CN102131601A - Powder of tungsten alloy with transition metal dissolved therein as solid solution and process for producing same - Google Patents
Powder of tungsten alloy with transition metal dissolved therein as solid solution and process for producing same Download PDFInfo
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- CN102131601A CN102131601A CN2009801335673A CN200980133567A CN102131601A CN 102131601 A CN102131601 A CN 102131601A CN 2009801335673 A CN2009801335673 A CN 2009801335673A CN 200980133567 A CN200980133567 A CN 200980133567A CN 102131601 A CN102131601 A CN 102131601A
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Abstract
Disclosed is a powder of a tungsten alloy with a transition metal dissolved therein as a solid solution, and a peak derived from a bcc tungsten phase appears in an X-ray diffraction diagram, the powder has the following formula [1]: M-W wherein M represents one or more elements selected from Co, Fe, Mn, or Ni. The use of the powder of the tungsten alloy can provide a tungsten carbide with a transition metal dissolved therein as a solid solution in which a solid solution phase of at least one transition metal element selected from the group consisting of cobalt, iron, manganese, and nickel, tungsten, and carbon is included in a tungsten carbide skeleton, and a tungsten carbide diffused cemented carbide.
Description
Technical field
The present invention relates to a kind of transition metal solid solution tungsten alloy powder and preparation method thereof.
Background technology
Therefore tungsten has the fusing point height, and the characteristics that elastic modelling quantity is high are widely used in the raw material of filament material or tungsten carbide (WC).Yet the overwhelming majority of its resource is from China, and along with the surge of Chinese domestic demand, its price is rising suddenly and sharply.In order to develop the material of saving tungsten resource, need to replace a part of tungsten with transition metal.
But tungsten is because its fusing point height is difficult to utilize fusion to be prepared.And even utilize PM technique in order to give its shape, the complex element method by tungsten powder and transition metal can't form alloy.And the method for sending forth (atomize) that is used to prepare alloy powder also is difficult to be suitable for.
In addition, the known coprecipitation of utilizing slaine and metal hydroxides prepares the method for tungsten alloy powder.(patent documentation 1, patent documentation 2)
Patent documentation 1: the special table of the open communique of Japan Patent 2002-527626 number
Patent documentation 2: No. 4913731 specification of United States Patent (USP)
Yet the preparation method that patent documentation 1, patent documentation 2 are put down in writing because except tungsten phase and transition metal alloyed tungsten phase, also there is the transition metal phase in co-precipitation step in the alloy powder, does not sufficiently obtain alloying.
Summary of the invention
The present invention does in view of the above problems, and novel tungsten alloy powder that provides a kind of transition metal solid solution (comprise and force solid solution) and preparation method thereof is provided its purpose.
To achieve these goals, the present inventor finds after deliberation, as long as in the aqueous solution, make the ion concentration homogeneous of tungsten ion and transition metal ions, carry out evaporate to dryness or spray-drying, make its pyrolysis then, carry out hot hydrogen reduction and obtain tungsten powder, just can prepare the tungsten alloy powder that transition metal is forced solid solution fully.
Promptly, transition metal solid solution tungsten alloy powder of the present invention, at least a transition metal solid solution that is selected from cobalt, iron, manganese and nickel group forms in the tungsten lattice, can observe bcc tungsten phase peak value in the X-ray diffraction figure, be expressed as formula (1): M-W (M represents to be selected from more than one of Co, Fe, Mn or Ni).
Transition metal solid solution tungsten alloy powder of the present invention has single transition metal solid solution in tungsten: 1) the cobalt solid solution forms in the tungsten lattice, being expressed as the transition metal solid solution tungsten alloy powder, 2 of Co-W) the iron solid solution forms in the tungsten lattice, being expressed as the transition metal solid solution tungsten alloy powder, 3 of Fe-W) the nickel solid solution forms in the tungsten lattice, is expressed as the transition metal solid solution tungsten alloy powder of Ni-W.
The part of above-mentioned cobalt, iron, nickel, can be selected from other transition metal iron, manganese and nickel group more than one replace, thereby can obtain composite transition metal solid solution tungsten powder.Wherein, comparatively it is desirable to, 4) part of cobalt is replaced as more than chosen from Fe, manganese, iron-manganese and nickel group at least a, being expressed as formula (2): the Co-M1-W transition metal solid solution tungsten alloy powder, 5 of (M1 represents to be selected from more than one of Fe, Mn or Ni)) the iron solid solution is in the tungsten lattice, the part of iron is replaced as and is selected from more than cobalt, manganese and nickel group at least a, is expressed as formula (3): the Fe-M2-W transition metal solid solution tungsten alloy powder of (M2 represents to be selected from more than one of Co, Mn or Ni).
To the solid solution capacity of the transition metal of tungsten, can reach the isodose mole of tungsten.As solid solution element, when selecting cobalt, to the tungsten of 60～90mol%, the cobalt of 40～10mol% is an amount of, and other transition metal are also identical with it.
The 2nd purpose of the present invention is to provide the preparation method of above-mentioned transition metal solid solution tungsten powder, to contain the aqueous solution of tungsten ion and contain and be selected from cobalt, iron, the aqueous solution of manganese and nickel group's at least a transition metal ions, so that tungsten ion accounts for more than the 60mol%, transition metal ions accounts for below the 40mol%, with this mixed aqueous solution evaporate to dryness or spray-drying, with the pyrolysis of gained solid, carry out hot hydrogen reduction then, prepare the formula that is expressed as (1) of transition metal solid solution thus: (M represents to be selected from Co to M-W, Fe, more than one of Mn or Ni) transition metal solid solution tungsten alloy powder.
In the present invention, comparatively it is desirable to, the aqueous solution that contains tungsten ion is ammonium metatungstate (5 (NH
4)
2O12WO
35H
2O) aqueous solution, the aqueous solution that contains at least a transition metal ions that is selected from cobalt, iron, manganese and nickel group is the transition metal complex saline solution.As transition metal complex salt, can use acetate (Fe (OH) (C
2H
3OO)
2, Co (C
2H
3O
3)
24H
2O, Mn (CH
3COO)
24H
2O, Ni (C2H
3O
3)
2XH
2O) and sulfate (FeSO
47H
2O, CoSO
47H
2O, NiSO
46H
2O, MnSO
45H
2O).
Utilize gained tungsten alloy powder of the present invention, it is characterized by the transition metal solid solution in the tungsten lattice, in the X-ray diffraction figure, can observe bcc phase peak value, therefore, this transition metal solid solution tungsten alloy powder does not exist transition metal or its metallic compound in fact in the tungsten crystal boundary.
Tungsten alloy powder involved in the present invention, as representing with components by weight percent, it is the transition metal solid solution tungsten alloy powder shown in formula (1): the M-W (M represents to be selected from more than one of Co, Fe, Mn or Ni), the cobalt that wherein comprises 0.3～20.8 weight %, the tungsten of surplus, but this transition metal solid solution tungsten alloy powder is to form with the whole or a part of cobalts of more than one element substitutions of iron, manganese and nickel.At this, if comprise the 0.3 weight % of the M composition of cobalt less than tungsten alloy powder, if the effect that can't obtain economizing on resources then is the opposite 20.8 weight % that surpass, then in the tungsten crystal boundary, separate out the 2nd phase, can not become the tungsten alloy powder of transition metal solid solution (pressure solid solution).
Cobalt is replaced on the lattice position of tungsten, thereby it can become the replacement element of tungsten, can save the tungsten resource of big bulge in price effectively.And by solid solution (pressure solid solution) cobalt, its catalyst activity increases, and this clearly demarcated alloy powder can also have the function of catalyst.
On the other hand, nickel have the function similar with cobalt, and price is cheaper than cobalt.And the catalyst activity of nickel is on cobalt.Iron, the intensity of enhancing tungsten powder, and also cheap.And iron and iron-manganese can effectively utilize its abnormality, help improving the destruction toughness of superhard alloy mould.
As the aqueous solution that contains transition metal ions, if use metal complex salt, for example, the acetate of iron, nickel, manganese and cobalt (Co (C
2H
3O
3)
24H
2O, Fe (OH) (C
2H
3OO)
2, Mn (CH
3COO)
24H
2O, Ni (C
2H
3O
3)
2XH
2O), then become water-solublely, and can not produce harmful substance, less to the influence of environment.And, the transition metal sulfate (CoSO of use iron, nickel and cobalt
47H
2O, FeSO
47H
2O, NiSO
46H
2O), also help realizing circular form society.Usually, in the electrolytic copper refining process, the transition metal of iron, nickel and cobalt is concentrated in the sulfuric acid in the electrolyte.Therefore, the waste liquid that is produced in the electrolytic copper refining can be used for the raw material of tungsten alloy powder of the present invention, and the sulfuric acid that produces can utilize effectively also as byproduct when evaporate to dryness or spray-drying.
Description of drawings
Fig. 1 is the EPMA observed result of tungsten carbide of the interior containing metal phase of material sample No.23 of the present invention.(a) be the SEM image, white portion is the WC skeleton, and black part is divided for the territory that is made of metal Co.(b) be the X line image of W, the formation of expression WC skeleton.(c) be the X line image of Co, the formation in the Co territory in the expression WC skeleton.(d) be the X line image of C, the formation of expression WC skeleton.
Fig. 2 is the EPMA observed result of tungsten carbide of the interior containing metal phase of material sample No.34 of the present invention.(a) be the SEM image, white portion is the WC skeleton, and black part is divided for the territory that is made of mutually Fe-Mn solid solution.(b) be the X line image of W, the formation of expression WC skeleton.(c) be the X line image of Fe, the formation in expression Fe-Mn solid solution territory.(d) be the X line image of Co, expression is assigned to Fe-Mn solid solution territory in conjunction with the part of phase Co in sintering.(e) be the X line image of C, the formation of expression WC skeleton.(f) be the X line image of Mn, the formation in expression Fe-Mn solid solution territory.
The specific embodiment
Below, according to specific embodiment, the present invention is described.As the aqueous solution that contains transition metal ions, use separately various metal complex salt or and with two or more various metal complex salt, make a kind or 2 kinds of transition metal solid solutions in the tungsten metal, thereby can replace the part of tungsten metal, this point, those skilled in the art should be understood from embodiment.
Embodiment 1
Preparation has the material in the past (No.1) of chemical composition shown in the table 1 (mol%), material of the present invention, and (No.2～No.9), comparative material (No.10, No.11) by X-ray diffraction and EPMA, check and force solid solution whether to generate whether the 2nd separate out mutually.
Table 1
Whether chemical composition (mol%) and pressure solid solution form
In table 1, solwution method is a process of the present invention, is meant transition metal acetate (Co (C
2H
3O
3)
24H
2O, Fe (OH) (C
2H
3OO)
2, Mn (CH
3COO)
24H
2O and/or Ni (C
2H
3O
3)
2XH
2O) aqueous solution and ammonium metatungstate (Ammonium paratungstate, APT) (5 (NH
4)
2O12WO
35H
2O) after the aqueous solution, evaporate to dryness (spray-drying also can) becomes oxide with the 823K pyrolysis with the gained solid in atmosphere, keeps 1h to carry out hot hydrogen reduction with 1073K in hydrogen then, obtains the method for tungsten alloy thus.
Sample No.1 is that to utilize the conventional art of powder metallurgy be complex element method (Blended Elemental Method), after the pure cobalt dust of 7.42 weight % and the weighing of surplus pure tungsten powder are mixed, with 2ton/cm
2The pressure compression forming, in hydrogen, keep the material in the past with chemical constituent shown in the table 1 of 1h gained then with 1073K.Mutually residual pure cobalt phase arranged as the 2nd, show to form alloy with tungsten.
Sample No.2 is the material of the present invention that utilizes the solwution method gained.Mixed transition metal acetate (Co (C
2H
3O
3)
24H
2O) aqueous solution and ammonium metatungstate.Can only observe the peak value of bccW phase in the X-ray diffraction figure of gained alloy powder, obtain the W alloy powder that Co forces solid solution equably.
Sample No.3 is the material of the present invention that utilizes the solwution method gained.Hybrid transition metal acetate (Co (C
2H
3O
3)
24H
2O) aqueous solution and ammonium metatungstate are so that its component becomes 80mol%W-20mol%Co.Can only observe the peak value of bccW phase in the X-ray diffraction figure of gained alloy powder, obtain the W alloy powder that Co forces solid solution equably.Equilibrium phase under the hot hydrogen reduction temperature 1073K environment of this component is W phase and Co
7W
6Phase.Utilize solwution method, at first make the cobalt ions in the aqueous solution and the ion concentration homogeneous of tungsten ion, after the then hot hydrogen reduction, cobalt also can be trapped among the tungsten lattice, can not form equilibrium phase Co
7W
6That is,, can under nonequilibrium condition, prepare and force the solid solution alloy powder if be suitable for solwution method.
Sample No.4 and sample No.5 are the materials of the present invention that utilizes the solwution method gained.Can know,, can obtain the W alloy powder that Co forces solid solution equably until the 60mol%W-40mol%Co component.If be suitable for solwution method, can not form equilibrium phase Co until this component
7W
6, can under nonequilibrium condition, prepare and force the solid solution alloy powder.
Sample No.6 utilizes Co (C
2H
3O
3)
24H
2The part of the O aqueous solution is replaced as Fe (OH) (C
2H
3OO)
2The solwution method gained material of the present invention of the aqueous solution.Discovery is replaced a part of Co with Fe, also can prepare to force the solid solution alloy powder.
Sample No.7 utilizes Co (C
2H
3O
3)
24H
2The part of the O aqueous solution is replaced as Fe (OH) (C
2H
3OO)
2, Mn (CH
3COO)
24H
2O and Ni (C
2H
3O
3)
2XH
2The solwution method gained material of the present invention of the O aqueous solution.Replace a part of Co with Fe, Mn, Ni as can be known, also can prepare and force the solid solution alloy powder.
Sample No.8 utilizes Co (C
2H
3O
3)
24H
2The part of the O aqueous solution is replaced as Ni (C
2H
3O
3)
2XH
2The solwution method gained material of the present invention of the O aqueous solution.Replace a part of Co with Ni, also can prepare and force the solid solution alloy powder.
Sample No.9 utilizes Co (C
2H
3O
3)
24H
2The part of the O aqueous solution is replaced as Fe (OH) (C
2H
3OO)
2And Ni (C
2H
3O
3)
2XH
2The solwution method gained material of the present invention of the O aqueous solution.With Fe and the compound displacement part of Ni Co, also can prepare and force the solid solution alloy powder.
Sample No.10 utilizes the solwution method gained relatively to hand over material.In the 10mol%W-90mol%Co component, finally separated out equilibrium phase Co mutually as the 2nd
3W.Therefore, if the Co amount too much, even use solwution method, the W atom spreads easily in the Co lattice, thereby can't prepare pressure solid solution.
Sample No.11 utilizes the solwution method gained relatively to hand over material.In the 50mol%W-50mol%Co component, finally separated out equilibrium phase Co mutually as the 2nd
7W
6Therefore, in this component, the W atom also spreads, thereby can't prepare pressure solid solution.
Sample No.12 utilizes Co (C
2H
3O
3)
24H
2The part of the O aqueous solution is replaced as Fe (OH) (C
2H
3OO)
2The solwution method gained material of the present invention of the aqueous solution.It is the pressure solid solution alloy powder of replacing a part of Co with micro Fe.
Sample No.13 utilizes Co (C
2H
3O
3)
24H
2The part of the O aqueous solution is replaced as Fe (OH) (C
2H
3OO)
2The solwution method gained material of the present invention of the aqueous solution.Even do not add the Ni (C shown in the No.8
2H
3O
3)
2XH
2The O aqueous solution also can prepare and force the solid solution alloy powder.
Sample No.14 utilizes whole Co (C
2H
3O
3)
24H
2The O aqueous solution is replaced as Fe (OH) (C
2H
3OO)
2The solwution method gained material of the present invention of the aqueous solution.Replace whole Co with Fe and also can prepare pressure solid solution alloy powder.
Sample No.15 utilizes whole Co (C
2H
3O
3)
24H
2The O aqueous solution is replaced as Fe (OH) (C
2H
3OO)
2The aqueous solution and Mn (CH
3COO)
24H
2The solwution method gained material of the present invention of the O aqueous solution.Replace whole Co with Fe and Mn and also can prepare pressure solid solution alloy powder.
The tungsten carbide preparation example
The material in the past (No.21) with chemical composition shown in the table 2 (wt%), material of the present invention (No.22～No.28, No.31～No.34), comparative material (No.29, No.30) have been prepared.
Table 2
Whether form metal in the chemical composition of tungsten carbide (wt%) and the carbide mutually or the 2nd carbide phase
Be formed with metal phase zero in the carbide
Do not form in the carbide metal phase *
Material No.22～No.27 of the present invention in the table 2 forces the tungsten alloy powder of solid solution transition metal to utilizing solwution method, adds admixed graphite and is prepared from.That is, with transition metal acetate (Co (C
2H
3O
3)
24H
2O, Fe (OH) (C
2H
3OO)
2, Mn (CH
3COO)
24H
2O and/or Ni (C
2H
3O
3)
2XH
2O) aqueous solution and ammonium metatungstate (5 (NH
4)
2O12WO
35H
2O) after the aqueous solution, evaporate to dryness (perhaps spray-drying) becomes oxide with the 823K pyrolysis with the gained solid in atmosphere, keeps 1h to carry out hot hydrogen reduction with 1073K in hydrogen then, prepares the tungsten alloy powder that transition metal is forced solid solution thus.
Then, to this tungsten alloy powder admixed graphite, in Ar, keep 1h and prepare tungsten carbide with 1473K.
Sample No.21 is that conventional art by powder metallurgy is to WO
3Admixed graphite is carried out the WC carbide of 1h carbonization gained with 1473K.In the WC skeleton, do not contain the metal phase.
Sample No.22, sample No.23, sample No.24, sample No.25, sample No.26, sample No.27 and sample No.28 are by solwution method and carbonization gained material of the present invention.Obtained to contain in the WC skeleton particular tissues of metal phase.This metal phase helps saving tungsten resource, but also helps improving the mechanical property of carbide.Sample No.22, sample No.23, sample No.24 and sample No.25 contain more metal phases successively as can be known.
Sample No.26, sample No.27 and sample No.28 are the cobalts with iron, iron-manganese and nickel displacement institute containing metal phase, thereby reduce the carbide of price.
Sample No.29 and sample No.30 are by solwution method and carbonization gained comparative material.Shown in sample No.29, if the amount of cobalt more than the amount of tungsten, preparation is during tungsten alloy powder, in cobalt, tungsten spreads, and generates the Co of equilibrium phase
3W or Co
7W
6Its result carries out carbonization to this alloy powder, then metal be enclosed in mutually carbide around, can not contain the metal phase in the carbide.
Material No.31 of the present invention and No.32 in the table 2 force the tungsten alloy powder of solid solution transition metal to utilizing solwution method, add admixed graphite and are prepared from.That is, as sample No.26, with transition metal acetate (Co (C
2H
3O
3)
24H
2The O aqueous solution, Fe (OH) (C
2H
3OO)
2The aqueous solution and ammonium metatungstate (5 (NH
4)
2O12WO
35H
2O) after the aqueous solution, evaporate to dryness (perhaps spray-drying) becomes oxide with the 823K pyrolysis with the gained solid in atmosphere, keeps 1h to carry out hot hydrogen reduction with 1073K in hydrogen then, prepares the tungsten alloy powder that transition metal is forced solid solution thus.Then, to this tungsten alloy powder admixed graphite, in Ar, keep 1h and prepare tungsten carbide with 1473K.Obtained to contain in the WC skeleton particular tissues of Co-Fe solid solution phase.
Material No.33 of the present invention and No.34 in the table 2 force the tungsten alloy powder of solid solution Fe and Mn to utilizing solwution method, add admixed graphite and are prepared from.That is, with Fe (OH) (C
2H
3OO)
2The aqueous solution and Mn (CH
3COO)
24H
2The O aqueous solution, ammonium metatungstate (5 (NH
4)
2O12WO
35H
2O) after the aqueous solution, evaporate to dryness (perhaps spray-drying) becomes oxide with the 823K pyrolysis with the gained solid in atmosphere, keeps 1h to carry out hot hydrogen reduction with 1073K in hydrogen then, prepares the tungsten alloy powder that transition metal is forced solid solution thus.Then, to this tungsten alloy powder admixed graphite, in Ar, keep 1h and prepare tungsten carbide with 1473K.Replace whole Co with Fe or Fe and Mn, the WC carbide of containing metal Fe or Fe-Mn solid solution in then can preparing.
Fig. 1 is the EPMA observed result of material sample No.23 of the present invention.Can know from the X line image of SEM image and corresponding W and C and to be formed with the WC skeleton.And, from the X line image of Co, be appreciated that in the skeleton of WC to be formed with the metal phase.That is,
(a) be the SEM image.White portion is the WC skeleton, and black part is divided for the territory that is made of metal Co (domain).During with 1623K sintering 3.6ks, can grow up inevitably in the Co territory, yet still remain on below the 3mm.
(b) be the X line image of W.The formation of expression WC skeleton.
(c) be the X line image of Co.The formation in the Co territory in the expression WC skeleton.
(d) be the X line image of C.The formation of expression WC skeleton.
Being formed with of this metal phase is beneficial to the use amount that reduces tungsten, and, can also improve its mechanical property.Therefore, disperseing the superhard alloy of this new WC carbide, is good high-abrasive material.
Superhard alloy can be by known preparation method, that is, with tungsten carbide of the present invention and Co powder together the method for sintering be prepared.Fig. 2 be to material sample No.34 of the present invention add 5mass% in conjunction with phase Co, the EPMA photograph in the superhard alloy of preparing with 1623K sintering 3.6ks.As can be known,, be formed with Fe-Mn solid solution phase in the WC skeleton, in sintering, be assigned to this Fe-Mn solid solution phase in conjunction with the part of phase Co at superhard alloy.Vickers hardness is Hv1945, has high hardness.And the front end of testing impression in Vickers hardness does not crack, and shows to have good toughness.That is,
(a) be the SEM image.White portion is the WC skeleton, and black part is divided for the territory that is made of mutually Fe-Mn solid solution.During sintering, metalloproteinase domain can be grown up inevitably, yet still remains on below the 1mm.The Vickers hardness experiment impression of representing this SEM image.Vickers hardness is Hv1945, shows high hardness.And the front end of testing impression in Vickers hardness does not crack, and shows to have good toughness.
(b) be the X line image of W.The formation of expression WC skeleton.And the part of W is assigned to Fe-Mn solid solution territory.
(c) be the X line image of Fe.The formation in expression Fe-Mn solid solution territory.
(d) be the X line image of Co.Expression is assigned to Fe-Mn solid solution territory in conjunction with the part of phase Co in sintering.
(e) be the X line image of C.The formation of expression WC skeleton.
(f) be the X line image of Mn.The formation in expression Fe-Mn solid solution territory.
Why the WC carbide that includes metalloproteinase domain shows so high hardness, is because successfully createed the micro-structural of WC skeleton constraint metalloproteinase domain distortion in the present invention.
As mentioned above, alloy powder of the present invention forces solid solution that transition metal is arranged in the tungsten lattice equably.Therefore, replace the alloy powder of a part of tungsten, can be widely used in superhard alloy with the tungsten carbide raw material etc., help saving tungsten resource with transition metal.For example, tungsten alloy powder of the present invention equally with tungsten powder can form tungsten carbide, with Co together sintering can prepare superhard alloy.
Claims (6)
1. transition metal solid solution tungsten alloy powder is characterized in that:
At least a transition metal solid solution that is selected from cobalt, iron, manganese and nickel group forms in the tungsten lattice, can observe bcc tungsten phase peak value in the X-ray diffraction figure, is expressed as formula (1): M-W (M represents to be selected from more than one of Co, Fe, Mn or Ni).
2. transition metal solid solution tungsten alloy powder according to claim 1 is characterized in that:
The part of cobalt is replaced as more than one of chosen from Fe, manganese and nickel group, is expressed as formula (2): Co-M1-W (M1 represents to be selected from more than one of Fe, Mn or Ni).
3. transition metal solid solution tungsten alloy powder according to claim 1 is characterized in that:
The iron solid solution is in the tungsten lattice, and the part of iron is replaced as more than one that are selected from cobalt, manganese and nickel group, is expressed as formula (3): Fe-M2-W (M2 represents to be selected from more than one of Co, Mn or Ni).
4. according to any described transition metal solid solution tungsten alloy powder of claim 1 to 3, it is characterized in that:
Be selected from cobalt, iron, manganese and at least a of nickel group to tungsten solid solution 40～10mol% of 60～90mol% form.
5. the preparation method of a transition metal solid solution tungsten alloy powder is characterized in that:
To contain the aqueous solution and the aqueous solution that contains at least a transition metal ions that is selected from cobalt, iron, manganese and nickel group of tungsten ion, so that tungsten ion accounts for more than the 60mol%, transition metal ions accounts for below the 40mol%,
With this mixed aqueous solution evaporate to dryness or spray-drying,
The pyrolysis of gained solid is become oxide, carry out hot hydrogen reduction then, prepare the formula that is expressed as (1) of transition metal solid solution: the M-W transition metal solid solution tungsten alloy powder of (M represents to be selected from more than one of Co, Fe, Mn or Ni) thus.
6. the preparation method of transition metal solid solution tungsten alloy powder according to claim 5 is characterized in that:
The aqueous solution that contains tungsten ion is ammonium metatungstate aqueous solution, and the aqueous solution that contains at least a transition metal ions that is selected from cobalt, iron, manganese and nickel group is the transition metal complex saline solution.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008-215605 | 2008-08-25 | ||
| JP2008215605 | 2008-08-25 | ||
| PCT/JP2009/064494 WO2010024159A1 (en) | 2008-08-25 | 2009-08-19 | Powder of tungsten alloy with transition metal dissolved therein as solid solution and process for producing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102131601A true CN102131601A (en) | 2011-07-20 |
Family
ID=41721328
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| CN2009801335673A Pending CN102131601A (en) | 2008-08-25 | 2009-08-19 | Powder of tungsten alloy with transition metal dissolved therein as solid solution and process for producing same |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20110243787A1 (en) |
| EP (1) | EP2332675A1 (en) |
| JP (1) | JP5522713B2 (en) |
| CN (1) | CN102131601A (en) |
| WO (1) | WO2010024159A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109128163A (en) * | 2018-08-16 | 2019-01-04 | 北京科技大学 | A method of preparing High Performance W Base Metal components |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| IN2013CH04500A (en) | 2013-10-04 | 2015-04-10 | Kennametal India Ltd | |
| KR101752687B1 (en) | 2015-04-24 | 2017-06-30 | 서울대학교 산학협력단 | High strength tungsten alloy with low activation and manufacturing method for the same |
| JP2018035020A (en) | 2016-08-30 | 2018-03-08 | 住友電気工業株式会社 | Aqueous solution composition and method for producing the same, oxide powder and method for producing the same, carbide powder and method for producing the same, and cemented carbide and method for producing the same |
| CN106480347A (en) * | 2016-12-05 | 2017-03-08 | 郑州丽福爱生物技术有限公司 | A kind of high-strength aluminum alloy material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4498395A (en) * | 1982-07-16 | 1985-02-12 | Dornier System Gmbh | Powder comprising coated tungsten grains |
| US4913731A (en) * | 1988-10-03 | 1990-04-03 | Gte Products Corporation | Process of making prealloyed tungsten alloy powders |
| US5842108A (en) * | 1997-03-04 | 1998-11-24 | Korea Institute Of Machinery & Materials | Mechano-chemical process for production of high density and ultrafine W/Cu composite material |
| CN1590573A (en) * | 2003-08-25 | 2005-03-09 | 金益民 | Production technology of nano-grade tungsten cobalt mixed powder |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2987911B2 (en) * | 1990-09-12 | 1999-12-06 | 住友電気工業株式会社 | Tungsten alloy particles and method for producing the same |
| JPH04308003A (en) * | 1991-04-05 | 1992-10-30 | Sumitomo Electric Ind Ltd | Tungsten alloy granule for shielding radiation |
| JP3245893B2 (en) * | 1991-07-04 | 2002-01-15 | 住友電気工業株式会社 | Fine grain tungsten alloy and method for producing the same |
| WO1993002962A1 (en) * | 1991-08-07 | 1993-02-18 | Rutgers, The State University Of New Jersey | CARBOTHERMIC REACTION PROCESS FOR MAKING NANOPHASE WC-Co POWDERS |
| JP3252481B2 (en) * | 1992-09-18 | 2002-02-04 | 住友電気工業株式会社 | Tungsten alloy having fine crystal grains and method for producing the same |
| FR2784690B1 (en) | 1998-10-16 | 2001-10-12 | Eurotungstene Poudres | MICRONIC METAL POWDERS BASED ON TUNGSTENE AND / OR MOLYBDENE AND 3D TRANSITION MATERIALS |
| JP4492877B2 (en) * | 2005-09-27 | 2010-06-30 | 日本新金属株式会社 | Method for producing high purity molybdenum-tungsten alloy powder used as raw material powder for sputtering target |
| CN101316672B (en) * | 2005-11-28 | 2011-06-22 | 联合材料公司 | Tungsten alloy particles, machining process with the same, and process for production thereof |
| JP4651565B2 (en) * | 2006-03-28 | 2011-03-16 | 京セラ株式会社 | Manufacturing method of cemented carbide powder |
-
2009
- 2009-05-13 JP JP2009116291A patent/JP5522713B2/en active Active
- 2009-08-19 CN CN2009801335673A patent/CN102131601A/en active Pending
- 2009-08-19 US US12/737,875 patent/US20110243787A1/en not_active Abandoned
- 2009-08-19 WO PCT/JP2009/064494 patent/WO2010024159A1/en active Application Filing
- 2009-08-19 EP EP09809812A patent/EP2332675A1/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4498395A (en) * | 1982-07-16 | 1985-02-12 | Dornier System Gmbh | Powder comprising coated tungsten grains |
| US4913731A (en) * | 1988-10-03 | 1990-04-03 | Gte Products Corporation | Process of making prealloyed tungsten alloy powders |
| US5842108A (en) * | 1997-03-04 | 1998-11-24 | Korea Institute Of Machinery & Materials | Mechano-chemical process for production of high density and ultrafine W/Cu composite material |
| CN1590573A (en) * | 2003-08-25 | 2005-03-09 | 金益民 | Production technology of nano-grade tungsten cobalt mixed powder |
Non-Patent Citations (1)
| Title |
|---|
| 师昌绪 李恒德 周廉主编: "《材料科学与工程手册 上卷》", 31 January 2004, 化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109128163A (en) * | 2018-08-16 | 2019-01-04 | 北京科技大学 | A method of preparing High Performance W Base Metal components |
Also Published As
| Publication number | Publication date |
|---|---|
| US20110243787A1 (en) | 2011-10-06 |
| WO2010024159A1 (en) | 2010-03-04 |
| JP5522713B2 (en) | 2014-06-18 |
| JP2010077524A (en) | 2010-04-08 |
| EP2332675A1 (en) | 2011-06-15 |
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Application publication date: 20110720 |