CN100436006C - Preparation method of rare metal alloy nanometer powder - Google Patents
Preparation method of rare metal alloy nanometer powder Download PDFInfo
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- CN100436006C CN100436006C CNB2004100367619A CN200410036761A CN100436006C CN 100436006 C CN100436006 C CN 100436006C CN B2004100367619 A CNB2004100367619 A CN B2004100367619A CN 200410036761 A CN200410036761 A CN 200410036761A CN 100436006 C CN100436006 C CN 100436006C
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- 229910001092 metal group alloy Inorganic materials 0.000 title claims abstract description 23
- 239000000843 powder Substances 0.000 title abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 239000002270 dispersing agent Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000001681 protective effect Effects 0.000 claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 12
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003223 protective agent Substances 0.000 claims abstract description 12
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims description 48
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 36
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 36
- 229910052786 argon Inorganic materials 0.000 claims description 18
- 239000001569 carbon dioxide Substances 0.000 claims description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000011858 nanopowder Substances 0.000 claims description 16
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- 239000000463 material Substances 0.000 claims description 9
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- 238000002441 X-ray diffraction Methods 0.000 claims description 7
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
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- 125000000524 functional group Chemical group 0.000 claims description 4
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
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- 239000000178 monomer Substances 0.000 claims description 3
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- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical group C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims 1
- 125000002243 cyclohexanonyl group Chemical group *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 3
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- 238000000576 coating method Methods 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 238000000875 high-speed ball milling Methods 0.000 description 10
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 6
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- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
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- 239000013078 crystal Substances 0.000 description 2
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- 238000004821 distillation Methods 0.000 description 2
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- 239000003112 inhibitor Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
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- 238000001228 spectrum Methods 0.000 description 2
- 239000011882 ultra-fine particle Substances 0.000 description 2
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- UGJMVKGHAJNSHF-UHFFFAOYSA-N [Ta].[Zr].[Nb].[Ti] Chemical compound [Ta].[Zr].[Nb].[Ti] UGJMVKGHAJNSHF-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 230000002500 effect on skin Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- PZQADQWPBJVVGH-UHFFFAOYSA-N niobium titanium zirconium Chemical compound [Ti].[Zr].[Nb] PZQADQWPBJVVGH-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- FAUWSVSZYKETJJ-UHFFFAOYSA-N palladium titanium Chemical compound [Ti].[Pd] FAUWSVSZYKETJJ-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- VSSLEOGOUUKTNN-UHFFFAOYSA-N tantalum titanium Chemical compound [Ti].[Ta] VSSLEOGOUUKTNN-UHFFFAOYSA-N 0.000 description 1
- WILOFBYLLUPEHC-UHFFFAOYSA-N tantalum titanium zirconium Chemical compound [Ti].[Zr].[Ta] WILOFBYLLUPEHC-UHFFFAOYSA-N 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention provides a preparation method for a rare metal alloy nanometer powder. In the method, one or several kinds of a tantalum powder, a zirconium powder, a niobium powder, a palladium powder and a titanium powder which are in different proportion are mixed with a dispersing agent according to certain proportion, and the powders with the dispersing agent are put in a bonding reactor; a protective agent is added and protective gas is led in a vertical planetary high-energy ball machine, a bonding reactant is added by opening an inlet valve after the powders are ground to a certain extent, bonding reaction is realized in a protective atmosphere, and nanometer rare metal is prepared by grinding and bonding reaction so as to prepare an active rare metal alloy nanometer powder with the grain size of 20 to 30 nm. The present invention also provides a special bonding reactor which realizes the grinding and the reaction in the same device; in the present invention, a bonding network-type rare metal alloy nanometer coating is developed on the basis of the prepared rare metal alloy nanometer powder with the grain size of 20 to 30 nm, and has the advantage of outstanding corrosion resistance.
Description
Technical field
The present invention proposes a kind of method for preparing titanium and rare metal nano material, belongs to the rare metal manufacture field.The present invention also comprises the bonding reaction device of structure uniqueness, under the condition of high-energy ball milling, makes rare metal tantalum, zirconium, niobium, palladium, titanium alloy nano particle under process conditions provided by the invention.
Background technology
Material supplier author pursues rare metal tantalum, zirconium, niobium, palladium, the titanium of most economical use costliness always and makes its corrosion resisting property with wide spectrum, anti-wear performance and combination property, the small-size effect of alloying nano particle, skin effect, quantum size effect make it to have unique sound, light, electricity, mechanical property, and the rare metal alloy nano material is rare metal characteristic and the nanometer technology cutting edge technology that combines.A kind of brand-new technology that the present invention just has been based on above-mentioned target design and device preparation tantalum, zirconium, niobium, palladium, titanium rare metal alloy nano particle, this new material application prospect is unusual tempting.We make it to combine with macromolecule and obtain a series of brand-new rare metal alloy nano paints at present, have wide spectrum excellent corrosion resistance can and the excellent comprehensive performance.
Summary of the invention
The object of the present invention is achieved like this; one or more mix by a certain percentage and add the bonding reaction device with rare metal tantalum, zirconium, niobium, palladium, titanium; add dispersant then; feed protective gas ball milling on the high-energy ball milling device; charging valve by the bonding reaction device behind the certain hour adds the bonding reaction agent; feed protective gas simultaneously, once more ball milling and realize ultra-fineization and the bonding reactionization of rare metal tantalum, zirconium, niobium, palladium, titanium alloy on the high-energy ball milling device.Bonding reactionization and ultra-fineization are associated; the rare metal alloy of ultra-fineization helps realizing bonding reaction, and the organic rare metal alloy ultrafine particle of surface bond surface in addition adsorbs the reunion that the rare metal alloy ultrafine particle can be contained and avoid to protective gas effectively.
Another object of the present invention provides one and is exclusively used in the rare metal alloy nano powder high-energy ball milling device of implementing said method.This device is a vertical-type planetary formula high energy ball mill.Four ball grinders that are parallel to each other are our custom-designed bonding reaction devices.
The bonding reaction device be stamped four special service valves, wherein two valves are used to feed protectant protection gas, two other valve is used to add the bonding reaction agent.On a device, can realize ultra-fineization and the bonding reactionization of rare metal tantalum, zirconium, niobium, palladium, titanium alloy so simultaneously.
More specifically, the invention provides a kind of rare metal alloy nano powder, wherein the percentage by weight of tantalum, zirconium, niobium, palladium and titanium is respectively 0-40,0-20,0-5,0-0.5,0-99, and the percentage by weight sum of each rare metal is 100; And the particle diameter that the particle diameter of this nano powder is measured by the X-ray diffraction method is not for being higher than 25nm.
The present invention also provides a kind of method for preparing the rare metal alloy nano powder of claim 1 or 2, comprises,
(1) prepare following material, wherein each material is by weight:
Rare metal mixed powder 100
Dispersant 50-600
Protective agent and protective gas 0.2-20
Bonding reaction agent 2-50
Wherein, in the described rare metal mixed powder, the percentage by weight of tantalum, zirconium, niobium, palladium and titanium is respectively 0-40,0-20,0-5,0-0.5,0-99;
Said dispersant is ketone, alcohols or their mixture;
Said protective agent is glycidol ethers reactive compound, polyol surfactant, polyethylene glycol type non-ionic surface active agent or their mixture;
Said protective gas is argon gas, carbon dioxide or their mixture;
Said bonding reaction agent is a kind of of following material or their mixture: the molecule two ends all contain the reactive compound (comprising oligomer) of functional group, contain the reactive compound (monomer) of ethylene linkage, silane coupler RSiX
3, wherein the R representative has affinity or respond organo-functional group with polymer molecule, and X represents hydrolyzable alkoxyl;
(2) the rare metal mixed powder that will be furnished with dispersant is put into the bonding reaction device, successively feeds protective agent and protective gas, and the bonding reaction agent, and ultra-fineization and bonding reaction in the vertical-type planetary high energy ball mill are produced black rare metal alloy nano powder.
Description of drawings
Fig. 1 is vertical star ball mill schematic diagram, wherein: 1 rotating belt, 2 motor pulleys, 3 motors, 4 belt pulleys, 5 pinions, 6 gear wheels, 7 star-disc, 8 rotary tables.Motor pulley drives gear wheel; gear wheel rotates and drives the rotary table rotation; the large gear turn the small gear rotates; pinion drives the star-disc rotation; and the ball grinder of fixing on the planetary plate (bonding reaction device); jar airtightly be stamped four terminal valves, wherein two be the needle valve of protective gas and protective agent turnover, other two be bonding reaction agent inlet valve.
Accompanying drawing 2 is the photo of high-resolution transmission microscopy to the alloy nano powder that records, and it is as follows to obtain information: most particle sizes do not wait from several nanometers to 30 nanometers, and average dimension is no more than 20 nanometers.The process and the bonding reaction process that should be pointed out that ultra-fineization of ball milling are complementary mobilism processes.Because nanocrystal bonding difunctional organic matter is so the crystal grain behind the bonding can form the micelle particle greater than crystal grain each other.But this is not the reunion between the nanocrystal.This point is found out from high resolution transmission electron microscopy.The effect of the formation of micelle particle and protective agent and protective gas makes the metastable reason of rare metal alloy nano powder just.
Accompanying drawing 3 is X-ray diffractograms of the nano powder that makes, can reach a conclusion is that the powder for preparing is a crystalline state, its grain size is calculated according to the Scherrer formula, and the grain size of three highest peaks on average about 20 nanometers, is seen the grain size of finding with high resolution electron microscope and coincide.
The specific embodiment
The preparation method's of the rare metal alloy nano powder that the present invention says core technology content is that the prescription of rare metal alloy nano powder is as follows: by weight
The mixed powder 100 of tantalum, zirconium, niobium, palladium, titanium valve
Dispersant 50-600
Protective agent and protective gas 0.2-20
Bonding reaction agent 2-50
Wherein said dispersant is one or more a mixture of ester class, ethers, ketone, aromatic compound, alcohols, cyclic hydrocar-bons.
Said protective agent is that an a kind of end is that active group one end is the reactive compound of the inertia group of long-chain, comprise glycidol ethers reactive compound, as n-butyl glycidyl ether, 2-ethylhexyl glycidol ether, to tert-butyl-phenyl glycidol ether etc.; Nonionic surfactants is as polyol surfactant: this Pan 80, this Pan 85, soil temperature 80, soil temperature 85 etc.; The polyethylene glycol type non-ionic surface active agent, as polyoxyethylene (10) nonylplenyl ether, polyoxyethylene (40) nonylplenyl ether etc., said protective gas is high-purity argon, helium and carbon dioxide gas.
Said bonding reaction agent is one or more of following material: the reactive compound of functional group is all contained at the molecule two ends, as contains the compound (comprising oligomer) of amino, cyano group, epoxy radicals, isocyanate group; The reactive compound (monomer) that contains ethylene linkage is as acrylonitrile, methacrylaldehyde, styrene, benzaldehyde etc.; Coupling agent compounds such as silane coupler RSiX
3, wherein the R representative has affinity or respond organo-functional group as amino, sulfydryl, vinyl, epoxy radicals, cyano group and methacryloxy etc. with polymer molecule, and X represents hydrolyzable alkoxyl.
The tantalum titanium mixture (5: 95) of 100 weight portions is put into the bonding reaction device; under flow 100ml/min; fed argon gas 15 minutes; fed carbon dioxide gas 30 minutes; the high speed ball milling added phenyl glycidyl ether 10 weight portions by charging valve after 1 hour; 150 weight portion dispersant cyclohexanone; simultaneously under flow 100ml/min, fed argon gas once more 15 minutes; carbon dioxide gas 30 minutes; high speed ball milling 1 hour; leave standstill to 40 ℃; add bonding reaction agent γ-glycidyl trimethoxy silane 5 weight portions (the 5/100 cyclohexanone solution of 100ml) by charging valve; under flow 100ml/min, fed carbon dioxide gas 30 minutes simultaneously; argon gas 15 minutes reduces 1/2 of former rotating speed with rotating speed, bonding reaction 2 hours; shut down; treat to take out after temperature is reduced to normal temperature, separate through high speed centrifugation, drying obtains powder solid under inert gas shielding.Measure through X-ray diffraction, crystallite dimension 21 nanometers, high-resolution-ration transmission electric-lens is measured particle size range 10-50 nanometer.
The tantalum zirconium titanium mixture (5: 15: 80) of 100 weight portions is put into the bonding reaction device; under flow 100ml/min; fed argon gas 15 minutes; fed carbon dioxide gas 30 minutes; behind the high speed ball milling 1 hour; add sorbitan mono-oleic acid ester 10 weight portions by charging valve; 200 weight portion n-butanol dispersants; simultaneously under flow 100ml/min, fed carbon dioxide gas once more 30 minutes; argon gas 15 minutes; high speed ball milling 1 hour; leave standstill to 40 ℃; open charging valve and add bonding reaction agent 6 parts by weight of styrene (polymerization inhibitor is removed in new distillation), under flow 100ml/min, fed carbon dioxide gas 30 minutes simultaneously; argon gas 15 minutes reduces 1/2 of former rotating speed with rotating speed; bonding reaction 2 hours is shut down.Treat to take out after temperature is reduced to normal temperature, separate through high speed centrifugation, drying obtains powder solid under inert gas shielding.Measure through X-ray diffraction, crystallite dimension 25 nanometers are measured particle size range 8-50 nanometer through high-resolution-ration transmission electric-lens.
The zirconium niobium titanium mixture (5: 15: 80) of 100 weight portions is put into the bonding reaction device; under flow 100ml/min; fed argon gas 15 minutes; fed carbon dioxide gas 30 minutes; behind the high speed ball milling 1 hour; add allyl glycidyl ether 10 weight portions by charging valve; 120 weight portion n-butanols; 80 weight portion butanone dispersants; simultaneously under flow 100ml/min, fed carbon dioxide gas once more 30 minutes; argon gas 15 minutes; high speed ball milling 1 hour; leave standstill to 40 ℃; open charging valve and add 5 weight portion bisphenol A diglycidyl ether bonding reaction agent, under flow 100ml/min, fed carbon dioxide gas 30 minutes simultaneously; argon gas 15 minutes reduces 1/2 of former rotating speed with rotating speed; bonding reaction 2 hours is shut down.Treat to take out after temperature is reduced to normal temperature, separate through high speed centrifugation, drying obtains powder solid under inert gas shielding.Measure through X-ray diffraction, crystallite dimension 22 nanometers are measured particle size range 10-40 nanometer through high-resolution-ration transmission electric-lens.
With the tantalum zirconium niobium titanium mixture of 100 weight portions (5: 15: 5: 80) put into the bonding reaction device; under flow 100ml/min; fed argon gas 15 minutes; fed carbon dioxide gas 30 minutes; behind the high speed ball milling 1 hour; add tert-butyl-phenyl glycidol ether 12 weight portions by charging valve; 100 weight portion cyclohexanone dispersants; simultaneously under flow 100ml/min, fed carbon dioxide gas once more 30 minutes; argon gas 15 minutes; high speed ball milling 1 hour; leave standstill to 40 ℃; open charging valve and add bonding reaction agent hexamethylene diisocyanate 8 weight portions (the 10/100 cyclohexanone solution of 80ml), under flow 100ml/min, fed carbon dioxide gas 30 minutes simultaneously; argon gas 15 minutes reduces 1/2 of former rotating speed with rotating speed; bonding reaction 2 hours is shut down.Treat to take out after temperature is reduced to normal temperature, separate through high speed centrifugation, drying obtains powder solid under inert gas shielding.Measure through X-ray diffraction, crystallite dimension 20 nanometers are measured particle size range 10-50 nanometer through high-resolution-ration transmission electric-lens.
The palladium titanium mixture (0.2: 99.8) of 100 weight portions is put into the bonding reaction device; under flow 100ml/min; fed argon gas 15 minutes; fed carbon dioxide gas 30 minutes; behind the high speed ball milling 1 hour; add polyoxyethylene (10) nonylplenyl ether 1 weight portion by charging valve; phenyl glycidyl ether 10 weight portions; 100 weight portion n-butanols and 50 weight portion pentanone-2 dispersants; simultaneously under flow 100ml/min, fed carbon dioxide gas once more 30 minutes; argon gas 15 minutes; high speed ball milling 1 hour; leave standstill to 40 ℃; open charging valve and add acrylic acid 2-hydroxy methacrylate 8 weight portions (removing polymerization inhibitor), under flow 100ml/min, fed carbon dioxide gas 30 minutes simultaneously through distillation; argon gas 15 minutes reduces 1/2 of former rotating speed with rotating speed; bonding reaction 2 hours is shut down.Treat to take out after temperature is reduced to normal temperature, separate through high speed centrifugation, drying obtains powder solid under inert gas shielding.Measure through X-ray diffraction, crystallite dimension 22 nanometers are measured particle size range 10-50 nanometer through high-resolution-ration transmission electric-lens.
The used bonding reaction device of the present invention is the ball grinder of a vertical-type planetary high-energy ball milling equipment; it possesses ultra-fineization and bonding reaction function simultaneously; expect the rare metal nano material of ideal dimensions state; must strict provide relevant technological parameter, particularly will under protective gas atmosphere, carry out with reference to example.
Claims (9)
1. rare metal alloy nano powder, wherein the percentage by weight of tantalum, zirconium, niobium, palladium and titanium is respectively 0-40,0-20,0-5,0-0.5,0-99, and the percentage by weight sum of each rare metal is 100; And the particle diameter that the particle diameter of this nano powder is measured by the X-ray diffraction method is not for being higher than 25nm.
2. the rare metal alloy nano powder of claim 1, wherein the percentage by weight of titanium is 80-95.
3. a method for preparing the rare metal alloy nano powder of claim 1 or 2 comprises,
(1) prepare following material, wherein each material is by weight:
Rare metal mixed powder 100
Dispersant 50-600
Protective agent and protective gas 0.2-20
Bonding reaction agent 2-50
Wherein, in the described rare metal mixed powder, the percentage by weight of tantalum, zirconium, niobium, palladium and titanium is respectively 0-40,0-20,0-5,0-0.5,0-99;
Said dispersant is ketone, alcohols or their mixture;
Said protective agent is glycidol ethers reactive compound, polyol surfactant, polyethylene glycol type non-ionic surface active agent or their mixture;
Said protective gas is argon gas, carbon dioxide or their mixture;
Said bonding reaction agent is a kind of of following material or their mixture: the molecule two ends all contain the reactive compound of functional group, contain the reactive compound of ethylene linkage, silane coupler RSiX
3, wherein the R representative has affinity or respond organo-functional group with polymer molecule, and X represents hydrolyzable alkoxyl;
(2) the rare metal mixed powder that will be furnished with dispersant is put into the bonding reaction device, successively feeds protective agent and protective gas, and the bonding reaction agent, and ultra-fineization and bonding reaction in the vertical-type planetary high energy ball mill are produced black rare metal alloy nano powder.
4. the method for claim 3, wherein dispersant is cyclohexanone, butanone, pentanone, n-butanol or their mixture.
5. the method for claim 3, wherein protective agent be phenyl glycidyl ether, allyl glycidyl ether, to tert-butyl-phenyl glycidol ether, sorbitan mono-oleic acid ester, polyoxyethylene (10) nonylplenyl ether or their mixture.
6. the method for claim 3, wherein the bonding reaction agent is bisphenol A diglycidyl ether, hexamethylene diisocyanate, styrene, acrylic acid 2-hydroxy methacrylate, r-glycidyl trimethoxy silane or their mixture.
7. the method for claim 3, wherein in described rare metal mixed powder, the percentage by weight of titanium is 80-95.
8. the method for claim 3, wherein the molecule two ends reactive compound that all contains functional group comprises oligomer.
9. the method for claim 3, the reactive compound that wherein contains ethylene linkage is a monomer.
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| CN101081434B (en) * | 2006-05-29 | 2010-08-04 | 长沙科星纳米工程技术有限公司 | Method for preparing titanium alloy nanometer powder |
| CN101857192B (en) * | 2010-05-19 | 2012-10-31 | 许德成 | Titanium/rare earth hybrid nanomaterial and method for preparing same |
| CN103192086B (en) * | 2012-01-10 | 2015-05-13 | 中国科学院宁波材料技术与工程研究所 | Preparation method for controllable duplex metal alloy nano particle |
| CN106141164A (en) * | 2015-04-22 | 2016-11-23 | 薛俊峰 | A kind of preparation method of nm-class Ti polymer |
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