CN107081424B - A kind of thick titanium or thick titanium alloy powder injection moulding PP Pipe Compound and preparation method thereof - Google Patents
A kind of thick titanium or thick titanium alloy powder injection moulding PP Pipe Compound and preparation method thereof Download PDFInfo
- Publication number
- CN107081424B CN107081424B CN201710299684.3A CN201710299684A CN107081424B CN 107081424 B CN107081424 B CN 107081424B CN 201710299684 A CN201710299684 A CN 201710299684A CN 107081424 B CN107081424 B CN 107081424B
- Authority
- CN
- China
- Prior art keywords
- thick titanium
- alloy powder
- titanium alloy
- thick
- pipe compound
- 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
- 239000000843 powder Substances 0.000 title claims abstract description 107
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 105
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000010936 titanium Substances 0.000 title claims abstract description 63
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 62
- 150000001875 compounds Chemical class 0.000 title claims abstract description 30
- 238000001746 injection moulding Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 82
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 71
- 238000005238 degreasing Methods 0.000 claims abstract description 37
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 30
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 26
- 239000011258 core-shell material Substances 0.000 claims abstract description 24
- 238000005245 sintering Methods 0.000 claims abstract description 19
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 13
- 239000008187 granular material Substances 0.000 claims abstract description 12
- 229920002873 Polyethylenimine Polymers 0.000 claims description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 13
- 238000012986 modification Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 229920000447 polyanionic polymer Polymers 0.000 claims description 11
- 238000002347 injection Methods 0.000 claims description 10
- 239000007924 injection Substances 0.000 claims description 10
- -1 polyethylene Polymers 0.000 claims description 9
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 8
- 235000019256 formaldehyde Nutrition 0.000 claims description 8
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 8
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 8
- 229920001464 poly(sodium 4-styrenesulfonate) Polymers 0.000 claims description 8
- 229920006324 polyoxymethylene Polymers 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 230000009881 electrostatic interaction Effects 0.000 claims description 4
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 238000001338 self-assembly Methods 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 229920005596 polymer binder Polymers 0.000 abstract description 4
- 239000002491 polymer binding agent Substances 0.000 abstract description 4
- 238000004663 powder metallurgy Methods 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 description 26
- 239000000853 adhesive Substances 0.000 description 24
- 230000001070 adhesive effect Effects 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 239000010410 layer Substances 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 230000009102 absorption Effects 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 12
- 235000019580 granularity Nutrition 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 238000007171 acid catalysis Methods 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000008468 bone growth Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003380 quartz crystal microbalance Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical class OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008202 granule composition Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1017—Multiple heating or additional steps
- B22F3/1021—Removal of binder or filler
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
- B22F3/225—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by injection molding
Abstract
The invention belongs to high polymer binder material and field of powder metallurgy, and in particular to a kind of titanium alloy powder injection moulding PP Pipe Compound and preparation method thereof.It only needs to be surface modified thick titanium or titanium alloy powder, use simple layer-by-layer, titanium dioxide granule and polyelectrolyte are introduced into existing thick titanium or titanium alloy powder particle surface, the thick titanium or titanium alloy powder particle of core-shell structure is prepared；Again by being kneaded with high polymer binder, powder injection-molded, catalysis degreasing and vacuum-sintering preparation low cost, low-shrinkage, low frit density and porous structure titanium alloy product.
Description
Technical field
The invention belongs to high polymer binder material and field of powder metallurgy, and in particular to a kind of thick titanium or thick Titanium Powder
End injection moulding PP Pipe Compound and preparation method thereof.
Background technique
Metal powder injection molding (MIM) is the production skill that a kind of magnanimity prepares micro metal component with complex shape
Art.The research of modern MIM technology starts from phase early 1970s, the 1980s mid-term, due to raw material production cost
The continuous Improvement of decline and binder design theory and degreasing theory, MIM technology are rapidly developed and become current
Most popular note type processing technology, is widely used in a variety of industries such as aerospace, automobile, computer, instrument and meter.China
The research and application of MIM technology are started late, and since phase late 1980s, and achieve a series of research achievement.
Metal powder injection molding has design flexibility, it is possible to reduce waste of material, these advantages become MIM
Produce titanium alloy component one of technique of greatest concern.When preparing titanium alloy component, there are some technical problems, such as
Prepare the higher cost of the fine powder powder stock of titanium alloy component；There is titanium or titanium alloy very high reaction to live at relatively high temperatures
Property, it is easy to react with the decomposition product of the adhesive during thermal debinding and sintering, so that a part of titanium or titanium alloy are suitable
In being etched, lead to high interstitial content；Powder usually in injection moulding using partial size lower than 45 μm, so as in sample
It is interior generate the smallest porosity and close to the density of theoretical value to improve mechanical performance, but titanium alloy powder partial size is smaller, table
Area is higher, and titanium or titanium alloy is susceptible to pollution in processing, degreasing and sintering process and oxygen uptake is more；In addition, using thin
Powder can lead to more contractions, because the particle used is smaller, sintering rate is bigger, be sintered finer and close.
Summary of the invention
The present invention provides a kind of thick titaniums or thick titanium alloy powder to be injection moulded PP Pipe Compound, wherein the thick titanium in PP Pipe Compound
Or thick titanium alloy powder is coreshell type structure, specially polyelectrolyte/titanium dioxide multilayer film modified thick titanium or thick titanium alloy
Powder particle, polyanion electrolyte and titanium dioxide shown in shell branched polyethylene imine as shown in formula A1, formula A2
Grain LBL self-assembly forms,
Formula A1 is
Formula A2 is
The partial size of thick titanium or thick titanium alloy powder particle is 60-75 μm,
The weight average molecular weight Mw of branched polyethylene imine in 10000-100000,
Polyanion electrolyte is sodium carboxymethylcellulose, in polyacrylic acid, Sodium Polyacrylate, poly (sodium 4-styrenesulfonate)
One or more kinds of mixtures, wherein the weight average molecular weight of each ingredient is 10000,16000,70000 or 75000,
The partial size of titanium dioxide granule is 20nm~50nm.
The present invention also provides a kind of above-mentioned thick titanium or the preparation methods of thick titanium alloy powder injection moulding PP Pipe Compound, are not required to
Want the thin titanium alloy powder (< 45 μm) of higher operating costs, it is only necessary to be surface modified, make to thick titanium or thick titanium alloy powder
With simple layer-by-layer, titanium dioxide granule and polyelectrolyte are introduced into existing thick titanium or thick titanium alloy powder
Particle surface is prepared the thick titanium or thick titanium alloy powder particle of core-shell structure, carries out in aqueous solution, and generation environment is not dirty
Dye；Again by being kneaded with high polymer binder, powder injection-molded, catalysis degreasing and vacuum-sintering preparation low cost, low receipts
The titanium alloy product of shrinkage, low frit density and porous structure is realized and is used as bio-medical implantation material, is applied to bone growth
And the fields such as cell adherence,
Specific steps are as follows:
(1) surface is carried out to thick titanium or thick titanium alloy powder particle by the layer-by-layer of static-electronic driving to repair
Decorations,
Branched polyethylene imine shown in formula A1 is first chemically adsorbed to thick titanium or thick titanium alloy powder particle surface, then at
The branched polyethylene imine surface is then electronegative in this using polyanion electrolyte shown in electrostatic interaction absorption type A2
The positively charged titanium dioxide granule of polyanion electrolyte adsorption, by multiple alternating deposit polyanion electrolyte and two
The hud typed thick titanium or thick titanium alloy powder particle of plural layers modification are obtained after titan oxide particles,
Step (1) carries out in aqueous dispersions environment, branched polyethylene imine, polyanion electrolyte, titanium dioxide
Mass percent of the grain in aqueous dispersions is respectively 0.2-0.5%, 0.05-0.2%, 0.1-0.7%,
It, can be with metal and metal surface since branched polyethylene imine organic polymer is rich in amino in this step
Harsh chemical effect occurs for hydroxyl, forms one layer of macromolecule layer in thick titanium or thick titanium alloy powder particle surface；It is water-soluble poly-
Anion electrolyte macromolecule can be adsorbed onto thick titanium or thick titanium by the electrostatic interaction of the branched polyethylene imine with positive charge
Alloy powder particle surface；Titanium dioxide granule is positively charged in aqueous solution, and it is heavy further to be adsorbed by electrostatic interaction
Product arrives surface, the polyelectrolyte and titanium dioxide granule of alternating deposit oppositely charged, to realize to thick titanium or thick titanium alloy
The surface modification of powder particle forms core-shell structure, by the number of plies of regulation deposition, can regulate and control thick titanium or thick titanium alloy powder
The thickness of particle shell；
(2) the hud typed thick titanium that plural layers modification is obtained in step (1) or thick titanium alloy powder particle and catalysis are taken off
Epoxy-type binder is kneaded, and prepares thick titanium using injection moulding, catalysis degreasing, vacuum-sintering or thick titanium alloy powder is injected into
Type PP Pipe Compound,
The weight ratio of hud typed thick titanium or thick titanium alloy powder particle and catalysis degreasing type adhesive be 50~56:44~
50,
Each component includes count by weight percentage in catalysis degreasing type adhesive, polyformaldehyde 85%, conformal dose of polypropylene 6
~8%, surplus be processing aid, as ethylene-vinyl acetate copolymer 2~4%, stabilizer copolymerized methanal 1%, antioxidant 1%,
Lithium stearate 1%, lubricant 2%,
Sintering temperature is 1200 DEG C,
In this step, hud typed thick titanium or thick titanium alloy powder particle and catalysis degreasing type adhesive prepare dedicated through mixing
Material becomes green compact through injection moulding, becomes degreased blank, the shell structurre after high-temperature vacuum is sintered through catalysis degreasing removing macromolecule
Middle organic polymer is substantially completely removed, and leaves the stable inorganic titanium dioxide granule composition micro channel of chemical property, average hole
Diameter range is at 0.8~2 μm, by regulating and controlling the thickness of shell, i.e. polyelectrolyte/titanium dioxide multilayer film number of plies, it is available not
With the thick titanium of porous structure of pore size and distributed degrees or thick titanium alloy product.
The beneficial effects of the present invention are: layer-by-layer is introduced thick titanium to the present invention or thick titanium alloy powder is injected
In the preparation process for forming PP Pipe Compound, thick titanium or thick titanium alloy powder particle (60-75 μm) are surface modified, form nucleocapsid
Structure, since multiple alternating deposit forms coating on surface, this for thick titanium or thick titanium alloy powder particulate material,
It will cause the decline of surface roughness, but when the organic principle in shell structurre is after catalysis degreasing and vacuum-sintering
Removing leaves the inorganic TiO 2 porous channel design with cavity, forms more coarse surface layer, and by interconnected
Micro channel composition, average pore size titanium thicker than commercial materials or the thick big several times of titanium alloy powder particle,
And the formation of pore structure, surface roughness and specific surface area are increased, the space of cell growth and breeding is provided,
The absorption, growth and differentiation for facilitating cell can satisfy bio-medical implantation material to bone growth and cell adherence etc.
The demand in field；
The present invention directlys adopt the biggish thick titanium of partial size or thick titanium alloy powder particle, reduces cost, can guarantee powder
Lower reactivity, oxygen uptake are less, it is not easy to which table is added in the pollution of binder decomposition product during being degreased and sintered
The titanium dioxide property of layer modification is also sufficiently stable, will not equally occur to chemically react and be contaminated, and makes finally obtained thick
Titanium or thick titanium alloy product impurity and oxygen content are low, have compared with low-shrinkage, more advantageous；
The present invention uses simple layer-by-layer, carries out in water environment, and generation environment does not pollute.
Detailed description of the invention
Fig. 1 is in embodiment 1, by depositing multilayer film on quartz crystal microbalance research branched polyethylene imine surface certainly
Frequency variation diagram when assembling process.
Fig. 2 is in embodiment 2, and step (2) mixes the thick titanium alloy powder particle of core-shell structure with catalysis degreasing type adhesive
After refining, the rheological property of mixture, it can be seen that the viscosity of the mixture declines with the raising of shear rate, shows vacation
The rheological behaviour of plastic fluid, so that guaranteeing that the mixture can sufficiently flow is filled to mold inner-cavity, prepare thin-walled titanium and
Titanium alloy product.
Fig. 3 is the SEM shape appearance figure of the porous structure titanium alloy product obtained after vacuum-sintering in 3 step of embodiment (2).
Specific embodiment
Embodiment 1
(1) the thick titanium alloy powder particle of 60 μm of granularities is placed in the branched polyethylene imine (Mw=that concentration is 2g/L
10000) it is adsorbed 30 minutes in aqueous solution, particle and aqueous solution mass ratio are 1:4, then with deionized water to thick titanium alloy powder
Particle is washed 10 minutes, and electronegative poly (sodium 4-styrenesulfonate) (Mw=10000) aqueous solution for being subsequently added to 0.5g/L is inhaled
Attached 30 minutes, particle and aqueous solution mass ratio were 1:4, were then washed 10 minutes with deionized water again, were adding the band of 1g/L just
The TiO of charge2It is adsorbed 30 minutes in (partial size 20nm) dispersion liquid, particle and aqueous dispersions mass ratio are 1:4, finally use deionization
Water is washed 10 minutes, using above-mentioned technique totally 3 alternating deposit poly (sodium 4-styrenesulfonate)s and TiO2, make thick titanium alloy powder
Grain pipe absocped with polyelectrolyte on surface/titanium dioxide multilayer film PEI (PSS/TiO2)3, the absorption number of plies is 7 layers altogether, the nucleocapsid knot after modification
The thick titanium alloy powder particle drying of structure is stand-by,
Fig. 1, which is shown, utilizes the self assembly that multilayer film is deposited on quartz crystal microbalance research branched polyethylene imine surface
Process, it can be observed that one strata electrolyte of every absorption or TiO2, frequency decline, after alternating deposit frequency occur it is steps under
Drop, shows that steps increase is presented in the quality of adsorption；
It (2), first will step according to the mass ratio 56:44 of core-shell structure thick titanium alloy powder particle and catalysis degreasing type adhesive
Suddenly 170 DEG C of preheatings 5min, revolving speed 15r/ in torque rheometer are added in the thick titanium alloy powder particle of core-shell structure obtained in (1)
Min, then catalysis degreasing type adhesive is added thereto equally under the conditions of 170 DEG C, with revolving speed mixing 30 minutes of 15r/min,
Using injection moulding, and nitric acid catalysis degreasing 6h is carried out at 120 DEG C, thick Titanium Powder is obtained after 1200 DEG C of vacuum-sintering
End injection moulding PP Pipe Compound,
Catalysis degreasing type adhesive each component in the present embodiment is count by weight percentage are as follows: polyformaldehyde 85%, conformal
Agent polypropylene 6%, ethylene-vinyl acetate copolymer 4%, stabilizer copolymerized methanal 1%, 1790 antioxidant 1%, lithium stearate
1%, lubricant 2%.
The physical property of thick titanium alloy powder injection moulding PP Pipe Compound manufactured in the present embodiment is as shown in table 1, sintered density
It is less than the 4.38g/cm of raw materials used thick titanium alloy powder particle in step (1)3, this illustrates that titanium alloy particle surface is provided with
The bigger porous structure of roughness.
Embodiment 2
(1) the thick titanium alloy powder of 65 μm of granularities is placed in the branched polyethylene imine (Mw=40000) that concentration is 3g/L
It is adsorbed 30 minutes in aqueous solution, particle and aqueous solution mass ratio are 1:4, then with deionized water to thick titanium alloy powder particle water
It washes 10 minutes, electronegative sodium cellulose glycolate (Mw=16000) adsorption from aqueous solution 30 for being subsequently added to 1.03g/L divides
Clock, particle and aqueous solution mass ratio are 1:4, are then washed 10 minutes with deionized water again, add the positively charged of 2g/L
TiO2It is adsorbed 30 minutes in (partial size 30nm) dispersion liquid, particle and aqueous dispersions mass ratio are 1:4, are finally washed with deionized water
10 minutes, using above-mentioned technique totally 8 alternating deposit sodium cellulose glycolates and TiO2, make thick titanium alloy powder particle surface
Polyelectrolyte/titanium dioxide multilayer film is adsorbed, the absorption number of plies is 17 layers altogether, the thick titanium alloy powder particle of the core-shell structure after modification
Drying is stand-by；
It (2), first will step according to the mass ratio 54:46 of core-shell structure thick titanium alloy powder particle and catalysis degreasing type adhesive
Suddenly 170 DEG C of preheating 5min in torque rheometer are added in the thick titanium alloy powder particle of core-shell structure obtained in (1), and revolving speed is
15r/min, then catalysis degreasing type adhesive is added thereto equally under the conditions of 170 DEG C, with the revolving speed mixing 30 of 15r/min
Minute, using injection moulding, and nitric acid catalysis degreasing 6h is carried out at 120 DEG C, thick titanium is obtained after 1200 DEG C of vacuum-sintering
Alloy powder is injection moulded PP Pipe Compound,
Catalysis degreasing type adhesive each component in the present embodiment is count by weight percentage are as follows: polyformaldehyde 86%, conformal
Agent polypropylene 6%, ethylene-vinyl acetate copolymer 3%, stabilizer copolymerized methanal 1%, 1790 antioxidant 1%, lithium stearate
1%, lubricant 2%.
The physical property of thick titanium alloy powder injection moulding PP Pipe Compound manufactured in the present embodiment is as shown in table 1, with embodiment 1
It compares, the film layer number in the present embodiment due to surface modification increases to 17 layers, titanium alloy useful load decline, so volume contraction
Rate increases, yield stress reduces, sintered density reduces, aperture size increases.
Embodiment 3
(1) the thick titanium alloy powder of 70 μm of granularities is placed in the branched polyethylene imine (Mw=60000) that concentration is 4g/L
It is adsorbed 30 minutes in aqueous solution, particle and aqueous solution mass ratio are 1:4, then with deionized water to thick titanium alloy powder particle water
It washes 10 minutes, is subsequently added to electronegative polyacrylic acid (Mw=70000) of 1.5g/L adsorption from aqueous solution 30 minutes, particle
It is 1:4 with aqueous solution mass ratio, is then washed 10 minutes with deionized water again, add the positively charged TiO of 3g/L2(grain
Diameter 40nm) it adsorbs 30 minutes in dispersion liquid, particle and aqueous dispersions mass ratio are 1:4, finally washed 10 minutes with deionized water,
Using above-mentioned technique totally 11 alternating deposit polyacrylic acid and TiO2, make thick titanium alloy powder particle surface absorption polyelectrolyte/
Titanium dioxide multilayer film, the absorption number of plies is 23 layers altogether, and the thick titanium alloy powder particle drying of the core-shell structure after modification is stand-by；
It (2), first will step according to the mass ratio 52:48 of core-shell structure thick titanium alloy powder particle and catalysis degreasing type adhesive
Suddenly 170 DEG C of preheating 5min in torque rheometer are added in the thick titanium alloy powder particle of core-shell structure obtained in (1), and revolving speed is
15r/min, then catalysis degreasing type adhesive is added thereto equally under the conditions of 170 DEG C, with the revolving speed mixing 30 of 15r/min
Minute, using injection moulding, and nitric acid catalysis degreasing 6h is carried out at 120 DEG C, thick titanium is obtained after 1200 DEG C of vacuum-sintering
Alloy powder is injection moulded PP Pipe Compound,
Catalysis degreasing type adhesive each component in the present embodiment is count by weight percentage are as follows: polyformaldehyde 87%, conformal
Agent polypropylene 6%, ethylene-vinyl acetate copolymer 2%, stabilizer copolymerized methanal 1%, 1790 antioxidant 1%, lithium stearate
1%, lubricant 2%.
Embodiment 4
(1) the thick titanium alloy powder of 75 μm of granularities is placed in the branched polyethylene imine (Mw=80000) that concentration is 5g/L
It is adsorbed 30 minutes in aqueous solution, particle and aqueous solution mass ratio are 1:4, then with deionized water to thick titanium alloy powder particle water
It washes 10 minutes, is subsequently added to electronegative Sodium Polyacrylate (Mw=75000) of 2g/L adsorption from aqueous solution 30 minutes, particle
It is 1:4 with aqueous solution mass ratio, is then washed 10 minutes with deionized water again, add the positively charged TiO of 4g/L2(grain
Diameter 50nm) it adsorbs 30 minutes in dispersion liquid, particle and aqueous dispersions mass ratio are 1:4, finally washed 10 minutes with deionized water,
Using above-mentioned technique totally 3 alternating deposit Sodium Polyacrylates and TiO2, make thick titanium alloy powder particle surface absorption polyelectrolyte/
Titanium dioxide multilayer film, the absorption number of plies is 7 layers altogether, and the thick titanium alloy powder particle drying of the core-shell structure after modification is stand-by；
It (2), first will step according to the mass ratio 50:50 of core-shell structure thick titanium alloy powder particle and catalysis degreasing type adhesive
Suddenly 170 DEG C of preheating 5min in torque rheometer are added in the thick titanium alloy powder particle of core-shell structure obtained in (1), and revolving speed is
15r/min, then catalysis degreasing type adhesive is added thereto equally under the conditions of 170 DEG C, with the revolving speed mixing 30 of 15r/min
Minute, using injection moulding, and nitric acid catalysis degreasing 6h is carried out at 120 DEG C, thick titanium is obtained after 1200 DEG C of vacuum-sintering
Alloy powder is injection moulded PP Pipe Compound,
Catalysis degreasing type adhesive each component in the present embodiment is count by weight percentage are as follows: polyformaldehyde 88%, conformal
Agent polypropylene 6%, ethylene-vinyl acetate copolymer 1%, stabilizer copolymerized methanal 1%, 1790 antioxidant 1%, lithium stearate
1%, lubricant 2%.
Embodiment 5
(1) the thick titanium alloy powder of 60 μm of granularities is placed in the branched polyethylene imine (Mw=that concentration is 2g/L
100000) it is adsorbed 30 minutes in aqueous solution, particle and aqueous solution mass ratio are 1:4, then with deionized water to thick Titanium Powder
Last particle is washed 10 minutes, and electronegative poly (sodium 4-styrenesulfonate) (Mw=70000) aqueous solution of 0.5g/L is subsequently added to
Absorption 30 minutes, particle and aqueous solution mass ratio are 1:4, are then washed 10 minutes with deionized water again, add the band of 5g/L
The TiO of positive charge2Adsorbed 30 minutes in (partial size 40nm) dispersion liquid, particle and aqueous dispersions mass ratio are 1:4, finally spend from
Sub- water is washed 10 minutes, using above-mentioned technique totally 4 alternating deposit poly (sodium 4-styrenesulfonate)s and TiO2, make thick Titanium Powder
Last particle surface adsorbs polyelectrolyte/titanium dioxide multilayer film, and the absorption number of plies is 9 layers altogether, and the thick titanium of the core-shell structure after modification closes
Golden powder particle drying is stand-by；
It (2), first will step according to the mass ratio 55:45 of core-shell structure thick titanium alloy powder particle and catalysis degreasing type adhesive
Suddenly 170 DEG C of preheating 5min in torque rheometer are added in the thick titanium alloy powder particle of core-shell structure obtained in (1), and revolving speed is
15r/min, then catalysis degreasing type adhesive is added thereto equally under the conditions of 170 DEG C, with the revolving speed mixing 30 of 15r/min
Minute, using injection moulding, and nitric acid catalysis degreasing 6h is carried out at 120 DEG C, thick titanium is obtained after 1200 DEG C of vacuum-sintering
Alloy powder is injection moulded PP Pipe Compound,
Catalysis degreasing type adhesive each component in the present embodiment is count by weight percentage are as follows: polyformaldehyde 84%, conformal
Agent polypropylene 7%, ethylene-vinyl acetate copolymer 4%, stabilizer copolymerized methanal 1%, 1790 antioxidant 1%, lithium stearate
1%, lubricant 2%.
Embodiment 6
(1) the thick titanium alloy powder of 75 μm of granularities is placed in the branched polyethylene imine (Mw=75000) that concentration is 4g/L
It is adsorbed 30 minutes in aqueous solution, particle and aqueous solution mass ratio are 1:4, then with deionized water to thick titanium alloy powder particle water
It washes 10 minutes, is subsequently added to electronegative poly (sodium 4-styrenesulfonate) (Mw=75000) adsorption from aqueous solution 30 of 1.03g/L
Minute, particle and aqueous solution mass ratio are 1:4, are then washed 10 minutes with deionized water again, add the positively charged of 7g/L
TiO2It is adsorbed 30 minutes in (partial size 50nm) dispersion liquid, particle and aqueous dispersions mass ratio are 1:4, finally use deionized water water
It washes 10 minutes, using above-mentioned technique totally 12 alternating deposit poly (sodium 4-styrenesulfonate)s and TiO2, make thick titanium alloy powder particle
Pipe absocped with polyelectrolyte on surface/titanium dioxide multilayer film, the absorption number of plies is 25 layers altogether, the core-shell structure titanium alloy powder after modification
Particle drying is stand-by；
It (2), first will step according to the mass ratio 50:50 of core-shell structure thick titanium alloy powder particle and catalysis degreasing type adhesive
Suddenly 170 DEG C of preheating 5min in torque rheometer are added in the thick titanium alloy powder particle of core-shell structure obtained in (1), and revolving speed is
15r/min, then catalysis degreasing type adhesive is added thereto equally under the conditions of 170 DEG C, with the revolving speed mixing 30 of 15r/min
Minute, using injection moulding, and nitric acid catalysis degreasing 6h is carried out at 120 DEG C, thick titanium is obtained after 1200 DEG C of vacuum-sintering
Alloy powder is injection moulded PP Pipe Compound,
Catalysis degreasing type adhesive each component in the present embodiment is count by weight percentage are as follows: polyformaldehyde 87%, conformal
Agent polypropylene 6%, ethylene-vinyl acetate copolymer 2%, stabilizer copolymerized methanal 1%, 1790 antioxidant 1%, lithium stearate
1%, lubricant 2%.
Table 1
Comparative example 1
(1) corresponding adhesive substance is selected to be uniformly mixed with the titanium dioxide granule of partial size 40nm and be coated to 70 μm
The thick titanium alloy powder particle surface of granularity controls in coating thickness and clad content of titanium dioxide with embodiment 3；
(2) with embodiment 3, as a result in vacuum-sintering, clad is completely fallen off, and leads to the thick Titanium Powder finally obtained
End injection moulding PP Pipe Compound is not implemented expected modified.
Claims (10)
1. a kind of thick titanium or thick titanium alloy powder are injection moulded PP Pipe Compound, it is characterised in that: in the injection moulding PP Pipe Compound
Thick titanium or thick titanium alloy powder be coreshell type structure, the specially film modified thick titanium of polyelectrolyte/titanium dioxide multilayer or thick
Titanium alloy powder particle, shell by branched polyethylene imine, polyanion electrolyte and titanium dioxide granule LBL self-assembly and
At.
2. thick titanium as described in claim 1 or thick titanium alloy powder are injection moulded PP Pipe Compound, it is characterised in that: the thick titanium
Or the partial size of thick titanium alloy powder particle is 60-75 μm.
3. thick titanium as described in claim 1 or thick titanium alloy powder are injection moulded PP Pipe Compound, it is characterised in that: the poly- yin
Ionic electrolytes are one or both of sodium carboxymethylcellulose, polyacrylic acid, Sodium Polyacrylate, poly (sodium 4-styrenesulfonate)
Above mixture.
4. thick titanium as described in claim 1 or thick titanium alloy powder are injection moulded PP Pipe Compound, it is characterised in that: the dioxy
The partial size for changing titanium particle is 20nm~50nm.
5. the preparation side of a kind of such as described in any item thick titaniums of Claims 1-4 or thick titanium alloy powder injection moulding PP Pipe Compound
Method, it is characterised in that: the preparation method is, using layer-by-layer, titanium dioxide granule and polyelectrolyte to be drawn
Enter into thick titanium or thick titanium alloy powder grain structure, the thick titanium or thick titanium alloy powder particle of core-shell structure is prepared；Again
It is kneaded with binder, powder injection-molded, catalysis degreasing, vacuum-sintering.
6. the preparation method of thick titanium as claimed in claim 5 or thick titanium alloy powder injection moulding PP Pipe Compound, it is characterised in that:
The preparation method the specific steps are,
(1) thick titanium or thick titanium alloy powder particle are surface modified by the layer-by-layer of static-electronic driving,
Branched polyethylene imine is first chemically adsorbed to thick titanium or thick titanium alloy powder particle surface, then at branched polyethylene Asia
Polyanion electrolyte is adsorbed using electrostatic interaction in amine surface, then in the electronegative polyanion electrolyte adsorption band
The titanium dioxide granule of positive electricity obtains plural layers after multiple alternating deposit polyanion electrolyte and titanium dioxide granule
The hud typed thick titanium or thick titanium alloy powder particle of modification；
(2) the hud typed thick titanium that plural layers modification is obtained in step (1) or thick titanium alloy powder particle and binder are kneaded,
Thick titanium or thick titanium alloy powder injection moulding PP Pipe Compound are prepared using injection moulding, catalysis degreasing, vacuum-sintering.
7. the preparation method of thick titanium as claimed in claim 6 or thick titanium alloy powder injection moulding PP Pipe Compound, it is characterised in that:
Step (1) carries out in aqueous dispersions environment, and branched polyethylene imine, polyanion electrolyte, titanium dioxide granule are in moisture
Mass percent in dispersion liquid is respectively 0.2-0.5%, 0.05-0.2%, 0.1-0.7%.
8. the preparation method of thick titanium as claimed in claim 6 or thick titanium alloy powder injection moulding PP Pipe Compound, it is characterised in that:
In step (2), the weight ratio of hud typed thick titanium or thick titanium alloy powder particle and binder is 50~56:44~50.
9. the preparation method of thick titanium as claimed in claim 6 or thick titanium alloy powder injection moulding PP Pipe Compound, it is characterised in that:
Each component includes count by weight percentage in binder described in step (2), and polyformaldehyde 85%, conformal dose of polypropylene 6~
8%, ethylene-vinyl acetate copolymer 2~4%, stabilizer copolymerized methanal 1%, antioxidant 1%, lithium stearate 1%, lubricant
2%.
10. the preparation method of thick titanium as claimed in claim 6 or thick titanium alloy powder injection moulding PP Pipe Compound, feature exist
In: in step (2), vacuum-sintering temperature is 1200 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710299684.3A CN107081424B (en) | 2017-05-02 | 2017-05-02 | A kind of thick titanium or thick titanium alloy powder injection moulding PP Pipe Compound and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710299684.3A CN107081424B (en) | 2017-05-02 | 2017-05-02 | A kind of thick titanium or thick titanium alloy powder injection moulding PP Pipe Compound and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107081424A CN107081424A (en) | 2017-08-22 |
| CN107081424B true CN107081424B (en) | 2018-12-28 |
Family
ID=59611731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710299684.3A Active CN107081424B (en) | 2017-05-02 | 2017-05-02 | A kind of thick titanium or thick titanium alloy powder injection moulding PP Pipe Compound and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107081424B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113510241A (en) * | 2021-04-25 | 2021-10-19 | 福建尚辉润德新材料科技有限公司 | Magnetic powder injection molding binder, preparation method and application method |
| CN113751708A (en) * | 2021-09-15 | 2021-12-07 | 西安航空职业技术学院 | Special material for titanium alloy powder injection molding and preparation method thereof |
| CN114015905B (en) * | 2021-11-04 | 2022-05-10 | 安徽有研吸气材料有限公司 | Process for preparing nano-grade zirconium-based non-evaporable getter material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1566296A (en) * | 2003-06-27 | 2005-01-19 | 中国科学院兰州化学物理研究所 | Process for preparation of self-assembly lubricant film |
| CN101274222A (en) * | 2007-12-12 | 2008-10-01 | 浙江大学 | Dynamic self-assembled process for preparing low-pressure high-throughput charged nanofiltration membrane |
| CN101905122A (en) * | 2010-07-23 | 2010-12-08 | 北京工业大学 | Self-assembly method for high-load inorganic nano particle hybridized organic membrane |
| WO2011026201A2 (en) * | 2009-09-04 | 2011-03-10 | Katholieke Universiteit Leuven | Metallic coatings on metallic substrates |
| CN106237984A (en) * | 2016-07-29 | 2016-12-21 | 燕山大学 | A kind of method that graphene oxide and chemical modification thereof are prepared in diadust surface |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101278204B1 (en) * | 2011-12-22 | 2013-06-27 | 경북대학교 산학협력단 | Method for preparing biomedical metal/alloy material with multi-drug delivery system |
-
2017
- 2017-05-02 CN CN201710299684.3A patent/CN107081424B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1566296A (en) * | 2003-06-27 | 2005-01-19 | 中国科学院兰州化学物理研究所 | Process for preparation of self-assembly lubricant film |
| CN101274222A (en) * | 2007-12-12 | 2008-10-01 | 浙江大学 | Dynamic self-assembled process for preparing low-pressure high-throughput charged nanofiltration membrane |
| WO2011026201A2 (en) * | 2009-09-04 | 2011-03-10 | Katholieke Universiteit Leuven | Metallic coatings on metallic substrates |
| CN101905122A (en) * | 2010-07-23 | 2010-12-08 | 北京工业大学 | Self-assembly method for high-load inorganic nano particle hybridized organic membrane |
| CN106237984A (en) * | 2016-07-29 | 2016-12-21 | 燕山大学 | A kind of method that graphene oxide and chemical modification thereof are prepared in diadust surface |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107081424A (en) | 2017-08-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107081424B (en) | A kind of thick titanium or thick titanium alloy powder injection moulding PP Pipe Compound and preparation method thereof | |
| CN107200583B (en) | A kind of porous material and preparation method thereof with porosity continuous gradient | |
| CN111732132A (en) | Nickel-cobalt-manganese core-shell structure precursor, preparation method thereof and positive electrode material | |
| CN104201359B (en) | Carbon-coated nano-antimony composite material as well as preparation method and application thereof | |
| US20160028089A1 (en) | Monolithic porous open-cell structures | |
| CN108788175B (en) | Spherical silver particles, method for producing same, conductive paste, and device comprising same | |
| CN101898749B (en) | Method for preparing metal oxide hollow particles or fibers | |
| CN110997198B (en) | Silver particles and method for producing same | |
| CN106495671B (en) | Cellulose nanocrystal modified ceramic green body and preparation method thereof | |
| CN102386391A (en) | Method for preparing ternary complex anode material (LiNixCoyMn1-x-yO2) | |
| CN110255629A (en) | A kind of preparation method of ultra-fine grain diameter cobaltosic oxide | |
| CN109692971A (en) | A kind of nano-silver powder and its preparation and the application in low-temperature cured conductive silver paste | |
| JPWO2019181788A1 (en) | Compound for positive electrode | |
| CN104016708B (en) | A kind of preparation method of high breaking strength earthenware supporter | |
| KR101222867B1 (en) | Anode support using spherical pore former and solid oxide fuel cell and the fabrication method therefor | |
| CN110391411B (en) | Nickel-cobalt sulfide/carbon composite material and preparation method and energy storage application thereof | |
| CN109396447B (en) | Hollow pipe forming method based on grain-size-graded titanium diboride and titanium gradient composite material | |
| CN111492513B (en) | Positive electrode active material for lithium secondary battery, method for preparing same, and lithium secondary battery comprising same | |
| KR101928809B1 (en) | Manufacturing method for catalyst structure using porous metal power | |
| CN110395978A (en) | A method of filtering molding machine and preparation ITO planar targets | |
| CN108573815B (en) | Preparation method of porous spherical NiO serving as electrode material of super capacitor | |
| CN103165361B (en) | A kind of preparation method containing cesium compound negative electrode and this negative electrode | |
| JP4524425B2 (en) | Ceramic nanoparticle-coated organic resin sphere particles, molded body thereof, porous ceramics, and production method thereof | |
| CN101950680B (en) | Nano nickel oxide composite electrode for super capacitor and preparation method thereof | |
| KR100581259B1 (en) | Method for Manufacturing Metal-Coated Amorphous Powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231020 Address after: Room 2102, Building 7, Wuyue Garden, Puji Street Office, Kangming Road, Wuhua District, Kunming City, Yunnan Province, 650000 Patentee after: Yunnan Lvao New Technology Development Co.,Ltd. Address before: 230000 floor 1, building 2, phase I, e-commerce Park, Jinggang Road, Shushan Economic Development Zone, Hefei City, Anhui Province Patentee before: Dragon totem Technology (Hefei) Co.,Ltd. Effective date of registration: 20231020 Address after: 230000 floor 1, building 2, phase I, e-commerce Park, Jinggang Road, Shushan Economic Development Zone, Hefei City, Anhui Province Patentee after: Dragon totem Technology (Hefei) Co.,Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: CHANGZHOU University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231127 Address after: 650031 No. 86 Yuantong North Road, Wuhua District, Yunnan, Kunming Patentee after: Kunming Metallurgical Research Institute Co.,Ltd. Address before: Room 2102, Building 7, Wuyue Garden, Puji Street Office, Kangming Road, Wuhua District, Kunming City, Yunnan Province, 650000 Patentee before: Yunnan Lvao New Technology Development Co.,Ltd. |