CN102187005A - Molybdenum-contained alloy powders used to produce sintered hard metals based on tungsten carbide - Google Patents
Molybdenum-contained alloy powders used to produce sintered hard metals based on tungsten carbide Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
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- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0433—Nickel- or cobalt-based alloys
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- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
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- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
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- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
Abstract
The invention relates to the use of binder alloy powders containing molybdenum to produce sintered hard metals based on tungsten carbide, wherein the binder alloy powder used has an FSSS value of 0.5 to 3 [mu]m measured with the "Fisher Sub-Sieve Sizer" device according to the ASTM B330 standard, and comprises 0.1 to 65 wt % of iron, 0.1 to 99.9 wt % of cobalt, and 0.1 to 99.9 wt % of nickel, and contains 0.1 to 10 wt % of Mo in alloyed form.
Description
Technical field
The present invention relates to contain the purposes of the adhesive alloy powder of molybdenum, its be used to produce based on wolfram varbide through the agglomerating hard metal.Hard metal is by the material of giving hardness (for example carbide) and successive adhesive alloy agglomerating matrix material.Very extensive through the application of agglomerating hard metal, and be used for for example timber of the actual whole known materials of processing, metal, stone and matrix material be glass-Resins, epoxy for example, fiber board, concrete or asphalt-cocrete.Here, as cutting, the result of distortion and friction process has occurred until the local temperature that surpasses 1000 ℃.In other situation, the deformation process of metal works is carried out at high temperature, forging, is exactly like this in the wire drawing or the operation of rolling for example.In whole situations, hard metal tools can experience oxidation, corrosion and diffusion and adhesive wear, and be in simultaneously under the high mechanical stress, this can cause the hard metal tools distortion.Term " adhesive wear " refers to any such phenomenon, it takes place under situation below: weld and firm being connected when two objects contact with each other and at least temporarily formed, it relies on external force and discharges again, and the material adhesive of one of them object is to another object.Term " diffusive wear " refers to any such phenomenon, and it takes place under situation below: two materials contact with each other, and composition from a diffuse to another material, make in first material, to have formed pit.
Background technology
WO 2007/057533 (Eurotungstene Poudres) has described the powdered alloy based on FeCoCu, and it contains the Cu of 15-35% and the Mo of 1.9-8.5%, is used to produce diamond cutter.The FSSS value is 3 μ m typically.These powder are not suitable for the hard metal field, and this is owing to high FSSS value (this value is measured by the Fisher particle size determination or according to iso standard 10070) with owing to the Cu content that surpasses 500ppm.Molybdenum is to join in the oxide compound as water soluble salt of ammonia, relies on hydrogen reducing to become metal-powder the latter subsequently.
EP 1492897 B1 (Umicore) describe the powdered alloy based on FeCoNiMoWCuSn, are used to produce diamond cutter, and Cu and Sn content summation are 5-45% here.But two kinds of elements are deleterious for hard metal all, because Cu " oozes out " in sintering process and Sn has caused pore-forming.Therefore these powdered alloys are unsuitable for producing hard metal.
EP 0865511 B9 (Umicore) has described powdered alloy, and it is based on FeCoNi, and the FSSS value is not more than 8 μ m, can also comprise 15% Mo at the most, though this exists as oxide compound to small part.In addition, these powder comprise the Fe of 10-80%, 40% Co and 60% Ni at the most at the most, and be used to produce diamond cutter.In addition, also described similarly, but comprised each 30% Co and the powder of 30% Ni at the most at the most.
WO 98/49361 (Umicore), EP 1042523 B1 (Eurotungstene Poudres) and KR 062925 described powdered alloy are also because copper content but inappropriate.
EP 1043411 B1 have described carbide-Co-, and (this adhesive alloy is to produce by the pyrolysis of organic precursor compound therein for W, Mo) composite powder.The appearance of hole has been avoided in the formation of the alloy of cobalt and Mo and/or W, as what metal occurred by adding.But, described method is with the shortcoming of using powdered alloy of the present invention to compare, change (carbon laydown or be removed by forming methane) has taken place in the carbon content of this composite powder in organic precursor compound pyrolytic process, therefore must reanalyse and adjust carbon content before sintering.The existence form of Mo or W also is unclear behind sintering, because both do not provided the comparison test or the indication of preceding Mo of sintering and W alloy state, does not also provide the magneticsaturation value.Described method has produced the fixedly prescription of carbide and adhesive alloy phase content and composition, is very inflexible in practice therefore, and this is because depend on that the prescription of the purposes that hard metal to be produced is arranged is unworkable with changing fast simply.
Be known that such powdered alloy equally, it is based on FeCoMo, FSSS value＜8 μ m, and specific surface area is greater than 0.5m
2/ g (DE 102006057004 A1), and they are used to produce carbon-free rapid steel via powder metallurgy process.They can randomly comprise 10% or 25% Ni at the most, but particularly advantageous be not comprise any nickel that exceeds inevitable pollution level.They are preferably by the Fe of 20-90%, at the most the Mo of 65% Co and 3-60%.Because the pure FeCo alloy that does not have an other Ni alloying is unsuitable for hard metal owing to their fragility and the erosion resistance and the scale resistance of difference, so these powdered alloys obviously can not provide the scheme that solves described problem.In addition, preferred range is not described, that is, high Mo content be used for production liquid phase-agglomerating carbon containing hard metal (it has as the mechanically resistant material of hardness imparting agent carbide for example mutually).
The invention target
Be known that cobalt metal when as unique binder metal, during especially for wolfram varbide, has Health hazard.So alloying element that target detection is other of the present invention, and it is used for producing through the agglomerating hard metal material, its permission use FeNi and FeCoNi tackiness agent come replaced C o at 400-800 ℃ elevated operating temperature, and immaculate for example tackiness agent shallow lake (Binderseen), lack to magnetically saturated interpreting line or tackiness agent mutually in relevant element ratio be unknown, and related element has caused the increase of hot hardness in 400-800 ℃ temperature range.On the other hand, the content of involved element should be low as far as possible, and in order to raise the efficiency, distribution as well as possible equally also is possible.
This target is to realize by the adhesive alloy powder that use contains molybdenum, this powder be used to produce based on wolfram varbide through the agglomerating hard metal, be characterised in that:
A) the FSSS value of used adhesive alloy powder is 0.5-3 μ m, this value measure according to ASTM B 330 and
B) used adhesive alloy powder comprises the iron of 0.1-65 weight % amount, the nickel of the cobalt of 0.1-99.9 weight % amount and 0.1-99.9 weight % amount and
C) used adhesive alloy powder comprises the alloy form of 0.1-10 weight % or the Mo of prealloy form.
This molybdenum preferably exists with metallic forms fully.Used adhesive alloy powder comprises the nickel of at least 10 weight %, based on the total binder alloy.
Used adhesive alloy powder comprises the highest 20 weight %, the particularly tungsten of the highest 10 weight %, based on the total binder alloy.
At least a composition of this adhesive alloy exists as the powdery alloy of at least a metal and molybdenum, each all the other composition of this adhesive alloy exist as element or alloy (it does not all contain any molybdenum), promptly, what use is Mo-contained alloy powder and the powdered alloy of at least a alloy or prealloy or the made alloy of powdered mixture of element powders by at least a alloy or prealloy, and the latter's powder contains and only is in the interior molybdenum of unavoidable impurities scope.
The adhesive alloy powder that contains molybdenum of the present invention is used for producing through the agglomerating hard metal, and sintering is to carry out with the form of liquid phase sintering.
The adhesive alloy powder that contains molybdenum of the present invention can comprise the organic additive of 30 weight % at the most.
Description of drawings
Fig. 1 has represented to compare with the hot hardness (tip square symbols down) of the hard metal of the embodiment 2 with cobalt binder, embodiment 1 (triangle with FeCoNi tackiness agent, solid line is represented " low-carbon (LC) " flexible program, and dotted line is represented " high-carbon " flexible program) the hot hardness curve.
Fig. 2 has represented (to use the FeCoNi tackiness agent of Mo alloying with embodiment 4, the square symbols of falling) and embodiment 2 (cobalt is as tackiness agent, tip square symbols down) compares, embodiment 3 (FeCoNi tackiness agent, Mo is as element powders, circle symbol, 1% Mo=dotted line, 3% Mo=solid line) the hot hardness curve of hard metal.
Embodiment
This target be by use contain iron-, cobalt-or nickel-the binder metal powder realize that this powder comprises the iron of 0.1-65 weight % amount, the nickel of the cobalt of 0.1-99.9 weight % amount and 0.1-99.9 weight % amount.
Used adhesive alloy powder comprises the molybdenum of the alloy form of 0.1-10 weight % in addition, based on the total binder metal-powder.Used adhesive alloy powder preferably comprises the molybdenum of 0.10 weight %-3 weight %, the molybdenum of preferred especially 0.5 weight %-2 weight %, and the molybdenum of 0.5 weight %-1.7 weight % very particularly preferably is in each case based on the total binder metal-powder.
The FSSS value of used adhesive alloy powder is 0.5-3 μ m, preferred 0.8-2 μ m, particularly 1-2 μ m, and this value is to use " Fisher Sub Siever Sizer " equipment, measures according to standard A STM B 330.
Preferred each the amount of element M n and Cr is less than 1%.Used adhesive alloy powder preferably comprises the molybdenum that is in non-oxidised form fully or is in the metal of alloying form fully.
Used adhesive alloy powder preferably comprises the nickel of at least 20 weight %, based on the total binder alloy.Used adhesive alloy powder preferably comprises the tungsten of the highest 20 weight %, and the more preferably tungsten of the highest 10 weight % is based on the total binder alloy.Especially, preferred powdered alloy does not have tungsten basically, and W content is less than 1 weight %.
In used adhesive alloy powder, what preferably provide is at least a composition of adhesive alloy to be introduced as the powdery alloy of at least a metal and molybdenum and each all the other composition of this adhesive alloy are introduced as the element that does not all comprise any molybdenum or alloy.
According to the present invention, this adhesive alloy powder is carried out as liquid phase sintering with the mechanically resistant material sintering.The appearing and subsiding that this means the liquid metal phase only is attributable simply to used temperature variation, and this mechanically resistant material dissolves post crystallization (uml sen) in adhesive alloy, and has therefore experienced granularity rising (Ostwald slaking).These are different with solid state sintering, in solid state sintering, do not form melt, do not have yet since the moment of forming, partial variation and temporarily form any melt, but the mechanically resistant material that may exist for example diamond be not take place to dissolve post crystallization and experience granularity and raise in melt.
Invention description
The hard metal of producing by method of the present invention need have enough stability aspect viscous deformation and the temperature dependency creep behaviour, so that it can be used in their target purposes.The creep of material, for example viscous deformation is a kind of main material failure mechanism, in any case and must be avoided.This deformation mechanism is the creep time rule of the known load dependence of experience, and creep speed not only depends on this load, also depends on temperature to a great extent.In addition, this creep mechanism mainly changes as the function of temperature in each case.In the situation of hard metal, be known that the creep speed when about 800 ℃ of temperature at the most mainly is to measure by the distortion of metal-to-metal adhesive phase, and when being higher than about 800 ℃, this tackiness agent is so soft mutually, to such an extent as to it does not have tangible creep resistance in fact, that is, when temperature was higher than 800 ℃, the loading strength of mechanically resistant material phase was a deciding factor.This supporting capacity and then depend on the particle shape and the size-grade distribution of mechanically resistant material phase and the ratio that depends on heat-stable cubic carbide.Reason for this reason, the whole hard metal materials that are used to cut steel not only comprise WC, but also comprise for example TiC of a certain proportion of cubic carbide, TaC, NbC, VC, ZrC or mixed carbide be TaNbC for example, WTiC or WVC.
Because the temperature dependent test determination of creep behaviour is very complicated during high temperature, therefore uses hot hardness to measure and replace.Material hardness is the indirect measurement of its plastic deformation ability.Therefore clou is that plastic deformation method is to be dominant in indentation hardness forms, and the size of this indentation hardness is material the measuring of plastic deformation ability under given compression load in the time of the duration of sufficiently high load and load.
In sintering process, based on WC and have Co as adhesive alloy, tungsten, the hard metal of carbon and little metal (it has formed cubic carbide, V for example, Ta, Ti and Nb) in the liquid phase sintering process, be dissolved into tackiness agent mutually in.If during the WC microstructural that the sintering process that during as so-called " particle growth inhibitor " (that is, as the reagent that suppresses particle growth), is used for carbonization Cr suppressing takes place, this also is applicable to Cr.
Term " liquid phase sintering " refers to the sintering that is in such high-temperature: make adhesive alloy partial melting at least.Liquid phase is the result of sintering temperature in the hard metal sintering process, normally 1100 ℃-1550 ℃ of this temperature.Melt flow phase (being for example cobalt or one or more binder metal alloys of used binder metal basically) is and the mechanically resistant material equilibrated to meet employed solubility product principle.This means that many more tungsten is present in the melt, few more carbon dissolution is in melt, and vice versa.The W content of adhesive alloy is to set by W:C ratio total in the hard metal, wherein always satisfies mutually W:C=1 for mechanically resistant material, therefore exists the different concns that is not equal to 1 W:C ratio in the binder metal melt.When the tungsten in the melt: when carbon ratio reached critical low value, the carbide of poor carbon is Co for example
3W
3C, known is as eta phase (η phase), separates out when cooling.These η are stone mutually, but also are highly brittle, and therefore are considered to the mass defect of hard metal.
Usually find also that the content that concrete metal can reach in the adhesive alloy is low more, the chemical stability of corresponding carbide is high more.The chemical stability of corresponding carbide is known, and can represent with the form of the free enthalpy that forms this carbide.If these values sort with unconventional expression, that is, based on the metal content of 1mol, then this order is in the time of 1000 ℃:
Cr
3C
2?<?Mo
2C?<?WC?<?VC?<?NbC?<?TaC?<?ZrC?<?TiC?<?HfC。
Here can see that as what expect, chromium carbide has discharged chromium metal as first carbide when carbon lacks gradually, it is dissolved in the adhesive alloy, but surprising, and molybdenum is next least stable carbide, even is in before the tungsten.So can come alloying hard metal tackiness agent with the molybdenum of big relatively content in theory, and the result who does not lack as the middle mutually carbon of tackiness agent forms eta phase (η phase).Top metallic carbide sequence also is measuring of metal and carbon avidity.For example, titanium and Cr
3C
2Competition carbon, so chromium preferentially exists as metal, and titanium preferentially exists as carbide.Wolfram varbide must be present in the material as the hardness imparting agent; Whole carbide on the wolfram varbide left side (promptly in the top sequence, from corresponding carbide, discharging connection metal, do not have the stable carbide of wolfram varbide) so be suitable for improving hot hardness, because they can enter metal-to-metal adhesive mutually in, and do not form the carbide of poor carbon, that is, so-called " η phase " takes place.
Because whole above-mentioned concentration of metal are subjected to the control of solubility product rule (carbide are unstable more in the tackiness agent, this solubility product is big more), and because a carbon potential is only arranged in balance here, therefore this sequence has also been represented such order, the metal that is dissolved in therein in the tackiness agent is separated out with the form of carbide along with increasing gradually of carbon supply, and therefore no longer can utilize tackiness agent to improve hot hardness.
The content of chromium or tungsten is extremely important for the high-temperature behavior of adhesive alloy, because these elements have caused the hot hardness rising, has therefore caused the deformation resistance rising.Reason for this reason, (it plans as instrument (blade (Schneidplatte)) hard metal of the type, for example be used for the turning steel) be to come agglomerating with such carbon balance, promptly, the W content of this adhesive alloy (it comprises cobalt usually) is maximized, and the formation of eta phase (η phase) does not take place.Containing the Cr carbide equally, be used for carrying out the situation of the mach instrument of metal, carbon content is set at is making Cr as much as possible be present in this adhesive alloy by boring and milling.Because the magneticsaturation of cobalt reduces continuously along with the increase of Cr and W content, therefore can be by the measurement magneticsaturation, the non-destructive testing that comes to carry out very simply alloy state, this measuring method is an industrial standards.
But because its antiferromagnetism characteristic, chromium makes in the hard metal mensuration of the carbon content difficulty that becomes, and therefore makes the mensuration of chromium and the W content difficulty that becomes, and this is because the relation between magneticsaturation and chromium and the W content no longer is clear and definite.As a result, lacking η can not only judge based on magnetically saturated measurement mutually.
Because with WC with as the combination associated health harm of the cobalt of adhesive alloy, interesting is to replace cobalt, makes for the powdered alloy based on FeCoNi or FeNi it is possible.Though they are confirmed for the suitability of the instrument of abrasion piece and converted timber or stone, do not confirm its suitability for the high temperature related application.Causing this a major cause is to compare with cobalt, and the hot strength of hard metal in 400 ℃-800 ℃ temperature range with Fe (Co) Ni tackiness agent is lower.
The hot hardness of adhesive alloy can rely on other metal separated out or or alloying come in and improve.But possible alloying element only is such metal, and it does not form stable carbide (that is, stability is no more than the carbide of wolfram varbide), and therefore satisfies the prerequisite of the solubleness of measuring in adhesive alloy.For example, if Ta is alloyed in this tackiness agent, then this will (carbon content that depends on hard metal) in fact fully mutually or behind sintering, exist as TaC as eta, and therefore do not represent a kind of high-heat strength adhesive alloy of high quality hard metal, because eta does not expect that owing to their fragility this fragility has caused the reduction of intensity in hard metal mutually.
In principle, metal W, Mn, Cr, Mo, Re and Ru especially improve the possible element of hot hardness.
The solvability of tungsten in adhesive alloy is subject to the solubility product of wolfram varbide in this adhesive alloy.In the limit that eta forms mutually, can divide into two kinds of situations with regard to the W content aspect: a) reduce when carbon content, and cobalt is when being used as binder metal, the tungsten of 20 weight % is dissolved in the cobalt binder at the most; B) reduce when carbon content, and when using the FeCoNi adhesive alloy, significantly less tungsten (that is only about at the most 5 weight %) is dissolved in this FeCoNi adhesive alloy.Thereby, tungsten in FeCoNi and FeNi alloy solubleness in addition be lower than pure cobalt, this is a reason that causes the low hot hardness that relies on FeCoNi bonded hard metal.
Manganese has relatively very high vapour pressure, and therefore, by the manganiferous hard metal of sintering, has obtained the concentration gradient and the precipitation of the Mn-metal condensate of pyrophoricity.Therefore, the concentration of Mn in sintered part can not accurately be set, and is estimated as in that to be abutted against the workpiece surface place lower than workpiece core place.
Rhenium metal, osmium and ruthenium have limited available property, and are extremely rare, but are suitable in principle.Rhenium for example is used in the used high-heat strength alloy of aircraft turbine, and purpose is to suppress the high temperature creep of parts.Ruthenium and rhenium are used for extraordinary hard metal based on cobalt commercial by limited extent ground.
Chromium is suitable equally, and in FeNi and FeCoNi alloy, has high solubleness, but have the shortcoming that causes owing to its antiferromagnetism characteristic, this makes and is difficult to explain magneticsaturation (die Interpretation der magnetischen S ttigung erschwert).This is a shortcoming, approaches to form the limit of eta phase as far as possible because be used for the hard metal of metal machining cutting, but does not have the latter of discernable amount.
Equally, be in the molybdenum (Mo of the molybdenum carbide form of adding
2C, 5 weight % join in the hard metal that contains 10% Fe based adhesive as additive) show the rising that (paper of Prakash) caused the hot hardness of FeCoNi alloy.But, because being the form with carbide, the Mo of unknown portions exists, at WC be dissolved between wherein recessive variant (Kryptomodification) MoC and formed the blended carbide, this has caused the undesired and not controlled reduction of this mechanically resistant material inherent strength.The formation of mixed carbide can be described by following reaction equation in the situation of molybdenum:
Mo
2C-〉Mo (in the tackiness agent interalloyization)+(W, Mo) C.
The solubleness of molybdenum in the alloy that contains Fe-and Ni-is higher than tungsten.The curve of the effectiveness of Mo in improving 427 ℃ the creep resistance of pure iron is obviously than Cr more precipitous (Trans. Amer. Inst. Min. Met. Eng. 162, (1945), 84), and only observes very slowly when being higher than 0.5% chromium and increase.Even 1% Mo also caused the creep resistance of 38 kpsi (262 MPa), and 1% Cr has only provided 16 kpsi (110 MPa), even 4% chromium does not have to obtain to surpass the value of 18 kpsi (124 MPa) yet.Hot hardness-temperature curve of Mn does not have platform, but has obviously lower slope.Therefore for improving hot hardness, particularly the iron content tackiness agent in the agglomerating hard metal is preferably to select element to Mo.L. the molybdenum of Prakash discovery even percentum also is enough to realize produce the significantly influence (paper of Leo J. Prakash for the hot hardness that contains the Fe hard metal, Universit t Karlsruhe1979, Fakult t f ü r Maschinenbau, KfK 2984).But, because used Mo
2C, the ratio that therefore actually exists in the Mo in this tackiness agent remains unclear.
The metal that causes the tackiness agent hot hardness to raise must be present in this tackiness agent, rather than is present in the mechanically resistant material, and hot hardness when being lower than 800 ℃ raises so that they can cause hard metal.Therefore must take preventive measures and guarantee that in fact metal is present in the binder metal alloy, rather than be present in the mechanically resistant material.In the situation of W and Cr, industrial standards is to use carbide, metal or nitride, and the carbon content of hard metal is set in the measure in dependence prescription and the sintering process, so that hard metal is in the edge that there is the zone in eta phase (η phase), and the W of maximum possible ratio and Cr are present in this tackiness agent.Therefore, Cr normally adds as chromium carbide, its in sintering process for example according to following equation generation disproportionation:
Cr
3C
2-Cr (alloying in tackiness agent)+2 CrC (alloying in WC)
Therefore, only the used Cr of sub-fraction (that is, 1/3) is effective in tackiness agent.Mo
2C also is similar to this situation:
Mo
2C-〉Mo (in the tackiness agent interalloyization)+(W, Mo) C.
Therefore, when using molybdenum carbide, only being about 50% to the maximum is effective in adhesive alloy; Reason uses the elements Mo metal-powder to replace Mo for this reason
2C.But, even when using very finely divided Mo metal-powder, behind sintering, having formed such zone, it is only by the adhesive alloy phase composite, and does not contain mechanically resistant material.This behavior can not be pulverized in the mixed grinding process effectively owing to Mo metal-powder aggregate, and this is because the high elastic coefficient of molybdenum; And formed deformed aggregate dissolves in this fused adhesive alloy process of liquid phase sintering, itself so that filled by the Mo particle being dissolved in the fused tackiness agent in the formed hole.This causes having formed " tackiness agent shallow lake ", and it is the term in the concrete zone of expression adhesive alloy, and this regional size does not still comprise wolfram varbide or hard material particle greater than the particle diameter of mechanically resistant material phase.
The two is disadvantageous and unacceptable for intensity and local wear resistance for these.Owing to limited diffusion time (corresponding to such time, that is, the time that the fused tackiness agent exists mutually in sintering process), unclear dissolving and the uniform alloyization of Mo in adhesive alloy fully that whether has realized the Mo metal-powder fully.
If this fused tackiness agent is not filled in the secondary apertures that forms in the sintering, then they are visible in sintered compact, as described in EP 1043411 B1 the 1st hurdle the 29/30th row.These secondary apertures have reduced intensity.
According to the present invention, iron content-, cobalt-or nickel-binder metal powder (it comprises the iron of 0.1-65 weight % amount, the nickel of the cobalt of 0.1-99.9 weight % amount and 0.1-99.9 weight % amount) be used to produce through the agglomerating hard metal.These per-cent data are weight percents, and in principle based on the adhesive alloy powder, unless indication is arranged in addition.
Used adhesive alloy powder comprises the molybdenum of the alloy form of 0.1-10 weight %, based on the total binder metal-powder.The adhesive therefor metal-powder preferably comprises the molybdenum of 0.10 weight %-3 weight %, the molybdenum of preferred especially 0.5 weight %-2 weight %, and the molybdenum of 0.5 weight %-1.5 weight % very particularly preferably is in each case based on the total binder metal-powder.Too high molybdenum content has caused the too high reinforcement of binder powders, and the force of compression and the contraction of formed sintering of producing like this in the hard metal become too high, and low excessively content has caused hot hardness to increase deficiency.
Preferred mechanically resistant material is a carbide, particularly tungsten carbide wc.Preferred adhesive is an iron, the alloy of cobalt and nickel, particularly iron and nickel, iron and cobalt, the combination of cobalt and nickel and iron, cobalt and nickel.Can use cobalt separately as tackiness agent equally.
This binder metal powder (it has carried out alloying with molybdenum) is coming dispersion behavior good in the production hard metal powders owing to their physicals shows with the carbide mixed grinding.FSSS value (use " Fisher Sub Siever Sizer " equipment, measure according to ASTM standard B 330) is 0.5-3 μ m therefore, preferred 1.0-2 μ m.Thinner powder is a pyrophoricity; Thicker powder no longer has gratifying dispersion behavior, and has caused " tackiness agent shallow lake " again.The distribution of sizes of described aggregate is because identical reason is 0.5-10 μ m.Specific surface area is because identical reason, preferably 2.5-0.5m
2/ g.Oxygen level preferably is lower than 1.5%.
Preferred cobalt contents is 60 weight % at the most in this adhesive alloy.Preferred nickel content is 10-80 weight % or 20-60 weight % or 30-75 weight % in this adhesive alloy.
Also can there be the organic additive that adds subsequently.In order to determine above-mentioned parameter, they must be for example by coming optionally to remove again with suitable solvent cleaning.This organic additive comprises wax, passivation and inhibitor, corrosion protection, compression aid.Possible example is paraffin and polyoxyethylene glycol.The other purpose of organic additive is to prevent that powder is aging, and this will cause oxygen level to increase.The amount of this additive can be 30 weight %, based on the summation of adhesive alloy powder and additive.
This binder powders that contains Mo can comprise Fe, Ni and Co.Because caking power and hot hardness raise along with Fe content and reduce, so iron level is less than 65%, preferably less than 60%.Supplying 100% surplus is that Mo adds Co and/or Ni.What preferably provide is alloy in system FeCoNi, it is at austenite stable in the agglomerating hard metal, FeCoNi 30/40/30 or 40/20/40 or 20/60/20 or 25/25/50 for example, and FeNi 50/50 or 30/70 or 20/80, perhaps ratio is 50/50,70/30 or 30/70 CoNi is as adhesive alloy.But, can also use element powders for example Co or Ni, it is that therefore it become powdered alloy with 10% Mo alloying at the most.
(DE 102006057004 A1) that this powdered alloy that contains molybdenum is preferably produced by following method: with MoO
2(it has pulverized the distribution of sizes that reduces aggregate) serves as the molybdenum source.With this MoO
2Join in the oxalic acid suspension, as EP 1079950 B1 are used, be used to prepare FeNi or FeCoNi mixing oxalate, this salt heats under the oxidisability condition subsequently, and relies on hydrogen reducing to become powdered alloy.The powdered alloy that obtains is in this way fully reduced after with hydrogen reducing, that is, no longer can rely on X-ray diffraction to measure MoO
2Randomly, rely on disaggregation further to reduce this aggregate size, purpose be raising with the mixed grinding of carbide in dispersiveness.This aggregate is made up of accumulative primary granule each other.Aggregate size and aggregate distribute and can rely on laser light scattering and sedimentation to measure.
Replace MoO
2, can also use other particulate Mo compound that is insoluble to oxalic acid, for example sulfide or carbide.They are to be oxidized to oxide compound in the air calcination of precipitation oxalate.Molybdenum oxide is MoO for example
3In calcination process, form, and owing to they high vapour pressures, formed mixed oxide very fast with Fe (Co) Ni mixed oxide, and show good transportation performance, in the reduction with hydrogen subsequently, formed FeCoNi powdered alloy (its be with the Mo uniform alloyization of small proportion) like this.
But other known method also is suitable; For example, replace oxalic acid to precipitate, precipitate, precipitate with formic acid and toxilic acid with hydroxide Na or K with the ammonium salt of oxalic acid.In whole situations, what preferably provide is to use MoO
2, it should be pure as far as possible phase, and only comprises the Mo or the MoO of trace
3Perhaps Mo
4O
11Use MoO
2Reason be because and MoO
3Compare, it both had been insoluble in the acid, also was insoluble in the alkali, therefore was retained in fully in the alloyed metal powder in entire method.MoO
3To be dissolved into and be used for precipitating the alkali of Fe (Co) Ni composition or being dissolved in the organic acid of complexing; Elements Mo will be too thick, and incomplete oxidation becomes MoO in calcining subsequently
3, therefore alloying inadequately in the hydrogen reducing process.Trickle MoO with high-specific surface area
2In Fe (Co) Ni oxalate air calcination process, be completely oxidized to MoO
3(it has high vapour pressure), and via gas phase, formed molybdate and with the mixed oxide of these metal oxides, this has produced very uniformly that molybdenum distributes, it is kept in hydrogen reducing subsequently.
Be known that to be used to rely on solid state sintering to produce sintered part in the powder that contains alloying Mo of the present invention, in diamond cutter industry, but be not used in sintering process, intermediate formation the hard metal industry of fusion phase.
But what especially preferably provide is the FeCoNi powder of Mo-alloying, and it comprises the Mo of complete metal form.In these powder, rely on X-ray diffraction no longer can measure the Mo oxide compound, the therefore existing oxygen existence that must on powder surface, be dominant very much.Very useful especially powder is such powder according to the present invention, and its FSSS value is 0.5-3 μ m, because this has improved the dispersiveness in mixed grinding.In this case, they do not comprise the additional metals that exists with oxide form as far as possible.
Because in the sintered hard metal process, molybdenum oxide and carbon reaction formation CO, and therefore can cause local carbon shortage and therefore cause local eta mutually, when guaranteeing when in the hard metal sintering process, taking preventive measures that therefore the main oxygen that discharges with the form of carbon monoxide can be overflowed from sintered compact, be suitable for hard metal production at the powdered alloy described in the epimere.Being suitable for the present invention during below situation of these powder uses: when they have the preferred physicals of the present invention, but what only comprised such degree is in the above-mentioned element M n of oxide form to small part, Cr, V, Al and Ti, the viewpoint of described degree microstructural defects (hole and tackiness agent form sediment) from hard metal allows.
According to the present invention, based on the powder of the Mo-alloying of FeCoNi or FeNi can be other usefulness at the most 20% tungsten carry out alloying, beginning of for example sintering being shunk passes higher temperature or the induced precipitation thing forms (this throw out has strengthened the tackiness agent phase), but this only can be successful in the situation of very thick wolfram varbide.
According to the present invention, used powdered alloy can be in the FeCoNi of wide compositing range.In high Fe content range (90-60%), find that the adhesive alloy system has a certain proportion of martensitic phase behind sintering, so have high rigidity and wear resistance in room temperature.Example is FeNi 90/10,82/18,85/15, FeCoNi 72/10/18,70/15/15 and 65/25/10.But above-mentioned alloy has low-down hot hardness in the agglomerating hard metal.In the Fe scope of about 80-25%, find that this adhesive alloy is austenitic behind sintering, though and they have lower intrinsic hardness, they have high fatigue strength and can experience limited viscous deformation.Example is FeNi 80/20,75/25, and FeCoNi 60/20/20,40/20/40,25/25/50,30/40/30,20/60/20.In most of situation, if in addition Mo or other alloying element are not blended in this alloy, then the hot hardness of the hard metal in 400-600 ℃ is lower than and has pure Co as these of tackiness agent.Though using the particularly preferred target of the present invention is to produce the hard metal of the hot hardness with raising, but it also is suitable for producing the hard metal with other target, the hard metal with the corrosion-resistant adhesive alloy system that contains molybdenum (as described in EP 0028620 B2) that for example uses molybdenum element or carbonization to produce at present perhaps is used for the cutting machine blade (as described in US5305840) of drill bit.
The adhesive alloy of the hard metal that exists at sintering can also use multiple different powdered alloy and optional element powders (described in WO 2008/034903) to obtain according to the present invention, and at least a molybdenum alloyization of using of these powder.The advantage of such method is compressed capability and control that sintering is shunk.
If with suitable, have the tool geometries of regulation by the hard metal spare that grinds or the final processing of electrocorrosion exists behind the sintering.This can be especially preferably microscler (for example by agglomerating pole grind), but also especially preferably flaky, be used for coming work material for example metal, stone and matrix material by turning or milling.In whole situations, this hard metal tools can preferably have and is selected from one or more following coatings: nitride, boride, oxide compound and superabrasive layer (for example diamond, cubic boron nitride).They can be apply by PVD or CVD method or its combination or deformation program, and variation can take place their residual stress state after applying.But the hard metal spare of the geometrical shape that they are can also be preferably any other is used for any other purposes, forging tools for example, shaping jig, spot-facing cutter, parts, milling cutter, beater, roller, press tool, the five angular bit heads that are used to be solded into, mining cutting machine, the milling tool that is used for concrete and pitch Milling Process, rotatory mechanical seal bar and any other geometrical shape and application.
The present invention describes in detail by the following examples.
Embodiment
Embodiment 1 (Comparative Examples, non-the present invention)
With the wolfram varbide 0.6 μ m of 462.5g and the FeCoNi powdered alloy 40/20/40 (Ampersint of 37.5g
MAP A6050; Manufacturers: H.C.Starck, Germany) and 94% concentration ethanol of 0.57L in ball mill, changeed the per minute mixed grindings 14 hours with 63.5 kg mechanically resistant material balls are used for this purpose.Used FeCoNi powder has following performance: Fe 38.8%, and Co 20.22%, and Ni 40.38%, and O 0.71%, specific surface area=1.63m
2/ g, FSSS value=0.90.Produce have different carbon contents (" high-carbon " and " low-carbon (LC) ") 2 batches, behind sintering, produced different carbon contents like this.The result is illustrated in the following table.
By underpressure distillation ethanol is separated from formed suspension, with the hard metal powders that obtained in 150 MPa uniaxial compression, and 1450 ℃ of decompression sintering 45 minutes.This sheet hard metal piece is ground, polish and check their performance.As sintered compact, two batches all do not show the eta phase, do not have carbon to separate out yet, but have relatively little tackiness agent to form sediment.In two kinds of situations, room temperature hardness and under protective gas, measure in selected 800 ℃ the hot hardness of temperature at the most.Fig. 1 has represented described result: two batches all show the big decline of hot hardness in about 600 ℃ zone.So under high relatively stress, producing the hard metal tools that is used for metal turning, this adhesive alloy obviously is inferior to pure cobalt, this is owing to the viscous deformation of the cutting edge that produces owing to desired cutting force, and it is because low hot hardness (particularly at 600 ℃) causes.
| Carbon | " low-carbon (LC) " | " high-carbon " |
| Hardness (HV30) (kg/mm 2) | 1582 | 1585 |
| Magneticsaturation (Gcm 3/g) | 137 | 140 |
| Porosity (ISO4505) | <A02<B02C00 | A02B00C00 |
| Fracture toughness (MPam 1/2) | 9.5 | 8.2 |
| Density (g/cm 3) | 14.69 | 14.65 |
Embodiment 2 (Comparative Examples, WC-Co, non-the present invention)
Have with the tackiness agent WC-Co mutually of embodiment 1 equal volume share and produce in the mode that is similar to embodiment 1.Because Co has the density higher than FeCoNi 40/20/40, so the weight quota of cobalt is 8 weight %, based on total hard metal.Having carried out 45 minutes compression and sintering decompression and 1420 ℃, to have produced flawless magneticsaturation be 133 Gcm
3The hard metal of/g, it is corresponding to 82% theoretical magneticsaturation.Room temperature hardness (HV30 1597 kg/mm have been measured
2) and hot hardness, and be plotted among Fig. 1.Can see that from 350 during until 800 ℃, Co is better than the FeCoNi tackiness agent, when being higher than this temperature, the principal element of carbide skeleton decision hot hardness.Hard metal is at the K of room temperature
1C (fracture toughness is determined by the fracture length of indentation hardness corner, and calculates by the Shetty formula) is 10.1 MPam
1/2Therefore this cobalt binder has than the better hardness/K of the tackiness agent of embodiment 1 in addition in room temperature
1The C relation.
Embodiment 3 (Comparative Examples is not according to the present invention)
| Mo addition in the |
1% | 3% |
| Hardness (HV30) | 1635 | 1652 |
| Magneticsaturation (Gcm 3/g) | 137.5 | 136.2 |
| Porosity (ISO4505) | <A02<B02C04 | <A02<B02C00 |
| Fracture toughness (MPam 1/2) | 9.2 | 9.0 |
| Microstructure | Many and sometimes big tackiness agent forms sediment | Very many and sometimes big tackiness agent forms sediment |
Surprising, eta does not have to take place when the molybdenum of 1 weight % and 3 weight %; More definite, carbon hole even when the molybdenum of 1 weight %, also take place.Compare with embodiment 1, hardness improves surprisingly, and K
1The C value does not reduce, and has obtained a kind of performance combination in room temperature like this, and it equals Co-bonded hard metal, and is better than pure FeCoNi-adherent hard metal.Surprising, the molybdenum of 1 weight % is enough in tackiness agent; Observe when the molybdenum of 3 weight %, compare K with 1% Mo
1C and hardness do not have intensive to change.Therefore the molybdenum that is alloyed in the tackiness agent has not only improved the intrinsic hardness of tackiness agent, but also has improved fracture toughness simultaneously.The behavior is different from the situation of the W of alloying in this respect: at Co-base hard metal with in the material based on FeCoNi, referring to embodiment 1, though also found the raising of the intrinsic hardness of tackiness agent here, also have K here simultaneously
1The reduction of C value.
But, very many tackiness agents having occurred and formed sediment, it is that Mo is dissolved into the evidence in the tackiness agent, it has filled formed pore volume then.But it is unacceptable in hard metal that these tackiness agents form sediment.
The comparison sheet of the hot hardness of these of embodiment 2 is shown among Fig. 2.At the most 800 ℃ whole temperature hot hardness surprisingly even be lower than these of embodiment 1.
Embodiment 4 (the present invention)
| Sintering | Open pot | Close crucible |
| Hardness (HV30) | 1661 | 1626 |
| Magneticsaturation (Gcm 3/g) | 128.8 | 134.2 |
| Porosity (ISO4505) | A02-A04，<B02，C00 | A02，<B02，C00 |
| Fracture toughness (MPam 1/2) | 13.6 | 7.9 |
| Microstructure | Adhesive-free forms sediment | Adhesive-free forms sediment |
Derive from the low carbon teminal that opening agglomerating hard metal is in two phase region, compare low-down magneticsaturation because it has with embodiment 1.But eta can not measure mutually.Mo concentration of maximum possible in tackiness agent has caused the strong reinforcement of adhesive alloy, improves when it is reflected in hardness and fracture toughness.From airtight agglomerating hard metal also in the carbon content of 2 regions, but comprise more carbon, this can find out from high magneticsaturation.Because there be (supplying with owing to higher carbon) in obviously more Mo as carbide, and therefore be not present in the tackiness agent, so fracture toughness (it depends on tackiness agent fatefully) is reduced to the degree of " high-carbon " flexible program of embodiment 1 very bigly.The theory that this embodiment has confirmed in specification sheets and discussed is considered.
Produce other compression body, and under reduced pressure at 1420 ℃ of sintering, but the argon gas of 40 bar that exert pressure is up to the sintering end point in outlet temperature.Cooling is carried out under pressure.Obtained to have the hard metal piece of following parameter: hardness 1643 HV30, fracture toughness 8.2 MPam
1/2With magneticsaturation 123 Gcm
3/ g.The two is function as temperature for room temperature hardness and hot hardness, on the hard metal piece, in other hardness test airborne measurements.The two evaluation result of room temperature hardness and hot hardness is illustrated among Fig. 2, represent with square, and embodiment 2 is compared with 3 curve plottings: compare with cobalt-adherent hard metal, the hard metal of embodiment 4 is starkly lower than these of embodiment 2 600 ℃ hot hardness.This hot hardness is higher than the hard metal of producing with adhesive alloy powder (this powder Mo of institute of no use alloying) (embodiment 3) now.(, in room temperature hardness, existing difference) owing to affiliated other testing machine.
Can see and use binder powders of the present invention (its with molybdenum (in advance) alloying) can produce the zero defect hard metal, and not have the tackiness agent shallow lake, and the hot hardness curve is in fact identical with cobalt binder.Concrete, the hot hardness of having eliminated basically about 600 ℃ reduces.In addition, compare with embodiment 1 when suitably setting when carbon balance, compare with embodiment 1, the obvious raising and the hardness that exist room temperature strength here improve the two, the advantage that it provides in room temperature equally or has used during near room temperature.In addition, can anticipate the erosion resistance that improves than embodiment 1, this is because the corrosion on hard metal normally takes place mutually via tackiness agent.
The principle that improves the hard metal performance of this dependence tackiness agent interalloy molybdenum not only can be applied to described FeCoNi 40/20/40 tackiness agent, and can be applied to pure cobalt and pure Ni as the hard metal tackiness agent, be applied to CoNi and FeNi alloy and be applied to other FeCoNi alloy.
Claims (12)
1. the adhesive alloy powder that contains molybdenum is used to produce the purposes based on the hard metal of the liquid phase sintering of wolfram varbide, is characterised in that:
A) the FSSS value of used adhesive alloy powder is 0.5-3 μ m, this value measure according to ASTM B 330 and
B) used adhesive alloy powder comprises the iron less than 60 weight % amount, at the most the nickel of the cobalt of 60 weight % amount and 20-60 weight % amount and
C) used adhesive alloy powder comprises the alloy form of 0.1-10 weight % or the Mo of prealloy form.
2. according to the purposes of claim 1, wherein this molybdenum is to exist with metallic forms fully.
3. according to one of claim 1-2 or both purposes, wherein used adhesive alloy powder comprises the nickel of at least 10 weight %, based on the total binder alloy.
4. according to one or multinomial purposes among the claim 1-3, wherein used adhesive alloy powder comprises the tungsten of the highest 20 weight %, based on the total binder alloy.
5. according to one or multinomial purposes among the claim 1-4, wherein at least a composition of this adhesive alloy is introduced as the powdery alloy of at least a metal and molybdenum, and all the other compositions of each of this adhesive alloy are introduced as the element or the alloy that all do not contain any molybdenum.
6. according to one or multinomial purposes among the claim 1-5, it is used for producing through the agglomerating hard metal, and wherein said sintering is to carry out with the form of liquid phase sintering.
7. according to one or multinomial purposes among the claim 1-6, be characterised in that this adhesive alloy powder comprises one or more organic additives of 30 weight % at the most.
8. according to one or multinomial purposes among the claim 1-7, wherein used adhesive alloy powder comprises the tungsten that is not more than 10 weight %, based on the total binder alloy.
9. pre-alloyed powder, it contains the iron of 0.1-65 weight %, the cobalt of 0.1-60 weight %, the molybdenum of the metallic forms of the nickel of 10-80 weight % and 0.1-20 weight %, wherein the FSSS value according to ASTM B 330 is 3 μ m to the maximum, and all the other compositions of this powder are unavoidable impurities.
10. according to the pre-alloyed powder of claim 9, it comprises at the most the alloy of 10 weight % or the tungsten of prealloy form in addition.
11., be characterised in that this pre-alloyed powder comprises the molybdenum of 0.1-20 weight % according to one of claim 9-10 or both pre-alloyed powders.
12., be characterised in that it comprises the iron of 0.1-65 weight % and the nickel of 10-60 weight % according to one or multinomial pre-alloyed powder among the claim 9-11.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102008052104 | 2008-10-20 | ||
| DE102008052104.3 | 2008-10-20 | ||
| DE102008052559A DE102008052559A1 (en) | 2008-10-21 | 2008-10-21 | Use of binder alloy powder containing specific range of molybdenum (in alloyed form), iron, cobalt, and nickel to produce sintered hard metals based on tungsten carbide |
| DE102008052559.6 | 2008-10-21 | ||
| PCT/EP2009/062844 WO2010046224A2 (en) | 2008-10-20 | 2009-10-02 | Metal powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102187005A true CN102187005A (en) | 2011-09-14 |
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ID=41327342
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009801406255A Pending CN102187005A (en) | 2008-10-20 | 2009-10-02 | Molybdenum-contained alloy powders used to produce sintered hard metals based on tungsten carbide |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20110286877A1 (en) |
| EP (2) | EP2337874B1 (en) |
| JP (1) | JP2012505971A (en) |
| KR (1) | KR20110079901A (en) |
| CN (1) | CN102187005A (en) |
| IL (1) | IL211913A0 (en) |
| TW (1) | TW201026858A (en) |
| WO (1) | WO2010046224A2 (en) |
| ZA (1) | ZA201102839B (en) |
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| CN104162476A (en) * | 2013-05-16 | 2014-11-26 | 钴碳化钨硬质合金印度有限公司 | Methods of milling carbide and applications thereof |
| CN105695837A (en) * | 2014-11-26 | 2016-06-22 | 自贡硬质合金有限责任公司 | Preparation method of WC-Ni fine grain cemented carbide |
| CN109641753A (en) * | 2016-09-15 | 2019-04-16 | H.C.施塔克钨业股份有限公司 | Novel tungsten-carbide powder and its preparation |
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| US11130205B2 (en) | 2014-06-09 | 2021-09-28 | Oerlikon Metco (Us) Inc. | Crack resistant hardfacing alloys |
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| ES2802401T3 (en) * | 2017-05-05 | 2021-01-19 | Hyperion Materials & Tech Sweden Ab | Body comprising a piece of cermet and its manufacturing process |
| CA3117043A1 (en) | 2018-10-26 | 2020-04-30 | Oerlikon Metco (Us) Inc. | Corrosion and wear resistant nickel based alloys |
| DE102019110950A1 (en) | 2019-04-29 | 2020-10-29 | Kennametal Inc. | Hard metal compositions and their applications |
| CN114051446A (en) * | 2019-07-03 | 2022-02-15 | 日本特殊陶业株式会社 | Kitchen knife and knife body |
| CN113652594B (en) * | 2021-08-02 | 2022-11-22 | 自贡硬质合金有限责任公司 | Refractory metal-based alloy and preparation method thereof |
| CN114226714B (en) * | 2021-12-17 | 2023-07-21 | 武汉苏泊尔炊具有限公司 | Powder metallurgy material, preparation method and application thereof |
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2009
- 2009-10-02 WO PCT/EP2009/062844 patent/WO2010046224A2/en active Application Filing
- 2009-10-02 EP EP09783704.1A patent/EP2337874B1/en not_active Not-in-force
- 2009-10-02 US US13/123,533 patent/US20110286877A1/en not_active Abandoned
- 2009-10-02 CN CN2009801406255A patent/CN102187005A/en active Pending
- 2009-10-02 EP EP11193910A patent/EP2436793A1/en not_active Withdrawn
- 2009-10-02 KR KR1020117011394A patent/KR20110079901A/en not_active Application Discontinuation
- 2009-10-02 JP JP2011532569A patent/JP2012505971A/en not_active Withdrawn
- 2009-10-20 TW TW098135324A patent/TW201026858A/en unknown
-
2011
- 2011-03-24 IL IL211913A patent/IL211913A0/en unknown
- 2011-04-15 ZA ZA2011/02839A patent/ZA201102839B/en unknown
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| JPS5831061A (en) * | 1981-08-17 | 1983-02-23 | Mitsubishi Metal Corp | Superhard tungsten carbide alloy with high strength and high oxidation resistance |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102776429A (en) * | 2012-07-18 | 2012-11-14 | 株洲新科硬质合金有限公司 | Novel bonding phase ultrafine hard alloy |
| CN104162476A (en) * | 2013-05-16 | 2014-11-26 | 钴碳化钨硬质合金印度有限公司 | Methods of milling carbide and applications thereof |
| CN105695837A (en) * | 2014-11-26 | 2016-06-22 | 自贡硬质合金有限责任公司 | Preparation method of WC-Ni fine grain cemented carbide |
| CN109641753A (en) * | 2016-09-15 | 2019-04-16 | H.C.施塔克钨业股份有限公司 | Novel tungsten-carbide powder and its preparation |
| CN109641753B (en) * | 2016-09-15 | 2022-12-02 | H.C.施塔克钨业股份有限公司 | Tungsten carbide powder and preparation thereof |
| CN110418688A (en) * | 2017-03-14 | 2019-11-05 | Vbn组件有限公司 | High-carbon content cobalt-base alloys |
| CN110418688B (en) * | 2017-03-14 | 2022-04-05 | Vbn组件有限公司 | High carbon content cobalt-based alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| US20110286877A1 (en) | 2011-11-24 |
| ZA201102839B (en) | 2012-06-27 |
| EP2337874A2 (en) | 2011-06-29 |
| TW201026858A (en) | 2010-07-16 |
| EP2436793A1 (en) | 2012-04-04 |
| WO2010046224A2 (en) | 2010-04-29 |
| JP2012505971A (en) | 2012-03-08 |
| EP2337874B1 (en) | 2015-08-26 |
| WO2010046224A3 (en) | 2010-10-14 |
| IL211913A0 (en) | 2011-06-30 |
| KR20110079901A (en) | 2011-07-11 |
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