技术领域technical field
本发明属于材料制备领域，特别是一种碳氮化钛基复合金属陶瓷材料微波烧结工艺。The invention belongs to the field of material preparation, in particular to a microwave sintering process for a titanium carbonitride-based composite cermet material.
背景技术Background technique
碳氮化钛基金属陶瓷是硬度高、耐磨性好、高温化学稳定性出色、对金属的摩擦系数极低、热变形抗力强和力学性能优良的金属陶瓷材料，尤其是它优良的高温特性，即使在1300℃温度下其仍具备较高的强度，可应用于航空航天用部件、轴承、高速切削刀具等领域。目前，碳氮化钛金属陶瓷多使用传统烧结方式制备，如反应烧结、无压烧结、气压烧结、热压烧结、热等静压烧结等。然而传统烧结存在许多弊端，如设备和维护成本高昂；采用热辐射、热传导的加热方式会引起材料内的温度梯度较大，材料内部容易产生残余应力；制备周期长，效率低，不利于材料的批量生产等。随着科学技术的发展，一些新技术也随之产生，微波烧结作为一种高效、节能、环保的新型烧结方式，引起了很多学者的关注和研究。Titanium carbonitride-based cermet is a cermet material with high hardness, good wear resistance, excellent high temperature chemical stability, extremely low friction coefficient against metal, strong thermal deformation resistance and excellent mechanical properties, especially its excellent high temperature characteristics , Even at a temperature of 1300 ° C, it still has high strength, and can be used in aerospace components, bearings, high-speed cutting tools and other fields. At present, titanium carbonitride cermets are mostly prepared by traditional sintering methods, such as reaction sintering, pressureless sintering, pressure sintering, hot pressing sintering, hot isostatic pressing sintering, etc. However, there are many disadvantages in traditional sintering, such as high equipment and maintenance costs; the use of heat radiation and heat conduction heating methods will cause a large temperature gradient in the material, and residual stress is easily generated inside the material; the preparation period is long and the efficiency is low, which is not conducive to the production of materials. mass production etc. With the development of science and technology, some new technologies have also emerged. As a new sintering method with high efficiency, energy saving and environmental protection, microwave sintering has attracted the attention and research of many scholars.
目前，碳氮化钛金属陶瓷材料的微波烧结工艺仍不完善，其报道也相对较少。从现有文章(H.Hu,Y.Cheng,Z.Yin,Y.Zhang,T.Lu,MechanicalpropertiesandmicrostructureofTi(C,N)basedcermetcuttingtoolmaterialsfabricatedbymicrowavesintering,Ceramics International.41(2015)15017–15023)可得知，添加质量分数7.5％Ni和7.5％Co作为粘结剂，使用微波烧结方式可制备出硬度最高达到15.49±0.21GPa，断裂韧性达到10±0.55MPa.m1/2的碳氮化钛基金属陶瓷材料。与其它陶瓷材料相比，其韧性相对较高，但硬度偏低。At present, the microwave sintering process of titanium carbonitride cermet materials is still not perfect, and its reports are relatively few. From existing articles (H.Hu, Y.Cheng, Z.Yin, Y.Zhang, T.Lu, Mechanical properties and microstructure of Ti (C, N) basedcermetcuttingtoolmaterialsfabricatedbymicrowavesintering, Ceramics International.41 (2015) 15017–15023), it can be known that adding mass Fractions of 7.5% Ni and 7.5% Co are used as binders, and titanium carbonitride-based cermet materials with a hardness of up to 15.49±0.21GPa and a fracture toughness of 10±0.55MPa.m1/2 can be prepared by microwave sintering. Compared with other ceramic materials, its toughness is relatively high, but its hardness is low.
专利申请号为201510779093.7的发明专利中，制备了一种氧化铝/碳氮化钛复合陶瓷，其以Al2O3为主体，以Ti(C,N)作为增强增韧相，当氧化铝含量为61％，碳氮化钛含量为30％、烧结温度为1550℃时，其最高硬度达到18.4GPa，韧性为6.72MPa·m1/2，其硬度有所提高，但韧性仍较低，较低的韧性会导致材料容易发生脆性断裂，极大地限制了材料的使用范围。In the invention patent with the patent application number 201510779093.7, an alumina/titanium carbonitride composite ceramic is prepared, which is mainly composed of Al2 O3 and Ti(C,N) is used as a strengthening and toughening phase. When the alumina content When the content of titanium carbonitride is 30% and the sintering temperature is 1550℃, its maximum hardness reaches 18.4GPa, and its toughness is 6.72MPa·m1/2 . Low toughness will lead to brittle fracture of the material, which greatly limits the application range of the material.
综上所述，现有的碳氮化钛金属陶瓷材料的微波烧结工艺仍存在不足，所制备的碳氮化钛金属陶瓷综合力学性能仍不理想。To sum up, the existing microwave sintering process of titanium carbonitride cermet materials still has deficiencies, and the comprehensive mechanical properties of the prepared titanium carbonitride cermets are still unsatisfactory.
发明内容Contents of the invention
本发明所解决的技术问题在于提供一种碳氮化钛基复合金属陶瓷材料微波烧结工艺。The technical problem solved by the present invention is to provide a microwave sintering process for titanium carbonitride-based composite cermet materials.
实现本发明目的的技术解决方案为：The technical solution that realizes the object of the present invention is:
一种碳氮化钛基复合金属陶瓷材料微波烧结工艺，所述碳氮化钛基复合金属陶瓷材料以重量百分数计，包含如下成分：Ti(C,N)62％-68％、Mo2C 15％、WC 5％、Ni 3％-6％、Co 6％-9％、Mo 3％-6％；包括如下步骤：A microwave sintering process for a titanium carbonitride-based composite cermet material, the titanium carbonitride-based composite cermet material comprises the following components in weight percent: Ti(C,N)62%-68%, Mo2 C 15%, WC 5%, Ni 3%-6%, Co 6%-9%, Mo 3%-6%; including the following steps:
步骤1：按比例称取Ti(C,N)、Mo2C、WC、Ni、Co和Mo粉末，进行球磨混合，在球磨结束前1.5-2.5小时加入浓度为1-5％的聚乙烯醇溶液，球磨结束后，干燥，研磨，过筛；Step 1: Weigh Ti(C,N), Mo2 C, WC, Ni, Co and Mo powders in proportion, perform ball milling and mix, and add polyvinyl alcohol with a concentration of 1-5% 1.5-2.5 hours before the end of ball milling Solution, after ball milling, drying, grinding and sieving;
步骤2：将筛选好的粉料在100-300MPa的压力下压制成型，得到金属陶瓷素坯(4)；Step 2: Compressing the screened powder under a pressure of 100-300 MPa to obtain a cermet green body (4);
步骤3：惰性气体氛围中，采用微波烧结工艺，将样品放入碳化硅片辅助加热装置并置于保温箱中，以20～40℃/min的升温速率持续升温到1550～1650℃，保温5～20min，随后随炉冷却，制得碳氮化钛基复合金属陶瓷材料。Step 3: In an inert gas atmosphere, using a microwave sintering process, put the sample into a silicon carbide wafer auxiliary heating device and place it in an incubator, and continue to heat up to 1550-1650°C at a heating rate of 20-40°C/min, and hold for 5 ~20min, and then cooled with the furnace to prepare a titanium carbonitride-based composite cermet material.
进一步的，所述步骤(1)中，所述的球磨混合是将称取的粉料放入刚玉球磨罐中，以无水乙醇为球磨介质，磨球为碳化钨球。Further, in the step (1), the ball mill mixing is to put the weighed powder into a corundum ball mill pot, use absolute ethanol as the ball mill medium, and the balls are tungsten carbide balls.
进一步的，所述步骤(3)中的惰性气体为氮气，氮气气压在0.1-0.12MPa范围内，且处于流动状态。Further, the inert gas in the step (3) is nitrogen, the pressure of nitrogen is in the range of 0.1-0.12MPa, and it is in a flowing state.
进一步的，所述步骤(3)中的辅助加热装置包括碳化硅环和碳化硅片，所述碳化硅环套设在金属陶瓷素坯的外周，所述碳化硅片为两片，分别设置在金属陶瓷素坯的上下两侧。Further, the auxiliary heating device in the step (3) includes a silicon carbide ring and a silicon carbide sheet, the silicon carbide ring is set on the outer periphery of the cermet green body, and the silicon carbide sheet is two pieces, respectively arranged on The upper and lower sides of the cermet biscuit.
进一步的，放置有金属陶瓷素坯的辅助加热装置置于坩埚中，坩埚置于保温箱中。Further, the auxiliary heating device on which the cermet green body is placed is placed in the crucible, and the crucible is placed in the incubator.
本发明与现有技术相比，其显著优点如下：Compared with the prior art, the present invention has the following significant advantages:
(1)在微波烧结中采用碳化硅片辅助加热取代传统的埋粉辅助烧结，使聚乙烯醇能够在烧结过程中充分挥发，减少材料在烧结过程中的内部气孔，提高了产品的致密度，从而提高性能；且采用碳化硅片辅助加热不需要后续处理，简化了制备流程，提高了其生产效率，降低生产成本。(1) In the microwave sintering, silicon carbide sheet auxiliary heating is used to replace the traditional embedded powder auxiliary sintering, so that the polyvinyl alcohol can be fully volatilized during the sintering process, reducing the internal pores of the material during the sintering process, and improving the density of the product. Therefore, the performance is improved; and the auxiliary heating of the silicon carbide sheet does not require subsequent treatment, which simplifies the preparation process, improves the production efficiency, and reduces the production cost.
(2)通过Ni，Co，Mo作为金属添加剂来提高金属陶瓷的致密度和综合力学性能；Ni，Co在高温下液化，在高温驱动能的作用下产生横向流动，从而使Ti(C,N)固体颗粒发生颗粒重排，使得金属陶瓷的微观组织变得更为均匀；Mo的加入能够提高液相Ni与固体颗粒Ti(C,N)之间的润湿性，从而使液相Ni能更好地填充固体颗粒之间的间隙，使得金属陶瓷的致密度得到提升；在烧结过程中，Ti(C,N)颗粒部分会溶解于液相Ni和Co之中，通过沉淀析出形成(Ti,W,Mo)(C,N)-Ni-Co固溶体；这种结构能有效抑制晶粒的长大，从而提高材料的硬度；金属本身具有良好的韧性，因此金属相的加入能极大地提高材料的断裂韧性。(2) Use Ni, Co, Mo as metal additives to improve the density and comprehensive mechanical properties of cermets; Ni, Co liquefy at high temperature, and generate lateral flow under the action of high temperature driving energy, so that Ti(C,N ) particle rearrangement of solid particles, making the microstructure of cermet become more uniform; the addition of Mo can improve the wettability between liquid phase Ni and solid particle Ti(C,N), so that liquid phase Ni can Better fill the gaps between solid particles, so that the density of cermets is improved; during the sintering process, Ti(C,N) particles will be partially dissolved in liquid phase Ni and Co, and formed by precipitation (Ti ,W,Mo)(C,N)-Ni-Co solid solution; this structure can effectively inhibit the growth of grains, thereby improving the hardness of the material; the metal itself has good toughness, so the addition of the metal phase can greatly improve the hardness of the material. The fracture toughness of the material.
下面结合附图对本发明作进一步详细描述。The present invention will be described in further detail below in conjunction with the accompanying drawings.
附图说明Description of drawings
图1本申请所用的辅助加热装置。Figure 1 Auxiliary heating device used in this application.
图2实施例9制得的碳氮化钛基复合金属陶瓷材料的断面表现SEM图。Fig. 2 shows the SEM image of the cross-section of the titanium carbonitride-based composite cermet material prepared in Example 9.
附图标记说明：Explanation of reference signs:
1-高温莫来石，2-高温莫来石纤维，3-碳化硅片，4-金属陶瓷素坯。1-high temperature mullite, 2-high temperature mullite fiber, 3-silicon carbide sheet, 4-cermet green body.
具体实施方式Detailed ways
一种碳氮化钛基复合金属陶瓷材料，以重量百分数计，包含如下成分：Ti(C,N)62％-68％、Mo2C 15％、WC 5％、Ni 3％-6％、Co 6％-9％、Mo 3％-6％。A titanium carbonitride-based composite cermet material, comprising the following components by weight percentage: Ti(C,N) 62%-68%, Mo2 C 15%, WC 5%, Ni 3%-6%, Co 6%-9%, Mo 3%-6%.
优选的材料组分为Ti(C,N)62％、Mo2C 15％、WC 5％、Ni 6％、Co 6％、Mo 6％，样品硬度达到16.25±0.09GPa，韧性达到12.41±0.33MPa.m1/2。The preferred material composition is Ti(C,N) 62%, Mo2 C 15%, WC 5%, Ni 6%, Co 6%, Mo 6%, the hardness of the sample reaches 16.25±0.09GPa, and the toughness reaches 12.41±0.33 MPa.m1/2 .
本发明还提供了上述碳氮化钛复合金属陶瓷材料的微波烧结方法，采用高效节能的微波烧结技术，通过改进辅热装置、优化物相含量、烧结温度和保温时间等参数，实现在短周期内制备出具有较高综合力学性能的碳氮化钛复合金属陶瓷材料，包括如下步骤：The present invention also provides a microwave sintering method for the above-mentioned titanium carbonitride composite cermet material, adopting high-efficiency and energy-saving microwave sintering technology, by improving the auxiliary heating device, optimizing the parameters such as phase content, sintering temperature and holding time, etc. Prepare a titanium carbonitride composite cermet material with higher comprehensive mechanical properties, including the following steps:
步骤1，按比例称取Ti(C,N)、Mo2C、WC、Ni、Co和Mo粉末，进行球磨混合，在球磨结束前1.5-2.5小时加入浓度为1-3％的聚乙烯醇溶液，球磨结束后，干燥，研磨，过筛；所述的球磨混合是将称取得到的粉料放入刚玉球磨罐中，以无水乙醇为球磨介质，磨球选用碳化钨球。Step 1: Weigh Ti(C,N), Mo2 C, WC, Ni, Co and Mo powders in proportion, perform ball milling and mix, and add polyvinyl alcohol with a concentration of 1-3% 1.5-2.5 hours before the end of ball milling After the ball milling, the solution is dried, ground, and sieved; the ball mill mixing is to put the powder obtained by weighing into a corundum ball mill jar, use absolute ethanol as the ball mill medium, and use tungsten carbide balls for the ball mill.
步骤2，将筛选好的粉料在100-300MPa的压力下压制成型；Step 2, compressing the screened powder under a pressure of 100-300MPa;
步骤3，氮气氛围中，采用微波烧结工艺，将样品放入碳化硅片辅助加热装置并置于保温箱中，以20～40℃/min的升温速率持续升温到1550～1650℃，保温5～20min，随后随炉冷却，制得碳氮化钛基复合金属陶瓷材料；所述的氮气气氛，其压力在标准大气压以上，气压在0.1-0.12MPa范围内且处于流动状态。Step 3: In a nitrogen atmosphere, using a microwave sintering process, put the sample into a silicon carbide wafer auxiliary heating device and place it in an incubator, and continue to heat up to 1550-1650°C at a heating rate of 20-40°C/min, and keep it warm for 5- 20 minutes, followed by cooling in the furnace to produce a titanium carbonitride-based composite cermet material; the pressure of the nitrogen atmosphere is above the standard atmospheric pressure, and the pressure is in the range of 0.1-0.12 MPa and is in a flowing state.
步骤3中，所述的辅助加热装置如图1所示是由两片碳化硅片和一个碳化硅环组成，金属陶瓷素坯4置于两个碳化硅片之间，碳化硅环套在样片周围，置于坩埚中。保温箱由高温莫来石材料制成，并用高温莫来石纤维填充，坩埚置于保温箱中部。In step 3, the auxiliary heating device is composed of two silicon carbide sheets and a silicon carbide ring as shown in FIG. around, placed in a crucible. The incubator is made of high-temperature mullite material and filled with high-temperature mullite fiber, and the crucible is placed in the middle of the incubator.
本申请采用Ni，Co，Mo作为金属添加剂来提高金属陶瓷的致密度和综合力学性能。Ni，Co在高温下液化，在高温驱动能的作用下产生横向流动，从而使Ti(C,N)固体颗粒发生颗粒重排，使得金属陶瓷的微观组织变得更为均匀。Mo的加入能够提高液相Ni与固体颗粒Ti(C,N)之间的润湿性，从而使液相Ni能更好地填充固体颗粒之间的间隙，使得金属陶瓷的致密度得到提升。在烧结过程中，Ti(C,N)颗粒部分会溶解于液相Ni和Co之中，通过沉淀析出形成(Ti,W,Mo)(C,N)-Ni-Co固溶体(如附图2所示)。这种结构能包裹Ti(C,N)颗粒从而有效抑制晶粒的长大，提高材料的硬度。金属本身具有良好的韧性，因此金属相的加入能极大地提高材料的断裂韧性。综上所述，通过优化金属添加剂的组分配比能够制备出兼具良好硬度和断裂韧性的金属陶瓷。(创新点采用技术手段的形式描述)，生成xxx组织(微观或者远离上来讲)，具有效果(兼具硬度和韧性)This application uses Ni, Co, and Mo as metal additives to improve the density and comprehensive mechanical properties of cermets. Ni and Co liquefy at high temperature, and generate lateral flow under the action of high temperature driving energy, so that Ti(C,N) solid particles undergo particle rearrangement, making the microstructure of cermet more uniform. The addition of Mo can improve the wettability between the liquid phase Ni and the solid Ti(C,N) particles, so that the liquid phase Ni can better fill the gap between the solid particles, and the density of the cermet can be improved. During the sintering process, part of the Ti(C,N) particles will be dissolved in the liquid phase Ni and Co, and the (Ti,W,Mo)(C,N)-Ni-Co solid solution will be formed by precipitation (see Figure 2 shown). This structure can wrap Ti(C,N) particles to effectively inhibit the growth of grains and improve the hardness of the material. Metal itself has good toughness, so the addition of metal phase can greatly improve the fracture toughness of the material. In summary, cermets with good hardness and fracture toughness can be prepared by optimizing the component distribution ratio of metal additives. (Innovative points are described in the form of technical means), generate xxx organization (microcosmic or far away), and have effects (both hardness and toughness)
下面结合实施例做进一步详细说明。The following will be further described in detail in conjunction with the embodiments.
实施例1：Example 1:
一种碳氮化钛基复合金属陶瓷材料及其微波烧结方法，具体为：按质量百分数Ti(C,N)68％、Mo2C15％、WC 5％、Ni 3％、Co9％进行配料，将配制的混合粉末以无水乙醇为介质，碳化钨球为磨球，放入刚玉球磨罐中球磨24小时，球料比为8:1，并在球磨结束2小时前加入浓度为3wt％的聚乙烯醇水溶液；球磨后烘干研磨，并过100目筛，将过筛后的粉料进行干压成型，压力为300MPa，保压2分钟；将压坯放入碳化硅片辅热装置并置于微波烧结炉中，将炉腔内抽成真空状态，然后冲入0.11MPa氮气；开启微波电源进行加热，以20℃/min的升温速率将试样加热至1600℃，保温10min，然后随炉冷却。经测试得，材料的维氏硬度为14.92±0.90GPa，断裂韧性为11.58±2.22MPa.m1/2。A titanium carbonitride-based composite cermet material and a microwave sintering method thereof, specifically: proportioning Ti(C,N) 68%, Mo2 C 15%, WC 5%, Ni 3%, and Co 9% by mass percentage, Put the prepared mixed powder into anhydrous ethanol as the medium and tungsten carbide balls as the grinding balls, put them into a corundum ball milling tank for ball milling for 24 hours, the ball-to-material ratio is 8:1, and add a concentration of 3wt% Polyvinyl alcohol aqueous solution; dry and grind after ball milling, and pass through a 100-mesh sieve, dry-press the sieved powder at a pressure of 300 MPa, and hold the pressure for 2 minutes; put the compact into the silicon carbide auxiliary heating device and Put it in a microwave sintering furnace, evacuate the furnace cavity into a vacuum state, and then rush into 0.11MPa nitrogen gas; turn on the microwave power supply for heating, heat the sample to 1600°C at a heating rate of 20°C/min, keep it for 10min, and then Furnace cools. After testing, the Vickers hardness of the material is 14.92±0.90GPa, and the fracture toughness is 11.58±2.22MPa.m1/2 .
实施例2：Example 2:
一种碳氮化钛基复合金属陶瓷材料及其微波烧结方法，具体为：按质量百分数Ti(C,N)68％、Mo2C 15％、WC 5％、Ni 3％、Co 6％、Mo 3％进行配料，将配制的混合粉末以无水乙醇为介质，碳化钨球为磨球，放入刚玉球磨罐中球磨24小时，球料比为8:1，并在球磨结束2小时前加入浓度为3wt％的聚乙烯醇水溶液；球磨后烘干研磨，并过100目筛，将过筛后的粉料进行干压成型，压力为300MPa，保压2分钟；将压坯放入碳化硅片辅热装置并置于微波烧结炉中，将炉腔内抽成真空状态，然后冲入0.11MPa氮气；开启微波电源进行加热，以20℃/min的升温速率将试样加热至1600℃，保温10min，然后随炉冷却。经测试得，材料的维氏硬度为13.14±0.88GPa，断裂韧性为13.92±3.31MPa.m1/2。A titanium carbonitride-based composite cermet material and a microwave sintering method thereof, specifically: Ti(C,N) 68%, Mo2 C 15%, WC 5%, Ni 3%, Co 6%, Mo 3% is used for batching, the prepared mixed powder is made of absolute ethanol as the medium, and tungsten carbide balls are used as the grinding balls, and put into the corundum ball milling tank for ball milling for 24 hours. Add a polyvinyl alcohol aqueous solution with a concentration of 3wt%; dry and grind after ball milling, and pass through a 100-mesh sieve, dry press the sieved powder at a pressure of 300 MPa, and hold the pressure for 2 minutes; put the compact into carbonization The silicon wafer auxiliary heating device is placed in the microwave sintering furnace, the furnace cavity is evacuated, and then 0.11MPa nitrogen gas is injected; the microwave power is turned on for heating, and the sample is heated to 1600°C at a heating rate of 20°C/min , keep warm for 10min, and then cool down with the furnace. After testing, the Vickers hardness of the material is 13.14±0.88GPa, and the fracture toughness is 13.92±3.31MPa.m1/2 .
与实例1对比可知，采用Mo部分替代Co时，在同样的烧结工艺下，其性能有差异，断裂韧性有所提高，维氏硬度有所下降。Compared with Example 1, it can be seen that when Mo is partially substituted for Co, under the same sintering process, the performance is different, the fracture toughness is improved, and the Vickers hardness is decreased.
实施例3：Example 3:
一种碳氮化钛基复合金属陶瓷材料及其微波烧结方法，具体为：按质量百分数Ti(C,N)68％、Mo2C 15％、WC 5％、Ni 3％、Co 3％、Mo 6％进行配料，将配制的混合粉末以无水乙醇为介质，碳化钨球为磨球，放入刚玉球磨罐中球磨24小时，球料比为8:1，并在球磨结束2小时前加入浓度为3wt％的聚乙烯醇水溶液；球磨后烘干研磨，并过100目筛，将过筛后的粉料进行干压成型，压力为300MPa，保压2分钟；将压坯放入碳化硅片辅热装置并置于微波烧结炉中，将炉腔内抽成真空状态，然后冲入0.11MPa氮气；开启微波电源进行加热，以20℃/min的升温速率将试样加热至1600℃，保温10min，然后随炉冷却。经测试得，材料的维氏硬度为6.08±0.15GPa，断裂韧性为6.02±1.26MPa.m1/2。A titanium carbonitride-based composite cermet material and a microwave sintering method thereof, specifically: Ti(C,N) 68%, Mo2 C 15%, WC 5%, Ni 3%, Co 3%, Mo 6% is used for batching, the prepared mixed powder is made of absolute ethanol as the medium, and tungsten carbide balls are used as the grinding balls, put into the corundum ball milling tank for 24 hours, the ball-to-material ratio is 8:1, and 2 hours before the end of ball milling Add a polyvinyl alcohol aqueous solution with a concentration of 3wt%; dry and grind after ball milling, and pass through a 100-mesh sieve, dry press the sieved powder at a pressure of 300 MPa, and hold the pressure for 2 minutes; put the compact into carbonization The silicon wafer auxiliary heating device is placed in the microwave sintering furnace, the furnace cavity is evacuated, and then 0.11MPa nitrogen gas is injected; the microwave power is turned on for heating, and the sample is heated to 1600°C at a heating rate of 20°C/min , keep warm for 10min, and then cool down with the furnace. After testing, the Vickers hardness of the material is 6.08±0.15GPa, and the fracture toughness is 6.02±1.26MPa.m1/2 .
实施例4：Example 4:
一种碳氮化钛基复合金属陶瓷材料及其微波烧结方法，具体为：按质量百分数Ti(C,N)62％、Mo2C 15％、WC 5％、Ni 6％、Co 6％、Mo 6％进行配料，将配制的混合粉末以无水乙醇为介质，碳化钨球为磨球，放入刚玉球磨罐中球磨24小时，球料比为8:1，并在球磨结束2小时前加入浓度为3wt％的聚乙烯醇水溶液；球磨后烘干研磨，并过100目筛，将过筛后的粉料进行干压成型，压力为300MPa，保压2分钟；将压坯放入碳化硅片辅热装置并置于微波烧结炉中，将炉腔内抽成真空状态，然后冲入0.11MPa氮气；开启微波电源进行加热，以20℃/min的升温速率将试样加热至1600℃，保温10min，然后随炉冷却。经测试得，材料的维氏硬度为16.43±0.65GPa，断裂韧性为7.61±0.94MPa.m1/2。A titanium carbonitride-based composite cermet material and a microwave sintering method thereof, specifically: Ti(C,N) 62%, Mo2 C 15%, WC 5%, Ni 6%, Co 6%, Mo 6% is used for batching, the prepared mixed powder is made of absolute ethanol as the medium, and tungsten carbide balls are used as the grinding balls, put into the corundum ball milling tank for 24 hours, the ball-to-material ratio is 8:1, and 2 hours before the end of ball milling Add a polyvinyl alcohol aqueous solution with a concentration of 3wt%; dry and grind after ball milling, and pass through a 100-mesh sieve, dry press the sieved powder at a pressure of 300 MPa, and hold the pressure for 2 minutes; put the compact into carbonization The silicon wafer auxiliary heating device is placed in the microwave sintering furnace, the furnace cavity is evacuated, and then 0.11MPa nitrogen gas is injected; the microwave power is turned on for heating, and the sample is heated to 1600°C at a heating rate of 20°C/min , keep warm for 10min, and then cool down with the furnace. After testing, the Vickers hardness of the material is 16.43±0.65GPa, and the fracture toughness is 7.61±0.94MPa.m1/2 .
与实例3对比可知，增加粘结相Ni和Co的含量，在相同的烧结工艺下可显著提升维氏硬度和断裂韧性。Compared with Example 3, it can be seen that increasing the content of Ni and Co in the binder phase can significantly improve Vickers hardness and fracture toughness under the same sintering process.
实施例5：Example 5:
一种碳氮化钛基复合金属陶瓷材料及其微波烧结方法，具体为：按质量百分数Ti(C,N)62％、Mo2C 15％、WC 5％、Ni 6％、Co 6％、Mo 6％进行配料，将配制的混合粉末以无水乙醇为介质，碳化钨球为磨球，放入刚玉球磨罐中球磨24小时，球料比为8:1，并在球磨结束2小时前加入浓度为3wt％的聚乙烯醇水溶液；球磨后烘干研磨，并过100目筛，将过筛后的粉料进行干压成型，压力为300MPa，保压2分钟；将压坯放入碳化硅片辅热装置并置于微波烧结炉中，将炉腔内抽成真空状态，然后冲入0.11MPa氮气；开启微波电源进行加热，以20℃/min的升温速率将试样加热至1550℃，保温10min，然后随炉冷却。经测试得，材料的维氏硬度为15.93±0.15GPa，断裂韧性为6.01±0.92MPa.m1/2。A titanium carbonitride-based composite cermet material and a microwave sintering method thereof, specifically: Ti(C,N) 62%, Mo2C 15%, WC 5%, Ni 6%, Co 6%, Mo 6 by mass percentage % For batching, the prepared mixed powder is made of absolute ethanol as the medium, tungsten carbide balls as the grinding balls, put into the corundum ball milling tank for 24 hours, the ball-to-material ratio is 8:1, and the concentration is added 2 hours before the end of the ball milling It is a 3wt% polyvinyl alcohol aqueous solution; after ball milling, dry and grind, and pass through a 100-mesh sieve, dry press the sieved powder at a pressure of 300MPa, and hold the pressure for 2 minutes; put the compact into a silicon carbide sheet The auxiliary heating device is placed in the microwave sintering furnace, the furnace cavity is evacuated into a vacuum state, and then 0.11MPa nitrogen gas is injected; the microwave power supply is turned on for heating, and the sample is heated to 1550°C at a heating rate of 20°C/min. 10min, then cool down with the furnace. After testing, the Vickers hardness of the material is 15.93±0.15GPa, and the fracture toughness is 6.01±0.92MPa.m1/2 .
实施例6：Embodiment 6:
一种碳氮化钛基复合金属陶瓷材料及其微波烧结方法，具体为：按质量百分数Ti(C,N)62％、Mo2C 15％、WC 5％、Ni 6％、Co 6％、Mo 6％进行配料，将配制的混合粉末以无水乙醇为介质，碳化钨球为磨球，放入刚玉球磨罐中球磨24小时，球料比为8:1，并在球磨结束2小时前加入浓度为3wt％的聚乙烯醇水溶液；球磨后烘干研磨，并过100目筛，将过筛后的粉料进行干压成型，压力为300MPa，保压2分钟；将压坯放入碳化硅片辅热装置并置于微波烧结炉中，将炉腔内抽成真空状态，然后冲入0.11MPa氮气；开启微波电源进行加热，以20℃/min的升温速率将试样加热至1650℃，保温10min，然后随炉冷却。经测试得，材料的维氏硬度为16.67±0.42GPa，断裂韧性为7.20±1.44MPa.m1/2。A titanium carbonitride-based composite cermet material and a microwave sintering method thereof, specifically: Ti(C,N) 62%, Mo2C 15%, WC 5%, Ni 6%, Co 6%, Mo 6 by mass percentage % For batching, the prepared mixed powder is made of absolute ethanol as the medium, tungsten carbide balls as the grinding balls, put into the corundum ball milling tank for 24 hours, the ball-to-material ratio is 8:1, and the concentration is added 2 hours before the end of the ball milling It is a 3wt% polyvinyl alcohol aqueous solution; after ball milling, dry and grind, and pass through a 100-mesh sieve, dry press the sieved powder at a pressure of 300MPa, and hold the pressure for 2 minutes; put the compact into a silicon carbide sheet The auxiliary heating device is placed in the microwave sintering furnace, the furnace cavity is evacuated into a vacuum state, and then 0.11MPa nitrogen gas is injected; the microwave power supply is turned on for heating, and the sample is heated to 1650°C at a heating rate of 20°C/min. 10min, then cool down with the furnace. After testing, the Vickers hardness of the material is 16.67±0.42GPa, and the fracture toughness is 7.20±1.44MPa.m1/2 .
实例4—6说明在材料组分相同的情况下，烧结温度对材料性能有影响，且温度越高，综合力学性能越好。Examples 4-6 show that in the case of the same material components, the sintering temperature has an impact on the material properties, and the higher the temperature, the better the comprehensive mechanical properties.
实施例7：Embodiment 7:
一种碳氮化钛基复合金属陶瓷材料及其微波烧结方法，具体为：按质量百分数Ti(C,N)62％、Mo2C 15％、WC 5％、Ni 6％、Co 6％、Mo 6％进行配料，将配制的混合粉末以无水乙醇为介质，碳化钨球为磨球，放入刚玉球磨罐中球磨24小时，球料比为8:1，并在球磨结束2小时前加入浓度为3wt％的聚乙烯醇水溶液；球磨后烘干研磨，并过100目筛，将过筛后的粉料进行干压成型，压力为300MPa，保压2分钟；将压坯放入碳化硅片辅热装置并置于微波烧结炉中，将炉腔内抽成真空状态，然后冲入0.11MPa氮气；开启微波电源进行加热，以20℃/min的升温速率将试样加热至1600℃，保温0min，然后随炉冷却。经测试得，材料的维氏硬度为16.58±0.12GPa，断裂韧性为6.79±0.24MPa.m1/2。A titanium carbonitride-based composite cermet material and a microwave sintering method thereof, specifically: Ti(C,N) 62%, Mo2 C 15%, WC 5%, Ni 6%, Co 6%, Mo 6% is used for batching, the prepared mixed powder is made of absolute ethanol as the medium, and tungsten carbide balls are used as the grinding balls, put into the corundum ball milling tank for 24 hours, the ball-to-material ratio is 8:1, and 2 hours before the end of ball milling Add a polyvinyl alcohol aqueous solution with a concentration of 3wt%; dry and grind after ball milling, and pass through a 100-mesh sieve, dry press the sieved powder at a pressure of 300 MPa, and hold the pressure for 2 minutes; put the compact into carbonization The silicon wafer auxiliary heating device is placed in the microwave sintering furnace, the furnace cavity is evacuated, and then 0.11MPa nitrogen gas is injected; the microwave power is turned on for heating, and the sample is heated to 1600°C at a heating rate of 20°C/min , keep warm for 0min, and then cool down with the furnace. After testing, the Vickers hardness of the material is 16.58±0.12GPa, and the fracture toughness is 6.79±0.24MPa.m1/2 .
实施例8：Embodiment 8:
一种碳氮化钛基复合金属陶瓷材料及其微波烧结方法，具体为：按质量百分数Ti(C,N)62％、Mo2C 15％、WC 5％、Ni 6％、Co 6％、Mo 6％进行配料，将配制的混合粉末以无水乙醇为介质，碳化钨球为磨球，放入刚玉球磨罐中球磨24小时，球料比为8:1，并在球磨结束2小时前加入浓度为3wt％的聚乙烯醇水溶液；球磨后烘干研磨，并过100目筛，将过筛后的粉料进行干压成型，压力为300MPa，保压2分钟；将压坯放入碳化硅片辅热装置并置于微波烧结炉中，将炉腔内抽成真空状态，然后冲入0.11MPa氮气；开启微波电源进行加热，以20℃/min的升温速率将试样加热至1600℃，保温5min，然后随炉冷却。经测试得，材料的维氏硬度为15.85±0.31GPa，断裂韧性为9.27±0.82MPa.m1/2。A titanium carbonitride-based composite cermet material and a microwave sintering method thereof, specifically: Ti(C,N) 62%, Mo2 C 15%, WC 5%, Ni 6%, Co 6%, Mo 6% is used for batching, the prepared mixed powder is made of absolute ethanol as the medium, and tungsten carbide balls are used as the grinding balls, put into the corundum ball milling tank for 24 hours, the ball-to-material ratio is 8:1, and 2 hours before the end of ball milling Add a polyvinyl alcohol aqueous solution with a concentration of 3wt%; dry and grind after ball milling, and pass through a 100-mesh sieve, dry press the sieved powder at a pressure of 300 MPa, and hold the pressure for 2 minutes; put the compact into carbonization The silicon wafer auxiliary heating device is placed in the microwave sintering furnace, the furnace cavity is evacuated, and then 0.11MPa nitrogen gas is injected; the microwave power is turned on for heating, and the sample is heated to 1600°C at a heating rate of 20°C/min , keep warm for 5 minutes, and then cool with the furnace. After testing, the Vickers hardness of the material is 15.85±0.31GPa, and the fracture toughness is 9.27±0.82MPa.m1/2 .
实施例9：Embodiment 9:
一种碳氮化钛基复合金属陶瓷材料及其微波烧结方法，具体为：按质量百分数Ti(C,N)62％、Mo2C 15％、WC 5％、Ni 6％、Co 6％、Mo 6％进行配料，将配制的混合粉末以无水乙醇为介质，碳化钨球为磨球，放入刚玉球磨罐中球磨24小时，球料比为8:1，并在球磨结束2小时前加入浓度为3wt％的聚乙烯醇水溶液；球磨后烘干研磨，并过100目筛，将过筛后的粉料进行干压成型，压力为300MPa，保压2分钟；将压坯放入碳化硅片辅热装置并置于微波烧结炉中，将炉腔内抽成真空状态，然后冲入0.11MPa氮气；开启微波电源进行加热，以20℃/min的升温速率将试样加热至1600℃，保温20min，然后随炉冷却。经测试得，材料的维氏硬度为16.25±0.09GPa，断裂韧性为12.41±0.33MPa.m1/2。A titanium carbonitride-based composite cermet material and a microwave sintering method thereof, specifically: Ti(C,N) 62%, Mo2 C 15%, WC 5%, Ni 6%, Co 6%, Mo 6% is used for batching, the prepared mixed powder is made of absolute ethanol as the medium, and tungsten carbide balls are used as the grinding balls, put into the corundum ball milling tank for 24 hours, the ball-to-material ratio is 8:1, and 2 hours before the end of ball milling Add a polyvinyl alcohol aqueous solution with a concentration of 3wt%; dry and grind after ball milling, and pass through a 100-mesh sieve, dry press the sieved powder at a pressure of 300 MPa, and hold the pressure for 2 minutes; put the compact into carbonization The silicon wafer auxiliary heating device is placed in the microwave sintering furnace, the furnace cavity is evacuated, and then 0.11MPa nitrogen gas is injected; the microwave power is turned on for heating, and the sample is heated to 1600°C at a heating rate of 20°C/min , keep warm for 20min, and then cool with the furnace. After testing, the Vickers hardness of the material is 16.25±0.09GPa, and the fracture toughness is 12.41±0.33MPa.m1/2 .
实施例7—9相比，说明在材料组分相同的条件下，在1600℃下保温不同时间对材料性能有影响。The comparison of Examples 7-9 shows that under the condition of the same material components, different times of heat preservation at 1600°C have an impact on the properties of the material.
综上，加入适量的碳化物和金属添加剂，通过升级辅热装置，优化烧结温度和保温时间能够有效地提高金属陶瓷的致密度，硬度和断裂韧性。该制备工艺极大地提高了金属陶瓷的综合性能，扩大了材料的使用范围。In summary, adding an appropriate amount of carbides and metal additives, upgrading the auxiliary heating device, optimizing the sintering temperature and holding time can effectively improve the density, hardness and fracture toughness of cermets. The preparation process greatly improves the comprehensive performance of the cermet and expands the application range of the material.
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| CN111519115A (en)* | 2020-03-25 | 2020-08-11 | 成都美奢锐新材料有限公司 | High-toughness high-wear-resistance titanium carbonitride based cermet material and preparation method thereof |
| CN112142479A (en)* | 2020-09-04 | 2020-12-29 | 华侨大学 | Preparation method of SiC @ Ti (C, N) core-shell structure ceramic powder |
| CN118685674A (en)* | 2024-06-04 | 2024-09-24 | 宜昌永鑫精工科技股份有限公司 | Titanium carbonitride-based metal ceramic material and preparation method thereof |
| CN118957380A (en)* | 2024-07-31 | 2024-11-15 | 苏州新锐新材料科技有限公司 | A method for preparing wear-resistant high-strength titanium-based metal ceramic material |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4066451A (en)* | 1976-02-17 | 1978-01-03 | Erwin Rudy | Carbide compositions for wear-resistant facings and method of fabrication |
| EP0374358A1 (en)* | 1988-11-29 | 1990-06-27 | Toshiba Tungaloy Co. Ltd. | High strength nitrogen-containing cermet and process for preparation thereof |
| JPH04231469A (en)* | 1990-12-27 | 1992-08-20 | Kyocera Corp | Coated TiCN-based cermet |
| CN1079996A (en)* | 1992-06-08 | 1993-12-29 | 东北机器制造总厂 | The light hard alloy that hot-work is used |
| CN1178254A (en)* | 1997-09-30 | 1998-04-08 | 武汉工业大学 | High strength, high toughness and low specific weight hard composite materials |
| CN1632150A (en)* | 2003-12-22 | 2005-06-29 | 山东大学 | Titanium Carbonitride Based Ceramic Bearing Material |
| CN102115841A (en)* | 2009-12-30 | 2011-07-06 | 常熟市东涛金属复合材料有限公司 | Method for processing metal ceramic composite material |
| CN102294473A (en)* | 2011-08-31 | 2011-12-28 | 株洲钻石切削刀具股份有限公司 | TiC/Ti(C,N)-Mo-Ni/Co composite powder and preparation method and application thereof |
| CN102382997A (en)* | 2011-10-24 | 2012-03-21 | 中南大学 | Method for preparing WC-Co cemented carbide through microwave sintering |
| CN102816964A (en)* | 2012-03-30 | 2012-12-12 | 刘昭晖 | Manufacturing method for ultra-fine grain Ti (C, N) based metal ceramic tools |
| CN103695685A (en)* | 2013-12-26 | 2014-04-02 | 昆明理工大学 | A method for preparing WC-Co cemented carbide by microwave reaction sintering |
| CN104878267A (en)* | 2015-05-29 | 2015-09-02 | 南京理工大学 | TiCN-base metal ceramic tool material and its microwave sintering process |
| JP2018080375A (en)* | 2016-11-18 | 2018-05-24 | 新日鐵住金株式会社 | Cemented carbide and cemented carbide tool |
| CN108624772A (en)* | 2018-06-26 | 2018-10-09 | 南京理工大学 | Ultra-fine Grained tungsten carbide base carbide alloy material and preparation method thereof |
| CN108637268A (en)* | 2018-04-24 | 2018-10-12 | 海南大学 | A kind of method that microwave carbon thermal reduction prepares composite Ti (C, N) cermet powder |
| CN108950342A (en)* | 2018-07-24 | 2018-12-07 | 三峡大学 | Ti (C, N) based ceramic metal and preparation method thereof |
| CN109898004A (en)* | 2019-03-20 | 2019-06-18 | 莱芜职业技术学院 | A kind of high tough titanium carbide-high manganese steel bonded carbide and preparation method and application |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4066451A (en)* | 1976-02-17 | 1978-01-03 | Erwin Rudy | Carbide compositions for wear-resistant facings and method of fabrication |
| EP0374358A1 (en)* | 1988-11-29 | 1990-06-27 | Toshiba Tungaloy Co. Ltd. | High strength nitrogen-containing cermet and process for preparation thereof |
| JPH04231469A (en)* | 1990-12-27 | 1992-08-20 | Kyocera Corp | Coated TiCN-based cermet |
| CN1079996A (en)* | 1992-06-08 | 1993-12-29 | 东北机器制造总厂 | The light hard alloy that hot-work is used |
| CN1178254A (en)* | 1997-09-30 | 1998-04-08 | 武汉工业大学 | High strength, high toughness and low specific weight hard composite materials |
| CN1632150A (en)* | 2003-12-22 | 2005-06-29 | 山东大学 | Titanium Carbonitride Based Ceramic Bearing Material |
| CN102115841A (en)* | 2009-12-30 | 2011-07-06 | 常熟市东涛金属复合材料有限公司 | Method for processing metal ceramic composite material |
| CN102294473A (en)* | 2011-08-31 | 2011-12-28 | 株洲钻石切削刀具股份有限公司 | TiC/Ti(C,N)-Mo-Ni/Co composite powder and preparation method and application thereof |
| CN102382997A (en)* | 2011-10-24 | 2012-03-21 | 中南大学 | Method for preparing WC-Co cemented carbide through microwave sintering |
| CN102816964A (en)* | 2012-03-30 | 2012-12-12 | 刘昭晖 | Manufacturing method for ultra-fine grain Ti (C, N) based metal ceramic tools |
| CN103695685A (en)* | 2013-12-26 | 2014-04-02 | 昆明理工大学 | A method for preparing WC-Co cemented carbide by microwave reaction sintering |
| CN104878267A (en)* | 2015-05-29 | 2015-09-02 | 南京理工大学 | TiCN-base metal ceramic tool material and its microwave sintering process |
| JP2018080375A (en)* | 2016-11-18 | 2018-05-24 | 新日鐵住金株式会社 | Cemented carbide and cemented carbide tool |
| CN108637268A (en)* | 2018-04-24 | 2018-10-12 | 海南大学 | A kind of method that microwave carbon thermal reduction prepares composite Ti (C, N) cermet powder |
| CN108624772A (en)* | 2018-06-26 | 2018-10-09 | 南京理工大学 | Ultra-fine Grained tungsten carbide base carbide alloy material and preparation method thereof |
| CN108950342A (en)* | 2018-07-24 | 2018-12-07 | 三峡大学 | Ti (C, N) based ceramic metal and preparation method thereof |
| CN109898004A (en)* | 2019-03-20 | 2019-06-18 | 莱芜职业技术学院 | A kind of high tough titanium carbide-high manganese steel bonded carbide and preparation method and application |
| Title |
|---|
| HANPENG HU等: "Mechanical properties and microstructure of Ti(C, N) based cermet cutting tool materials fabricated by microwave sintering", 《CERAMICS INTERNATIONAL》* |
| ZENGBIN YIN等: "Microwave sintering of Ti(C, N)-based cermet cutting tool material", 《CERAMICS INTERNATIONAL》* |
| 唐思文等: "真空微波烧结制备TiCN基金属陶瓷", 《粉末冶金技术》* |
| 孙万昌等: "Ti(C,N)基金属陶瓷材料的强韧化研究进展", 《热加工工艺》* |
| 李英: "《机械材料成型技术》", 31 August 2011, 北京师范大学出版社* |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111519115A (en)* | 2020-03-25 | 2020-08-11 | 成都美奢锐新材料有限公司 | High-toughness high-wear-resistance titanium carbonitride based cermet material and preparation method thereof |
| CN111519115B (en)* | 2020-03-25 | 2021-12-28 | 成都美奢锐新材料有限公司 | High-toughness high-wear-resistance titanium carbonitride based cermet material and preparation method thereof |
| CN112142479A (en)* | 2020-09-04 | 2020-12-29 | 华侨大学 | Preparation method of SiC @ Ti (C, N) core-shell structure ceramic powder |
| CN112142479B (en)* | 2020-09-04 | 2022-07-29 | 华侨大学 | A kind of preparation method of SiC@Ti(C,N) core-shell structure ceramic powder |
| CN118685674A (en)* | 2024-06-04 | 2024-09-24 | 宜昌永鑫精工科技股份有限公司 | Titanium carbonitride-based metal ceramic material and preparation method thereof |
| CN118685674B (en)* | 2024-06-04 | 2025-03-04 | 宜昌永鑫精工科技股份有限公司 | Titanium carbonitride-based metal ceramic material and preparation method thereof |
| CN118957380A (en)* | 2024-07-31 | 2024-11-15 | 苏州新锐新材料科技有限公司 | A method for preparing wear-resistant high-strength titanium-based metal ceramic material |
| Publication number | Publication date |
|---|---|
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