WO2022183564A1 - 一种可控网络陶瓷/金属复合材料制备工艺 - Google Patents

一种可控网络陶瓷/金属复合材料制备工艺 Download PDF

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WO2022183564A1
WO2022183564A1 PCT/CN2021/086079 CN2021086079W WO2022183564A1 WO 2022183564 A1 WO2022183564 A1 WO 2022183564A1 CN 2021086079 W CN2021086079 W CN 2021086079W WO 2022183564 A1 WO2022183564 A1 WO 2022183564A1
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ceramic
composite material
metal composite
oxide
sintering
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French (fr)
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沈理达
陈志鹏
焦晨
周凯
吕非
陆彬
张寒旭
叶昀
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南京航空航天大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/001—Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D23/00—Casting processes not provided for in groups B22D1/00 - B22D21/00
    • B22D23/04—Casting by dipping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
    • C04B41/515—Other specific metals
    • C04B41/5155—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/88—Metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • C04B2235/6026—Computer aided shaping, e.g. rapid prototyping
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Definitions

  • the invention belongs to the technical field of special materials, and in particular relates to a preparation process of a controllable network ceramic/metal composite material.
  • Multifunctional, lightweight and high-performance specialty materials have always been the focus of attention in the fields of engineering construction, special manufacturing, military protection and aerospace.
  • the demand for these special materials is increasing day by day, and their design and manufacture have recently attracted widespread attention.
  • no single material can meet at the same time, which requires the continuous development and improvement of material systems, and the fusion and manufacture of various materials in a better combination way, so that they have various advantages at the same time. And try to remove the shortcomings of raw materials.
  • 3D printing technology has provided us with a customizable design idea, which can design and optimize the structure for different application backgrounds, improve the functionality and reliability of material applications, and greatly improve production efficiency.
  • 3D printing technology is mostly applicable to a single material, so a new type of manufacturing process is needed to bring out the advantages of 3D printing.
  • the invention provides a process for preparing a controllable network ceramic/metal composite material, which utilizes the ceramic 3D printing technology to design the component content on a three-dimensional scale, so that the design and manufacture can be used for different application backgrounds, which have both the high hardness of ceramics and the properties of metals.
  • the excellent special material with high toughness solves the problem that conventional 3D printing manufacturing can only form one material, and the formed parts have single function and limited performance.
  • the present invention adopts the following technical solutions:
  • a process for preparing a controllable network ceramic/metal composite material comprising the following steps:
  • Step 1 Modeling: 3D mesh modeling is performed according to different application backgrounds;
  • Step 2 ball-milling mixture: mixing oxide ceramic powder with additives and sintering aids, and then ball-milling to obtain mixed ceramic powder;
  • Step 3 slurry preparation: add the mixed ceramic powder obtained in step 2 to the photosensitive resin and dispersant, and mix uniformly;
  • Step 4 body forming: import the model file obtained in step 1 into a light-curing 3D printer, and use the slurry obtained in step 3 to print a three-dimensional network scaffold blank by a light-curing forming method;
  • Step 5 ultrasonic cleaning: ultrasonically clean the three-dimensional network scaffold blank for 3 to 5 minutes to remove the surface bonding slurry;
  • Step 6 degreasing and sintering: degreasing and sintering the stent blank after cleaning in step 5, and taking it out after cooling to room temperature in a furnace to obtain an oxide three-dimensional network ceramic stent;
  • Step 7 Vacuum pressure infiltration: After the metal blank is treated to remove the surface oxide layer, it is placed in the vacuum pressure infiltration equipment together with the oxide three-dimensional network ceramic support obtained in Step 6, and the pressure in the vacuum chamber is maintained at 0.1 standard atmosphere. The temperature is heated to 5% above the melting point of the metal and kept for 2 minutes, and the graphite pressure rod is used to slowly press down at a speed of 2mm/s until the penetration is completed;
  • Step 8 cooling and forming in an argon atmosphere: After the vacuum pressure infiltration in step 7 is completed, the network ceramic/metal composite material is obtained by cooling and forming in an argon atmosphere.
  • the mass ratio of the oxide-based ceramic powder to additives and sintering aids in step 2 is 90:8:2;
  • the oxide-based ceramics include alumina, titania, and zirconia. At least one of them has a particle size of 50nm to 30um, and the additive is the same oxide ceramic nano-powder.
  • the addition of the additive is to reconstruct the particle size distribution curve of the ceramic powder, which is used to fill the gap between the large-diameter ceramic particles and increase the size of the ceramic powder. Density of sintered products;
  • step 3 the mass ratio of the mixed ceramic powder to the photosensitive resin is (2.5:1) ⁇ (3.5:1), and the added amount of the dispersant is 3% ⁇ 5% of the total mass of the slurry;
  • the parameters when using a light-curing 3D printer in step 4 are: the light intensity is 8000-10000 uw/cm 2 , the exposure time is 8-12s, the number of reinforcing layers at the bottom is 3-5 layers, and the light intensity at the bottom is 3-5 times.
  • the thickness of the light-cured printing layer is 0.05-0.08mm;
  • step 6 the degreasing and sintering temperature is 0-1600°C, and the heating rate is controlled at 0.5-3°C/min; 0-900°C is the degreasing stage, and the temperature is 120°C, 240°C, 300°C, 420°C, and 500°C, respectively. , 900 °C for two hours each; 900-1600 °C is the sintering stage, respectively, at 1100 °C, 1300 °C, 1500 °C for two hours each;
  • the metal blank is a metal or alloy with a melting point lower than 1500 degrees; in step 7, it is necessary to perform an argon purge cycle operation in the vacuum chamber for 3 times before heating, and then vacuumize to start heating, and the heating rate is controlled at 5 ° C /min; the crucible material in the vacuum pressure infiltration equipment described in step 7 is selected from graphite, which can effectively avoid the bonding between the forming composite material and the crucible, and ensure the quality of taking out and the forming effect;
  • step 8 after the heating is completed, argon is injected into the vacuum chamber to restore the pressure in the vacuum chamber to 1 standard atmospheric pressure.
  • the present invention provides a process for preparing a controllable network ceramic/metal composite material. Through the good combination of 3D modeling and 3D printing, the component content and internal structure of the composite material can be directly designed and manufactured, and the composite material processing can be innovated.
  • the invention can realize the ceramic/metal composite
  • the structure can be designed with gradient according to the needs to meet the requirements of special mechanical properties.
  • the three-dimensional infiltration of various metals can be realized through the vacuum pressure infiltration device.
  • a paradigm is proposed for the fusion of various oxide ceramics and low-temperature metals; the processed materials can be Completely abandon complex procedures such as production molds and multi-unit collaborative production.
  • the process is simple and the production cycle is short, especially suitable for product design and development and small batch production.
  • Fig. 1 is the preparation process flow of controllable network ceramic/metal composite material in the embodiment of the present invention
  • Fig. 2 is the schematic diagram of the vacuum pressure infiltration equipment used in the embodiment of the present invention.
  • FIG. 3 is a schematic diagram of the composite material molding sample (a) and the oxide three-dimensional network ceramic support (b) prepared in the embodiment of the present invention.
  • a preparation process of a controllable network ceramic/metal composite material includes the following steps:
  • 3D modeling use the 3D modeling software in the computer to establish the alumina ceramic skeleton model and export it as an STL file for use;
  • Powder ball milling Here, alumina powder with a particle size of 50um is selected, 2wt% of titanium oxide powder with a particle size of 50um is added as a sintering aid, put into a planetary ball mill, the ball-to-material ratio is 1:3, and zirconia with a diameter of 8mm is selected. Ball, the ball milling speed is 300r/min, and the time is 2 hours;
  • Light curing molding put the slurry into the DLP light curing printer, import the pre-designed ceramic skeleton model, the light intensity is 8000uw/cm 2 , the exposure time is 10s, the number of reinforcing layers at the bottom is 5, and the light intensity at the bottom is strengthened. 5 times, and the thickness of the light-cured printing layer is 0.05mm;
  • Post-treatment remove the finished skeleton and put it into anhydrous ethanol for ultrasonic cleaning for 5 minutes, take out and blow off the residual liquid on the surface with a high-pressure spray gun, put it into a hot air circulating furnace for drying, and finally put it into an ultraviolet curing furnace for secondary curing.
  • Degreasing and sintering put the ceramic skeleton into the degreasing and sintering furnace, and the temperature is set to: 0 ⁇ 900 °C degreasing stage at 120 °C, 240 °C, 300 °C, 420 °C, 500 °C, 900 °C for two hours each; 900 °C In the sintering stage at ⁇ 1600°C, the temperature was kept at 1100°C, 1300°C, and 1500°C for two hours respectively, and the heating rate was 3°C/min, to obtain the oxide three-dimensional network ceramic scaffold shown in Figure 3(b);
  • Vacuum pressure infiltration First, grind the surface of the 6061 aluminum alloy block to remove the oxide layer, and then put it into a graphite crucible together with the sintered and dense alumina ceramic skeleton and place it in the vacuum pressure infiltration equipment as shown in Figure 2.
  • the argon gas was circulated and washed for 3 times, and then vacuumed for heating.
  • the temperature was set to 850 °C, and the heating rate was 5 °C/min. After reaching 850 °C, the temperature was maintained for 2 minutes to ensure that the metal was completely melted. Speed down until the impregnation is complete.

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Abstract

一种可控网络陶瓷/金属复合材料制备工艺，以氧化物陶瓷粉体为原料，将氧化物陶瓷粉体与光敏树脂混合制备浆料，利用光固化3D打印技术成型三维网络陶瓷坯体，坯体经超声清洗后，高温脱脂烧结制得致密陶瓷骨架，随后陶瓷骨架与金属一同装进石墨坩埚放入真空压力浸渗设备中进行成型，最后向设备中充入氩气冷却，制得陶瓷/金属复合材料，该制备工艺能够实现陶瓷/金属复合材料在三维尺度上的致密结合，通过对陶瓷骨架的整体外观、晶格形状与孔隙大小进行优化设计，解决了常规3D打印制造只能成形一种材料且成形部件功能单一、性能有限的问题，使该复合材料在不同应用背景下，都具有良好的力学性能。

Description

一种可控网络陶瓷/金属复合材料制备工艺 技术领域
本发明属于特种材料技术领域，尤其涉及一种可控网络陶瓷/金属复合材料制备工艺。
背景技术
多功能、轻量化和高性能的特种材料一直以来都是工程建设、特种制造、军事防护和航空航天领域关注的焦点。随着科技不断发展，这些特种材料的需求日益增大，它们的设计和制造近来引起了人们的广泛关注。然而针对多样化的需求，没有任何一种单质材料能够同时满足，这就需要不断发展和改进材料系统，以更好地组合方式将多种材料进行融合制造，使之同时具备多样化的优点，并尽量去除原材料的缺点。
近年来，3D打印技术的发展为我们提供了一种可定制化设计的思路，可以针对不同应用背景进行结构设计与优化，提高材料应用的功能性和可靠性，大大提高了生产效率。但是3D打印技术多适用于单材料，因此需要一种新型的制造工艺将3D打印的优势发挥出来。
发明内容
本发明提供了一种可控网络陶瓷/金属复合材料制备工艺，利用陶瓷3D打印技术在三维尺度进行组分含量设计，从而使设计制造可用于不同应用背景的兼具陶瓷的高硬度与金属的高韧性的优异特种材料，解决了常规3D打印制造只能成形一种材料且成形部件功能单一、性能有限的问题。
为实现以上目的，本发明采用以下技术方案：
一种可控网络陶瓷/金属复合材料制备工艺，包括以下步骤：
步骤1、建模：根据不同应用背景，进行三维网格建模；
步骤2、球磨混料：将氧化物类陶瓷粉体与添加剂、助烧剂混合后球磨得到混合陶瓷粉料；
步骤3、浆料制备：将步骤2得到的混合陶瓷粉料加入光敏树脂和分散剂，混合均匀；
步骤4、坯体成型：将步骤1得到的模型文件导入光固化3D打印机，将步骤3得到的浆料用光固化成形的方法打印出三维网络支架坯体；
步骤5、超声清洗：将所述三维网络支架坯体超声清洗3～5min，去除表面粘结浆料；
步骤6、脱脂烧结：将步骤5清洗后的支架坯体脱脂烧结，随炉冷却到室温后取出得到氧化物三维网络陶瓷支架；
步骤7、真空压力浸渗：将金属坯体处理去除表面氧化层后与步骤6得到的氧化物三维网络陶瓷支架一同放入真空压力浸渗设备中，真空腔内气压保持0.1个标准大气压，将温度加热至金属熔点之上5％保温2min，使用石墨压杆以2mm/s速度缓慢压下直至渗透完毕；
步骤8、氩气氛围冷却成型：步骤7真空压力浸渗完成后，氩气气氛中冷却成型得到网络陶瓷/金属复合材料。
以上所述步骤中，步骤2中所述氧化物类陶瓷粉体与添加剂、助烧剂的添加量质量比为90:8:2；所述氧化物类陶瓷包括氧化铝、氧化钛、氧化锆中的至少一种，粒径为50nm～30um，所述添加剂为同种氧化物陶瓷纳米粉末，增加添加剂是为了重构陶瓷粉末粒径分布曲线，用于填充大粒径陶瓷颗粒间缝隙，增加烧结成品致密度；
步骤3中混合陶瓷粉料与光敏树脂质量比为(2.5：1)～(3.5：1)，分散剂添加量为浆料总体质量的3％～5％；
步骤4中使用光固化3D打印机时的参数为：光强为8000～10000uw/cm 2，曝光时间为8～12s，底部加强层数为3～5层，底部加强光强为3～5倍，光固化打印层厚为0.05～0.08mm；
步骤6中所述脱脂烧结温度为0-1600℃，升温速度控制在0.5～3℃/min；其中0～900℃为脱脂阶段，分别在120℃、240℃、300℃、420℃、500℃、900℃各保温两小时；900～1600℃为烧结阶段，分别在1100℃、1300℃、1500℃各保温两小时；
步骤7中金属坯体为熔点低于1500度的金属或合金；步骤7中加热前需要在真空腔内先进行氩气洗气循环操作3遍，随后抽真空开始加热，升温速度控制在5℃/min；步骤7中所述真空压力浸渗设备中的坩埚材料选用石墨，能够有效避免成型复材与坩埚粘结，确保取出质量与成型效果；
步骤8中加热结束后冲入氩气使真空腔内气压恢复1个标准大气压环冷。
有益效果：本发明提供了一种可控网络陶瓷/金属复合材料制备工艺，通过三维建模与3D打印的良好结合，能够对复合材料的组分含量与内部构造直接设计制造，创新复材加工方式；基于光固化3D打印技术，可实现多样化晶格单元的组合打印，拓宽设计渠道，针对不同应用场景针对性优化结构设计，使复材实现多样化功能；本发明能够实现陶瓷/金属复合材料在三维尺度上的致密结合，通过对陶瓷骨架的整体外观、晶格形状与孔隙大小进行优化设计，实现在不同应用背景下该材料都能够有良好的力学性能，具有功能可设计性，骨架结构可根据需要进行梯度设计，满足特种力学性能要求，通过真空压力浸渗装置实现多种金属的三维渗透，提出一种范式适用于多种氧化物陶瓷与低温金属的融合；加工出来的材料可完全摒弃生产模具、多单位协作生产等复杂程序，工艺简单，生产周期短，尤其适合产品设计研发和小批量生产。
附图说明
图1是本发明实施例中可控网络陶瓷/金属复合材料制备工艺流程；
图2是本发明实施例中使用的真空压力渗透设备示意图；
图3是本发明实施例中制备的复合材料成型样件(a)和氧化物三维网络陶瓷支架(b)示意图。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明：
如图1所示，一种可控网络陶瓷/金属复合材料制备工艺，包括以下步骤：
(1)基础材料选择：在当前军事应用背景下，拟设计一种新型复合材料防弹衣，为了抵抗子弹的冲击，装甲材料需要拥有高强度与高韧性，这里选择氧化铝陶瓷与6061铝合金进行组合；
(2)三维建模：运用计算机中的三维建模软件建立氧化铝陶瓷骨架模型并导出为STL文件备用；
(3)粉末球磨：这里选用50um粒径的氧化铝粉，添加2wt％粒径为50um的氧化钛粉末为助烧剂，放入行星球磨机，球料比为1：3，选用直径8mm氧化锆球，球磨转速为300r/min，时间为2小时；
(4)配置浆料：按照2.5：1的配比往料缸加入氧化铝粉末与丙烯酸树脂，最后加入3wt％聚丙烯酸钠作为分散剂，放上真空分散机，转速800r/min，时间15min；
(5)光固化成型：将浆料放入DLP光固化打印机，导入预先设计的陶瓷骨架模型，光强为8000uw/cm 2，曝光时间为10s，底部加强层数为5层，底部加强光强为5倍，光固化打印层厚为0.05mm；
(6)后处理：将成品骨架取下放入无水乙醇中超声清洗5min，取出用高压喷枪吹掉表面残留液体，放入热风循环炉烘干，最后放入紫外光固化炉二次固化。
(7)脱脂烧结：将陶瓷骨架放入脱脂烧结炉，温度设置为：0～900℃脱脂阶段分别在120℃、240℃、300℃、420℃、500℃、900℃各保温两小时；900～1600℃烧结阶段分别在1100℃、1300℃、1500℃各保温两小时，升温速度为3℃/min，得到如图3(b)所示的氧化物三维网络陶瓷支架；
(8)真空压力浸渗：首先将6061铝合金块表面进行打磨去除氧化层，再与烧结致密的氧化铝陶瓷骨架一起放入石墨坩埚置入如图2所示的真空压力渗透设备中，冲入氩气循环洗气3遍后抽真空进行加热，温度设定为850℃，升温速度为5℃/min，到达850℃后保温2分钟确保金属完全融化，使用石磨压杆以2mm/s速度下压至浸渗完成。
(9)冷却取出：冲入氩气让工件随炉冷却至环境温度取出进行后处理，得到图3(a)的成品网络陶瓷/金属复合材料。
以下所述仅为本发明的较佳实施例而已，并非用于限定本发明的保护范围。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，均包含在本发明的保护范围内。

Claims (9)

  1. 一种可控网络陶瓷/金属复合材料制备工艺，其特征在于，包括以下步骤：
    步骤1、建模：根据不同应用背景，进行三维网格建模；
    步骤2、球磨混料：将氧化物类陶瓷粉体与添加剂、助烧剂混合后球磨得到混合陶瓷粉料；
    步骤3、浆料制备：将步骤2得到的混合陶瓷粉料加入光敏树脂和分散剂，混合均匀；
    步骤4、坯体成型：将步骤1得到的模型文件导入光固化3D打印机，将步骤3得到的浆料用光固化成形的方法打印出三维网络支架坯体；
    步骤5、超声清洗：将所述三维网络支架坯体超声清洗3～5min，去除表面粘结浆料；
    步骤6、脱脂烧结：将步骤5清洗后的支架坯体脱脂烧结，随炉冷却到室温后取出得到氧化物三维网络陶瓷支架；
    步骤7、真空压力浸渗：将金属坯体处理去除表面氧化层后与步骤6得到的氧化物三维网络陶瓷支架一同放入真空压力浸渗设备中，真空腔内气压保持0.1个标准大气压，将温度加热至金属熔点之上5％保温2min，使用石墨压杆以2mm/s速度缓慢压下直至渗透完毕；
    步骤8、氩气氛围冷却成型：步骤7真空压力浸渗完成后，氩气气氛中冷却成型得到网络陶瓷/金属复合材料。
  2. 根据权利要求1所述的可控网络陶瓷/金属复合材料制备工艺，其特征在于，步骤2中所述氧化物类陶瓷粉体与添加剂、助烧剂的添加量质量比为90:8:2。
  3. 根据权利要求1或2所述的可控网络陶瓷/金属复合材料制备工艺，其特征在于，步骤2中所述氧化物类陶瓷粒径为50nm～30um；所述氧化物类陶瓷包括氧化铝、氧化钛、氧化锆中的至少一种。
  4. 根据权利要求1所述的可控网络陶瓷/金属复合材料制备工艺，其特征在于，步骤3中混合陶瓷粉料与光敏树脂质量比为(2.5：1)～(3.5：1)，所述分散剂添加量为浆料总体质量的3％～5％。
  5. 根据权利要求1所述的可控网络陶瓷/金属复合材料制备工艺，其特征在于，步骤4中使用光固化3D打印机时的参数为：光强为8000～10000uw/cm 2，曝光时间为8～12s，底部加强层数为3～5层，底部加强光强为3～5倍，光固化打印层厚 为0.05～0.08mm。
  6. 根据权利要求1所述的可控网络陶瓷/金属复合材料制备工艺，其特征在于，步骤6中所述脱脂烧结温度为0-1600℃，升温速度控制在0.5～3℃/min。
  7. 根据权利要求6所述的可控网络陶瓷/金属复合材料制备工艺，其特征在于，步骤6中0～900℃为脱脂阶段，分别在120℃、240℃、300℃、420℃、500℃、900℃各保温两小时；900～1600℃为烧结阶段，分别在1100℃、1300℃、1500℃各保温两小时。
  8. 根据权利要求1所述的可控网络陶瓷/金属复合材料制备工艺，其特征在于，步骤7中金属坯体为熔点低于1500度的金属或合金；所述真空压力浸渗设备中的坩埚材料选用石墨；加热前需要在真空腔内先进行氩气洗气循环操作3遍，随后抽真空开始加热，升温速度控制在5℃/min。
  9. 根据权利要求1所述的可控网络陶瓷/金属复合材料制备工艺，其特征在于，步骤8中加热结束后冲入氩气使真空腔内气压恢复1个标准大气压环冷。
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