 DEG C after mixing mixing, continues mechanical agitation until emulsification completion.
Churned mechanically speed is 600rpm/min~1000rpm/min, to control the grain size point of organic polymeric microspheres
Cloth and shape characteristic.Mechanical agitation is completed using stainless steel stirring rod on chip, on the one hand can effectively be increased churned mechanically
Shearing force reduces the foam volume that emulsion process generates, promotes the progress of reaction；On the other hand, stirring can also be passed through so that oil
The distribution of phase drop is more uniform, and product obtained can also have better monodispersity.
In other implementations, by organic polymeric microspheres be added to emulsifier solution to organic polymeric microspheres into
Row emulsification operation can also be：Organic polymer monomer is added in emulsifier solution, then high speed shear mixing until
Emulsification is completed.
High speed shear may be used above-mentioned stainless steel stirring rod on chip and complete, mixing speed be 600rpm/min~
1000rpm/min。
Organic polymer monomer can be methyl methacrylate.
Emulsifier can be neopelex.
Initiator can be ammonium persulfate.
S20, surface activation process is carried out to the organic polymeric microspheres that S10 is obtained.
To organic polymeric microspheres carry out surface activation process operation be：Organic polymeric microspheres are dissolved in water,
Ultrasound 10min~15min after addition colloid palladium retains solid and solid is washed drying after filtering.
By palladium particle and Bivalent Tin redox reaction occurs for colloid palladium, and one layer is formed on organic polymeric microspheres surface
Metal Palladium can be such that metal deposits so that organic polymeric microspheres have good catalytic activity, form coating.
Colloid palladium can be obtained by following operation preparation：Using palladium bichloride and a certain amount of stannous chloride in hydrochloric acid condition
Lower heat preservation a period of time, you can obtain.
The mass ratio of organic polymeric microspheres and colloid palladium is 0.5：0.05~2：0.05.
S30, the organic polymeric microspheres for obtaining S20 are added in silver-colored ammonia complexing solution, and mixing is simultaneously heated to 40 DEG C~55
DEG C, it is subsequently added into reducing agent, filters and retain solid after reacting 30min~1h, solid is the organic polymer-based of electroplate
Heat conduction microballoon.
Silver nitrate may be used for silver-colored ammonia complexing solution and ammonium hydroxide configures.
Organic polymeric microspheres and the mass ratio of content silver-colored in silver-colored ammonia complexing solution are 0.5：1.07~2：1.07.
Reducing agent can be glucose, formaldehyde, tartaric acid, the mass ratio of reducing agent and content silver-colored in silver-colored ammonia complexing solution
It is 1.6：1.07~1.6：1.
The organic polymer-based heat conduction microsphere surface silver-plated specific reaction time can according to the needs of electroplate into
Row, the time is more long, and surface distribution is more.
The preparation method of this organic polymer-based heat conduction microballoon is deposited in the outer layer of organic polymer-based heat conduction microballoon
Silver, the advantages that on the one hand remaining good mechanical performance, thermal stability and the low-density of organic polymeric microspheres, on the other hand
Significantly increase the heat-conductive characteristic of organic polymer-based heat conduction microballoon.The preparation side of this organic polymer-based heat conduction microballoon
Method is modified by the outer layer to organic polymer material, and it is micro- to have obtained the preferably organic polymer-based heat conduction of heat-conductive characteristic
Ball.
It is specific embodiment below, the methyl methacrylate used in embodiment (analysis is pure) is purchased from Tianjin great Mao, mistake
Ammonium sulfate (analysis is pure) is provided purchased from Shanghai Ling Feng chemical reagent Co., Ltd, and silver nitrate (analysis is pure) is purchased from Shanghai Ling Feng chemistry
Reagent Co., Ltd provides, and ammonium hydroxide (analysis is pure) provides, dodecyl benzene sulfonic acid purchased from Shanghai Ling Feng chemical reagent Co., Ltd
Sodium (analysis is pure) causes remote chemical reagent factory purchased from Tianjin.
Embodiment 1
1g neopelexes are dissolved in 42.5ml deionized waters, mechanical agitation rotating speed 600rpm, water-bath is adjusted
Temperature is 60 DEG C, 11.25g methyl methacrylates is added after 10min, it is 80 that temperature of reaction system is adjusted after mechanical agitation mixing
DEG C, ammonium persulfate aqueous solution (containing 1g ammonium persulfates) initiated polymerization is added after 30min, is warming up to 85 DEG C, keeps the temperature 30min
After be cooled to 80 DEG C, after 2h by reaction solution filter retain filter residue, filter residue be cleaned and dried after be white powdery solids, white powder
Shape solid is poly (methyl methacrylate) micro-sphere.Mechanical agitation is completed using stainless steel stirring rod on chip, churned mechanically speed
Degree is 600rpm/min.
Poly (methyl methacrylate) micro-sphere obtained is soluble in water, few drops of colloid palladiums are added and carry out surface activation process,
Filter residue is filtered and retained after ultrasonic 15min, and filter residue is for use after being cleaned and dried.
It weighs 1.02g silver nitrates and is configured to solution, ammonium hydroxide is added and generates black precipitate to disappearing, is subsequently added into KNO3To going out
Existing black precipitate, adds ammonium hydroxide, until precipitation adds one to two drop ammonium hydroxide after just disappearing, obtains silver-colored ammonia complexing solution.
The poly (methyl methacrylate) micro-sphere for completing surface activation process is added in silver-colored ammonia complexing solution, magnetic is then carried out
Power stirs, and rotating speed setting is 50 DEG C in 400rpm, heating water bath, temperature.After 10min, tartaric acid is slowly added dropwise, it after the completion, will
Solution is adjusted to 200mL, reacts 30min.Retain solid after suction filtration and wash drying, it is surface plating to obtain dark brown powder
The polymethyl methacrylate base heat conduction microballoon of silver.
Polymethyl methacrylate base heat conduction microballoon made from embodiment 1 is observed using scanning electron microscope,
Obtain Fig. 2 and Fig. 3.
The average grain diameter 4 of polymethyl methacrylate base heat conduction microballoon made from embodiment 1 it can be seen from Fig. 2 and Fig. 3
μm or so.
X-ray diffraction analysis is carried out to polymethyl methacrylate base heat conduction microballoon made from embodiment 1, obtains Fig. 4.
As seen from Figure 4, there are Ag in polymethyl methacrylate base heat conduction microballoon made from embodiment 1.
Thermal conductivity is measured using Hot-disk methods, by the way that poly (methyl methacrylate) micro-sphere and embodiment 1 to be made
Polymethyl methacrylate base heat conduction microballoon be doped in epoxy resin solidification and carry out heat conduction measurement, with the ring not being doped
Oxygen resin is comparison, and measurement result is as shown in the table.
As can be seen from the above table, the doping of poly (methyl methacrylate) micro-sphere almost pair does not have with the thermal conductivity of epoxy resin
Any promotion, and it is doped with the epoxy resin of polymethyl methacrylate base heat conduction microballoon made from the embodiment 1 of 20wt%, it leads
Heating rate is promoted to original 1.7 times or more.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
Cannot the limitation to the scope of the claims of the present invention therefore be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (3)
1. a kind of preparation method of organic polymer-based heat conduction microballoon, which is characterized in that include the following steps：
Organic polymeric microspheres are provided；
Surface activation process is carried out to the organic polymeric microspheres；And
The organic polymeric microspheres for completing surface active are added in silver-colored ammonia complexing solution, mixing is simultaneously heated to 40 DEG C~55
Between DEG C, it is subsequently added into reducing agent, filters and retain solid after reacting 30min~1h, the solid is the described of electroplate
Organic polymer-based heat conduction microballoon；
To the organic polymeric microspheres carry out surface activation process operation be：The organic polymeric microspheres are dissolved in water
In, ultrasound 10min~15min after colloid palladium is added, solid is retained after filtering and the solid is washed into drying；
The colloid palladium is obtained by following operation preparation：It is kept the temperature under the conditions of by palladium bichloride and stannous chloride existing for hydrochloric acid,
It can be obtained；
The organic polymeric microspheres and the mass ratio of content silver-colored in the silver-colored ammonia complexing solution are 0.5：1.07~2：1.07；
The organic polymeric microspheres are prepared via a method which to obtain：Organic polymer monomer is added to emulsifier solution pair
The organic polymer monomer is emulsified, and is subsequently added into initiator and is warming up to 82 DEG C~85 DEG C, heat preservation 20min~30min
After be cooled to 78 DEG C~80 DEG C until fully reaction, reaction solution filtering after retain filter residue, the filter residue is the organic polymer
Object microballoon, wherein the mass ratio of the organic polymer monomer and the emulsifier is 11.5：1~14.5：1, it is described organic poly-
The mass ratio of monomer adduct and the initiator is 11.5：1~14.5：0.8；The organic polymer monomer is added to emulsification
The operation that agent solution emulsifies the organic polymer monomer is：It is 55 that the organic polymer monomer, which is added to temperature,
DEG C~60 DEG C of emulsifier solution in, it is 78 DEG C~80 DEG C that temperature of reaction system is adjusted after mechanical agitation mixing, continues machinery and stirs
It mixes until emulsification is completed；
The mass ratio of the organic polymeric microspheres and the colloid palladium is 0.5：0.05~2：0.05；
The reducing agent is glucose, formaldehyde or tartaric acid, the reducing agent and content silver-colored in the silver-colored ammonia complexing solution
Mass ratio is 1.6：1.07~1.6：1.
2. the preparation method of organic polymer-based heat conduction microballoon according to claim 1, which is characterized in that will be described organic
Polymer monomer is added to the operation that emulsifier solution emulsifies the organic polymer monomer：By the organic polymer
Object monomer is added in emulsifier solution, and then high speed shear mixing is until emulsification is completed.
3. according to the preparation method of organic polymer-based heat conduction microballoon according to any one of claims 1 to 2, feature exists
In the organic polymer monomer is methyl methacrylate；
The emulsifier is neopelex；
The initiator is ammonium persulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410564178.9A CN105521745B (en) | 2014-10-21 | 2014-10-21 | The preparation method of organic polymer-based heat conduction microballoon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410564178.9A CN105521745B (en) | 2014-10-21 | 2014-10-21 | The preparation method of organic polymer-based heat conduction microballoon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105521745A CN105521745A (en) | 2016-04-27 |
| CN105521745B true CN105521745B (en) | 2018-10-16 |
Family
ID=55764470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410564178.9A Active CN105521745B (en) | 2014-10-21 | 2014-10-21 | The preparation method of organic polymer-based heat conduction microballoon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105521745B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109401442A (en) * | 2018-11-09 | 2019-03-01 | 广东彩乐智能包装科技有限公司 | A kind of silver-plated electrically conductive ink of UV curing nano and preparation method thereof |
| CN111534016B (en) * | 2020-06-01 | 2023-03-21 | 中国科学院合肥物质科学研究院 | Electronic packaging material with heat conduction and electromagnetic shielding performance and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245148A (en) * | 2007-02-13 | 2008-08-20 | 镇江爱邦电子科技有限公司 | Monodisperse high-performance conductive silver particle |
| KR20080084438A (en) * | 2007-03-16 | 2008-09-19 | 한국생산기술연구원 | A method for coating silvering on aerogel and silver-coated aerogel |
| CN102212801A (en) * | 2011-05-25 | 2011-10-12 | 中北大学 | Chemical silvering method for PS (polystyrene) microspheres |
| CN103627107A (en) * | 2013-12-03 | 2014-03-12 | 齐鲁工业大学 | Preparation method for polystyrene/silver/polypyrrole composite material |
| CN103752821A (en) * | 2014-01-24 | 2014-04-30 | 云南大学 | Method for preparing conductive composite microsphere material with surface covered by metal micro powder |
-
2014
- 2014-10-21 CN CN201410564178.9A patent/CN105521745B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245148A (en) * | 2007-02-13 | 2008-08-20 | 镇江爱邦电子科技有限公司 | Monodisperse high-performance conductive silver particle |
| KR20080084438A (en) * | 2007-03-16 | 2008-09-19 | 한국생산기술연구원 | A method for coating silvering on aerogel and silver-coated aerogel |
| CN102212801A (en) * | 2011-05-25 | 2011-10-12 | 中北大学 | Chemical silvering method for PS (polystyrene) microspheres |
| CN103627107A (en) * | 2013-12-03 | 2014-03-12 | 齐鲁工业大学 | Preparation method for polystyrene/silver/polypyrrole composite material |
| CN103752821A (en) * | 2014-01-24 | 2014-04-30 | 云南大学 | Method for preparing conductive composite microsphere material with surface covered by metal micro powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105521745A (en) | 2016-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106009428B (en) | A kind of silica-filled PTFE composite and preparation method thereof | |
| CN104259473B (en) | Hollow spherical precious metal nanometer material preparation method | |
| EP2883922B1 (en) | Metal nanoparticle synthesis and conductive ink formulation | |
| Wang et al. | A facile approach to synthesize microencapsulated phase change materials embedded with silver nanoparicle for both thermal energy storage and antimicrobial purpose | |
| CN108247077B (en) | Method for preparing copper powder by micro-reaction | |
| CN106238727B (en) | A kind of preparation method of Cu bags W composite granules | |
| CN103736996B (en) | A kind of method being covered with the composite microsphere material of conductive submicron line/rod preparing porous | |
| CN105521745B (en) | The preparation method of organic polymer-based heat conduction microballoon | |
| JP5451710B2 (en) | Microscale flaky silver particles and method for producing the same | |
| CN109295532A (en) | A kind of antibacterial composite functional fibre and preparation method thereof | |
| TW201139012A (en) | Fine silver-plated copper powder and method for producing same | |
| CN104625087A (en) | Method for hydrothermally manufacturing silver nanowires | |
| CN103737018A (en) | Method for continuous and rapid preparation of nano nickel by microfluidics technology | |
| CN105153453A (en) | Nano-copper/polymer hollow composite microsphere and preparation method thereof | |
| CN104355307A (en) | Preparation method of RGO/Cu nano composite powder | |
| CN104744712A (en) | Method for quickly preparing binary colloid crystals | |
| CN104830248A (en) | Heat-conducting glue with high thermal conductivity and preparation method thereof | |
| CN106282628A (en) | A kind of preparation method of carbon nanotube reinforced copper-base composite material | |
| CN106133029B (en) | Manufacturing method, emulsion polymerization latex condensate and the coagulated particles from emulsion polymerization latex of coagulated particles from emulsion polymerization latex | |
| CN105440303A (en) | Processing method of polydimethylsiloxane membrane with porous surface microstructure and friction generator comprising polydimethylsiloxane membrane | |
| CN106064239A (en) | A kind of hollow anti-type Cu/SiO 2 core shell nanoparticles and preparation method thereof of ringing a bell of high degree of dispersion | |
| CN102962470B (en) | Method for preparing spherical ultrafine nickel powder at room temperature | |
| CN105597780B (en) | Self assembly Pd-Cu bimetallic racemosus shape nanocrystalline catalyst and its preparation and use | |
| CN108461172A (en) | Conductive particle and preparation method and application thereof | |
| CN104177642B (en) | Expanded bed adsorption matrix and preparation method thereof |
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 |