WO2019098183A1 - 炭化タングステンを含む粉末 - Google Patents
炭化タングステンを含む粉末 Download PDFInfo
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- WO2019098183A1 WO2019098183A1 PCT/JP2018/041953 JP2018041953W WO2019098183A1 WO 2019098183 A1 WO2019098183 A1 WO 2019098183A1 JP 2018041953 W JP2018041953 W JP 2018041953W WO 2019098183 A1 WO2019098183 A1 WO 2019098183A1
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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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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
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Definitions
- the present invention relates to a powder comprising tungsten carbide.
- the present application claims priority based on Japanese Patent Application No. 2017-219191, which is a Japanese patent application filed on November 14, 2017. The entire contents of the description of the Japanese patent application are incorporated herein by reference.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2005-335997
- Patent Document 2 Japanese Patent Application Laid-Open No. 2005-335997
- the powder containing tungsten carbide according to one aspect of the present invention has an Fsss particle size of 0.3 ⁇ m to 1.5 ⁇ m, a content of tungsten carbide of 90 mass% or more, and a crystallite size (average particle diameter) Y
- the following condition is satisfied: Y ⁇ 0.1 ⁇ X + 0.20 (X: Fsss particle size of powder containing tungsten carbide).
- FIG. 1 is an SEM photograph showing the appearance of the tungsten carbide-containing powder of the sample No. 8 example.
- FIG. 2 is a SEM photograph showing the appearance of a powder containing tungsten carbide of Conventional production method 1 of Sample No. 27.
- FIG. 3 is a crystallite mapping image of the tungsten carbide-containing powder of the example of sample No. 8.
- FIG. 4 is a crystallite mapping image of tungsten powder of Conventional production method 1 of Sample No. 27.
- FIG. 5 shows the Fsss particle size of the powder containing tungsten carbide and the crystallite size (average particle diameter) of the cross section of the powder containing tungsten carbide according to the EBSD method in each of sample numbers 1 to 14, 26 to 29, 30 to 32.
- FIG. 6 is a graph showing the relationship between the Fsss particle size and the Hc (coercivity) of the powder containing tungsten carbide in each of the sample numbers 1 to 17, 26 to 29, and 30 to 32.
- FIG. 7 is a metallographic picture of a cemented carbide produced from a powder containing tungsten carbide of the example of sample No. 8.
- FIG. 8 is a metallographic picture of a cemented carbide produced from a powder containing tungsten carbide of Conventional production method 1 of Sample No. 27.
- the present invention was made to solve the above-mentioned problems, and it is an object of the present invention to provide a powder containing tungsten carbide which is easy to handle and which can produce an ultrafine grained cemented carbide. It is [Effect of the present disclosure] According to the above, it is possible to provide a powder containing tungsten carbide which is easy to handle and which can produce an ultrafine grained cemented carbide.
- the powder containing tungsten carbide according to one embodiment of the present invention has an Fsss particle size of 0.3 ⁇ m to 1.5 ⁇ m, and a crystallite size (average particle size) Y of Y ⁇ 0.1 ⁇ X + 0.20 X: Fss particle size of powder containing tungsten carbide is satisfied.
- crystallite refers to the largest group that can be regarded as a single crystal, and a powder containing one tungsten carbide is constituted by a plurality of crystallites.
- the amount of oxygen adsorbed to the surface of the powder containing tungsten carbide increases as the particle size of the powder decreases. If the amount of oxygen is large, the amount of gas generated in the sintering step in producing the cemented carbide increases, and there is a problem that pores are easily generated in the alloy. In addition, since there is a large amount of oxygen, the fluctuation range of the carbon content of the cemented carbide also becomes large, so that it is difficult to obtain a sound structure and the mechanical characteristics do not improve. Such problems are less likely to occur if the powder contains tungsten carbide with a large particle size.
- chromium is contained in an amount of 0.2% by mass or more and 2.5% by mass or less. Chromium is an element used as a grain growth inhibitor of cemented carbide.
- the abundance ratio of crystallites whose crystallite size is in the range of Y ⁇ 0.5Y exceeds 85%.
- the particles of tungsten carbide are homogenized, and when sintering tungsten carbide to form a cemented carbide, Abnormal grain growth can be suppressed, and grains in the cemented carbide can be homogenized to increase the coercive force Hc.
- the abundance ratio of crystallites whose crystallite size is in the range of Y ⁇ 0.5Y exceeds 90%.
- Patent Document 1 discloses a conventional production method 1 as a method for producing tungsten carbide powder.
- Conventional production method 1 is a method of producing tungsten carbide powder using tungsten powder.
- a diffusion layer of Cr, Ta, Mo, Nb, Zr, V, etc. is formed to form a composite carbide composed of fine primary crystals of tungsten carbide (in powder form).
- Patent Document 2 discloses a conventional production method 1 as a method for producing tungsten carbide.
- Tungsten carbide composed of tungsten carbide consisting of fine primary crystals (in powder form) containing C and Cr or chromium oxide or chromium compound in tungsten powder and containing chromium in the range of 0.2 to 2.5 mass%
- a composite carbide having an average particle diameter of 1 ⁇ m or more according to a Fisher (Fsss) method, and a Y-value half width of 211 face (JCPDS card 25-1047, d: 0.9020) of tungsten carbide crystal by X-ray diffraction; Assuming that the particle diameter by the Fsss method is X, the relationship of Y> 0.61-0.33 log (X) is satisfied, and the shrinkage rate when producing a cemented carbide is 16.7% or more and less than 20%. Discloses a composite carbide characterized in that.
- Patent Document 3 discloses a conventional production method 2.
- Conventional production method 2 is a method of producing tungsten carbide powder by reducing tungsten oxide powder with carbon powder.
- Disclosed is a method for producing ultrafine tungsten carbide powder by mixing WO 3 powder and carbon powder, heating in an N 2 atmosphere and an H 2 atmosphere, and having a uniform particle size (powder) of 0.5 ⁇ m or less.
- Patent Document 4 discloses a conventional production method 2. During the carbonization step, a step of grinding the intermediate product is added to obtain a tungsten carbide powder having a nano particle diameter of 100 nm or less in average particle diameter (powder).
- the tungsten carbide powder used as a raw material of cemented carbide has the following problems, respectively.
- W oxide is heated in a reducing atmosphere furnace to be reduced to W, and the obtained tungsten and carbon are mixed and then heated again in a heat treatment furnace and carbonized to tungsten carbide.
- a tungsten carbide powder is obtained.
- the grain size of the tungsten carbide powder thus obtained is a grain size in the range of a moderately coarse grain size that is easy to handle in producing a cemented carbide, while the size of the crystallite is larger than that of other production methods.
- a cemented carbide manufactured using tungsten carbide powder having a large crystallite has a problem that the tungsten carbide particle size becomes large. That is, in the conventional production method 1, it is difficult to obtain fine WC powder and it is difficult to obtain coarse WC powder having a small crystallite size.
- the powder containing tungsten carbide according to one aspect of the present invention is a polycrystalline body with fine crystallites.
- the crystallite size of each crystal is very small, and the Fsss particle size of the powder containing tungsten carbide is moderately coarse. That is, when a cemented carbide is produced using a powder containing tungsten carbide according to one aspect of the present invention, an alloy structure of ultrafine particles is obtained, and handling in the powder state containing tungsten carbide (handling property) is easy. It also has the effect of
- the powder containing tungsten carbide contains 90% by mass or more of tungsten carbide. In addition to tungsten carbide, cobalt, chromium, etc. may be contained. More preferably, the powder containing tungsten carbide contains 95% by mass or more of tungsten carbide.
- the Fsss particle size can be measured using Fisher Sub-Sieve Sizer Model 95 manufactured by Fisher Scientific.
- the crystallite size Y is preferably 0.05 ⁇ m ⁇ Y ⁇ 0.3 ⁇ m.
- the measurement method of the size (average particle diameter) of crystallites is by EBSD method or Rietveld method (X-ray diffraction).
- EBSD means backscattered electron diffraction (Electron BackScatter Diffraction). Also called EBSP (Electron Back Scattering Pattern: EBSP).
- a microcrystal orientation and a crystal system are measured by analyzing a pseudo Kikuchi pattern while combining an SEM (Scanning Electron Microscope) and manipulating an electron beam. Unlike X-ray diffraction, where average information is obtained, information for each crystal grain is obtained. Further, from the crystal orientation data, it is possible to analyze the orientation distribution (texture) of the crystal grains and the crystal phase distribution.
- the pseudo Kikuchi pattern refers to a band-like pattern in which reflected electrons are diffracted by atomic planes in the sample when the sample is irradiated with electrons. The symmetry of the bands corresponds to the crystal system, and the spacing of the bands corresponds to the atomic face spacing.
- the size (average particle diameter) of crystallites, the measurement range of crystallite size (Y ⁇ 0.5Y), and the abundance ratio of crystallites whose crystallite size is in the range of (Y ⁇ 0.5Y) is measured by the EBSD method. Specifically, it measures using the following models.
- the Rietveld method is a crystal structure by fitting a diffraction pattern obtained by powder X-ray diffraction experiment or powder neutron diffraction experiment using a least squares method with a diffraction pattern calculated from parameters related to crystal structure, peak shape, etc. Refine parameters related to the peak and peak shape.
- the Rietveld method uses an X-ray diffractometer (model name: Panalytical Enpyrean, software name: High Score Plus). In the present invention, although the numerical value by the EBSD method is described, fine crystallites are similarly confirmed in the Rietveld method.
- the crystallite size of 0.5 ⁇ m or more is measured by the EBSD method, and the crystallite size of less than 0.5 ⁇ m is the value of the Rietveld method converted to the value of the EBSD method. Specifically, for sample numbers 7 and 13 described later, the average grain size of the crystallites was measured by both the EBSD method and the Rietveld method, and the average value of the correlation coefficient between the respective measurement results was used as the conversion factor. .
- Tungsten carbide Fsss particle size If the Fsss particle size of powder containing tungsten carbide is 0.3 ⁇ m or more and 1.5 ⁇ m or less, handling (handling property) of powder containing tungsten carbide is good, and adsorption in tungsten carbide The amount of oxygen does not increase. When the amount of adsorbed oxygen is large, when an alloy is prepared from a powder containing tungsten carbide, the adsorbed oxygen and carbon in tungsten carbide react with each other and carbon is consumed, so that it is difficult to obtain a sound superfine alloy structure. If the Fsss particle size is within the above range, such a problem will not easily occur because the amount of adsorbed oxygen is not increased.
- the Fsss particle size is 0.5 ⁇ m or more and 1.2 ⁇ m or less, and most preferably, the Fsss particle size is 0.5 ⁇ m or more and 1.0 ⁇ m or less.
- the content of chromium is preferably 0.2% by mass or more.
- the content of chromium is preferably 2.5% by mass or less. If the chromium content is 0.2% by mass or more, the necessary amount of chromium for refining the crystallite is reached. If the content of chromium is 2.5% by mass or more, the third phase causing a decrease in strength may exceed the solid solution limit of chromium in the binder phase of the cemented carbide and it may become brittle due to precipitation in the binder phase. is there. Note that "at risk” indicates that there is a slight possibility of such a situation, and does not mean that such a situation occurs with a high probability.
- tungsten When carbonization is performed in the presence of chromium, part of tungsten is replaced with chromium.
- the chemical formula is presumed to be (W, Cr) 2 C.
- the lower carbides of tungsten include W 2 C, and some of the tungsten is replaced with chromium by (W, Cr) 2 C, which is a kind of composite carbide of tungsten and chromium.
- ICP Inductively Coupled Plasma
- ICP can measure the chromium content, it can not detect whether a part of tungsten is replaced by chromium. It can be confirmed using TEM (Transmission Electron Microscope) -EDX (Energy Dispersive X-ray spectrometry) what form chromium is contained in the powder.
- Amount of oxygen (unit: mass%)
- the content of oxygen is preferably 0.3% by mass or less. More preferably, the oxygen content is 0.2% by mass or less.
- the measuring method is an infrared absorption method. For example, it can be measured by the “infrared absorption method” of 13.4 of JIS H 1403 (2001) using a TC-600 type oxygen / nitrogen analyzer manufactured by LECO.
- the crystallite size (average particle diameter) of tungsten carbide powder is Y
- the percentage of crystallites in the range of Y ⁇ 0.5Y is 85% or less
- Ostwald growth occurs in which fine particles are taken into the coarse particles during cemented carbide sintering and abnormally grow, and the alloy particle size becomes uneven.
- the crystallite size ratio in the range of Y ⁇ 0.5Y exceeds 85%, an alloy structure of uniform grain size can be obtained.
- the crystal orientation data obtained by using the above-mentioned EBSD method is subjected to image analysis to obtain 0.1 ⁇ m intervals within the range of 0.0 ⁇ m to 1.5 ⁇ m of the crystallite size.
- a histogram can be obtained which indicates the abundance ratio of the crystal grain size for each.
- the crystallite size (average particle diameter) Y and (Y ⁇ 0.5 Y) are calculated from the obtained histogram. At this time, count up to the second decimal place.
- the composition of the powder containing tungsten carbide contains 0.2% by mass or more and 2.5% by mass or less of chromium, 0.3% by mass or less of oxygen, and the balance is substantially free of 0.2% by mass or less of tungsten carbide It is preferable that they are carbon and an unavoidable impurity. Unavoidable impurities are impurities which are inevitably mixed in the powder containing tungsten carbide from at least one of the raw materials and equipment during the production process, and specifically, aluminum, calcium, copper, magnesium, manganese, silicon and tin is there. The content of these elements can be measured using ICP.
- the total content of the content of the said element is 100 ppm or less as content in the range which does not have a bad influence on a cemented carbide.
- calcium and silicon are likely to adversely affect the properties of cemented carbide.
- a carbon measuring apparatus WC 230 manufactured by LECO is used. It can measure by examining the said insoluble matter.
- Powders comprising tungsten carbide are, for example, at least one intentionally added addition of titanium, vanadium, zirconium, niobium, molybdenum, hafnium, tantalum, iron, cobalt and nickel, which are additives of conventional cemented carbides. It can contain elements. The content rate of these additive elements can be measured using ICP.
- the content (mass%) of tungsten carbide can be calculated from the following relationship: 100 ⁇ (content of chromium + content of oxygen + content of unavoidable impurities + content of added elements + content of free carbon) is there. That is, in the present specification, the content of tungsten carbide is not the content of tungsten carbide alone, but the composition excluding chromium, oxygen, unavoidable impurities, additive elements and free carbon calculated from the above relational expression. It means the content rate.
- tungsten carbide in cemented carbide is finer than tungsten carbide in cemented carbide when powder of conventional equivalent particle size is used. It becomes. This is also shown from the value of Hc of cemented carbide.
- Hc coercivity
- Hc indicates the strength of the oppositely directed external magnetic field necessary to return the magnetized magnetic body to the non-magnetized state. Therefore, in the case of a cemented carbide, it is the cobalt phase that is magnetized, and the cobalt phase becomes thinner as the tungsten carbide becomes finer, so the external magnetic field strength to return the magnetized cobalt phase to the unmagnetized state become stronger.
- Hc cobalt phase thickness
- Hc cobalt phase thickness
- Hc (coercivity) can be measured, for example, using KOERZIMATCS-1.096 manufactured by FOERSTER. The measurement method of Hc (coercivity) is based on ISO 3326-1975.
- One production method of the product of the invention (hereinafter referred to as an example production method) is mixing tungsten oxide and carbon and heating in a furnace of hydrogen atmosphere to carry out reduction and carbonization in series.
- a furnace of hydrogen atmosphere By heating in a furnace under a hydrogen atmosphere to reduce the tungsten oxide with hydrogen, it is possible to obtain a powder containing tungsten carbide of an appropriate particle size similar to that of Conventional Process 1 of Patent Documents 1 and 2.
- the reduction of tungsten oxide to tungsten and the carbonization of tungsten progress continuously, so the time for tungsten to exist as a metal at high temperature is shortened. As a result, ultrafine crystallites can be obtained.
- the conventional production method 1 is a method in which each step of reduction and carbonization is performed separately. By adjusting the conditions in this reduction step, very fine particles of tungsten can be produced, but the reduced particles of tungsten may react with oxygen in the atmosphere and ignite due to an oxidation reaction on the surface. On the other hand, in the example manufacturing method, since tungsten oxide and carbon powder are mixed in advance and reduction and carbonization are continuously performed, there is no possibility of ignition due to oxidation reaction. Further, the time during which the tungsten particles are held at a high temperature is made as short as possible as compared with the conventional production method 1. It is presumed that this makes it possible to suppress coarsening of crystallites by recrystallization and to obtain ultrafine crystallites.
- the mixture was heat-treated according to “heat treatment conditions using a rotary furnace” in Tables 4 to 7, and pulverized according to “Pulverization conditions” of Tables 4 to 7 to prepare sample numbers 1 to 25 of Tables 4 to 7.
- the tungsten powder reduced under the conditions indicated by sample numbers 26 to 29 in Table 8, and the above-mentioned carbon powder and chromium oxide (Cr 2 O 3 ) in mass ratio 92.2: 6.4: 1.4
- the mixture was weighed, and mixed at 500 rpm for 10 minutes using the aforementioned mixer.
- the mixture was heat treated (hydrogen atmosphere, 1000 to 1800 ° C., 30 to 300 minutes) on a carbon tray to a thickness of 20 mm in a hydrogen atmosphere to carbonize tungsten.
- Tungsten carbide was ground in the above-mentioned ball mill to obtain a powder (conventional production method 1) containing tungsten carbide of each of sample numbers 26 to 29 in Table 9.
- the “heat treatment conditions” in Table 9 particularly indicate the maximum temperature range of the carbonization reaction, and after the temperature rise, the temperature was cooled in the cooling zone of the heat treatment furnace.
- the particle cross section was observed by SEM. Crystallite size and distribution of crystallite size were analyzed by EBSD method and Rietveld method. In the powder containing tungsten carbide, the content of chromium, the content of oxygen, and the content of free carbon were measured, and the content of tungsten carbide was calculated from the measurement results. The results are shown in Tables 11-13. In the above powder, the blending of the raw materials is adjusted so that the content of free carbon is 0.2% by mass or less.
- the content of the above-mentioned unavoidable impurities in the powders produced by each of the example production method, conventional production method 1 and conventional production method 2 is 10 ppm or less in each of aluminum, copper, magnesium and manganese, calcium, silicon and tin respectively. At 20 ppm or less. That is, the total content of the unavoidable impurities was 100 ppm or less. If the size of the inevitable impurities is not such that it becomes foreign matter in the alloy structure, a sound cemented carbide can be obtained by the content of the unavoidable impurities being in the above range.
- the crystallite size of sample numbers 1, 2, 18, and 19 is a value which converted the value in the Rietveld method using the said conversion factor.
- the Rietveld method can not measure the proportion of crystallites whose crystallite size is in the range of (Y ⁇ 0.5Y)
- the sample numbers 1, 2, 18, and 19 have crystallite sizes
- the abundance ratio of crystallites in the range of (Y ⁇ 0.5Y) is estimated to be 85% or more from the tendency of sample numbers 3 to 17 and 20 to 25.
- FIG. 1 is an SEM photograph showing the appearance of the tungsten carbide-containing powder of the sample No. 8 example.
- FIG. 2 is a SEM photograph showing the appearance of a powder containing tungsten carbide of Conventional production method 1 of Sample No. 27. As shown in FIGS. 1 and 2, sample numbers 8 and 27 are difficult to distinguish in appearance because the Fsss particle size is equivalent.
- FIG. 3 is a crystallite mapping image of the tungsten carbide-containing powder of the example of sample No. 8.
- FIG. 4 is a crystallite mapping image of tungsten powder of Conventional production method 1 of Sample No. 27. As shown in FIGS. 3 and 4, it can be seen that in the tungsten carbide particles of sample No. 8, one tungsten carbide particle is composed of many crystallites as compared with the tungsten carbide particles of sample No. 27.
- FIG. 5 shows the Fsss particle size of the powder containing tungsten carbide and the crystallite size of the cross section of the powder containing tungsten carbide according to the EBSD method and the Rietveld method in each of the sample numbers 1 to 14, 26 to 29, and 30 to 32. It is the graph which showed the relationship with average particle diameter). It can be confirmed that the tungsten carbide according to the embodiment has a fine crystallite size at the same Fsss particle size as compared with the powder containing tungsten carbide of each of Conventional production method 1 and Conventional production method 2.
- the relationship between the Fsss particle size X and the crystallite size Y of the tungsten carbide-containing powder of the example is represented by the formula Y ⁇ 0.1 ⁇ X + 0.20.
- FIG. 6 is a graph showing the relationship between the Fsss particle size and the Hc (coercivity) of the powder containing tungsten carbide in each of the sample numbers 1 to 17, 26 to 29, and 30 to 32. From FIG. 6, when comparing samples having similar Fsss grain size, Hc of cemented carbide according to the example becomes larger than Hc of cemented carbide according to the conventional production methods 1 and 2. I understand that For example, Hc of a cemented carbide composed of tungsten carbide (sample No. 26) of the conventional production method 1 is 26.3 kA / m for sample Nos. 5 and 26 in which the Fsss particle size of powder containing tungsten carbide is around 0.6 ⁇ m.
- Hc is particularly large in sample numbers 1 to 12, 15, 16 and 18 to 23 in which the Fsss particle size ( ⁇ m) X of the powder containing tungsten carbide is 1.2 ⁇ m or less. That is, it is understood that an alloy of finer particle size was obtained in the example production process as compared with the conventional production processes 1 and 2.
- Hc coercivity
- a cemented carbide was produced from the powder containing tungsten carbide of each of sample numbers 8 and 27. Specifically, 10 wt% of Co powder was blended with the powder containing tungsten carbide of each of sample numbers 8 and 27, and wet mixed in ethanol with an attritor for 8 hours. The mixed powder was dried, and the dried powder was press-molded at a pressure of 98 MPa to produce a molded body of 10 mm long, 30 mm wide, and 5 mm high. The molded body was sintered in vacuum at 1380 ° C. for 1 hour. The hardness and bending strength of the cemented carbide after sintering were evaluated. The results are shown in Table 16.
- the cemented carbide manufactured from the powder containing tungsten carbide of the example is compared with the cemented carbide manufactured from the powder containing tungsten carbide of the conventional production method 1 (sample No. 27), It was found that the hardness and breaking strength were large. It is considered that this is because, in the powder containing tungsten carbide of the example, the size of the crystallite is small and the structure of the cemented carbide is ultrafine.
- FIG. 7 is a metallographic picture of a cemented carbide produced from a powder containing tungsten carbide of the example of sample No. 8.
- FIG. 8 is a metallographic picture of a cemented carbide produced from a powder containing tungsten carbide of Conventional production method 1 of Sample No. 27.
- the metal structure of the cemented carbide manufactured from the powder containing tungsten carbide of the embodiment is the metal of the cemented carbide manufactured from the powder containing tungsten carbide of the conventional production method 1 of sample No. 27. It was finer than the tissue.
- a cemented carbide was prepared from the powder containing tungsten carbide of each of sample numbers 1 and 30. Specifically, 10 wt% of Co powder was blended with the powder containing tungsten carbide of each of sample numbers 1 and 30, and wet mixed in ethanol with an attritor for 8 hours. The mixed powder was dried, and the dried powder was press-molded at a pressure of 98 MPa to produce a molded body of 10 mm long, 30 mm wide, and 5 mm high. The molded body was sintered in vacuum at 1380 ° C. for 1 hour. The hardness and bending strength of the cemented carbide after sintering were evaluated. The results are shown in Table 17.
- the Fsss particle size of the powder is larger than that of the powder containing tungsten carbide obtained by the conventional production method 2, and the oxygen content is Since the rate is low and both the hardness and bending strength are exceeded as the alloy characteristics, it can be said that a healthy alloy structure is obtained and the characteristics are improved.
- the cemented carbide structure was more homogeneous in sample number 15.
- the powder containing tungsten carbide of each of sample numbers 3 and 15 is a powder containing tungsten carbide obtained by the example manufacturing method, but the crystallite size is obtained even if the powder has the same Fsss particle size and crystallite size. It was inferred that the homogeneity of the cemented carbide structure was different due to the difference in the homogeneity of. Generally, when the cemented carbide structure is uniform, the variation of the bending strength decreases, so that when the crystallite size of the powder is more uniform, the properties of the cemented carbide become better.
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Abstract
Description
しかしながら、従来の技術では、取り扱いが容易で、かつ、超微粒の超硬合金を製造することができる炭化タングステンを含む粉末を提供することができなかった。
[本開示の効果]
上記によれば、取り扱いが容易で、かつ、超微粒の超硬合金を製造することができる炭化タングステンを含む粉末を提供することができる。
最初に本発明の実施態様を列記して説明する。
本発明の一態様に係る炭化タングステンを含む粉末は、Fsss粒度が0.3μm以上1.5μm以下であり、結晶子サイズ(平均粒径)YがY≦0.1×X+0.20(X:炭化タングステンを含む粉末のFsss粒度)の関係式を満たす。
好ましくは、炭化タングステンを含む粉末において、結晶子サイズがY±0.5Yの範囲内である結晶子の存在比率が、85%を超えている。結晶子サイズがY±0.5Yの範囲内の結晶子の存在比率が85%を超えると、炭化タングステンの粒子が均粒化され、炭化タングステンを焼結して超硬合金を形成する際に異常な粒成長が起きることを抑制することができ、超硬合金中の粒子を均粒化して抗磁力Hcを高くすることができる。より好ましくは、炭化タングステンを含む粉末において、結晶子サイズがY±0.5Yの範囲内である結晶子の存在比率が、90%を超えている。
特許文献1は、炭化タングステン粉末の製造方法として、従来製法1を開示している。従来製法1とは、タングステン粉末を用いて炭化タングステン粉末を製造する方法である。Cr、Ta、Mo、Nb、Zr、V等の拡散層を形成し、炭化タングステンの微細一次結晶(粉末時)からなる複合炭化物が形成される。
本発明の一態様に係る炭化タングステンを含む粉末は、結晶子が微細な多結晶体である。各々の結晶の結晶子サイズが非常に小さく、且つ炭化タングステンを含む粉末のFsss粒度は適度に粗い。すなわち、本発明の一態様に係る炭化タングステンを含む粉末を用いて超硬合金を作製すると超微粒の合金組織が得られるとともに、炭化タングステンを含む粉末状態での取り扱い(ハンドリング性)が容易であるという効果を併せ持つものである。炭化タングステンを含む粉末は90質量%以上の炭化タングステンを含む。炭化タングステン以外に、コバルト、クロムなどを含んでいてもよい。より好ましくは、炭化タングステンを含む粉末は95質量%以上の炭化タングステンを含む。
Xを炭化タングステンのFsss粒度、Yを結晶子サイズ(平均粒径)とすると、これらの間には以下の関係式が成立する。
なお、Fsss粒度は、Fisher Scientific製のFisher Sub-Sieve Sizer Model 95 を用いて測定可能である。
炭化タングステンを含む粉末のFsss粒度が0.3μm以上1.5μm以下であれば、炭化タングステンを含む粉末の取り扱い(ハンドリング性)が良く、かつ、炭化タングステン中の吸着酸素量が増加しない。吸着酸素量が多いと、炭化タングステンを含む粉末から合金を作製したとき、吸着酸素と炭化タングステン中の炭素が反応し、炭素が消費されるため、健全な超微粒合金組織が得られにくい。Fsss粒度が上記の範囲内であれば、吸着酸素量を増加させないため、そのような不具合も生じ難くなる。微粒合金が得られ且つハンドリング性をより向上させるためには、好ましくは、Fsss粒度が0.5μm以上1.2μm以下、最も好ましくは、Fsss粒度が0.5μm以上1.0μm以下である。
クロムの含有率は、0.2質量%以上が好ましい。クロムの含有率は、2.5質量%以下が好ましい。クロムの含有率が0.2質量%以上であれば、結晶子を微細化するためのクロムの必要量に達する。クロムの含有率が2.5質量%以上であれば、超硬合金の結合相におけるクロムの固溶限界を超え、強度の低下を招く第三相が結合相中に析出して脆くなるおそれがある。なお、「おそれがある」とは、僅かながらそのようになる可能性があることを示し、高い確率でそのようになることを意味するものではない。
酸素の含有率は、0.3質量%以下が好ましい。より好ましくは酸素の含有率は、0.2質量%以下である。
炭化タングステン粉末の結晶子サイズ(平均粒径)をYとすると、結晶子サイズがY±0.5Yの範囲内の結晶子の存在比率が85%以下であれば、微粒と粗粒の結晶子が混在していることから、超硬合金焼結中に微粒子が粗粒子に取り込まれて異常成長するオストワルド成長が起こり、合金粒度が不均一となる。一方、結晶子サイズがY±0.5Yの範囲内の結晶子の存在比率が85%を超えると、均一な粒度の合金組織が得られる。
発明品の1つの製法(以下、実施例製法という)は、タングステン酸化物と炭素とを混合後に、水素雰囲気の炉で加熱し、還元および炭化を一連で行う。水素雰囲気の炉で加熱し、タングステン酸化物を水素還元することにより、特許文献1および2の従来製法1と同様な適度な粒度の炭化タングステンを含む粉末を得ることができる。また、還元および炭化を一連の工程で行うことにより、タングステン酸化物のタングステンへの還元とタングステンの炭化が連続して進行するため、タングステンが高温下でメタルとして存在する時間が短縮される。その結果、超微粒な結晶子を得ることができる。
実施例の炭化タングステンを含む粉末の製造
SEM観察にて平均粒径が約3.0μmのWO3と、平均粒径が約1.0μmの炭素粉末と、平均粒径が約0.5μmのクロム酸化物(Cr2O3)を用いた。WO3と炭素粉末とクロム酸化物(Cr2O3)との質量配合比は、試料番号1~17において93.6:5.2:1.2とし、試料番号18,20,22,24において94.7:5.0:0.3とし、試料番号19,21,23,25において90.3:6.1:3.6とした。撹拌羽根のある一般的な混合機で、表4~7における混合条件で混合した。タングステン酸化物と炭素粉末およびクロム酸化物の混合方法については、何れの方式の混合機を使用してもよく、均一に混合されていればよい。
試料番号26~29を作製するために、300gのWO3を厚さ約5mmとなるように金属トレイ上で熱処理および還元(水素雰囲気、表8参照)してタングステン粉末を得た。表8は特に還元反応の最高温度域を示しており、昇温後は熱処理炉の冷却ゾーンにて冷却した。
従来製法1で用いたWO3、炭素粉末およびクロム酸化物(Cr2O3)を質量比83.3:15.8:0.9で配合し、前述と同様撹拌羽根のある一般的な混合機にて回転数500rpmで5分間混合した。混合物を表10に示す様々な条件で還元熱処理および炭化熱処理した後、表10のボールミルで粉砕して比較例試料番号30~32を作製した。
Claims (3)
- 炭化タングステンを含む粉末であって、
Fsss粒度が0.3μm以上1.5μm以下であり、
前記炭化タングステンの含有率が90質量%以上であり、
結晶子サイズ(平均粒径)YがY≦0.1×X+0.20(X:前記炭化タングステンを含む粉末のFsss粒度)の関係式を満たす、炭化タングステンを含む粉末。 - クロムを0.2質量%以上2.5質量%以下含有する、請求項1に記載の炭化タングステンを含む粉末。
- 酸素を0.3質量%以下含有する、請求項1または2に記載の炭化タングステンを含む粉末。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112760543A (zh) * | 2020-12-25 | 2021-05-07 | 四川川钨硬质合金有限公司 | 一种高强韧硬质合金及其制备方法和应用 |
CN113993813A (zh) * | 2019-05-13 | 2022-01-28 | 住友电气工业株式会社 | 碳化钨粉末 |
Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4834800A (ja) * | 1971-09-09 | 1973-05-22 | ||
JPH03208811A (ja) | 1990-01-12 | 1991-09-12 | Tokyo Tungsten Co Ltd | 超微粒wc粉,及びその製造方法 |
JPH09309715A (ja) | 1996-05-21 | 1997-12-02 | Tokyo Tungsten Co Ltd | 複合炭化物粉末及びその製造方法 |
JPH1121119A (ja) | 1997-07-03 | 1999-01-26 | Tokyo Tungsten Co Ltd | 複合炭化物及びそれを用いた超硬合金の製造方法 |
JP2004142993A (ja) * | 2002-10-24 | 2004-05-20 | Toshiba Tungaloy Co Ltd | 六方晶複合炭化物およびその製造方法 |
JP2005519018A (ja) * | 2001-11-06 | 2005-06-30 | サーバイド | 高密度炭化タングステンのセラミック体を作製する方法 |
JP2005335997A (ja) | 2004-05-26 | 2005-12-08 | Allied Material Corp | ナノ粒径の炭化タングステン粉末およびその製造方法 |
JP2006205354A (ja) * | 2006-03-20 | 2006-08-10 | Toshiba Corp | 切削工具用焼結体とそれを用いた切削工具 |
CN1850595A (zh) * | 2006-05-18 | 2006-10-25 | 梁光佳 | 石墨舟及用该舟将wo3+c+h2直接碳化生产碳化钨的方法 |
JP2009242181A (ja) * | 2008-03-31 | 2009-10-22 | Allied Material Corp | 炭化タングステン粉末、炭化タングステン粉末の製造方法 |
CN106077668A (zh) * | 2016-08-22 | 2016-11-09 | 合肥东方节能科技股份有限公司 | 一种基于热等静压的硬质合金烧结成型导轮的方法 |
JP2017219191A (ja) | 2016-06-01 | 2017-12-14 | 愛三工業株式会社 | 二重偏心弁 |
WO2018050474A1 (de) * | 2016-09-15 | 2018-03-22 | H.C. Starck Tungsten Gmbh | Neuartiges wolframcarbidpulver und dessen herstellung |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6495115B1 (en) * | 1995-09-12 | 2002-12-17 | Omg Americas, Inc. | Method to produce a transition metal carbide from a partially reduced transition metal compound |
EP1420076A1 (en) | 2002-10-24 | 2004-05-19 | Toshiba Tungaloy Co., Ltd. | Hard alloy and W-based composite carbide powder used as starting material |
JP4593173B2 (ja) * | 2004-05-26 | 2010-12-08 | 株式会社アライドマテリアル | ナノ粒径を備えた複合炭化物粉末およびその製造方法 |
CN1302883C (zh) * | 2005-05-04 | 2007-03-07 | 浙江天石粉末冶金有限公司 | 纳米晶粒WC-Co-VC-Cr3C2合金粉末制造方法 |
CN102517467A (zh) * | 2012-01-06 | 2012-06-27 | 周毅 | 一种粗晶粒硬质合金的制备方法 |
-
2018
- 2018-11-13 KR KR1020207016697A patent/KR102403390B1/ko active IP Right Grant
- 2018-11-13 US US16/762,903 patent/US11293082B2/en active Active
- 2018-11-13 JP JP2019554222A patent/JP7216656B2/ja active Active
- 2018-11-13 CN CN201880073396.9A patent/CN111344255B/zh active Active
- 2018-11-13 EP EP18879803.7A patent/EP3712109B1/en active Active
- 2018-11-13 WO PCT/JP2018/041953 patent/WO2019098183A1/ja unknown
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4834800A (ja) * | 1971-09-09 | 1973-05-22 | ||
JPH03208811A (ja) | 1990-01-12 | 1991-09-12 | Tokyo Tungsten Co Ltd | 超微粒wc粉,及びその製造方法 |
JPH09309715A (ja) | 1996-05-21 | 1997-12-02 | Tokyo Tungsten Co Ltd | 複合炭化物粉末及びその製造方法 |
JPH1121119A (ja) | 1997-07-03 | 1999-01-26 | Tokyo Tungsten Co Ltd | 複合炭化物及びそれを用いた超硬合金の製造方法 |
JP2005519018A (ja) * | 2001-11-06 | 2005-06-30 | サーバイド | 高密度炭化タングステンのセラミック体を作製する方法 |
JP2004142993A (ja) * | 2002-10-24 | 2004-05-20 | Toshiba Tungaloy Co Ltd | 六方晶複合炭化物およびその製造方法 |
JP2005335997A (ja) | 2004-05-26 | 2005-12-08 | Allied Material Corp | ナノ粒径の炭化タングステン粉末およびその製造方法 |
JP2006205354A (ja) * | 2006-03-20 | 2006-08-10 | Toshiba Corp | 切削工具用焼結体とそれを用いた切削工具 |
CN1850595A (zh) * | 2006-05-18 | 2006-10-25 | 梁光佳 | 石墨舟及用该舟将wo3+c+h2直接碳化生产碳化钨的方法 |
JP2009242181A (ja) * | 2008-03-31 | 2009-10-22 | Allied Material Corp | 炭化タングステン粉末、炭化タングステン粉末の製造方法 |
JP2017219191A (ja) | 2016-06-01 | 2017-12-14 | 愛三工業株式会社 | 二重偏心弁 |
CN106077668A (zh) * | 2016-08-22 | 2016-11-09 | 合肥东方节能科技股份有限公司 | 一种基于热等静压的硬质合金烧结成型导轮的方法 |
WO2018050474A1 (de) * | 2016-09-15 | 2018-03-22 | H.C. Starck Tungsten Gmbh | Neuartiges wolframcarbidpulver und dessen herstellung |
Non-Patent Citations (3)
Title |
---|
MADHAV REDDY, K. ET AL.: "Nanostructured tungsten carbides by thermochemical processing", JOURNAL OF ALLOYS AND COMPOUNDS, vol. 494, 22 January 2010 (2010-01-22), pages 404 - 409, XP026941565, DOI: doi:10.1016/j.jallcom.2010.01.059 * |
See also references of EP3712109A4 |
ZHONG, Y. ET AL.: "A study on the synthesis of nanostructured WC-10 wt% Co particles from WO 3, Co3O4, and graphite", JOURNAL OF MATERIALS SCIENCE, vol. 46, 30 October 2010 (2010-10-30), pages 6323 - 6331, XP019926638, DOI: doi:10.1007/s10853-010-4937-y * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113993813A (zh) * | 2019-05-13 | 2022-01-28 | 住友电气工业株式会社 | 碳化钨粉末 |
CN112760543A (zh) * | 2020-12-25 | 2021-05-07 | 四川川钨硬质合金有限公司 | 一种高强韧硬质合金及其制备方法和应用 |
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