技术领域Technical field
本发明涉及陶瓷材料制备的技术领域，具体涉及一种高硬度透明陶瓷微球及其制备方法。The invention relates to the technical field of ceramic material preparation, and in particular to a high-hardness transparent ceramic microsphere and a preparation method thereof.
背景技术Background technique
陶瓷微球作为一种新型功能材料，其制备方法主要分为三大类：机械法、湿法及其他方法。机械法能够满足自动化生产，但是很难制备出尺寸微小、球形度理想、抗压强度相对较高的微球。湿法能够制备出球形度好、密度高的陶瓷微球，但生产过程中要严格把控pH值、反应物浓度比、温度、有机物杂质等条件。其他方法有石墨床流化法、微流控湿法和选择性激光烧结法，但是都无法大规模制备高硬度透明陶瓷微球。As a new type of functional material, the preparation methods of ceramic microspheres are mainly divided into three categories: mechanical methods, wet methods and other methods. The mechanical method can satisfy automated production, but it is difficult to prepare microspheres with small size, ideal sphericity and relatively high compressive strength. The wet method can prepare ceramic microspheres with good sphericity and high density, but conditions such as pH value, reactant concentration ratio, temperature, and organic impurities must be strictly controlled during the production process. Other methods include graphite bed fluidization method, microfluidic wet method and selective laser sintering method, but none of them can prepare high-hardness transparent ceramic microspheres on a large scale.
发明内容Contents of the invention
本发明的目的之一在于提供一种高硬度透明陶瓷微球，具有良好的硬度及透明度。One of the purposes of the present invention is to provide a high-hardness transparent ceramic microsphere with good hardness and transparency.
本发明的目的之二在于提供一种高硬度透明陶瓷微球的制备方法，制备工艺简便，易于调节。The second object of the present invention is to provide a method for preparing high-hardness transparent ceramic microspheres, which has a simple preparation process and is easy to adjust.
本发明实现目的之一所采用的方案是：一种高硬度透明陶瓷微球，按照重量百分数计，包括以下原料：氧化铝46％～88％、氧化镁12％～54％；或氧化铝37％～85％、氧化钙15％～63％；或氧化铝25％～75％、氧化锶25％～75％，上述各原料组合合计百分比为100％。The solution used to achieve one of the goals of the present invention is: a high-hardness transparent ceramic microsphere, including the following raw materials in terms of weight percentage: alumina 46% to 88%, magnesium oxide 12% to 54%; or alumina 37% % to 85%, calcium oxide 15% to 63%; or aluminum oxide 25% to 75%, strontium oxide 25% to 75%, the total percentage of the above raw material combinations is 100%.
优选地，所述原料为氧化铝和氧化镁时，高硬度透明陶瓷微球的晶相为MgAl2O4；原料为氧化铝和氧化钙时，高硬度透明陶瓷微球的晶相为CaAl2O4、Ca3Al10O18、CaAl4O7中的至少一种；原料为氧化铝和氧化锶时，高硬度透明陶瓷微球的晶相为SrAl2O4、SrAl4O7、Sr3Al2O6中的至少一种。Preferably, when the raw materials are alumina and magnesium oxide, the crystal phase of the high-hardness transparent ceramic microspheres is MgAl2 O4 ; when the raw materials are alumina and calcium oxide, the crystal phase of the high-hardness transparent ceramic microspheres is CaAl2 At least one of O4 , Ca3 Al10 O18 , and CaAl4 O7 ; when the raw materials are alumina and strontium oxide, the crystal phase of the high-hardness transparent ceramic microspheres is SrAl2 O4 , SrAl4 O7 , Sr3 At least one of Al2 O6 .
优选地，所述高硬度透明陶瓷微球为圆球形，球形度为0.5～1.0，直径为0.5～100μm。Preferably, the high-hardness transparent ceramic microspheres are spherical, with a sphericity of 0.5-1.0 and a diameter of 0.5-100 μm.
本发明实现目的之二所采用的方案是：一种所述的高硬度透明陶瓷微球的制备方法，包含以下步骤：The solution adopted by the present invention to achieve the second object is: a method for preparing the high-hardness transparent ceramic microspheres, which includes the following steps:
(1)按计量比取各原料组分球磨后进行造粒形成粗坯颗粒，得到陶瓷微球前驱体；(1) Take each raw material component according to the measurement ratio and ball-mill it, then granulate to form rough particles, and obtain the ceramic microsphere precursor;
(2)采用射频等离子体加热熔融陶瓷微球前驱体，即得到高硬度透明陶瓷微球。(2) Use radio frequency plasma to heat the molten ceramic microsphere precursor to obtain high-hardness transparent ceramic microspheres.
所述的造粒方法为喷雾造粒。The granulation method is spray granulation.
优选地，其特征在于：所述步骤(1)中，球磨时，还加入有分散剂，所述分散剂为柠檬酸三铵、聚羧酸铵盐、丙烯酸胺盐中的至少一种，所述分散剂占原料组分的质量百分数为0.3％～2％。Preferably, it is characterized in that: in the step (1), during ball milling, a dispersant is added, and the dispersant is at least one of triammonium citrate, polycarboxylate ammonium salt, and acrylic acid amine salt, so The mass percentage of the dispersant in the raw material components is 0.3% to 2%.
优选地，其特征在于：所述步骤(1)中，球磨时，还加入有悬浮稳定剂，所述悬浮稳定剂为阿拉伯树胶粉、聚乙烯醇、聚乙烯亚胺中的至少一种，所述悬浮稳定剂占原料组分的质量百分数为0.5％～5％。Preferably, it is characterized in that: in the step (1), during ball milling, a suspension stabilizer is also added, and the suspension stabilizer is at least one of gum arabic powder, polyvinyl alcohol, and polyethyleneimine, The mass percentage of the suspension stabilizer in the raw material components is 0.5% to 5%.
优选地，所述步骤(2)中，采用射频等离子体加热熔融陶瓷微球前驱体过程中，以氩气为中心气体，中心气体的流量为5～30L/min。Preferably, in step (2), during the process of using radio frequency plasma to heat the molten ceramic microsphere precursor, argon gas is used as the central gas, and the flow rate of the central gas is 5 to 30 L/min.
优选地，所述步骤(2)中，射频等离子体加热的具体工艺参数为：射频电流频率为2～5MHz，等离子体火焰的功率为30～40KW，压力为1.5～15pisa。Preferably, in step (2), the specific process parameters of radio frequency plasma heating are: radio frequency current frequency is 2 to 5 MHz, plasma flame power is 30 to 40 KW, and pressure is 1.5 to 15 pisa.
优选地，所述步骤(2)中，陶瓷微球前驱体的进料速率为0.2～10g/min。Preferably, in the step (2), the feeding rate of the ceramic microsphere precursor is 0.2 to 10 g/min.
优选地，所述步骤(2)中，采用射频等离子体加热熔融陶瓷微球前驱体过程中，可根据需要通入分散气体和载气，分散气体流量为0～5L/min，载气流量为0～3L/min，分散气体为氩气，载气为氩气。Preferably, in the step (2), during the process of using radio frequency plasma to heat the molten ceramic microsphere precursor, dispersion gas and carrier gas can be introduced as needed, the dispersion gas flow rate is 0 to 5L/min, and the carrier gas flow rate is 0~3L/min, the dispersing gas is argon and the carrier gas is argon.
分散气体是用来分散原料颗粒的，使颗粒进入火焰时呈现良好分散状态，从而被较好的熔融，随微球前驱体一起进入等离子火焰。载流气体用于保证进料的稳定，当原料流动性较差时通入载气可以确保进料连续稳定。The dispersing gas is used to disperse the raw material particles so that they are in a well-dispersed state when entering the flame, thereby being better melted and entering the plasma flame together with the microsphere precursor. The carrier gas is used to ensure the stability of the feed. When the fluidity of the raw material is poor, introducing the carrier gas can ensure the continuous and stable feed.
本发明具有以下优点和有益效果：The invention has the following advantages and beneficial effects:
本发明的高硬度透明陶瓷微球，维氏硬度范围在8～15GPa，杨氏模量范围在80～170GPa，可见光范围内透过率在40％以上，进一步可达到70％以上。The high-hardness transparent ceramic microspheres of the present invention have a Vickers hardness ranging from 8 to 15 GPa, a Young's modulus ranging from 80 to 170 GPa, and a transmittance in the visible light range of more than 40%, which can further reach more than 70%.
本发明的高硬度透明陶瓷微球可以应用于电子封装、电子器件、3D打印、建筑涂料、树脂复合材料等领域。The high-hardness transparent ceramic microspheres of the present invention can be used in fields such as electronic packaging, electronic devices, 3D printing, architectural coatings, and resin composite materials.
本发明的制备方法通过射频等离子体高温加热，减少了矿物燃料的使用和温室气体的排放，通过内部系统的净化和气体纯度的控制，极小的减小了生产过程中杂质的引入，保证了陶瓷微球的纯度、成球率与透明度。The preparation method of the present invention reduces the use of fossil fuels and the emission of greenhouse gases through high-temperature heating by radio frequency plasma. Through the purification of the internal system and the control of gas purity, the introduction of impurities in the production process is minimized, ensuring that Purity, balling rate and transparency of ceramic microspheres.
附图说明Description of drawings
图1是实施例1制备的高硬度透明陶瓷微球的光学显微镜图片；Figure 1 is an optical microscope picture of the high-hardness transparent ceramic microspheres prepared in Example 1;
图2是实施例1制备的高硬度透明陶瓷微球的XRD测试图；Figure 2 is an XRD test pattern of the high-hardness transparent ceramic microspheres prepared in Example 1;
图3是实施例2制备的高硬度透明陶瓷微球的光学显微镜图片；Figure 3 is an optical microscope picture of the high-hardness transparent ceramic microspheres prepared in Example 2;
图4是实施例2制备的高硬度透明陶瓷微球的光XRD测试图；Figure 4 is an optical XRD test chart of the high-hardness transparent ceramic microspheres prepared in Example 2;
图5是实施例3制备的高硬度透明陶瓷微球的光学显微镜图片；Figure 5 is an optical microscope picture of the high-hardness transparent ceramic microspheres prepared in Example 3;
图6是实施例3制备的高硬度透明陶瓷微球的XRD测试图。Figure 6 is an XRD test pattern of the high-hardness transparent ceramic microspheres prepared in Example 3.
具体实施方式Detailed ways
为更好的理解本发明，下面的实施例是对本发明的进一步说明，但本发明的内容不仅仅局限于下面的实施例。In order to better understand the present invention, the following examples further illustrate the present invention, but the content of the present invention is not limited to the following examples.
实施例1Example 1
一种高硬度透明陶瓷微球的制备方法，具体工艺步骤如下：A method for preparing high-hardness transparent ceramic microspheres. The specific process steps are as follows:
(1)称取氧化铝392g、碳酸钙108g、4g柠檬酸三铵、10g阿拉伯树胶粉和1000g去离子水置于球磨罐内球磨24h；(1) Weigh 392g of alumina, 108g of calcium carbonate, 4g of triammonium citrate, 10g of gum arabic powder and 1000g of deionized water and place them in a ball mill tank for ball milling for 24 hours;
(2)将球磨好的浆料经100目筛分后进行喷雾造粒得到组分均匀的陶瓷微球前驱体；(2) Sieve the ball-milled slurry through 100 mesh and perform spray granulation to obtain a ceramic microsphere precursor with uniform components;
(3)将陶瓷微球前驱体再次经100目筛分后放入进料机内备用；(3) Screen the ceramic microsphere precursor again with 100 mesh and put it into the feeder for later use;
(4)在射频感应等离子体装置中首先通入作为保护气体的鞘气组成中40L/min的氩气、作为中心气体的20L/min的氩气和作为分散气体的1L/min的氩气，之后通入高频电源产生等离子体火焰并不断加大功率，功率至38KW，压力至15psia，并持续稳定；(4) First, in the radio frequency induction plasma device, the sheath gas composition of the protective gas is 40L/min argon, the center gas is 20L/min argon, and the dispersion gas is 1L/min argon. Then, a high-frequency power supply is introduced to generate a plasma flame and the power is continuously increased until the power reaches 38KW and the pressure reaches 15psia, which remains stable;
(5)继续往射频感应等离子体装置中通入作为载气的2L/min的氩气，将原料以4.17g/min的速率通入等离子体炬的等离子体火焰中熔化，在表面张力作用下变为球形颗粒，接着从安设于等离子体炬下方的不锈钢套管的内管继续下落过程中被急速冷却，最终得到高硬度陶瓷微球。(5) Continue to pass 2L/min argon as the carrier gas into the radio frequency induction plasma device, and pass the raw material into the plasma flame of the plasma torch at a rate of 4.17g/min to melt. Under the action of surface tension It turns into spherical particles, and then is rapidly cooled while continuing to fall from the inner tube of the stainless steel casing installed under the plasma torch, and finally obtains high-hardness ceramic microspheres.
如图1和图2所示，本实施例得到的高硬度透明陶瓷微球粒度分布均匀，球形度良好，球形度为0.95，具有良好透明度，可见光透过率大于70％，主要晶相为Ca3Al10O18、CaAl4O7，平均硬度在9.58GPa，最高可达10.63GPa。As shown in Figures 1 and 2, the high-hardness transparent ceramic microspheres obtained in this example have a uniform particle size distribution, good sphericity, sphericity of 0.95, good transparency, visible light transmittance greater than 70%, and the main crystal phase is Ca3 Al10 O18 , CaAl4 O7 , the average hardness is 9.58GPa, and the highest is 10.63GPa.
实施例2Example 2
一种高硬度透明陶瓷微球的制备方法，具体工艺步骤如下：A method for preparing high-hardness transparent ceramic microspheres. The specific process steps are as follows:
(1)称取氧化铝323g、碳酸钙177g、4g柠檬酸三铵、10g阿拉伯树胶粉和1000g去离子水置于球磨罐内球磨24h；(1) Weigh 323g of alumina, 177g of calcium carbonate, 4g of triammonium citrate, 10g of gum arabic powder and 1000g of deionized water and place them in a ball mill tank for ball milling for 24 hours;
(2)将球磨好的浆料经100目筛分后进行喷雾造粒得到组分均匀的陶瓷微球前驱体；(2) Sieve the ball-milled slurry through 100 mesh and perform spray granulation to obtain a ceramic microsphere precursor with uniform components;
(3)将陶瓷微球前驱体再次经100目筛分后放入进料机内备用；(3) Screen the ceramic microsphere precursor again with 100 mesh and put it into the feeder for later use;
(4)在射频感应等离子体装置中首先通入作为保护气体的鞘气组成中40L/min的氩气、作为中心气体的20L/min的氩气和作为分散气体的1L/min的氩气，之后通入高频电源产生等离子体火焰并不断加大功率，功率至38KW，压力至15psia，并持续稳定；(4) First, in the radio frequency induction plasma device, the sheath gas composition of the protective gas is 40L/min argon, the center gas is 20L/min argon, and the dispersion gas is 1L/min argon. Then, a high-frequency power supply is introduced to generate a plasma flame and the power is continuously increased until the power reaches 38KW and the pressure reaches 15psia, which remains stable;
(5)继续往射频感应等离子体装置中通入作为载气的2L/min的氩气，将原料以4.17g/min的速率通入等离子体炬的等离子体火焰中熔化，在表面张力作用下变为球形颗粒，接着从安设于等离子体炬下方的不锈钢套管的内管继续下落过程中被急速冷却，最终得到高硬度透明陶瓷微球。(5) Continue to pass 2L/min argon as the carrier gas into the radio frequency induction plasma device, and pass the raw material into the plasma flame of the plasma torch at a rate of 4.17g/min to melt. Under the action of surface tension It turns into spherical particles, and then is rapidly cooled while continuing to fall from the inner tube of the stainless steel casing installed under the plasma torch, and finally obtains high-hardness transparent ceramic microspheres.
如图3和图4所示，本实施例得到的高硬度透明陶瓷微球粒度分布均匀，球形度良好，球形度为0.97，具有良好透明度，可见光透过率大于75％，主要晶相为CaAl2O4、Ca3Al10O18、CaAl4O7，平均硬度在10.93GPa，最高可达12.76GPa。As shown in Figures 3 and 4, the high-hardness transparent ceramic microspheres obtained in this example have a uniform particle size distribution, good sphericity, sphericity of 0.97, good transparency, visible light transmittance greater than 75%, and the main crystal phase is CaAl.2 O4 , Ca3 Al10 O18 , CaAl4 O7, the average hardness is 10.93GPa, and the highest is 12.76GPa.
实施例3Example 3
一种高硬度透明陶瓷微球的制备方法，具体工艺步骤如下：A method for preparing high-hardness transparent ceramic microspheres. The specific process steps are as follows:
(1)称取氧化铝360g、碳酸钙140g、4g柠檬酸三铵、10g阿拉伯树胶粉和1000g去离子水置于球磨罐内球磨24h；(1) Weigh 360g of alumina, 140g of calcium carbonate, 4g of triammonium citrate, 10g of gum arabic powder and 1000g of deionized water and place them in a ball mill tank for ball milling for 24 hours;
(2)将球磨好的浆料经100目筛分后进行喷雾造粒得到组分均匀的陶瓷微球前驱体；(2) Sieve the ball-milled slurry through 100 mesh and perform spray granulation to obtain a ceramic microsphere precursor with uniform components;
(3)将陶瓷微球前驱体再次经100目筛分后放入进料机内备用；(3) Screen the ceramic microsphere precursor again with 100 mesh and put it into the feeder for later use;
(4)在射频感应等离子体装置中首先通入作为保护气体的鞘气组成中40L/min的氩气、作为中心气体的20L/min的氩气和作为分散气体的1L/min的氩气，之后通入高频电源产生等离子体火焰并不断加大功率，功率至38KW，压力至15psia，并持续稳定；(4) First, in the radio frequency induction plasma device, the sheath gas composition of the protective gas is 40L/min argon, the center gas is 20L/min argon, and the dispersion gas is 1L/min argon. Then, a high-frequency power supply is introduced to generate a plasma flame and the power is continuously increased until the power reaches 38KW and the pressure reaches 15psia, which remains stable;
(5)继续往射频感应等离子体装置中通入作为载气的2L/min的氩气，将原料以4.17g/min的速率通入等离子体炬的等离子体火焰中熔化，在表面张力作用下变为球形颗粒，接着从安设于等离子体炬下方的不锈钢套管的内管继续下落过程中被急速冷却，最终得到高硬度透明陶瓷微球。(5) Continue to pass 2L/min argon as the carrier gas into the radio frequency induction plasma device, and pass the raw material into the plasma flame of the plasma torch at a rate of 4.17g/min to melt. Under the action of surface tension It turns into spherical particles, and then is rapidly cooled while continuing to fall from the inner tube of the stainless steel casing installed under the plasma torch, and finally obtains high-hardness transparent ceramic microspheres.
如图5和图6所示，本实施例得到的高硬度透明陶瓷微球粒度分布均匀，球形度良好，球形度为0.98，具有良好透明度，可见光透过率大于80％，主要晶相为CaAl2O4、Ca3Al10O18，平均硬度在12.73GPa，最高可达14.45GPa。As shown in Figures 5 and 6, the high-hardness transparent ceramic microspheres obtained in this example have a uniform particle size distribution, good sphericity, 0.98, good transparency, visible light transmittance greater than 80%, and the main crystal phase is CaAl.2 O4 , Ca3 Al10 O18 , the average hardness is 12.73GPa, and the highest is 14.45GPa.
实施例4Example 4
一种高硬度透明陶瓷微球的制备方法，具体工艺步骤如下：A method for preparing high-hardness transparent ceramic microspheres. The specific process steps are as follows:
(1)称取氧化铝440g、碳酸镁60g、4g柠檬酸三铵、13gPVA和1000g去离子水置于球磨罐内球磨24h；(1) Weigh 440g of alumina, 60g of magnesium carbonate, 4g of triammonium citrate, 13g of PVA and 1000g of deionized water and place them in a ball mill tank for ball milling for 24 hours;
(2)将球磨好的浆料经100目筛分后进行喷雾造粒得到组分均匀的陶瓷微球前驱体；(2) Sieve the ball-milled slurry through 100 mesh and perform spray granulation to obtain a ceramic microsphere precursor with uniform components;
(3)将陶瓷微球前驱体再次经100目筛分后放入进料机内备用；(3) Screen the ceramic microsphere precursor again with 100 mesh and put it into the feeder for later use;
(4)在射频感应等离子体装置中首先通入作为保护气体的鞘气组成中40L/min的氩气、作为中心气体的20L/min的氩气和作为分散气体的1L/min的氩气，之后通入高频电源产生等离子体火焰并不断加大功率，功率至38KW，压力至15psia，并持续稳定；(4) First, in the radio frequency induction plasma device, the sheath gas composition of the protective gas is 40L/min argon, the center gas is 20L/min argon, and the dispersion gas is 1L/min argon. Then, a high-frequency power supply is introduced to generate a plasma flame and the power is continuously increased until the power reaches 38KW and the pressure reaches 15psia, which remains stable;
(5)继续往射频感应等离子体装置中通入作为载气的2L/min的氩气，将原料以4.17g/min的速率通入等离子体炬的等离子体火焰中熔化，在表面张力作用下变为球形颗粒，接着从安设于等离子体炬下方的不锈钢套管的内管继续下落过程中被急速冷却，最终得到高硬度透明陶瓷微球。(5) Continue to pass 2L/min argon as the carrier gas into the radio frequency induction plasma device, and pass the raw material into the plasma flame of the plasma torch at a rate of 4.17g/min to melt. Under the action of surface tension It turns into spherical particles, and then is rapidly cooled while continuing to fall from the inner tube of the stainless steel casing installed under the plasma torch, and finally obtains high-hardness transparent ceramic microspheres.
本实施例得到的高硬度透明陶瓷微球粒度分布均匀，球形度良好，球形度为0.98，具有良好透明度，可见光透过率大于80％，主要晶相为MgAl2O4，平均硬度在17.73GPa，最高可达18GPa。The high-hardness transparent ceramic microspheres obtained in this example have uniform particle size distribution, good sphericity, sphericity of 0.98, good transparency, visible light transmittance greater than 80%, the main crystal phase is MgAl2 O4 , and the average hardness is 17.73GPa , up to 18GPa.
实施例5Example 5
一种高硬度透明陶瓷微球的制备方法，具体工艺步骤如下：A method for preparing high-hardness transparent ceramic microspheres. The specific process steps are as follows:
(1)称取氧化铝230g、碳酸镁270g、4g聚羧酸铵盐、5gPEI和1000g去离子水置于球磨罐内球磨24h；(1) Weigh 230g of alumina, 270g of magnesium carbonate, 4g of ammonium polycarboxylate, 5g of PEI and 1000g of deionized water and place them in a ball mill tank for ball milling for 24 hours;
(2)将球磨好的浆料经100目筛分后进行喷雾造粒得到组分均匀的陶瓷微球前驱体；(2) Sieve the ball-milled slurry through 100 mesh and perform spray granulation to obtain a ceramic microsphere precursor with uniform components;
(3)将陶瓷微球前驱体再次经100目筛分后放入进料机内备用；(3) Screen the ceramic microsphere precursor again with 100 mesh and put it into the feeder for later use;
(4)在射频感应等离子体装置中首先通入作为保护气体的鞘气组成中40L/min的氩气、作为中心气体的20L/min的氩气和作为分散气体的1L/min的氩气，之后通入高频电源产生等离子体火焰并不断加大功率，功率至38KW，压力至15psia，并持续稳定；(4) First, in the radio frequency induction plasma device, the sheath gas composition of the protective gas is 40L/min argon, the center gas is 20L/min argon, and the dispersion gas is 1L/min argon. Then, a high-frequency power supply is introduced to generate a plasma flame and the power is continuously increased until the power reaches 38KW and the pressure reaches 15psia, which remains stable;
(5)继续往射频感应等离子体装置中通入作为载气的2L/min的氩气，将原料以4.17g/min的速率通入等离子体炬的等离子体火焰中熔化，在表面张力作用下变为球形颗粒，接着从安设于等离子体炬下方的不锈钢套管的内管继续下落过程中被急速冷却，最终得到高硬度透明陶瓷微球。(5) Continue to pass 2L/min argon as the carrier gas into the radio frequency induction plasma device, and pass the raw material into the plasma flame of the plasma torch at a rate of 4.17g/min to melt. Under the action of surface tension It turns into spherical particles, and then is rapidly cooled while continuing to fall from the inner tube of the stainless steel casing installed under the plasma torch, and finally obtains high-hardness transparent ceramic microspheres.
本实施例得到的高硬度透明陶瓷微球粒度分布均匀，球形度良好，球形度为0.98，具有良好透明度，可见光透过率大于80％，主要晶相为MgAl2O4，平均硬度在18.5GPa，最高可达19GPa。The high-hardness transparent ceramic microspheres obtained in this example have uniform particle size distribution, good sphericity, sphericity of 0.98, good transparency, visible light transmittance greater than 80%, the main crystal phase is MgAl2 O4 , and the average hardness is 18.5GPa. , up to 19GPa.
实施例6Example 6
一种高硬度透明陶瓷微球的制备方法，具体工艺步骤如下：A method for preparing high-hardness transparent ceramic microspheres. The specific process steps are as follows:
(1)称取氧化铝125g、碳酸锶375g、6.5g丙烯酸胺盐、15g阿拉伯树胶粉和1000g去离子水置于球磨罐内球磨24h；(1) Weigh 125g of alumina, 375g of strontium carbonate, 6.5g of acrylic acid amine salt, 15g of gum arabic powder and 1000g of deionized water and place them in a ball mill tank for ball milling for 24 hours;
(2)将球磨好的浆料经100目筛分后进行喷雾造粒得到组分均匀的陶瓷微球前驱体；(2) Sieve the ball-milled slurry through 100 mesh and perform spray granulation to obtain a ceramic microsphere precursor with uniform components;
(3)将陶瓷微球前驱体再次经100目筛分后放入进料机内备用；(3) Screen the ceramic microsphere precursor again with 100 mesh and put it into the feeder for later use;
(4)在射频感应等离子体装置中首先通入作为保护气体的鞘气组成中40L/min的氩气、作为中心气体的20L/min的氩气和作为分散气体的1L/min的氩气，之后通入高频电源产生等离子体火焰并不断加大功率，功率至38KW，压力至15psia，并持续稳定；(4) First, in the radio frequency induction plasma device, the sheath gas composition of the protective gas is 40L/min argon, the center gas is 20L/min argon, and the dispersion gas is 1L/min argon. Then, a high-frequency power supply is introduced to generate a plasma flame and the power is continuously increased until the power reaches 38KW and the pressure reaches 15psia, which remains stable;
(5)继续往射频感应等离子体装置中通入作为载气的2L/min的氩气，将原料以5g/min的速率通入等离子体炬的等离子体火焰中熔化，在表面张力作用下变为球形颗粒，接着从安设于等离子体炬下方的不锈钢套管的内管继续下落过程中被急速冷却，最终得到高硬度透明陶瓷微球。(5) Continue to pass 2L/min argon as a carrier gas into the radio frequency induction plasma device, and melt the raw materials into the plasma flame of the plasma torch at a rate of 5g/min. The particles are spherical and then rapidly cooled as they continue to fall from the inner tube of the stainless steel casing installed below the plasma torch, finally obtaining high-hardness transparent ceramic microspheres.
本实施例得到的高硬度透明陶瓷微球粒度分布均匀，球形度良好，球形度为0.98，具有良好透明度，可见光透过率大于80％，主要晶相为SrAl2O4、Sr3Al2O6，平均硬度在9GPa，最高可达10.43GPa。The high-hardness transparent ceramic microspheres obtained in this example have uniform particle size distribution, good sphericity, sphericity is 0.98, good transparency, visible light transmittance greater than 80%, and the main crystal phases are SrAl2 O4 and Sr3 Al2 O6 , the average hardness is 9GPa, and the highest is 10.43GPa.
实施例7Example 7
一种高硬度透明陶瓷微球的制备方法，具体工艺步骤如下：A method for preparing high-hardness transparent ceramic microspheres. The specific process steps are as follows:
(1)称取氧化铝375g、碳酸锶125g、4g丙烯酸胺盐、10gPEI和1000g去离子水置于球磨罐内球磨24h；(1) Weigh 375g of alumina, 125g of strontium carbonate, 4g of acrylic acid amine salt, 10g of PEI and 1000g of deionized water and place them in a ball mill tank for ball milling for 24 hours;
(2)将球磨好的浆料经100目筛分后进行喷雾造粒得到组分均匀的陶瓷微球前驱体；(2) Sieve the ball-milled slurry through 100 mesh and perform spray granulation to obtain a ceramic microsphere precursor with uniform components;
(3)将陶瓷微球前驱体再次经100目筛分后放入进料机内备用；(3) Screen the ceramic microsphere precursor again with 100 mesh and put it into the feeder for later use;
(4)在射频感应等离子体装置中首先通入作为保护气体的鞘气组成中40L/min的氩气、作为中心气体的20L/min的氩气和作为分散气体的1L/min的氩气，之后通入高频电源产生等离子体火焰并不断加大功率，功率至38KW，压力至15psia，并持续稳定；(4) First, in the radio frequency induction plasma device, the sheath gas composition of the protective gas is 40L/min argon, the center gas is 20L/min argon, and the dispersion gas is 1L/min argon. Then, a high-frequency power supply is introduced to generate a plasma flame and the power is continuously increased until the power reaches 38KW and the pressure reaches 15psia, which remains stable;
(5)继续往射频感应等离子体装置中通入作为载气的2L/min的氩气，将原料以4.17g/min的速率通入等离子体炬的等离子体火焰中熔化，在表面张力作用下变为球形颗粒，接着从安设于等离子体炬下方的不锈钢套管的内管继续下落过程中被急速冷却，最终得到高硬度透明陶瓷微球。(5) Continue to pass 2L/min argon as the carrier gas into the radio frequency induction plasma device, and pass the raw material into the plasma flame of the plasma torch at a rate of 4.17g/min to melt. Under the action of surface tension It turns into spherical particles, and then is rapidly cooled while continuing to fall from the inner tube of the stainless steel casing installed under the plasma torch, and finally obtains high-hardness transparent ceramic microspheres.
本实施例得到的高硬度透明陶瓷微球粒度分布均匀，球形度良好，球形度为0.98，具有良好透明度，可见光透过率大于80％，主要晶相为SrAl2O4、SrAl4O7，平均硬度在11GPa，最高可达11.75GPa。The high-hardness transparent ceramic microspheres obtained in this example have uniform particle size distribution, good sphericity, sphericity of 0.98, good transparency, visible light transmittance greater than 80%, and the main crystal phases are SrAl2 O4 and SrAl4 O7 . The average hardness is 11GPa and can reach up to 11.75GPa.
以上所述是本发明的优选实施方式而已，当然不能以此来限定本发明之权利范围，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和变动，这些改进和变动也视为本发明的保护范围。The above are only preferred embodiments of the present invention. Of course, they cannot be used to limit the scope of rights of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the principles of the present invention, they can also Several improvements and changes are made, and these improvements and changes are also considered to be within the protection scope of the present invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211706232.XACN116023125B (en) | 2022-12-29 | 2022-12-29 | High-hardness transparent ceramic microsphere and preparation method thereof |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211706232.XACN116023125B (en) | 2022-12-29 | 2022-12-29 | High-hardness transparent ceramic microsphere and preparation method thereof |
| Publication Number | Publication Date |
|---|---|
| CN116023125A CN116023125A (en) | 2023-04-28 |
| CN116023125Btrue CN116023125B (en) | 2024-02-27 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211706232.XAActiveCN116023125B (en) | 2022-12-29 | 2022-12-29 | High-hardness transparent ceramic microsphere and preparation method thereof |
| Country | Link |
|---|---|
| CN (1) | CN116023125B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86107671A (en)* | 1985-11-22 | 1987-07-15 | 明尼苏达州采矿制造公司 | Transparent non-vitrified zirconia microspheres |
| CN107140991A (en)* | 2017-05-27 | 2017-09-08 | 山东工业陶瓷研究设计院有限公司 | It is a kind of for ceramic spherical material of 3D printing and preparation method and application |
| CN108910885A (en)* | 2018-07-27 | 2018-11-30 | 广东正德材料表面科技有限公司 | Spherical TiC powder and preparation method thereof |
| CN110014161A (en)* | 2019-04-18 | 2019-07-16 | 北京科技大学 | A kind of method for preparing spherical tungsten-based powder |
| CN111792849A (en)* | 2019-04-09 | 2020-10-20 | 武汉理工大学 | A method for preparing quartz glass microspheres by radio frequency plasma |
| CN114031391A (en)* | 2021-11-26 | 2022-02-11 | 天津津航技术物理研究所 | Preparation method of high-strength magnesia-alumina spinel transparent ceramic |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005021147A2 (en)* | 2003-02-06 | 2005-03-10 | William Marsh Rice University | High strength polycrystalline ceramic spheres |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86107671A (en)* | 1985-11-22 | 1987-07-15 | 明尼苏达州采矿制造公司 | Transparent non-vitrified zirconia microspheres |
| US4772511A (en)* | 1985-11-22 | 1988-09-20 | Minnesota Mining And Manufacturing Company | Transparent non-vitreous zirconia microspheres |
| CN107140991A (en)* | 2017-05-27 | 2017-09-08 | 山东工业陶瓷研究设计院有限公司 | It is a kind of for ceramic spherical material of 3D printing and preparation method and application |
| CN108910885A (en)* | 2018-07-27 | 2018-11-30 | 广东正德材料表面科技有限公司 | Spherical TiC powder and preparation method thereof |
| CN111792849A (en)* | 2019-04-09 | 2020-10-20 | 武汉理工大学 | A method for preparing quartz glass microspheres by radio frequency plasma |
| CN110014161A (en)* | 2019-04-18 | 2019-07-16 | 北京科技大学 | A kind of method for preparing spherical tungsten-based powder |
| CN114031391A (en)* | 2021-11-26 | 2022-02-11 | 天津津航技术物理研究所 | Preparation method of high-strength magnesia-alumina spinel transparent ceramic |
| Title |
|---|
| 《Fabrication of transparent MgAl2O4 spinel via spray freeze drying of microfluidized slurry》;Ha-Neul Kim et al.;《Ceramics International》(第43期);第11312-11317页* |
| Ha-Neul Kim et al..《Fabrication of transparent MgAl2O4 spinel via spray freeze drying of microfluidized slurry》.《Ceramics International》.2017,(第43期),第11312-11317页.* |
| Publication number | Publication date |
|---|---|
| CN116023125A (en) | 2023-04-28 |
| Publication | Publication Date | Title |
|---|---|---|
| CN102363728A (en) | Phosphor particle, light emitting diode, and lighting equipment and liquid crystal panel backlight device using them | |
| KR100438228B1 (en) | Doped and pyrolyzed oxides | |
| CN101182207B (en) | A kind of spraying powder containing yttrium oxide and preparation method thereof | |
| CN111362698A (en) | A new isotropic nuclear grade graphite material and preparation method thereof | |
| CN104470873A (en) | Sintered spherical BN particles with concave part, method for producing same, and polymer material | |
| JP2015520094A (en) | Method for producing synthetic quartz glass particles | |
| KR20100024663A (en) | Method and plasma torch for direct and continous synthesis of nano-scaled composite powders using thermal plasmas | |
| US20150315034A1 (en) | Flame spray synthesis of lu2o3 nanoparticles | |
| CN112209420A (en) | Preparation method of nano-scale yttrium oxide powder | |
| CN105883812A (en) | Process for producing silicon carbide through microwave sintering | |
| KR20040002393A (en) | Phosphor and production method therefor | |
| CN116023125B (en) | High-hardness transparent ceramic microsphere and preparation method thereof | |
| CN109867448B (en) | Composite material and adhesive material comprising the same | |
| JP5296993B2 (en) | Yttrium oxide powder | |
| JPH0891874A (en) | Glass spherical powder and its production | |
| KR101157460B1 (en) | Aluminium doped zinc oxide particle and manufacturing method of producing the same using spray pyrolysis | |
| CN114477254B (en) | Preparation method of hollow alumina balls | |
| JP7164787B2 (en) | Phosphorescent fine particle powder and method for producing the same | |
| JPS6131315A (en) | Production of alumina balloon | |
| CN114605149B (en) | Preparation method and application of zirconia microspheres | |
| CN110014165A (en) | A kind of preparation method of high-purity micron spherical molybdenum powder | |
| KR101929342B1 (en) | Apparatus for fused beads using high temperature flow tube and Manufacturing method using the same | |
| CN103274680B (en) | Method for casting Y3Al5O12 ceramics by combustion synthesis | |
| CN108557832A (en) | A kind of preparation method of negative expansion coefficient spherical powder | |
| CN108349820A (en) | zirconium boride and preparation method thereof |
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |