技术领域technical field
本发明涉及粉末3D打印技术领域，具体涉及一种基于水基无机粘结剂的粉末3D打印方法。The invention relates to the technical field of powder 3D printing, in particular to a powder 3D printing method based on a water-based inorganic binder.
背景技术Background technique
粉末3D打印(3DP)是一种利用微滴喷射、粉末粘结技术的3D打印方法。喷头在计算机控制下，按照当前分层截面的信息，在事先铺好的一层粉末材料上，有选择性地喷射粘结剂，使部分粉末粘结，形成一层截面薄层；一层成形完后，工作台下降一个层厚，进行下一层的铺粉，继而选区喷射粘结剂，成形薄层同时也会与已成形零件粘为一体；不断循环此过程，直至零件加工完为止；通常所成形的零件还需要一定的后处理，如干燥、烧结等，从而得到最后的零件。Powder 3D printing (3DP) is a 3D printing method that utilizes droplet jetting, powder bonding technology. Under the control of the computer, according to the information of the current layered cross-section, the nozzle selectively sprays the binder on the pre-laid layer of powder material, so that part of the powder is bonded to form a thin layer of cross-section; After completion, the workbench is lowered by one layer thickness, and the next layer of powder is spread, and then the adhesive is sprayed on the selected area, and the formed thin layer will also be bonded to the formed part at the same time; this process is continuously cycled until the part is processed; Usually the formed parts also need certain post-processing, such as drying, sintering, etc., so as to obtain the final parts.
在粉末3D打印工艺过程中，一般要求用于打印头喷射的粘结剂其性能稳定、能长期储存、对喷头无腐蚀作用、粘度低以及表面张力适宜等。通常，可以采用的液体粘结剂能够分为这三种类型：一、本身既不与粉末反应也不起粘结作用的液体，如氯仿、乙醇等，它们只起到为粉末相互结合提供介质的作用，其本身在模具制作完毕之后会挥发到几乎不剩下任何物质，对于本身就可以通过自反应硬化的粉末适用；二、本身会与粉末反应的液体及本身有部分粘结作用的液体，如目前较为常用的有机粘结剂，它们通过液体浸润并连接粉末，然后部分液体挥发，剩下的具有粘结作用的粘结剂会将粉末相互结合，其中，可添加的粘结组分包括缩丁醛树脂、聚氯乙烯、聚碳硅烷、聚乙烯吡咯烷酮以及一些其他高分子树脂等；三、粘结剂本身可以与粉末之间能反应的，如以氧化铝为主要成分的粉末，可通过酸性粘结剂的喷射反应固化，通常对于金属粉末，常常是在粘结剂中加入一些金属盐来诱发其反应。In the powder 3D printing process, it is generally required that the binder used for printing head injection has stable performance, long-term storage, no corrosion to the nozzle, low viscosity, and suitable surface tension. Generally, the liquid binders that can be used can be divided into these three types: 1. Liquids that neither react with the powder nor act as a bond, such as chloroform, ethanol, etc., they only serve as a medium for the powder to combine with each other After the mold is made, it will volatilize until there is almost no substance left. It is suitable for powders that can harden by self-reaction; 2. Liquids that react with powders and liquids that have a partial bonding effect , such as the more commonly used organic binders at present, they infiltrate and connect the powder through liquid, and then part of the liquid volatilizes, and the remaining binder with binding effect will combine the powder with each other. Among them, the bonding component that can be added Including butyral resin, polyvinyl chloride, polycarbosilane, polyvinylpyrrolidone and some other polymer resins; 3. The binder itself can react with the powder, such as the powder with alumina as the main component. It can be cured by the spray reaction of the acidic binder. Usually, for metal powder, some metal salts are often added to the binder to induce its reaction.
然而，正如以上内容所述，传统粉末3D打印工艺多采用有机粘结剂体系，而这种粘结剂体系主要存在以下两个方面的缺点：However, as mentioned above, the traditional powder 3D printing process mostly uses an organic binder system, and this binder system mainly has the following two disadvantages:
1)有机物粘结剂稳定性不好，在受到外界影响后，容易变质，不以存储，同时，有机粘结剂也容易腐蚀粘结剂的输送管道和打印喷头，容易造成喷头的堵塞；1) The stability of the organic binder is not good. After being affected by the outside world, it is easy to deteriorate and cannot be stored. At the same time, the organic binder is also easy to corrode the delivery pipeline of the binder and the printing nozzle, and it is easy to cause the nozzle to be blocked;
2)粉末3D打印所得到的零件通常需要进行脱脂、煅烧等后处理，但是，由于传统的有机物粘结剂在高温中性能不稳定，容易分解，达不到粘结效果，并可能释放有毒气体，使粉末3D打印制造出来的零件在脱脂、煅烧后，难以获得较高的致密度及强度。2) Parts obtained by powder 3D printing usually need post-processing such as degreasing and calcination. However, due to the unstable performance of traditional organic binders at high temperatures, they are easy to decompose, fail to achieve the bonding effect, and may release toxic gases , It is difficult to obtain higher density and strength after degreasing and calcination of parts manufactured by powder 3D printing.
发明内容Contents of the invention
为了克服上述现有技术的缺点，本发明的目的在于提供一种基于水基无机粘结剂的粉末3D打印方法，保证了制造过程的环保性，降低了生产成本，提高了产品质量。In order to overcome the above-mentioned shortcomings of the prior art, the purpose of the present invention is to provide a powder 3D printing method based on water-based inorganic binders, which ensures the environmental protection of the manufacturing process, reduces production costs, and improves product quality.
为了达到上述目的，本发明采用如下的技术方案：In order to achieve the above object, the present invention adopts following technical scheme:
一种基于水基无机粘结剂的粉末3D打印方法，包括以下步骤：A powder 3D printing method based on a water-based inorganic binder, comprising the following steps:
1)采用35-50份去离子水为粘结剂溶剂，加入50-65份氯化物盐作为粘结剂组分，添加0-50份助挥发剂提高粘结剂的干燥速度，添加0-5份着色剂进行粘结剂的着色，加入0-5份改性剂进行粘结剂的改性，混合形成的无机盐水溶液作为粉末3D打印机的粘结剂，将这种无机盐水溶液作为粘结剂粘结反应的第一个反应物；1) Use 35-50 parts of deionized water as the binder solvent, add 50-65 parts of chloride salt as the binder component, add 0-50 parts of co-volatile agent to improve the drying speed of the binder, add 0- 5 parts of colorant are used for coloring the binder, 0-5 parts of modifier are added for modification of the binder, and the inorganic salt solution formed by mixing is used as the binder of the powder 3D printer, and this inorganic salt solution is used as the adhesive The first reactant of the binder bonding reaction;
2)采用与步骤1)所用氯化物相对应的无机盐氧化物粉末作为反应材料，即采用15-30份氧化镁(MgO)或是15-30份氧化锌(ZnO)作为第二反应物，第二反应物与70-85份3D打印机原料粉末进行混合，再加入0-10份助熔剂进行粉末性能的调节，以上所形成的混合粉末作为粉末3D打印的材料；2) using the inorganic salt oxide powder corresponding to the chloride used in step 1) as the reaction material, that is, using 15-30 parts of magnesium oxide (MgO) or 15-30 parts of zinc oxide (ZnO) as the second reactant, The second reactant is mixed with 70-85 parts of 3D printer raw material powder, and then 0-10 parts of flux are added to adjust the properties of the powder, and the mixed powder formed above is used as the material for powder 3D printing;
3)采用20-40份步骤1)配制的粘结剂与60-80份步骤2)制备的混合粉末进行粉末3D打印，打印完成后保存打印零件在粉末3D打印机内部进行自然干燥，或者送入到热干燥箱或微波干燥箱中进行干燥；干燥完成后，去除未粘结粉末，直接获得无机粘结剂粘结陶瓷零件；3) Use 20-40 parts of the binder prepared in step 1) and 60-80 parts of the mixed powder prepared in step 2) for powder 3D printing. After printing, save the printed parts in the powder 3D printer for natural drying, or send them into Dry in a thermal drying oven or a microwave drying oven; after drying, remove the unbonded powder and directly obtain inorganic binder bonded ceramic parts;
4)根据材料组成需要，进行高温烧结，获得高强度零件；4) According to the requirements of material composition, high-temperature sintering is carried out to obtain high-strength parts;
所述份数为质量份数。The parts are parts by mass.
所述氯化物盐是氯化镁(MgCl2)或氯化锌(ZnCl2)的浓度为5％～70％水溶液。The chloride salt is an aqueous solution of magnesium chloride (MgCl2 ) or zinc chloride (ZnCl2 ) with a concentration of 5% to 70%.
所述的助挥发剂为酒精、丙酮或甲醇。Described co-volatile agent is alcohol, acetone or methanol.
所述的着色剂为有机墨水或无机墨水。The coloring agent is organic ink or inorganic ink.
所述的改性剂为增稠剂、表面改性剂或分散剂。The modifier is a thickener, a surface modifier or a dispersant.
所述的原料粉末为陶瓷、硅藻土、砂或石膏的粉末。The raw material powder is powder of ceramics, diatomite, sand or gypsum.
所述的助熔剂为氧化钙(CaO)、氧化钾(K2O)、氧化钠(Na2O)、氧化铅(PbO)或氧化硼(B2O3)。The fluxing agent is calcium oxide (CaO), potassium oxide (K2 O), sodium oxide (Na2 O), lead oxide (PbO) or boron oxide (B2 O3 ).
本发明的优点是采用氯化物溶液与对应氧化物粉末形成的水基无机粘结剂体系作为粉末3D打印工艺的粘结剂，这种粘结剂体系相对于有机物粘结剂的不稳定性而言，其性能稳定、更易于保存；同时，基于水基的无机粘结剂，其粘度低，不易堵塞喷头，对喷头无腐蚀作用，可以获得更加适宜的表面张力，从而可以实现具有复杂结构制品的粉末3D打印快速制造，也保证了制造过程的环保性，降低了生产成本，提高了产品质量。The advantage of the present invention is that the water-based inorganic binder system formed by the chloride solution and the corresponding oxide powder is used as the binder of the powder 3D printing process, and this binder system is relatively stable compared to the instability of the organic binder. In other words, its performance is stable and easier to store; at the same time, the water-based inorganic binder has low viscosity, is not easy to block the nozzle, has no corrosion effect on the nozzle, and can obtain a more suitable surface tension, so that products with complex structures can be realized. The rapid manufacturing of powder 3D printing also ensures the environmental protection of the manufacturing process, reduces production costs and improves product quality.
具体实施方式Detailed ways
下面结合具体实施例对本发明做详细描述。The present invention will be described in detail below in conjunction with specific embodiments.
实施例1Example 1
一种基于水基无机粘结剂的粉末3D打印方法，包括以下步骤：A powder 3D printing method based on a water-based inorganic binder, comprising the following steps:
1)采用35份去离子水为粘结剂溶剂，加入64份氯化镁(MgCl2)40％水溶液作为粘结剂组分，添加1份酒精作为助挥发剂提高粘结剂的干燥速度，不添加着色剂进行粘结剂的着色，也不添加改性剂进行粘结剂的改性，混合形成的无机盐水溶液作为粉末3D打印机的粘结剂，将这种无机盐水溶液作为粘结剂粘结反应的第一个反应物；1) Use 35 parts of deionized water as the binder solvent, add 64 parts of magnesium chloride (MgCl2 ) 40% aqueous solution as the binder component, add 1 part of alcohol as a volatilization aid to improve the drying speed of the binder, do not add The coloring agent is used to color the binder, and no modifier is added to modify the binder. The inorganic salt solution formed by mixing is used as the binder of the powder 3D printer, and the inorganic salt solution is used as the binder for bonding the first reactant of the reaction;
2)采用与步骤1)所用氯化物相对应的无机盐氧化物粉末作为反应材料，即采用15份氧化镁(MgO)作为第二反应物，第二反应物与85份3D打印机的陶瓷粉末进行混合，不添加助熔剂进行粉末性能的调节，以上所形成的混合粉末作为粉末3D打印的材料；2) Using the inorganic salt oxide powder corresponding to the chloride used in step 1) as the reaction material, that is, using 15 parts of magnesium oxide (MgO) as the second reactant, and the second reactant is carried out with 85 parts of ceramic powder of the 3D printer. Mixing, without adding flux to adjust the powder properties, the mixed powder formed above is used as the material for powder 3D printing;
3)采用40份步骤1)配制的粘结剂与60份步骤2)制备的混合粉末进行粉末3D打印，打印完成后保存打印零件在粉末3D打印机内部进行自然干燥，或者送入到热干燥箱或微波干燥箱中进行干燥；干燥完成后，去除未粘结粉末，可直接获得无机粘结剂粘结陶瓷零件；3) Use 40 parts of the binder prepared in step 1) and 60 parts of the mixed powder prepared in step 2) for powder 3D printing. After printing, save the printed parts in the powder 3D printer for natural drying, or send them to a heat drying box Or dry in a microwave drying oven; after drying, remove the unbonded powder, and directly obtain inorganic binder bonded ceramic parts;
4)根据材料组成需要，进行高温烧结，获得高强度零件，所述份数为质量份数。4) According to the requirements of material composition, high-temperature sintering is carried out to obtain high-strength parts, and the stated parts are parts by mass.
采用实施例1方案得到的液体粘结剂溶液，在室温下，其粘度<2×10-3Pa·s，粘度较低，氯化镁与其相对应的无机盐氧化镁形成的粘结剂粘结强度>0.8MPa，粘结效果好，可以很好地满足粉末彩色3D打印要求。The liquid binder solution obtained by using the scheme of Example 1 has a viscosity of <2×10-3 Pa·s at room temperature, and the viscosity is relatively low. The bonding strength of the binder formed by magnesium chloride and its corresponding inorganic salt magnesium oxide is >0.8MPa, the bonding effect is good, which can well meet the requirements of powder color 3D printing.
实施例2Example 2
一种基于水基无机粘结剂的粉末3D打印方法，包括以下步骤：A powder 3D printing method based on a water-based inorganic binder, comprising the following steps:
1)采用35份去离子水为粘结剂溶剂，加入64份氯化锌(ZnCl2)40％水溶液作为粘结剂组分，添加1份酒精作为助挥发剂提高粘结剂的干燥速度，不添加着色剂进行粘结剂的着色，也不添加改性剂进行粘结剂的改性，混合形成的无机盐水溶液作为粉末3D打印机的粘结剂，将这种无机盐水溶液作为粘结剂粘结反应的第一个反应物；1) Using 35 parts of deionized water as a binder solvent, adding 64 parts of zinc chloride (ZnCl2 ) 40% aqueous solution as a binder component, adding 1 part of alcohol as a volatilization aid to improve the drying speed of the binder, Do not add colorant to color the binder, do not add modifier to modify the binder, mix the formed inorganic salt solution as the binder of the powder 3D printer, and use this inorganic salt solution as the binder The first reactant of the bonding reaction;
2)采用与步骤1)所用氯化物相对应的无机盐氧化物粉末作为反应材料，即采用30份氧化锌(ZnO)作为第二反应物，第二反应物与70份3D打印机的硅藻土粉末进行混合，不添加助熔剂进行粉末性能的调节，以上所形成的混合粉末作为粉末3D打印的材料；2) Adopt the inorganic salt oxide powder corresponding to the chloride used in step 1) as the reaction material, that is, adopt 30 parts of zinc oxide (ZnO) as the second reactant, and the second reactant and 70 parts of diatomite of the 3D printer The powder is mixed, and the properties of the powder are adjusted without adding flux. The mixed powder formed above is used as the material for powder 3D printing;
3)采用40份步骤1)配制的粘结剂与60份步骤2)制备的混合粉末进行粉末3D打印，打印完成后保存打印零件在粉末3D打印机内部进行自然干燥，或者送入到热干燥箱或微波干燥箱中进行干燥；干燥完成后，去除未粘结粉末，可直接获得无机粘结剂粘结陶瓷零件；3) Use 40 parts of the binder prepared in step 1) and 60 parts of the mixed powder prepared in step 2) for powder 3D printing. After printing, save the printed parts in the powder 3D printer for natural drying, or send them to a heat drying box Or dry in a microwave drying oven; after drying, remove the unbonded powder, and directly obtain inorganic binder bonded ceramic parts;
4)根据材料组成需要，进行高温烧结，获得高强度零件，所述份数为质量份数。4) According to the requirements of material composition, high-temperature sintering is carried out to obtain high-strength parts, and the stated parts are parts by mass.
采用实施例2方案得到的液体粘结剂溶液，在室温下，其粘度<2×10-3Pa·s，粘度较低，氯化锌与其相对应的无机盐氧化锌形成的粘结剂粘结强度>0.8MPa，粘结效果好，可以很好地满足粉末彩色3D打印要求。The liquid binder solution obtained by adopting the scheme of Example 2 has a viscosity of <2×10-3 Pa·s at room temperature, and the viscosity is relatively low. The binder formed by zinc chloride and its corresponding inorganic salt zinc oxide is sticky The junction strength is >0.8MPa, and the bonding effect is good, which can well meet the requirements of powder color 3D printing.
实施例3Example 3
一种基于水基无机粘结剂的粉末3D打印方法，包括以下步骤：A powder 3D printing method based on a water-based inorganic binder, comprising the following steps:
1)采用45份去离子水为粘结剂溶剂，加入50份氯化锌(ZnCl2)40％水溶液作为粘结剂组分，添加1份酒精作为助挥发剂提高粘结剂的干燥速度，添加3份无机墨水作为着色剂进行粘结剂的着色，添加1份增稠剂作为改性剂进行粘结剂的改性，混合形成的无机盐水溶液作为粉末3D打印机的粘结剂，将这种无机盐水溶液作为粘结剂粘结反应的第一个反应物；1) Using 45 parts of deionized water as a binder solvent, adding 50 parts of zinc chloride (ZnCl2 ) 40% aqueous solution as a binder component, adding 1 part of alcohol as a volatilization aid to improve the drying speed of the binder, Add 3 parts of inorganic ink as a colorant to color the binder, add 1 part of thickener as a modifier to modify the binder, and mix the formed inorganic salt solution as the binder of the powder 3D printer. A kind of inorganic salt aqueous solution is used as the first reactant of binder bonding reaction;
2)采用与步骤1)所用氯化物相对应的无机盐氧化物粉末作为反应材料，即采用30份氧化锌(ZnO)作为第二反应物，第二反应物与65份3D打印机的砂粉末进行混合，添加5份氧化钙(CaO)作为助熔剂进行粉末性能的调节，以上所形成的混合粉末作为粉末3D打印的材料；2) Use the inorganic salt oxide powder corresponding to the chloride used in step 1) as the reaction material, that is, use 30 parts of zinc oxide (ZnO) as the second reactant, and the second reactant is carried out with 65 parts of sand powder of the 3D printer. Mix, add 5 parts of calcium oxide (CaO) as a flux to adjust the properties of the powder, and the mixed powder formed above is used as the material for powder 3D printing;
3)采用40份步骤1)配制的粘结剂与60份步骤2)制备的混合粉末进行粉末3D打印，打印完成后保存打印零件在粉末3D打印机内部进行自然干燥，或者送入到热干燥箱或微波干燥箱中进行干燥；干燥完成后，去除未粘结粉末，可直接获得无机粘结剂粘结陶瓷零件；3) Use 40 parts of the binder prepared in step 1) and 60 parts of the mixed powder prepared in step 2) for powder 3D printing. After printing, save the printed parts in the powder 3D printer for natural drying, or send them to a heat drying box Or dry in a microwave drying oven; after drying, remove the unbonded powder, and directly obtain inorganic binder bonded ceramic parts;
4)根据材料组成需要，进行高温烧结，获得高强度零件，所述份数为质量份数。4) According to the requirements of material composition, high-temperature sintering is carried out to obtain high-strength parts, and the stated parts are parts by mass.
采用实施例3方案得到的液体粘结剂溶液，在室温下，其粘度<1.5×10-3Pa·s，粘度近乎于纯水；氯化锌与其相对应的无机盐氧化锌形成的粘结剂粘结强度>0.5MPa，粘结效果较好；加入了着色剂，增加了颜色，可以实现粉末彩色3D打印；加入助挥发剂，挥发效果较好，增加了粘结效果；加入了助熔剂，可以降低零件在后处理高温烧结的温度，可以很好地满足粉末彩色3D打印要求。The liquid binder solution obtained by using the scheme of Example 3 has a viscosity of <1.5×10-3 Pa·s at room temperature, and its viscosity is close to that of pure water; the bond formed by zinc chloride and its corresponding inorganic salt zinc oxide The bonding strength of the agent is >0.5MPa, and the bonding effect is better; the colorant is added to increase the color, and the powder color 3D printing can be realized; the volatilization aid is added, the volatilization effect is better, and the bonding effect is increased; the flux is added , can reduce the temperature of parts after high-temperature sintering in post-processing, and can well meet the requirements of powder color 3D printing.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410384306.1ACN104150915B (en) | 2014-08-06 | 2014-08-06 | A kind of powder 3D Method of printing based on water-based inorganic binding agent |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410384306.1ACN104150915B (en) | 2014-08-06 | 2014-08-06 | A kind of powder 3D Method of printing based on water-based inorganic binding agent |
| Publication Number | Publication Date |
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| CN104150915A CN104150915A (en) | 2014-11-19 |
| CN104150915Btrue CN104150915B (en) | 2015-08-26 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410384306.1AActiveCN104150915B (en) | 2014-08-06 | 2014-08-06 | A kind of powder 3D Method of printing based on water-based inorganic binding agent |
| Country | Link |
|---|---|
| CN (1) | CN104150915B (en) |
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