技术领域Technical field
本发明涉及多孔陶瓷技术领域，特别涉及一种氧化铝多孔陶瓷膏料及其制备方法和增材制造成形方法。The present invention relates to the technical field of porous ceramics, and in particular to an alumina porous ceramic paste and its preparation method and additive manufacturing forming method.
背景技术Background technique
多孔陶瓷又称为微孔陶瓷或泡沫陶瓷，是指具有一定尺寸和数量的孔隙结构的新型陶瓷材料，其主要利用材料中的孔洞结构与材质本身结合而具有的性质来达到所需的功能。作为一种新型绿色环保的材料，其具有孔隙率高、渗透率高、比表面积大、体积密度小、热导率低、耐腐蚀、高的化学稳定性和尺寸稳定性等优异特性。Porous ceramics, also known as microporous ceramics or foam ceramics, refer to new ceramic materials with a certain size and number of pore structures. They mainly use the properties of the pore structure in the material and the material itself to achieve the required functions. As a new type of green and environmentally friendly material, it has excellent properties such as high porosity, high permeability, large specific surface area, low volume density, low thermal conductivity, corrosion resistance, high chemical stability and dimensional stability.
现有的制备多孔陶瓷的工艺已经比较多，包括有机泡沫前驱体法、添加造孔剂法、发泡法、颗粒堆积法等。其中，有机泡沫前驱体法不能达到制成微米级孔的多孔陶瓷；加造孔剂法和发泡法所制备的多孔陶瓷的孔隙比较不均匀，在有些方面制成的多孔陶瓷的孔与孔之间不能连续贯通，且发泡法多为闭气孔；使用颗粒堆积法制备的多孔陶瓷，孔隙分布比较均匀，能形成多种孔隙大小并连通的孔隙，但由于要涉及到颗粒的成型并添加粘结剂压制成型等工艺过程，整个工艺过程比较复杂。因此，有必要寻找一种多孔陶瓷的制备方法，以制成孔隙率高、空隙均匀、每个孔隙全部是密封空隙的多孔陶瓷。There are many existing processes for preparing porous ceramics, including organic foam precursor method, pore-forming agent addition method, foaming method, particle accumulation method, etc. Among them, the organic foam precursor method cannot produce porous ceramics with micron-sized pores; the pores of porous ceramics prepared by the pore-forming agent method and the foaming method are relatively uneven, and in some aspects, the pores of the porous ceramics produced are There is no continuous connection between them, and the foaming method is mostly closed pores; the porous ceramics prepared using the particle accumulation method have a relatively uniform pore distribution and can form multiple pore sizes and connected pores. However, since it involves the molding of particles and the addition of The entire process of binder pressing and molding is relatively complex. Therefore, it is necessary to find a method for preparing porous ceramics to produce porous ceramics with high porosity, uniform voids, and all pores are sealed voids.
发明内容Contents of the invention
为解决现有多孔陶瓷制备工艺制得的多孔陶瓷的不足，本发明提供一种氧化铝多孔陶瓷膏料的制备方法，包括以下步骤：In order to solve the shortcomings of porous ceramics produced by existing porous ceramic preparation processes, the present invention provides a preparation method of alumina porous ceramic paste, which includes the following steps:
S1、将1000目的氧化铝、500目的氧化铝纤维粉和第一部分无水乙醇加入反应容器中，调节体系温度为60±2℃，搅拌5-10min,搅拌的速率为100r/min，搅拌混匀得到第一混合物；S1. Add 1000 mesh alumina, 500 mesh alumina fiber powder and the first part of absolute ethanol into the reaction vessel, adjust the system temperature to 60±2℃, stir for 5-10min, the stirring rate is 100r/min, stir and mix A first mixture is obtained;
S2、持续搅拌下向所述第一混合物中加入第一部分聚碳硅烷和浓度大于40wt％的氢氧化钠溶液，使之絮凝沉淀后加入第二部分无水乙醇，继续搅拌6-8min，搅拌的速率为300r/min，得到第二混合物；S2. Add the first part of polycarbosilane and a sodium hydroxide solution with a concentration greater than 40wt% to the first mixture under continuous stirring, make it flocculate and precipitate, add the second part of absolute ethanol, and continue stirring for 6-8 minutes. The speed is 300r/min, and the second mixture is obtained;
S3、将所述第二混合物静置10min后，向所述第二混合物中加入第二部分聚碳硅烷、第三部分无水乙醇和液态光敏树脂，调节体系温度为30±2℃，搅拌10-15min，搅拌的速率为100r/min，得到所述氧化铝多孔陶瓷膏料。S3. After letting the second mixture stand for 10 minutes, add the second part of polycarbosilane, the third part of absolute ethanol and liquid photosensitive resin to the second mixture, adjust the system temperature to 30±2°C, and stir for 10 -15min, the stirring rate is 100r/min, and the alumina porous ceramic paste is obtained.
通过在氧化铝粉和氧化铝纤维粉基体中引入第一部分聚碳硅烷和分散剂，使之絮凝沉淀，通过搅拌使水相中分散的陶瓷粉料团聚，通过在液相中均匀沉降堆积，从而形成高孔隙率的多孔结构；并且，在絮凝的过程中引入第二部分聚碳硅烷，使其生成的气泡不至于由于长期的搅拌而破碎，制成的多孔陶瓷的孔隙可以比单单絮凝法制备的多孔陶瓷的空隙率要高。By introducing the first part of polycarbosilane and dispersant into the alumina powder and alumina fiber powder matrix to cause flocculation and precipitation, the ceramic powder dispersed in the water phase is agglomerated through stirring, and the ceramic powder dispersed in the water phase is agglomerated through uniform sedimentation and accumulation in the liquid phase. A porous structure with high porosity is formed; and the second part of polycarbosilane is introduced during the flocculation process so that the bubbles generated will not be broken due to long-term stirring. The pores of the porous ceramics produced can be smaller than those prepared by the single flocculation method. The porosity of porous ceramics is higher.
进一步的，以质量百分比计，所述膏料的原料包括所述氧化铝40wt％-60wt％、氧化铝纤维粉5wt％-10wt％、聚碳硅烷10wt％-15wt％、液态光敏树脂5wt％-10wt％、浓度大于40wt％的氢氧化钠溶液5wt％-10wt％和无水乙醇15wt％；Further, in terms of mass percentage, the raw materials of the paste include the alumina 40wt%-60wt%, alumina fiber powder 5wt%-10wt%, polycarbosilane 10wt%-15wt%, liquid photosensitive resin 5wt%- 10wt%, 5wt%-10wt% sodium hydroxide solution with a concentration greater than 40wt% and absolute ethanol 15wt%;
其中，其中，所述第一部分无水乙醇、第二部分无水乙醇和第三部分无水乙醇用量之和为所述无水乙醇总量；所述第一部分聚碳硅烷和第二部分聚碳硅烷的用量之和为所述聚碳硅烷总量。Wherein, the sum of the amounts of the first part of absolute ethanol, the second part of absolute ethanol and the third part of absolute ethanol is the total amount of absolute ethanol; the first part of polycarbosilane and the second part of polycarbonate The sum of the amounts of silanes is the total amount of polycarbosilane.
进一步的，步骤S2中，所述第一部分聚碳硅烷与所述氧化铝的质量比为(5-10)：(40-60)。Further, in step S2, the mass ratio of the first part of polycarbosilane to the alumina is (5-10): (40-60).
进一步的，步骤S3中，所述第二部分聚碳硅烷与所述氧化铝的质量比为5：(40-60)。Further, in step S3, the mass ratio of the second part of polycarbosilane to the alumina is 5: (40-60).
本发明还提供一种氧化铝多孔陶瓷膏料，由上述的制备方法制得。The invention also provides an alumina porous ceramic paste, which is prepared by the above preparation method.
本发明还提供一种氧化铝多孔陶瓷增材制造成形方法，采用上述的氧化铝多孔陶瓷膏料作为原料。The invention also provides an alumina porous ceramic additive manufacturing and forming method, using the above-mentioned alumina porous ceramic paste as a raw material.
进一步的，所述增材制造成形方法包括：3D打印制备坯体、坯体预氧化和坯体烧结，其中所述预氧化的温度为1000-1200℃。Further, the additive manufacturing forming method includes: 3D printing to prepare a green body, pre-oxidation of the green body and sintering of the green body, wherein the temperature of the pre-oxidation is 1000-1200°C.
在预氧化烧结期间，主要是在该温度下，使膏料中的聚碳硅烷处于较高的活性，进而被均匀气化，形成闭孔，同时，在该温度下，氧化铝粉及氧化铝纤维粉的活性进一步增加，使其的晶粒更细化。通过预氧化烧结，可以得到均质闭孔细晶化的氧化铝多孔陶瓷坯体，为进一步的高温烧结做好更均质更细晶化的氧化铝多孔陶瓷做好基础准备。During the pre-oxidation sintering, it is mainly at this temperature that the polycarbosilane in the paste is highly active and then uniformly vaporized to form closed pores. At the same time, at this temperature, the alumina powder and alumina The activity of fiber powder is further increased, making its grains more refined. Through pre-oxidation sintering, a homogeneous closed-pore fine-grained alumina porous ceramic body can be obtained, which lays the foundation for further high-temperature sintering to prepare a more homogeneous and fine-grained alumina porous ceramic.
进一步的，所述3D打印制备坯体包括如下步骤：Further, the 3D printing preparation body includes the following steps:
(1)设计三维实体模型；(1) Design a three-dimensional solid model;
(2)STL文件数据转换；(2) STL file data conversion;
(3)分层切片及模型分析；(3) Layered slicing and model analysis;
(4)加入支撑物及分析支撑受力；(4) Add supports and analyze the stress of the supports;
(5)激光扫描逐层成型，得到产品三维模型坯体；(5) Laser scanning is used to form layer by layer to obtain a three-dimensional model of the product;
(6)对所述坯体余料及所述坯体表面进行处理；(6) Treat the remaining material of the green body and the surface of the green body;
将氧化铝陶瓷粉末和氧化铝纤维粉均匀分散在制备的有机聚合物溶液中，制成氧化铝陶瓷粉末和氧化铝纤维粉状膏料；再使氧化铝陶瓷粉末和氧化铝纤维粉状膏料中的有机聚合物析出，经过增材制造的激光固化，有机聚合物析出成絮状多孔结构后，加热蒸发所有溶剂，形成陶瓷生坯，絮状的有机聚合物均匀分布于陶瓷生坯中；然后继续加热，烧除絮状的有机聚合物，形成多孔的陶瓷生坯；最后高温烧结形成高强度的多孔陶瓷。Disperse alumina ceramic powder and alumina fiber powder evenly in the prepared organic polymer solution to prepare alumina ceramic powder and alumina fiber powdery paste; then make alumina ceramic powder and alumina fiber powdery paste The organic polymer in the ceramic is precipitated. After the laser curing of additive manufacturing, the organic polymer is precipitated into a flocculent porous structure, and then all solvents are heated to evaporate to form a ceramic green body. The flocculent organic polymer is evenly distributed in the ceramic green body; Then continue to heat to burn out the flocculent organic polymer to form a porous ceramic green body; finally, it is sintered at high temperature to form a high-strength porous ceramic.
与现有技术相比，本发明提供的氧化铝多孔陶瓷膏料以氧化铝粉和氧化铝纤维粉为基体材料，配合聚碳硅烷、氢氧化钠溶液、无水乙醇，通过控制各组分的质量含量，制作成分散性好，流动性高，稳定的多孔陶瓷膏料，可作为增材制造的膏料；同时，该膏料成型过程简单，只需要于在反应釜里加热即可，并具有颗粒堆积法的优点，但又省却了颗粒的机械成型过程，成本低廉；通过采用该膏料进行增材制造成型工艺，制成的多孔陶瓷孔隙率高，且孔隙多为闭孔、孔隙分布更为均匀。Compared with the existing technology, the alumina porous ceramic paste provided by the present invention uses alumina powder and alumina fiber powder as base materials, and is combined with polycarbosilane, sodium hydroxide solution, and absolute ethanol. By controlling the composition of each component Mass content, it can be made into a porous ceramic paste with good dispersion, high fluidity and stability, which can be used as a paste for additive manufacturing; at the same time, the paste forming process is simple and only needs to be heated in a reaction kettle and It has the advantages of particle accumulation method, but saves the mechanical molding process of particles and is low-cost; by using this paste for additive manufacturing molding process, the porous ceramics produced have high porosity, and the pores are mostly closed pores and pore distribution. More uniform.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作一简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the drawings in the following description These are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without exerting creative efforts.
图1为本发明实施例1提供的氧化铝多孔陶瓷电镜图，标尺为6μm；Figure 1 is an electron microscope image of the alumina porous ceramic provided in Example 1 of the present invention, the scale bar is 6 μm;
图2为本发明对比例1提供的氧化铝多孔陶瓷电镜图，标尺为6μm；Figure 2 is an electron microscope image of the alumina porous ceramic provided in Comparative Example 1 of the present invention, the scale bar is 6 μm;
图3为本发明实施例1提供的氧化铝多孔陶瓷电镜图，标尺为1μm；Figure 3 is an electron microscope image of the alumina porous ceramic provided in Example 1 of the present invention, the scale bar is 1 μm;
图4为本发明对比例2提供的氧化铝多孔陶瓷电镜图，标尺为1μm；Figure 4 is an electron microscope image of the alumina porous ceramic provided in Comparative Example 2 of the present invention, the scale bar is 1 μm;
图5为本发明实施例1提供的氧化铝多孔陶瓷电镜图，标尺为4μm；Figure 5 is an electron microscope image of the alumina porous ceramic provided in Example 1 of the present invention, the scale bar is 4 μm;
图6为本发明对比例3提供的氧化铝多孔陶瓷电镜图，标尺为4μm；Figure 6 is an electron microscope image of the alumina porous ceramic provided in Comparative Example 3 of the present invention, the scale bar is 4 μm;
附图标记：1、氧化铝；2、氧化铝纤维；3、闭孔；4、氧化铝陶瓷颗粒。Reference signs: 1. Alumina; 2. Alumina fiber; 3. Closed pores; 4. Alumina ceramic particles.
具体实施方式Detailed ways
为使本发明实施例的目的、技术方案和优点更加清楚，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作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。In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments These are some embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts fall within the scope of protection of the present invention.
本发明提供一种氧化铝多孔陶瓷膏料的制备方法操作示例，包括以下步骤：The invention provides an operational example of a method for preparing alumina porous ceramic paste, which includes the following steps:
S1、将1000目的氧化铝、500目的氧化铝纤维粉和第一部分无水乙醇加入反应容器中，调节体系温度为60±2℃，搅拌5-10min,搅拌的速率为100r/min，搅拌混匀得到第一混合物；S1. Add 1000 mesh alumina, 500 mesh alumina fiber powder and the first part of absolute ethanol into the reaction vessel, adjust the system temperature to 60±2℃, stir for 5-10min, the stirring rate is 100r/min, stir and mix A first mixture is obtained;
S2、持续搅拌下向所述第一混合物中加入第一部分聚碳硅烷和浓度大于40wt％的氢氧化钠溶液，使之絮凝沉淀后加入第二部分无水乙醇，继续搅拌6-8min，搅拌的速率为300r/min，得到第二混合物；其中第一部分聚碳硅烷与氧化铝的质量比为(5-10)：(40-60)；S2. Add the first part of polycarbosilane and a sodium hydroxide solution with a concentration greater than 40wt% to the first mixture under continuous stirring, make it flocculate and precipitate, add the second part of absolute ethanol, and continue stirring for 6-8 minutes. The speed is 300r/min, and a second mixture is obtained; the mass ratio of the first part of polycarbosilane to alumina is (5-10): (40-60);
S3、将所述第二混合物静置10min后，向所述第二混合物中加入第二部分聚碳硅烷、第三部分无水乙醇和液态光敏树脂，调节体系温度为30±2℃，搅拌10-15min，搅拌的速率为100r/min，得到所述氧化铝多孔陶瓷膏料，其中第二部分聚碳硅烷与氧化铝的质量比为5：(40-60)。S3. After letting the second mixture stand for 10 minutes, add the second part of polycarbosilane, the third part of absolute ethanol and liquid photosensitive resin to the second mixture, adjust the system temperature to 30±2°C, and stir for 10 -15 min, the stirring rate is 100 r/min, and the alumina porous ceramic paste is obtained, in which the mass ratio of the second part of polycarbosilane to alumina is 5: (40-60).
其中，以质量百分比计，所述氧化铝多孔陶瓷膏料的原料包括：氧化铝40wt％-60wt％、氧化铝纤维粉5wt％-10wt％、聚碳硅烷10wt％-15wt％、液态光敏树脂5wt％-10wt％、浓度大于40wt％的氢氧化钠溶液5wt％-10wt％和无水乙醇15wt％。Among them, in terms of mass percentage, the raw materials of the alumina porous ceramic paste include: alumina 40wt%-60wt%, alumina fiber powder 5wt%-10wt%, polycarbosilane 10wt%-15wt%, liquid photosensitive resin 5wt %-10wt%, sodium hydroxide solution with a concentration greater than 40wt% 5wt%-10wt% and absolute ethanol 15wt%.
本发明还提供一种氧化铝多孔陶瓷增材制造成形方法，包括3D打印制备坯体、坯体预氧化和坯体烧结。The invention also provides an alumina porous ceramic additive manufacturing and forming method, which includes preparing a green body by 3D printing, pre-oxidizing the green body and sintering the green body.
其中，所述增材制造成形方法采用的原料为上述的氧化铝多孔陶瓷膏料；Wherein, the raw material used in the additive manufacturing forming method is the above-mentioned alumina porous ceramic paste;
所述预氧化的温度为1000-1200℃。The pre-oxidation temperature is 1000-1200°C.
所述3D打印制备坯体包括如下步骤：The 3D printing preparation body includes the following steps:
(1)设计三维实体模型；(1) Design a three-dimensional solid model;
(2)STL文件数据转换；(2) STL file data conversion;
(3)分层切片及模型分析；(3) Layered slicing and model analysis;
(4)加入支撑物及分析支撑受力；(4) Add supports and analyze the stress of the supports;
(5)激光扫描逐层成型，得到产品三维模型坯体；(5) Laser scanning is used to form layer by layer to obtain a three-dimensional model of the product;
(6)对所述坯体余料及所述坯体表面进行处理。(6) Treat the remaining material of the green body and the surface of the green body.
本发明提供如下实施例和对比例的氧化铝多孔陶瓷的原料组成，见表1：The present invention provides the raw material composition of the alumina porous ceramics of the following examples and comparative examples, see Table 1:
表1(单位：质量百分比)Table 1 (unit: mass percentage)
本发明还提供实施例1-3和对比例1-2的氧化铝多孔陶瓷增材制造成形方法，包括如下步骤：The present invention also provides the alumina porous ceramic additive manufacturing and forming method of Examples 1-3 and Comparative Examples 1-2, which includes the following steps:
S10、制备氧化铝多孔陶瓷膏料；S10. Prepare alumina porous ceramic paste;
S20、通过3D打印，采用S10制得的氧化铝多孔陶瓷膏料作为原料，制备坯体；S20. Prepare the green body through 3D printing, using the alumina porous ceramic paste prepared in S10 as raw material;
S30、将坯体在1000℃、空气气氛下预氧化烧结20h；S30. Pre-oxidize and sinter the green body at 1000°C in air atmosphere for 20 hours;
S40、将S30预氧化后的坯体继续进行烧结，烧结温度为2000℃，时间为40h，得到氧化铝多孔陶瓷。S40. Continue to sinter the pre-oxidized body in S30 at a sintering temperature of 2000°C and a time of 40 hours to obtain alumina porous ceramics.
其中，S10中氧化铝多孔陶瓷膏料的制备方法包括如下步骤：Among them, the preparation method of alumina porous ceramic paste in S10 includes the following steps:
S11、将1000目的氧化铝、500目的氧化铝纤维粉和第一部分无水乙醇加入反应容器中，调节体系温度为60℃，搅拌5min,搅拌的速率为100r/min，搅拌混匀得到第一混合物；S11. Add 1000 mesh alumina, 500 mesh alumina fiber powder and the first part of absolute ethanol into the reaction vessel, adjust the system temperature to 60°C, stir for 5 minutes, the stirring rate is 100r/min, stir and mix to obtain the first mixture ;
S12、持续搅拌下向所述第一混合物中加入第一部分聚碳硅烷和45wt％的氢氧化钠溶液，使之絮凝沉淀后加入第二部分无水乙醇，继续搅拌8min，搅拌的速率为300r/min，得到第二混合物；S12. Add the first part of polycarbosilane and 45wt% sodium hydroxide solution to the first mixture under continuous stirring, allow it to flocculate and precipitate, add the second part of absolute ethanol, and continue stirring for 8 minutes at a stirring rate of 300 r/ min, get the second mixture;
S13、将所述第二混合物静置10min后，向所述第二混合物中加入第二部分聚碳硅烷、第三部分无水乙醇和液态光敏树脂，调节体系温度为30℃，搅拌10min，搅拌的速率为100r/min，得到所述氧化铝多孔陶瓷膏料。S13. After letting the second mixture stand for 10 minutes, add the second part of polycarbosilane, the third part of absolute ethanol and liquid photosensitive resin to the second mixture, adjust the system temperature to 30°C, stir for 10 min, and stir The speed is 100r/min, and the alumina porous ceramic paste is obtained.
对比例3Comparative example 3
与实施例1不同的是，S10中氧化铝多孔陶瓷膏料的制备方法为：将所有原料加入反应容器中，调节体系温度为60℃，搅拌混匀得到氧化铝多孔陶瓷膏料，其中搅拌转速为300r/min，搅拌时间为20min。其余处理步骤同实施例1。Different from Example 1, the preparation method of alumina porous ceramic paste in S10 is: add all raw materials into the reaction vessel, adjust the system temperature to 60°C, stir and mix to obtain alumina porous ceramic paste, where the stirring speed It is 300r/min, and the stirring time is 20min. The remaining processing steps are the same as in Example 1.
采用电镜对实施例1和对比例1-3制得的氧化铝多孔陶瓷进行表征，得到图1-6。图1、3和5为本发明实施例1提供的氧化铝多孔陶瓷在不同放大倍率下的电镜图，图2为对比例1提供的氧化铝多孔陶瓷电镜图，图4为对比例2提供的氧化铝多孔陶瓷电镜图，图6为对比例3提供的氧化铝多孔陶瓷电镜图；The alumina porous ceramics prepared in Example 1 and Comparative Examples 1-3 were characterized using an electron microscope, and Figures 1-6 were obtained. Figures 1, 3 and 5 are electron microscopy images of the alumina porous ceramic provided in Example 1 of the present invention at different magnifications. Figure 2 is an electron microscopy image of the alumina porous ceramic provided in Comparative Example 1. Figure 4 is an electron microscopy image provided in Comparative Example 2. Electron microscopy image of alumina porous ceramics. Figure 6 is an electron microscopy image of alumina porous ceramics provided in Comparative Example 3;
图1、3和5可知，通过本发明提供的氧化铝多孔陶瓷膏料特定配比和制备工艺，得到的氧化铝多孔陶瓷形成明显的、紧凑的网状结构，并且内部闭孔多且闭孔均匀，孔隙率高。It can be seen from Figures 1, 3 and 5 that through the specific ratio and preparation process of the alumina porous ceramic paste provided by the present invention, the alumina porous ceramic obtained forms an obvious and compact network structure, and has many closed pores inside. Uniform and high porosity.
对比例1和实施例1的区别在于：加入的氧化铝较少，氧化铝纤维粉较多。图1和图2对比可以看出，由于对比例1氧化铝较少，无法对氧化铝纤维形成完全包裹，从而形成的结构杂乱无章，不利于形成均匀闭孔结构。The difference between Comparative Example 1 and Example 1 is that less alumina is added and more alumina fiber powder is added. Comparing Figure 1 and Figure 2, it can be seen that since Comparative Example 1 has less alumina, it cannot completely wrap the alumina fiber, and the resulting structure is messy, which is not conducive to the formation of a uniform closed-pore structure.
对比例2和实施例1的区别在于：将全部聚碳硅烷在步骤S12中加入，步骤S13不加入聚碳硅烷。图3和图4对比可以看出，对比例2制得的氧化铝多孔陶瓷内部孔洞虽多，但孔洞大小不均匀，对产品的性能有较大影响。The difference between Comparative Example 2 and Example 1 is that all polycarbosilane is added in step S12, and no polycarbosilane is added in step S13. Comparing Figure 3 and Figure 4, it can be seen that although the alumina porous ceramic prepared in Comparative Example 2 has many internal pores, the size of the pores is uneven, which has a great impact on the performance of the product.
对比例3和实施例1的区别在于：将所有原料一次性混合。图5和图6的对比可以看出，对比例3制得的氧化铝多孔陶瓷内部孔洞少，且大小不均匀，从而得到的氧化铝多孔陶瓷孔隙率低、密度大。The difference between Comparative Example 3 and Example 1 is that all raw materials are mixed at one time. It can be seen from the comparison between Figure 5 and Figure 6 that the alumina porous ceramic prepared in Comparative Example 3 has fewer internal pores and uneven sizes, resulting in a low porosity and high density of the alumina porous ceramic.
本发明提供的氧化铝多孔陶瓷膏料以氧化铝粉和氧化铝纤维粉为基体材料，配合聚碳硅烷、氢氧化钠溶液、无水乙醇，通过控制各组分的质量含量，制作成分散性好，流动性高，稳定的多孔陶瓷膏料，可作为增材制造的膏料；同时，该膏料成型过程简单，只需要于在反应釜里加热即可，并具有颗粒堆积法的优点，但又省却了颗粒的机械成型过程，成本低廉；通过采用该膏料进行增材制造成型工艺，制成的多孔陶瓷孔隙率高，且孔隙多为闭孔、孔隙分布更为均匀。The alumina porous ceramic paste provided by the invention uses alumina powder and alumina fiber powder as base materials, and is blended with polycarbosilane, sodium hydroxide solution, and absolute ethanol. By controlling the mass content of each component, it is made into a dispersible A porous ceramic paste with good, high fluidity and stability can be used as a paste for additive manufacturing. At the same time, the paste has a simple molding process and only needs to be heated in a reaction kettle. It also has the advantages of the particle accumulation method. However, the mechanical molding process of particles is omitted, and the cost is low; by using this paste for additive manufacturing and molding process, the porous ceramics produced have high porosity, and the pores are mostly closed pores and the pore distribution is more uniform.
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention, but not to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: The technical solutions described in the foregoing embodiments can still be modified, or some or all of the technical features can be equivalently replaced; and these modifications or substitutions do not deviate from the essence of the corresponding technical solutions from the technical solutions of the embodiments of the present invention. scope.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311763850.2ACN117534446B (en) | 2023-12-20 | Alumina porous ceramic paste, preparation method thereof, and additive manufacturing forming method |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311763850.2ACN117534446B (en) | 2023-12-20 | Alumina porous ceramic paste, preparation method thereof, and additive manufacturing forming method |
| Publication Number | Publication Date |
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| CN117534446Atrue CN117534446A (en) | 2024-02-09 |
| CN117534446B CN117534446B (en) | 2025-10-14 |
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| CN1807355A (en)* | 2005-06-23 | 2006-07-26 | 华东理工大学 | Porous ceramics preparation method |
| CN105254304A (en)* | 2015-09-29 | 2016-01-20 | 中南大学 | Preparing method for wave-transparent closed-cell beryllium-containing silicon carbide foamed ceramic |
| CN105541306A (en)* | 2015-12-25 | 2016-05-04 | 江苏和腾热工装备科技有限公司 | Alumina fiber reinforced alumina closed-cell foamed ceramic and preparation method thereof |
| CN109851327A (en)* | 2018-12-20 | 2019-06-07 | 山东大学 | A kind of compound photosensitive creme of silicon carbide/aluminium oxide ceramics and preparation method thereof towards SLA-3D printing |
| CN110204348A (en)* | 2019-06-05 | 2019-09-06 | 南京航空航天大学 | A kind of preparation method of 3d printing SiC whisker reinforcement C/SiC porous ceramics |
| CN115180965A (en)* | 2021-10-19 | 2022-10-14 | 中国科学院沈阳自动化研究所 | Preparation method of polycarbosilane reinforced alumina ceramic slurry and 3D printing photocuring forming process |
| US20220380260A1 (en)* | 2019-08-06 | 2022-12-01 | 3M Innovative Properties Company | Continuous Additive Manufacturing Method for Making Ceramic Articles, and Ceramic Articles |
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| CN1807355A (en)* | 2005-06-23 | 2006-07-26 | 华东理工大学 | Porous ceramics preparation method |
| CN105254304A (en)* | 2015-09-29 | 2016-01-20 | 中南大学 | Preparing method for wave-transparent closed-cell beryllium-containing silicon carbide foamed ceramic |
| CN105541306A (en)* | 2015-12-25 | 2016-05-04 | 江苏和腾热工装备科技有限公司 | Alumina fiber reinforced alumina closed-cell foamed ceramic and preparation method thereof |
| CN109851327A (en)* | 2018-12-20 | 2019-06-07 | 山东大学 | A kind of compound photosensitive creme of silicon carbide/aluminium oxide ceramics and preparation method thereof towards SLA-3D printing |
| CN110204348A (en)* | 2019-06-05 | 2019-09-06 | 南京航空航天大学 | A kind of preparation method of 3d printing SiC whisker reinforcement C/SiC porous ceramics |
| US20220380260A1 (en)* | 2019-08-06 | 2022-12-01 | 3M Innovative Properties Company | Continuous Additive Manufacturing Method for Making Ceramic Articles, and Ceramic Articles |
| CN115180965A (en)* | 2021-10-19 | 2022-10-14 | 中国科学院沈阳自动化研究所 | Preparation method of polycarbosilane reinforced alumina ceramic slurry and 3D printing photocuring forming process |
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