技术领域technical field
本发明涉及3D技术领域，更具体地，涉及一种水性纳米银3D打印坯体方法及其成型方法。The present invention relates to the field of 3D technology, and more specifically, to a method for printing an aqueous nano-silver 3D body and a forming method thereof.
背景技术Background technique
3D打印技术是一种新兴的快速成型技术，通过逐层叠加材料制造三维立体3D printing technology is an emerging rapid prototyping technology that manufactures three-dimensional objects by layering materials
结构实物的技术，不同于传统的去除材料制造技术，因此又称为增材制造，3D打印主要有选择性激光烧结技术(SLS)、熔融沉淀技术(FDM)和立体光固化技术(SLA)。The technology of structural objects is different from the traditional material removal manufacturing technology, so it is also called additive manufacturing. 3D printing mainly includes selective laser sintering technology (SLS), fusion deposition technology (FDM) and stereolithography technology (SLA).
先进陶瓷材料及硬质材料的高强高硬特性，使其难以加工成型，科技发展对陶瓷、硬质合金制件复杂程度与精度要求越来越高，这已成为其应用的最大障碍。而增材制造（3D打印）技术的出现，则使突破先进陶瓷应用的最大障碍即成型困难成为可能。3D打印陶瓷无需原胚和模具，也不需加工，就能直接根据计算机图形数据，通过增加材料的方法生成任何形状的复杂形状物体，因此受到国内外陶瓷领域专家高度的关注。陶瓷与硬质合金的高熔点、高硬脆性导致其增材制造最难打印成型的材料，通常要借助高分子材料或金属材料作为粘结剂进行3D打印。采激光选区烧结、激光选区熔化、激光近净成型、电子束选区熔化等直接成型方式往往在快速凝固过程中会产生较大的热应力，从而形成较多的微裂纹，不适合增材制造陶瓷材料。熔融沉积成型即将陶瓷粉末和有机粘结剂相混合，用挤出机或毛细血管流变仪做成丝，然后分层堆积成型方式做出陶瓷件生胚，后续烧结制备。此方法的缺点是表面出现层状纹理，成型精度差，需后续打磨处理。光固化是3D打印技术成型精度最高，并且高效，高集成化，材料利用率高，其打印陶瓷粉末的工作原理是将通过激光在加有陶瓷粉体或前驱体液态光敏树脂选择性地固化成型复杂零件，然后经干燥、脱脂、烧结，故而可以保征成型陶瓷产品的虽然高精度，但是其设备较为昂贵，系统对液体操作要求苛刻，成型件多为树脂，材料价格贵且性能有限，不利于长期储存，对环境污染严重。The high-strength and high-hardness characteristics of advanced ceramic materials and hard materials make them difficult to process and form. The development of science and technology requires higher and higher complexity and precision of ceramic and hard alloy parts, which has become the biggest obstacle to their application. The emergence of additive manufacturing (3D printing) technology has made it possible to break through the biggest obstacle in the application of advanced ceramics, namely the difficulty in molding. 3D printing ceramics does not require original embryos, molds, or processing. It can directly generate complex objects of any shape by adding materials based on computer graphics data. Therefore, it has attracted high attention from experts in the field of ceramics at home and abroad. The high melting point and high hardness and brittleness of ceramics and cemented carbides make them the most difficult materials to print in additive manufacturing. Usually, polymer materials or metal materials are used as binders for 3D printing. Direct forming methods such as laser selective sintering, laser selective melting, laser near-net shaping, and electron beam selective melting often produce large thermal stress during rapid solidification, resulting in the formation of more microcracks, which are not suitable for additive manufacturing of ceramics. Material. Fused deposition molding is to mix ceramic powder and organic binder, use an extruder or capillary rheometer to make filaments, and then make ceramic green embryos by layered stacking molding, followed by sintering. The disadvantage of this method is that there is a layered texture on the surface, the forming accuracy is poor, and subsequent grinding is required. Photocuring is a 3D printing technology with the highest molding precision, high efficiency, high integration, and high material utilization rate. The working principle of printing ceramic powder is to selectively solidify the liquid photosensitive resin with ceramic powder or precursor by laser. Complicated parts are then dried, degreased, and sintered, so that although the high precision of the molded ceramic products can be guaranteed, the equipment is relatively expensive, and the system has strict requirements for liquid operation. Most of the molded parts are resins, and the materials are expensive and have limited performance. It is beneficial to long-term storage and has serious environmental pollution.
针对现有3D打印技术存在的缺陷，本发明将注凝成型技术与3D打印相结合，提出一种水性纳米银3D打印成型方法，凝胶注模成型工艺的原理是原位凝胶固化，成型速度较快，能够近净尺寸成型复杂部件，并且坯体均匀性好、机械强度高、烧结性能优异，因此拓展凝胶注模成型技术与 3D 打印技术结合，将提供一种全新的3D打印技术，从而解决现有3D打印技术的缺陷，大大拓展应用3D成型的材料领域。In view of the defects existing in the existing 3D printing technology, the present invention combines the gel injection molding technology with 3D printing, and proposes a water-based nano silver 3D printing molding method. The principle of the gel injection molding process is in-situ gel curing, forming The speed is fast, and complex parts can be formed in near-net dimensions, and the green body has good uniformity, high mechanical strength, and excellent sintering performance. Therefore, expanding the combination of gel injection molding technology and 3D printing technology will provide a new 3D printing technology , so as to solve the defects of the existing 3D printing technology and greatly expand the field of materials for 3D molding.
发明内容Contents of the invention
本发明要解决的技术问题针对现有技术的不足，引入注凝成型工艺，以水为载体，结合3D打印技术，提供一种全新的水性纳米银3D打印坯体方法。The technical problem to be solved in the present invention aims at the deficiencies of the existing technology, introduces the gel injection molding process, uses water as the carrier, and combines with 3D printing technology to provide a brand new method of water-based nano silver 3D printing green body.
本发明还提供一种水性纳米银3D打印成型方法。The invention also provides a water-based nano-silver 3D printing forming method.
本发明的目的通过以下技术方案予以实现：The purpose of the present invention is achieved through the following technical solutions:
提供一种水性纳米银3D打印成型方法，包括以下步骤：A water-based nano-silver 3D printing molding method is provided, comprising the following steps:
S1.以水为载体，向去离子水中加入单体N,N-亚甲基双丙烯酰、交联剂亚甲基双丙烯酰胺、添加剂乙酸乙酯，再加入体积比为20～65%的纳米银粉体，球磨搅拌后得到低粘度、高固相体积分数的悬浮料浆A备用；S1. Using water as a carrier, add monomer N,N-methylenebisacryloyl, crosslinking agent methylenebisacrylamide, additive ethyl acetate to deionized water, and then add 20-65% volume ratio Nano-silver powder, after ball milling and stirring, suspension slurry A with low viscosity and high solid phase volume fraction is obtained for subsequent use;
S2.配好能与步骤S1有机单体发生胶凝反应的光固化剂作为物质B备用；S2. Prepare a photocuring agent capable of gelling reaction with the organic monomer in step S1 as substance B for later use;
S3.将步骤S1中浆料A和步骤S2中物质B均匀混合，得到混合物C；S3. Uniformly mixing the slurry A in the step S1 and the substance B in the step S2 to obtain a mixture C;
S4.将混合物C输送至3D打印头并给予能加速有机单体聚合的紫外光或激光束，使得3D打印头在紫外光或激光束氛围下实施打印，按照三维模型数据进行打印，层层堆积成型，最终得到所需形状的坯体。S4. Transport the mixture C to the 3D printing head and give ultraviolet light or laser beam that can accelerate the polymerization of organic monomers, so that the 3D printing head can print in the atmosphere of ultraviolet light or laser beam, and print according to the three-dimensional model data, layer by layer Forming, and finally get the green body of the desired shape.
本发明的原理在于以水为载体，加入低密度的ZrO2粉体材料后形成分散性较好的粉体悬浮液，所述粉体悬浮液粘度低，固相含量高、流动性好，加入有机单体后，将分散均匀的粉体悬浮液中的颗粒包覆使之原位固定，从而得到粉体与高分子有机物的复合材料的悬浮液，通过与有机单体发生胶凝反应的物质B混合使悬浮液体中的有机单体发生化学交联或物理交联成三维网络状结构，结合3D打印技术快速制备得到高深坯强度和精准度的坯体。The principle of the present invention is to use water as a carrier, add low-densityZrO2 powder material to form a powder suspension with good dispersibility, the powder suspension has low viscosity, high solid phase content, and good fluidity. After the organic monomer, the particles in the uniformly dispersed powder suspension are coated to fix them in situ, so as to obtain the suspension of the composite material of the powder and the high molecular organic matter, and the substance through the gelation reaction with the organic monomer B mixing makes the organic monomers in the suspension liquid chemically or physically cross-linked into a three-dimensional network structure, combined with 3D printing technology to quickly prepare green bodies with high strength and precision.
优选地，步骤S1中所述N,N-亚甲基双丙烯酰加入量为45～55wt%，所述乙酸乙酯加入量为7～9wt%，亚甲基双丙烯酰胺加入量为0.5～2wt%。Preferably, the added amount of N,N-methylenebisacryloyl in step S1 is 45-55wt%, the added amount of ethyl acetate is 7-9wt%, and the added amount of methylenebisacrylamide is 0.5- 2wt%.
优选地，步骤S1中所述去离子水中还加入了0.1～1wt%%的除泡剂。Preferably, 0.1-1 wt% of a defoamer is added to the deionized water in step S1.
优选地，步骤S2中所述光固化剂为光固化剂819。Preferably, the photocuring agent in step S2 is a photocuring agent 819 .
优选地，步骤 S4中所述三维模型数据为使用三维造型软件设计出所需结构形状的零件模型，将零件模型进行分层切片处理，层片厚度为0.05～0.2mm。Preferably, the three-dimensional model data in step S4 is a part model with a required structural shape designed using three-dimensional modeling software, and the part model is subjected to layered slice processing, and the layer thickness is 0.05-0.2mm.
本发明还提供一种水性纳米银3D打印成型方法，包括以下步骤：将上述水性纳米银3D打印坯体方法制备得到的坯体进行干燥，得到高强度坯体，然后排胶并烧结，得到最终产品。The present invention also provides a water-based nano-silver 3D printing molding method, which includes the following steps: drying the green body prepared by the above-mentioned water-based nano-silver 3D printing green body method to obtain a high-strength green body, and then debinding and sintering to obtain the final product.
优选地，所述干燥是指在将坯体在室温放置24～72h，然后在60℃下真空干燥。Preferably, the drying refers to placing the green body at room temperature for 24-72 hours, and then vacuum drying at 60°C.
优选地，所述排胶并烧结是指坯体在600℃保温3h进行排胶处理，再放置在真空条件下，温度为1000～1300℃下烧结2h。Preferably, the debinding and sintering means that the green body is kept at 600° C. for 3 hours for debinding treatment, and then placed under vacuum conditions for sintering at a temperature of 1000-1300° C. for 2 hours.
与现有技术相比，本发明的有益效果是：Compared with prior art, the beneficial effect of the present invention is:
本发明针对现有3D打印技术存在的缺陷，将注凝成型技术与3D打印相结合，提出一种水性纳米银3D打印成型方法，将原位凝胶固化原理与3D打印结合，无需原胚和开发模具，也不需加工，就能直接根据计算机图形数据，通过增加材料的方法生成任何形状的复杂形状物体，该方法在保证了注凝成型技术中坯体均匀性好、机械强度高、烧结性能优异的优点同时，还极大地提高了生产效率，打印得到的坯体生坯强度高、精准度高。Aiming at the defects existing in the existing 3D printing technology, the present invention combines the injection molding technology with 3D printing, and proposes a water-based nano silver 3D printing molding method, which combines the principle of in-situ gel solidification with 3D printing, without the need for the original embryo and 3D printing. The development of molds can directly generate complex objects of any shape by adding materials based on computer graphics data without processing. This method ensures good uniformity, high mechanical strength, and sintered At the same time, the advantages of excellent performance also greatly improve the production efficiency, and the green body obtained by printing has high strength and high precision.
本发明以低粘度、高固相体积分数、流动性好的粉体悬浮液作为3D打印原料，无需借助外界压力即可在3D打印设备中实现输送、混合和挤出，具有成本低、可靠性高、操作性强等优点，并且固化时间快，固化精度高，易于实现工业化生产。The present invention uses low viscosity, high solid phase volume fraction, and good fluidity powder suspension as the 3D printing raw material, which can realize transportation, mixing and extrusion in the 3D printing equipment without external pressure, and has low cost and high reliability. High performance, strong operability, fast curing time, high curing precision, easy to realize industrial production.
本发明以水作为溶剂，可降低胶凝前躯物的粘度，避免使用有机物溶剂所带来的环境污染问题，并且干燥过程简单，属于环境友好型工艺，适应于工业化生产。The invention uses water as a solvent, can reduce the viscosity of the gelled precursor, avoids the problem of environmental pollution caused by the use of organic solvents, has a simple drying process, belongs to an environment-friendly process, and is suitable for industrial production.
附图说明Description of drawings
图1 本发明工艺流程图。Fig. 1 Process flow diagram of the present invention.
图2 本发明设备示意图。Fig. 2 is a schematic diagram of the device of the present invention.
具体实施方式Detailed ways
本发明提供一种水性纳米银3D打印成型方法，具体工艺方法如图1所示，包括以下步骤：The present invention provides a water-based nano-silver 3D printing molding method, the specific process method is shown in Figure 1, including the following steps:
S1.以水为载体，向去离子水中加入单体N,N-亚甲基双丙烯酰、交联剂亚甲基双丙烯酰胺、添加剂乙酸乙酯、再加入体积比为20～65%的纳米银粉体，球磨搅拌后得到低粘度、高固相体积分数的悬浮料浆A备用；S1. Using water as a carrier, add monomer N,N-methylenebisacrylamide, crosslinking agent methylenebisacrylamide, additive ethyl acetate, and then add 20-65% volume ratio to deionized water Nano-silver powder, after ball milling and stirring, suspension slurry A with low viscosity and high solid phase volume fraction is obtained for subsequent use;
S2.配好能与步骤S1有机单体发生胶凝反应的光固化剂作为物质B备用；S2. Prepare a photocuring agent capable of gelling reaction with the organic monomer in step S1 as substance B for later use;
S3.将步骤S1中浆料A和步骤S2中物质B均匀混合，得到混合物C；S3. Uniformly mixing the slurry A in the step S1 and the substance B in the step S2 to obtain a mixture C;
S4.将混合物C输送至3D打印头并给予能加速有机单体聚合的紫外光或激光束，使得3D打印头在紫外光或激光束氛围下实施打印，按照三维模型数据进行打印，层层堆积成型，最终得到所需形状的坯体；S4. Transport the mixture C to the 3D printing head and give ultraviolet light or laser beam that can accelerate the polymerization of organic monomers, so that the 3D printing head can print in the atmosphere of ultraviolet light or laser beam, and print according to the three-dimensional model data, layer by layer Forming, and finally get the green body of the desired shape;
S6.将步骤S5得到的坯体进行干燥，得到高强度坯体，然后排胶并烧结，得到最终产品。S6. Drying the green body obtained in step S5 to obtain a high-strength green body, and then debinding and sintering to obtain a final product.
其中，步骤S1中是将低密度的纳米银粉体和水配成低粘度、高固相体积分数、流动性好的粉体悬浮液（可以根据实际情况选择添加分散剂来提高固相含量），并同时选择合适的有机单体加入到粉体悬浮液中组成单元胶凝体系，或者选择合适的有机单体和交联剂加入到粉体悬浮液中组成多元凝胶体系；步骤S2中物质B光固化剂，采用光引的方法，步骤S4中能加速有机单体聚合的条件为紫外光或激光束。Among them, in step S1, the low-density nano-silver powder and water are formulated into a low-viscosity, high solid phase volume fraction, and good fluidity powder suspension (you can choose to add a dispersant to increase the solid phase content according to the actual situation) , and simultaneously select a suitable organic monomer to be added to the powder suspension to form a unit gel system, or select a suitable organic monomer and a cross-linking agent to be added to the powder suspension to form a multi-component gel system; the substance in step S2 B photocuring agent adopts the method of light induction, and the condition that can accelerate the polymerization of the organic monomer in step S4 is ultraviolet light or laser beam.
针对上述方法，本发明水性3D打印成型设备可设计成如图2所示，包括浆料罐1、储料罐2、混料罐3和3D打印设备4，浆料罐1、储料罐2分别与混料罐3连接，混料罐3与3D打印设备4内的3D打印头41连接；For the above method, the water-based 3D printing molding equipment of the present invention can be designed as shown in Figure 2, including a slurry tank 1, a storage tank 2, a mixing tank 3 and a 3D printing device 4, a slurry tank 1, a storage tank 2 Connect with the mixing tank 3 respectively, and the mixing tank 3 is connected with the 3D printing head 41 in the 3D printing device 4;
浆料罐1内设有搅拌装置11，出料口处设有计量装置12，储料罐2出料口处设有计量装置21，混料罐3内设有搅拌装置31。The slurry tank 1 is provided with a stirring device 11 , the discharge port is provided with a metering device 12 , the storage tank 2 is provided with a metering device 21 at the discharge port, and the mixing tank 3 is provided with a stirring device 31 .
本发明水性3D打印成型设备工作原理如下：将配好的浆料A和能与有机单体发生胶凝反应的物质B分别放置在浆料罐1和储料罐2内，如果需要同时添加引发剂和催化剂，储料罐2至少需要准备2个分开储存引发剂和催化剂，然后分别与浆料混合，也可以直接在浆料中先添加催化剂，浆料灌1内的搅拌装置11保持搅拌的工作状态防止浆料A沉积，需要打印的时候，将三维模型数据导入3D打印设备4，浆料罐1和储料罐2内的物料分别通过通过计量装置12和计量装置21按比例配好输送至混料罐3中，混料罐3内的搅拌装置31保持工作状态，混合均匀后将混合物C输送至3D打印设备4的3D打印头内，3D打印设备4根据三维模型数据实施打印，打印过程中需要给予3D打印设备4内能加速有机单体聚合的紫外光或激光束，得到坯体再进行干燥、排胶、烧结，最终得到产品。The working principle of the water-based 3D printing molding equipment of the present invention is as follows: the prepared slurry A and the substance B capable of gelling reaction with organic monomers are placed in the slurry tank 1 and the storage tank 2 respectively, and if necessary, add triggering agent and catalyst, the storage tank 2 needs to prepare at least two separate storage initiators and catalysts, and then mix them with the slurry respectively, or directly add the catalyst in the slurry, and the stirring device 11 in the slurry tank 1 keeps stirring The working state prevents the deposition of slurry A. When printing is required, the three-dimensional model data is imported into the 3D printing device 4, and the materials in the slurry tank 1 and the storage tank 2 are transported in proportion through the metering device 12 and the metering device 21 respectively. In the mixing tank 3, the stirring device 31 in the mixing tank 3 remains in working condition, and after mixing evenly, the mixture C is transported to the 3D printing head of the 3D printing device 4, and the 3D printing device 4 performs printing according to the three-dimensional model data, printing In the process, it is necessary to give ultraviolet light or laser beams that can accelerate the polymerization of organic monomers in the 3D printing equipment 4, and then dry, degrease, and sinter the green body to obtain the final product.
其中，由于浆料A流动性好，通过重力作用（例如阀门的控制下）即可完成输送、混合，无需外界压力，考虑到某些情况需要加快3D打印的效率，也可以通过压力作用（例如注射或泵）来加快物料输送、混合。本发明实现加速有机单体聚合的条件的设备是光照设备，施加对象可以是在3D打印设备的打印平台上。具体的装置和结构本领域技术人员可以根据实际情况选择和设计。Among them, due to the good fluidity of the slurry A, it can be transported and mixed through the action of gravity (such as under the control of a valve) without external pressure. Considering the need to speed up the efficiency of 3D printing in some cases, it can also be achieved through the action of pressure (such as Injection or pump) to speed up material delivery, mixing. The device for realizing the conditions for accelerating the polymerization of organic monomers in the present invention is a lighting device, and the application object may be on a printing platform of a 3D printing device. The specific devices and structures can be selected and designed by those skilled in the art according to actual conditions.
下面结合具体实施例进一步说明本发明。以下实施例仅为示意性实施例，并不构成对本发明的不当限定，本发明可以由发明内容限定和覆盖的多种不同方式实施。除非特别说明，本发明采用的试剂、化合物和设备为本技术领域常规试剂、化合物和设备。The present invention will be further described below in conjunction with specific examples. The following examples are only illustrative examples and do not constitute improper limitations to the present invention. The present invention can be implemented in various ways defined and covered by the content of the invention. Unless otherwise specified, the reagents, compounds and equipment used in the present invention are conventional reagents, compounds and equipment in the technical field.
实施例1Example 1
本实施例提供一种水性纳米银3D打印成型方法，包括以下步骤：This embodiment provides a water-based nano silver 3D printing molding method, comprising the following steps:
S1.以水为载体，向去离子水中加入质量比为单体N,N-亚甲基双丙烯酰（DMAA）为50wt%，添加剂乙酸乙酯（EA）为8wt%、交联剂亚甲基双丙烯酰胺（MBAM）为1wt%、除泡剂为0.1～1wt%%，，再加入体积比为50%的纳米银粉体，球磨搅拌后得到低粘度、高固相体积分数的悬浮料浆A备用；S1. Using water as the carrier, add 50wt% monomer N,N-methylenebisacryloyl (DMAA), 8wt% additive ethyl acetate (EA), and 8wt% crosslinking agent methylene to deionized water. Base bisacrylamide (MBAM) is 1wt%, defoaming agent is 0.1~1wt%, and then add nano-silver powder with a volume ratio of 50%, and after ball milling and stirring, a suspension material with low viscosity and high solid phase volume fraction is obtained Pulp A is spare;
S2.配置一定量能引发胶凝反应的光固化剂（光固化剂819），得到物质B备用；S2. Prepare a certain amount of photocuring agent (photocuring agent 819) capable of initiating a gelation reaction to obtain substance B for later use;
S3.将步骤S1制备的A料放置图2中浆料罐1内，并搅拌。将步骤S2制备的B料放置图2中储料罐2内；S3. Place the material A prepared in step S1 in the slurry tank 1 in FIG. 2 and stir it. Place the B material prepared in step S2 in the storage tank 2 in Fig. 2;
S4.数据建模：使用三维造型软件设计出所需结构形状的零件模型，将零件模型进行分层切片处理，层片厚度为0.05～0.2mm，得到零件的三维模型数据，并导入3D打印设备中；S4. Data modeling: Use 3D modeling software to design the part model of the required structural shape, and slice the part model in layers with a thickness of 0.05-0.2mm to obtain the 3D model data of the part and import it into the 3D printing equipment middle;
S5.设备按设定配比分别将A料与B料通过计量按质量比90～100:2输送至图2中混料罐3内，经搅拌得混合料C，然后混合物C输送至3D打印设备中的打印头内，按照三维模型数据进行打印，打印过程中给予能加速有机单体聚合的紫外光或激光束，具体在波长365～405氛围下打印，使得混合物C迅速固化，层层堆积成型，最终得到所需形状的坯体；S5. According to the set ratio, the equipment transports material A and material B to the mixing tank 3 in Figure 2 according to the mass ratio of 90 to 100:2 through metering, and mixes C to obtain the mixture C, which is then transported to the 3D printing machine In the printing head of the equipment, printing is carried out according to the three-dimensional model data. During the printing process, ultraviolet light or laser beams which can accelerate the polymerization of organic monomers are given. Specifically, the printing is performed in an atmosphere with a wavelength of 365-405, so that the mixture C is rapidly solidified and piled up layer by layer. Forming, and finally get the green body of the desired shape;
S6.将步骤S5得到的坯体在室温放置24～72h，然后在60℃下真空干燥，得到高强度坯体，随后在流动气氛条件下，将高强度坯体在600℃保温3h进行排胶处理，再放置在真空条件下，温度为1000～1300℃下烧结2h，得到最终产品。S6. Place the green body obtained in step S5 at room temperature for 24 to 72 hours, and then vacuum-dry it at 60°C to obtain a high-strength green body. Then, under the condition of flowing atmosphere, keep the high-strength green body at 600°C for 3 hours for debinding treatment, and then placed under vacuum conditions and sintered at a temperature of 1000-1300° C. for 2 hours to obtain the final product.
本实施为保证3D打印过程中成型快（层层堆积时各层不会产生形变）、提高固化速率和生坯强度，优化了浆料A的配比，适当（太高反而会引起杂质过多）提高了单体添加的重量百分比，并添加了添加剂乙酸乙酯（EA），在紫外光或激光束氛围下实施打印。In this implementation, in order to ensure fast forming in the 3D printing process (the layers will not deform when layers are piled up), improve the curing rate and green strength, the proportion of slurry A is optimized, and it is appropriate (too high will cause too many impurities) ) increased the weight percentage of the monomer added, and added the additive ethyl acetate (EA), and printed under the atmosphere of ultraviolet light or laser beam.
本实施例制备得到的坯体生坯强度达24MPa,常温空气中烧结相对密度98%以上。The green body prepared in this example has a green strength of 24 MPa and a relative density of sintered in air at room temperature above 98%.
实施例2Example 2
本实施例提供一种水性纳米银3D打印成型方法，包括以下步骤：This embodiment provides a water-based nano silver 3D printing molding method, comprising the following steps:
S1.以水为载体，向去离子水中加入质量比为单体N,N-亚甲基双丙烯酰（DMAA）为45wt%，添加剂乙酸乙酯（EA）为7wt%、交联剂亚甲基双丙烯酰胺（MBAM）为0.5wt%、除泡剂为0.1～1wt%%，，再加入体积比为50%的纳米银粉体，球磨搅拌后得到低粘度、高固相体积分数的悬浮料浆A备用；S1. Using water as the carrier, add 45wt% monomer N,N-methylenebisacryloyl (DMAA), 7wt% additive ethyl acetate (EA), and 7wt% crosslinking agent methylene to deionized water. Base bisacrylamide (MBAM) is 0.5wt%, defoaming agent is 0.1~1wt%, and then add nano-silver powder with a volume ratio of 50%, and after ball milling and stirring, a suspension with low viscosity and high solid volume fraction is obtained. Slurry A is standby;
S2.配置一定量能引发胶凝反应的光固化剂（光固化剂819），得到物质B备用；S2. Prepare a certain amount of photocuring agent (photocuring agent 819) capable of initiating a gelation reaction to obtain substance B for later use;
S3.将步骤S1制备的A料放置图2中浆料罐1内，并搅拌。将步骤S2制备的B料放置图2中储料罐2内；S3. Place the material A prepared in step S1 in the slurry tank 1 in FIG. 2 and stir it. Place the B material prepared in step S2 in the storage tank 2 in Fig. 2;
S4.数据建模：使用三维造型软件设计出所需结构形状的零件模型，将零件模型进行分层切片处理，层片厚度为0.05～0.2mm，得到零件的三维模型数据，并导入3D打印设备中；S4. Data modeling: Use 3D modeling software to design the part model of the required structural shape, and slice the part model in layers with a thickness of 0.05-0.2mm to obtain the 3D model data of the part and import it into the 3D printing equipment middle;
S5.设备按设定配比分别将A料与B料通过计量按质量比90～100:2输送至图2中混料罐3内，经搅拌得混合料C，然后混合物C输送至3D打印设备中的打印头内，按照三维模型数据进行打印，打印过程中给予能加速有机单体聚合的紫外光或激光束，具体在波长365～405氛围下打印，使得混合物C迅速固化，层层堆积成型，最终得到所需形状的坯体；S5. According to the set ratio, the equipment transports material A and material B to the mixing tank 3 in Figure 2 according to the mass ratio of 90 to 100:2 through metering, and mixes C to obtain the mixture C, which is then transported to the 3D printing machine In the printing head of the equipment, printing is carried out according to the three-dimensional model data. During the printing process, ultraviolet light or laser beams which can accelerate the polymerization of organic monomers are given. Specifically, the printing is performed in an atmosphere with a wavelength of 365-405, so that the mixture C is rapidly solidified and piled up layer by layer. Forming, and finally get the green body of the desired shape;
S6.将步骤S5得到的坯体在室温放置24～72h，然后在60℃下真空干燥，得到高强度坯体，随后在流动气氛条件下，将高强度坯体在600℃保温3h进行排胶处理，再放置在真空条件下，温度为1000～1300℃下烧结2h，得到最终产品。S6. Place the green body obtained in step S5 at room temperature for 24 to 72 hours, and then vacuum-dry it at 60°C to obtain a high-strength green body. Then, under the condition of flowing atmosphere, keep the high-strength green body at 600°C for 3 hours for debinding treatment, and then placed under vacuum conditions and sintered at a temperature of 1000-1300° C. for 2 hours to obtain the final product.
本实施例制备得到的坯体生坯强度达18MPa,常温空气中烧结相对密度97%以上。The green body prepared in this example has a green strength of 18 MPa, and a relative density of sintered in air at room temperature is above 97%.
实施例3Example 3
本实施例提供一种水性纳米银3D打印成型方法，包括以下步骤：This embodiment provides a water-based nano silver 3D printing molding method, comprising the following steps:
S1.以水为载体，向去离子水中加入质量比为单体N,N-亚甲基双丙烯酰（DMAA）为55wt%，添加剂乙酸乙酯（EA）为9wt%、交联剂亚甲基双丙烯酰胺（MBAM）为2wt%、除泡剂为0.1～1wt%%，，再加入体积比为65%的纳米银粉体，球磨搅拌后得到低粘度、高固相体积分数的悬浮料浆A备用；S1. Using water as the carrier, add 55wt% monomer N,N-methylenebisacryloyl (DMAA), 9wt% additive ethyl acetate (EA) and 9wt% crosslinking agent methylene to deionized water. Base bisacrylamide (MBAM) is 2wt%, defoaming agent is 0.1~1wt%, and then add nano-silver powder with a volume ratio of 65%, and after ball milling and stirring, a suspension material with low viscosity and high solid phase volume fraction is obtained Pulp A is spare;
S2.配置一定量能引发胶凝反应的光固化剂（光固化剂819），得到物质B备用；S2. Prepare a certain amount of photocuring agent (photocuring agent 819) capable of initiating a gelation reaction to obtain substance B for later use;
S3.将步骤S1制备的A料放置图2中浆料罐1内，并搅拌。将步骤S2制备的B料放置图2中储料罐2内；S3. Place the material A prepared in step S1 in the slurry tank 1 in FIG. 2 and stir it. Place the B material prepared in step S2 in the storage tank 2 in Fig. 2;
S4.数据建模：使用三维造型软件设计出所需结构形状的零件模型，将零件模型进行分层切片处理，层片厚度为0.05～0.2mm，得到零件的三维模型数据，并导入3D打印设备中；S4. Data modeling: Use 3D modeling software to design the part model of the required structural shape, and slice the part model in layers with a thickness of 0.05-0.2mm to obtain the 3D model data of the part and import it into the 3D printing equipment middle;
S5.设备按设定配比分别将A料与B料通过计量按质量比90～100:2输送至图2中混料罐3内，经搅拌得混合料C，然后混合物C输送至3D打印设备中的打印头内，按照三维模型数据进行打印，打印过程中给予能加速有机单体聚合的紫外光或激光束，具体在波长365～405氛围下打印，使得混合物C迅速固化，层层堆积成型，最终得到所需形状的坯体；S5. According to the set ratio, the equipment transports material A and material B to the mixing tank 3 in Figure 2 according to the mass ratio of 90 to 100:2 through metering, and mixes C to obtain the mixture C, which is then transported to the 3D printing machine In the printing head of the equipment, printing is carried out according to the three-dimensional model data. During the printing process, ultraviolet light or laser beams which can accelerate the polymerization of organic monomers are given. Specifically, the printing is performed in an atmosphere with a wavelength of 365-405, so that the mixture C is rapidly solidified and piled up layer by layer. Forming, and finally get the green body of the desired shape;
S6.将步骤S5得到的坯体在室温放置24～72h，然后在60℃下真空干燥，得到高强度坯体，随后在流动气氛条件下，将高强度坯体在600℃保温3h进行排胶处理，再放置在真空条件下，温度为1000～1300℃下烧结2h，得到最终产品。S6. Place the green body obtained in step S5 at room temperature for 24 to 72 hours, and then vacuum-dry it at 60°C to obtain a high-strength green body. Then, under the condition of flowing atmosphere, keep the high-strength green body at 600°C for 3 hours for debinding treatment, and then placed under vacuum conditions and sintered at a temperature of 1000-1300° C. for 2 hours to obtain the final product.
本实施例制备得到的坯体生坯强度达21MPa,常温空气中烧结相对密度98%以上。The green body prepared in this example has a green strength of 21 MPa and a relative density of sintered in air at room temperature above 98%.
实施例4Example 4
本实施例与实施例1基本相同，不同之处在于，步骤S1中所述纳米银粉体的体积分数为65%。This embodiment is basically the same as Embodiment 1, except that the volume fraction of the nano-silver powder in step S1 is 65%.
本实施例改变了纳米银粉体体积分数，制备得到的坯体生坯强度达到23MPA，烧结后得相对密度达到98%以上。In this embodiment, the volume fraction of the nano-silver powder is changed, and the green strength of the prepared green body reaches 23MPA, and the relative density after sintering reaches more than 98%.
实施例5Example 5
本实施例与实施例1基本相同，不同之处在于，步骤S1中所述纳米银粉体的体积分数为20%。This embodiment is basically the same as Embodiment 1, except that the volume fraction of the nano-silver powder in step S1 is 20%.
本实施例改变了纳米银粉体体积分数，制备得到的坯体生坯强度达到16MPA，烧结后得相对密度达到97%以上。In this embodiment, the volume fraction of the nano-silver powder is changed, and the green body strength of the prepared green body reaches 16MPA, and the relative density after sintering reaches more than 97%.
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| CN201711413239.1ACN107876779A (en) | 2017-12-24 | 2017-12-24 | A kind of water nano silver 3D printing base substrate method and its forming method |
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| CN201711413239.1ACN107876779A (en) | 2017-12-24 | 2017-12-24 | A kind of water nano silver 3D printing base substrate method and its forming method |
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| CN107876779Atrue CN107876779A (en) | 2018-04-06 |
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| CN201711413239.1APendingCN107876779A (en) | 2017-12-24 | 2017-12-24 | A kind of water nano silver 3D printing base substrate method and its forming method |
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