CN1068067C - Plate-crystalline tungsten carbide-containing hard alloy, composition for forming plate-crystalline tungsten carbide and process for preparing said hard alloy - Google Patents
Plate-crystalline tungsten carbide-containing hard alloy, composition for forming plate-crystalline tungsten carbide and process for preparing said hard alloy Download PDFInfo
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- CN1068067C CN1068067C CN95116624A CN95116624A CN1068067C CN 1068067 C CN1068067 C CN 1068067C CN 95116624 A CN95116624 A CN 95116624A CN 95116624 A CN95116624 A CN 95116624A CN 1068067 C CN1068067 C CN 1068067C
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Abstract
The present invention discloses hard alloy comprising piece crystal tungsten carbide, which comprises 4 to 40% (volume) of binding agent phases comprising at least one kind of Co, Ni and Fe of iron family metal as a main component, unavoidable impurities and a hard phase as the rest, wherein the hard phase only comprises tungsten carbide or comprises the tungsten carbide and no more than 50% (volume) of at least one of carbides, nitrides and the solid solution of the nitrides of a 4b family (Ti, Zr and Hf) and a 5b family (V, Nb and Ta) or a 6b family (Cr, Mo and W) in a periodic table. When X-ray diffraction is carried out by Cu-Ka and the peak intensity of a (001) crystal surface and the peak intensity of a (101) crystal surface are respectively expressed as h (001) and h (101), the tungsten carbide meets the following formula: h (001) / h (101) is at least 0.50. The present invention also discloses a composition for forming the piece crystal tungsten carbide and a method for preparing the hard alloy.
Description
The present invention relates to a kind of Wimet, it has good hardness, toughness, wear resistance, intensity, anti-plastic deformation and heat-resisting cracking performance, it wherein has sheet wolfram varbide (this paper is to call " platelet WC " in the following text) crystallization, the invention particularly relates to a kind of Wimet that contains platelet WC, it is suitable as cutter such as indexable insert tip, throw away tip, drill bit and face cutter, the body material of coating sintered carbide tools, plastic working instrument such as wire poking module, punching die and forging die, and shear tool such as punching mould and cutting knife, the invention still further relates to the composition that is used to form platelet WC, and be used for preparing this method that contains the Wimet of platelet WC.
Usually, can be by changing the granularity of WC, the addition of Co content and other carbide changes hardness (being wear resistance) and the intensity and the toughness (being break resistance) of Wimet, thereby makes Wimet be widely used in various occasions.But the problem that has a contradiction: if increased wear resistance, then can reduce break resistance, opposite if increased break resistance, then wear resistance can descend again.
As a kind of approach that addresses this problem, can mention the obtainable method of anisotropic mechanical property that the crystal face by WC causes, in detail, the method that for example relates to the Wimet that has platelet WC, platelet WC wherein has the shape of triangular piece or hexagon sheet, preferably make its (001) crystal face along (001) crystal plane direction preferential growth, because WC crystalline (001) crystal face has the highest hardness, and (100) crystal plane direction has high elastic coefficient, or a kind of method that is used for preparing this Wimet.
The representational example that relates to the prior art of platelet WC has, Japanese patent laid-open publication gazette No.23049/1972 and No.23050/1972, and Japanese defensive patent disclosure No.34008/1992, No.47239/1990, No.51408/1990, No.138434/1990, No.274827/1990 and No.339659/1993.
In the prior art that relates to platelet WC, open No.23049/1972 of Japanese Patent and No.23050/1972, a kind of method of using mixed powder to prepare to contain the Wimet of platelet WC has been described, the powder that contains colloid tungsten-carbide powder and Fe, Ni, Co or its alloy in this mixed powder contains the porous coacervate of the platelet WC that is used for growing in the described colloid powder.
In the defensive patent disclosure No.34008/1982 of Japan, a kind of method of making the twin crystal wolfram varbide has been described, it passes through to add a spot of iron family metal salt in the mixed powder of the W of abundant pulverizing and C, under heating condition, mixture is carried out carbonization then, make (001) crystal face in conjunction with forming twining plane.
In addition, in the defensive patent disclosure No.47239/1990 of Japan and 138434/1990, a kind of method for preparing Wimet has been described, it uses (W, Ti, Ta) C sosoloid as raw material, wherein contained wolfram varbide is in the supersaturation attitude, and during sintering, crystallization is platelet WC under heating.
In the defensive patent disclosure No.274827/1990 of Japan, described a kind of method of making the anisotropy Wimet, it is with after the oxidation of exhausted Wimet, reducing, and recarbonize makes powder, with powder compacting, sintering or hot pressed sintering obtain moulded product then.
In addition, in the defensive patent disclosure No.339659/1993 of Japan, narrated a kind of preparation method who contains the Wimet of platelet WC, it will contain the mixed powder of the Co of the compound with cubic structure of WC, 3-40% (weight) and 1-25% (weight) and/or Ni at 1450 ℃ or higher sintering temperature, and wherein the granularity of contained WC is no more than 0.5 μ m.
In Wimet of in above-mentioned 8 kinds of publications, narrating or the Wimet with the preparation of method described in the above-mentioned publication, (001) crystal face speed of growth of WC is low, so WC crystalline a shaft length, c shaft length and c/a are very littler than, contained platelet WC ratio is lower, this can produce such problem, and promptly the various characteristics of Wimet, especially hardness, wear resistance, intensity, toughness and resistance to fracture can not be improved.In addition, in above-mentioned preparation method, be difficult to control the granularity of WC, also be difficult to improve the ratio of contained platelet WC, aforesaid method only can be used in the Wimet that component limited to, and makes and this height.
The present invention has now solved the problems referred to above, and an object of the present invention is to provide a kind of Wimet that contains platelet WC, it has best synergy, promptly has high hardness simultaneously, high toughness, high wear resistance, high intensity, and resistance to fracture is fine, this can not obtain in conventional Wimet, by improving the speed of growth of WC (001) crystal face, can improve WC crystalline a shaft length, c shaft length and c/a ratio, and platelet WC crystal ratio is increased, thereby increase the work-ing life of Wimet, the present invention also provides a kind of method for preparing above-mentioned Wimet, method thus, the mixed powder that forms powder by sintering platelet WC can be easy to form platelet WC in Wimet, wherein platelet WC formation powder comprises iron content family metal, the double carbide of W and C or its precursor, and carbon dust.
The inventor is under the prerequisite of hardness that does not reduce Wimet and wear resistance, improve its intensity, toughness and resistance to fracture, years of researches have been carried out, found that by improving the speed of growth of WC (001) crystal face, WC crystalline a shaft length, c shaft length and c/a ratio, and contained platelet WC crystalline ratio, can realize this purpose.In order to obtain this Wimet, can be to the double carbide that comprises iron family metal, W and C, or during heating can form in the powder of precursor of this double carbide and add carbon dust, heating powder mixture then, can be easy to form the platelet WC that satisfies above-mentioned characteristic by reaction and crystallization, thereby finish the present invention.
That is to say that the Wimet that contains platelet WC of the present invention comprises the tackiness agent phase of 4-40% (volume), this tackiness agent comprises at least a iron family metal (cobalt (Co), nickel (Ni) and iron (Fe)) mutually as main ingredient; And the hard of surplus phase and unavoidable impurities, this hard only contains wolfram varbide mutually, or contain a kind of compound and the wolfram varbide that is no more than 50% (volume) with cubic structure, this compound with cubic structure is selected from 4b family in the periodic table of elements (titanium (Ti), zirconium (Zr) and hafnium (Hf)), at least a in the carbide of 5b family (vanadium (V), niobium (Nb) and tantalum (Ta)) or 6b family (chromium (Cr), molybdenum (Mo) and tungsten (W)) or nitride or its sosoloid.
When the peak that the K alpha-ray with the Cu target carries out (001) crystal face that X-ray diffraction analysis obtains and (101) crystal face is expressed as h (001) and h (101) by force respectively, above-mentioned wolfram varbide satisfies h (001)/h (101) 〉=0.50, and the Wimet that contains platelet WC of the present invention has following three features, promptly has good toughness, intensity and hardness.To be described in detail the present invention below.
Contain the tackiness agent phase of platelet WC Wimet as the present invention, can mention specifically that for example, Co, Ni, Fe and alloy are as Co-Ni, Co-W, Ni-Cr and Fe-Ni-Cr.If the amount of tackiness agent phase is lower than 4% (volume), sintering is very difficult, makes sintered compact inside also have pore, perhaps forms platelet WC crystalline speed and reduces, and Wimet intensity and hardness are significantly reduced.On the other hand,, comprise that the amount of the WC of platelet reduces relatively, Wimet hardness and wear resistance are significantly reduced if the amount of tackiness agent phase surpasses 40% (volume).
As the compound that has cubic structure in the platelet WC Wimet that contains of the present invention, can specifically mention, for example TaC, NbC, V
4C
3, VC, (W, Ti) C, (W, Ti, Ta) C, TiN, ZrN, (W, Ti) (C, N) and (W, Nb, Zr) CN.Surpass 50% (volume) if having the amount of the compound of cubic structure, comprise that then the amount of the WC of platelet WC reduces relatively, the hardness of Wimet and toughness are significantly reduced.
In first preferred embodiment of the present invention, the Wimet that contains platelet WC comprise 4-40% (volume) with at least a iron family metal (Co, Ni and Fe) be main ingredient tackiness agent mutually; With the WC of surplus, when the peak of (001) crystal face and (101) crystal face was used h (001) and h (101) expression by force respectively in using the Alpha-ray X-ray diffraction analysis of Cu target K, above-mentioned WC satisfied h (001)/h (101) 〉=0.50.If the peak is lower than at 0.50 o'clock than h (001)/h (101) by force, the speed of growth of the WC of the hardness of putting up the best performance (001) crystal face is lower, so the increase of hardness is less.The peak is preferably 0.55 or bigger, is preferably 0.60 or bigger especially than h (001)/h (101) by force.
In second embodiment of the present invention, a feature that contains platelet WC Wimet is, WC crystalline a axial length is 0.2907nm or bigger, and c axial length is 0.2840nm or bigger.If a axial length is lower than 0.2907nm, or c axial length is lower than 0.2840nm, and the inside distortion of WC lattice is less, and the effect that increases hardness is also little.In addition, another feature that contains the Wimet of platelet WC of the present invention is the ratio of c shaft length and a shaft length in the crystallographic axis, and promptly the c/a ratio is preferably 0.9770 or bigger.
In the 3rd preferred embodiment of the present invention, a feature that contains the Wimet of platelet WC is that the orientation of WC crystalline (001) crystal face is parallel to the pressure surface that adds in the forming step, shows preferred orientation.Promptly, when to being parallel to the above-mentioned P face that adds pressure surface, when carrying out the x ray diffraction respectively perpendicular to the above-mentioned h face that adds pressure surface, the peak of WC crystalline (001) crystal face and (101) crystal face is expressed as P (001) by force respectively, P (101), when h (001) and h (101), satisfy p (001)/p (101)＞1.2 * h (001)/h (101).If relatively the peak is strong than can not satisfy following formula the time, WC (001) crystal face in the preferred orientation of specific direction than reducing, thereby reduced the anisotropy of hardness, thereby can not show hardness property by the hardness of raising on specific direction or crystal face.
In the above-mentioned Wimet that contains platelet WC, preferably its ratio of containing 20% (volume) or above maximum length on the WC particle cross section and minimum length is not less than 3.0 platelet WC, and its various performances such as hardness, wear resistance, intensity, toughness, resistance to fracture are improved.Particularly preferred situation is that the particle diameter of WC is 0.5 μ m or littler.Contained platelet WC is preferably 40% (volume) or bigger on the cross section of Wimet, especially preferred 50% (volume) or bigger.
The composition that is used for forming platelet WC in the preparation Wimet that closes platelet WC of the present invention comprises: the W that contains 60-90% (weight), the double carbide of the carbon of 0.5-3.0% (weight) and at least a iron family metal of its surplus, the Wimet that can obtain to have high platelet WC content thus.As for above-mentioned double carbide, can for example specifically mention: Co
3W
9C
4, Co
2W
4C, Co
3W
3C, Co
6W
6C, Ni
2W
4C, Fe
2W
4C, Fe
3W
3C, Fe
4W
2C and sosoloid thereof.
Being used for preparing the method that contains the Wimet of platelet WC of the present invention comprises: will form the mixed powder moulding of platelet WC powder, this mixed powder comprises and contains a kind of iron family metal, the double carbide of W and C and/or its precursor, carbon dust, and if desired, form the powder of cube compound; Then under 1200-1600 ℃ of temperature, the briquet of heat-agglomerating moulding in vacuum or non-oxidizing atmosphere.The inventive method is carried out under the same conditions with the conventional Wimet method of making, for example, in a kind of non-oxidizing gas such as a kind of rare gas element or hydrogen atmosphere, in decompression, under normal pressure or the supercharging sintering 30-90 minute.
Preparing the present invention, to contain double carbide used in the method for platelet WC Wimet identical with above-mentioned double carbide.In addition, can mention those double carbides that in above-mentioned double carbide, are dissolved with 4b, 5b in the periodic table of elements that is no more than 20% (weight) or 6b family metal (except that W), as Co
3(W, Ti)
9C
4, Co
2(W, V)
4C, Co
3(W, Ta)
3C, (Ni, Cr)
2W
4C and (Fe, Mo)
3W
3C.It is preferred being dissolved with 4b, 5b or 6b family metal in some cases, because when sintering, it has the size of the platelet WC particle of crystallization control, the effect of shape and distribution when forming carbide.
As at the preparation precursor that contains double carbide used in the method for platelet WC Wimet of the present invention, can specifically mention the W alloy that contains a kind of iron family metal, W and/or W
2The mixture of C and a kind of iron family metal, and WC, 4b in the periodic table of elements, 5b or the oxide compound of 6b family metal and a kind of mixture of iron family metal.Also can more specifically mention the powdered alloy of W-10% (weight) Co for example, W
2The mixed powder of C-10% (weight) Co, WC-10% (weight) TiO
2The mixed powder of-10% (weight) Co, and W-10% (weight) WC-2% (weight) Cr
2O
3The mixed powder of-10% (weight) Ni, above-mentioned every kind of mixture forms above-mentioned double carbide with the carbon dust that a part is added when sintering.
As for the carbon-source cpd in the above-mentioned preparation method who contains platelet WC Wimet, can specifically mention graphite, carbon, petroleum pitch and thermosetting resin.When using the precursor powder of above-mentioned double carbide, preferably use the graphite of mean particle size 2-20 μ m, because this will speed up the formation of platelet WC, thereby increase hardness of alloy and toughness.The amount of carbon can be chosen wantonly, if it when sintering, can be enough to be used for to reduce in the mixed powder residual oxygen and form platelet WC with the W component, and the carbon amount also should make and no longer has double carbide or do not separate out free carbon in the Wimet that obtains by sintering.
In the preparation Wimet method that contains platelet WC of the present invention, if desired,, can for example specifically mention TaC, NbC, V as the powder of the formation cubic structure compound that adds
4C
3, VC, TiC, (W, Ti) C, (W, Ti, Ta) C, TiN, ZrN and Ti (CN).
Preferably, contain the heat-agglomerating of carrying out in the method for platelet WC Wimet and comprise that formation is by M in that preparation is of the present invention
3-xW
3+xFs of the double carbide of C (wherein M represents a kind of iron family metal, and 0≤x≤1) expression and forms the subordinate phase of platelet WC by above-mentioned double carbide is because the formation of acceleration platelet WC can increase hardness and toughness.
In the preparation method that contains platelet WC Wimet of the present invention, preferably, contain W alloy powder and/or metal W powder as above-mentioned precursor, because can make WC (001) crystal face preferred orientation on specific direction of Wimet like this, thus the anisotropy of raising hardness.That is to say, make in W alloy powder and/or the metal W powder by mixing and pulverize and the plane that forms is parallel in forming step and adds pressure surface and be orientated, thereby (001) crystal face of the WC that forms by heat-agglomerating being parallel to add pressure surface is orientated.
The Wimet that contains platelet WC of the present invention has the effect that improves Wimet hardness, intensity, toughness and break resistance, improve simultaneously the speed of growth of WC (001) crystal face again, WC (001) crystalline a shaft length, c shaft length and c/a ratio, and raising platelet WC crystalline ratio, and the method for preparing above-mentioned alloy comprises a kind of iron family metal by making, and the double carbide of W and C and carbon reaction can formation platelet WC and tackiness agent are mutually.
Below with reference to embodiment the present invention is described in detail.
Embodiment 1
At first, form the following powder of weighing according to the prescription shown in the table 1: the mean particle size that can buy on the market is respectively 0.5 μ m, 1.5 the W powder of μ m and 3.2 μ m (is expressed as " W/F " respectively in the table afterwards, " W/M " and " W/L "), granularity is the carbon black (" C " shown in the table) of 0.02 μ m, and the Co of granularity between 1-2 μ m, Ni, Fe, Cr, Cr
3C
2And TaH
2These powder are packed in the stainless cylinder of steel with acetone solvent and sintered carbide ball.Powder mixes and pulverize 24 hours after, drying makes mixed powder.Mixed powder is packed in the plumbago crucible, and under vacuum (the about 1OPa of atmosphere pressures), heating is 1 hour under temperature shown in the table 1, makes powder composition P of the present invention (1) to P (6) be used to prepare the precursor P (7) and the P (8) of powder composition of the present invention.Carry out the x ray diffraction, utilize inner mark method ration to measure the composition and the component of these powder.The results are shown in table 1.
Then, form the following component of weighing: powder composition shown in the table 1, above-mentioned W, C, Co, Ni, Fe, Cr and Cr according to prescription shown in the table 2
3C
2Powder, mean particle size are respectively 0.5 μ m, the commercially available WC of 1.5 μ m and 3.2 μ m (being expressed as " WC/F " in the table respectively, " WC/M " and " WC/L "), and granularity is the W of 1.4 μ m
2C, the graphite of granularity 6.0 μ m (representing with " G " in the table), the WO of granularity 0.4 μ m
3, the TiO of granularity 0.03 μ m
2(W, Ti, Ta) C sosoloid (WC/TiC/TaC=50/20/30, weight ratio are represented with " WTT " in the table) with granularity 1.5 μ m; They are packed in the jar that stainless steel makes with acetone solvent and sintered carbide ball.Powder mixes and grinding 48 hours, drying makes mixed powder then.Mixed powder is packed in the metal pattern, under 200MPa pressure, add the biscuit that is pressed into about 5.5 * 9.5 * 29mm size.Biscuit spare is placed on the sheet of being made by aluminum oxide and carbon fiber, under vacuum (under the about 10Pa of atmosphere pressures),, obtains the Wimet of sample 1 to 17 of the present invention and control sample 1 to 17 sintering temperature shown in the table 21 hour.
The Wimet sample that obtains carries out wet grinding with #230 diamond lap sand, makes the sample that is of a size of 4.0 * 8.0 * 25.0mm.Measure the transverse strength (bending strength) (using the Japanese Industrial Standards JIS B4140 corresponding method similar) of every sample with ISO 2422804.Then, after a face (be parallel to and the add pressure surface) polishing of the diamond polishing cream of 1 μ m to each sample, with the load measurement of 198N the Vickers' hardness and the fracture toughness property value K of alloy
IC(utilize so-called IM method, undertaken) by measuring from crack length with the border extended of Vickers hardness tester gained impression.Taken the structure photo of polished surface with electron microscope.By image processor, measured the mean particle size of WC, and the ratio of overall dimension and minimum size is more than or equal to 3.0 platelet WC and whole volume ratios of WC.In addition, measured with Cu-Ka penetrate strong peak with (101) crystal face, the peak of (001) crystal face of WC when becoming to carry out X-ray diffraction analysis by force than, and WC crystalline lattice parameter (a axial length, c axial length) and c/a ratio.The results are shown in table 3.
In addition, the estimation of being measured by above-mentioned microstructure photograph is formed and is also listed in table 2.
Table 1
| Test piece number (Test pc No.) | Prescription is formed (weight %) | Heating temperature (C) | Composition (weight %) |
| Sample of the present invention P(1) | 88.4W/M-9.1Co-2.5C | 1,300 | 90Co 3W 9C 4-5Co 2W 4C-5WC |
| Sample of the present invention P(2) | 85.5W/F-13.1Co-1.4C | 1,100 | 90Co 2W 4C-5Co 6W 6C-5WC |
| Sample of the present invention P(3) | 87.6W/M-8.0Ni-2.0Cr 3C 2-2.4C | 1,300 | 100(Ni,Cr) 2W 4C |
| Sample of the present invention P(4) | 75.3W/M-23.1Co-1.6C | 1,300 | 90Co 3W 3C-5Co 2W 4C-5WC |
| Sample of the present invention P(5) | 75.0W/M-23.4Fe-1.6C | 1,200 | 90Fe 3W 3C-5Fe 4W 2C-5WC |
| Sample of the present invention P(6) | 86.5W/M-9.0Co-2.0TaH 2-2.5C | 1,300 | 95Co 3(W,Ta) 9C 4-10WC |
| Control sample P(7) | 90.0W/L-10.0Co | 1.400 | 65W-35W 6Co 7 |
| Control sample P(8) | 88.0W/F-2.0Cr-10.0Ni | 1,100 | 85(W-Cr)-15WNi 4 |
Table 2
| Test piece number (Test pc No.) | Prescription is formed (weight %) | Sintering temperature (℃) | Synthetic composition (volume %) |
| Sample 1 of the present invention | 96.8P(1)-3.2C | 1,400 | 85.5WC-14.5Co |
| Sample 2 of the present invention | 96.0P(2)-1.0Cr 3C 2-3.0C | 1,380 | 78.5WC-21.5(Co-Cr) |
| Sample 3 of the present invention | 97.1P(3)-2.9C | 1,420 | 84.5WC-15.5(Ni-Cr) |
| Sample 4 of the present invention | 96.8P(4)-3.2C | 1,380 | 66.5WC-33.5Co |
| Sample 5 of the present invention | 96.7P(5)-3.3C | 1,360 | 64WC-36Fe |
| Sample 6 of the present invention | 94.4P(7)-5.6G | 1,400 | 84.5WC-15.5Co |
| Sample 7 of the present invention | 94.8P(8)-5.2G | 1,420 | 82WC-18(Ni-Cr) |
| Sample 8 of the present invention | 67.1W 2C-30,0P(1)-2.9C | 1,480 | 95.5WC-4.5Co |
| Sample 9 of the present invention | 59.2W 2C-30.0W/M-7.0Co-3.8G | 1,420 | 88.5WC-11.5Co |
| Sample 10 of the present invention | 81.0WC/M-10.0WO 3-6.8Co-2.2Gr | 1,420 | 88.5WC-11.5Co |
| Sample 11 of the present invention | 83.4W 2C-7.0Fe-5.0Ni-2.0Cr 3C 2-2.6C | 1,420 | 77WC-23(Fe-Ni-Cr) |
| Sample 12 of the present invention | 96.8P(6)-3.2G | 1,400 | 83.5WC-2TaC-14.5Co |
| Sample 13 of the present invention | 66.0P(1)-28.9W 2C-2.0TaC-3.1C | 1,440 | 88WC-2TaC-10Co |
| Sample 14 of the present invention | 77.5P(1)-20.0WTT-2.5C | 1,400 | 63WC-26(W,Ti,Ta)C-11Co |
| Sample 15 of the present invention | 68.5W/M-20.0WTT-7.0Co-4.5G | 1,400 | 63WC-26(W,Ti,Ta)C-11Co |
| Sample 16 of the present invention | 79.8WC/M-5.4TiO 2-6.1TaC-7.1Co-1.7G | 1,400 | 63WC-26(W,Ti,Ta)C-11Co |
| Sample 17 of the present invention | 58.1P(4)-40.0WTT-1.9C | 1,440 | 37WC-45(W,Ti,Ta)C-18Co |
Table 2 (continuing)
| Test piece number (Test pc No.) | Prescription is formed (weight %) | Sintering temperature (℃) | Synthetic composition (volume %) |
| Control sample 1 | 91.2WC/M-8.8Co | 1,400 | 85.5WC-14.5Co |
| Control sample 2 | 86.5WC/F-1.0Cr 3C 2-12.7Co | 1,380 | 78.5WC-21.5(Co-Cr) |
| Control sample 3 | 90.3WC/M-7.8Ni-1.9Cr 3C 2 | 1,420 | 84.5WC-15.5(Ni-Cr) |
| Control sample 4 | 77.6WC/M-22.4Co | 1,380 | 66.5WC-33.5Co |
| Control sample 5 | 77.4WC/M-22.6Fe | 1,360 | 64WC-36Fe |
| Control sample 6 | 90.5WC/L-9.5Co | 1,400 | 84.5WC-15.5Co |
| Control sample 7 | 88.6WC/F-1.8Cr 3C 2-9.6Ni | 1,420 | 82WC-18(Ni-Cr) |
| Control sample 8 | 97.3WC/M-2.7Co | 1,480 | 95.5WC-4.5Co |
| Control sample 9 | 93.0WC/M-7.0Co | 1,420 | 88.5WC-11.5Co |
| Control sample 10 | 86.0WC/M-7.0Fe-5.0Ni-2.0Cr 3C 2 | 1,420 | 77WC-23(Fe-Ni-Cr) |
| Control sample 11 | 89.2WC/M-2.1TaC-8.7Co | 1,400 | 83.5WC-2TaC-14.5Co |
| Control sample 12 | 92.0WC/M-2.0TaC-6.0Co | 1,440 | 88WC-2TaC-10Co |
| Control sample 13 | 73.0WC/M-20.0WTT-7.0Co | 1,400 | 63WC-26(W,Ti,Ta)C-11Co |
| Control sample 14 | 46.6WC/M-40.0WTT-13.4Co | 1,440 | 37WC-45(W,Ti,Ta)C-18Co |
| Control sample 15 | 76.9W 2C-20.0P(1)-3.1C | 1,520 | 97WC-3Co |
| Control sample 16 | 72.7P(7)-23.0Co-4.3G | 1,360 | 57WC-43Co |
| Control sample 17 | 51.3P(4)-47.0WTT-1.7C | 1,440 | 31WC-53(W,Ti,Ta)C-16Co |
Table 3
| Test piece number (Test pc No.) | Bending strength (GPa) | Hardness HV20 | Fracture toughness property value KIC (MPam 1/2) | WC mean particle size (μ m) | The ratio of platelet WC (% volume) | WC crystal 001/101 crystal face peak by force than | WC lattice parameter (nm) | Axial length compares c/a | |
| The a axle | The c axle | ||||||||
| Sample 1 of the present invention | 2.7 | 1,750 | 10.3 | 1.5 | About 70 | 0.65 | 0.29084 | 0.28412 | 0.9776 |
| Sample 2 of the present invention | 3.6 | 1,590 | 13.6 | 0.3 | About 80 | 0.69 | 0.29082 | 0.28422 | 0.9778 |
| Sample 3 of the present invention | 2.8 | 1,700 | 10.9 | 1.5 | About 60 | 0.63 | 0.29085 | 0.28419 | 0.9776 |
| Sample 4 of the present invention | 3.5 | 1,270 | - | 1.6 | About 80 | 0.75 | 0.29084 | 0.28418 | 0.9776 |
| Sample 5 of the present invention | 2.6 | 1,380 | 14.3 | 1.4 | About 40 | 0.62 | 0.29086 | 0.28415 | 0.9773 |
| Sample 6 of the present invention | 3.1 | 1,370 | 15.5 | 3.2 | About 60 | 0.71 | 0.29082 | 0.28415 | 0.9777 |
| Sample 7 of the present invention | 2.8 | 1,620 | 11.1 | 0.4 | About 70 | 0.74 | 0.29085 | 0.28421 | 0.9779 |
| Sample 8 of the present invention | 1.7 | 2,110 | 7.8 | 1.8 | About 40 | 0.65 | 0.29084 | 0.28420 | 0.9775 |
| Sample 9 of the present invention | 2.9 | 1,890 | 9.8 | 1.3 | About 60 | 0.67 | 0.29082 | 0.28414 | 0.9774 |
| Sample 10 of the present invention | 2.7 | 1,870 | 9.7 | 1.4 | About 50 | 0.59 | 0.29084 | 0.28412 | 0.9776 |
| Sample 11 of the present invention | 2.6 | 1,610 | 12.6 | 1.6 | About 60 | 0.67 | 0.29085 | 0.28419 | 0.9776 |
| Sample 12 of the present invention | 2.6 | 1,780 | 10.0 | 1.4 | About 70 | 0.60 | 0.29082 | 0.28415 | 0.9777 |
| Sample 13 of the present invention | 2.4 | 1,950 | 8.9 | 1.4 | About 50 | 0.62 | 0.29086 | 0.28415 | 0.9773 |
| Sample 14 of the present invention | 2.2 | 1,890 | 8.5 | 1.5 | About 60 | 0.68 | 0.29082 | 0.28422 | 0.9778 |
| Sample 15 of the present invention | 2.4 | 1,900 | 8.6 | 1.4 | About 70 | 0.75 | 0.29084 | 0.28420 | 0.9775 |
| Sample 16 of the present invention | 2.0 | 1,870 | 8.7 | 1.4 | About 50 | 0.56 | 0.29084 | 0.28412 | 0.9776 |
| Sample 17 of the present invention | 2.2 | 1,540 | 10.7 | 1.6 | About 70 | 0.65 | 0.29082 | 0.28414 | 0.9774 |
Table 3 (continuing)
Embodiment 2
| Test piece number (Test pc No.) | Bending strength (GPa) | Hardness HV20 | Fracture toughness property value KIC (MPam 1/2) | WC mean particle size (μ m) | The ratio of platelet WC (% volume) | WC crystal 001/101 crystal face peak by force than | WC lattice parameter (nm) | Axial length compares c/a | |
| The a axle | The c axle | ||||||||
| Control sample 1 | 2.5 | 1,650 | 9.4 | 1.5 | About 0 | 0.35 | 0.29063 | 0.28378 | 0.9764 |
| Control sample 2 | 3.3 | 1,470 | 11.2 | 0.3 | About 0 | 0.30 | 0.29061 | 0.28377 | 0.9765 |
| Control sample 3 | 2.6 | 1,640 | 10.1 | 1.4 | About 0 | 0.32 | 0.29065 | 0.28382 | 0.9765 |
| Control sample 4 | 2.1 | 1,180 | - | 1.5 | About 0 | 0.35 | 0.29070 | 0.28390 | 0.9765 |
| Control sample 5 | 2.7 | 1,300 | 12.9 | 1.5 | About 0 | 0.32 | 0.29066 | 0.28382 | 0.9765 |
| Control sample 6 | 2.9 | 1,270 | 14.5 | 3.1 | About 0 | 0.31 | 0.29067 | 0.28385 | 0.9764 |
| Control sample 7 | 2.6 | 1,540 | 10.1 | 0.3 | About 5 | 0.36 | 0.29062 | 0.28378 | 0.9767 |
| Control sample 8 | 1.8 | 2,090 | 7.1 | 1.9 | About 5 | 0.42 | 0.29060 | 0.28376 | 0.9766 |
| Control sample 9 | 2.7 | 1,800 | 8.9 | 1.4 | About 0 | 0.33 | 0.29062 | 0.28377 | 0.9767 |
| Control sample 10 | 2.3 | 1,520 | 8.9 | 1.5 | About 0 | 0.31 | 0.29061 | 0.28374 | 0.9764 |
| Control sample 11 | 2.5 | 1,700 | 9.0 | 1.3 | About 0 | 0.33 | 0.29066 | 0.28382 | 0.9765 |
| Control sample 12 | 2.2 | 1,830 | 8.0 | 1.5 | About 0 | 0.36 | 0.29061 | 0.28377 | 0.9765 |
| Control sample 13 | 2.0 | 1,810 | 7.8 | 1.5 | About 0 | 0.30 | 0.29065 | 0.28382 | 0.9765 |
| Control sample 14 | 2.0 | 1,470 | 9.7 | 1.5 | About 0 | 0.33 | 0.29062 | 0.28378 | 0.9767 |
| Control sample 15 | 1.2 | 2,010 | 6.8 | 2.0 | About 40 | 0.60 | 0.29063 | 0.28378 | 0.9764 |
| Control sample 16 | 2.9 | 1,070 | - | 1.6 | About 70 | 0.71 | 0.29060 | 0.28376 | 0.9766 |
| Control sample 17 | 1.7 | 1,640 | 8.7 | 1.5 | About 60 | 0.67 | 0.29069 | 0.28390 | 0.9765 |
With sample 1,6,7,9,10,11,15 of the present invention among the embodiment 1 and 16 and control sample 1,6,7,9,10 and 13 biscuit heats with embodiment 1 same procedure and under embodiment 1 the same terms, keeps 5 minutes at 950 ℃ and 1100 ℃ respectively, and take out the cooling back.To the briquet that heated, by x ray diffraction its about composition of internal mark method determination.The results are shown in table 4.
Table 4
Embodiment 3
| Test piece number (Test pc No.) | The component of the composition during heat-agglomerating (weight %) | |
| 950℃ | 1,100℃ | |
| Sample 1 of the present invention | 35WC-25Co 3W 9C 4-20Co 3W 3C-20Co 6W 6C | 75WC-20Co 3W 3C-5Co |
| Sample 6 of the present invention | 30WC-30(W-Co)-20Co 3W 3C-20Co 6W 6C | 60WC-40Co 3W 3C |
| Sample 7 of the present invention | 70Ni 2W 4C-20(W-Cr)-10WC | 55WC-40Ni 2W 4C-5(Ni-Cr) |
| Sample 9 of the present invention | 40W2C-30Co 3W 3C-20WC-10Co 6W 6C | 80WC-15Co 3W 3C-5Co |
| Sample 10 of the present invention | 40W-20WC-20Co 3W 3C-20Co 6W 6C | 70WC-30Co 3W 3C |
| Sample 11 of the present invention | 50(Fe,Ni,Cr) 3W 3C-30WC-20Fe 4W 2C | 80WC-20Fe 3W 3C-10(Fe-Ni-Cr) |
| Sample 15 of the present invention | 30WC-30Co 3W 3C-20W-20(W,Ti,Ta)C | 65WC-20(W,Ti,Ta)C-10Co 3W 3C-5Co |
| Sample 16 of the present invention | 50WC-20Co 3W 3C-10Co 6W 6C-10(Ti,Ta)C | 55WC-30Co 3W 3C-15(W,Ti,Ta)C |
| Control sample 1 | 91WC-9Co | 91WC-9Co |
| Control sample 6 | 90WC-10Co | 90WC-10Co |
| Control sample 7 | 90WC-10(Ni-Cr) | 90WC-10(Ni-Cr) |
| Control sample 9 | 93WC-7Co | 93WC-7Co |
| Control sample 10 | 86WC-14(Fe-Ni-Cr) | 86WC-14(Fe-Ni-Cr) |
| Control sample 13 | 73WC-20(W,Ti,Ta)C-7Co | 73WC-20(W,Ti,Ta)C-7Co |
With used sample 6 of the present invention among the embodiment 1,7,9 and 15, and the mixed powder of control sample 6,7,9 and 13 cross-sectional shape of packing into is about in the metal pattern of 16 * 16mm, use, push-down head extrusion forming under 200MPa pressure, make the biscuit of about 16 * 16 * 6.2mm of size.With embodiment 1 same procedure and heating under the same conditions, the biscuit sheet is carried out sintering.
With #230 diamond lap sand the Wimet sample that obtains is carried out wet grinding, use the diamond polishing cream of 1 μ m that the one side (" h face " in the table 5) in one side in the above and below (in the table 5 " P face ") and the side is polished again.The peak of p face and h face being measured WC crystal (001) face and (101) face respectively with X-ray diffraction by force than.In addition, from the peak that obtains respectively by force than, calculate the ratio of p face and h face.The results are shown in table 5.
Table 5
| Test piece number (Test pc No.) | The peak by force than | P/h is compared on the plane that the peak is strong | |
| The p face | The h face | ||
| Sample 6 of the present invention | 0.74 | 0.42 | 1.76 |
| Sample 7 of the present invention | 0.80 | 0.49 | 1.63 |
| Sample 9 of the present invention | 0.67 | 0.44 | 1.52 |
| Sample 15 of the present invention | 0.75 | 0.51 | 1.47 |
| Control sample 6 | 0.31 | 0.32 | 0.96 |
| Control sample 7 | 0.36 | 0.33 | 1.09 |
| Control sample 9 | 0.33 | 0.33 | 1.00 |
| Control sample 13 | 0.30 | 0.29 | 1.03 |
From table 3, the result shown in 4 and 5, the Wimet that contains platelet WC of the present invention is as can be seen compared with the contrast Wimet that contains same composition, has higher bending strength, hardness and fracture toughness property.
Embodiment 4
With used sample 9 of the present invention and 13 among the embodiment 1, and the mixed powder of control sample 9 and 12 sectional area of packing into is about in the metal pattern of 16 * 16mm, uses, push-down head pressurizes under 200MPa pressure and make the biscuit that is of a size of 16 * 16 * 6.2mm.Then with the same procedure among the embodiment 1 and heating and sintering biscuit under the same conditions, carry out wet grinding then and obtain SNGN120408 cutting tip according to iso standard.Listed parameter was carried out the turning experiment below these blades were used, and measured its work work-ing life when the blade side wearing and tearing reach 0.35mm.The results are shown in table 6.
Be cut material: FC350
Cutting speed: V=100m/min
Cutting-in: d=1.5mm
The amount of feed: f=0.3mm
Cutting fluid: dry method
Embodiment 5
With used sample 12 of the present invention and 15 among the embodiment 1, and the mixed powder of control sample 11 and 13 sectional area of packing into is about in the metal pattern of 16 * 16mm, uses, push-down head heats under 200MPa pressure and make the biscuit that is of a size of 16 * 16 * 6.2mm.Then with the same procedure among the embodiment 1 and heating and sintering biscuit under the same conditions, carry out wet grinding then and obtain SNGN120408 cutting tip according to iso standard.These blades are carried out pre-chamfered edge-30 ° * 0.15mm, and the CVD that then they packed into applies stove.On blade face, apply the TiN of 1.0 μ m continuously, the TiCN of 5.0 μ m, the TiC of 2.0 μ m, the Al of 2.0 μ m
2O
3TiN (total coat-thickness: 11 μ m) with 1.0 μ m.The coated chip that use obtains carries out turning at intermittence under the test conditions below with steel, measures until point of a knife to burst apart or the working life of flank wear amount cutter when reaching 0.35mm.The results are shown in table 6.
Be cut material: S48C (being with 4 road grooves)
Cutting speed: V=150m/min
Cutting-in: d=2.0mm
The amount of feed: f=0.25mm
Cutting fluid: dry type
Embodiment 6:
Under about 200MPa pressure, suppress the sample of the present invention 2 used among the embodiment 1 and the mixed powder of control sample 2 with dry type hydraulic pressure press, make diameter 10mm, the pole of length 66mm.Heat and the sintering pole with embodiment 1 same procedure and under similarity condition, carry out wet grinding then, obtain end mill, its length 42.0mm, point diameter 6mm, cutter number are 2, helix angle is 30 degree.To these end mills, use the metal die steel, carry out cutting test under the test conditions below, measure the cutter working life when the flank wear amount reaches 0.25mm.The results are shown in table 6.
Be cut material: SKD11
Cutting speed: V=45m/min
Cutting-in: d=6.0mm
The amount of feed: f=0.02mm
Cut wide: W=3.5mm
Cutting fluid: wet method (a kind of water-soluble oiliness agent)
Embodiment 7
Approximately suppressing used sample 3 of the present invention and 7 among the embodiment 1 under the 200MPa pressure with dry type hydraulic pressure press, and the mixed powder of control sample 3 and 7, make the cylinder base, outside diameter of cylinder 52mm, internal diameter 12mm, high 40mm, with the pole base, pole diameter 14mm, long 40mm.Also under the same conditions these cylinders and pole are carried out heat-agglomerating with embodiment 1 same procedure, carry out wet grinding and make external diameter 40.0mm, internal diameter 10.00mm, the die sleeve of high 30.0mm, and diameter 9.95mm, the pressure head of length 30.0mm.Use is by the mould that the combination of above-mentioned alloy die sleeve and pressure head obtains, and under the condition powder carried out dry-pressing formedly below, measures the die life when forming fin on mould.The results are shown in table 6.
By the powder of moulding: ferrite
Briquet size: diameter 10.0mm, thickness 2.0mm
Molding time: 1 second
Shaping cycle: 5 seconds/base
Forming pressure: 3 tons/cm
2
Table 6
| Test subject | Test piece number (Test pc No.) | Life-span |
| The turning of mould (embodiment 4) | Sample 9 sample 13 control sample 9 control sample 12 of the present invention of the present invention | 27 minutes 34 minutes 15 minutes 20 minutes |
| The turning at intermittence of steel (embodiment 5) | Sample 12 sample 15 control sample 11 control sample 13 of the present invention of the present invention | 18 minutes 25 minutes 7 minutes (causing inordinate wear) 12 minutes (blade abrasion) by plastic deformation |
| The cutting of metal die steel (embodiment 6) | Sample 2 control sample 2 of the present invention | 25 minutes 17 minutes (blade abrasion) |
| Dry-pressing formed (embodiment 7) | Sample 3 sample 7 control sample 3 control sample 7 of the present invention of the present invention | 324 hours 517 hours 178 hours 15 hours (fracture) |
The Wimet that contains platelet WC of the present invention is compared with the conventional Wimet with same composition and granularity has significant effect, and its Vickers' hardness is not less than 500 when HV20, fracture toughness property K
1cFor being not less than 0.5MPam
1/2, and the method for preparing this Wimet has this effect: can make to simple and inexpensive and have the high platelet WC content and the Wimet of controllable granularity.
In addition, when the surface that applies Wimet of the present invention by the hard films that comprises one or more layers, and when making coated carbides, the Wimet expection that contains platelet WC of the present invention has better effect, hard films wherein comprises 4b (Ti in the periodic table of elements, Zr and Hf), 5b (V, Nb and Ta) or carbide, nitride, oxycarbide and the oxynitride of 6b (W, Mo and Cr) family's element, the oxide compound of Al and nitride, and their sosoloid, diamond, diamond-like carbon, at least a in cubic boron nitride and the hard boron nitride.
Claims (5)
1. Wimet that contains the platelet wolfram varbide, it comprises: the tackiness agent phase of 4-40% (volume), tackiness agent comprise mutually and at least aly are selected from that to form one group iron family metal by cobalt (Co), nickel (Ni) and iron (Fe) be main ingredient; And the hard of surplus phase and unavoidable impurities, hard only contains wolfram varbide mutually, or contain wolfram varbide and be no more than the compound that 50% (volume) has cubic structure, this cubic structure compound is selected from the periodic table of elements by titanium (Ti), the 4b family element that zirconium (Zr) and hafnium (Hf) are formed, by vanadium (V), the 5b family element that niobium (Nb) and tantalum (Ta) are formed, or by chromium (Cr), the carbide and the nitride of the 6b family element that molybdenum (Mo) and tungsten (W) are formed, and at least a in their sosoloid
Wherein, when using Cu target K
αRay carries out X-ray diffraction analysis, and when the peak of (001) crystal face and (101) crystal face was expressed as h (001) and h (101) by force respectively, above-mentioned wolfram varbide satisfied h (001)/h (101) 〉=0.05,
Wherein wolfram varbide contains the plate crystal tungsten carbide that is not less than 20% (volume), based on total wolfram varbide meter, this plate crystal tungsten carbide on the Wimet cross section maximum length and the ratio of minimum length be not less than 3.0.
2. the Wimet of claim 1, wherein the mean particle size of wolfram varbide is no more than 0.5 μ m.
3. the Wimet of claim 1, its interalloy has polyhedral shape, and (001) crystal face of plate crystal tungsten carbide is parallel to an above-mentioned polyhedral face and is orientated.
4. one kind prepares the described method that contains the Wimet of platelet wolfram varbide of claim 1, and it may further comprise the steps:
Plate crystal tungsten carbide is formed powder and a kind of carbon-source cpd or carbon-source cpd and composition adjusting compound, make mixed powder, wherein plate crystal tungsten carbide formation powder comprises a kind of cobalt (Co) that contains, nickel (Ni), at least a in iron (Fe) and the chromium (Cr), the solid solution compound of tungsten (W) and carbon (C) and/or its precursor, described carbon-source cpd comprises carbon, graphite and its precursor at least a, forming the adjusting compound is to be selected from the periodic table of elements by titanium (Ti), the 4b family element that zirconium (Zr) and hafnium (Hf) are formed, by vanadium (V), the 5b family element that niobium (Nb) and tantalum (Ta) are formed, or by chromium (Cr), the carbide and the nitride of the 6b family element that molybdenum (Mo) and tungsten (W) are formed, and their sosoloid, and cobalt metal (Co), at least a in iron (Fe) and chromium (Cr) and the alloy thereof
Above-mentioned mixed powder is shaped to a kind of base substrate; With
With above-mentioned base substrate under 1200-1600 ℃, heat-agglomerating in vacuum or non-oxidizing atmosphere.
5. the method for claim 4, wherein plate crystal tungsten carbide forms powder and is: comprise CO
3W
9C
4, CO
2W
4C, Co
3W
3C, Co
6W
6C, Ni
2W
4C, Fe
2W
4C, Fe
3W
3C, Fe
4W
2A kind of solid solution compound of C and sosoloid thereof, tungsten (W), W
2C, at least a alloy of cobalt (Co), nickel (Ni), iron (Fe) and chromium (Cr) and tungsten (W), at least a with in the precursor of solid solution compound, the precursor of solid solution compound wherein comprises the 4b family element of being made up of titanium (Ti), zirconium (Zr) and hafnium (Hf) in the periodic table of elements, the 5b family element of forming by vanadium (V), niobium (Nb) and tantalum (Ta), or the oxide compound of the 6b family element of forming by chromium (Cr), molybdenum (Mo) and tungsten (W).
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| US20130039800A1 (en) * | 2010-02-05 | 2013-02-14 | Weir Minerals Australia Ltd | Hard metal materials |
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| US8834594B2 (en) * | 2011-12-21 | 2014-09-16 | Kennametal Inc. | Cemented carbide body and applications thereof |
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| CN102965559B (en) * | 2012-12-14 | 2014-11-19 | 株洲硬质合金集团有限公司 | Material containing sheet-shaped wolfram carbide grain and preparation method thereof as well as method for using same to prepare alloy |
| CN103014472A (en) * | 2012-12-14 | 2013-04-03 | 苏州新锐合金工具股份有限公司 | Hard alloy with iron-nickel as binder metal and preparation method thereof |
| CN104328489B (en) * | 2014-10-14 | 2016-09-21 | 中国工程物理研究院流体物理研究所 | The three-dimensional orientation preparation method of WC alloy |
| WO2017027038A1 (en) * | 2015-08-13 | 2017-02-16 | Halliburton Energy Services, Inc. | Drill bits manufactured with copper nickel manganese alloys |
| US11060155B2 (en) * | 2016-04-01 | 2021-07-13 | Pramet Tools, S.R.O. | Surface hardening of cemented carbide body |
| CN108130517B (en) * | 2017-12-26 | 2019-10-29 | 浙江大学 | A kind of electrically conducting transparent WC crystalline film and preparation method thereof |
| CN108499577B (en) * | 2018-05-04 | 2020-12-11 | 华北理工大学 | Load sandwich type TiO on carbon fiber surface2Base photocatalyst and application thereof |
| CN109266941B (en) * | 2018-10-24 | 2020-09-04 | 崇义章源钨业股份有限公司 | Plate-shaped tungsten carbide-cobalt alloy and preparation method thereof |
| CN109913729B (en) * | 2019-03-12 | 2021-05-25 | 广东工业大学 | Method for synthesizing hard alloy matrix and polycrystalline diamond compact |
| CN115323235B (en) * | 2022-07-27 | 2023-12-01 | 自贡硬质合金有限责任公司 | Near-spherical WC grain hard alloy and preparation method and application thereof |
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