CN107128921A - A kind of method for preparing niobium tungsten binary double carbide nano powder - Google Patents
A kind of method for preparing niobium tungsten binary double carbide nano powder Download PDFInfo
- Publication number
- CN107128921A CN107128921A CN201710270171.XA CN201710270171A CN107128921A CN 107128921 A CN107128921 A CN 107128921A CN 201710270171 A CN201710270171 A CN 201710270171A CN 107128921 A CN107128921 A CN 107128921A
- Authority
- CN
- China
- Prior art keywords
- powder
- niobium
- tungsten
- niobium tungsten
- double carbide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- GAYPVYLCOOFYAP-UHFFFAOYSA-N [Nb].[W] Chemical compound [Nb].[W] GAYPVYLCOOFYAP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000011858 nanopowder Substances 0.000 title claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 88
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002131 composite material Substances 0.000 claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 33
- 239000013049 sediment Substances 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 23
- KQJUULBHUBLISU-UHFFFAOYSA-N [O-2].[Nb+5].[W+4] Chemical compound [O-2].[Nb+5].[W+4] KQJUULBHUBLISU-UHFFFAOYSA-N 0.000 claims abstract description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 17
- 239000011737 fluorine Substances 0.000 claims abstract description 17
- 230000009467 reduction Effects 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000003763 carbonization Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 9
- 239000010439 graphite Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims abstract description 4
- 235000011613 Pinus brutia Nutrition 0.000 claims abstract description 4
- 241000018646 Pinus brutia Species 0.000 claims abstract description 4
- 239000000919 ceramic Substances 0.000 claims abstract description 3
- 239000011812 mixed powder Substances 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 44
- 229910021529 ammonia Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000010955 niobium Substances 0.000 claims description 16
- 229910052721 tungsten Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 15
- 238000005516 engineering process Methods 0.000 claims description 14
- 229910052758 niobium Inorganic materials 0.000 claims description 12
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 238000005255 carburizing Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 11
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 11
- 239000010937 tungsten Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000004364 calculation method Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 230000002940 repellent Effects 0.000 claims description 6
- 239000005871 repellent Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000012263 liquid product Substances 0.000 claims 1
- 238000000643 oven drying Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 5
- 230000006872 improvement Effects 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- 238000004176 ammonification Methods 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241001080061 Talides Species 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 229910009043 WC-Co Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000010237 hybrid technique Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- -1 ramet Chemical compound 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/60—Compounds characterised by their crystallite size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a kind of method for preparing niobium tungsten binary double carbide nano powder, its step is：S1, wolframic acid salt powder is added in fluorine niobic acid solution, then adds surfactant, to pH value 9~12, it is still aging after filter；S2, niobium tungsten presoma sediment is obtained, washed；S3, the drying of the sediment of washing, mill sieved, obtain niobium tungsten presoma composite powder；S4, to niobium tungsten presoma composite powder carry out reduction treatment, obtain niobium oxide tungsten composite powder；S5, selection are actual with carbon ratio；S6, addition carbon, it is well mixed with raw material powder；S7, by well mixed powder pine in graphite boat or ceramic boat, make carbonization treatment, the cooling that is disposed is come out of the stove；S8, will come out of the stove after niobium tungsten double carbide mill sieve, obtain niobium tungsten binary complex carbide powder.This method realizes niobium tungsten binary double carbide in the mixing of molecular scale, and not only powder particle is tiny, and chemical uniformity and purity are very high.
Description
Technical field
The present invention relates to powder metallurgical technology, relate in particular to a kind of using chemical coprecipitation-hydrogen reduction-carbonization
The method for preparing ultra-fine/nanometer niobium tungsten binary complex carbide powder.
Background technology
Tungsten carbide is the most frequently used hard phase of hard alloy, and WC-Co hard alloy is because with high intensity, hardness and excellent
Good wearability and inoxidizability, is widely used in the fields such as machining, oil, mine, mould and structure wearing piece.
Ultra-fine cemented carbide, efficiently solves the contradiction between conventional rigid alloy rigidity and intensity, with higher intensity, firmly
Degree and wearability, meet the development of modern industry and extraordinary difficult-to-machine material, are widely used in making surface-mounted integrated circuit miniature
Drill bit, dot-matrix printer drill bit, difficult-to-machine material cutter, medical dental drill etc..
However, there are the technological difficulties of two aspects always in the preparation of Ultra-fine Grained Talide：Prepare nanoscale
Powder and the crystal grain suppressed during sintering are grown up.Mainly there is the method for 3 kinds of acquisition nanometer grade powders at present：Mechanical ball mill, spray
Mist is dried, chemical synthesis.High-energy ball milling method be used to prepare nanometer grade powder, but need higher energy, and commercialization
Purity is low, and chemical uniformity is poor.Drying process with atomizing is that spray drying forms chemistry after precursor compound solution is mixed
The mixture of uniform properties, then carburizing obtains nanometer grade powder.Although mechanical ball mill and drying process with atomizing are in industrial circle
Using relatively wide and achieve certain progress, but chemical synthesis route is always the prefered method of most researchers, this method
It is to mix metallic element on a molecular scale with chemical method, so that by the uniformity controlling in chemistry and microstructure in sub-micro
Metrical scale, the powder prepared in this way, with very high chemical uniformity, degree of purity and nano level crystallite dimension.
Another problem prepared by ultra-fine cemented carbide be how to suppress sintering during the rapid of crystal grain grow up.Grind at present
It is addition transition metal carbide to study carefully at most most widely used method（Such as VC, Cr3C2, NbC, TaC etc.）Or rare earth addition comes
Suppress growing up for WC crystal.There is uneven ask always yet with the inhibitor and tungsten-carbide powder mixed process of addition
Topic, inhibitor can not be evenly distributed on around tungsten carbide powder, there is localized clusters phenomenon, causing can not be fine in sintering process
Suppression tungsten carbide crystal grain grow up.
With science and technology and the fast development of processing manufacturing industry, the performance to hard alloy proposes higher requirement,
Research and development and the production of Ultra-fine Grained even Nanograin Cemented Carbide have obtained increasing concern, and the preparation of nano powder and suppression
Crystal grain the two problems of growing up could not be solved effectively always, become the bottleneck of cemented carbide industry development.
The content of the invention
It is an object of the invention to the defect for above-mentioned prior art niobium tungsten binary double carbide is prepared there is provided one kind
The method of nano powder, ultra-fine/nanometer niobium tungsten binary double carbide is prepared using chemical coprecipitation nanometer in situ complex technique
Powder.The technology has overturned the simple and mechanical hybrid technique of traditional raw material tungsten-carbide powder and inhibitor niobium carbide powder, real
Niobium tungsten binary double carbide is showed in the mixing of molecular scale, not only powder particle is tiny, and chemical uniformity and purity
It is very high, solve the problem of nano tungsten carbide prepares difficult uneven with inhibitor mixed, the powder can be used for preparing it is ultra-fine/
Nanograin Cemented Carbide.
To achieve these goals, the technical scheme is that：
A kind of method for preparing niobium tungsten binary double carbide nano powder, steps of the method are：
S1, the wolframic acid salt powder of amount of calculation is added in fluorine niobic acid solution, adds the surfactant of amount of calculation, mixing is equal
After even, alkaline precipitating agent is continuously added, to pH value 9~12, then still aging 0.1~2h is filtered；
Obtained niobium tungsten presoma sediment is washed with drum ammonia hot pure water after S2, filtering, reduces in sediment Oil repellent extremely
Less than 0.3%；
S3, the sediment after washing dried in baking oven device, mill sieve then carried out to the hardened shape sediment of drying,
Obtain niobium tungsten presoma composite powder；
S4, using hydrogen to niobium tungsten presoma composite powder carry out reduction treatment, obtain niobium oxide-tungsten composite powder；
S5, the proportioning according to niobium oxide and tungsten in niobium oxide-tungsten composite powder, by niobium oxide and tungsten be each carbonized it is anti-
Equation is answered, theory is calculated and matches somebody with somebody carbon ratio, and according to the condition of actual carburizing reagent（Reaction atmosphere, the material of loading boat,
Stove calandria etc.）Selection is actual to match somebody with somebody carbon ratio；
S6, proportioning and total amount according to niobium oxide-tungsten composite powder, add the carbon of amount of calculation, and carbon black or graphite may be selected in carbon,
Then it is well mixed with raw material powder；
S7, by well mixed powder pine in graphite boat or ceramic boat, under vacuum or hydrogen atmosphere, 1000
DEG C~1800 DEG C in the range of carry out carbonization treatment, 0.5~5h of soaking time comes out of the stove after furnace cooling；
S8, will come out of the stove after niobium tungsten double carbide carry out mill sieve, obtain niobium tungsten binary complex carbide powder, and detect powder
Granularity, purity and composition are constituted.
As the improvement to above-mentioned technical proposal, tungstates selects ammonium paratungstate or ammonium metatungstate, more preferably secondary tungsten
Sour ammonium.
As the improvement to above-mentioned technical proposal, fluorine niobic acid solution selects the niobium of niobium anti-stripping agent, more preferably high-purity
Anti-stripping agent, in terms of niobium oxide, content is 20~150g/L, 0.2~2mol/L of HF concentration.
As the improvement to above-mentioned technical proposal, surfactant selects PEG-400, PEG-600, PEG-1000 and PEG-
One or more in 2000, more preferably PEG-600, consumption（Volume）For the 0.1%-2% of fluorine niobic acid solution, it is more preferably
0.2-0.6%。
The one kind or two selected as the improvement to above-mentioned technical proposal, alkaline precipitating agent in ammoniacal liquor and ammonium hydrogen carbonate
Plant, more preferably ammoniacal liquor.
As the improvement to above-mentioned technical proposal, solution is stirred during addition alkaline precipitating agent or ultrasound shake
Swing, slowly at the uniform velocity add, until solution ph 9~10.
As the improvement to above-mentioned technical proposal, the still aging time is preferably 0.2~0.5h.
As the improvement to above-mentioned technical proposal, suction filtration or press filtration, more preferably suction filtration are selected in filtering.
As the improvement to above-mentioned technical proposal, ammonia density elects 0.1~1mol/L as in drum ammonia hot pure water, more preferably
0.3~0.5 mol/L；Drum ammonia hot pure water temperature elects 40~100 DEG C, more preferably 50~80 DEG C as.
As the improvement to above-mentioned technical proposal, the optional heated-air circulation oven of drying unit or vacuum drying chamber, more preferably
For heated-air circulation oven；Baking temperature elects 80~200 DEG C as, and drying time elects 2~12h as.
As the improvement to above-mentioned technical proposal, niobium tungsten presoma composite powder hydrogen reduction temperature selects 600~1000 DEG C,
More preferably 700~900 DEG C；0.3~3h of soaking time, more preferably 0.5~1.5h.
As the improvement to above-mentioned technical proposal, the carbonisation of niobium oxide-tungsten composite powder can hydrogen shield carbon
Change in stove or vacuum carbon tube furnace and carry out, more preferably vacuum carbon tube furnace；Carburizing temperature is preferably 1200~1600 DEG C.
Compared with prior art, the present invention has the advantages and positive effects of：
（1）Niobium tungsten binary complex carbide powder prepared by the present invention, niobium tungsten molecular scale is realized using chemical coprecipitation
Mixing, thoroughly solve the problem of raw material tungsten-carbide powder and inhibitor mixed are uneven in conventional rigid alloy, and obtain
Nanoscale niobium tungsten complex carbide powder purity it is high, crystallite dimension is tiny, and crystallite dimension is in 10~200nm；
（2）The ratio of niobium tungsten can be by controlling to add tungstates in niobium tungsten binary complex carbide powder prepared by the present invention
Content changes, and the niobium tungsten binary complex carbide powder of different ratio needed for obtaining, the powder can be used alone as preparing hard
The hard phase powder of alloy, also can be with other hard phases（Such as titanium carbide, ramet, titanium nitride, titanium boride, aluminum oxide）Powder
Used after mixing, for preparing polynary hard phase cemented carbide.
Embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, institute
Any modification, equivalent substitution and improvements of work etc., should be included in the scope of the protection.
The present invention method the step of be：
（1）Chemical coprecipitation.
First by the proportioning of niobium and tungsten in final required niobium tungsten complex carbide powder, and according to the species of selected tungstates
（Ammonium metatungstate or ammonium paratungstate）With the concentration of fluorine niobic acid solution, the weight of tungstates and fluorine niobic acid solution needed for calculating；
The tungstates of amount of calculation is added in the fluorine niobic acid solution of amount of calculation, the PEG tables of fluorine niobic acid liquor capacity 0.1~2% are added
Face activating agent, stirs and is prepared into sol solution；Then ammoniacal liquor is slowly homogeneously added into solution ph 9~12, in ammoniacal liquor
Solution is stirred or ultrasonic vibration during the entire process of addition；Then still aging 0.1~2h, then carry out suction filtration or
Person's press filtration；Sediment after filtering washs small to Oil repellent with 50~80 DEG C of ammonia densities for 0.1~1mol/L drum ammonia hot pure water
In 0.3%；Then sediment after washing carries out mill sieve, obtains niobium tungsten presoma composite powder in drying in oven.
（2）Hydrogen reduction.
By the niobium tungsten presoma composite powder of acquisition in a hydrogen atmosphere, in the range of 600~1000 DEG C, insulation 0.3~
3h, cooling of then coming out of the stove, obtains niobium oxide-tungsten composite powder.
（3）Carbonization
Respectively the respective theoretical carburizing reagent for matching somebody with somebody carbon ratio, wherein niobium oxide is calculated according to the carbonation equation formula of niobium oxide and tungsten
Equation is：Nb2O5+ 7C=2NbC+5CO, W carburizing reagent equation is：W+C=WC；The theory for obtaining niobium oxide is calculated with carbon
COEFFICIENT KReason（Niobium oxide）=0.316, W theory match somebody with somebody carbon ratio KReason（Tungsten）=0.065；Then according to niobium oxide in niobium oxide-tungsten composite powder
With the respective shared mass fraction ω (Nb of tungsten2O5) and ω (W), calculate the theory obtained needed for 1kg niobium oxide-tungsten composite powder
Mixed carbon comtent m (C)（Reason）=0.316×ω(Nb2O5)+0.065×ω(W)；Then according to the difference of actual Carbonization Conditions（Blowing boat
Ware, carburizing atmosphere etc.）With addition carbon raw material（Carbon black or graphite）The mass fraction ω (C) of middle fixed carbonGu, determine 1kg oxygen
Change the actual mixed carbon comtent m (C) needed for niobium-tungsten composite powder（It is real）=K(0.316×ω(Nb2O5)+0.065×ω(W))/ ω
(C)Gu, wherein K matches somebody with somebody carbon ratio for selection, between 0.90~1.10；Then the carbon and niobium oxide-tungsten added needed for calculating
Composite powder is well mixed, and is carbonized under vacuum or hydrogen atmosphere, carburizing temperature 1000~1800, carbonization time 0.5
~5h, comes out of the stove after furnace cooling to room temperature, obtains niobium tungsten binary carbide composite powder.
（4）Mill sieve and detection
Niobium tungsten binary carbide composite powder after coming out of the stove carries out mill sieve, then carries out granularity, purity, chemical composition composition, pine
Fill the analysis of the powder physical and chemical performances such as density.
The Nb-30wt%W of embodiment 1 is ultra-fine/preparation of nanometer niobium tungsten binary complex carbide powder
（1）It is prepared by sol solution
Weigh the ammonium paratungstate of 5 crystallizations water of 1276g bands（5(NH4)2O-12WO3-5H2O）, and it is dissolved into 30L fluorine niobic acids
In solution, 300ml Surfactant PEG -600 are then added, sol solution is uniformly mixing to obtain；Wherein fluorine niobic acid concentration is with oxygen
Change niobium and be calculated as 100g/L, HF acid concentrations 1.2mol/L.
（2）Ammonia neutralization precipitation
Concentration is slowly added into sol solution for 9.6N concentrated ammonia liquor, until solution ph=9~10, stops ammonification water, and
Still aging 30min；The stirring to solution is always maintained in ammoniacal liquor adition process.
（3）Filtering and washing
Sediment after ammonia is neutralized is filtered with Suction filtration device, and sediment is fully washed with drum ammonia hot pure water,
Until the Oil repellent in sediment is less than 0.3%.
（4）Drying mill sieve
Sediment after washing is placed in heated-air circulation oven at 120 DEG C and dried 5 hours, then takes out and 100 mesh is crossed after grinding
Sieve, is obtained by Nb (OH)5、（NH4）(10H2W12O42)·4H2The niobium tungsten presoma composite powder of O phase compositions.
（5）Hydrogen reduction
The niobium tungsten presoma composite powder of acquisition is subjected to reduction treatment in 14 pipe hydrogen reducing furnaces, 800 DEG C of reduction temperature,
Soaking time 1 hour, obtains niobium oxide-tungsten composite powder.
（6）Carbonization
The carbon black 815g that fixed carbon content is more than 95% is weighed, after being well mixed with 3000g niobium oxide-tungsten composite powder, is loaded
In graphite boat and it is compacted, is then carbonized in vacuum carbon pipe, 1350 DEG C of carburizing temperature, furnace cooling is to room after insulation 1h
Come out of the stove after temperature, obtain niobium tungsten binary double carbide powder.
（7）Mill sieve and detection
Niobium tungsten binary double carbide powder after coming out of the stove crosses 100 mesh sieves, detects powder property, wherein powder grain size 50~
200nm, 1.12 μm of Fisher particle size, total carbon content 9.83%, free carbon content 0.06%, oxygen content ＜ 0.1%, nitrogen content ＜
0.01%, W content 26.9%, surplus is niobium.
The Nb-50wt%W of embodiment 2 is ultra-fine/preparation of nanometer niobium tungsten binary complex carbide powder
（1）It is prepared by sol solution
Weigh the ammonium paratungstate of 5 crystallizations water of 2332g bands（5(NH4)2O-12WO3-5H2O）, and it is dissolved into 30L fluorine niobic acids
In solution, 300ml Surfactant PEG -600 are then added, sol solution is uniformly mixing to obtain；Wherein fluorine niobic acid concentration is with oxygen
Change niobium and be calculated as 80g/L, HF acid concentrations 1.0mol/L.
（2）Ammonia neutralization precipitation
Concentration is slowly added into sol solution for 9.6N concentrated ammonia liquor, until solution ph=9~10, stops ammonification water, and
Still aging 30min；The stirring to solution is always maintained in ammoniacal liquor adition process.
（3）Filtering and washing
Sediment after ammonia is neutralized is filtered with Suction filtration device, and sediment is fully washed with drum ammonia hot pure water,
Until the Oil repellent in sediment is less than 0.3%.
（4）Drying mill sieve
Sediment after washing is placed in heated-air circulation oven at 120 DEG C and dried 5 hours, then takes out and 100 mesh is crossed after grinding
Sieve, is obtained by Nb (OH)5、（NH4）(10H2W12O42)·4H2The niobium tungsten presoma composite powder of O phase compositions.
（5）Hydrogen reduction
The niobium tungsten presoma composite powder of acquisition is subjected to reduction treatment in 14 pipe hydrogen reducing furnaces, 780 DEG C of reduction temperature,
Soaking time 1 hour, obtains niobium oxide-tungsten composite powder.
（6）Carbonization
The carbon black 900g that fixed carbon content is more than 95% is weighed, after being well mixed with 4078g niobium oxide-tungsten composite powder, is loaded
In graphite boat and it is compacted, is then carbonized in vacuum carbon pipe, 1320 DEG C of carburizing temperature, furnace cooling is to room after insulation 1h
Come out of the stove after temperature, obtain niobium tungsten binary double carbide powder.
（7）Mill sieve and detection
Niobium tungsten binary double carbide powder after coming out of the stove crosses 100 mesh sieves, detects powder property, wherein powder grain size 50~
200nm, 1.07 μm of Fisher particle size, total carbon content 8.76%, free carbon content 0.07%, oxygen content ＜ 0.1%, nitrogen content ＜
0.01%, W content 45.6%, surplus is niobium.
The Nb-70wt%W of embodiment 3 is ultra-fine/preparation of nanometer niobium tungsten binary complex carbide powder
（1）It is prepared by sol solution
Weigh the ammonium paratungstate of 5 crystallizations water of 1488g bands（5(NH4)2O-12WO3-5H2O）, and it is dissolved into 30L fluorine niobic acids
In solution, 300ml Surfactant PEG -600 are then added, sol solution is uniformly mixing to obtain；Wherein fluorine niobic acid concentration is with oxygen
Change niobium and be calculated as 50g/L, HF acid concentrations 0.7mol/L.
（2）Ammonia neutralization precipitation
Concentration is slowly added into sol solution for 9.6N concentrated ammonia liquor, until solution ph=9~10, stops ammonification water, and
Still aging 30min；The stirring to solution is always maintained in ammoniacal liquor adition process.
（3）Filtering and washing
Sediment after ammonia is neutralized is filtered with Suction filtration device, and sediment is fully washed with drum ammonia hot pure water,
Until the Oil repellent in sediment is less than 0.3%.
（4）Drying mill sieve
Sediment after washing is placed in heated-air circulation oven at 120 DEG C and dried 5 hours, then takes out and 100 mesh is crossed after grinding
Sieve, is obtained by Nb (OH)5、（NH4）(10H2W12O42)·4H2The niobium tungsten presoma composite powder of O phase compositions.
（5）Hydrogen reduction
The niobium tungsten presoma composite powder of acquisition is subjected to reduction treatment in 14 pipe hydrogen reducing furnaces, 760 DEG C of reduction temperature,
Soaking time 1 hour, obtains niobium oxide-tungsten composite powder.
（6）Carbonization
The carbon black 565g that fixed carbon content is more than 95% is weighed, after being well mixed with 2548g niobium oxide-tungsten composite powder, is loaded
In graphite boat and it is compacted, is then carbonized in vacuum carbon pipe, 1300 DEG C of carburizing temperature, furnace cooling is to room after insulation 1h
Come out of the stove after temperature, obtain niobium tungsten binary double carbide powder.
（7）Mill sieve and detection
Niobium tungsten binary double carbide powder after coming out of the stove crosses 100 mesh sieves, detects powder property, wherein powder grain size 50~
200nm, 1.03 μm of Fisher particle size, total carbon content 7.72%, free carbon content 0.09%, oxygen content ＜ 0.1%, nitrogen content ＜
0.01%, W content 64.6%, surplus is niobium.
Claims (10)
1. a kind of preparation technology for the method for preparing niobium tungsten binary double carbide nano powder, it is characterised in that：The step of this method
Suddenly it is：
S1, the wolframic acid salt powder of amount of calculation is added in fluorine niobic acid solution, adds the surfactant of amount of calculation, mixing is equal
After even, alkaline precipitating agent is continuously added, to pH value 9~12, then still aging 0.1~2h is filtered；
Obtained niobium tungsten presoma sediment is washed with drum ammonia hot pure water after S2, filtering, reduces in sediment Oil repellent extremely
Less than 0.3%；
S3, the sediment after washing dried in baking oven device, mill sieve then carried out to the hardened shape sediment of drying,
Obtain niobium tungsten presoma composite powder；
S4, using hydrogen to niobium tungsten presoma composite powder carry out reduction treatment, obtain niobium oxide-tungsten composite powder；
S5, the proportioning according to niobium oxide and tungsten in niobium oxide-tungsten composite powder, by niobium oxide and tungsten be each carbonized it is anti-
Equation is answered, is calculated theoretical with carbon ratio and actual with carbon ratio according to the selection of the condition of actual carburizing reagent；
S6, proportioning and total amount according to niobium oxide-tungsten composite powder, add the carbon of amount of calculation, and carbon black or graphite may be selected in carbon,
Then it is well mixed with raw material powder；
S7, by well mixed powder pine in graphite boat or ceramic boat, under vacuum or hydrogen atmosphere, 1000
DEG C~1800 DEG C in the range of carry out carbonization treatment, 0.5~5h of soaking time comes out of the stove after furnace cooling；
S8, will come out of the stove after niobium tungsten double carbide carry out mill sieve, obtain niobium tungsten binary complex carbide powder, and detect powder
Granularity, purity and composition are constituted.
2. the preparation technology of the method for niobium tungsten binary double carbide nano powder is prepared as claimed in claim 1, it is characterised in that：
Tungstates selects ammonium paratungstate or ammonium metatungstate.
3. the preparation technology of the method for niobium tungsten binary double carbide nano powder is prepared as claimed in claim 1, it is characterised in that：
Fluorine niobic acid solution selects niobium anti-stripping agent, in terms of niobium oxide, and content is 20~150g/L, 0.2~2mol/L of HF concentration.
4. the preparation technology of the method for niobium tungsten binary double carbide nano powder is prepared as claimed in claim 1, it is characterised in that：
The one or more that surfactant is selected in PEG-400, PEG-600, PEG-1000 and PEG-2000, consumption is that fluorine niobic acid is molten
The 0.1%-2% of liquid product.
5. the preparation technology of the method for niobium tungsten binary double carbide nano powder is prepared as claimed in claim 1, it is characterised in that：
Alkaline precipitating agent is from one or both of ammoniacal liquor and ammonium hydrogen carbonate.
6. the preparation technology of the method for niobium tungsten binary double carbide nano powder is prepared as claimed in claim 1, it is characterised in that：
Add alkaline precipitating agent during solution is stirred or ultrasonic vibration, slowly at the uniform velocity add, until solution ph 9~
10。
7. the preparation technology of the method for niobium tungsten binary double carbide nano powder is prepared as claimed in claim 1, it is characterised in that：
Suction filtration or press filtration are selected in filtering.
8. the preparation technology of the method for niobium tungsten binary double carbide nano powder is prepared as claimed in claim 1, it is characterised in that：
Ammonia density elects 0.1~1mol/L as in drum ammonia hot pure water, and drum ammonia hot pure water temperature elects 40~100 DEG C as.
9. the preparation technology of the method for niobium tungsten binary double carbide nano powder is prepared as claimed in claim 1, it is characterised in that：
Drying unit selects heated-air circulation oven or vacuum drying chamber.
10. preparing the preparation technology of the method for niobium tungsten binary double carbide nano powder as claimed in claim 1, its feature exists
In：Niobium tungsten presoma composite powder hydrogen reduction temperature selects 600~1000 DEG C, and soaking time is 0.3~3h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710270171.XA CN107128921B (en) | 2017-04-24 | 2017-04-24 | A method of preparing niobium tungsten binary double carbide nano powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710270171.XA CN107128921B (en) | 2017-04-24 | 2017-04-24 | A method of preparing niobium tungsten binary double carbide nano powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107128921A true CN107128921A (en) | 2017-09-05 |
| CN107128921B CN107128921B (en) | 2019-03-05 |
Family
ID=59716040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710270171.XA Active CN107128921B (en) | 2017-04-24 | 2017-04-24 | A method of preparing niobium tungsten binary double carbide nano powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107128921B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119265506A (en) * | 2024-12-09 | 2025-01-07 | 赣州有色冶金研究所有限公司 | A carburizing agent and a method for preparing ultra-coarse tungsten carbide powder |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4822594B1 (en) * | 1969-09-22 | 1973-07-06 | ||
| CN1226881A (en) * | 1996-06-04 | 1999-08-25 | Omg美国公司 | Metallic carbide-group VIII metal powder and its preparation |
| CN1751990A (en) * | 2005-11-03 | 2006-03-29 | 武汉科技大学 | Preparation method of transition metal carbide material |
| CN101663237A (en) * | 2007-03-26 | 2010-03-03 | 杰富意矿物股份有限公司 | Method for producing transition metal carbides and/or composite carbides |
| CN106185944A (en) * | 2016-07-01 | 2016-12-07 | 南昌大学 | A kind of method preparing superfine tungsten carbide containing arsenic and the ammonium paratungstate of phosphorus or ammonium metatungstate |
-
2017
- 2017-04-24 CN CN201710270171.XA patent/CN107128921B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4822594B1 (en) * | 1969-09-22 | 1973-07-06 | ||
| CN1226881A (en) * | 1996-06-04 | 1999-08-25 | Omg美国公司 | Metallic carbide-group VIII metal powder and its preparation |
| CN1751990A (en) * | 2005-11-03 | 2006-03-29 | 武汉科技大学 | Preparation method of transition metal carbide material |
| CN101663237A (en) * | 2007-03-26 | 2010-03-03 | 杰富意矿物股份有限公司 | Method for producing transition metal carbides and/or composite carbides |
| CN106185944A (en) * | 2016-07-01 | 2016-12-07 | 南昌大学 | A kind of method preparing superfine tungsten carbide containing arsenic and the ammonium paratungstate of phosphorus or ammonium metatungstate |
Non-Patent Citations (2)
| Title |
|---|
| 王玉香等: "共沉淀-直接碳化原位合成WC-Co复合粉的研究", 《中国钨业》 * |
| 王玉香等: "化学沉淀法制备超细WC-Co复合粉的研究", 《中国钨业》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119265506A (en) * | 2024-12-09 | 2025-01-07 | 赣州有色冶金研究所有限公司 | A carburizing agent and a method for preparing ultra-coarse tungsten carbide powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107128921B (en) | 2019-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110330341B (en) | High-purity superfine transition metal carbide single-phase high-entropy ceramic powder and preparation method thereof | |
| KR100747805B1 (en) | Powder mixtures or composite powders, methods for their preparation and their use in composite materials | |
| KR100545897B1 (en) | Ultrafine TiC- Transition Metal Composite Powder Manufacturing Method | |
| WO2015161732A1 (en) | Method for preparing cobalt-coated nanometer wc crystal composite powder and ultra-fine grain cemented carbide | |
| CN110396632B (en) | Ti (C, N) -based metal ceramic with homogeneous ring core structure and preparation method thereof | |
| CN106636834B (en) | Inhibit the method and ultra-fine cemented carbide preparation process that hard alloy crystal grain is grown up | |
| CN110102752B (en) | A kind of solid solution alloy powder for cermet and preparation method thereof | |
| KR100468299B1 (en) | Method for producing platinum material reinforced with dispersed oxide | |
| CN102251130B (en) | Preparation method of superfine grain cemented carbide | |
| CN112430770A (en) | Multi-scale structure non-uniform hard alloy and preparation method thereof | |
| CN106041111B (en) | The method that a kind of ammonium paratungstate or ammonium metatungstate containing arsenic and phosphorus prepare nano-tungsten powder | |
| CN104628385A (en) | Boric nano titanium carbonitride solid solution powder and preparation method thereof | |
| KR100536062B1 (en) | Process for Manufacturing Nano TaC- Transition Metal Based Composite Powder | |
| CN108941583B (en) | Submicron diamond composite sheet and preparation process thereof | |
| CN107128921B (en) | A method of preparing niobium tungsten binary double carbide nano powder | |
| CN112359259A (en) | Non-uniform bicrystal hard alloy containing grain inhibiting element and having carbon uniformly distributed and preparation method thereof | |
| CN115652122B (en) | Hard alloy and preparation process thereof | |
| CN112209446A (en) | Method for recycling Cr-containing tungsten carbide waste and its application | |
| KR20040074828A (en) | Method for manufacturing nanophase tic composite powders by metallothermic reduction | |
| CN106087060B (en) | Nanometer (Ti, M) C solid solution whiskers and preparation method thereof | |
| CN112063871B (en) | A kind of preparation method of coarse grained cemented carbide | |
| CN101624289B (en) | Production method of macrocrystalline Cr3C2 ceramic powder | |
| CN111020337B (en) | Inhibitor applied to preparation of superfine tungsten carbide and preparation method thereof | |
| CN100584753C (en) | Preparation method of nano WC powder synthesized in situ by porous carbonaceous material | |
| JPH0587441B2 (en) |
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 | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 341000 Yingbin Road, Ganzhou economic and Technological Development Zone, Jiangxi 62, China Patentee after: Ganzhou Nonferrous Metallurgy Research Institute Co.,Ltd. Address before: 341000 Yingbin Road, Ganzhou economic and Technological Development Zone, Jiangxi 62, China Patentee before: GANZHOU NONFERROUS METALLURGICAL Research Institute |