CN102601381A - Copper nano powder and preparation method of copper nano powder - Google Patents
Copper nano powder and preparation method of copper nano powder Download PDFInfo
- Publication number
- CN102601381A CN102601381A CN2012100629688A CN201210062968A CN102601381A CN 102601381 A CN102601381 A CN 102601381A CN 2012100629688 A CN2012100629688 A CN 2012100629688A CN 201210062968 A CN201210062968 A CN 201210062968A CN 102601381 A CN102601381 A CN 102601381A
- Authority
- CN
- China
- Prior art keywords
- copper
- nano powder
- processing step
- copper nano
- solution
- 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.)
- Granted
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000012545 processing Methods 0.000 claims abstract description 90
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 89
- 239000000243 solution Substances 0.000 claims abstract description 70
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 239000010949 copper Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910052802 copper Inorganic materials 0.000 claims abstract description 28
- 239000003112 inhibitor Substances 0.000 claims abstract description 28
- 150000001879 copper Chemical class 0.000 claims abstract description 26
- 239000012266 salt solution Substances 0.000 claims abstract description 26
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 230000032683 aging Effects 0.000 claims abstract description 12
- 238000001291 vacuum drying Methods 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005202 decontamination Methods 0.000 claims description 7
- 230000003588 decontaminative effect Effects 0.000 claims description 7
- 238000009736 wetting Methods 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000001488 sodium phosphate Substances 0.000 claims description 5
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 5
- 235000010265 sodium sulphite Nutrition 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 26
- 238000009826 distribution Methods 0.000 abstract description 12
- 230000009467 reduction Effects 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000000843 powder Substances 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 239000000725 suspension Substances 0.000 abstract 3
- 239000000203 mixture Substances 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 8
- 229910001431 copper ion Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000003860 storage Methods 0.000 description 5
- 239000004020 conductor Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 polyoxyethylene Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses copper nano powder and a preparation method of the copper nano powder. The powder is prepared by the following methods: preparing copper salt solution from copper salt, adding a drag reduction agent and an inhibitor into the copper salt solution to prepare copper salt mixing solution and pre-heating the copper salt mixing solution; preparing reducing agent solution, adjusting the pH value of the reducing agent solution, and pre-heating the reducing agent solution; uniformly mixing and agitating the copper salt mixing solution and the reducing agent solution, heating the mixture to the reaction temperature to enable the mixture to react for a certain time so as to obtain nano copper suspension solution; aging the nano copper suspension solution; performing vacuum filtration on the suspension solution obtained from the above steps to obtain the copper nano powder in which the impurity is not removed; processing the copper nano powder to obtain the copper nano powder cladded by organic solvent; performing vacuum filtration on the copper nano powder to obtain wet copper nano powder, and performing low-temperature vacuum drying on the copper nano powder obtained from the above steps so as to obtain the copper nano powder product. The powder is small in particle size and narrow in particle size distribution. The method is controllable in reaction process, simple in technology and suitable for industrial production.
Description
Technical field
The present invention relates to a kind of copper nano powder, simultaneously, the invention still further relates to a kind of preparation method of said copper nano powder.
Background technology
The basic principle that liquid phase method prepares copper nano powder is that copper ion is accepted the process that electron reduction is an elemental copper, and promptly in higher temperature and strong acid (or highly basic) environment, reducing agent at first produces the required electronics of reduction process, and the copper ion electron gain generates elemental copper.Based on redox basic principle, electricity, high-energy ray and chemical reducing agent all are the common reducing agents of preparation copper nano powder, and wherein the use of chemical reducing agent is the most general.
In order to obtain the copper particle of the little and narrow particle size distribution of size, the explosive nucleation rate that must possess uniform degree of supersaturation in the reaction system and form than high degree of supersaturation.
By half-reaction equation Cu
2+Can+2e → Cu can know, be only the basic of preparation copper nano powder for copper ion provides required reduction components 2e with uniform reaction environment.
At present, the problem that liquid phase method exists exactly can not address this problem well, causes the mass production of copper nano powder to be difficult for realizing.This mainly shows:
1) adopt mechanical agitator to add the mode of reactant while stirring gradually, concentration in the reaction system and temperature are constantly to change, and degree of supersaturation control is difficult to, and reinforced time and reaction time are very long.And for the bigger container of volume; Conventional mechanical agitation can't the even distribution of realization response component in container in the short time; The local concentration and the local temperature of reactive component are too high, cause local degree of supersaturation too high easily, form local explosive nucleation too early; Cause the granularity of final products big, size distribution is wide, produce copper nano powder in batches and be difficult to control;
2) in order to prevent the too high phenomenon of the inhomogeneous and local degree of supersaturation of degree of supersaturation appears in the course of reaction; Need to add complexant and in reaction system, set up the coordination balance; For realizing that the whole uniformity of degree of supersaturation provides time enough, reaches the purpose of control degree of supersaturation homogenising.Though the initial reaction stage reductant concentration is in hypersaturated state with respect to copper ion concentration, can form the nanosized copper particle.But, along with the carrying out of reaction, can form competition between chemical reaction and the coordination balance, and newborn copper can grow on the surface of the copper nano powder that has generated preferentially, the product that obtains is the powder of big particle diameter, size distribution also can broaden accordingly; In addition, owing to have the coordination balance in the system, the conversion ratio of copper ion is on the low side, and Cu
2+And the easy cuprous oxide that generates that reacts between the Cu, cause purity reduction, the quality of copper nano powder to descend;
3) in order to prepare copper nano powder, the low concentration copper solution also is common preparation condition, and is the most representative with hydro-thermal method and sol method.Use the low concentration copper solution prepare copper nano powder the most directly consequence be yield poorly, the reaction time is long, production cost and energy consumption are high;
4) in order to eliminate the surface-active of nascent state copper nano powder, surfactant and nonaqueous solvents can be adsorbed on powder surface, suppress grain growth and reduce surperficial ability.But too much not only cost is high in the use of auxiliary agent, and the effumability of organic additive, toxicity and environment refractory organics all are the unfavorable factors in producing;
5) in the production process of copper nano powder, newborn copper nano powder, its surface-active is very high, and copper particle surface oxidation easily in oxygen-enriched environment need be by inert gas shieldings such as nitrogen, so that the cost of mass production is higher relatively.
Summary of the invention
Technical problem to be solved by this invention provides that a kind of granularity is little, the copper nano powder of narrow particle size distribution; Simultaneously, another technical problem to be solved by this invention provides a kind of preparation method of said copper nano powder, and the course of reaction of this method is controlled, technology simple, be suitable for suitability for industrialized production.
For solving the problems of the technologies described above, the invention provides a kind of copper nano powder, this copper nano powder is prepared by following method:
(1) earlier mantoquita is made into copper salt solution, in copper salt solution, adds drag reducer and inhibitor again, make the mantoquita mixed liquor that contains drag reducer and inhibitor, the mantoquita mixed liquor is preheated to uniform temperature, subsequent use;
(2) make reductant solution, and the pH value of adjustment reductant solution, be preheated to uniform temperature again, subsequent use;
(3) the mantoquita mixed liquor and the reductant solution that obtain in (1), (2) processing step are stirred while mixing, then, heat temperature raising is to reaction temperature, and keeps the reaction certain hour, nanometer copper aaerosol solution;
(4) keep the reaction temperature of the nanometer copper aaerosol solution that obtains in (3) processing step, carry out ageing and handle;
(5) aaerosol solution that obtains in (4) processing step is carried out vacuum filtration, the copper nano powder of the decontamination that obtains not eliminating;
(6) copper nano powder that obtains in (5) processing step is washed earlier, replace expelling water through organic solvent again, obtain the copper nano powder of organic solvent parcel;
(7) copper nano powder that obtains in (6) processing step is carried out vacuum filtration, the copper nano powder that obtains wetting;
(8) copper nano powder that obtains in (7) processing step is carried out low-temperature vacuum drying after, obtain the copper nano powder finished product.
For solving the problems of the technologies described above, the present invention also provides a kind of preparation method of copper nano powder, and this method comprises following processing step:
(1) earlier mantoquita is made into copper salt solution, in copper salt solution, adds drag reducer and inhibitor again, make the mantoquita mixed liquor that contains drag reducer and inhibitor, the mantoquita mixed liquor is preheated to uniform temperature, subsequent use;
(2) make reductant solution, and the pH value of adjustment reductant solution, be preheated to uniform temperature again, subsequent use;
(3) the mantoquita mixed liquor and the reductant solution that obtain in (1), (2) processing step are stirred while mixing, then, heat temperature raising is to reaction temperature, and keeps the reaction certain hour, nanometer copper aaerosol solution;
(4) keep the reaction temperature of the nanometer copper aaerosol solution that obtains in (3) processing step, carry out ageing and handle;
(5) aaerosol solution that obtains in (4) processing step is carried out vacuum filtration, the copper nano powder of the decontamination that obtains not eliminating;
(6) copper nano powder that obtains in (5) processing step is washed earlier, replace expelling water through organic solvent again, obtain the copper nano powder of organic solvent parcel;
(7) copper nano powder that obtains in (6) processing step is carried out vacuum filtration, the copper nano powder that obtains wetting;
(8) copper nano powder that obtains in (7) processing step is carried out low-temperature vacuum drying after, obtain the copper nano powder finished product.
This method is a basic principle with the heated condition of little temperature differential method simulated microwave field, the drag reduction effect of inhibition dissipativeness vortex, for chemical reaction provides uniform reaction environment, makes a concrete analysis of as follows:
(1) drag reducer and inhibitor add in the copper salt solution in advance in the processing step; Can be re-dubbed pluronic polymer; Can be adsorbed on the copper nano powder surface during reaction; The macromolecule layer that forms can stop the reunion between grain growth and the particle, and in the low-temperature vacuum drying of (8) processing step and later preservation process, also can play certain antioxidation.
(1) in the processing step in mantoquita mixed liquor, (2) processing step the preheat temperature of reductant solution all be lower than the reaction temperature in (3) processing step; Thereby before in (3) processing step, implementing heat temperature raising and reaching reaction temperature; (in other words reducing agent can't provide required reduction components for copper ion; Reducing agent is temporarily inoperative); For high-quality even mixing between the reactant provides buffer time, form concentration and the uniform reaction mixture of temperature, guarantee that course of reaction is in uniform one-tenth nuclear environment.
(3) in the processing step when stirring (intensity of stirring is comparatively strong), can produce dissipativeness turbulent flow whirlpool in the reaction mixture.In order to guarantee uniform liquid-phase mixing effect between mantoquita mixed liquor and the reductant solution; The drag reducer of being introduced in the mantoquita mixed liquor; The flow resistance of liquid phase in the time of can reducing turbulent flow; Suppress to stir the dissipativeness turbulent vortices that is produced, make solution that flowing velocity faster arranged, help keeping the uniform state of interior concentration of reaction system and temperature; In addition; (3) in the processing step mantoquita mixed liquor and reductant solution are stirred, make that the heat that heats up is in time propagated, easily the heat balance in the realization response system; Formation is similar to the even heated condition of microwave field; Guaranteed that course of reaction is in the uniform heating state, this makes course of reaction be easy to control just for nucleation reaction uniformity and burst provide very advantageous conditions.
(6) in the processing step copper nano powder is adopted organic solvent displacement expelling water, in (8) processing step copper nano powder is adopted low-temperature vacuum drying, all can reduce copper nano powder and contact, reach the purpose that suppresses grain oxidation, prevents particle agglomeration with oxygen.
In sum, the course of reaction of this method is controlled, technology simple, be suitable for suitability for industrialized production; The copper nano powder that adopts this method to make, granularity little (particle mean size is 100 nanometers), narrow particle size distribution.
In addition, the reducing agent wide material sources that this method reaction time is short, production cost is low, used have good application prospects.
In preparation method of the present invention:
(1) mantoquita described in the processing step is any in copper sulphate, copper nitrate, copper chloride, the Schweinfurt green, and said copper salt solution concentration is 0.1～1molL
-1
Drag reducer is PEO or polyacrylamide, and for every liter of copper salt solution, the addition of drag reducer is 50～60mg;
Inhibitor is any in octyl phenol polyoxyethylene (10) ether, polyvinylpyrrolidone, dodecyl sodium sulfate, the softex kw; The weight percent concentration of octyl phenol polyoxyethylene (10) ether is 90～99%, and the addition of inhibitor is 0.1～4% of a mantoquita quality;
The preheat temperature of mantoquita mixed liquor is 60～65 ℃.
(2) reducing agent described in the processing step is any in inferior sodium phosphate, sodium sulfite, sodium borohydride, hydrazine hydrate, the formaldehyde, and the concentration of reductant solution is 0.2～2molL
-1
When reducing agent was in inferior sodium phosphate, the sodium sulfite any, to adopt weight percent concentration be 90～98% sulfuric acid was adjusted to 1～2 with the pH value of reductant solution;
When reducing agent is in sodium borohydride, hydrazine hydrate, the formaldehyde any, adopt solid sodium hydroxide that the pH value of reductant solution is adjusted to 11～12;
The preheat temperature of reductant solution is 60～65 ℃.
(3) the mantoquita mixed liquor described in the processing step is 1: 1 with the volume ratio that reductant solution mixes mutually; Speed of agitator is 200～600 rev/mins, and mixing time is 0.5～1min; The time of heat temperature raising is 2～5min, and reaction temperature is 70～80 ℃, and the reaction time is 15～20min.
(4) the ageing treatment temperature described in the processing step is 70～80 ℃, and the time that ageing is handled is 15～20min.
(5) vacuum of the vacuum filtration described in the processing step is 0.05～0.1Mpa.
(6) process conditions of the washing described in the processing step are: adopt the deionized water of normal temperature that the copper nano powder that obtains in (5) processing step is washed 3～5 times; Described organic solvent employing weight percent concentration is 95% ethanol.
(7) vacuum of the vacuum filtration described in the processing step is 0.05～0.1Mpa.
(8) process conditions of the low-temperature vacuum drying described in the processing step are: temperature is 20～40 ℃, and vacuum is 0.05～0.1Mpa, and be 2～4h drying time.
Because of the concentration of said copper salt solution is 0.1～1molL
-1, the concentration of reductant solution is 0.2～2molL
-1So reducing agent is excessive state with respect to copper ion, excessive reducing agent both can provide reaction required reduction components fast, improved reaction rate; Guarantee that one step of copper ion is reduced to elemental copper; Avoid occurring cuprous product, can guarantee that again copper nano powder is in the reproducibility environment, has avoided the powder surface oxidation.
(1) in the processing step in mantoquita mixed liquor, (2) processing step the temperature interval between the reaction temperature (being 70～80 ℃) in the preheat temperature of reductant solution (being 60～65 ℃) and (3) processing step little, make that to implement heat temperature raising in (3) processing step more or less freely.
The storage life of the prepared copper nano powder of this method can reach more than 1 year.
Analyze and research in the face of the correlation properties of the prepared copper nano powder of this method down.
Referring to Fig. 1, scale is 1 μ m, and as can beappreciated from fig. 1: the particle size of copper nano powder is about 100nm, narrow particle size distribution.
Referring to Fig. 2; Abscissa among Fig. 2 is that the angle of diffraction, ordinate are diffracted intensity; As can beappreciated from fig. 2: 43.25 °, 50.39 °, 74.03 ° characteristic diffraction peaks of locating to metallic copper of the angle of diffraction; (111), (200), (220) crystal face of corresponding copper prove that the prepared nanometer powder of this method is an elemental copper respectively.
Description of drawings
Fig. 1 is the sem photograph of the prepared copper nano powder of this method.
Fig. 2 is the X-ray diffractogram of the prepared copper nano powder of this method.
The sem photograph of the copper nano powder that Fig. 3 makes for embodiment 1 said method.
The sem photograph of the copper nano powder that Fig. 4 makes for embodiment 2 said methods.
The sem photograph of the copper nano powder that Fig. 5 makes for embodiment 3 said methods.
The sem photograph of the copper nano powder that Fig. 6 makes for embodiment 4 said methods.
The specific embodiment
Below can further be well understood to the present invention through embodiment given below.But they are not to qualification of the present invention.
Embodiment 1:
The preparation method of copper nano powder, it comprises following processing step:
(1) earlier copper sulphate being made into concentration is 0.1molL
-1Copper salt solution, in copper salt solution, add drag reducer and inhibitor again, make the mantoquita mixed liquor that contains drag reducer and inhibitor; The mantoquita mixed liquor is preheated to 60 ℃, and subsequent use, drag reducer is a PEO; For every liter of copper salt solution; The addition of drag reducer is 50mg, and inhibitor is a polyvinylpyrrolidone, and the addition of inhibitor is 0.1% of a copper sulphate quality;
(2) making concentration is 0.2molL
-1Reductant solution, reducing agent is an inferior sodium phosphate, to adopt weight percent concentration be 90% sulfuric acid is adjusted to 2 with the pH value of reductant solution, is preheated to 60 ℃ again, subsequent use;
(3) be that 1: 1 ratio arm mixing limit stirs by volume with the mantoquita mixed liquor that obtains in (1), (2) processing step and reductant solution; Speed of agitator is 200 rev/mins, and mixing time is 1min, then; Heat temperature raising to 70 ℃ in the time of 2min; Reach reaction temperature, and keep reaction 20min, get nanometer copper aaerosol solution;
(4) reaction temperature of keeping the nanometer copper aaerosol solution that obtains in (3) processing step is carried out ageing and is handled 20min at 70 ℃;
(5) be to carry out vacuum filtration under the condition of 0.05Mpa in vacuum to the aaerosol solution that obtains in (4) processing step, the copper nano powder of the decontamination that obtains not eliminating;
(6) deionized water that adopts normal temperature is to the copper nano powder washing earlier that obtains in (5) processing step 3 times, is that 95% ethanol is replaced expelling water through weight percent concentration again, obtains the copper nano powder of ethanol parcel;
(7) be to carry out vacuum filtration, the copper nano powder that obtains wetting under the condition of 0.05Mpa in vacuum to the copper nano powder that obtains in (6) processing step;
(8) to the copper nano powder that obtains in (7) processing step temperature be 20 ℃, vacuum be 0.05Mpa, drying time are to carry out low-temperature vacuum drying under the condition of 4h after, obtain the copper nano powder finished product.
The sem photograph of the copper nano powder that Fig. 3 makes for embodiment 1 said method, scale are 5 μ m, the uniform particle diameter of copper nano powder; About particle size 100nm; Narrow particle size distribution, the storage life can reach more than 1 year, was convenient to use as the raw material of producing nano-fluid, nanometer conductive material etc.
Embodiment 2:
The preparation method of copper nano powder, it comprises following processing step:
(1) earlier copper chloride being made into concentration is 0.2molL
-1Copper salt solution, in copper salt solution, add drag reducer and inhibitor again, make the mantoquita mixed liquor that contains drag reducer and inhibitor; The mantoquita mixed liquor is preheated to 63 ℃, and subsequent use, drag reducer is a PEO; For every liter of copper salt solution, the addition of drag reducer is 55mg, and inhibitor is octyl phenol polyoxyethylene (a 10) ether; Its weight percent concentration is 95%, and the addition of inhibitor is 2% of a copper chloride quality;
(2) making concentration is 0.5molL
-1Reductant solution, reducing agent is a sodium borohydride, adopts solid sodium hydroxide that the pH value of reductant solution is adjusted to 11, is preheated to 62 ℃ again, and is subsequent use;
(3) be that 1: 1 ratio arm mixing limit stirs by volume with the mantoquita mixed liquor that obtains in (1), (2) processing step and reductant solution; Speed of agitator is 400 rev/mins, and mixing time is 0.8min, then; Heat temperature raising to 75 ℃ in the time of 3min; Reach reaction temperature, and keep reaction 18min, get nanometer copper aaerosol solution;
(4) reaction temperature of keeping the nanometer copper aaerosol solution that obtains in (3) processing step is carried out ageing and is handled 17min at 75 ℃;
(5) be to carry out vacuum filtration under the condition of 0.07Mpa in vacuum to the aaerosol solution that obtains in (4) processing step, the copper nano powder of the decontamination that obtains not eliminating;
(6) deionized water that adopts normal temperature is to the copper nano powder washing earlier that obtains in (5) processing step 4 times, is that 95% ethanol is replaced expelling water through weight percent concentration again, obtains the copper nano powder of ethanol parcel;
(7) be to carry out vacuum filtration, the copper nano powder that obtains wetting under the condition of 0.07Mpa in vacuum to the copper nano powder that obtains in (6) processing step;
(8) to the copper nano powder that obtains in (7) processing step temperature be 30 ℃, vacuum be 0.07Mpa, drying time are to carry out low-temperature vacuum drying under the condition of 3h after, obtain the copper nano powder finished product.
The sem photograph of the copper nano powder that Fig. 4 makes for embodiment 2 said methods, scale are 5 μ m, the uniform particle diameter of copper nano powder; About particle size 100nm; Narrow particle size distribution, the storage life can reach more than 1 year, was convenient to use as the raw material of producing nano-fluid, nanometer conductive material etc.
Embodiment 3:
The preparation method of copper nano powder, it comprises following processing step:
(1) earlier copper nitrate being made into concentration is 1molL
-1Copper salt solution, in copper salt solution, add drag reducer and inhibitor again, make the mantoquita mixed liquor that contains drag reducer and inhibitor; The mantoquita mixed liquor is preheated to 65 ℃, and subsequent use, drag reducer is a polyacrylamide; For every liter of copper salt solution; The addition of drag reducer is 60mg, and inhibitor is a softex kw, and the addition of inhibitor is 4% of a copper nitrate quality;
(2) making concentration is 2molL
-1Reductant solution, reducing agent is a sodium sulfite, to adopt weight percent concentration be 98% sulfuric acid is adjusted to 1 with the pH value of reductant solution, is preheated to 65 ℃ again, subsequent use;
(3) be that 1: 1 ratio arm mixing limit stirs by volume with the mantoquita mixed liquor that obtains in (1), (2) processing step and reductant solution; Speed of agitator is 600 rev/mins, and mixing time is 0.5min, then; Heat temperature raising to 80 ℃ in the time of 5min; Reach reaction temperature, and keep reaction 15min, get nanometer copper aaerosol solution;
(4) reaction temperature of keeping the nanometer copper aaerosol solution that obtains in (3) processing step is carried out ageing and is handled 15min at 80 ℃;
(5) be to carry out vacuum filtration under the condition of 0.1Mpa in vacuum to the aaerosol solution that obtains in (4) processing step, the copper nano powder of the decontamination that obtains not eliminating;
(6) deionized water that adopts normal temperature is to the copper nano powder washing earlier that obtains in (5) processing step 5 times, is that 95% ethanol is replaced expelling water through weight percent concentration again, obtains the copper nano powder of ethanol parcel;
(7) be to carry out vacuum filtration, the copper nano powder that obtains wetting under the condition of 0.1Mpa in vacuum to the copper nano powder that obtains in (6) processing step;
(8) to the copper nano powder that obtains in (7) processing step temperature be 40 ℃, vacuum be 0.1Mpa, drying time are to carry out low-temperature vacuum drying under the condition of 2h after, obtain the copper nano powder finished product.
The sem photograph of the copper nano powder that Fig. 5 makes for embodiment 3 said methods, scale are 2 μ m, the uniform particle diameter of copper nano powder; About particle size 100nm; Narrow particle size distribution, the storage life can reach more than 1 year, was convenient to use as the raw material of producing nano-fluid, nanometer conductive material etc.
Embodiment 4:
The preparation method of copper nano powder, it comprises following processing step:
(1) earlier Schweinfurt green being made into concentration is 0.5molL
-1Copper salt solution, in copper salt solution, add drag reducer and inhibitor again, make the mantoquita mixed liquor that contains drag reducer and inhibitor; The mantoquita mixed liquor is preheated to 64 ℃, and subsequent use, drag reducer is a polyacrylamide; For every liter of copper salt solution; The addition of drag reducer is 59mg, and inhibitor is a dodecyl sodium sulfate, and the addition of inhibitor is 3.5% of a Schweinfurt green quality;
(2) making concentration is 1.5molL
-1Reductant solution, reducing agent is a formaldehyde, adopts solid sodium hydroxide that the pH value of reductant solution is adjusted to 12, is preheated to 64 ℃ again, and is subsequent use;
(3) be that 1: 1 ratio arm mixing limit stirs by volume with the mantoquita mixed liquor that obtains in (1), (2) processing step and reductant solution; Speed of agitator is 500 rev/mins, and mixing time is 0.8min, then; Heat temperature raising to 78 ℃ in the time of 4min; Reach reaction temperature, and keep reaction 16min, get nanometer copper aaerosol solution;
(4) reaction temperature of keeping the nanometer copper aaerosol solution that obtains in (3) processing step is carried out ageing and is handled 16min at 78 ℃;
(5) be to carry out vacuum filtration under the condition of 0.09Mpa in vacuum to the aaerosol solution that obtains in (4) processing step, the copper nano powder of the decontamination that obtains not eliminating;
(6) deionized water that adopts normal temperature is to the copper nano powder washing earlier that obtains in (5) processing step 4 times, is that 95% ethanol is replaced expelling water through weight percent concentration again, obtains the copper nano powder of ethanol parcel;
(7) be to carry out vacuum filtration, the copper nano powder that obtains wetting under the condition of 0.09Mpa in vacuum to the copper nano powder that obtains in (6) processing step;
(8) to the copper nano powder that obtains in (7) processing step temperature be 38 ℃, vacuum be 0.09Mpa, drying time are to carry out low-temperature vacuum drying under the condition of 2.5h after, obtain the copper nano powder finished product.
The sem photograph of the copper nano powder that Fig. 6 makes for embodiment 4 said methods, scale are 2 μ m, the uniform particle diameter of copper nano powder; About particle size 100nm; Narrow particle size distribution, the storage life can reach more than 1 year, was convenient to use as the raw material of producing nano-fluid, nanometer conductive material etc.
Above-described only is four kinds of embodiments of the present invention.Should be understood that; For the person of ordinary skill of the art; Under the prerequisite that does not break away from the principle of the invention, can also make some modification and improvement, these also should be regarded as belonging to protection scope of the present invention; As: in preparation method of the present invention, the reducing agent described in (2) processing step also can be hydrazine hydrate.
Claims (10)
1. the preparation method of copper nano powder, it comprises following processing step:
(1) earlier mantoquita is made into copper salt solution, in copper salt solution, adds drag reducer and inhibitor again, make the mantoquita mixed liquor that contains drag reducer and inhibitor, the mantoquita mixed liquor is preheated to uniform temperature, subsequent use;
(2) make reductant solution, and the pH value of adjustment reductant solution, be preheated to uniform temperature again, subsequent use;
(3) the mantoquita mixed liquor and the reductant solution that obtain in (1), (2) processing step are stirred while mixing, then, heat temperature raising is to reaction temperature, and keeps the reaction certain hour, nanometer copper aaerosol solution;
(4) keep the reaction temperature of the nanometer copper aaerosol solution that obtains in (3) processing step, carry out ageing and handle;
(5) aaerosol solution that obtains in (4) processing step is carried out vacuum filtration, the copper nano powder of the decontamination that obtains not eliminating;
(6) copper nano powder that obtains in (5) processing step is washed earlier, replace expelling water through organic solvent again, obtain the copper nano powder of organic solvent parcel;
(7) copper nano powder that obtains in (6) processing step is carried out vacuum filtration, the copper nano powder that obtains wetting;
(8) copper nano powder that obtains in (7) processing step is carried out low-temperature vacuum drying after, obtain the copper nano powder finished product.
2. the preparation method of copper nano powder according to claim 1 comprises following processing step:
(1) mantoquita described in the processing step is any in copper sulphate, copper nitrate, copper chloride, the Schweinfurt green, and said copper salt solution concentration is 0.1～1molL
-1
Drag reducer is PEO or polyacrylamide, and for every liter of copper salt solution, the addition of drag reducer is 50～60mg;
Inhibitor is any in octyl phenol polyoxyethylene (10) ether, polyvinylpyrrolidone, dodecyl sodium sulfate, the softex kw; The weight percent concentration of octyl phenol polyoxyethylene (10) ether is 90～99%, and the addition of inhibitor is 0.1～4% of a mantoquita quality;
The preheat temperature of mantoquita mixed liquor is 60～65 ℃.
3. the preparation method of copper nano powder according to claim 1 comprises following processing step:
(2) reducing agent described in the processing step is any in inferior sodium phosphate, sodium sulfite, sodium borohydride, hydrazine hydrate, the formaldehyde, and the concentration of reductant solution is 0.2～2molL
-1
When reducing agent was in inferior sodium phosphate, the sodium sulfite any, to adopt weight percent concentration be 90～98% sulfuric acid was adjusted to 1～2 with the pH value of reductant solution;
When reducing agent is in sodium borohydride, hydrazine hydrate, the formaldehyde any, adopt solid sodium hydroxide that the pH value of reductant solution is adjusted to 11～12;
The preheat temperature of reductant solution is 60～65 ℃.
4. the preparation method of copper nano powder according to claim 1 comprises following processing step:
(3) the mantoquita mixed liquor described in the processing step is 1: 1 with the volume ratio that reductant solution mixes mutually; Speed of agitator is 200～600 rev/mins, and mixing time is 0.5～1min; The time of heat temperature raising is 2～5min, and reaction temperature is 70～80 ℃, and the reaction time is 15～20min.
5. the preparation method of copper nano powder according to claim 1 comprises following processing step:
(4) the ageing treatment temperature described in the processing step is 70～80 ℃, and the time that ageing is handled is 15～20min.
6. the preparation method of copper nano powder according to claim 1 comprises following processing step:
(5) vacuum of the vacuum filtration described in the processing step is 0.05～0.1Mpa.
7. the preparation method of copper nano powder according to claim 1 comprises following processing step:
(6) process conditions of the washing described in the processing step are: adopt the deionized water of normal temperature that the copper nano powder that obtains in (5) processing step is washed 3～5 times; Described organic solvent employing weight percent concentration is 95% ethanol.
8. the preparation method of copper nano powder according to claim 1 comprises following processing step:
(7) vacuum of the vacuum filtration described in the processing step is 0.05～0.1Mpa.
9. the preparation method of copper nano powder according to claim 1 comprises following processing step:
(8) process conditions of the low-temperature vacuum drying described in the processing step are: temperature is 20～40 ℃, and vacuum is 0.05～0.1Mpa, and be 2～4h drying time.
10. the copper nano powder that makes according to the preparation method of each described copper nano powder in the claim 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210062968.8A CN102601381B (en) | 2012-03-11 | 2012-03-11 | Preparation method of copper nano powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210062968.8A CN102601381B (en) | 2012-03-11 | 2012-03-11 | Preparation method of copper nano powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102601381A true CN102601381A (en) | 2012-07-25 |
| CN102601381B CN102601381B (en) | 2014-01-29 |
Family
ID=46519362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210062968.8A Expired - Fee Related CN102601381B (en) | 2012-03-11 | 2012-03-11 | Preparation method of copper nano powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102601381B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102896322A (en) * | 2012-11-01 | 2013-01-30 | 广东东硕科技有限公司 | Preparation method for nano-copper with oxidation resistance and dispersibility |
| CN103028739A (en) * | 2013-01-05 | 2013-04-10 | 河北工业大学 | Preparation method of long-range ordered, layered and self-assembled nano-structure superlattice copper |
| CN103100723A (en) * | 2013-02-05 | 2013-05-15 | 中北大学 | Controllable hydrothermal preparation method of preparing metallic copper nanometer materials |
| CN106270542A (en) * | 2015-05-19 | 2017-01-04 | 东又悦（苏州）电子科技新材料有限公司 | A kind of vacuum method prepares the method for copper powder |
| CN106513696A (en) * | 2015-09-09 | 2017-03-22 | 广州千顺工业材料有限公司 | Micro-nano copper powder and preparation method thereof |
| CN107498068A (en) * | 2017-09-22 | 2017-12-22 | 大连理工大学 | A kind of preparation method of flower-shaped nano-copper |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040147618A1 (en) * | 2001-04-30 | 2004-07-29 | Lee Mu Sang | Colloid solution of metal nanoparticles, metal-polymer nanocomposites and methods for preparation thereof |
| CN1686648A (en) * | 2005-04-26 | 2005-10-26 | 黄德欢 | Preparation method of nano-bronze powder |
| CN101195170A (en) * | 2006-12-06 | 2008-06-11 | 比亚迪股份有限公司 | Preparation method of ultrafine copper powder |
| CN101342590A (en) * | 2008-08-26 | 2009-01-14 | 郑州大学 | A kind of copper nanoparticles and preparation method thereof |
| JP2009526132A (en) * | 2006-02-08 | 2009-07-16 | アクリメッド インコーポレイテッド | Methods and compositions for metal nanoparticle treated surfaces |
-
2012
- 2012-03-11 CN CN201210062968.8A patent/CN102601381B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040147618A1 (en) * | 2001-04-30 | 2004-07-29 | Lee Mu Sang | Colloid solution of metal nanoparticles, metal-polymer nanocomposites and methods for preparation thereof |
| CN1686648A (en) * | 2005-04-26 | 2005-10-26 | 黄德欢 | Preparation method of nano-bronze powder |
| JP2009526132A (en) * | 2006-02-08 | 2009-07-16 | アクリメッド インコーポレイテッド | Methods and compositions for metal nanoparticle treated surfaces |
| CN101195170A (en) * | 2006-12-06 | 2008-06-11 | 比亚迪股份有限公司 | Preparation method of ultrafine copper powder |
| CN101342590A (en) * | 2008-08-26 | 2009-01-14 | 郑州大学 | A kind of copper nanoparticles and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 郭雨等: "均相还原法制备铜纳米粒子", 《材料导报》, vol. 22, 31 May 2008 (2008-05-31), pages 131 - 132 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102896322A (en) * | 2012-11-01 | 2013-01-30 | 广东东硕科技有限公司 | Preparation method for nano-copper with oxidation resistance and dispersibility |
| CN103028739A (en) * | 2013-01-05 | 2013-04-10 | 河北工业大学 | Preparation method of long-range ordered, layered and self-assembled nano-structure superlattice copper |
| CN103100723A (en) * | 2013-02-05 | 2013-05-15 | 中北大学 | Controllable hydrothermal preparation method of preparing metallic copper nanometer materials |
| CN103100723B (en) * | 2013-02-05 | 2014-12-24 | 中北大学 | Controllable hydrothermal preparation method of preparing metallic copper nanometer materials |
| CN106270542A (en) * | 2015-05-19 | 2017-01-04 | 东又悦（苏州）电子科技新材料有限公司 | A kind of vacuum method prepares the method for copper powder |
| CN106513696A (en) * | 2015-09-09 | 2017-03-22 | 广州千顺工业材料有限公司 | Micro-nano copper powder and preparation method thereof |
| CN106513696B (en) * | 2015-09-09 | 2019-08-02 | 广州千顺工业材料有限公司 | Micro-nano copper powder and preparation method thereof |
| CN107498068A (en) * | 2017-09-22 | 2017-12-22 | 大连理工大学 | A kind of preparation method of flower-shaped nano-copper |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102601381B (en) | 2014-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104646683B (en) | Controllable ball shape silver powder of a kind of granularity and preparation method thereof | |
| CN102601381B (en) | Preparation method of copper nano powder | |
| Gao et al. | One-step seeded growth of Au nanoparticles with widely tunable sizes | |
| JP6766166B2 (en) | Preparation method in silver powder production using micro-nano bubbles as seed crystal induction | |
| CN111804905B (en) | Micron-sized spherical hollow gold powder and preparation method thereof | |
| US20020194958A1 (en) | Process for preparing noble metal nanoparticles | |
| CN106583746A (en) | Preparation method of solar battery panel silver powder | |
| CN105436517A (en) | Method for preparing metal powder by utilizing nano crystal seed induction | |
| CN113579246B (en) | Preparation method of nano high-entropy alloy powder | |
| CN1785558A (en) | Preparation method of micron grade ball shape silver powder for conductive silver paste | |
| CN101693297A (en) | Preparation method of copper nanoparticles with different particle diameters | |
| CN107322002A (en) | A kind of doped tungsten-based composite granule of rare earth oxide and preparation method thereof | |
| Xu et al. | Synthesis of copper nanoparticles by a T-shaped microfluidic device | |
| CN106903324A (en) | A kind of preparation method of Graphene-nano silver dispersion | |
| CN109079151B (en) | Method for preparing ultra-coarse tungsten powder by high-temperature liquid-phase reduction of tungsten oxide | |
| CN103769598A (en) | Method for stably preparing nano-copper powder | |
| CN112705721B (en) | Preparation method of silver nanowires | |
| CN116618675A (en) | Preparation method of low-temperature sintering silver powder for heterojunction solar cell | |
| CN106513706B (en) | A kind of preparation method for being used for Nano Silver nucleus in ball shape silver powder production technology | |
| CN116833418B (en) | Cauliflower-like metal silver powder with hollow structure and preparation method thereof | |
| CN110102778B (en) | Preparation method of low-temperature sintered high-crystallinity silver powder | |
| Wang et al. | The hydrothermal synthesis of ultra-high aspect ratio Ag nanoflakes and their performance as conductive fillers in heaters and pastes | |
| CN117415327A (en) | Preparation method of silver particles | |
| CN104759632A (en) | Method of preparing nano-crystalline powdered alloy powder | |
| CN110560702A (en) | method for preparing micron-sized single crystal copper powder at room temperature |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Guo Yu Inventor after: Li Wenbin Inventor after: Chen Junhua Inventor after: Pan Shouhua Inventor after: Shi Guoliang Inventor before: Guo Yu |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: GUO YU TO: GUO YU LI WENBIN CHEN JUNHUA PAN SHOUHUA SHI GUOLIANG |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140129 Termination date: 20150311 |
|
| EXPY | Termination of patent right or utility model |