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WO2022089379A1 - Silicon nitride/titanium carbide ceramic material preparation method based on spark plasma sintering - Google Patents

Silicon nitride/titanium carbide ceramic material preparation method based on spark plasma sintering Download PDF

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WO2022089379A1
WO2022089379A1 PCT/CN2021/126175 CN2021126175W WO2022089379A1 WO 2022089379 A1 WO2022089379 A1 WO 2022089379A1 CN 2021126175 W CN2021126175 W CN 2021126175W WO 2022089379 A1 WO2022089379 A1 WO 2022089379A1
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ceramic material
spark plasma
plasma sintering
preparation
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PCT/CN2021/126175
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French (fr)
Chinese (zh)
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陈照强
肖光春
许崇海
衣明东
张静婕
张帅
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齐鲁工业大学
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Definitions

  • the invention belongs to the technical field of ceramic material preparation, and in particular relates to a preparation method of silicon nitride/titanium carbide (Si 3 N 4 /TiC) ceramic material based on spark plasma sintering, and the Si 3 N 4 /TiC ceramic material prepared by the method and applications.
  • Si 3 N 4 /TiC silicon nitride/titanium carbide
  • spark plasma sintering As the most popular ultrafast sintering technology, spark plasma sintering (SPS) is mostly used to prepare nanostructured materials, amorphous materials, intermetallic compounds, metal matrix and ceramic matrix composites. Compared with traditional sintering methods, spark plasma sintering (SPS) technology has a faster heating rate and can achieve the same sintering effect in a shorter sintering time.
  • SPS spark plasma sintering
  • the rapid heating of materials prepared by spark plasma sintering (SPS) is due to the skin effect of the DC and AC components in the pulsed current, as well as the small heat capacity of the heating system. During sintering, most of the heat is generated by the inner edge of the mold, and the higher the temperature, the higher the temperature of the powder surface.
  • the powder In spark plasma sintering (SPS), the powder is placed in a graphite mold, and while pressure is applied to the powder, an electric current is passed through the mold and the sample (if the latter is a conductive material) to heat the powder body, if the powder is a non-conductive material , the current mainly flows through the mold to generate heat.
  • SPS spark plasma sintering
  • the SPS process has the following advantages in the preparation of ceramic materials due to its unique heating system: clean grain boundaries, It can significantly increase superplasticity, reduce grain boundary segregation, enhance bonding quality, improve thermoelectric properties, and improve ductility of alloy ceramics.
  • Silicon nitride-based ceramic materials have high fracture toughness and strength and excellent thermal shock resistance, corrosion resistance and wear resistance, and are widely used in industrial fields. Therefore, many researchers focus their attention on how to prepare high-performance Si 3 N 4 based ceramic materials by suitable sintering methods.
  • the commonly used sintering methods for sintering silicon nitride ceramic materials are as follows: pressureless sintering, reaction sintering, gas pressure sintering (GPS), hot isostatic pressing (HIP) and hot pressing (HP) sintering.
  • GPS gas pressure sintering
  • HIP hot isostatic pressing
  • HP hot pressing
  • the Si 3 N 4 /SiC composite ceramic material uses Si 3 N 4 and SiC as raw material powders, with Tm 2 O 3 and MgO as sintering aids were prepared by hot pressing sintering. Although this method can obtain a high-density Si 3 N 4 /SiC ceramic material, the sintering time is relatively long.
  • Spark plasma sintering is a kind of The plasma generated by the electric current and the pressure during the sintering process are beneficial to reduce the sintering temperature of the powder. At the same time, the characteristics of low voltage and high current can make the powder sinter and densify quickly.
  • the present invention applies it to the sintering of Si 3 N 4 /SiC ceramic materials, and successfully shortens the sintering time to half of the pressure sintering time.
  • the Si 3 N 4 /SiC ceramic materials prepared by sintering by the method provided by the present invention also has excellent mechanical properties.
  • a first aspect of the present invention provides a preparation method of Si 3 N 4 /TiC ceramic material based on spark plasma sintering.
  • the preparation method includes: using Si 3 N 4 as a matrix, TiC as a reinforcing phase, Al 2 O 3 and Y 2 O 3 is a sintering aid, which is prepared by mixing the above raw materials through wet ball milling and spark plasma sintering.
  • the present invention proposes a corresponding heating and sintering procedure for spark plasma sintering. It can inhibit the excessive growth of ⁇ -Si 3 N 4 and increase the proportion of ⁇ crystal phase in the sintered product. Since the ⁇ -Si 3 N 4 crystal phase has higher strength, the ceramic material prepared by the method of the present invention is more suitable for cutting Preparation of tools, especially for the preparation of ceramic knives. And the introduction of TiC can better improve the electrical conductivity and EDM performance of Si 3 N 4 .
  • the preparation process of the invention is simple, the sintering time is short, and the sintering of the Si 3 N 4 /TiC ceramic material can be completed in a short time. Compared with hot pressing sintering, spark plasma sintering takes only half the time of hot pressing sintering.
  • the Si 3 N 4 /TiC ceramic material prepared by the present invention has excellent mechanical properties, flexural strength, fracture toughness and Vickers hardness, and at the same time, due to the unique sintering mechanism of SPS, the growth of ⁇ -Si 3 N 4 is inhibited, avoiding A larger ⁇ -Si 3 N 4 is obtained, which is beneficial to the performance of Si 3 N 4 /TiC ceramic material.
  • Example 1 is a graph showing the sintering temperature and the displacement of the upper indenter during spark plasma sintering for the Si 3 N 4 /TiC ceramic material prepared in Example 1;
  • Fig. 2 is the XRD detection diagram of the Si 3 N 4 /TiC ceramic material prepared in Example 1;
  • FIG. 3 is a SEM image of the fracture surface of the Si 3 N 4 /TiC ceramic material prepared in Example 1.
  • FIG. 3 is a SEM image of the fracture surface of the Si 3 N 4 /TiC ceramic material prepared in Example 1.
  • the present invention proposes a preparation method of Si 3 N 4 /TiC ceramic material based on spark plasma sintering. Compared with the existing hot pressing sintering time, the preparation method shortens 1/2, and the The Si 3 N 4 /TiC ceramics prepared by the method have good mechanical properties.
  • a first aspect of the present invention provides a preparation method of Si 3 N 4 /TiC ceramic material based on spark plasma sintering.
  • the preparation method includes: using Si 3 N 4 as a matrix, TiC as a reinforcing phase, Al 2 O 3 and Y 2 O 3 is a sintering aid, which is prepared by mixing the above raw materials through wet ball milling and spark plasma sintering.
  • the volume percentages of the raw materials are as follows: ⁇ -Si 3 N 4 70-85%, TiC 5-15%, Al 2 O 3 1-6%, Y 2 O 3 3-7% %.
  • volume percentage of the TiC is 7-10%, or the volume percentage of the Al 2 O 3 is 2-4%, or the volume percentage of the Y 2 O 3 is 4-6%, and the above raw materials are in Adjust within the volume percentage range, and the sum of the remaining components is 100%.
  • the volume percentages of the raw materials are as follows: ⁇ -Si 3 N 4 80%, TiC 10%, Al 2 O 3 4%, Y 2 O 3 6%.
  • the volume percentages of the raw materials are as follows: ⁇ -Si 3 N 4 82%, TiC 10%, Al 2 O 3 3%, Y 2 O 3 5%.
  • the volume percentages of the raw materials are as follows: ⁇ -Si 3 N 4 75%, TiC 15%, Al 2 O 3 4%, Y 2 O 3 6%.
  • the average particle size of the ⁇ -Si 3 N 4 powder is 0.5-1 ⁇ m.
  • the average particle size of the TiC powder is 0.5-1 ⁇ m.
  • the average particle size of the Al 2 O 3 powder is 0.5-2 ⁇ m.
  • the average particle size of the Y 2 O 3 powder is 0.1-0.5 ⁇ m.
  • the preparation method specifically comprises the following steps:
  • step (3) the mixing system obtained in step (2) is transferred to the ball-milling tank and ball-milled; the ball-milling liquid after the completion is dried and sieved to obtain mixed powder;
  • step (3) The mixed powder described in step (3) is loaded into a mold for molding, and then spark plasma sintering is performed.
  • the dispersion medium includes but is not limited to anhydrous ethanol or anhydrous methanol.
  • the dispersing agent includes but not limited to polyethylene glycol, specifically, polyethylene glycol 6000.
  • the ball mill is added with ball milling balls according to a weight ratio of 10:0.5-1.5 to the balls, and the ball-milling is performed under a protective atmosphere for 40-50 hours; specifically, the protective atmosphere is nitrogen.
  • the ball grinding balls are cemented carbide balls YG6 or YG8.
  • the drying method of the ball milling liquid includes but is not limited to one of atmospheric drying, vacuum drying, spray drying or freeze drying.
  • the drying adopts vacuum drying at 80-120° C. for 12-24 hours.
  • the ball milling liquid is dried and sieved through a 100-120 mesh sieve to obtain a mixed powder.
  • the spark plasma sintering parameters heating rate: before 1300 °C, 90-110 °C/min, higher than 1300 °C, 30-50 °C/min; sintering temperature 1650-1750 °C; holding time 20-35min, respectively at 1600°C and after reaching the sintering temperature for 10-17min; axial pressure 25-35MPa.
  • the preparation method comprises the following steps:
  • step (3) Pour the final suspension obtained in step (2) into the ball milling tank, add ball milling balls according to the ball-to-material weight ratio of 10:1, carry out ball milling for 48 hours under a protective atmosphere, and place the ball milling liquid in a vacuum drying oven at 80-120° C. Dry for 12-24 hours, then sieve through a 100-120 mesh sieve to obtain mixed powder, which is sealed and stored for later use;
  • step (3) The mixed powder obtained in step (3) is put into a graphite mold, and after being cold-pressed, it is put into a spark plasma sintering furnace for sintering.
  • a second aspect of the present invention provides a Si 3 N 4 /TiC ceramic material prepared by the method for preparing a Si 3 N 4 /TiC ceramic material based on spark plasma sintering according to the first aspect.
  • a third aspect of the present invention provides the application of the Si 3 N 4 /TiC ceramic material described in the first aspect in the production of cutting tools, wear-resistant parts, inserts, and products for the aviation industry.
  • SPS spark plasma sintering
  • the obtained ball milling liquid was dried in a vacuum drying oven at 110 ° C for 12 hours, and then sieved through a 100-mesh sieve to obtain a mixed powder.
  • the ceramic material prepared in this example is cut into standard strip samples of 3mm ⁇ 4mm ⁇ 35mm, and then the strips are subjected to rough grinding, grinding, chamfering and polishing.
  • the mechanical properties were tested, and the results showed that the flexural strength of the material was 959MPa, the hardness was 15.21GPa, and the fracture toughness was 8.61MPa ⁇ M 1/2 .
  • the process of densification and crystal growth of the spark plasma sintered Si 3 N 4 ceramic material can be seen from Figure 1. Before 1200°C, the powder expands due to heat, the lower indenter moves down, and the Z-axis displacement decreases. The densification process occurs after 1200 °C, when the lower indenter moves up and the Z-axis displacement increases.
  • the crystal begins to grow and the ceramic material begins to expand, and the Z-axis displacement decreases.
  • the phase composition of the sintered Si 3 N 4 /TiC ceramic material is ⁇ -Si 3 N 4 , TiC 0.3 N 0.7 and a small amount of ⁇ -Si 3 N 4 , of which TiC0.3N0.7 is mainly due to During the sintering process, Si 3 N 4 and TiC react to form.
  • the crystallinity of the ceramic materials is good.
  • Figure 3 shows the SEM image of the fracture surface of the Si 3 N 4 /TiC ceramic material, it can be found that the grains are uniform, no larger ⁇ -Si 3 N 4 is found, and the density is good, and no obvious pores are found, which is also The reason for the excellent mechanical properties of ceramic materials.
  • SPS spark plasma sintering
  • the obtained ball milling liquid was dried in a vacuum drying oven at 110 ° C for 12 hours, and then sieved through a 100-mesh sieve to obtain a mixed powder.
  • the ceramic material prepared in this example is cut into standard strip samples of 3mm ⁇ 4mm ⁇ 35mm, and then the strips are subjected to rough grinding, grinding, chamfering and polishing.
  • the mechanical properties were tested, and the results showed that the flexural strength of the material was 768MPa, the hardness was 15.81GPa, and the fracture toughness was 6.19MPa ⁇ M 1/2 .
  • the introduction of TiC can better improve the electrical conductivity and EDM performance of Si 3 N 4 .
  • SPS spark plasma sintering
  • the obtained ball milling liquid was dried in a vacuum drying oven at 110 ° C for 12 hours, and then sieved through a 100-mesh sieve to obtain a mixed powder.
  • the ceramic material prepared in this example is cut into standard strip samples of 3mm ⁇ 4mm ⁇ 35mm, and then the strips are subjected to rough grinding, grinding, chamfering and polishing.
  • the mechanical properties were tested, and the results showed that the flexural strength of the material was 886MPa, the hardness was 13.73GPa, and the fracture toughness was 7.85MPa ⁇ M 1/2 .
  • SPS spark plasma sintering
  • the obtained ball milling liquid was dried in a vacuum drying oven at 110 ° C for 12 hours, and then sieved through a 100-mesh sieve to obtain a mixed powder.
  • the ceramic material prepared in this example is cut into standard strip samples of 3mm ⁇ 4mm ⁇ 35mm, and then the strips are subjected to rough grinding, grinding, chamfering and polishing.
  • the mechanical properties were tested, and the results showed that the flexural strength of the material was 891 MPa, the hardness was 13.21 GPa, and the fracture toughness was 8.37 MPa ⁇ M 1/2 .
  • SPS spark plasma sintering
  • the obtained ball milling liquid was dried in a vacuum drying oven at 110 ° C for 12 hours, and then sieved through a 100-mesh sieve to obtain a mixed powder.
  • the ceramic material prepared in this example is cut into standard strip samples of 3mm ⁇ 4mm ⁇ 35mm, and then the strips are subjected to rough grinding, grinding, chamfering and polishing.
  • the mechanical properties were tested, and the results showed that the flexural strength of the material was 801MPa, the hardness was 14.63GPa, and the fracture toughness was 7.26MPa ⁇ M 1/2 .

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Abstract

An Si3N4/TiC ceramic material preparation method based on spark plasma sintering, comprising: by using α-Si3N4 as a matrix, TiC as an additive phase, and Al2O3 and Y2O3 as sintering aids, performing wet ball mill mixing and drying, and then performing spark plasma sintering, the sintering temperature being 1650-1750℃, and the holding time being 20-35 min. The prepared Si3N4/TiC ceramic material has good sintering density, and the bending strength, fracture toughness and hardness of the ceramic material are not less than 700 MPa, 6.1 MPa•m1/2, and 13 GPa.

Description

一种基于放电等离子烧结的氮化硅/碳化钛陶瓷材料制备方法A kind of preparation method of silicon nitride/titanium carbide ceramic material based on spark plasma sintering 技术领域technical field
本发明属于陶瓷材料制备技术领域，具体涉及一种基于放电等离子烧结的氮化硅/碳化钛(Si 3N 4/TiC)陶瓷材料制备方法、该方法制备得到的Si 3N 4/TiC陶瓷材料及应用。 The invention belongs to the technical field of ceramic material preparation, and in particular relates to a preparation method of silicon nitride/titanium carbide (Si 3 N 4 /TiC) ceramic material based on spark plasma sintering, and the Si 3 N 4 /TiC ceramic material prepared by the method and applications.
背景技术Background technique
公开该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。The disclosure of information in this Background section is only for enhancement of understanding of the general background of the invention and should not necessarily be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
作为目前最流行的超快烧结技术，放电等离子烧结(SPS)多用于制备纳米结构材料、非晶材料、金属间化合物、金属基体以及陶瓷基复合材料。与传统烧结方式相比，放电等离子烧结(SPS)技术具有更快的加热速度，可在更短的烧结时间内达到相同的烧结效果。放电等离子烧结(SPS)制备材料可以快速升温是由于脉冲电流中的直流分量与交流分量的集肤效应，以及加热系统较小的热容量。烧结时，热量大部分由模具内边缘产生，其温度越高，粉体表面的温度就越高。在放电等离子烧结(SPS)中，粉末放置在石墨模具中，在对粉末施加压力的同时，电流通过模具和样品(如果后者为导电材料)来加热粉末坯体，若粉体为非导电材料，电流主要流过模具产生热量。除了因为较低的烧结温度与较短的烧结时间可成功制备晶粒无明显生长的纳米材料之外，SPS工艺因其独特的加热体系，在制备陶瓷材料 时具有以下优势：可清洁晶界、可显著增加超塑性、降低晶界偏聚、增强键合质量、改善热电性能以及合金陶瓷的延性改善。As the most popular ultrafast sintering technology, spark plasma sintering (SPS) is mostly used to prepare nanostructured materials, amorphous materials, intermetallic compounds, metal matrix and ceramic matrix composites. Compared with traditional sintering methods, spark plasma sintering (SPS) technology has a faster heating rate and can achieve the same sintering effect in a shorter sintering time. The rapid heating of materials prepared by spark plasma sintering (SPS) is due to the skin effect of the DC and AC components in the pulsed current, as well as the small heat capacity of the heating system. During sintering, most of the heat is generated by the inner edge of the mold, and the higher the temperature, the higher the temperature of the powder surface. In spark plasma sintering (SPS), the powder is placed in a graphite mold, and while pressure is applied to the powder, an electric current is passed through the mold and the sample (if the latter is a conductive material) to heat the powder body, if the powder is a non-conductive material , the current mainly flows through the mold to generate heat. In addition to the successful preparation of nanomaterials with no obvious grain growth due to the lower sintering temperature and shorter sintering time, the SPS process has the following advantages in the preparation of ceramic materials due to its unique heating system: clean grain boundaries, It can significantly increase superplasticity, reduce grain boundary segregation, enhance bonding quality, improve thermoelectric properties, and improve ductility of alloy ceramics.
氮化硅基陶瓷材料具有较高的断裂韧性与强度和优异的耐热冲击、耐腐蚀与耐磨性能，在工业领域具有广泛应用。因此，许多研究者把眼光聚焦到如何采用合适的烧结方法制备高性能的Si 3N 4基陶瓷材料。目前烧结氮化硅陶瓷材料常用的烧结方式有以下几种：无压烧结、反应烧结、气压烧结(GPS)、热等静压烧结(HIP)以及热压(HP)烧结。中国专利CN 109516814 A公开了一种Si 3N 4/SiC复相陶瓷材料及其制备方法，所述Si 3N 4/SiC复相陶瓷材料是以Si 3N 4和SiC作为原料粉体，以Tm 2O 3和MgO作为烧结助剂，采用热压烧结制备得到。此方法虽然得到了高致密度的Si 3N 4/SiC陶瓷材料，但是其烧结时间较长。 Silicon nitride-based ceramic materials have high fracture toughness and strength and excellent thermal shock resistance, corrosion resistance and wear resistance, and are widely used in industrial fields. Therefore, many researchers focus their attention on how to prepare high-performance Si 3 N 4 based ceramic materials by suitable sintering methods. At present, the commonly used sintering methods for sintering silicon nitride ceramic materials are as follows: pressureless sintering, reaction sintering, gas pressure sintering (GPS), hot isostatic pressing (HIP) and hot pressing (HP) sintering. Chinese patent CN 109516814 A discloses a Si 3 N 4 /SiC composite ceramic material and a preparation method thereof. The Si 3 N 4 /SiC composite ceramic material uses Si 3 N 4 and SiC as raw material powders, with Tm 2 O 3 and MgO as sintering aids were prepared by hot pressing sintering. Although this method can obtain a high-density Si 3 N 4 /SiC ceramic material, the sintering time is relatively long.
发明内容SUMMARY OF THE INVENTION
针对上述研究背景，发明人认为，提供一种烧结效率更高的制备方法有利于提高Si 3N 4/SiC陶瓷材料的产能，放电等离子烧结是一种具有在加压过程中烧结的特点，脉冲电流产生的等离子体及烧结过程中的加压有利于降低粉末的烧结温度。同时低电压、高电流的特征，能使粉末快速烧结致密。本发明将其应用于Si 3N 4/SiC陶瓷材料的烧结，成功的将其烧结时间缩短为加压烧结时间的一半，另外，采用本发明提供方法烧结制备的Si 3N 4/SiC陶瓷材料还具有优良的力学性能。 In view of the above research background, the inventor believes that providing a preparation method with higher sintering efficiency is beneficial to improve the productivity of Si 3 N 4 /SiC ceramic materials. Spark plasma sintering is a kind of The plasma generated by the electric current and the pressure during the sintering process are beneficial to reduce the sintering temperature of the powder. At the same time, the characteristics of low voltage and high current can make the powder sinter and densify quickly. The present invention applies it to the sintering of Si 3 N 4 /SiC ceramic materials, and successfully shortens the sintering time to half of the pressure sintering time. In addition, the Si 3 N 4 /SiC ceramic materials prepared by sintering by the method provided by the present invention Also has excellent mechanical properties.
基于上述技术效果，本发明提供以下技术方案：Based on the above technical effects, the present invention provides the following technical solutions:
本发明第一方面，提供一种基于放电等离子烧结的Si 3N 4/TiC陶瓷材料的制备方法，所述制备方法包括：以Si 3N 4为基体，TiC为增强相，Al 2O 3和Y 2O 3为烧结助剂，将上述原料经湿法球磨混料和放电等离子烧结制备而成。 A first aspect of the present invention provides a preparation method of Si 3 N 4 /TiC ceramic material based on spark plasma sintering. The preparation method includes: using Si 3 N 4 as a matrix, TiC as a reinforcing phase, Al 2 O 3 and Y 2 O 3 is a sintering aid, which is prepared by mixing the above raw materials through wet ball milling and spark plasma sintering.
采用放电等离子烧结后，所述Si 3N 4/TiC陶瓷材料的制备时间显著的缩短，本发明针对放电等离子烧结提出了相应的升温烧结程序，根据检测结果表明，基于本发明提供的烧结方法，能够抑制β-Si 3N 4的过分生长，增加烧结产品中α晶相的占比，由于α-Si 3N 4晶相具有更高的强度，采用本发明方法制备的陶瓷材料更适用于切削工具的制备，特别是应用于陶瓷刀具的制备。并且TiC的引入可以更好的改善Si 3N 4的导电性能及电火花加工性能。 After spark plasma sintering is used, the preparation time of the Si 3 N 4 /TiC ceramic material is significantly shortened. The present invention proposes a corresponding heating and sintering procedure for spark plasma sintering. It can inhibit the excessive growth of β-Si 3 N 4 and increase the proportion of α crystal phase in the sintered product. Since the α-Si 3 N 4 crystal phase has higher strength, the ceramic material prepared by the method of the present invention is more suitable for cutting Preparation of tools, especially for the preparation of ceramic knives. And the introduction of TiC can better improve the electrical conductivity and EDM performance of Si 3 N 4 .
以上一个或多个技术方案的有益效果是：The beneficial effects of the above one or more technical solutions are:
本发明的制备工艺简单，烧结时间短，在较短的时间内就可以完成Si 3N 4/TiC陶瓷材料的烧结。相比于热压烧结，放电等离子烧结所用时间仅为热压烧结的1/2。并且本发明制备的Si 3N 4/TiC陶瓷材料的力学性能优异、抗弯强度、断裂韧性、维氏硬度可以达到同时由于SPS的独特烧结机制，抑制了β-Si 3N 4的生长，避免了较大的β-Si 3N 4，这对Si 3N 4/TiC陶瓷材料的性能是有益的。 The preparation process of the invention is simple, the sintering time is short, and the sintering of the Si 3 N 4 /TiC ceramic material can be completed in a short time. Compared with hot pressing sintering, spark plasma sintering takes only half the time of hot pressing sintering. In addition, the Si 3 N 4 /TiC ceramic material prepared by the present invention has excellent mechanical properties, flexural strength, fracture toughness and Vickers hardness, and at the same time, due to the unique sintering mechanism of SPS, the growth of β-Si 3 N 4 is inhibited, avoiding A larger β-Si 3 N 4 is obtained, which is beneficial to the performance of Si 3 N 4 /TiC ceramic material.
附图说明Description of drawings
构成本发明的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。The accompanying drawings forming a part of the present invention are used to provide further understanding of the present invention, and the exemplary embodiments of the present invention and their descriptions are used to explain the present invention, and do not constitute an improper limitation of the present invention.
图1为实施例1制备的Si 3N 4/TiC陶瓷材料时放电等离子烧结过程中烧结温度和上压头的位移的曲线图； 1 is a graph showing the sintering temperature and the displacement of the upper indenter during spark plasma sintering for the Si 3 N 4 /TiC ceramic material prepared in Example 1;
图2为实施例1制备的Si 3N 4/TiC陶瓷材料的XRD检测图； Fig. 2 is the XRD detection diagram of the Si 3 N 4 /TiC ceramic material prepared in Example 1;
图3为实施例1制备的Si 3N 4/TiC陶瓷材料的断裂表面SEM图。 FIG. 3 is a SEM image of the fracture surface of the Si 3 N 4 /TiC ceramic material prepared in Example 1. FIG.
具体实施方式Detailed ways
应该指出，以下详细说明都是例示性的，旨在对本发明提供进一步的说明。除非另有指明，本文使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。It should be noted that the following detailed description is exemplary and intended to provide further explanation of the invention. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本发明的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。It should be noted that the terminology used herein is for the purpose of describing specific embodiments only, and is not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly dictates otherwise, the singular is intended to include the plural as well, furthermore, it is to be understood that when the terms "comprising" and/or "including" are used in this specification, it indicates that There are features, steps, operations, devices, components and/or combinations thereof.
正如背景技术所介绍的，针对现有技术高致密度的Si 3N 4/SiC陶瓷材料烧结时间较长，生产效率低的技术问题。为了解决如上的技术问题，本发明提出了一种基于放电等离子烧结的Si 3N 4/TiC陶瓷材料的制备方法，该制备方法相比现有的热压烧结时间缩短了1/2，并且该方法制备得到的Si 3N 4/TiC陶瓷具有良好的力学性能。 As described in the background art, in view of the technical problems of long sintering time and low production efficiency of high-density Si 3 N 4 /SiC ceramic materials in the prior art. In order to solve the above technical problems, the present invention proposes a preparation method of Si 3 N 4 /TiC ceramic material based on spark plasma sintering. Compared with the existing hot pressing sintering time, the preparation method shortens 1/2, and the The Si 3 N 4 /TiC ceramics prepared by the method have good mechanical properties.
本发明第一方面，提供一种基于放电等离子烧结的Si 3N 4/TiC陶瓷材料的制备方法，所述制备方法包括：以Si 3N 4为基体，TiC为增强相，Al 2O 3和Y 2O 3为烧结助剂，将上述原料经湿法球磨混料和放电等离子烧结制备而成。 A first aspect of the present invention provides a preparation method of Si 3 N 4 /TiC ceramic material based on spark plasma sintering. The preparation method includes: using Si 3 N 4 as a matrix, TiC as a reinforcing phase, Al 2 O 3 and Y 2 O 3 is a sintering aid, which is prepared by mixing the above raw materials through wet ball milling and spark plasma sintering.
优选的，所述制备方法中，所述原料的体积百分比如下：α-Si 3N 4 70-85％，TiC 5-15％，Al 2O 3 1-6％，Y 2O 3 3-7％。 Preferably, in the preparation method, the volume percentages of the raw materials are as follows: α-Si 3 N 4 70-85%, TiC 5-15%, Al 2 O 3 1-6%, Y 2 O 3 3-7% %.
进一步的，所述TiC的体积百分比为7-10％，或所述Al 2O 3的体积百分比为2-4％，或所述Y 2O 3的体积百分比为4-6％，上述原料在所述体积百分比范围内进行调整，其余各组成之和为100％。 Further, the volume percentage of the TiC is 7-10%, or the volume percentage of the Al 2 O 3 is 2-4%, or the volume percentage of the Y 2 O 3 is 4-6%, and the above raw materials are in Adjust within the volume percentage range, and the sum of the remaining components is 100%.
在上述优选技术方案的一些具体实施方式中，所述原料的体积百分比如下：α-Si 3N 4 80％，TiC 10％，Al 2O 3 4％，Y 2O 3 6％。 In some specific embodiments of the above preferred technical solutions, the volume percentages of the raw materials are as follows: α-Si 3 N 4 80%, TiC 10%, Al 2 O 3 4%, Y 2 O 3 6%.
在上述优选技术方案的一些具体实施方式中，所述原料的体积百分比如下：α-Si 3N 4 82％，TiC 10％，Al 2O 3 3％，Y 2O 3 5％。 In some specific embodiments of the above preferred technical solutions, the volume percentages of the raw materials are as follows: α-Si 3 N 4 82%, TiC 10%, Al 2 O 3 3%, Y 2 O 3 5%.
在上述优选技术方案的一些具体实施方式中，所述原料的体积百分比如下：α-Si 3N 4 75％，TiC 15％，Al 2O 3 4％，Y 2O 3 6％。 In some specific embodiments of the above preferred technical solutions, the volume percentages of the raw materials are as follows: α-Si 3 N 4 75%, TiC 15%, Al 2 O 3 4%, Y 2 O 3 6%.
优选的，所述α-Si 3N 4粉体平均粒径为0.5-1μm。 Preferably, the average particle size of the α-Si 3 N 4 powder is 0.5-1 μm.
优选的，所述TiC粉体平均粒径为0.5-1μm。Preferably, the average particle size of the TiC powder is 0.5-1 μm.
优选的，所述Al 2O 3粉体平均粒径为0.5-2μm。 Preferably, the average particle size of the Al 2 O 3 powder is 0.5-2 μm.
优选的，所述Y 2O 3粉体平均粒径为0.1-0.5μm。 Preferably, the average particle size of the Y 2 O 3 powder is 0.1-0.5 μm.
优选的，所述制备方法具体包括以下步骤：Preferably, the preparation method specifically comprises the following steps:
(1)将α-Si 3N 4、TiC粉体分别加入分散介质中使其分散均匀得到α-Si 3N 4悬浮液及TiC悬浮液，将其混合得到复相悬浮液； (1) adding the α-Si 3 N 4 and TiC powders into the dispersion medium respectively to make them disperse uniformly to obtain the α-Si 3 N 4 suspension and the TiC suspension, and mixing them to obtain the multiphase suspension;
(2)称取α-Si 3N 4重量1-5wt％的分散剂，加入分散介质中溶解后将分散剂溶液加入上述复相悬浮液中，再添加Al 2O 3和Y 2O 3粉体使其分散均匀得到混合体系； (2) Weigh 1-5wt% dispersant of α-Si 3 N 4 , add the dispersant solution in the dispersion medium to dissolve, add the dispersant solution to the above-mentioned multiphase suspension, and then add Al 2 O 3 and Y 2 O 3 powder disperse it uniformly to obtain a mixed system;
(3)将步骤(2)得到的混合体系转移至球磨罐中进行球磨；完 成后的球磨液干燥后过筛得到混合粉料；(3) the mixing system obtained in step (2) is transferred to the ball-milling tank and ball-milled; the ball-milling liquid after the completion is dried and sieved to obtain mixed powder;
(4)将步骤(3)所述混合粉料装入模具成型，再进行放电等离子烧结。(4) The mixed powder described in step (3) is loaded into a mold for molding, and then spark plasma sintering is performed.
进一步的，所述步骤(1)或(2)中，所述分散介质为包括但不限于无水乙醇或无水甲醇。Further, in the step (1) or (2), the dispersion medium includes but is not limited to anhydrous ethanol or anhydrous methanol.
进一步的，所述步骤(2)中，所述分散剂为包括但不限于聚乙二醇，具体的，为聚乙二醇6000。Further, in the step (2), the dispersing agent includes but not limited to polyethylene glycol, specifically, polyethylene glycol 6000.
进一步的，所述步骤(3)中，所述球磨按照球料重量比10:0.5～1.5加入球磨球，在保护气氛下进行球磨40～50h；具体的，所述保护气氛为氮气。Further, in the step (3), the ball mill is added with ball milling balls according to a weight ratio of 10:0.5-1.5 to the balls, and the ball-milling is performed under a protective atmosphere for 40-50 hours; specifically, the protective atmosphere is nitrogen.
进一步的，所述步骤(3)中，所述球磨球为硬质合金小球YG6或YG8。Further, in the step (3), the ball grinding balls are cemented carbide balls YG6 or YG8.
进一步的，所述步骤(3)中，球磨液的干燥方式包括但不限于常压干燥、真空干燥、喷雾干燥或冷冻干燥中的一种。Further, in the step (3), the drying method of the ball milling liquid includes but is not limited to one of atmospheric drying, vacuum drying, spray drying or freeze drying.
具体的实施方式中，所述干燥采用真空干燥，80-120℃下干燥12-24小时。In a specific embodiment, the drying adopts vacuum drying at 80-120° C. for 12-24 hours.
进一步的，所述步骤(3)中，球磨液干燥后经100-120目筛过筛，得到混合粉料。Further, in the step (3), the ball milling liquid is dried and sieved through a 100-120 mesh sieve to obtain a mixed powder.
进一步的，所述步骤(4)中，所述放电等离子烧结参数：升温速率：在1300℃之前，90-110℃/min，高于1300℃，30-50℃/min；烧结温度1650-1750℃；保温时间20-35min，分别在1600℃和达到烧结温度后保温10-17min；轴向压力25-35MPa。Further, in the step (4), the spark plasma sintering parameters: heating rate: before 1300 ℃, 90-110 ℃/min, higher than 1300 ℃, 30-50 ℃/min; sintering temperature 1650-1750 ℃; holding time 20-35min, respectively at 1600℃ and after reaching the sintering temperature for 10-17min; axial pressure 25-35MPa.
上述优选的技术方案的一种具体实施方式中，所述制备方法包括以下步骤：In a specific embodiment of the above-mentioned preferred technical solution, the preparation method comprises the following steps:
(1)按比例称取α-Si 3N 4、TiC粉体，分别加入适量的无水乙醇为分散介质，超声分散并机械搅拌10-20min，制得α-Si 3N 4悬浮液、TiC悬浮液，将两种悬浮液混合得到复相悬浮液； (1) Weigh α-Si 3 N 4 and TiC powder in proportion, add an appropriate amount of anhydrous ethanol as dispersion medium, ultrasonically disperse and mechanically stir for 10-20 min to obtain α-Si 3 N 4 suspension, TiC suspension, the two suspensions are mixed to obtain a complex suspension;
(2)称取α-Si 3N 4重量的1-5wt％的聚乙二醇6000，以无水乙醇溶解后加入复相悬浮液中然后按比例添加Al 2O 3和Y 2O 3粉体，超声分散并机械搅拌30-50min； (2) Weigh 1-5wt% polyethylene glycol 6000 by weight of α-Si 3 N 4 , dissolve it in absolute ethanol, add it to the multiphase suspension, and then add Al 2 O 3 and Y 2 O 3 powder in proportion body, ultrasonic dispersion and mechanical stirring for 30-50min;
(3)将步骤(2)所得的最终悬浮液倒入球磨罐，按照球料重量比10:1加入球磨球，在保护气氛下进行球磨48h，将球磨液在真空干燥箱80-120℃下干燥12-24小时，然后经100-120目筛过筛，得到混合粉料，密封保存备用；(3) Pour the final suspension obtained in step (2) into the ball milling tank, add ball milling balls according to the ball-to-material weight ratio of 10:1, carry out ball milling for 48 hours under a protective atmosphere, and place the ball milling liquid in a vacuum drying oven at 80-120° C. Dry for 12-24 hours, then sieve through a 100-120 mesh sieve to obtain mixed powder, which is sealed and stored for later use;
(4)将步骤(3)得到的混合粉料装入石墨模具中，经冷压成型后放入放电等离子烧结炉中进行烧结。(4) The mixed powder obtained in step (3) is put into a graphite mold, and after being cold-pressed, it is put into a spark plasma sintering furnace for sintering.
本发明第二方面，提供第一方面所述基于放电等离子烧结的Si 3N 4/TiC陶瓷材料的制备方法制备得到的Si 3N 4/TiC陶瓷材料。 A second aspect of the present invention provides a Si 3 N 4 /TiC ceramic material prepared by the method for preparing a Si 3 N 4 /TiC ceramic material based on spark plasma sintering according to the first aspect.
本发明第三方面，提供第一方面所述Si 3N 4/TiC陶瓷材料在生产切削工具、耐磨零件、插件以及航空工业用产品等领域的应用。 A third aspect of the present invention provides the application of the Si 3 N 4 /TiC ceramic material described in the first aspect in the production of cutting tools, wear-resistant parts, inserts, and products for the aviation industry.
为了使得本领域技术人员能够更加清楚地了解本发明的技术方案，以下将结合具体的实施例详细说明本发明的技术方案，以下实施例中所涉及的原料均为市售产品。In order to enable those skilled in the art to understand the technical solutions of the present invention more clearly, the technical solutions of the present invention will be described in detail below with reference to specific examples, and the raw materials involved in the following examples are all commercially available products.
实施例1Example 1
一种基于放电等离子烧结(SPS)的Si 3N 4/TiC陶瓷材料的制备方法，原料组分的体积百分比为α-Si 3N 4 82％，TiC 10％，Al 2O 3 3％，Y 2O 3 5％。 A preparation method of Si 3 N 4 /TiC ceramic material based on spark plasma sintering (SPS), the volume percentage of raw material components is α-Si 3 N 4 82%, TiC 10%, Al 2 O 3 3%, Y 2 O 3 5%.
按比例称取α-Si 3N 4、TiC粉体，分别加入适量的无水乙醇为分散介质，超声分散并机械搅拌15min，制得α-Si 3N 4悬浮液，TiC悬浮液；将上述两种悬浮液混合得到复相悬浮液。称取Si 3N 4粉体重量的3wt％的聚乙二醇6000，以无水乙醇溶解后加入复相悬浮液中然后按比例添加Al 2O 3和Y 2O 3粉体，超声分散并机械搅拌45min；将所得的最终悬浮液倒入球磨罐，按照球料重量比10:1加入球磨球，在氮气气氛下进行球磨48h。 Weigh α-Si 3 N 4 and TiC powder in proportion, add an appropriate amount of absolute ethanol as dispersion medium, ultrasonically disperse and mechanically stir for 15 minutes to obtain α-Si 3 N 4 suspension and TiC suspension; The two suspensions were mixed to obtain a multiphase suspension. Weigh 3wt% of polyethylene glycol 6000 of Si 3 N 4 powder weight, dissolve it in absolute ethanol, add it to the multiphase suspension, then add Al 2 O 3 and Y 2 O 3 powder in proportion, disperse ultrasonically and dissolve it. Mechanical stirring was performed for 45 min; the resulting final suspension was poured into a ball milling jar, ball milling balls were added in a weight ratio of 10:1 to the balls, and ball milling was carried out under nitrogen atmosphere for 48 h.
将得到的球磨液在真空干燥箱110℃下干燥12小时，然后经100目筛过筛，得到混合粉料，将得到的混合粉料装入石墨模具中，经冷压成型后放入放电等离子烧结炉中进行热压烧结；放电等离子烧结参数：1300℃以前100℃/min；1300℃-1450℃50℃/min；1450℃-1600℃30℃/min；1600℃保温15min；1600℃-1700℃30℃/min；1700℃保温10min；压力30MPa。The obtained ball milling liquid was dried in a vacuum drying oven at 110 ° C for 12 hours, and then sieved through a 100-mesh sieve to obtain a mixed powder. Hot pressing sintering in a sintering furnace; Spark plasma sintering parameters: 100°C/min before 1300°C; 50°C/min at 1300°C-1450°C; 30°C/min at 1450°C-1600°C; ℃30℃/min; 1700℃ heat preservation for 10min; pressure 30MPa.
将本实施例制备的陶瓷材料切割成3mm×4mm×35mm的标准条状试样，然后将样条进行粗磨、研磨、倒角、抛光处理。对其进行力学性能测试，结果显示材料抗弯强度为959MPa，硬度为15.21GPa，断裂韧性为8.61MPa·M 1/2。从图1可以看出放电等离子烧结Si 3N 4陶瓷材料的致密化和晶体长大的过程。1200℃之前，粉体受热膨胀，下压头下移，Z轴位移下降。致密化的过程发生在1200℃以后，此时下 压头上移，Z轴位移升高。当温度达到1700℃后，晶体开始长大陶瓷材料开始膨胀，Z轴位移减小。根据图2可以发现烧结后的Si 3N 4/TiC陶瓷材料的物相组成为β-Si 3N 4、TiC 0.3N 0.7和少量α-Si 3N 4，其中TiC0.3N0.7主要是由于在烧结过程中Si 3N 4和TiC发生反应形成。并且从图2中可以发现陶瓷材料中各项结晶度良好。图3显示了Si 3N 4/TiC陶瓷材料的断裂表面的SEM图，可以发现晶粒均匀，没有发现较大的β-Si 3N 4，并且致密度良好，没有发现明显的气孔，这也是陶瓷材料具有优异的力学性能的原因。 The ceramic material prepared in this example is cut into standard strip samples of 3mm×4mm×35mm, and then the strips are subjected to rough grinding, grinding, chamfering and polishing. The mechanical properties were tested, and the results showed that the flexural strength of the material was 959MPa, the hardness was 15.21GPa, and the fracture toughness was 8.61MPa·M 1/2 . The process of densification and crystal growth of the spark plasma sintered Si 3 N 4 ceramic material can be seen from Figure 1. Before 1200°C, the powder expands due to heat, the lower indenter moves down, and the Z-axis displacement decreases. The densification process occurs after 1200 °C, when the lower indenter moves up and the Z-axis displacement increases. When the temperature reaches 1700 °C, the crystal begins to grow and the ceramic material begins to expand, and the Z-axis displacement decreases. According to Fig. 2, it can be found that the phase composition of the sintered Si 3 N 4 /TiC ceramic material is β-Si 3 N 4 , TiC 0.3 N 0.7 and a small amount of α-Si 3 N 4 , of which TiC0.3N0.7 is mainly due to During the sintering process, Si 3 N 4 and TiC react to form. And from Figure 2, it can be found that the crystallinity of the ceramic materials is good. Figure 3 shows the SEM image of the fracture surface of the Si 3 N 4 /TiC ceramic material, it can be found that the grains are uniform, no larger β-Si 3 N 4 is found, and the density is good, and no obvious pores are found, which is also The reason for the excellent mechanical properties of ceramic materials.
实施例2Example 2
一种基于放电等离子烧结(SPS)的Si 3N 4/TiC陶瓷材料的制备方法，原料组分的体积百分比为α-Si 3N 4 82％，TiC 10％，Al 2O 3 3％，Y 2O 3 5％。 A preparation method of Si 3 N 4 /TiC ceramic material based on spark plasma sintering (SPS), the volume percentage of raw material components is α-Si 3 N 4 82%, TiC 10%, Al 2 O 3 3%, Y 2 O 3 5%.
按比例称取α-Si 3N 4，TiC粉体，分别加入适量的无水乙醇为分散介质，超声分散并机械搅拌15min，制得α-Si 3N 4悬浮液，TiC悬浮液；将上述三种悬浮液混合得到复相悬浮液。称取Si 3N 4粉体重量的3wt％的分散剂，以无水乙醇溶解后加入复相悬浮液中然后按比例添加Al 2O 3和Y 2O 3粉体，超声分散并机械搅拌45min；将所得的最终悬浮液倒入球磨罐，按照球料重量比10:1加入球磨球，在氮气气氛下进行球磨48h。 Weigh α-Si 3 N 4 and TiC powder in proportion, add an appropriate amount of anhydrous ethanol as the dispersion medium, ultrasonically disperse and stir mechanically for 15 minutes to obtain α-Si 3 N 4 suspension and TiC suspension; The three suspensions were mixed to obtain a multiphase suspension. Weigh 3wt% of the Si 3 N 4 powder by weight, dissolve it in absolute ethanol, add it to the multiphase suspension, then add Al 2 O 3 and Y 2 O 3 powders in proportion, disperse ultrasonically and mechanically stir for 45min ; Pour the resulting final suspension into the ball milling tank, add ball milling balls according to the weight ratio of balls to material 10:1, and carry out ball milling for 48h under nitrogen atmosphere.
将得到的球磨液在真空干燥箱110℃下干燥12小时，然后经100目筛过筛，得到混合粉料，将得到的混合粉料装入石墨模具中，经冷压成型后放入放电等离子烧结炉中进行热压烧结；放电等离子烧结参 数：1300℃以前100℃/min；1300℃-1450℃50℃/min；1450℃-1600℃30℃/min；1600℃保温15min；1600℃-1650℃30℃/min；1650℃保温10min；压力30MPa。The obtained ball milling liquid was dried in a vacuum drying oven at 110 ° C for 12 hours, and then sieved through a 100-mesh sieve to obtain a mixed powder. Hot pressing sintering in a sintering furnace; Spark plasma sintering parameters: 100°C/min before 1300°C; 1300°C-1450°C 50°C/min; 1450°C-1600°C 30°C/min; 1600°C hold for 15min; ℃30℃/min; 1650℃ heat preservation for 10min; pressure 30MPa.
将本实施例制备的陶瓷材料切割成3mm×4mm×35mm的标准条状试样，然后将样条进行粗磨、研磨、倒角、抛光处理。对其进行力学性能测试，结果显示材料抗弯强度为768MPa，硬度为15.81GPa，断裂韧性为6.19MPa·M 1/2。并且TiC的引入可以更好的改善Si 3N 4的导电性能及电火花加工性能。 The ceramic material prepared in this example is cut into standard strip samples of 3mm×4mm×35mm, and then the strips are subjected to rough grinding, grinding, chamfering and polishing. The mechanical properties were tested, and the results showed that the flexural strength of the material was 768MPa, the hardness was 15.81GPa, and the fracture toughness was 6.19MPa·M 1/2 . And the introduction of TiC can better improve the electrical conductivity and EDM performance of Si 3 N 4 .
实施例3Example 3
一种基于放电等离子烧结(SPS)的Si 3N 4/TiC陶瓷材料的制备方法，原料组分的体积百分比为α-Si 3N 4 82％，TiC 10％，Al 2O 3 3％，Y 2O 3 5％。 A preparation method of Si 3 N 4 /TiC ceramic material based on spark plasma sintering (SPS), the volume percentage of raw material components is α-Si 3 N 4 82%, TiC 10%, Al 2 O 3 3%, Y 2 O 3 5%.
按比例称取α-Si 3N 4，TiC粉体，分别加入适量的无水乙醇为分散介质，超声分散并机械搅拌15min，制得α-Si 3N 4悬浮液，TiC悬浮液；将上述三种悬浮液混合得到复相悬浮液。称取Si 3N 4粉体重量的3wt％的分散剂，以无水乙醇溶解后加入复相悬浮液中然后按比例添加Al 2O 3和Y 2O 3粉体，超声分散并机械搅拌45min；将所得的最终悬浮液倒入球磨罐，按照球料重量比10:1加入球磨球，在氮气气氛下进行球磨48h。 Weigh α-Si 3 N 4 and TiC powder in proportion, add an appropriate amount of anhydrous ethanol as the dispersion medium, ultrasonically disperse and stir mechanically for 15 minutes to obtain α-Si 3 N 4 suspension and TiC suspension; The three suspensions were mixed to obtain a multiphase suspension. Weigh 3wt% of the Si 3 N 4 powder by weight, dissolve it in absolute ethanol, add it to the multiphase suspension, then add Al 2 O 3 and Y 2 O 3 powders in proportion, disperse ultrasonically and mechanically stir for 45min ; Pour the resulting final suspension into the ball milling tank, add ball milling balls according to the weight ratio of balls to material 10:1, and carry out ball milling for 48h under nitrogen atmosphere.
将得到的球磨液在真空干燥箱110℃下干燥12小时，然后经100目筛过筛，得到混合粉料，将得到的混合粉料装入石墨模具中，经冷压成型后放入放电等离子烧结炉中进行热压烧结；放电等离子烧结参 数：1300℃以前100℃/min；1300℃-1450℃50℃/min；1450℃-1600℃30℃/min；1600℃保温15min；1600℃-1700℃30℃/min；1700℃保温15min；压力30MPa。The obtained ball milling liquid was dried in a vacuum drying oven at 110 ° C for 12 hours, and then sieved through a 100-mesh sieve to obtain a mixed powder. Hot pressing sintering in a sintering furnace; Spark plasma sintering parameters: 100°C/min before 1300°C; 50°C/min at 1300°C-1450°C; 30°C/min at 1450°C-1600°C; ℃30℃/min; 1700℃ heat preservation for 15min; pressure 30MPa.
将本实施例制备的陶瓷材料切割成3mm×4mm×35mm的标准条状试样，然后将样条进行粗磨、研磨、倒角、抛光处理。对其进行力学性能测试，结果显示材料抗弯强度为886MPa，硬度为13.73GPa，断裂韧性为7.85MPa·M 1/2。 The ceramic material prepared in this example is cut into standard strip samples of 3mm×4mm×35mm, and then the strips are subjected to rough grinding, grinding, chamfering and polishing. The mechanical properties were tested, and the results showed that the flexural strength of the material was 886MPa, the hardness was 13.73GPa, and the fracture toughness was 7.85MPa·M 1/2 .
实施例4Example 4
一种基于放电等离子烧结(SPS)的Si 3N 4/TiC陶瓷材料的制备方法，原料组分的体积百分比为α-Si 3N 4 82％，TiC 10％，Al 2O 3 4％，Y 2O 3 6％。 A preparation method of Si 3 N 4 /TiC ceramic material based on spark plasma sintering (SPS), the volume percentage of raw material components is α-Si 3 N 4 82%, TiC 10%, Al 2 O 3 4%, Y 2O3 6 %.
按比例称取α-Si 3N 4，TiC粉体，分别加入适量的无水乙醇为分散介质，超声分散并机械搅拌15min，制得α-Si 3N 4悬浮液，TiC悬浮液；将上述三种悬浮液混合得到复相悬浮液。称取Si 3N 4粉体重量的3wt％的分散剂，以无水乙醇溶解后加入复相悬浮液中然后按比例添加Al 2O 3和Y 2O 3粉体，超声分散并机械搅拌45min；将所得的最终悬浮液倒入球磨罐，按照球料重量比10:1加入球磨球，在氮气气氛下进行球磨48h； Weigh α-Si 3 N 4 and TiC powder in proportion, add an appropriate amount of anhydrous ethanol as the dispersion medium, ultrasonically disperse and stir mechanically for 15 minutes to obtain α-Si 3 N 4 suspension and TiC suspension; The three suspensions were mixed to obtain a multiphase suspension. Weigh 3wt% of the Si 3 N 4 powder by weight, dissolve it in absolute ethanol, add it to the multiphase suspension, then add Al 2 O 3 and Y 2 O 3 powders in proportion, disperse ultrasonically and mechanically stir for 45min ; Pour the final suspension of gained into the ball mill tank, add ball mill balls according to the weight ratio of balls to material 10:1, and carry out ball milling for 48h under nitrogen atmosphere;
将得到的球磨液在真空干燥箱110℃下干燥12小时，然后经100目筛过筛，得到混合粉料，将得到的混合粉料装入石墨模具中，经冷压成型后放入放电等离子烧结炉中进行热压烧结；放电等离子烧结参数：1300℃以前100℃/min；1300℃-1450℃50℃/min；1450℃-1600℃ 30℃/min；1600℃保温15min；1600℃-1700℃30℃/min；1700℃保温10min；压力30MPa。The obtained ball milling liquid was dried in a vacuum drying oven at 110 ° C for 12 hours, and then sieved through a 100-mesh sieve to obtain a mixed powder. Hot pressing sintering in a sintering furnace; Spark plasma sintering parameters: 100°C/min before 1300°C; 1300°C-1450°C 50°C/min; 1450°C-1600°C 30°C/min; 1600°C hold for 15min; ℃30℃/min; 1700℃ heat preservation for 10min; pressure 30MPa.
将本实施例制备的陶瓷材料切割成3mm×4mm×35mm的标准条状试样，然后将样条进行粗磨、研磨、倒角、抛光处理。对其进行力学性能测试，结果显示材料抗弯强度为891MPa，硬度为13.21GPa，断裂韧性为8.37MPa·M 1/2。 The ceramic material prepared in this example is cut into standard strip samples of 3mm×4mm×35mm, and then the strips are subjected to rough grinding, grinding, chamfering and polishing. The mechanical properties were tested, and the results showed that the flexural strength of the material was 891 MPa, the hardness was 13.21 GPa, and the fracture toughness was 8.37 MPa·M 1/2 .
实施例5Example 5
一种基于放电等离子烧结(SPS)的Si 3N 4/TiC陶瓷材料的制备方法，原料组分的体积百分比为α-Si 3N 4 82％，TiC 10％，Al 2O 3 3％，Y 2O 3 5％。 A preparation method of Si 3 N 4 /TiC ceramic material based on spark plasma sintering (SPS), the volume percentage of raw material components is α-Si 3 N 4 82%, TiC 10%, Al 2 O 3 3%, Y 2 O 3 5%.
按比例称取α-Si 3N 4，TiC粉体，分别加入适量的无水乙醇为分散介质，超声分散并机械搅拌15min，制得α-Si 3N 4悬浮液，TiC悬浮液；将上述三种悬浮液混合得到复相悬浮液。称取Si 3N 4粉体重量的3wt％的分散剂，以无水乙醇溶解后加入复相悬浮液中然后按比例添加Al 2O 3和Y 2O 3粉体，超声分散并机械搅拌45min；将所得的最终悬浮液倒入球磨罐，按照球料重量比10:1加入球磨球，在氮气气氛下进行球磨48h。 Weigh α-Si 3 N 4 and TiC powder in proportion, add an appropriate amount of anhydrous ethanol as the dispersion medium, ultrasonically disperse and stir mechanically for 15 minutes to obtain α-Si 3 N 4 suspension and TiC suspension; The three suspensions were mixed to obtain a multiphase suspension. Weigh 3wt% of the Si 3 N 4 powder by weight, dissolve it in absolute ethanol, add it to the multiphase suspension, then add Al 2 O 3 and Y 2 O 3 powders in proportion, disperse ultrasonically and mechanically stir for 45min ; Pour the resulting final suspension into the ball milling tank, add ball milling balls according to the weight ratio of balls to material 10:1, and carry out ball milling for 48h under nitrogen atmosphere.
将得到的球磨液在真空干燥箱110℃下干燥12小时，然后经100目筛过筛，得到混合粉料，将得到的混合粉料装入石墨模具中，经冷压成型后放入放电等离子烧结炉中进行热压烧结；放电等离子烧结参数：1300℃以前100℃/min；1300℃-1450℃50℃/min；1450℃-1600℃30℃/min；1600℃保温15min；1600℃-1700℃30℃/min；1700℃保 温10min；压力40MPa。The obtained ball milling liquid was dried in a vacuum drying oven at 110 ° C for 12 hours, and then sieved through a 100-mesh sieve to obtain a mixed powder. Hot pressing sintering in a sintering furnace; Spark plasma sintering parameters: 100°C/min before 1300°C; 50°C/min at 1300°C-1450°C; 30°C/min at 1450°C-1600°C; ℃30℃/min; 1700℃ heat preservation for 10min; pressure 40MPa.
将本实施例制备的陶瓷材料切割成3mm×4mm×35mm的标准条状试样，然后将样条进行粗磨、研磨、倒角、抛光处理。对其进行力学性能测试，结果显示材料抗弯强度为801MPa，硬度为14.63GPa，断裂韧性为7.26MPa·M 1/2。 The ceramic material prepared in this example is cut into standard strip samples of 3mm×4mm×35mm, and then the strips are subjected to rough grinding, grinding, chamfering and polishing. The mechanical properties were tested, and the results showed that the flexural strength of the material was 801MPa, the hardness was 14.63GPa, and the fracture toughness was 7.26MPa·M 1/2 .
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (10)

  1. 一种基于放电等离子烧结的Si 3N 4/TiC陶瓷材料的制备方法，其特征在于，所述制备方法包括：以Si 3N 4为基体，TiC为增强相，Al 2O 3和Y 2O 3为烧结助剂，将上述原料经湿法球磨混料和放电等离子烧结制备而成。 A preparation method of Si 3 N 4 /TiC ceramic material based on spark plasma sintering, characterized in that the preparation method comprises: taking Si 3 N 4 as a matrix, TiC as a reinforcing phase, Al 2 O 3 and Y 2 O 3 is a sintering aid, prepared by mixing the above raw materials through wet ball milling and spark plasma sintering.
  2. 如权利要求1所述基于放电等离子烧结的Si 3N 4/TiC陶瓷材料的制备方法，其特征在于，所述制备方法中，所述原料的体积百分比如下：α-Si 3N 4 70-85％，TiC 5-15％，Al 2O 3 1-6％，Y 2O 3 3-7％。 The preparation method of Si 3 N 4 /TiC ceramic material based on spark plasma sintering according to claim 1, wherein, in the preparation method, the volume percentage of the raw material is as follows: α-Si 3 N 4 70-85 %, TiC 5-15%, Al2O3 1-6 %, Y2O3 3-7 %.
  3. 如权利要求2所述基于放电等离子烧结的Si 3N 4/TiC陶瓷材料的制备方法，其特征在于，所述TiC的体积百分比为7-10％，或所述Al 2O 3的体积百分比为2-4％，或所述Y 2O 3的体积百分比为4-6％。 The preparation method of Si 3 N 4 /TiC ceramic material based on spark plasma sintering according to claim 2, wherein the volume percentage of TiC is 7-10%, or the volume percentage of Al 2 O 3 is 2-4%, or the volume percentage of the Y 2 O 3 is 4-6%.
  4. 如权利要求3所述基于放电等离子烧结的Si 3N 4/TiC陶瓷材料的制备方法，其特征在于，所述原料的体积百分比如下：α-Si 3N 4 82％，TiC 10％，Al 2O 3 4％，Y 2O 3 6％； The preparation method of Si 3 N 4 /TiC ceramic material based on spark plasma sintering according to claim 3, wherein the volume percentage of the raw materials is as follows: α-Si 3 N 4 82%, TiC 10%, Al 2 O 3 4%, Y 2 O 3 6%;
    或，所述原料的体积百分比如下：α-Si 3N 4 82％，TiC 10％，Al 2O 3 3％，Y 2O 3 5％； Or, the volume percentages of the raw materials are as follows: α-Si 3 N 4 82%, TiC 10%, Al 2 O 3 3%, Y 2 O 3 5%;
    或，所述原料的体积百分比如下：α-Si 3N 4 75％，TiC 15％，Al 2O 3 4％，Y 2O 3 6％。 Or, the volume percentages of the raw materials are as follows: α-Si 3 N 4 75%, TiC 15%, Al 2 O 3 4%, Y 2 O 3 6%.
  5. 如权利要求3所述基于放电等离子烧结的Si 3N 4/TiC陶瓷材料的制备方法，其特征在于，所述α-Si 3N 4粉体平均粒径为0.5-1μm； The preparation method of the Si 3 N 4 /TiC ceramic material based on spark plasma sintering according to claim 3, wherein the average particle size of the α-Si 3 N 4 powder is 0.5-1 μm;
    或，所述TiC粉体平均粒径为0.5-1μm；Or, the average particle size of the TiC powder is 0.5-1 μm;
    或，所述Al 2O 3粉体平均粒径为0.5-2μm； Or, the average particle size of the Al 2 O 3 powder is 0.5-2 μm;
    或，所述Y 2O 3粉体平均粒径为0.1-0.5μm。 Or, the average particle size of the Y 2 O 3 powder is 0.1-0.5 μm.
  6. 如权利要求1所述基于放电等离子烧结的Si 3N 4/TiC陶瓷材料的制备方法，其特征在于，所述制备方法具体包括以下步骤： The preparation method of the Si 3 N 4 /TiC ceramic material based on spark plasma sintering according to claim 1, wherein the preparation method specifically comprises the following steps:
    (1)将α-Si 3N 4、TiC粉体分别加入分散介质中使其分散均匀得到α-Si 3N 4悬浮液及TiC悬浮液，将其混合得到复相悬浮液； (1) adding the α-Si 3 N 4 and TiC powders into the dispersion medium respectively to make them disperse uniformly to obtain the α-Si 3 N 4 suspension and the TiC suspension, and mixing them to obtain the multiphase suspension;
    (2)称取α-Si 3N 4重量1-5wt％的分散剂，加入分散介质中溶解后将分散剂溶液加入上述复相悬浮液中，再添加Al 2O 3和Y 2O 3粉体使其分散均匀得到混合体系； (2) Weigh 1-5wt% dispersant of α-Si 3 N 4 , add the dispersant solution in the dispersion medium to dissolve, add the dispersant solution to the above-mentioned multiphase suspension, and then add Al 2 O 3 and Y 2 O 3 powder disperse it uniformly to obtain a mixed system;
    (3)将步骤(2)得到的混合体系转移至球磨罐中进行球磨；完成后的球磨液干燥后过筛得到混合粉料；(3) transfer the mixing system obtained in step (2) to the ball milling tank and carry out ball milling; the ball milling liquid after the completion is dried and sieved to obtain mixed powder;
    (4)将步骤(3)所述混合粉料装入模具成型，再进行放电等离子烧结。(4) The mixed powder described in step (3) is loaded into a mold for molding, and then spark plasma sintering is performed.
  7. 如权利要求6所述基于放电等离子烧结的Si 3N 4/TiC陶瓷材料的制备方法，其特征在于，所述步骤(1)或(2)中，所述分散介质为包括但不限于无水乙醇或无水甲醇； The method for preparing a Si 3 N 4 /TiC ceramic material based on spark plasma sintering according to claim 6, wherein in the step (1) or (2), the dispersion medium includes but is not limited to anhydrous Ethanol or anhydrous methanol;
    或，所述步骤(2)中，所述分散剂为包括但不限于聚乙二醇，具体的，为聚乙二醇6000；Or, in the step (2), the dispersing agent includes but not limited to polyethylene glycol, specifically, polyethylene glycol 6000;
    或，所述步骤(3)中，所述球磨按照球料重量比10:0.5～1.5加入球磨球，在保护气氛下进行球磨40～50h；具体的，所述保护气氛为氮气；Or, in the step (3), the ball mill is added with ball milling balls according to a weight ratio of 10:0.5 to 1.5 to the ball material, and the ball milling is carried out under a protective atmosphere for 40 to 50 hours; specifically, the protective atmosphere is nitrogen;
    或，所述步骤(3)中，所述球磨球为硬质合金小球YG6或YG8；Or, in described step (3), described ball grinding ball is cemented carbide small ball YG6 or YG8;
    或，所述步骤(3)中，球磨液的干燥方式包括但不限于常压干燥、真空干燥、喷雾干燥或冷冻干燥中的一种；具体的，所述干燥采 用真空干燥，80-120℃下干燥12-24小时；Or, in the step (3), the drying method of the ball milling liquid includes but is not limited to one of atmospheric drying, vacuum drying, spray drying or freeze drying; specifically, the drying adopts vacuum drying at 80-120° C. under drying for 12-24 hours;
    或，所述步骤(3)中，球磨液干燥后经100-120目筛过筛，得到混合粉料；Or, in the step (3), after the ball milling liquid is dried, it is sieved through a 100-120 mesh sieve to obtain a mixed powder;
    或，所述步骤(4)中，所述放电等离子烧结参数：升温速率：在1300℃之前，90-110℃/min，高于1300℃，30-50℃/min；烧结温度1650-1750℃；保温时间20-35min，分别在1600℃和达到烧结温度后保温10-17min；轴向压力25-35MPa。Or, in the step (4), the spark plasma sintering parameters: heating rate: before 1300°C, 90-110°C/min, higher than 1300°C, 30-50°C/min; sintering temperature 1650-1750°C ; The holding time is 20-35min, respectively at 1600℃ and after reaching the sintering temperature for 10-17min; the axial pressure is 25-35MPa.
  8. 如权利要求7所述基于放电等离子烧结的Si 3N 4/TiC陶瓷材料的制备方法，其特征在于，所述制备方法包括以下步骤： The preparation method of the Si 3 N 4 /TiC ceramic material based on spark plasma sintering according to claim 7, wherein the preparation method comprises the following steps:
    (1)按比例称取α-Si 3N 4、TiC粉体，分别加入适量的无水乙醇为分散介质，超声分散并机械搅拌10-20min，制得α-Si 3N 4悬浮液、TiC悬浮液，将两种悬浮液混合得到复相悬浮液； (1) Weigh α-Si 3 N 4 and TiC powder in proportion, add an appropriate amount of anhydrous ethanol as dispersion medium, ultrasonically disperse and mechanically stir for 10-20 min to obtain α-Si 3 N 4 suspension, TiC suspension, the two suspensions are mixed to obtain a complex suspension;
    (2)称取α-Si 3N 4重量的1-5wt％的聚乙二醇6000，以无水乙醇溶解后加入复相悬浮液中然后按比例添加Al 2O 3和Y 2O 3粉体，超声分散并机械搅拌30-50min； (2) Weigh 1-5wt% polyethylene glycol 6000 by weight of α-Si 3 N 4 , dissolve it in absolute ethanol, add it to the multiphase suspension, and then add Al 2 O 3 and Y 2 O 3 powder in proportion body, ultrasonic dispersion and mechanical stirring for 30-50min;
    (3)将步骤(2)所得的最终悬浮液倒入球磨罐，按照球料重量比10:1加入球磨球，在保护气氛下进行球磨48h，将球磨液在真空干燥箱80-120℃下干燥12-24小时，然后经100-120目筛过筛，得到混合粉料，密封保存备用；(3) Pour the final suspension obtained in step (2) into the ball milling tank, add ball milling balls according to the ball-to-material weight ratio of 10:1, carry out ball milling for 48 hours under a protective atmosphere, and place the ball milling liquid in a vacuum drying oven at 80-120° C. Dry for 12-24 hours, then sieve through a 100-120 mesh sieve to obtain mixed powder, which is sealed and stored for later use;
    (4)将步骤(3)得到的混合粉料装入石墨模具中，经冷压成型后放入放电等离子烧结炉中进行烧结。(4) The mixed powder obtained in step (3) is put into a graphite mold, and after being cold-pressed, it is put into a spark plasma sintering furnace for sintering.
  9. 权利要求1-8任一项所述基于放电等离子烧结的Si 3N 4/TiC陶 瓷材料的制备方法制备得到的Si 3N 4/TiC陶瓷材料。 The Si 3 N 4 /TiC ceramic material prepared by the method for preparing a Si 3 N 4 /TiC ceramic material based on spark plasma sintering according to any one of claims 1-8.
  10. 权利要求9所述Si 3N 4/TiC陶瓷材料在生产切削工具、耐磨零件、插件以及航空工业用产品等领域的应用。 The application of the Si 3 N 4 /TiC ceramic material of claim 9 in the production of cutting tools, wear-resistant parts, inserts, and products for the aviation industry.
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