WO2019169744A1 - 一种(WMo)C基硬质合金材质及其制备方法 - Google Patents

一种(WMo)C基硬质合金材质及其制备方法 Download PDF

Info

Publication number
WO2019169744A1
WO2019169744A1 PCT/CN2018/088330 CN2018088330W WO2019169744A1 WO 2019169744 A1 WO2019169744 A1 WO 2019169744A1 CN 2018088330 W CN2018088330 W CN 2018088330W WO 2019169744 A1 WO2019169744 A1 WO 2019169744A1
Authority
WO
WIPO (PCT)
Prior art keywords
powder
cemented carbide
wmo
preparation
preparing
Prior art date
Application number
PCT/CN2018/088330
Other languages
English (en)
French (fr)
Inventor
时凯华
董凯林
昝秀颀
Original Assignee
自贡硬质合金有限责任公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 自贡硬质合金有限责任公司 filed Critical 自贡硬质合金有限责任公司
Publication of WO2019169744A1 publication Critical patent/WO2019169744A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C22C1/053—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds
    • C22C1/055—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds using carbon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C22C1/053—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds
    • C22C1/056—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds using gas
    • C—CHEMISTRY; METALLURGY
    • 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
    • C22C29/067—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 comprising a particular metallic binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

Definitions

  • the invention belongs to the technical field of cemented carbide preparation, and particularly relates to a (WMo) C-based hard alloy material and a preparation method thereof.
  • Cemented carbide is a composite material prepared by powder metallurgy process from refractory metal carbides (such as WC, TiC, TaC, etc.) and bonding metals (such as Co, Ni, Fe, etc.) as main components.
  • WC-based cemented carbide is widely used in the fields of machining, metallurgy, mining, electronic communication, construction, etc. due to its high hardness and wear resistance.
  • the application of cemented carbide in cutting and other fields depends on the good properties of carbides such as high strength and hardness.
  • a preferred method is to solidify other carbides in the WC without reducing or improving the properties of the alloy.
  • the WC of the hexagonal structure is consistent with the C and W atomic ratios and has no vacancies, and its structure can only dissolve a very small amount of other metal atoms and N atoms during the sintering process. Only a very small number of carbides can be dissolved in WC, such as chromium carbide (very low in solid solution). Mo and its carbides are the only metal elements that can be dissolved in a large amount in WC.
  • the ball-milled Mo powder and W powder are heat-treated at 1400-1500 ° C to obtain Mo-W solid solution metal; (3) the Mo-W solid solution is crushed and mixed with C powder and Co/Ni/Fe powder ball mill; 4)
  • the mixed powder obtained in the step (3) is heat-treated at 1100 to 1400 ° C to obtain a WC-MoC alloy.
  • the preparation method has relatively many process steps, and the solid solution metal needs to be broken during the process, and the powder particle size is difficult to ensure; and the final product contains a certain amount of (Co/Ni/Fe), which is not a pure carbide phase. Therefore, pure (W, Mo) C powder cannot be obtained.
  • the object of the present invention is to overcome the deficiencies of the prior art and to provide a (WMo) C-based cemented carbide material and a preparation method thereof.
  • a (WMo) C-based cemented carbide material comprising the following mass percentage components:
  • a (WMo) C-based cemented carbide material comprises the following mass percentage components:
  • the preparation method of the above (WMo) C-based cemented carbide material comprises the following steps:
  • Step 1 The WO 3 powder and the MoO 3 powder are subjected to reduction treatment according to the weight ratio;
  • Step 2 mixing the C powder with the powder obtained by the reduction in the step 1 by weight ratio, and then performing carbonization treatment;
  • Step 3 After the powder obtained by carbonizing in step 2 is stirred, it is obtained.
  • the reduction treatment in the step 1 employs hydrogen as a reducing gas.
  • Ar gas is used as a shielding gas during stirring.
  • the invention realizes the replacement of W by Mo to prepare cemented carbide, and provides a development direction for the alternative application of non-renewable tungsten resources.
  • the (WMo) C-based cemented carbide is prepared by the method of the invention, which makes up for the deficiencies of the conventional method for preparing the Mo-containing cemented carbide, and the Mo content in the prepared base cemented carbide is uniformly dispersed, and the Mo solid solution is improved.
  • the role in the binder phase; and the formation of the third phase ((WMo)xC) increased, which has a better effect on the properties of the alloy.
  • the present invention solves the problem that the amount of Mo added in the process of preparing the cemented carbide cannot be higher than 5 wt%, and the prepared cemented carbide has higher hardness, toughness and wear resistance.
  • the method for preparing (WMo) C-based cemented carbide material has simple process steps, no need to be broken in the whole process, powder particle size can be ensured, and pure (W, Mo) C powder can be obtained at the same time.
  • Example 1 is an XRD chart of a (W5Mo) C powder in Example 1.
  • Example 2 is a metallographic photograph of a (W5Mo)-10Co cemented carbide in Example 1.
  • Example 3 is an XRD chart of the (W15Mo) C powder in Example 3.
  • Example 4 is a metallographic photograph of a (W15Mo)-10Co cemented carbide in Example 3.
  • the method of preparing a (W5Mo) C powder comprises the following steps:
  • Step 1 Weigh each component according to the quality of each component in Example 1 of Table 1;
  • Step 2 according to the mass of the components in the first embodiment of Table 1, WO 3 powder (particle size of 40 ⁇ m), MoO 3 (particle size 25 ⁇ m) was added to the Mo boat and reduced by hydrogen in a tubular reduction furnace for 2 h, the reduction temperature was 1000 ° C. , the heating rate is 2 ° C / min, the cooling rate is 3 ° C / min;
  • Step 3 the component powder of the composition of Table 1 in Table 1 and the powder obtained by the reduction of step 2 are placed in a mixer and mixed for 3 hours to obtain a mixed powder; then the mixed powder is placed in a graphite boat and carbonized in an induction furnace. 1.5h, carbonization temperature 1500 ° C; XRD results of the powder obtained after carbonization are shown in Figure 1;
  • Step 4 The powder obtained by carbonization in the step 3 is added to a stirring ball mill (Type NETZSCH PE075, Antriebstechnic) and stirred for 4 hours.
  • a stirring ball mill Type NETZSCH PE075, Antriebstechnic
  • the rotation speed of the ball mill is 400 r/min
  • Ar gas is used as a shielding gas
  • the flow rate of the Ar gas is 0.1 L/ Min;
  • Step 5 the step 4 stirred ball milled powder was sieved through a -400 mesh (38 ⁇ m) sieve to obtain (W5Mo) C powder;
  • Step 6 Weigh each component according to the quality of each component in Example 1 of Table 2;
  • Step 7 According to the component quality in the first embodiment of Table 2, (W5Mo)C powder, Co powder, VC powder, Cr 3 C 2 powder and W powder are added into the ball mill barrel, and WC is added in a ratio of ball to material ratio of 5:1. - 6% Co alloy ball ( ⁇ 6 mm), adding 2 wt% paraffin, 0.1 wt% stearic acid, and then adding hexane according to the ratio of 400 ml/kg, ball milling, ball mill rotation speed of 63 rpm, ball milling time of 46 h ;
  • Step 8 The slurry obtained by the ball milling in step 7 is dried in a vacuum oven at 70 ° C for 2 hours, and after being cooled to below 40 ° C, it is subjected to rubbing and granulation;
  • Step 9 The 10% Co-containing mixture obtained in the step 8 is press-formed by a 25-ton single-column hydraulic press, and the compact size is 20.9*20.9*7.4 mm.
  • Step 10 The compact sample is sintered in a hydrogen dewaxing-low pressure sintering integrated furnace for 90 minutes, the sintering temperature is 1400 ° C, the atmosphere is Ar gas, and the pressure is 5 MPa, thereby obtaining (W5Mo) C-10Co cemented carbide. Its metallographic diagram is shown in Figure 2. The sintered (W5Mo) C-10Co cemented carbide sample was tested for physical properties, and its Vickers hardness and fracture toughness are shown in Table 3.
  • the method of preparing the (W10Mo) C powder comprises the following steps:
  • Step 1 Weigh each component according to the quality of each component in Example 2 of Table 1;
  • Step 2 according to the mass of the components in Table 2, WO 3 powder (particle size 40 ⁇ m), MoO 3 (particle size 25 ⁇ m) was added to the Mo boat to reduce hydrogen in the tube reduction furnace for 2 h, the reduction temperature was 1000 ° C. , the heating rate is 2 ° C / min, the cooling rate is 3 ° C / min;
  • Step 3 the component powder of the component of Table 1 in Table 2 and the powder obtained by the reduction of step 2 are placed in a mixer and mixed for 3 hours to obtain a mixed powder; then the mixed powder is placed in a graphite boat and carbonized in an induction furnace. 1.5h, carbonization temperature 1500 ° C;
  • Step 4 The powder obtained by carbonization in the step 3 is added to a stirring ball mill (Type NETZSCH PE075, Antriebstechnic) and stirred for 4 hours.
  • a stirring ball mill Type NETZSCH PE075, Antriebstechnic
  • the rotation speed of the ball mill is 400 r/min
  • Ar gas is used as a shielding gas
  • the flow rate of the Ar gas is 0.1 L/ Min;
  • Step 5 the step 4 stirred ball milled powder was sieved through a -400 mesh (38 ⁇ m) sieve to obtain (W10Mo) C powder;
  • Step 6 Weigh each component according to the quality of each component in Example 2 of Table 2;
  • Step 7 According to the component quality in the second embodiment of Table 2, (W10Mo)C powder, Co powder, VC powder, Cr 3 C 2 powder and W powder are added into the ball mill cylinder, and WC is added in a ratio of ball to material ratio of 5:1. - 6% Co alloy ball ( ⁇ 6 mm), adding 2 wt% paraffin, 0.1 wt% stearic acid, and then adding hexane according to the ratio of 400 ml/kg, ball milling, ball mill rotation speed of 63 rpm, ball milling time of 46 h ;
  • Step 8 The slurry obtained by the ball milling in step 7 is dried in a vacuum oven at 70 ° C for 2 hours, and after being cooled to below 40 ° C, it is subjected to rubbing and granulation;
  • Step 9 The 10% Co-containing mixture obtained in the step 8 is press-formed by a 25-ton single-column hydraulic press, and the compact size is 20.9*20.9*7.4 mm.
  • Step 10 The green compact sample is sintered in a hydrogen dewaxing-low pressure sintering integrated furnace for 90 minutes, the sintering temperature is 1400 ° C, the atmosphere is Ar gas, and the pressure is 5 MPa, thereby obtaining (W10Mo) C-10Co cemented carbide.
  • the sintered (W10Mo) C-10Co cemented carbide sample was tested for physical properties, and its Vickers hardness and fracture toughness are shown in Table 3.
  • the method of preparing a (W15Mo) C powder comprises the following steps:
  • Step 1 Weigh each component according to the quality of each component in Example 3 of Table 1;
  • Step 2 according to the component quality in Example 3 of Table 1, WO 3 powder (particle size 40 ⁇ m), MoO 3 (particle size 25 ⁇ m) was added to the Mo boat for reduction in a tubular reduction furnace for 5 h, and the reduction temperature was 1000 ° C. , the heating rate is 2 ° C / min, the cooling rate is 3 ° C / min;
  • Step 3 the component powder of the component of Table 1 in Table 3 and the powder obtained by the reduction of step 2 are placed in a mixer and mixed for 3 hours to obtain a mixed powder; then the mixed powder is placed in a graphite boat and carbonized in an induction furnace. 1h, the carbonization temperature is 1600 ° C; the XRD results of the powder obtained after carbonization are shown in Figure 3;
  • Step 4 The powder obtained by carbonization in the step 3 is added to a stirring ball mill (Type NETZSCH PE075, Antriebstechnic) and stirred for 4 hours.
  • a stirring ball mill Type NETZSCH PE075, Antriebstechnic
  • the rotation speed of the ball mill is 400 r/min
  • Ar gas is used as a shielding gas
  • the flow rate of the Ar gas is 0.1 L/ Min;
  • Step 5 the step 4 stirred ball milled powder was sieved through a -400 mesh (38 ⁇ m) sieve to obtain (W15Mo) C powder;
  • Step 6 Weigh each component according to the quality of each component in Example 3 of Table 2;
  • Step 7 According to the component quality in the embodiment 3 of Table 2, (W15Mo) C powder, Co powder, VC powder, Cr 3 C 2 powder, W powder are added into the ball mill cylinder, and WC is added in a ratio of ball to material ratio of 5:1. - 6% Co alloy ball ( ⁇ 6 mm), adding 2 wt% paraffin, 0.1 wt% stearic acid, and then adding hexane according to the ratio of 400 ml/kg, ball milling, ball mill rotation speed of 63 rpm, ball milling time 54 h ;
  • Step 8 The slurry obtained by the ball milling in step 7 is dried in a vacuum oven at 70 ° C for 2 hours, and after being cooled to below 40 ° C, it is subjected to rubbing and granulation;
  • Step 9 The 10% Co-containing mixture obtained in the step 8 is press-formed by a 25-ton single-column hydraulic press, and the compact size is 20.9*20.9*7.4 mm.
  • Step 10 The compact sample is sintered in a hydrogen dewaxing-low pressure sintering integrated furnace for 90 minutes, the sintering temperature is 1420 ° C, the atmosphere is Ar gas, and the pressure is 5 MPa, thereby obtaining (W15Mo) C-10Co cemented carbide. Its metallographic diagram is shown in Figure 4. The sintered (W15Mo) C-10Co cemented carbide sample was tested for physical properties, and its Vickers hardness and fracture toughness are shown in Table 3.
  • the invention is not limited to the specific embodiments described above.
  • the invention extends to any new feature or any new combination disclosed in this specification, as well as any novel method or process steps or any new combination disclosed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

本发明属于硬质合金制备技术领域，具体涉及一种(WMo)C基硬质合金材质，包括如下质量百分比的组分：WO 3粉74～87.7％，MoO 3粉5.1～14.8％，C粉7.1～11.2％。其制备方法为：先将WO 3粉和MoO 3粉加入还原炉进行还原处理，再将C粉与还原所得粉末混合进行碳化处理，最后将碳化所得粉末进行搅拌后即得。本发明实现了Mo部分替代W来制备硬质合金，为不可再生钨资源的替代应用提供了一个发展方向；同时采用本发明方法制备(WMo)C基硬质合金，弥补了传统制备含Mo硬质合金方法所存在的不足，其制备得到的基硬质合金中Mo元素分散均匀，提高了Mo固溶于粘结相中的作用。

Description

一种(WMo)C基硬质合金材质及其制备方法 技术领域
本发明属于硬质合金制备技术领域，具体涉及一种(WMo)C基硬质合金材质及其制备方法。
背景技术
硬质合金是由难熔金属碳化物(如WC、TiC、TaC等)和粘结金属(如Co、Ni、Fe等)作为主要成分，采用粉末冶金工艺制备而成的一种复合材料。以WC为基体的硬质合金由于其高硬度和耐磨性广泛应用于制备高性能的切刀、铣刀和钻头工具，应用于机械加工、冶金、矿山、电子通讯、建筑等领域，伴随着新兴的天然气、航空航天、深海石油等产业的不断发展，硬质合金需求将继续扩大。硬质合金在切削等领域的应用则有赖于碳化物的良好性能：如高强度和硬度。但越来越大的工业需要使得WC的价格持续较高，且由于地球钨储量有限，亟待研究人员寻找更好的部分或整体替代品。一种较好的方法是将其他碳化物固溶在WC中，不降低或提高合金的性能。然而，六方结构的WC因C和W原子比相符且没有空位，其结构在烧结过程中只能溶入极少量的其他金属原子及N原子。只有极少数碳化物可以固溶在WC中，如碳化铬(固溶量非常低)等。Mo及其碳化物则是唯一一种可以在WC中大量固溶的金属元素。
近年来，国内外的科技工作者开展了大量的关于添加Mo或Mo2C对硬质合金组织及性能的影响的研究。如余玖明等在《江西科学》，第33卷第6期于2015年12月发表的期刊《Mo含量对WC-8(Fe-Co-Ni)硬质合金组织和性能的影响》，该期刊的结果表明：Mo含量的增加可以降低WC在液相中的溶解度，起到细化晶粒的作用，合金的硬度得到明显提升；由于Mo的固溶强化作用，改善了合金的抗弯强度；当Mo添加量增加到5wt％时，WC-8(Fe-Co-Ni)硬质合金的综合性能最好。其余大多数研究是以Mo或Mo2C的形式加入(Ti,W,Ta)C基金属陶瓷或WC-Co/Ni系合金中，当添加量较少时，Mo或Mo2C很难分散均匀。另外，在烧结温度下，Mo或Mo2C大部分都是固溶在粘结相中，阻止了WC的溶解-析出，起到细化晶粒的作用，只有少部分固溶在WC中形成(WMo)C或(WMo)xC(第三相)，因此，以Mo或Mo2C的形式加入合金中未必能真正发挥其应有的作用。而采用铵 盐溶液法制备W和Mo的氧化物，再将氧化物(WO3、MoO3)经还原-碳化制备(Mo,W)C粉末时，工艺流程较多，且部分流程对环境有污染，因此，不利于工业化生产。
公开号为US04257809的美国专利于1981年3月24日公开的一种(WC-MoC)固溶体的制备方法，其步骤包括：(1)使用金属Mo粉和W粉作为原料进行球磨混合；(2)将球磨后的Mo粉和W粉在1400～1500℃条件下热处理得到Mo-W固溶金属；(3)将Mo-W固溶体破碎并与C粉和Co/Ni/Fe粉球磨混合；(4)将第(3)步得到的混合粉在1100～1400℃条件下热处理得到WC-MoC合金。该制备方法的工艺步骤相对较多，在工艺过程中需要对固溶金属进行破碎，其粉末粒度难以保证；同时其最终产品中含有一定量的(Co/Ni/Fe)，不是纯碳化物相，所以无法得到纯的(W,Mo)C粉末。
发明内容
本发明的目的是克服现有技术的不足，提供一种(WMo)C基硬质合金材质及其制备方法。
为了达到上述目的，本发明采用了下列技术方案：
一种(WMo)C基硬质合金材质，包括如下质量百分比的组分：
WO 3粉               74～87.7％，
MoO 3粉              5.1～14.8％，
C粉                 7.1～11.2％。
作为优选，一种(WMo)C基硬质合金材质，包括如下质量百分比的组分：
WO 3粉               74.071～87.661％，
MoO 3粉              5.197～14.724％，
C粉                 7.142～11.205％。
上述(WMo)C基硬质合金材质的制备方法，包括以下步骤：
步骤1、按重量配比将WO 3粉和MoO 3粉进行还原处理；
步骤2、将C粉按重量配比与步骤1还原所得粉末混合后进行碳化处理；
步骤3、将步骤2碳化所得粉末进行搅拌后即得。
作为优选，所述步骤1中还原处理采用氢气作为还原气体。
作为优选，所述步骤3中搅拌时采用Ar气作为保护气体。
本发明具有以下优点：
1、本发明实现了Mo部分替代W来制备硬质合金，为不可再生钨资源的替代应用提供了一个发展方向。
2、采用本发明方法制备(WMo)C基硬质合金，弥补了传统制备含Mo硬质合金方法所存在的不足，其制备得到的基硬质合金中Mo元素分散均匀，提高了Mo固溶于粘结相中的作用；且第三相((WMo)xC)形成数量增多，对合金性能影响更好。
3、本发明解决了在制备硬质合金的过程中Mo的添加量不能高于5wt％的问题，且其制备得到的硬质合金具有更高的硬度、韧性和耐磨性。
4、本发明制备(WMo)C基硬质合金材质的方法工艺步骤简单，全程不需要破碎，粉末粒度可以保证，同时可以得到纯的(W,Mo)C粉末。
附图说明
图1是实施例1中(W5Mo)C粉末的XRD图。
图2是实施例1中(W5Mo)-10Co硬质合金的金相照片。
图3是实施例3中(W15Mo)C粉末的XRD图。
图4是实施例3中(W15Mo)-10Co硬质合金的金相照片。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
实施例1：
制备(W5Mo)C粉末的方法包括以下步骤：
步骤1、按表1实施例1中各组分质量称取各组分；
步骤2、按表1实施例1中的组分质量将WO 3粉(粒度为40μm)、MoO 3(粒度25μm)加入Mo舟皿中在管式还原炉内通氢还原2h，还原温度1000℃，升温速率为2℃/min，降温速率为3℃/min；
步骤3、将表1实施例1中组分质量的C粉和步骤2还原所得粉末置于混合器中混合3h，得到混合粉；然后将混合粉置于石墨舟皿中，在感应炉中碳化1.5h，碳化温度1500℃；碳化后所得粉末XRD结果如图1所示；
步骤4、将步骤3中碳化所得粉末加入搅拌球磨机(Type NETZSCH PE075, Antriebstechnic)中搅拌4h，搅拌过程中球磨机转速为400r/min，并采用Ar气作为保护气体，Ar气的流量为0.1L/min；
步骤5、将步骤4搅拌球磨后的粉末经-400目(38μm)筛网过筛得到(W5Mo)C粉末；
至此(W5Mo)C粉制备工艺完成，以下为(W5Mo)C-10Co硬质合金的制备步骤：
步骤6、按表2实施例1中各组分质量称取各组分；
步骤7、按表2实施例1中的组分质量将(W5Mo)C粉、Co粉、VC粉、Cr 3C 2粉、W粉加入球磨筒中，按球料比5：1的比例加入WC-6％Co合金球(φ6mm)，加入2wt％的石蜡、0.1wt％的硬脂酸，再按照400ml/kg的比例加入己烷，进行球磨，球磨机转速为63转/分钟，球磨时间为46h；
步骤8、将步骤7球磨所得料浆置于70℃真空干燥箱中干燥2h，待料冷却至40℃以下后对其进行擦筛、制粒；
步骤9、将步骤8所得的含10％Co的混合料经25吨单柱液压机压制成型，压坯尺寸为20.9*20.9*7.4mm。
步骤10、将压坯试样置于氢气脱蜡-低压烧结一体炉内烧结90分钟，烧结温度为1400℃、气氛为Ar气，压力为5Mpa，即得到(W5Mo)C-10Co硬质合金，其金相图如图2所示。将烧结后的(W5Mo)C-10Co硬质合金试样进行物理性能检测，其维氏硬度和断裂韧性如表3所示。
实施例2：
制备(W10Mo)C粉末的方法包括以下步骤：
步骤1、按表1实施例2中各组分质量称取各组分；
步骤2、按表1实施例2中的组分质量将WO 3粉(粒度为40μm)、MoO 3(粒度25μm)加入Mo舟皿中在管式还原炉内通氢还原2h，还原温度1000℃，升温速率为2℃/min，降温速率为3℃/min；
步骤3、将表1实施例2中组分质量的C粉和步骤2还原所得粉末置于混合器中混合3h，得到混合粉；然后将混合粉置于石墨舟皿中，在感应炉中碳化1.5h，碳化温度1500℃；
步骤4、将步骤3中碳化所得粉末加入搅拌球磨机(Type NETZSCH PE075,Antriebstechnic)中搅拌4h，搅拌过程中球磨机转速为400r/min，并采用Ar 气作为保护气体，Ar气的流量为0.1L/min；
步骤5、将步骤4搅拌球磨后的粉末经-400目(38μm)筛网过筛得到(W10Mo)C粉末；
至此(W10Mo)C粉制备工艺完成，以下为(W10Mo)C-10Co硬质合金的制备步骤：
步骤6、按表2实施例2中各组分质量称取各组分；
步骤7、按表2实施例2中的组分质量将(W10Mo)C粉、Co粉、VC粉、Cr 3C 2粉、W粉加入球磨筒中，按球料比5：1的比例加入WC-6％Co合金球(φ6mm)，加入2wt％的石蜡、0.1wt％的硬脂酸，再按照400ml/kg的比例加入己烷，进行球磨，球磨机转速为63转/分钟，球磨时间为46h；
步骤8、将步骤7球磨所得料浆置于70℃真空干燥箱中干燥2h，待料冷却至40℃以下后对其进行擦筛、制粒；
步骤9、将步骤8所得的含10％Co的混合料经25吨单柱液压机压制成型，压坯尺寸为20.9*20.9*7.4mm。
步骤10、将压坯试样置于氢气脱蜡-低压烧结一体炉内烧结90分钟，烧结温度为1400℃、气氛为Ar气，压力为5Mpa，即得到(W10Mo)C-10Co硬质合金。将烧结后的(W10Mo)C-10Co硬质合金试样进行物理性能检测，其维氏硬度和断裂韧性如表3所示。
实施例3：
制备(W15Mo)C粉末的方法包括以下步骤：
步骤1、按表1实施例3中各组分质量称取各组分；
步骤2、按表1实施例3中的组分质量将WO 3粉(粒度为40μm)、MoO 3(粒度25μm)加入Mo舟皿中在管式还原炉内通氢还原5h，还原温度1000℃，升温速率为2℃/min，降温速率为3℃/min；
步骤3、将表1实施例3中组分质量的C粉和步骤2还原所得粉末置于混合器中混合3h，得到混合粉；然后将混合粉置于石墨舟皿中，在感应炉中碳化1h，碳化温度1600℃；碳化后所得粉末XRD结果如图3所示；
步骤4、将步骤3中碳化所得粉末加入搅拌球磨机(Type NETZSCH PE075,Antriebstechnic)中搅拌4h，搅拌过程中球磨机转速为400r/min，并采用Ar 气作为保护气体，Ar气的流量为0.1L/min；
步骤5、将步骤4搅拌球磨后的粉末经-400目(38μm)筛网过筛得到(W15Mo)C粉末；
至此(W15Mo)C粉制备工艺完成，以下为(W15Mo)C-10Co硬质合金的制备步骤：
步骤6、按表2实施例3中各组分质量称取各组分；
步骤7、按表2实施例3中的组分质量将(W15Mo)C粉、Co粉、VC粉、Cr 3C 2粉、W粉加入球磨筒中，按球料比5：1的比例加入WC-6％Co合金球(φ6mm)，加入2wt％的石蜡、0.1wt％的硬脂酸，再按照400ml/kg的比例加入己烷，进行球磨，球磨机转速为63转/分钟，球磨时间为54h；
步骤8、将步骤7球磨所得料浆置于70℃真空干燥箱中干燥2h，待料冷却至40℃以下后对其进行擦筛、制粒；
步骤9、将步骤8所得的含10％Co的混合料经25吨单柱液压机压制成型，压坯尺寸为20.9*20.9*7.4mm。
步骤10、将压坯试样置于氢气脱蜡-低压烧结一体炉内烧结90分钟，烧结温度为1420℃、气氛为Ar气，压力为5Mpa，即得到(W15Mo)C-10Co硬质合金，其金相图如图4所示。将烧结后的(W15Mo)C-10Co硬质合金试样进行物理性能检测，其维氏硬度和断裂韧性如表3所示。
实施例4-5：
实施例4-5中制备(W15Mo)C粉末的方法与实施例3中的步骤1-5相同。
实施例4中制备(W15Mo)C-6Co硬质合金的方法中各组分质量如表2所示，其余原料性能及制备工艺参数与实施例3中步骤6-10相同。
实施例5中制备(W15Mo)C-12Co硬质合金的方法中各组分质量如表2所示，其余原料性能及制备工艺参数与实施例3中步骤6-10相同。
将实施例4、5烧结后的(W15Mo)C-6Co、(W15Mo)C-12Co硬质合金试样进行物理性能检测，其维氏硬度和断裂韧性如表3所示。
表1
Figure PCTCN2018088330-appb-000001
表2
Figure PCTCN2018088330-appb-000002
表3
Figure PCTCN2018088330-appb-000003
本发明并不局限于前述的具体实施方式。本发明扩展到任何在本说明书中披露的新特征或任何新的组合，以及披露的任一新的方法或过程的步骤或任何新的组合。

Claims (4)

  1. 一种(WMo)C基硬质合金材质，其特征在于，包括如下质量百分比的组分：
    WO 3粉             74～87.7％，
    MoO 3粉            5.1～14.8％，
    C粉               7.1～11.2％。
  2. 一种根据权利要求1所述的(WMo)C基硬质合金材质的制备方法，其特征在于：包括以下步骤：
    步骤1、按重量配比将WO 3粉和MoO 3粉进行还原处理；
    步骤2、将C粉按重量配比与步骤1还原所得粉末混合后进行碳化处理；
    步骤3、将步骤2碳化所得粉末进行搅拌后即得。
  3. 根据权利要求2所述的一种(WMo)C基硬质合金材质的制备方法，其特征在于：所述步骤1中还原处理采用氢气作为还原气体。
  4. 根据权利要求2所述的一种(WMo)C基硬质合金材质的制备方法，其特征在于：所述步骤3中搅拌时采用Ar气作为保护气体。
PCT/CN2018/088330 2018-03-09 2018-05-25 一种(WMo)C基硬质合金材质及其制备方法 WO2019169744A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201810193421.9A CN108425058A (zh) 2018-03-09 2018-03-09 一种(WMo)C基硬质合金材质及其制备方法
CN201810193421.9 2018-03-09

Publications (1)

Publication Number Publication Date
WO2019169744A1 true WO2019169744A1 (zh) 2019-09-12

Family

ID=63158008

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/088330 WO2019169744A1 (zh) 2018-03-09 2018-05-25 一种(WMo)C基硬质合金材质及其制备方法

Country Status (2)

Country Link
CN (1) CN108425058A (zh)
WO (1) WO2019169744A1 (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111979462A (zh) * 2020-08-21 2020-11-24 合肥工业大学 一种具有高硬度的WC-MoC-Co-Y2O3硬质合金及其制备方法
CN112708795B (zh) * 2020-12-24 2023-09-05 自贡硬质合金有限责任公司 一种纳米晶强化硬质合金的制备方法
CN113652594B (zh) * 2021-08-02 2022-11-22 自贡硬质合金有限责任公司 一种难熔金属基合金及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2033426A (en) * 1978-10-11 1980-05-21 Cabot Corp Molybdenum-tungsten Carbide Products
US4639352A (en) * 1985-05-29 1987-01-27 Sumitomo Electric Industries, Ltd. Hard alloy containing molybdenum
SU1406199A1 (ru) * 1987-01-08 1988-06-30 Белорусское республиканское научно-производственное объединение порошковой металлургии Способ получени твердых сплавов на основе сложных карбидов
SU1454572A1 (ru) * 1987-07-06 1989-01-30 Белорусское республиканское научно-производственное объединение порошковой металлургии Способ получени твердых сплавов на основе молибден-вольфрамовых карбидов
CN102296223A (zh) * 2011-08-15 2011-12-28 四川欧曼机械有限公司 一种细晶粒wc基硬质合金材料及其制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4216009A (en) * 1977-07-27 1980-08-05 Sumitomo Electric Industries, Ltd. Method of making alloy and carbide powders of molybdenum and tungsten
US4257809A (en) * 1979-01-05 1981-03-24 General Electric Company Molybdenum monocarbide-tungsten monocarbide solid solutions
JPS5938168B2 (ja) * 1979-02-14 1984-09-14 住友電気工業株式会社 モリブデンを含む硬質固溶体の製造法
CN1176314A (zh) * 1996-09-06 1998-03-18 汪兆泉 碳化钨钒的生产方法
DE10043792A1 (de) * 2000-09-06 2002-03-14 Starck H C Gmbh Ultragrobes, einkristallines Wolframkarbid und Verfahren zu dessen Herstellung; und daraus hergestelltes Hartmetall

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2033426A (en) * 1978-10-11 1980-05-21 Cabot Corp Molybdenum-tungsten Carbide Products
US4639352A (en) * 1985-05-29 1987-01-27 Sumitomo Electric Industries, Ltd. Hard alloy containing molybdenum
SU1406199A1 (ru) * 1987-01-08 1988-06-30 Белорусское республиканское научно-производственное объединение порошковой металлургии Способ получени твердых сплавов на основе сложных карбидов
SU1454572A1 (ru) * 1987-07-06 1989-01-30 Белорусское республиканское научно-производственное объединение порошковой металлургии Способ получени твердых сплавов на основе молибден-вольфрамовых карбидов
CN102296223A (zh) * 2011-08-15 2011-12-28 四川欧曼机械有限公司 一种细晶粒wc基硬质合金材料及其制备方法

Also Published As

Publication number Publication date
CN108425058A (zh) 2018-08-21

Similar Documents

Publication Publication Date Title
JP4257690B2 (ja) 粉末冶金用途のための焼結活性金属粉末及び合金粉末、それらの製造方法並びにそれらの使用
WO2019169744A1 (zh) 一种(WMo)C基硬质合金材质及其制备方法
CN102383021B (zh) 一种Ni3Al强化粘结相的WC-Co硬质合金及其制备方法
CN101985717A (zh) 高韧性超粗晶钨钴硬质合金的制备方法
CN111378857B (zh) 一种高性能超细晶硬质合金制备方法
CN106636834B (zh) 抑制硬质合金晶粒长大的方法及超细晶硬质合金制备工艺
CN112647006B (zh) 一种以碳化钨为基础的硬质合金及其制备方法
CN103981419A (zh) 一种高强度碳氮化钛金属陶瓷密封材料及其制备方法
CN113502426B (zh) 一种多晶粒尺度硬质合金及其制备方法
Qian et al. Effect of the carbon content on the morphology evolution of the η phase in cemented carbides with the CoNiFeCr high entropy alloy binder
CN102251130B (zh) 一种超细晶粒硬质合金的制备方法
CN110387496A (zh) 一种表层无TiC相的WC-TiC-Co基梯度硬质合金及其制备方法
CN113737040A (zh) 一种纳米氧化钇弥散强化钼合金及其制备方法
CN110240163B (zh) 一种采用中粗颗粒钨粉制备细晶粒wc粉的方法
CN109778046B (zh) 一种低成本高性能混晶结构WC-Co硬质合金的制备方法
CN113136514B (zh) 一种高强度高比重合金材料及其制备方法
CN102699337B (zh) 一种原生粉和再生粉混合的硬质合金粉合成制备方法
CN111893339A (zh) 一种湿化学法制备高性能WC-8Co-Y2O3硬质合金的方法
CN110066952B (zh) 一种氧化锆增强钼合金棒材的制备方法
CN115070042A (zh) 一种稀土氧化物改性硬质合金车刀片及其制备方法
CN111020337B (zh) 一种应用于超细碳化钨制备的抑制剂及其制备方法
CN112359241B (zh) 一种双晶非均匀硬质合金及其制备方法
CN114752801A (zh) 一种板状晶强化网状结构硬质合金及其制备方法
CN111392727A (zh) 一种模具材料用碳化钨粉末及其制备方法
CN107190167B (zh) 一种新型的硬质合金晶粒长大抑制剂及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18908517

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18908517

Country of ref document: EP

Kind code of ref document: A1