技术领域technical field
本发明属于硬质合金技术领域，尤其涉及一种梯度结构硬质合金及其制备方法和应用。The invention belongs to the technical field of hard alloys, and in particular relates to a hard alloy with a gradient structure and a preparation method and application thereof.
背景技术Background technique
硬质合金是由难熔金属的硬质化合物(WC，TiC，TaC，NbC)和粘结金属(Co，Ni，Fe等)通过粉末冶金工艺制成的一种复合材料，具有高强度、高硬度、耐腐蚀、高耐磨性、良好的韧性等独特性能，被广泛地应用于切削刀具、地质矿山刀具、成型模具和结构耐磨件等领域。Cemented carbide is a composite material made of hard compounds of refractory metals (WC, TiC, TaC, NbC) and bonding metals (Co, Ni, Fe, etc.) through powder metallurgy. Unique properties such as hardness, corrosion resistance, high wear resistance, and good toughness are widely used in cutting tools, geological and mining tools, forming molds, and structural wear-resistant parts.
但是，传统硬质合金存在高硬度和高韧性不能共存的矛盾，当硬度很高时，韧性就相对低；当韧性很高时，硬度相对低。随着社会的高速发展，工业生产制造对材料的性能要求越来越高，硬质合金因具有的这种矛盾性已经逐渐不能满足加工需要。However, traditional cemented carbide has the contradiction that high hardness and high toughness cannot coexist. When the hardness is high, the toughness is relatively low; when the toughness is high, the hardness is relatively low. With the rapid development of society, industrial production and manufacturing have higher and higher requirements on the performance of materials, and the contradiction of cemented carbide has gradually been unable to meet the processing needs.
发明内容Contents of the invention
有鉴于此，本发明提供了一种梯度结构硬质合金及其制备方法和应用，用于解决现有技术中硬质合金存在高硬度和高韧性不能共存的问题。In view of this, the present invention provides a cemented carbide with gradient structure and its preparation method and application, which are used to solve the problem that high hardness and high toughness cannot coexist in cemented carbide in the prior art.
本发明的技术方案如下：Technical scheme of the present invention is as follows:
一种梯度结构硬质合金，所述梯度结构硬质合金从外至内包括：第一梯度层、第二梯度层和芯部；A gradient structure cemented carbide, the gradient structure cemented carbide comprises from outside to inside: a first gradient layer, a second gradient layer and a core;
所述第一梯度层含有立方相，所述第二梯度层和所述芯部不含立方相；The first gradient layer contains a cubic phase, and the second gradient layer and the core do not contain a cubic phase;
所述第一梯度层的立方相包括富TiN立方相和/或富ZrN立方相；The cubic phase of the first gradient layer includes a TiN-rich cubic phase and/or a ZrN-rich cubic phase;
所述第二梯度层的钴含量高于所述梯度结构硬质合金中钴的平均含量，第二梯度层的碳化钨晶粒尺寸大于所述梯度结构硬质合金中碳化钨晶粒的平均尺寸；The cobalt content of the second gradient layer is higher than the average cobalt content in the gradient structure cemented carbide, and the tungsten carbide grain size of the second gradient layer is greater than the average size of the tungsten carbide grain in the gradient structure cemented carbide ;
所述梯度结构硬质合金的原料包括钴、碳化钨、第一组分和第二组分，所述第一组分为碳化钒和/或碳化铬，所述第二组分为纯钛和/或纯锆。The raw materials of the gradient structure cemented carbide include cobalt, tungsten carbide, a first component and a second component, the first component is vanadium carbide and/or chromium carbide, and the second component is pure titanium and / or pure zirconium.
优选的，以质量百分比计，所述梯度结构硬质合金的原料包括：Preferably, in terms of mass percentage, the raw materials of the gradient structure cemented carbide include:
钴6％～20％；Cobalt 6% ~ 20%;
第一组分 0.5％～3％；The first component 0.5% ~ 3%;
第二组分 1％～20％；The second component 1% ~ 20%;
余量为碳化钨。The balance is tungsten carbide.
更优选的，以质量百分比计，所述梯度结构硬质合金的原料包括：More preferably, in terms of mass percentage, the raw materials of the gradient structure cemented carbide include:
钴 10％-14％；Cobalt 10%-14%;
第一组分 0.5％～1％；The first component 0.5% ~ 1%;
第二组分 5％～10％；The second component 5% to 10%;
余量为碳化钨。The balance is tungsten carbide.
进一步优选的，以质量百分比计，所述梯度结构硬质合金的原料包括：Further preferably, in terms of mass percentage, the raw materials of the gradient structure cemented carbide include:
钴 12％；Cobalt 12%;
第一组分 0.5％；0.5% of the first component;
第二组分 5％；Second component 5%;
余量为碳化钨。The balance is tungsten carbide.
优选的，所述纯钛和所述纯锆的质量比为0:20～20:0。Preferably, the mass ratio of the pure titanium to the pure zirconium is 0:20˜20:0.
本发明中，第一梯度层的厚度为5μm～100μm，优选为20μm～30μm，更优选为25μm；第二梯度层的厚度为1μm～300μm，优选为20μm～300μm，更优选为100μm～150μm，进一步优选为100μm。In the present invention, the thickness of the first gradient layer is 5 μm to 100 μm, preferably 20 μm to 30 μm, more preferably 25 μm; the thickness of the second gradient layer is 1 μm to 300 μm, preferably 20 μm to 300 μm, more preferably 100 μm to 150 μm, More preferably, it is 100 μm.
本发明中，第一组分优选为碳化钒或碳化铬。梯度结构硬质合金的原料粒径优选为0.1μm～30μm，更优选为1μm。In the present invention, the first component is preferably vanadium carbide or chromium carbide. The grain size of the raw material of the gradient structure cemented carbide is preferably 0.1 μm to 30 μm, more preferably 1 μm.
本发明梯度结构硬质合金包括第一梯度层、第二梯度层和芯部，第一梯度层的立方相包括富TiN立方相和/或富ZrN立方相，第二梯度层的钴含量高于梯度结构硬质合金中钴的平均含量，梯度结构硬质合金的原料包括钴、碳化钨、第一组分和第二组分，第一组分为碳化钒和/或碳化铬，第二组分为纯钛和/或纯锆，第一梯度层的表层为富TiN立方相和/或富ZrN立方相的表层，几乎不含Co元素和C元素，表面平整、粗糙度小、致密度高，碳化钒和/或碳化铬主要起着抑制晶粒长大的作用，粘结相Co为梯度结构硬质合金提供高韧性，碳化钨为梯度结构硬质合金提供高硬度和高耐磨性，第一梯度层的立方相具有比碳化钨更高的硬度和耐磨性，该梯度结构硬质合金硬度、耐磨性和韧性高，并且耐热性和化学稳定性好。Gradient structure cemented carbide of the present invention comprises a first gradient layer, a second gradient layer and a core, the cubic phase of the first gradient layer includes a TiN-rich cubic phase and/or a ZrN-rich cubic phase, and the cobalt content of the second gradient layer is higher than The average content of cobalt in gradient structure cemented carbide, the raw materials of gradient structure cemented carbide include cobalt, tungsten carbide, the first component and the second component, the first component is vanadium carbide and/or chromium carbide, the second group Divided into pure titanium and/or pure zirconium, the surface layer of the first gradient layer is the surface layer of TiN-rich cubic phase and/or ZrN-rich cubic phase, which contains almost no Co element and C element, and the surface is smooth, with small roughness and high density. , vanadium carbide and/or chromium carbide mainly play the role of inhibiting grain growth, the binder phase Co provides high toughness for gradient structure cemented carbide, and tungsten carbide provides high hardness and high wear resistance for gradient structure cemented carbide, The cubic phase of the first gradient layer has higher hardness and wear resistance than tungsten carbide, and the graded cemented carbide has high hardness, wear resistance and toughness, and good heat resistance and chemical stability.
本发明还提供了一种梯度结构硬质合金的制备方法，包括以下步骤：The present invention also provides a kind of preparation method of gradient structure cemented carbide, comprising the following steps:
a)将梯度结构硬质合金的原料加入成形剂和/或润滑剂，得到混合料；a) Adding the raw material of gradient structure cemented carbide to forming agent and/or lubricant to obtain a mixture;
b)将所述混合料压制成型，得到成型胚体；b) compressing the mixture to obtain a shaped green body;
c)将所述成型胚体进行预烧结，再在含氮气的保护气氛下进行渗氮烧结，冷却后，得到梯度结构硬质合金；c) pre-sintering the shaped green body, then nitriding and sintering in a protective atmosphere containing nitrogen, and cooling to obtain a cemented carbide with a gradient structure;
其中，梯度结构硬质合金的原料包括钴、碳化钨、第一组分和第二组分，所述第一组分为碳化钒和/或碳化铬，所述第二组分为纯钛和/或纯锆。Wherein, the raw material of graded cemented carbide includes cobalt, tungsten carbide, a first component and a second component, the first component is vanadium carbide and/or chromium carbide, and the second component is pure titanium and / or pure zirconium.
本发明制备方法制得的梯度结构硬质合金包括第一梯度层、第二梯度层和芯部，第一梯度层的立方相包括富TiN立方相和/或富ZrN立方相，第二梯度层的钴含量高于梯度结构硬质合金中钴的平均含量。The cemented carbide with gradient structure prepared by the preparation method of the present invention includes a first gradient layer, a second gradient layer and a core, the cubic phase of the first gradient layer includes a TiN-rich cubic phase and/or a ZrN-rich cubic phase, and the second gradient layer The cobalt content is higher than the average cobalt content in gradient structure cemented carbide.
本发明中，在WC-Co的基础上加入纯钛和/或纯锆，并在含氮气的保护气氛下进行烧结，溶于钴中的钛和/或锆与氮原子在液相钴中生成致密的TiN和/或ZrN，制备出的梯度结构硬质合金的表层为富TiN立方相和/或富ZrN立方相的表层，硬度高且韧性高，耐磨性高，并且梯度结构硬质合金表层平整致密，粗糙度小，表层中几乎不含Co元素和C元素，该梯度结构硬质合金非常适用作为刀具涂层基体，用于金刚石涂层时，能够有效促进金刚石均匀形核和生长，提高金刚石涂层的质量，可以大幅度提高加工效率，延长刀具寿命，具有广阔的应用前景。In the present invention, pure titanium and/or pure zirconium are added on the basis of WC-Co, and sintered under a nitrogen-containing protective atmosphere, titanium and/or zirconium dissolved in cobalt and nitrogen atoms are generated in liquid cobalt Dense TiN and/or ZrN, the surface layer of the prepared gradient structure cemented carbide is the surface layer of TiN-rich cubic phase and/or ZrN-rich cubic phase, which has high hardness, high toughness, high wear resistance, and the gradient structure cemented carbide The surface layer is flat and dense, the roughness is small, and the surface layer hardly contains Co and C elements. This gradient structure cemented carbide is very suitable as a tool coating substrate. When used for diamond coating, it can effectively promote the uniform nucleation and growth of diamond. Improving the quality of diamond coating can greatly improve processing efficiency and prolong tool life, which has broad application prospects.
本发明中，步骤a)优选通过混合湿磨得到混合料，更优选为：将原料、成形剂和/或润滑剂及磨球置于球磨介质中，进行混合湿磨，干燥，得到混合料。In the present invention, step a) is preferably obtained by mixing and wet grinding, more preferably: placing raw materials, forming agents and/or lubricants and grinding balls in a ball milling medium, performing mixing and wet grinding, and drying to obtain a mixture.
成形剂选自石蜡、PEG和橡胶中的一种或多种；磨球优选为硬质合金球；球磨介质选自正庚烷和/或酒精；成形剂的质量为原料总质量的1％～5％，优选为2％～3％，更优选为2％；磨球与原料总质量的质量比为3～10：1；原料总质量与球磨介质的质量体积比为(100～500)g：250ml，优选为(100～300)g：250ml，更优选为100g：250ml。球磨速度为200r/min～350r/min，优选为250r/min；球磨时间为5h～72h，优选为12h。The forming agent is selected from one or more of paraffin, PEG and rubber; the grinding ball is preferably a cemented carbide ball; the ball milling medium is selected from n-heptane and/or alcohol; the quality of the forming agent is 1% to 1% of the total mass of raw materials 5%, preferably 2% to 3%, more preferably 2%; the mass ratio of the ball to the total mass of the raw material is 3 to 10:1; the mass to volume ratio of the total mass of the raw material to the ball milling medium is (100 to 500) g : 250ml, preferably (100-300)g: 250ml, more preferably 100g: 250ml. The ball milling speed is 200r/min-350r/min, preferably 250r/min; the ball milling time is 5h-72h, preferably 12h.
步骤b)优选在干压机中压制成型，压制的压力为150MPa～350MPa，优选为200MPa-300MPa，更优选为300MPa。Step b) is preferably compression-molded in a dry press, and the compression pressure is 150MPa-350MPa, preferably 200MPa-300MPa, more preferably 300MPa.
步骤c)预烧结为脱蜡处理和/或脱脂处理；预烧结优选在氩气气氛下进行；预烧结的温度优选为300℃～600℃，更优选为400℃～600℃，进一步优选为571；预烧结的保温时间优选为30min～90min，更优选为30min～75min，进一步优选为30min；预烧结的升温速率为5℃/min～10℃/min，优选为6℃/min；冷却优选为随炉冷却。Step c) pre-sintering is dewaxing treatment and/or degreasing treatment; pre-sintering is preferably carried out under an argon atmosphere; the temperature of pre-sintering is preferably 300°C to 600°C, more preferably 400°C to 600°C, and even more preferably 571 The holding time for pre-sintering is preferably 30min to 90min, more preferably 30min to 75min, further preferably 30min; the heating rate for presintering is 5°C/min to 10°C/min, preferably 6°C/min; cooling is preferably Cool in the furnace.
优选的，所述保护气氛为氮气与氩气的混合气体；Preferably, the protective atmosphere is a mixed gas of nitrogen and argon;
所述氮气与所述氩气的体积比为1:9～9:1。The volume ratio of the nitrogen to the argon is 1:9˜9:1.
优选的，所述在含氮气的保护气氛下进行烧结具体包括：Preferably, the sintering under a nitrogen-containing protective atmosphere specifically includes:
先通入氩气进行烧结，再通入氮气进行烧结。Argon gas is introduced first for sintering, and then nitrogen gas is introduced for sintering.
本发明中，先通入氩气进行烧结，能够使得胚体更加致密，再通入氮气进行烧结，能够减少直接通入氮气进行烧结梯度结构硬质合金的芯部有空隙产生的问题。并且，先通入氩气进行烧结，再通入氮气进行烧结，能够明显提高梯度结构硬质合金的富立方相表层的厚度，降低梯度结构硬质合金表面粗糙度。In the present invention, argon gas is first introduced for sintering, which can make the green body more dense, and then nitrogen gas is introduced for sintering, which can reduce the problem of voids in the core of the gradient structure cemented carbide that is directly injected with nitrogen for sintering. Moreover, the sintering by feeding argon gas first, and then feeding nitrogen gas for sintering can significantly increase the thickness of the cubic-rich phase surface layer of the gradient structure cemented carbide and reduce the surface roughness of the gradient structure cemented carbide.
优选的，所述烧结的温度为1300℃～1600℃；Preferably, the sintering temperature is 1300°C to 1600°C;
所述烧结的保温时间为30min～90min。The holding time for the sintering is 30 minutes to 90 minutes.
本发明中，烧结的升温速率为5℃/min～10℃/min，优选为6℃/min。In the present invention, the heating rate of sintering is 5° C./min˜10° C./min, preferably 6° C./min.
优选的，所述烧结的压强为0.1Mpa～0.15Mpa或1Mpa～10Mpa。Preferably, the sintering pressure is 0.1Mpa-0.15Mpa or 1Mpa-10Mpa.
本发明中，烧结的压强为1Mpa～10Mpa时，保护气氛中的高压氮气能够有效促进钛原子和/或锆原子向外迁移，形成更厚的富立方相层。In the present invention, when the sintering pressure is 1Mpa-10Mpa, the high-pressure nitrogen in the protective atmosphere can effectively promote the outward migration of titanium atoms and/or zirconium atoms to form a thicker cubic phase-rich layer.
优选的，所述在含氮气的保护气氛下进行烧结之前，还包括：Preferably, before the sintering under the protective atmosphere containing nitrogen, it also includes:
在温度达到1000℃～1600℃下通入保护气氛。When the temperature reaches 1000℃～1600℃, a protective atmosphere is introduced.
本发明还提供了上述技术方案所述梯度结构硬质合金和/或上述技术方案所述制备方法制得的梯度结构硬质合金可以直接在刀具切削、模具、盾构刀具、矿山开采、石油钻井、耐磨件等领域应用，同时还可以作为涂层硬质合金工具的硬质合金基体，尤其适用于金刚石涂层及其他常规工具涂层。The present invention also provides the gradient structure cemented carbide described in the above technical scheme and/or the gradient structure cemented carbide prepared by the preparation method described in the above technical scheme can be directly used in cutting tools, moulds, shield cutters, mining, oil drilling , wear-resistant parts and other fields, and can also be used as a cemented carbide substrate for coated carbide tools, especially for diamond coatings and other conventional tool coatings.
本发明梯度结构硬质合金具有梯度结构，硬度、韧性和耐磨性高，表层平整且致密，并且表层几乎不含Co元素和C元素，应用于涂层中，适用于金刚石涂层，涂层效果好，能够简化涂层复杂工序，降低成本，大幅度提高加工效率。The gradient structure cemented carbide of the present invention has a gradient structure, high hardness, toughness and wear resistance, a smooth and dense surface layer, and the surface layer hardly contains Co element and C element, and is applied in coatings, suitable for diamond coatings, coatings The effect is good, and the complex process of coating can be simplified, the cost can be reduced, and the processing efficiency can be greatly improved.
综上所述，本发明提供了一种梯度结构硬质合金，梯度结构硬质合金包括第一梯度层、第二梯度层和芯部，第一梯度层的立方相包括富TiN立方相和/或富ZrN立方相，第二梯度层的钴含量高于梯度结构硬质合金中钴的平均含量，梯度结构硬质合金的原料包括钴、碳化钨、第一组分和第二组分，第一组分为碳化钒和/或碳化铬，第二组分为纯钛和/或纯锆，第一梯度层的表层为富TiN立方相和/或富ZrN立方相的表层，几乎不含Co元素和C元素，表面平整、粗糙度小、致密度高，梯度结构硬质合金硬度、耐磨性和韧性高，并且耐热性和化学稳定性好。In summary, the present invention provides a gradient structure hard alloy, the gradient structure cemented carbide includes a first gradient layer, a second gradient layer and a core, the cubic phase of the first gradient layer includes a TiN-rich cubic phase and/or Or rich in ZrN cubic phase, the cobalt content of the second gradient layer is higher than the average content of cobalt in the gradient structure cemented carbide, the raw material of the gradient structure cemented carbide includes cobalt, tungsten carbide, the first component and the second component, the second One component is vanadium carbide and/or chromium carbide, the second component is pure titanium and/or pure zirconium, the surface layer of the first gradient layer is the surface layer of TiN-rich cubic phase and/or ZrN-rich cubic phase, and hardly contains Co element and C element, the surface is smooth, the roughness is small, the density is high, the hardness, wear resistance and toughness of the gradient structure cemented carbide are high, and the heat resistance and chemical stability are good.
具体实施方式Detailed ways
本发明提供了一种梯度结构硬质合金及其制备方法和应用，用于解决现有技术中硬质合金存在高硬度和高韧性不能共存的问题。The invention provides a gradient structure cemented carbide and its preparation method and application, which are used to solve the problem that high hardness and high toughness cannot coexist in cemented carbide in the prior art.
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
实施例1Example 1
本实施例进行梯度结构硬质合金的制备，原料的粒径为费氏粒径(FSSS)，原料按质量份计，包括碳化钨82.5份(FSSS 1μm)、钴12份(FSSS 1μm)、碳化钒0.5份(FSSS 0.8μm)和纯钛5份(FSSS 1μm)。This embodiment carries out the preparation of gradient structure cemented carbide, the particle size of raw material is Fischer particle size (FSSS), and raw material comprises 82.5 parts of tungsten carbide (FSSS 1 μm), 12 parts of cobalt (FSSS 1 μm), carbide 0.5 parts of vanadium (FSSS 0.8 μm) and 5 parts of pure titanium (FSSS 1 μm).
梯度结构硬质合金的制备方法，包括以下步骤：The preparation method of gradient structure cemented carbide comprises the following steps:
(1)混料：将原料按上述配比与石蜡、正庚烷、硬质合金球进行混合湿磨，石蜡质量为原料总质量的2％，硬质合金球的质量为原料总质量的3～5倍，原料与正庚烷的质量体积比为100g：250ml，球磨速度为200rpm，球磨时间为12h，再通过旋转蒸发仪得到较干燥的混合粉末，最后放进80℃烘箱干燥12～24h后，得到均匀干燥的混合料；(1) Mixing: the raw materials are mixed with paraffin, n-heptane, and cemented carbide balls according to the above ratio for wet grinding. The quality of paraffin wax is 2% of the total mass of raw materials, and the quality of cemented carbide balls is 3% of the total mass of raw materials. ~5 times, the mass volume ratio of raw materials and n-heptane is 100g:250ml, the ball milling speed is 200rpm, the ball milling time is 12h, and then the dry mixed powder is obtained through a rotary evaporator, and finally put into an oven at 80°C for 12~24h After that, a uniformly dry mixture is obtained;
(2)干压：将混合料放入模具，通过干压机压制成型，压制的压力为300MPa，得到成型胚体；(2) Dry pressing: the mixture is put into a mould, pressed into shape by a dry press, and the pressure of pressing is 300MPa to obtain a molded embryo body;
(3)烧结：通入氩气进行脱蜡处理，脱蜡处理的温度为500℃，脱蜡处理的保温时间为60min，随后进行升温，升温速率为6℃/min，最高温度达到1450℃，开始通入0.1MPa氮气进行烧结，烧结的保温时间为60min，再随炉冷却，得到梯度结构硬质合金。本实施例梯度结构硬质合金中，第一梯度层的厚度为20μm，第二梯度层的厚度为75μm。(3) Sintering: Introduce argon gas for dewaxing treatment, the temperature of dewaxing treatment is 500°C, the holding time of dewaxing treatment is 60min, and then the temperature is raised, the heating rate is 6°C/min, and the maximum temperature reaches 1450°C, Start to feed 0.1MPa nitrogen gas for sintering, the sintering holding time is 60min, and then cool with the furnace to obtain gradient structure cemented carbide. In the cemented carbide with gradient structure in this embodiment, the thickness of the first gradient layer is 20 μm, and the thickness of the second gradient layer is 75 μm.
实施例2Example 2
本实施例进行梯度结构硬质合金的制备，原料的粒径为费氏粒径(FSSS)，原料按质量份计，包括碳化钨82.5份(FSSS 1μm)、钴12份(FSSS 1μm)、碳化钒0.5份(FSSS 0.8μm)和纯钛5份(FSSS 1μm)。This embodiment carries out the preparation of gradient structure cemented carbide, the particle size of raw material is Fischer particle size (FSSS), and raw material comprises 82.5 parts of tungsten carbide (FSSS 1 μm), 12 parts of cobalt (FSSS 1 μm), carbide 0.5 parts of vanadium (FSSS 0.8 μm) and 5 parts of pure titanium (FSSS 1 μm).
梯度结构硬质合金的制备方法，包括以下步骤：The preparation method of gradient structure cemented carbide comprises the following steps:
(1)混料：将原料按上述配比与石蜡、正庚烷、硬质合金球进行混合湿磨，石蜡质量为原料总质量的2％，硬质合金球的质量为原料总质量的3～5倍，原料与正庚烷的质量体积比为100g：250ml，球磨速度为200rpm，球磨时间为12h，再通过旋转蒸发仪得到较干燥的混合粉末，最后放进80℃烘箱干燥12～24h后，得到均匀干燥的混合料；(1) Mixing: the raw materials are mixed with paraffin, n-heptane, and cemented carbide balls according to the above ratio for wet grinding. The quality of paraffin wax is 2% of the total mass of raw materials, and the quality of cemented carbide balls is 3% of the total mass of raw materials. ~5 times, the mass volume ratio of raw materials and n-heptane is 100g:250ml, the ball milling speed is 200rpm, the ball milling time is 12h, and then the dry mixed powder is obtained through a rotary evaporator, and finally put into an oven at 80°C for 12~24h After that, a uniformly dry mixture is obtained;
(2)干压：将混合料放入模具，通过干压机压制成型，压制的压力为300MPa，得到成型胚体；(2) Dry pressing: the mixture is put into a mould, pressed into shape by a dry press, and the pressure of pressing is 300MPa to obtain a molded embryo body;
(3)烧结：通入氩气进行脱蜡处理，脱蜡处理的温度为500℃，脱蜡处理的保温时间为60min，随后进行升温，升温速率为6℃/min，最高温度达到1450℃，开始通入6MPa氮气进行烧结，烧结的保温时间为60min，再随炉冷却，得到梯度结构硬质合金。本实施例梯度结构硬质合金中，第一梯度层的厚度为32μm，第二梯度层的厚度为86μm。(3) Sintering: Introduce argon gas for dewaxing treatment, the temperature of dewaxing treatment is 500°C, the holding time of dewaxing treatment is 60min, and then the temperature is raised, the heating rate is 6°C/min, and the maximum temperature reaches 1450°C, Start to feed 6MPa nitrogen gas for sintering, the sintering holding time is 60min, and then cool with the furnace to obtain gradient structure cemented carbide. In the cemented carbide with gradient structure in this embodiment, the thickness of the first gradient layer is 32 μm, and the thickness of the second gradient layer is 86 μm.
实施例3Example 3
本实施例进行梯度结构硬质合金的制备，原料的粒径为费氏粒径(FSSS)，原料按质量份计，包括碳化钨82.5份(FSSS 1μm)、钴12份(FSSS 1μm)、碳化钒0.5份(FSSS 0.8μm)和纯钛5份(FSSS 1μm)。This embodiment carries out the preparation of gradient structure cemented carbide, the particle size of raw material is Fischer particle size (FSSS), and raw material comprises 82.5 parts of tungsten carbide (FSSS 1 μm), 12 parts of cobalt (FSSS 1 μm), carbide 0.5 parts of vanadium (FSSS 0.8 μm) and 5 parts of pure titanium (FSSS 1 μm).
梯度结构硬质合金的制备方法，包括以下步骤：The preparation method of gradient structure cemented carbide comprises the following steps:
(1)混料：将原料按上述配比与石蜡、正庚烷、硬质合金球进行混合湿磨，石蜡质量为原料总质量的2％，硬质合金球的质量为原料总质量的3～5倍，原料与正庚烷的质量体积比为100g：250ml，球磨速度为200rpm，球磨时间为12h，再通过旋转蒸发仪得到较干燥的混合粉末，最后放进80℃烘箱干燥12～24h后，得到均匀干燥的混合料；(1) Mixing: the raw materials are mixed with paraffin, n-heptane, and cemented carbide balls according to the above ratio for wet grinding. The quality of paraffin wax is 2% of the total mass of raw materials, and the quality of cemented carbide balls is 3% of the total mass of raw materials. ~5 times, the mass volume ratio of raw materials and n-heptane is 100g:250ml, the ball milling speed is 200rpm, the ball milling time is 12h, and then the dry mixed powder is obtained through a rotary evaporator, and finally put into an oven at 80°C for 12~24h After that, a uniformly dry mixture is obtained;
(2)干压：将混合料放入模具，通过干压机压制成型，压制的压力为300MPa，得到成型胚体；(2) Dry pressing: the mixture is put into a mould, pressed into shape by a dry press, and the pressure of pressing is 300MPa to obtain a molded embryo body;
(3)烧结：通入氩气进行脱蜡处理，脱蜡处理的温度为500℃，脱蜡处理的保温时间为60min，随后进行升温，升温速率为6℃/min，最高温度达到1450℃，开始通入6MPa氩气进行烧结，保温时间30min，保温结束后，随炉冷却，重新升温至1450℃，再通入6Mpa氮气进行烧结，保温时间60min，再随炉冷却，得到梯度结构硬质合金。本实施例梯度结构硬质合金中，第一梯度层的厚度为48μm，第二梯度层的厚度为86μm。(3) Sintering: Introduce argon gas for dewaxing treatment, the temperature of dewaxing treatment is 500°C, the holding time of dewaxing treatment is 60min, and then the temperature is raised, the heating rate is 6°C/min, and the maximum temperature reaches 1450°C, Start to pass in 6MPa argon gas for sintering, holding time for 30min, after the holding time, cool with the furnace, heat up to 1450°C again, then pass in 6Mpa nitrogen for sintering, holding time for 60min, then cool with the furnace to get gradient structure cemented carbide . In the cemented carbide with gradient structure in this embodiment, the thickness of the first gradient layer is 48 μm, and the thickness of the second gradient layer is 86 μm.
实施例4Example 4
本实施例进行梯度结构硬质合金的制备，原料的粒径为费氏粒径(FSSS)，原料按质量份计，包括碳化钨82.5份(FSSS 1μm)、钴12份(FSSS 1μm)、碳化钒0.5份(FSSS 0.8μm)和纯钛5份(FSSS 1μm)。This embodiment carries out the preparation of gradient structure cemented carbide, the particle size of raw material is Fischer particle size (FSSS), and raw material comprises 82.5 parts of tungsten carbide (FSSS 1 μm), 12 parts of cobalt (FSSS 1 μm), carbide 0.5 parts of vanadium (FSSS 0.8 μm) and 5 parts of pure titanium (FSSS 1 μm).
梯度结构硬质合金的制备方法，包括以下步骤：The preparation method of gradient structure cemented carbide comprises the following steps:
(1)混料：将原料按上述配比与石蜡、正庚烷、硬质合金球进行混合湿磨，石蜡质量为原料总质量的2％，硬质合金球的质量为原料总质量的3～5倍，原料与正庚烷的质量体积比为100g：250ml，球磨速度为200rpm，球磨时间为12h，再通过旋转蒸发仪得到较干燥的混合粉末，最后放进80℃烘箱干燥12～24h后，得到均匀干燥的混合料；(1) Mixing: the raw materials are mixed with paraffin, n-heptane, and cemented carbide balls according to the above ratio for wet grinding. The quality of paraffin wax is 2% of the total mass of raw materials, and the quality of cemented carbide balls is 3% of the total mass of raw materials. ~5 times, the mass volume ratio of raw materials and n-heptane is 100g:250ml, the ball milling speed is 200rpm, the ball milling time is 12h, and then the dry mixed powder is obtained through a rotary evaporator, and finally put into an oven at 80°C for 12~24h After that, a uniformly dry mixture is obtained;
(2)干压：将混合料放入模具，通过干压机压制成型，压制的压力为300MPa，得到成型胚体；(2) Dry pressing: the mixture is put into a mould, pressed into shape by a dry press, and the pressure of pressing is 300MPa to obtain a molded embryo body;
(3)烧结：通入氩气进行脱蜡处理，脱蜡处理的温度为500℃，脱蜡处理的保温时间为60min，随后进行升温，升温速率为6℃/min，最高温度达到1450℃，开始通入2MPa氩气进行烧结，保温时间30min后，继续通入氮气至6Mpa，保温时间60min，再随炉冷却，得到梯度结构硬质合金。本实施例梯度结构硬质合金中，第一梯度层的厚度为45μm，第二梯度层的厚度为90μm。(3) Sintering: Introduce argon gas for dewaxing treatment, the temperature of dewaxing treatment is 500°C, the holding time of dewaxing treatment is 60min, and then the temperature is raised, the heating rate is 6°C/min, and the maximum temperature reaches 1450°C, Start to pass in 2MPa argon gas for sintering, after the holding time of 30min, continue to pass in nitrogen gas to 6Mpa, holding time for 60min, and then cool with the furnace to obtain a gradient structure cemented carbide. In the cemented carbide with gradient structure in this embodiment, the thickness of the first gradient layer is 45 μm, and the thickness of the second gradient layer is 90 μm.
实施例5Example 5
本实施例进行梯度结构硬质合金的制备，原料的粒径为费氏粒径(FSSS)，原料按质量份计，包括碳化钨72.5份(FSSS 1μm)、钴12份(FSSS 1μm)、碳化钒0.5份(FSSS 0.8μm)、纯钛10份(FSSS 1μm)和纯锆5份(FSSS 1μm)。This embodiment carries out the preparation of gradient structure cemented carbide, the particle size of raw material is Fischer particle size (FSSS), and raw material comprises 72.5 parts of tungsten carbide (FSSS 1 μm), 12 parts of cobalt (FSSS 1 μm), carbide 0.5 parts of vanadium (FSSS 0.8 μm), 10 parts of pure titanium (FSSS 1 μm) and 5 parts of pure zirconium (FSSS 1 μm).
梯度结构硬质合金的制备方法，包括以下步骤：The preparation method of gradient structure cemented carbide comprises the following steps:
(1)混料：将原料按上述配比与石蜡、正庚烷、硬质合金球进行混合湿磨，石蜡质量为原料总质量的2％，硬质合金球的质量为原料总质量的3～5倍，原料与正庚烷的质量体积比为100g：250ml，球磨速度为200rpm，球磨时间为12h，再通过旋转蒸发仪得到较干燥的混合粉末，最后放进80℃烘箱干燥12～24h后，得到均匀干燥的混合料；(1) Mixing: the raw materials are mixed with paraffin, n-heptane, and cemented carbide balls according to the above ratio for wet grinding. The quality of paraffin wax is 2% of the total mass of raw materials, and the quality of cemented carbide balls is 3% of the total mass of raw materials. ~5 times, the mass volume ratio of raw materials and n-heptane is 100g:250ml, the ball milling speed is 200rpm, the ball milling time is 12h, and then the dry mixed powder is obtained through a rotary evaporator, and finally put into an oven at 80°C for 12~24h After that, a uniformly dry mixture is obtained;
(2)干压：将混合料放入模具，通过干压机压制成型，压制的压力为300MPa，得到成型胚体；(2) Dry pressing: the mixture is put into a mould, pressed into shape by a dry press, and the pressure of pressing is 300MPa to obtain a molded embryo body;
(3)烧结：通入氩气进行脱蜡处理，脱蜡处理的温度为500℃，脱蜡处理的保温时间为60min，随后进行升温，升温速率为6℃/min，最高温度达到1450℃，开始通入2MPa氩气进行烧结，保温时间30min后，继续通入氮气至6Mpa，保温时间60min，再随炉冷却，得到梯度结构硬质合金。本实施例梯度结构硬质合金中，第一梯度层的厚度为52μm，第二梯度层的厚度为88μm。(3) Sintering: Introduce argon gas for dewaxing treatment, the temperature of dewaxing treatment is 500°C, the holding time of dewaxing treatment is 60min, and then the temperature is raised, the heating rate is 6°C/min, and the maximum temperature reaches 1450°C, Start to pass in 2MPa argon gas for sintering, after the holding time of 30min, continue to pass in nitrogen gas to 6Mpa, holding time for 60min, and then cool with the furnace to obtain a gradient structure cemented carbide. In the cemented carbide with gradient structure in this embodiment, the thickness of the first gradient layer is 52 μm, and the thickness of the second gradient layer is 88 μm.
实施例6Example 6
本实施例进行梯度结构硬质合金的制备，原料的粒径为费氏粒径(FSSS)，原料按质量份计，包括碳化钨82.5份(FSSS 1μm)、钴12份(FSSS 1μm)、碳化钒0.5份(FSSS 0.8μm)和纯锆5份(FSSS 1μm)。This embodiment carries out the preparation of gradient structure cemented carbide, the particle size of raw material is Fischer particle size (FSSS), and raw material comprises 82.5 parts of tungsten carbide (FSSS 1 μm), 12 parts of cobalt (FSSS 1 μm), carbide 0.5 parts of vanadium (FSSS 0.8 μm) and 5 parts of pure zirconium (FSSS 1 μm).
梯度结构硬质合金的制备方法，包括以下步骤：The preparation method of gradient structure cemented carbide comprises the following steps:
(1)混料：将原料按上述配比与石蜡、正庚烷、硬质合金球进行混合湿磨，石蜡质量为原料总质量的2％，硬质合金球的质量为原料总质量的3～5倍，原料与正庚烷的质量体积比为100g：250ml，球磨速度为200rpm，球磨时间为12h，再通过旋转蒸发仪得到较干燥的混合粉末，最后放进80℃烘箱干燥12～24h后，得到均匀干燥的混合料；(1) Mixing: the raw materials are mixed with paraffin, n-heptane, and cemented carbide balls according to the above ratio for wet grinding. The quality of paraffin wax is 2% of the total mass of raw materials, and the quality of cemented carbide balls is 3% of the total mass of raw materials. ~5 times, the mass volume ratio of raw materials and n-heptane is 100g:250ml, the ball milling speed is 200rpm, the ball milling time is 12h, and then the dry mixed powder is obtained through a rotary evaporator, and finally put into an oven at 80°C for 12~24h After that, a uniformly dry mixture is obtained;
(2)干压：将混合料放入模具，通过干压机压制成型，压制的压力为300MPa，得到成型胚体；(2) Dry pressing: the mixture is put into a mould, pressed into shape by a dry press, and the pressure of pressing is 300MPa to obtain a molded embryo body;
(3)烧结：通入氩气进行脱蜡处理，脱蜡处理的温度为500℃，脱蜡处理的保温时间为60min，随后进行升温，升温速率为6℃/min，最高温度达到1450℃，开始通入2MPa氩气进行烧结，保温时间30min后，继续通入氮气至6Mpa，保温时间60min，再随炉冷却，得到梯度结构硬质合金。本实施例梯度结构硬质合金中，第一梯度层的厚度为65μm，第二梯度层的厚度为98μm。(3) Sintering: Introduce argon gas for dewaxing treatment, the temperature of dewaxing treatment is 500°C, the holding time of dewaxing treatment is 60min, and then the temperature is raised, the heating rate is 6°C/min, and the maximum temperature reaches 1450°C, Start to pass in 2MPa argon gas for sintering, after the holding time of 30min, continue to pass in nitrogen gas to 6Mpa, holding time for 60min, and then cool with the furnace to obtain a gradient structure cemented carbide. In the cemented carbide with gradient structure in this embodiment, the thickness of the first gradient layer is 65 μm, and the thickness of the second gradient layer is 98 μm.
对比例1Comparative example 1
本对比例进行梯度结构硬质合金的制备，原料的粒径为费氏粒径(FSSS)，原料按质量份计，包括碳化钨82.5份(FSSS 1μm)、钴12份(FSSS 1μm)、碳化钒0.5份(FSSS 0.8μm)和碳化钛5份(FSSS 1μm)。This comparative example carries out the preparation of gradient structure cemented carbide, and the particle size of raw material is Fischer grain size (FSSS), and raw material comprises 82.5 parts of tungsten carbide (FSSS 1 μ m), cobalt 12 parts (FSSS 1 μ m), carbide Vanadium 0.5 parts (FSSS 0.8 μm) and titanium carbide 5 parts (FSSS 1 μm).
梯度结构硬质合金的制备方法，包括以下步骤：The preparation method of gradient structure cemented carbide comprises the following steps:
(1)混料：将原料按上述配比与石蜡、正庚烷、硬质合金球进行混合湿磨，石蜡质量为原料总质量的2％，硬质合金球的质量为原料总质量的3～5倍，原料与正庚烷的质量体积比为100g：250ml，球磨速度为200rpm，球磨时间为12h，再通过旋转蒸发仪得到较干燥的混合粉末，最后放进80℃烘箱干燥12～24h后，得到均匀干燥的混合料；(1) Mixing: the raw materials are mixed with paraffin, n-heptane, and cemented carbide balls according to the above ratio for wet grinding. The quality of paraffin wax is 2% of the total mass of raw materials, and the quality of cemented carbide balls is 3% of the total mass of raw materials. ~5 times, the mass volume ratio of raw materials and n-heptane is 100g:250ml, the ball milling speed is 200rpm, the ball milling time is 12h, and then the dry mixed powder is obtained through a rotary evaporator, and finally put into an oven at 80°C for 12~24h After that, a uniformly dry mixture is obtained;
(2)干压：将混合料放入模具，通过干压机压制成型，压制的压力为300MPa，得到成型胚体；(2) Dry pressing: the mixture is put into a mould, pressed into shape by a dry press, and the pressure of pressing is 300MPa to obtain a molded embryo body;
(3)烧结：通入氩气进行脱蜡处理，脱蜡处理的温度为500℃，脱蜡处理的保温时间为60min，随后进行升温，升温速率为6℃/min，最高温度达到1450℃，开始通入0.1Mpa氮气进行烧结，保温时间60min后，随炉冷却，得到梯度结构硬质合金。本实施例梯度结构硬质合金中，第一梯度层的厚度为105μm，第二梯度层的厚度为95μm。(3) Sintering: Introduce argon gas for dewaxing treatment, the temperature of dewaxing treatment is 500°C, the holding time of dewaxing treatment is 60min, and then the temperature is raised, the heating rate is 6°C/min, and the maximum temperature reaches 1450°C, Start to feed 0.1Mpa nitrogen gas for sintering, and after holding time for 60 minutes, cool with the furnace to obtain gradient structure cemented carbide. In the cemented carbide with gradient structure in this embodiment, the thickness of the first gradient layer is 105 μm, and the thickness of the second gradient layer is 95 μm.
对比例2Comparative example 2
本对比例进行硬质合金的制备，原料的粒径为费氏粒径(FSSS)，原料按质量份计，包括碳化钨82.5份(FSSS 1μm)、钴12份(FSSS 1μm)、碳化钒0.5份(FSSS 0.8μm)和碳化钛5份(FSSS 1μm)。This comparative example carries out the preparation of cemented carbide, and the particle diameter of raw material is Fischer particle size (FSSS), and raw material comprises 82.5 parts of tungsten carbide (FSSS 1 μ m), cobalt 12 parts (FSSS 1 μ m), vanadium carbide 0.5 parts by mass. Parts (FSSS 0.8μm) and 5 parts of titanium carbide (FSSS 1μm).
硬质合金的制备方法，包括以下步骤：The preparation method of cemented carbide comprises the following steps:
(1)混料：将原料按上述配比与石蜡、正庚烷、硬质合金球进行混合湿磨，石蜡质量为原料总质量的2％，硬质合金球的质量为原料总质量的3～5倍，原料与正庚烷的质量体积比为100g：250ml，球磨速度为200rpm，球磨时间为12h，再通过旋转蒸发仪得到较干燥的混合粉末，最后放进80℃烘箱干燥12～24h后，得到均匀干燥的混合料；(1) Mixing: the raw materials are mixed with paraffin, n-heptane, and cemented carbide balls according to the above ratio for wet grinding. The quality of paraffin wax is 2% of the total mass of raw materials, and the quality of cemented carbide balls is 3% of the total mass of raw materials. ~5 times, the mass volume ratio of raw materials and n-heptane is 100g:250ml, the ball milling speed is 200rpm, the ball milling time is 12h, and then the dry mixed powder is obtained through a rotary evaporator, and finally put into an oven at 80°C for 12~24h After that, a uniformly dry mixture is obtained;
(2)干压：将混合料放入模具，通过干压机压制成型，压制的压力为300MPa，得到成型胚体；(2) Dry pressing: the mixture is put into a mould, pressed into shape by a dry press, and the pressure of pressing is 300MPa to obtain a molded embryo body;
(3)烧结：通入氩气进行脱蜡处理，脱蜡处理的温度为500℃，脱蜡处理的保温时间为60min，随后进行升温，升温速率为6℃/min，最高温度达到1450℃，进行真空烧结，保温时间60min后，随炉冷却，得到硬质合金。(3) Sintering: Introduce argon gas for dewaxing treatment, the temperature of dewaxing treatment is 500°C, the holding time of dewaxing treatment is 60min, and then the temperature is raised, the heating rate is 6°C/min, and the maximum temperature reaches 1450°C, Vacuum sintering is carried out, and after a holding time of 60 minutes, it is cooled with the furnace to obtain cemented carbide.
对实施例1～6梯度结构硬质合金、对比例1梯度结构硬质合金和对比例2硬质合金采用ASTM-B611硬质合金耐磨试验标准，采用ASTM-B406进行抗弯强度测试，结果请参阅表1。Adopt ASTM-B611 cemented carbide wear-resistant test standard to embodiment 1～6 gradient structure cemented carbide, comparative example 1 gradient structure cemented carbide and comparative example 2 cemented carbide, adopt ASTM-B406 to carry out flexural strength test, the result See Table 1.
表1中，与对比例1梯度结构硬质合金和对比例2硬质合金相比，实施例1～6梯度结构硬质合金的原料中加入纯钛和/或纯锆，使得梯度结构硬质合金的耐磨数更高，表面硬度更大，抗弯强度更高，表面粗糙度小，能够用于金刚石涂层，且金刚石涂层硬度高；并且，在烧结过程中，先通入氩气进行烧结，再通入氮气进行烧结，能够明显提高梯度结构硬质合金的耐磨数、表面硬度和抗弯强度，减小表面粗糙度，并能够增强金刚石涂层硬度。In Table 1, compared with the cemented carbide with gradient structure of Comparative Example 1 and the cemented carbide of Comparative Example 2, pure titanium and/or pure zirconium are added to the raw materials of cemented carbide with gradient structure in Examples 1 to 6, so that the gradient structure is hard The alloy has higher wear resistance, higher surface hardness, higher bending strength, and small surface roughness. It can be used for diamond coating, and the diamond coating has high hardness; and, in the sintering process, argon gas is first introduced Sintering, and then sintering with nitrogen can significantly increase the wear resistance, surface hardness and bending strength of the gradient structure cemented carbide, reduce surface roughness, and enhance the hardness of the diamond coating.
表1实施例1～6和对比例1梯度结构硬质合金及对比例2硬质合金的性能参数Table 1 The performance parameters of Examples 1 to 6 and Comparative Example 1 Gradient Structure Cemented Carbide and Comparative Example 2 Cemented Carbide
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, and it should be pointed out that for those of ordinary skill in the art, some improvements and modifications can be made without departing from the principle of the present invention. It should be regarded as the protection scope of the present invention.
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| CN201910744910.3ACN110306092A (en) | 2019-08-13 | 2019-08-13 | A kind of hard alloy with gradient structure and its preparation method and application |
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