CN107081424A - A kind of titanium alloy powder injection moulding PP Pipe Compound and preparation method thereof - Google Patents
A kind of titanium alloy powder injection moulding PP Pipe Compound and preparation method thereof Download PDFInfo
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- CN107081424A CN107081424A CN201710299684.3A CN201710299684A CN107081424A CN 107081424 A CN107081424 A CN 107081424A CN 201710299684 A CN201710299684 A CN 201710299684A CN 107081424 A CN107081424 A CN 107081424A
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- titanium alloy
- alloy powder
- titanium
- injection moulding
- pipe compound
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 115
- 239000000843 powder Substances 0.000 title claims abstract description 112
- 238000001746 injection moulding Methods 0.000 title claims abstract description 35
- 150000001875 compounds Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 94
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 73
- 238000005238 degreasing Methods 0.000 claims abstract description 40
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000010936 titanium Substances 0.000 claims abstract description 37
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 36
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 30
- 239000011258 core-shell material Substances 0.000 claims abstract description 25
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 25
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 230000004048 modification Effects 0.000 claims abstract description 17
- 238000012986 modification Methods 0.000 claims abstract description 17
- 239000008187 granular material Substances 0.000 claims abstract description 14
- 229920000867 polyelectrolyte Polymers 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
- 238000000034 method Methods 0.000 claims description 14
- 229920000447 polyanionic polymer Polymers 0.000 claims description 11
- -1 polypropylene 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
- 239000011230 binding agent 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
- 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
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 8
- 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
- 238000002156 mixing Methods 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
- 238000005034 decoration Methods 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 229920001038 ethylene copolymer Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 229920005596 polymer binder Polymers 0.000 abstract description 3
- 239000002491 polymer binding agent Substances 0.000 abstract description 3
- 238000004663 powder metallurgy Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 239000000853 adhesive Substances 0.000 description 24
- 230000001070 adhesive effect Effects 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 230000009102 absorption Effects 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000005038 ethylene vinyl acetate Substances 0.000 description 7
- 229920001200 poly(ethylene-vinyl acetate) Polymers 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
- 239000003795 chemical substances by application Substances 0.000 description 6
- 235000019580 granularity Nutrition 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000013461 design Methods 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
- 238000011160 research Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 230000008468 bone growth Effects 0.000 description 2
- 230000010261 cell 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
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 229920002521 macromolecule Polymers 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
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000024245 cell differentiation Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 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
- 238000002242 deionisation method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008202 granule composition Substances 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
- 239000002052 molecular layer Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003746 surface roughness Effects 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Powder Metallurgy (AREA)
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.Only need to carry out surface modification to thick titanium or titanium alloy powder, use simple layer-by-layer, titanium dioxide granule and polyelectrolyte are incorporated 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 prepare the titanium alloy product of low cost, low-shrinkage, low frit density and loose structure.
Description
Technical field
The invention belongs to high polymer binder material and field of powder metallurgy, and in particular to a kind of titanium alloy powder is injected into
Type PP Pipe Compound and preparation method thereof.
Background technology
Metal powder injection molding (MIM) is the production skill that a kind of magnanimity prepares micro metal part with complex shape
Art.The research of modern MIM technologies starts from phase early 1970s, 1980s mid-term, due to raw material production cost
Decline and binding agent design theory and the theoretical continuous Improvement of degreasing, MIM technologies are developed rapidly and turn into current
Most popular note type process technology, is widely used in a variety of industries such as Aero-Space, automobile, computer, instrument and meter.China
The research and application of MIM technologies are started late, and since phase late 1980s, and achieve a series of achievement in research.
Metal powder injection molding has design flexibility, it is possible to reduce waste of material, and these advantages cause MIM to turn into life
Produce one of titanium alloy component technique of greatest concern.There are some technical problems when preparing titanium alloy component, such as making
The cost of the fine powder powder stock of standby titanium alloy component is higher；Titanium or titanium alloy at relatively high temperatures there is very high reaction to live
Property, easily the catabolite with the adhesive during thermal debinding and sintering reacts so that a part of titanium or titanium alloy are suitable
In being etched, cause high interstitial content；Powder generally in injection moulding using particle diameter less than 45 μm, so as in sample
It is interior produce minimum porosity and close to the density of theoretical value to improve mechanical performance, but titanium alloy powder particle diameter 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 cause more contractions, because the particle used is smaller, sintering rate is bigger, sinter finer and close.
The content of the invention
The invention provides a kind of titanium alloy powder injection moulding PP Pipe Compound, wherein, the titanium alloy powder in PP Pipe Compound is
Coreshell type structure, specially polyelectrolyte/titanium dioxide multilayer film modified thick titanium or titanium alloy powder particle, shell is by formula A1
Polyanion electrolyte and titanium dioxide granule LBL self-assembly shown in shown branched polyethylene imine, formula A2 are formed,
Formula A1 is
Formula A2 is
The particle diameter of thick titanium or titanium alloy powder particle is 60-75 μm,
The weight average molecular weight M of branched polyethylene iminewIn 10000-100000,
Polyanion electrolyte is in sodium carboxymethylcellulose, polyacrylic acid, Sodium Polyacrylate, poly (sodium 4-styrenesulfonate)
One or more kinds of mixtures, wherein the weight average molecular weight of each composition be 10000,16000,70000 or 75000,
The particle diameter of titanium dioxide granule is 20nm~50nm.
Present invention also offers a kind of preparation method of above-mentioned titanium alloy powder injection moulding PP Pipe Compound, it is not necessary to uses into
The higher thin titanium alloy powder of sheet (<45 μm), it is only necessary to surface modification is carried out to thick titanium or titanium alloy powder, simple layer is used
Layer self-assembling technique, existing thick titanium or titanium alloy powder particle surface are incorporated into by titanium dioxide granule and polyelectrolyte, are made
The standby thick titanium or titanium alloy powder particle for obtaining core shell structure, is carried out in aqueous, and generation environment does not pollute；Again by with height
It is close that molecular binder mixing, powder injection-molded, catalysis degreasing and vacuum-sintering prepare low cost, low-shrinkage, low frit
The titanium alloy product of degree and loose structure, realizes and is used as bio-medical implant, be applied to bone growth and cell adherence
Deng field,
Concretely comprise the following steps：
(1) surface modification is carried out to thick titanium or titanium alloy powder particle by the layer-by-layer of static-electronic driving,
The branched polyethylene imine shown in formula A1 is first chemically adsorbed to thick titanium or titanium alloy powder particle surface, then at this
Branched polyethylene imine surface is using the polyanion electrolyte shown in electrostatic interaction absorption type A2, with electronegative poly- after this
The titanium dioxide granule of anion electrolyte adsorption positively charged, by multiple alternating deposit polyanion electrolyte and dioxy
Change hud typed thick titanium or the titanium alloy powder particle that plural layers modification is obtained after titanium particle,
Step (1) is carried 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%,
, can be with metal and metal surface because branched polyethylene imine organic polymer is rich in amino in this step
Harsh chemical effect occurs for hydroxyl, in thick titanium or titanium alloy powder particle surface one floor height molecular layer of formation；Water miscible poly- the moon
Ionic electrolytes macromolecule can be adsorbed onto thick titanium or titanium alloy by the electrostatic interaction with the branched polyethylene imine of positive charge
Powder particle surface；Titanium dioxide granule is positively charged in aqueous, can further be adsorbed and deposited to by electrostatic interaction
Surface, the polyelectrolyte and titanium dioxide granule of alternating deposit oppositely charged, so as to realize to thick titanium or titanium alloy powder
The surface modification formation core shell structure of grain, by regulating and controlling the number of plies of deposition, can regulate and control the thickness of titanium alloy powder particle shell；
(2) hud typed thick titanium or the titanium alloy powder particle and catalysis degreasing of plural layers modification will be obtained in step (1)
Type binding agent is kneaded, then prepares titanium alloy powder injection moulding PP Pipe Compound by injection moulding, catalysis degreasing, vacuum-sintering,
The weight ratio of hud typed thick titanium or titanium alloy powder particle and catalysis degreasing type adhesive is 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, such 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 titanium alloy powder particle prepares special with catalysis degreasing type adhesive through mixing
Material, green compact are turned into through injection moulding, shell structurre after turning into degreasing base through catalysis degreasing removing macromolecule, sintered through high-temperature vacuum
Middle organic polymer is substantially completely removed, and leaves the stable inorganic titanium dioxide granule composition micro channel of chemical property, average hole
Footpath scope is at 0.8~2 μm, by regulating and controlling the thickness of shell, i.e. polyelectrolyte/titanium dioxide multilayer film number of plies, can obtain not
With pore size and the loose structure titanium alloy product of distributed degrees.
The beneficial effects of the present invention are：It is special that layer-by-layer is introduced titanium alloy powder injection moulding by the present invention
In the preparation process of material, to (60-75 μm) progress surface modification of thick titanium or titanium alloy powder particle, core shell structure is formed, due to
Multiple alternating deposit forms coating on surface, and this can cause surface for thick titanium or titanium alloy powder particulate material
The decline of roughness, but when the organic principle in shell structurre is being removed after catalysis degreasing and vacuum-sintering, leave
Inorganic TiO 2 porous channel design with cavity, forms more coarse top layer, and the micro channel by being connected with each other
Composition, its average pore size titanium thicker than commercial materials or the big several times of titanium alloy powder particle,
And the formation of pore structure, surface roughness and specific surface area are added there is provided cell growth and the space of breeding,
Contribute to the absorption, growth and differentiation of cell, bio-medical implant can be met to bone growth and cell adherence etc.
The demand in field；
The present invention directly larger thick titanium or titanium alloy powder particle of use particle diameter, reduces cost, ensure that powder compared with
Low reactivity, oxygen uptake is less, it is not easy to polluted by degreasing with binding agent analyte in sintering process, along with top layer
The titanium dioxide property of modification is also sufficiently stable, will not equally occur to chemically react and be contaminated, and closes the titanium finally given
Golden product impurity and oxygen content are low, more advantageous with compared with low-shrinkage；
The present invention uses simple layer-by-layer, is carried out in water environment, and generation environment does not pollute.
Brief description of the drawings
During Fig. 1 is embodiment 1, by QCM study on branched polyethylene imine surface deposition multilayer film from
Frequency variation diagram during assembling process.
Fig. 2 is in embodiment 2, step (2) kneads core shell structure titanium alloy powder particle and catalysis degreasing type adhesive
Afterwards, the rheological property of mixture, it can be seen that the viscosity of the mixture declines with the rise of shear rate, shows false modeling
The rheological behaviour of property fluid, so that ensureing that the mixture can fully flow is filled to dies cavity, prepares the titanium and titanium of thin-walled
Alloy product.
Fig. 3 be the step of embodiment 3 (2) in, the SEM shape appearance figures of the loose structure titanium alloy product obtained after vacuum-sintering.
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) adsorbed 30 minutes in the aqueous solution, particle is 1 with aqueous solution mass ratio: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 was 1 with aqueous solution mass ratio:4, then washed 10 minutes with deionized water again, adding 1g/L band just
The TiO of electric charge2Adsorbed 30 minutes in (particle diameter 20nm) dispersion liquid, particle is 1 with aqueous dispersions mass ratio: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, the nucleocapsid knot after modification altogether
The drying of structure titanium alloy powder particle is stand-by,
Fig. 1 shows the self assembly studied using QCM and multilayer film is deposited on branched polyethylene imine surface
Process, it is observed that often adsorbing a strata electrolyte or TiO2, frequency declines, under frequency generation is steps after alternating deposit
Drop, shows that steps increase is presented in the quality of adsorption；
(2) according to the mass ratio 56 of core shell structure titanium alloy powder particle and catalysis degreasing type adhesive：44, first by step
(1) the core shell structure titanium alloy powder particle obtained in adds 170 DEG C of preheating 5min in torque rheometer, and rotating speed is 15r/min,
Add catalysis degreasing type adhesive thereto again same under the conditions of 170 DEG C, kneaded 30 minutes with 15r/min rotating speed, then pass through
Injection moulding is crossed, and in carrying out nitric acid catalysis degreasing 6h at 120 DEG C, titanium alloy powder injection is obtained after 1200 DEG C of vacuum-sintering
It is molded PP Pipe Compound,
Catalysis degreasing type adhesive each component in the present embodiment is count by weight percentage：It is polyformaldehyde 85%, conformal
Agent polypropylene 6%, ethylene-vinyl acetate copolymer 4%, stabilizer copolymerized methanal 1%, 1790 antioxidant 1%, lithium stearate
1%th, lubricant 2%.
As shown in table 1, sintered density will for the physical property of titanium alloy powder injection moulding PP Pipe Compound manufactured in the present embodiment
Less than the 4.38g/cm of raw materials used thick titanium alloy powder particle in step (1)3, this explanation titanium alloy particle surface is provided with slightly
The bigger loose structure of rugosity.
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
Adsorbed 30 minutes in the aqueous solution, particle is 1 with aqueous solution mass ratio:4, then with deionized water to thick titanium alloy powder particle water
Wash 10 minutes, be subsequently added to 1.03g/L 30 points of electronegative sodium cellulose glycolate (Mw=16000) adsorption from aqueous solution
Clock, particle is 1 with aqueous solution mass ratio:4, then washed 10 minutes with deionized water again, add the positively charged of 2g/L
TiO2Adsorbed 30 minutes in (particle diameter 30nm) dispersion liquid, particle is 1 with aqueous dispersions mass ratio:4, finally washed with deionized water
10 minutes, using above-mentioned technique totally 8 alternating deposit sodium cellulose glycolates and TiO2, inhale thick titanium alloy powder particle surface
Agglomeration electrolyte/titanium dioxide multilayer film, the absorption number of plies is 17 layers altogether, the core shell structure titanium alloy powder particle drying after modification
It is stand-by；
(2) according to the mass ratio 54 of core shell structure titanium alloy powder particle and catalysis degreasing type adhesive：46, first by step
(1) the core shell structure titanium alloy powder particle obtained in adds 170 DEG C of preheating 5min in torque rheometer, and rotating speed is 15r/min,
Add catalysis degreasing type adhesive thereto again same under the conditions of 170 DEG C, kneaded 30 minutes with 15r/min rotating speed, then pass through
Injection moulding is crossed, and in carrying out nitric acid catalysis degreasing 6h at 120 DEG C, titanium alloy powder injection is obtained after 1200 DEG C of vacuum-sintering
It is molded PP Pipe Compound,
Catalysis degreasing type adhesive each component in the present embodiment is count by weight percentage：It is polyformaldehyde 86%, conformal
Agent polypropylene 6%, ethylene-vinyl acetate copolymer 3%, stabilizer copolymerized methanal 1%, 1790 antioxidant 1%, lithium stearate
1%th, lubricant 2%.
The physical property of titanium alloy powder injection moulding PP Pipe Compound manufactured in the present embodiment is as shown in table 1, with the phase of embodiment 1
Compare, because the film layer number of surface modification increases to 17 layers in the present embodiment, titanium alloy useful load declines, so cubical contraction
Rise, yield stress reduction, sintered density reduction, aperture size increase.
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
Adsorbed 30 minutes in the aqueous solution, particle is 1 with aqueous solution mass ratio:4, then with deionized water to thick titanium alloy powder particle water
Wash 10 minutes, be subsequently added to 1.5g/L electronegative polyacrylic acid (Mw=70000) adsorption from aqueous solution 30 minutes, particle with
Aqueous solution mass ratio is 1:4, then washed 10 minutes with deionized water again, add 3g/L positively charged TiO2(particle diameter
40nm) adsorbed 30 minutes in dispersion liquid, particle is 1 with aqueous dispersions mass ratio:4, finally washed 10 minutes, adopted with deionized water
With above-mentioned technique totally 11 alternating deposit polyacrylic acid and TiO2, make thick titanium alloy powder particle surface absorption polyelectrolyte/bis-
Titanium oxide multilayer film, the absorption number of plies is 23 layers altogether, and the core shell structure titanium alloy powder particle drying after modification is stand-by；
(2) according to the mass ratio 52 of core shell structure titanium alloy powder particle and catalysis degreasing type adhesive：48, first by step
(1) the core shell structure titanium alloy powder particle obtained in adds 170 DEG C of preheating 5min in torque rheometer, and rotating speed is 15r/min,
Add catalysis degreasing type adhesive thereto again same under the conditions of 170 DEG C, kneaded 30 minutes with 15r/min rotating speed, then pass through
Injection moulding is crossed, and in carrying out nitric acid catalysis degreasing 6h at 120 DEG C, titanium alloy powder injection is obtained after 1200 DEG C of vacuum-sintering
It is molded PP Pipe Compound,
Catalysis degreasing type adhesive each component in the present embodiment is count by weight percentage：It is polyformaldehyde 87%, conformal
Agent polypropylene 6%, ethylene-vinyl acetate copolymer 2%, stabilizer copolymerized methanal 1%, 1790 antioxidant 1%, lithium stearate
1%th, 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
Adsorbed 30 minutes in the aqueous solution, particle is 1 with aqueous solution mass ratio:4, then with deionized water to thick titanium alloy powder particle water
Wash 10 minutes, be subsequently added to 2g/L electronegative Sodium Polyacrylate (Mw=75000) adsorption from aqueous solution 30 minutes, particle with
Aqueous solution mass ratio is 1:4, then washed 10 minutes with deionized water again, add 4g/L positively charged TiO2(particle diameter
50nm) adsorbed 30 minutes in dispersion liquid, particle is 1 with aqueous dispersions mass ratio:4, finally washed 10 minutes, adopted with deionized water
With above-mentioned technique totally 3 alternating deposit Sodium Polyacrylates and TiO2, make thick titanium alloy powder particle surface absorption polyelectrolyte/bis-
Titanium oxide multilayer film, the absorption number of plies is 7 layers altogether, and the core shell structure titanium alloy powder particle drying after modification is stand-by；
(2) according to the mass ratio 50 of core shell structure titanium alloy powder particle and catalysis degreasing type adhesive：50, first by step
(1) the core shell structure titanium alloy powder particle obtained in adds 170 DEG C of preheating 5min in torque rheometer, and rotating speed is 15r/min,
Add catalysis degreasing type adhesive thereto again same under the conditions of 170 DEG C, kneaded 30 minutes with 15r/min rotating speed, then pass through
Injection moulding is crossed, and in carrying out nitric acid catalysis degreasing 6h at 120 DEG C, titanium alloy powder injection is obtained after 1200 DEG C of vacuum-sintering
It is molded PP Pipe Compound,
Catalysis degreasing type adhesive each component in the present embodiment is count by weight percentage：It is polyformaldehyde 88%, conformal
Agent polypropylene 6%, ethylene-vinyl acetate copolymer 1%, stabilizer copolymerized methanal 1%, 1790 antioxidant 1%, lithium stearate
1%th, lubricant 2%.
Embodiment 5
(1) the thick titanium alloy powder of 60 μm of granularities is placed in the branched polyethylene imine (Mw=100000) that concentration is 2g/L
Adsorbed 30 minutes in the aqueous solution, particle is 1 with aqueous solution mass ratio:4, then with deionized water to thick titanium alloy powder particle water
Wash 10 minutes, be subsequently added to 0.5g/L 30 points of electronegative poly (sodium 4-styrenesulfonate) (Mw=70000) adsorption from aqueous solution
Clock, particle is 1 with aqueous solution mass ratio:4, then washed 10 minutes with deionized water again, add the positively charged of 5g/L
TiO2Adsorbed 30 minutes in (particle diameter 40nm) dispersion liquid, particle is 1 with aqueous dispersions mass ratio:4, finally washed with deionized water
10 minutes, using above-mentioned technique totally 4 alternating deposit poly (sodium 4-styrenesulfonate)s and TiO2, make thick titanium alloy powder particle surface
Polyelectrolyte/titanium dioxide multilayer film is adsorbed, the absorption number of plies is 9 layers altogether, and the core shell structure titanium alloy powder particle after modification dries
It is dry stand-by；
(2) according to the mass ratio 55 of core shell structure titanium alloy powder particle and catalysis degreasing type adhesive：45, first by step
(1) the core shell structure titanium alloy powder particle obtained in adds 170 DEG C of preheating 5min in torque rheometer, and rotating speed is 15r/min,
Add catalysis degreasing type adhesive thereto again same under the conditions of 170 DEG C, kneaded 30 minutes with 15r/min rotating speed, then pass through
Injection moulding is crossed, and in carrying out nitric acid catalysis degreasing 6h at 120 DEG C, titanium alloy powder injection is obtained after 1200 DEG C of vacuum-sintering
It is molded PP Pipe Compound,
Catalysis degreasing type adhesive each component in the present embodiment is count by weight percentage：It is polyformaldehyde 84%, conformal
Agent polypropylene 7%, ethylene-vinyl acetate copolymer 4%, stabilizer copolymerized methanal 1%, 1790 antioxidant 1%, lithium stearate
1%th, 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
Adsorbed 30 minutes in the aqueous solution, particle is 1 with aqueous solution mass ratio:4, then with deionized water to thick titanium alloy powder particle water
Wash 10 minutes, be subsequently added to 1.03g/L 30 points of electronegative poly (sodium 4-styrenesulfonate) (Mw=75000) adsorption from aqueous solution
Clock, particle is 1 with aqueous solution mass ratio:4, then washed 10 minutes with deionized water again, add the positively charged of 7g/L
TiO2Adsorbed 30 minutes in (particle diameter 50nm) dispersion liquid, particle is 1 with aqueous dispersions mass ratio:4, finally washed with deionized water
10 minutes, using above-mentioned technique totally 12 alternating deposit poly (sodium 4-styrenesulfonate)s and TiO2, make thick titanium alloy powder particle table
Polyelectrolyte/titanium dioxide multilayer film is adsorbed in face, and the absorption number of plies is 25 layers, the core shell structure titanium alloy powder particle after modification altogether
Drying is stand-by；
(2) according to the mass ratio 50 of core shell structure titanium alloy powder particle and catalysis degreasing type adhesive：50, first by step
(1) the core shell structure titanium alloy powder particle obtained in adds 170 DEG C of preheating 5min in torque rheometer, and rotating speed is 15r/min,
Add catalysis degreasing type adhesive thereto again same under the conditions of 170 DEG C, kneaded 30 minutes with 15r/min rotating speed, then pass through
Injection moulding is crossed, and in carrying out nitric acid catalysis degreasing 6h at 120 DEG C, titanium alloy powder injection is obtained after 1200 DEG C of vacuum-sintering
It is molded PP Pipe Compound,
Catalysis degreasing type adhesive each component in the present embodiment is count by weight percentage：It is polyformaldehyde 87%, conformal
Agent polypropylene 6%, ethylene-vinyl acetate copolymer 2%, stabilizer copolymerized methanal 1%, 1790 antioxidant 1%, lithium stearate
1%th, lubricant 2%.
Table 1
Comparative example 1
(1) corresponding adhesive substance is selected to be well mixed with particle diameter 40nm titanium dioxide granule and be coated to 70 μm of grains
Content of titanium dioxide be the same as Example 3 in the thick titanium alloy powder particle surface of degree, control coating thickness and clad；
(2) be the same as Example 3, as a result in vacuum-sintering, clad is completely fallen off, and causes the titanium alloy powder finally obtained
Injection moulding PP Pipe Compound is unrealized expected modified.
Claims (10)
1. a kind of titanium alloy powder injection moulding PP Pipe Compound, it is characterised in that：Titanium alloy in described injection moulding PP Pipe Compound
Powder is coreshell type structure, specially polyelectrolyte/titanium dioxide multilayer film modified thick titanium or titanium alloy powder particle, shell
Formed by branched polyethylene imine, polyanion electrolyte and titanium dioxide granule LBL self-assembly.
2. titanium alloy powder injection moulding PP Pipe Compound as claimed in claim 1, it is characterised in that：Described thick titanium or titanium alloy
The particle diameter of powder particle is 60-75 μm.
3. titanium alloy powder injection moulding PP Pipe Compound as claimed in claim 1, it is characterised in that：Described polyanion electrolysis
Matter is more than one or both of sodium carboxymethylcellulose, polyacrylic acid, Sodium Polyacrylate, poly (sodium 4-styrenesulfonate) mixed
Compound.
4. titanium alloy powder injection moulding PP Pipe Compound as claimed in claim 1, it is characterised in that：Described titanium dioxide granule
Particle diameter be 20nm~50nm.
5. a kind of preparation method of titanium alloy powder injection moulding PP Pipe Compound as described in any one of Claims 1-4, its feature
It is：Described preparation method is, using layer-by-layer, by titanium dioxide granule and polyelectrolyte be incorporated into thick titanium or
In titanium alloy powder grain structure, the thick titanium or titanium alloy powder particle of core shell structure are prepared；Again with binding agent mixing, powder
Last injection moulding, catalysis degreasing, vacuum-sintering.
6. the preparation method of titanium alloy powder injection moulding PP Pipe Compound as claimed in claim 5, it is characterised in that：It is described to prepare
Method is concretely comprised the following steps,
(1) surface modification is carried out to thick titanium or titanium alloy powder particle by the layer-by-layer of static-electronic driving,
Branched polyethylene imine is first chemically adsorbed to thick titanium or titanium alloy powder particle surface, then at the branched polyethylene imine
Surface using electrostatic interaction adsorb polyanion electrolyte, with after the electronegative polyanion electrolyte adsorption band just
The titanium dioxide granule of electricity, after multiple alternating deposit polyanion electrolyte and titanium dioxide granule obtaining plural layers repaiies
Hud typed thick titanium or the titanium alloy powder particle of decorations；
(2) hud typed thick titanium or the titanium alloy powder particle that plural layers modification is obtained in step (1) is kneaded with binding agent, then
Titanium alloy powder injection moulding PP Pipe Compound is prepared by injection moulding, catalysis degreasing, vacuum-sintering.
7. the preparation method of titanium alloy powder injection moulding PP Pipe Compound as claimed in claim 6, it is characterised in that：Step (1)
Carried out in aqueous dispersions environment, branched polyethylene imine, polyanion electrolyte, titanium dioxide granule are in aqueous dispersions
Mass percent is respectively 0.2-0.5%, 0.05-0.2%, 0.1-0.7%.
8. the preparation method of titanium alloy powder injection moulding PP Pipe Compound as claimed in claim 6, it is characterised in that：Step (2)
In, the weight ratio of hud typed thick titanium or titanium alloy powder particle and binding agent is 50~56：44~50.
9. the preparation method of titanium alloy powder injection moulding PP Pipe Compound as claimed in claim 6, it is characterised in that：Step (2)
Described in binding agent in each component include count by weight percentage, polyformaldehyde 85%, conformal dose of polypropylene 6~8%, second
Alkene-acetate ethylene copolymer 2~4%, stabilizer copolymerized methanal 1%, antioxidant 1%, lithium stearate 1%, lubricant 2%.
10. the preparation method of titanium alloy powder injection moulding PP Pipe Compound as claimed in claim 6, it is characterised in that：Step (2)
In, vacuum-sintering temperature is 1200 DEG C.
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Cited By (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 |
| CN114015905A (en) * | 2021-11-04 | 2022-02-08 | 安徽有研吸气材料有限公司 | Process for preparing nano-grade zirconium-based non-evaporable getter material |
Citations (6)
| 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 |
| US20130164346A1 (en) * | 2011-12-22 | 2013-06-27 | Kwungpook National University Industry Academic Cooperation Foundation | Method for preparing biomedical metal alloy material with multi-drug delivery system |
| 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 |
-
2017
- 2017-05-02 CN CN201710299684.3A patent/CN107081424B/en active Active
Patent Citations (6)
| 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 |
| US20130164346A1 (en) * | 2011-12-22 | 2013-06-27 | Kwungpook National University Industry Academic Cooperation Foundation | Method for preparing biomedical metal alloy material with multi-drug delivery system |
| 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 |
Cited By (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 |
| CN114015905A (en) * | 2021-11-04 | 2022-02-08 | 安徽有研吸气材料有限公司 | Process for preparing nano-grade zirconium-based non-evaporable getter material |
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