CN117658632A - A kind of high hardness and high wear-resistant ceramic material for ceramic tiles and its preparation method - Google Patents
A kind of high hardness and high wear-resistant ceramic material for ceramic tiles and its preparation method Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 127
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000011159 matrix material Substances 0.000 claims abstract description 74
- 238000005245 sintering Methods 0.000 claims abstract description 47
- 238000003825 pressing Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims description 27
- 238000000498 ball milling Methods 0.000 claims description 26
- 239000003792 electrolyte Substances 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000011812 mixed powder Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims 1
- 229910052911 sodium silicate Inorganic materials 0.000 claims 1
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004408 titanium dioxide Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 238000010586 diagram Methods 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 4
- -1 aluminum ions Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 238000009770 conventional sintering Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
技术领域Technical field
本发明属于材料制备技术领域，具体是指一种瓷砖用高硬度高耐磨陶瓷材料及其制备方法。The invention belongs to the technical field of material preparation, and specifically refers to a high-hardness and high-wear-resistant ceramic material for ceramic tiles and a preparation method thereof.
背景技术Background technique
随着陶瓷材料的不断发展，陶瓷材料凭借其优秀的力学性能被广泛应用于生活中，近年来，市面上出现了一系列高硬度、耐磨陶瓷材料，如金刚釉、耐磨砖等；目前陶瓷材料提升硬度和耐磨性主要是调节釉料的成分来增加玻璃网络结构的致密性，如增加釉料中硅的含量，但传统陶瓷烧成温度在1200℃左右，硅、铝含量的大量增加会导致釉料的温度上升，造成粘度过大，导致表面平整度下降、陶瓷内部气泡不易排出，进而导致陶瓷的综合力学性能下降；日用陶瓷在使用过程中需经受如刀叉等硬质金属的长期刮擦，对陶瓷材料的硬度、耐磨性有更高的要求，因此，市场亟需一种具有高硬度、高耐磨性的陶瓷材料；With the continuous development of ceramic materials, ceramic materials are widely used in life with their excellent mechanical properties. In recent years, a series of high-hardness, wear-resistant ceramic materials have appeared on the market, such as diamond glaze, wear-resistant bricks, etc.; currently The main way to improve the hardness and wear resistance of ceramic materials is to adjust the composition of the glaze to increase the density of the glass network structure, such as increasing the silicon content in the glaze. However, the firing temperature of traditional ceramics is around 1200°C, and the content of silicon and aluminum is large. Increasing the temperature will cause the temperature of the glaze to rise, resulting in excessive viscosity, resulting in a decrease in surface flatness, making it difficult for the air bubbles inside the ceramic to be discharged, and thus a decrease in the comprehensive mechanical properties of the ceramic. Daily ceramics need to withstand hard objects such as knives and forks during use. Long-term scratching of metal places higher requirements on the hardness and wear resistance of ceramic materials. Therefore, the market is in urgent need of a ceramic material with high hardness and high wear resistance;
微弧氧化技术是一种新兴的表面改性技术，具有操控性强、效率高、成本低、污染小等特点，微弧氧化技术制备的膜层硬度高、耐磨及耐蚀性好，具有广阔的应用前景。Micro-arc oxidation technology is an emerging surface modification technology, which has the characteristics of strong controllability, high efficiency, low cost, and low pollution. The film layer prepared by micro-arc oxidation technology has high hardness, good wear resistance and corrosion resistance, and has Broad application prospects.
发明内容Contents of the invention
针对上述情况，为克服现有技术的缺陷，本发明提供了一种瓷砖用高硬度高耐磨陶瓷材料及其制备方法，为了解决陶瓷材料硬度低、耐磨性差的问题，本发明提出通过对原材料进行等离子放电烧结制得陶瓷基体，通过在陶瓷基体进行微弧氧化制备耐磨层的方式，实现了陶瓷材料硬度、耐磨性的提升。In view of the above situation, in order to overcome the shortcomings of the prior art, the present invention provides a high hardness and high wear-resistant ceramic material for ceramic tiles and a preparation method thereof. In order to solve the problems of low hardness and poor wear resistance of ceramic materials, the present invention proposes to The raw materials are subjected to plasma discharge sintering to obtain a ceramic matrix. Micro-arc oxidation is performed on the ceramic matrix to prepare a wear-resistant layer, thereby improving the hardness and wear resistance of the ceramic material.
为了实现上述目的，本发明采取的技术方案如下：本发明提出了一种瓷砖用高硬度高耐磨陶瓷材料，陶瓷材料自下而上具体包括：陶瓷基体8-10mm，耐磨层60-70μm。In order to achieve the above object, the technical solution adopted by the present invention is as follows: The present invention proposes a high hardness and high wear-resistant ceramic material for ceramic tiles. The ceramic material specifically includes from bottom to top: a ceramic matrix of 8-10 mm and a wear-resistant layer of 60-70 μm. .
所述陶瓷基体为经过原材料压制、烧结得到的坯体；The ceramic matrix is a green body obtained by pressing and sintering raw materials;
所述原材料具体包括如下重量份组分：TiO2：80-90份，Cr2O3：75-80份，Nb2O5：135-140份，Ta2O5：220-230份，MoO3：145-160份，C：48-60份。The raw materials specifically include the following components by weight: TiO 2 : 80-90 parts, Cr 2 O 3 : 75-80 parts, Nb 2 O 5 : 135-140 parts, Ta 2 O 5 : 220-230 parts, MoO 3 : 145-160 copies, C: 48-60 copies.
本发明还提供了一种瓷砖用高硬度高耐磨陶瓷材料的制备方法，具体包括如下步骤：The invention also provides a method for preparing high-hardness and high-wear-resistant ceramic materials for ceramic tiles, which specifically includes the following steps:
(1)陶瓷基体制备：称取TiO2、Cr2O3、Nb2O5、Ta2O5、MoO3、C置于滚筒球磨罐中，加入无水乙醇进行球磨，球磨介质为氮化硅，过滤，干燥，研磨过100目筛，制得混合粉体；(1) Ceramic matrix preparation: Weigh TiO 2 , Cr 2 O 3 , Nb 2 O 5 , Ta 2 O 5 , MoO 3 , and C and place them in a drum ball milling tank. Add absolute ethanol for ball milling. The ball milling medium is nitrided. Silicon is filtered, dried, and ground through a 100-mesh sieve to prepare a mixed powder;
(2)陶瓷基体制备：将步骤(1)所得混合粉体置于模具中，采用压片机进行预压处理，将装载有混合粉体的模具置于放电等离子烧结炉中，烧结过程中对模具进行压制，压力设置为3000MPa，采用直流脉冲进行烧结，电流持续15ms，间断3ms作为一个脉冲，10个电流脉冲后间隔5ms，加热保温，以100℃/min的降温速率降温至600℃，随炉冷却，制得陶瓷基体；(2) Preparation of ceramic matrix: Place the mixed powder obtained in step (1) into a mold, use a tablet press for pre-pressing treatment, place the mold loaded with mixed powder into a discharge plasma sintering furnace, and perform pre-pressure treatment during the sintering process. The mold is pressed, the pressure is set to 3000MPa, DC pulse is used for sintering, the current lasts for 15ms, and the interval is 3ms as one pulse. After 10 current pulses, there is an interval of 5ms. Heating and insulation, cooling to 600℃ at a cooling rate of 100℃/min, and then The furnace is cooled to obtain a ceramic matrix;
(3)耐磨层制备：采用2000目砂纸对步骤(2)所得陶瓷基体打磨2min，将打磨后的陶瓷基体置于电解池中，保证电解液可以完全没过陶瓷基体，电解液由Na(PO3)6、Na2SiO3、Na2WO4、NaAlO2与水组成，采用碳棒作为阴极，采用步骤(2)所得陶瓷基体作为阳极，调节电解液pH为10-11，设置正向电流密度5A/dm2，负向电流密度为1A/dm2，频率为500Hz，占空比30％，在5min内将电压从0V快速升高至500V，保持60-80min，冷却，干燥，制得陶瓷材料。(3) Preparation of wear-resistant layer: Use 2000-grit sandpaper to polish the ceramic matrix obtained in step (2) for 2 minutes. Place the polished ceramic matrix in an electrolytic cell to ensure that the electrolyte can completely submerge the ceramic matrix. The electrolyte is composed of Na ( PO 3 ) 6 , Na 2 SiO 3 , Na 2 WO 4 , NaAlO 2 and water are used. A carbon rod is used as the cathode, and the ceramic matrix obtained in step (2) is used as the anode. The pH of the electrolyte is adjusted to 10-11, and the positive direction is set. The current density is 5A/dm 2 , the negative current density is 1A/dm 2 , the frequency is 500Hz, and the duty cycle is 30%. Rapidly increase the voltage from 0V to 500V within 5min, keep it for 60-80min, cool, dry, and make Get ceramic materials.
优选地，在步骤(1)中，球料液比为4:1:2，球磨转速为80-100r/min，球磨时间为22-24h；干燥温度为60-65℃，干燥时间为24h；Preferably, in step (1), the ball-to-liquid ratio is 4:1:2, the ball milling speed is 80-100r/min, the ball milling time is 22-24h; the drying temperature is 60-65°C, and the drying time is 24h;
优选地，在步骤(2)中，预压处理压力设置为10MPa，预压处理时间为1.5-2h；加热速率为100℃/min，加热温度为1600-1700℃，保温时间为10-12min；Preferably, in step (2), the prepressure treatment pressure is set to 10MPa, the prepressure treatment time is 1.5-2h; the heating rate is 100°C/min, the heating temperature is 1600-1700°C, and the heat preservation time is 10-12min;
优选地，在步骤(3)中，Na(PO3)6与Na2SiO3的质量比为1:1，Na2WO4与NaAlO2的质量比为1:1，Na2SiO3与NaAlO2的质量比为2:1，电解液浓度为1.2-1.25g/cm3；干燥温度为60-65℃，干燥时间为8-10h。Preferably, in step (3), the mass ratio of Na(PO 3 ) 6 to Na 2 SiO 3 is 1:1, the mass ratio of Na 2 WO 4 to NaAlO 2 is 1:1, and the mass ratio of Na 2 SiO 3 to NaAlO The mass ratio of 2 is 2:1, the electrolyte concentration is 1.2-1.25g/cm 3 ; the drying temperature is 60-65°C, and the drying time is 8-10h.
本发明取得的有益效果如下：The beneficial effects achieved by the present invention are as follows:
本发明通过对原材料采用放电烧结制成陶瓷基体，采用微弧氧化制成耐磨层的方式，实现了陶瓷耐磨性、硬度的增强；原材料经过放电等离子烧结制成陶瓷基体，放电等离子烧结过程中会产生脉冲电流，脉冲电流中含有等离子体，烧结过程同时施加压力，等离子体与压力的共同作用有利于降低粉末的烧结温度，使粉末快速完成烧结、致密化；放电等离子烧结具有加热均匀、升温速度快、烧结温度低、烧结时间短、生产效率高的特点，升温速度快、烧结温度低、烧结时间短可以避免晶粒长大，陶瓷晶粒细小，产生细晶强化作用，组织致密度上升，陶瓷的硬度、耐磨性升高；加热均匀保证了陶瓷晶粒大小均匀，有效减少了陶瓷材料内部产生应力集中，陶瓷综合力学性能升高；电解液中的铝离子、钨离子在陶瓷基体表面形成耐磨层，在电流和压力的作用下发生微弧氧化，形成氧化钨和氧化铝复合金属层，氧化铝为六方结构，具有极高的硬度，可以显著提升陶瓷材料的硬度和耐磨性；耐磨层由晶相和非晶相组成，使耐磨层硬度和变形特性得到结合，耐磨层的耐磨性能提升；耐磨层从陶瓷基体上原位生长，与陶瓷基体冶金结合，耐磨层与陶瓷基体之间结合更加紧密，陶瓷材料的硬度和耐磨性得到增强。The present invention realizes the enhancement of the wear resistance and hardness of the ceramic by using discharge sintering of raw materials to form a ceramic matrix, and using micro-arc oxidation to form a wear-resistant layer; the raw materials are made into a ceramic matrix through discharge plasma sintering, and the discharge plasma sintering process A pulse current will be generated in the pulse current, which contains plasma, and pressure is applied at the same time during the sintering process. The combined effect of plasma and pressure is conducive to reducing the sintering temperature of the powder, allowing the powder to quickly complete sintering and densification; discharge plasma sintering has the characteristics of uniform heating, Fast heating speed, low sintering temperature, short sintering time, and high production efficiency. Fast heating speed, low sintering temperature, and short sintering time can avoid grain growth. Ceramic grains are small, resulting in fine grain strengthening and tissue density. As the temperature rises, the hardness and wear resistance of the ceramic increase; uniform heating ensures uniform ceramic grain size, effectively reducing stress concentration within the ceramic material, and the comprehensive mechanical properties of the ceramic increase; the aluminum ions and tungsten ions in the electrolyte in the ceramic A wear-resistant layer is formed on the surface of the substrate, and micro-arc oxidation occurs under the action of current and pressure, forming a composite metal layer of tungsten oxide and aluminum oxide. Aluminum oxide has a hexagonal structure and extremely high hardness, which can significantly improve the hardness and resistance of ceramic materials. Wear resistance; the wear-resistant layer is composed of crystalline phase and amorphous phase, which combines the hardness and deformation characteristics of the wear-resistant layer, and improves the wear-resistant performance of the wear-resistant layer; the wear-resistant layer grows in situ from the ceramic matrix and metallurgically interacts with the ceramic matrix The combination between the wear-resistant layer and the ceramic matrix is closer, and the hardness and wear resistance of the ceramic material are enhanced.
附图说明Description of drawings
图1为本发明所得的一种瓷砖用高硬度高耐磨陶瓷材料的显微硬度结果图；Figure 1 is a diagram showing the microhardness results of a high-hardness and high-wear-resistant ceramic material for ceramic tiles obtained by the present invention;
图2为本发明所得的一种瓷砖用高硬度高耐磨陶瓷材料的耐磨实验结果图；Figure 2 is a graph showing the wear resistance test results of a high-hardness and wear-resistant ceramic material for ceramic tiles obtained by the present invention;
图3为本发明所得的一种瓷砖用高硬度高耐磨陶瓷材料的表面SEM结果图；Figure 3 is a surface SEM result diagram of a high-hardness and high-wear-resistant ceramic material for ceramic tiles obtained by the present invention;
图4为本发明所得的一种瓷砖用高硬度高耐磨陶瓷材料的熔合截面SEM结果图；Figure 4 is a SEM result diagram of the fusion cross-section of a high-hardness and high-wear-resistant ceramic material for ceramic tiles obtained by the present invention;
图5为本发明所得的一种瓷砖用高硬度高耐磨陶瓷材料的宏观形貌结果图。Figure 5 is a macroscopic morphology result diagram of a high-hardness and high-wear-resistant ceramic material for ceramic tiles obtained by the present invention.
附图用来提供对本发明的进一步理解，并且构成说明书的一部分，与本发明的实施例一起用于解释本发明，并不构成对本发明的限制。The drawings are used to provide a further understanding of the present invention and constitute a part of the specification. They are used to explain the present invention together with the embodiments of the present invention and do not constitute a limitation of the present invention.
具体实施方式Detailed ways
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例；基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, not all of them; based on The embodiments of the present invention and all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.
除非另行定义，文中所使用的所有专业与科学用语与本领域技术人员所熟悉的意义相同。此外，任何与所记载内容相似或均等的方法及材料皆可应用于本发明中。文中所述的较佳实施方法与材料仅作示范之用，但不能限制本申请的内容。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as familiar to one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described can be used in the present invention. The preferred implementation methods and materials described in this article are for demonstration purposes only, but do not limit the content of this application.
下述实施例中的实验方法，如无特殊说明，均为常规方法；下述实施例中所用的试验材料，如无特殊说明，均为从商业渠道购买得到的。The experimental methods in the following examples, unless otherwise specified, are all conventional methods; the test materials used in the following examples, unless otherwise specified, are all purchased from commercial channels.
TiO2(CasNo:1317-70-0)，购于北京伊诺凯科技有限公司，货号A60660；TiO 2 (CasNo: 1317-70-0), purchased from Beijing Inokai Technology Co., Ltd., item number A60660;
Cr2O3(CasNo:1308-38-9)，购于北京伊诺凯科技有限公司，货号A95953；Cr 2 O 3 (CasNo: 1308-38-9), purchased from Beijing Inokai Technology Co., Ltd., item number A95953;
Nb2O5(CasNo:1313-96-8)，购于北京伊诺凯科技有限公司，货号A81394；Nb 2 O 5 (CasNo: 1313-96-8), purchased from Beijing Inokai Technology Co., Ltd., item number A81394;
Ta2O5(CasNo:1314-61-0)，购于北京伊诺凯科技有限公司，货号A54445；Ta 2 O 5 (CasNo: 1314-61-0), purchased from Beijing Inokai Technology Co., Ltd., product number A54445;
MoO3(CasNo:1313-27-5)，购于北京伊诺凯科技有限公司，货号A30070；MoO 3 (CasNo: 1313-27-5), purchased from Beijing Inokai Technology Co., Ltd., item number A30070;
C(CasNo:7440-44-0)，购于北京伊诺凯科技有限公司，货号I11113；C (CasNo:7440-44-0), purchased from Beijing Inokai Technology Co., Ltd., item number I11113;
无水乙醇(CasNo:64-17-5)，购于北京伊诺凯科技有限公司，货号G00004；Absolute ethanol (CasNo: 64-17-5), purchased from Beijing Inokai Technology Co., Ltd., item number G00004;
Na(PO3)6(CasNo:10124-56-8)，购于北京伊诺凯科技有限公司，货号A80460；Na(PO 3 ) 6 (CasNo:10124-56-8), purchased from Beijing Inokai Technology Co., Ltd., item number A80460;
Na2SiO3(CasNo:10213-79-3)，购于北京伊诺凯科技有限公司，货号A44948；Na 2 SiO 3 (CasNo: 10213-79-3), purchased from Beijing Inokai Technology Co., Ltd., item number A44948;
Na2WO4(CasNo:10213-10-2)，购于北京伊诺凯科技有限公司，货号A24099；Na 2 WO 4 (CasNo:10213-10-2), purchased from Beijing Inokai Technology Co., Ltd., item number A24099;
NaAlO2(CasNo:11138-49-1)，购于北京伊诺凯科技有限公司，货号A61847。NaAlO 2 (CasNo: 11138-49-1), purchased from Beijing Inokai Technology Co., Ltd., product number A61847.
实施例1Example 1
一种瓷砖用高硬度高耐磨陶瓷材料，陶瓷材料自下而上具体包括：陶瓷基体8mm，耐磨层60μm。A high-hardness and high-wear-resistant ceramic material for ceramic tiles. The ceramic material specifically includes from bottom to top: a ceramic base of 8 mm and a wear-resistant layer of 60 μm.
所述陶瓷基体为经过原材料压制、烧结得到的坯体；The ceramic matrix is a green body obtained by pressing and sintering raw materials;
所述原材料具体包括如下重量份组分：TiO2：80份，Cr2O3：75份，Nb2O5：135份，Ta2O5：220份，MoO3：145份，C：48份。The raw materials specifically include the following components by weight: TiO 2 : 80 parts, Cr 2 O 3 : 75 parts, Nb 2 O 5 : 135 parts, Ta 2 O 5 : 220 parts, MoO 3 : 145 parts, C: 48 share.
本发明还提供了一种瓷砖用高硬度高耐磨陶瓷材料的制备方法，具体包括如下步骤：The invention also provides a method for preparing high-hardness and high-wear-resistant ceramic materials for ceramic tiles, which specifically includes the following steps:
(1)陶瓷基体制备：称取TiO2、Cr2O3、Nb2O5、Ta2O5、MoO3、C置于滚筒球磨罐中，加入无水乙醇进行球磨，球磨介质为氮化硅，球料液比为4:1:2，在球磨转速为80r/min的条件下球磨22h，过滤，在60℃下干燥24h，研磨过100目筛，制得混合粉体；(1) Ceramic matrix preparation: Weigh TiO 2 , Cr 2 O 3 , Nb 2 O 5 , Ta 2 O 5 , MoO 3 , and C and place them in a drum ball milling tank. Add absolute ethanol for ball milling. The ball milling medium is nitrided. Silicon, the ball-to-liquid ratio is 4:1:2, ball-mill for 22 hours at a ball-milling speed of 80 r/min, filter, dry at 60°C for 24 hours, and grind through a 100-mesh sieve to prepare a mixed powder;
(2)陶瓷基体制备：将步骤(1)所得混合粉体置于模具中，采用压片机进行预压处理，预压处理压力设置为10MPa，预压处理时间为1.5h，将装载有混合粉体的模具置于放电等离子烧结炉中，烧结过程中对模具进行压制，压力设置为3000MPa，采用直流脉冲进行烧结，电流持续15ms，间断3ms作为一个脉冲，10个电流脉冲后间隔5ms，以100℃/min的升温速率加热至1600℃，保温10min，以100℃/min的降温速率降温至600℃，随炉冷却，制得陶瓷基体；(2) Ceramic matrix preparation: Place the mixed powder obtained in step (1) into the mold, and use a tablet press for pre-pressing treatment. The pre-pressing treatment pressure is set to 10MPa, and the pre-pressing treatment time is 1.5h. The mixed powder will be loaded with The powder mold is placed in a discharge plasma sintering furnace. The mold is pressed during the sintering process. The pressure is set to 3000MPa. DC pulses are used for sintering. The current lasts for 15ms and is interrupted by 3ms as one pulse. After 10 current pulses, the interval is 5ms. Heating to 1600°C at a heating rate of 100°C/min, holding for 10 minutes, cooling to 600°C at a cooling rate of 100°C/min, and cooling with the furnace to prepare a ceramic matrix;
(3)耐磨层制备：采用2000目砂纸对步骤(2)所得陶瓷基体打磨2min，将打磨后的陶瓷基体置于电解池中，保证电解液可以完全没过陶瓷基体，电解液由Na(PO3)6、Na2SiO3、Na2WO4、NaAlO2与水组成，Na(PO3)6与Na2SiO3的质量比为1:1，Na2WO4与NaAlO2的质量比为1:1，Na2SiO3与NaAlO2的质量比为2:1，电解液浓度为1.2g/cm3，采用碳棒作为阴极，采用步骤(2)所得陶瓷基体作为阳极，调节电解液pH为10，设置正向电流密度5A/dm2，负向电流密度为1A/dm2，频率为500Hz，占空比30％，在5min内将电压从0V快速升高至500V，保持60min，冷却，在60℃下干燥8h，制得陶瓷材料。(3) Preparation of wear-resistant layer: Use 2000-grit sandpaper to polish the ceramic matrix obtained in step (2) for 2 minutes. Place the polished ceramic matrix in an electrolytic cell to ensure that the electrolyte can completely submerge the ceramic matrix. The electrolyte is composed of Na ( PO 3 ) 6 , Na 2 SiO 3 , Na 2 WO 4 , NaAlO 2 and water, the mass ratio of Na(PO 3 ) 6 to Na 2 SiO 3 is 1:1, the mass ratio of Na 2 WO 4 to NaAlO 2 is 1:1, the mass ratio of Na 2 SiO 3 to NaAlO 2 is 2:1, the electrolyte concentration is 1.2g/cm 3 , a carbon rod is used as the cathode, and the ceramic matrix obtained in step (2) is used as the anode, and the electrolyte is adjusted The pH is 10, set the forward current density to 5A/dm 2 , the negative current density to 1A/dm 2 , the frequency to 500Hz, and the duty cycle to 30%. Rapidly increase the voltage from 0V to 500V within 5min and maintain it for 60min. Cool and dry at 60°C for 8 hours to prepare ceramic materials.
实施例2Example 2
一种瓷砖用高硬度高耐磨陶瓷材料，陶瓷材料自下而上具体包括：陶瓷基体8mm，耐磨层60μm。A high-hardness and high-wear-resistant ceramic material for ceramic tiles. The ceramic material specifically includes from bottom to top: a ceramic base of 8 mm and a wear-resistant layer of 60 μm.
所述陶瓷基体为经过原材料压制、烧结得到的坯体；The ceramic matrix is a green body obtained by pressing and sintering raw materials;
所述原材料具体包括如下重量份组分：TiO2：80份，Cr2O3：75份，Nb2O5：135份，Ta2O5：220份，MoO3：145份，C：48份。The raw materials specifically include the following components by weight: TiO 2 : 80 parts, Cr 2 O 3 : 75 parts, Nb 2 O 5 : 135 parts, Ta 2 O 5 : 220 parts, MoO 3 : 145 parts, C: 48 share.
本发明还提供了一种瓷砖用高硬度高耐磨陶瓷材料的制备方法，具体包括如下步骤：The invention also provides a method for preparing high-hardness and high-wear-resistant ceramic materials for ceramic tiles, which specifically includes the following steps:
(1)陶瓷基体制备：称取TiO2、Cr2O3、Nb2O5、Ta2O5、MoO3、C置于滚筒球磨罐中，加入无水乙醇进行球磨，球磨介质为氮化硅，球料液比为4:1:2，在球磨转速为100r/min的条件下球磨24h，过滤，在65℃下干燥24h，研磨过100目筛，制得混合粉体；(1) Ceramic matrix preparation: Weigh TiO 2 , Cr 2 O 3 , Nb 2 O 5 , Ta 2 O 5 , MoO 3 , and C and place them in a drum ball milling tank. Add absolute ethanol for ball milling. The ball milling medium is nitrided. Silicon, the ball-to-liquid ratio is 4:1:2, ball-mill for 24 hours at a ball-milling speed of 100 r/min, filter, dry at 65°C for 24 hours, and grind through a 100-mesh sieve to prepare a mixed powder;
(2)陶瓷基体制备：将步骤(1)所得混合粉体置于模具中，采用压片机进行预压处理，预压处理压力设置为10MPa，预压处理时间为2h，将装载有混合粉体的模具置于放电等离子烧结炉中，烧结过程中对模具进行压制，压力设置为3000MPa，采用直流脉冲进行烧结，电流持续15ms，间断3ms作为一个脉冲，10个电流脉冲后间隔5ms，以100℃/min的加热速率加热至1700℃，保温12min，以100℃/min的降温速率降温至600℃，随炉冷却，制得陶瓷基体；(2) Preparation of ceramic matrix: Place the mixed powder obtained in step (1) into the mold, and use a tablet press for pre-pressing treatment. The pre-pressing treatment pressure is set to 10MPa, and the pre-pressing treatment time is 2 hours. The mixed powder will be loaded with The solid mold is placed in a discharge plasma sintering furnace. The mold is pressed during the sintering process. The pressure is set to 3000MPa. DC pulses are used for sintering. The current lasts for 15ms and is interrupted by 3ms as one pulse. After 10 current pulses, the interval is 5ms and the interval is 100. Heating to 1700°C at a heating rate of ℃/min, holding for 12 minutes, cooling to 600°C at a cooling rate of 100°C/min, and cooling with the furnace to prepare a ceramic matrix;
(3)耐磨层制备：采用2000目砂纸对步骤(2)所得陶瓷基体打磨2min，将打磨后的陶瓷基体置于电解池中，保证电解液可以完全没过陶瓷基体，电解液由Na(PO3)6、Na2SiO3、Na2WO4、NaAlO2与水组成，Na(PO3)6与Na2SiO3的质量比为1:1，Na2WO4与NaAlO2的质量比为1:1，Na2SiO3与NaAlO2的质量比为2:1，电解液浓度为1.25g/cm3，采用碳棒作为阴极，采用步骤(2)所得陶瓷基体作为阳极，调节电解液pH为11，设置正向电流密度5A/dm2，负向电流密度为1A/dm2，频率为500Hz，占空比30％，在5min内将电压从0V快速升高至500V，保持80min，冷却，在65℃下干燥10h，制得陶瓷材料。(3) Preparation of wear-resistant layer: Use 2000-grit sandpaper to polish the ceramic matrix obtained in step (2) for 2 minutes. Place the polished ceramic matrix in the electrolytic cell to ensure that the electrolyte can completely submerge the ceramic matrix. The electrolyte is composed of Na ( PO 3 ) 6 , Na 2 SiO 3 , Na 2 WO 4 , NaAlO 2 and water, the mass ratio of Na(PO 3 ) 6 to Na 2 SiO 3 is 1:1, the mass ratio of Na 2 WO 4 to NaAlO 2 is 1:1, the mass ratio of Na 2 SiO 3 to NaAlO 2 is 2:1, the electrolyte concentration is 1.25g/cm 3 , a carbon rod is used as the cathode, and the ceramic matrix obtained in step (2) is used as the anode, and the electrolyte is adjusted The pH is 11, set the forward current density to 5A/dm 2 , the negative current density to 1A/dm 2 , the frequency to 500Hz, and the duty cycle to 30%. Rapidly increase the voltage from 0V to 500V within 5min and keep it for 80min. Cool and dry at 65°C for 10 hours to prepare ceramic materials.
实施例3Example 3
一种瓷砖用高硬度高耐磨陶瓷材料，陶瓷材料自下而上具体包括：陶瓷基体10mm，耐磨层70μm。A high-hardness and high-wear-resistant ceramic material for ceramic tiles. The ceramic material specifically includes from bottom to top: a ceramic base of 10 mm and a wear-resistant layer of 70 μm.
所述陶瓷基体为经过原材料压制、烧结得到的坯体；The ceramic matrix is a green body obtained by pressing and sintering raw materials;
所述原材料具体包括如下重量份组分：TiO2：90份，Cr2O3：80份，Nb2O5：140份，Ta2O5：230份，MoO3：160份，C：60份。The raw materials specifically include the following components by weight: TiO 2 : 90 parts, Cr 2 O 3 : 80 parts, Nb 2 O 5 : 140 parts, Ta 2 O 5 : 230 parts, MoO 3 : 160 parts, C: 60 share.
本发明还提供了一种瓷砖用高硬度高耐磨陶瓷材料的制备方法，具体包括如下步骤：The invention also provides a method for preparing high-hardness and high-wear-resistant ceramic materials for ceramic tiles, which specifically includes the following steps:
(1)陶瓷基体制备：称取TiO2、Cr2O3、Nb2O5、Ta2O5、MoO3、C置于滚筒球磨罐中，加入无水乙醇进行球磨，球磨介质为氮化硅，球料液比为4:1:2，在球磨转速为80r/min的条件下球磨22h，过滤，在60℃下干燥24h，研磨过100目筛，制得混合粉体；(1) Ceramic matrix preparation: Weigh TiO 2 , Cr 2 O 3 , Nb 2 O 5 , Ta 2 O 5 , MoO 3 , and C and place them in a drum ball milling tank. Add absolute ethanol for ball milling. The ball milling medium is nitrided. Silicon, the ball-to-liquid ratio is 4:1:2, ball-mill for 22 hours at a ball-milling speed of 80 r/min, filter, dry at 60°C for 24 hours, and grind through a 100-mesh sieve to prepare a mixed powder;
(2)陶瓷基体制备：将步骤(1)所得混合粉体置于模具中，采用压片机进行预压处理，预压处理压力设置为10MPa，预压处理时间为1.5h，将装载有混合粉体的模具置于放电等离子烧结炉中，烧结过程中对模具进行压制，压力设置为3000MPa，采用直流脉冲进行烧结，电流持续15ms，间断3ms作为一个脉冲，10个电流脉冲后间隔5ms，以100℃/min的加热速率加热至1600℃，保温10min，以100℃/min的降温速率降温至600℃，随炉冷却，制得陶瓷基体；(2) Ceramic matrix preparation: Place the mixed powder obtained in step (1) into the mold, and use a tablet press for pre-pressing treatment. The pre-pressing treatment pressure is set to 10MPa, and the pre-pressing treatment time is 1.5h. The mixed powder will be loaded with The powder mold is placed in a discharge plasma sintering furnace. The mold is pressed during the sintering process. The pressure is set to 3000MPa. DC pulses are used for sintering. The current lasts for 15ms and is interrupted by 3ms as one pulse. After 10 current pulses, the interval is 5ms. Heating to 1600°C at a heating rate of 100°C/min, holding for 10 minutes, cooling to 600°C at a cooling rate of 100°C/min, and cooling with the furnace to prepare a ceramic matrix;
(3)耐磨层制备：采用2000目砂纸对步骤(2)所得陶瓷基体打磨2min，将打磨后的陶瓷基体置于电解池中，保证电解液可以完全没过陶瓷基体，电解液由Na(PO3)6、Na2SiO3、Na2WO4、NaAlO2与水组成，Na(PO3)6与Na2SiO3的质量比为1:1，Na2WO4与NaAlO2的质量比为1:1，Na2SiO3与NaAlO2的质量比为2:1，电解液浓度为1.2g/cm3，采用碳棒作为阴极，采用步骤(2)所得陶瓷基体作为阳极，调节电解液pH为10，设置正向电流密度5A/dm2，负向电流密度为1A/dm2，频率为500Hz，占空比30％，在5min内将电压从0V快速升高至500V，保持60min，冷却，在60℃下干燥8h，制得陶瓷材料。(3) Preparation of wear-resistant layer: Use 2000-grit sandpaper to polish the ceramic matrix obtained in step (2) for 2 minutes. Place the polished ceramic matrix in an electrolytic cell to ensure that the electrolyte can completely submerge the ceramic matrix. The electrolyte is composed of Na ( PO 3 ) 6 , Na 2 SiO 3 , Na 2 WO 4 , NaAlO 2 and water, the mass ratio of Na(PO 3 ) 6 to Na 2 SiO 3 is 1:1, the mass ratio of Na 2 WO 4 to NaAlO 2 is 1:1, the mass ratio of Na 2 SiO 3 to NaAlO 2 is 2:1, the electrolyte concentration is 1.2g/cm 3 , a carbon rod is used as the cathode, and the ceramic matrix obtained in step (2) is used as the anode, and the electrolyte is adjusted The pH is 10, set the forward current density to 5A/dm 2 , the negative current density to 1A/dm 2 , the frequency to 500Hz, and the duty cycle to 30%. Rapidly increase the voltage from 0V to 500V within 5min and maintain it for 60min. Cool and dry at 60°C for 8 hours to prepare ceramic materials.
实施例4Example 4
一种瓷砖用高硬度高耐磨陶瓷材料，陶瓷材料自下而上具体包括：陶瓷基体10mm，耐磨层70μm。A high hardness and high wear-resistant ceramic material for ceramic tiles. The ceramic material specifically includes from bottom to top: a ceramic base of 10 mm and a wear-resistant layer of 70 μm.
所述陶瓷基体为经过原材料压制、烧结得到的坯体；The ceramic matrix is a green body obtained by pressing and sintering raw materials;
所述原材料具体包括如下重量份组分：TiO2：90份，Cr2O3：80份，Nb2O5：140份，Ta2O5：230份，MoO3：160份，C：60份。The raw materials specifically include the following components by weight: TiO 2 : 90 parts, Cr 2 O 3 : 80 parts, Nb 2 O 5 : 140 parts, Ta 2 O 5 : 230 parts, MoO 3 : 160 parts, C: 60 share.
本发明还提供了一种瓷砖用高硬度高耐磨陶瓷材料的制备方法，具体包括如下步骤：The invention also provides a method for preparing high-hardness and high-wear-resistant ceramic materials for ceramic tiles, which specifically includes the following steps:
(1)陶瓷基体制备：称取TiO2、Cr2O3、Nb2O5、Ta2O5、MoO3、C置于滚筒球磨罐中，加入无水乙醇进行球磨，球磨介质为氮化硅，球料液比为4:1:2，在球磨转速为100r/min的条件下球磨24h，过滤，在65℃下干燥24h，研磨过100目筛，制得混合粉体；(1) Ceramic matrix preparation: Weigh TiO 2 , Cr 2 O 3 , Nb 2 O 5 , Ta 2 O 5 , MoO 3 , and C and place them in a drum ball milling tank. Add absolute ethanol for ball milling. The ball milling medium is nitrided. Silicon, the ball-to-liquid ratio is 4:1:2, ball-mill for 24 hours at a ball-milling speed of 100 r/min, filter, dry at 65°C for 24 hours, and grind through a 100-mesh sieve to prepare a mixed powder;
(2)陶瓷基体制备：将步骤(1)所得混合粉体置于模具中，采用压片机进行预压处理，预压处理压力设置为10MPa，预压处理时间为2h，将装载有混合粉体的模具置于放电等离子烧结炉中，烧结过程中对模具进行压制，压力设置为3000MPa，采用直流脉冲进行烧结，电流持续15ms，间断3ms作为一个脉冲，10个电流脉冲后间隔5ms，以100℃/min的加热速率加热至1700℃，保温12min，以100℃/min的降温速率降温至600℃，随炉冷却，制得陶瓷基体；(2) Preparation of ceramic matrix: Place the mixed powder obtained in step (1) into the mold, and use a tablet press for pre-pressing treatment. The pre-pressing treatment pressure is set to 10MPa, and the pre-pressing treatment time is 2 hours. The mixed powder will be loaded with The solid mold is placed in a discharge plasma sintering furnace. The mold is pressed during the sintering process. The pressure is set to 3000MPa. DC pulses are used for sintering. The current lasts for 15ms and is interrupted by 3ms as one pulse. After 10 current pulses, the interval is 5ms and the interval is 100. Heating to 1700°C at a heating rate of ℃/min, holding for 12 minutes, cooling to 600°C at a cooling rate of 100°C/min, and cooling with the furnace to prepare a ceramic matrix;
(3)耐磨层制备：采用2000目砂纸对步骤(2)所得陶瓷基体打磨2min，将打磨后的陶瓷基体置于电解池中，保证电解液可以完全没过陶瓷基体，电解液由Na(PO3)6、Na2SiO3、Na2WO4、NaAlO2与水组成，Na(PO3)6与Na2SiO3的质量比为1:1，Na2WO4与NaAlO2的质量比为1:1，Na2SiO3与NaAlO2的质量比为2:1，电解液浓度为1.25g/cm3，采用碳棒作为阴极，采用步骤(2)所得陶瓷基体作为阳极，调节电解液pH为11，设置正向电流密度5A/dm2，负向电流密度为1A/dm2，频率为500Hz，占空比30％，在5min内将电压从0V快速升高至500V，保持80min，冷却，在65℃下干燥10h，制得陶瓷材料。(3) Preparation of wear-resistant layer: Use 2000-grit sandpaper to polish the ceramic matrix obtained in step (2) for 2 minutes. Place the polished ceramic matrix in an electrolytic cell to ensure that the electrolyte can completely submerge the ceramic matrix. The electrolyte is composed of Na( PO 3 ) 6 , Na 2 SiO 3 , Na 2 WO 4 , NaAlO 2 and water, the mass ratio of Na(PO 3 ) 6 to Na 2 SiO 3 is 1:1, the mass ratio of Na 2 WO 4 to NaAlO 2 is 1:1, the mass ratio of Na 2 SiO 3 to NaAlO 2 is 2:1, the electrolyte concentration is 1.25g/cm 3 , a carbon rod is used as the cathode, and the ceramic matrix obtained in step (2) is used as the anode, and the electrolyte is adjusted The pH is 11, set the forward current density to 5A/dm 2 , the negative current density to 1A/dm 2 , the frequency to 500Hz, and the duty cycle to 30%. Rapidly increase the voltage from 0V to 500V within 5min and keep it for 80min. Cool and dry at 65°C for 10 hours to prepare ceramic materials.
对比例1Comparative example 1
本对比例提供一种瓷砖用高硬度高耐磨陶瓷材料及其制备方法，其与实施例1的区别仅在于陶瓷基体采用常规烧结工艺来代替等离子放电烧结工艺，其余组分、组分含量与实施例1相同。This comparative example provides a high hardness and high wear-resistant ceramic material for ceramic tiles and a preparation method thereof. The only difference from Example 1 is that the ceramic matrix adopts a conventional sintering process instead of a plasma discharge sintering process. The remaining components and component contents are the same as those in Example 1. Same as Example 1.
对比例2Comparative example 2
本对比例提供一种瓷砖用高硬度高耐磨陶瓷材料及其制备方法，其与实施例1的区别仅在于所有组分中不包含耐磨层，其余组分、组分含量与实施例1相同。This comparative example provides a high-hardness and high-wear-resistant ceramic material for ceramic tiles and a preparation method thereof. The only difference between it and Example 1 is that all components do not include a wear-resistant layer. The remaining components and component contents are the same as those in Example 1. same.
实验例Experimental example
1、显微硬度测量1. Microhardness measurement
本发明采用维氏硬度计对本发明实施例1-4和对比例1-2进行硬度测定，采用0.02kg的试验力，施压15s。The present invention uses a Vickers hardness tester to measure the hardness of Examples 1-4 and Comparative Examples 1-2 of the present invention, using a test force of 0.02kg and applying pressure for 15 seconds.
2、耐磨实验2. Wear resistance test
将本发明实施例1-4和对比例1-2所得陶瓷材料加工为尺寸为15mm*20mm*4mm，使用UMT-TriboLab摩擦磨损试验机测试陶瓷层的干摩擦性能，选择GCr15钢球作为磨件，摩擦位移设定为5mm，摩擦频率选择20Hz，摩擦时间为10min，将磨损粉末收集，采用CP225D高精度分析天平称量，精度高达0.01mg，记录磨损量。The ceramic materials obtained in Examples 1-4 of the present invention and Comparative Examples 1-2 were processed into a size of 15mm*20mm*4mm. The UMT-TriboLab friction and wear testing machine was used to test the dry friction performance of the ceramic layer. GCr15 steel balls were selected as the abrasive parts. , the friction displacement is set to 5mm, the friction frequency is selected to 20Hz, the friction time is 10min, the wear powder is collected, weighed using a CP225D high-precision analytical balance, with an accuracy of up to 0.01mg, and the wear amount is recorded.
3、SEM分析3. SEM analysis
本发明采用jsm-6480型扫描电子显微镜对实施例1所得陶瓷材料进行微观结构观察。The present invention uses a jsm-6480 scanning electron microscope to observe the microstructure of the ceramic material obtained in Example 1.
4、宏观形貌观察4. Macromorphological observation
本发明采用奥林巴斯OLS4000激光共聚焦显微镜对实施例1所得陶瓷材料进行宏观形貌观察。The present invention uses an Olympus OLS4000 laser confocal microscope to observe the macroscopic morphology of the ceramic material obtained in Example 1.
结果分析Result analysis
图1为本发明所得的一种瓷砖用高硬度高耐磨陶瓷材料的显微硬度结果图，如图，实施例1-4的显微硬度均大于1350HV0.02，对比例1的显微硬度小于1150HV0.02，对比例2的显微硬度小于1100HV0.02；Figure 1 is a diagram of the microhardness results of a high-hardness and wear-resistant ceramic material for ceramic tiles obtained by the present invention. As shown in the figure, the microhardness of Examples 1-4 are all greater than 1350HV0.02, and the microhardness of Comparative Example 1 Less than 1150HV0.02, the microhardness of Comparative Example 2 is less than 1100HV0.02;
图2为本发明所得的一种瓷砖用高硬度高耐磨陶瓷材料的耐磨实验结果图，如图，实施例1-4与对比例1的磨损量均小于0.2mg，对比例2的磨损量大于0.6mg；Figure 2 is a graph showing the wear resistance test results of a high hardness and high wear-resistant ceramic material for ceramic tiles obtained by the present invention. As shown in the figure, the wear amounts of Examples 1-4 and Comparative Example 1 are both less than 0.2mg, and the wear of Comparative Example 2 The amount is greater than 0.6mg;
根据图1和图2的结果分析，与对比例1相比，放电等离子烧结具有加热均匀、升温速度快、烧结温度低、烧结时间短、生产效率高的特点，原材料经过放电等离子烧结制成陶瓷基体，放电等离子烧结过程中，脉冲电流中的等离子体与压力共同作用于陶瓷基体上，有利于降低粉末的烧结温度，放电等离子烧结以极大的升温速度在短时间内完成烧结，有效避免了晶粒长大，陶瓷基体中晶粒细小，产生细晶强化作用，组织致密度、晶界数目上升，位错在陶瓷基体中滑移的阻碍增加，位错滑移的距离变长，位错运动需要消耗更多的能量，陶瓷基体的硬度、耐磨性升高；放电等离子烧结使得陶瓷基体加热均匀，保证了陶瓷晶粒大小均匀，有效减少了陶瓷基体中少数晶粒的过分长大，有效避免了陶瓷材料内部产生应力集中，陶瓷基体的硬度、耐磨性增强；由于对比例1包含耐磨层，故对比例1中的磨损量与实施例1-4相差不大，由于对比例1中陶瓷基体由常规烧结方式制备，常规烧结方式中升温速度仅为5-15℃/min，晶粒在高温下容易发生晶体长大、甚至是晶粒二次再结晶现象，陶瓷基体中晶界数目降低，陶瓷的硬度显著下降；与对比例2相比，电解液中的铝离子、钨离子在陶瓷基体表面形成耐磨层，在电流和压力的作用下发生微弧氧化，形成氧化钨和氧化铝复合金属层，氧化铝为六方结构，具有极高的硬度，可以显著提升陶瓷材料的硬度和耐磨性；耐磨层由晶相和非晶相组成，使耐磨层硬度和变形特性得到结合，耐磨层的耐磨性能提升；耐磨层从陶瓷基体上原位生长，与陶瓷基体冶金结合，耐磨层与陶瓷基体之间结合更加紧密，陶瓷材料的硬度和耐磨性得到增强；由于对比例2中不包含耐磨层，耐磨层中的氧化铝、氧化钨成分具有较高的硬度，可以提供良好的耐磨性，相对于实施例1-4，对比例2的显微硬度、耐磨性显著下降。According to the analysis of the results in Figures 1 and 2, compared with Comparative Example 1, discharge plasma sintering has the characteristics of uniform heating, fast temperature rise, low sintering temperature, short sintering time, and high production efficiency. The raw materials are made into ceramics through discharge plasma sintering. Substrate, during the discharge plasma sintering process, the plasma and pressure in the pulse current act together on the ceramic substrate, which is beneficial to reducing the sintering temperature of the powder. The discharge plasma sintering completes the sintering in a short time at a very high temperature rise rate, effectively avoiding The grains grow larger and the grains in the ceramic matrix become smaller, resulting in fine grain strengthening. The density of the structure and the number of grain boundaries increase. The obstacles to dislocation slip in the ceramic matrix increase, the distance of dislocation slip becomes longer, and the dislocation Movement requires more energy, and the hardness and wear resistance of the ceramic matrix increase; discharge plasma sintering makes the ceramic matrix evenly heated, ensuring uniform ceramic grain size, effectively reducing the excessive growth of a few grains in the ceramic matrix. The stress concentration inside the ceramic material is effectively avoided, and the hardness and wear resistance of the ceramic matrix are enhanced; since Comparative Example 1 contains a wear-resistant layer, the wear amount in Comparative Example 1 is not much different from that of Examples 1-4. The ceramic matrix in 1 is prepared by the conventional sintering method. In the conventional sintering method, the temperature rise rate is only 5-15°C/min. The crystal grains are prone to crystal growth and even secondary recrystallization at high temperatures. The crystallization of the ceramic matrix is The number of boundaries decreases, and the hardness of the ceramic decreases significantly; compared with Comparative Example 2, the aluminum ions and tungsten ions in the electrolyte form a wear-resistant layer on the surface of the ceramic matrix, and micro-arc oxidation occurs under the action of current and pressure to form tungsten oxide. and alumina composite metal layer. Aluminum oxide has a hexagonal structure and has extremely high hardness, which can significantly improve the hardness and wear resistance of ceramic materials. The wear-resistant layer is composed of crystalline and amorphous phases, which makes the wear-resistant layer harden and deform. The characteristics are combined, and the wear resistance of the wear-resistant layer is improved; the wear-resistant layer grows in situ from the ceramic matrix and is metallurgically bonded with the ceramic matrix. The bond between the wear-resistant layer and the ceramic matrix is closer, and the hardness and wear resistance of the ceramic material are improved. be enhanced; since Comparative Example 2 does not include a wear-resistant layer, the aluminum oxide and tungsten oxide components in the wear-resistant layer have high hardness and can provide good wear resistance. Compared with Examples 1-4, Comparative Example 2 The microhardness and wear resistance are significantly reduced.
图3为本发明所得的一种瓷砖用高硬度高耐磨陶瓷材料的表面SEM结果图，如图，实施例1所得陶瓷材料表面有明显的放电孔和少量裂纹，这是由于微弧氧化是一个“击穿-熔融-冷却-再击穿”的过程，阳极电解与阳极表面镀层的产生是同时发生的。Figure 3 is a surface SEM result diagram of a high-hardness and high-wear-resistant ceramic material for ceramic tiles obtained by the present invention. As shown in the figure, the surface of the ceramic material obtained in Example 1 has obvious discharge holes and a small amount of cracks. This is due to micro-arc oxidation. A process of "breakdown-melting-cooling-rebreakdown", anodic electrolysis and the production of anode surface coating occur simultaneously.
图4为本发明所得的一种瓷砖用高硬度高耐磨陶瓷材料的熔合截面SEM结果图，如图，耐磨层从陶瓷基体上原位生长，在高温下，耐磨层与陶瓷基体间产生明显的熔合，截面处熔合线呈犬牙交错结构。Figure 4 is a SEM result diagram of the fusion cross-section of a high-hardness and high-wear-resistant ceramic material for ceramic tiles obtained by the present invention. As shown in the figure, the wear-resistant layer grows in situ from the ceramic matrix. At high temperatures, the gap between the wear-resistant layer and the ceramic matrix Obvious fusion is produced, and the fusion line in the cross section has a staggered structure.
图5为本发明所得的一种瓷砖用高硬度高耐磨陶瓷材料的宏观形貌结果图，如图，在微弧氧化过程中，铝、钨在陶瓷基体表面形成了氧化物颗粒，宏观观察下，陶瓷材料表面颗粒生长较为均匀，陶瓷材料表面较为光滑。Figure 5 is a macroscopic morphology result diagram of a high-hardness and high-wear-resistant ceramic material for ceramic tiles obtained by the present invention. As shown in the figure, during the micro-arc oxidation process, aluminum and tungsten formed oxide particles on the surface of the ceramic substrate. Macroscopic observation Under this condition, the particle growth on the surface of the ceramic material is relatively uniform, and the surface of the ceramic material is smooth.
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art will understand that various changes, modifications, and substitutions can be made to these embodiments without departing from the principles and spirit of the invention. and modifications, the scope of the invention is defined by the appended claims and their equivalents.
以上对本发明及其实施方式进行了描述，这种描述没有限制性，附图中所示的也只是本发明的实施方式之一，实际的应用并不局限于此。总而言之如果本领域的普通技术人员受其启示，在不脱离本发明创造宗旨的情况下，不经创造性的设计出与该技术方案相似的方式及实施例，均应属于本发明的保护范围。The present invention and its embodiments have been described above. This description is not limiting. What is shown in the drawings is only one embodiment of the present invention, and the actual application is not limited thereto. In short, if a person of ordinary skill in the art is inspired by the invention, and without departing from the spirit of the invention, can devise methods and embodiments similar to the technical solution without creativity, they shall all fall within the protection scope of the invention.
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