CN111807842B - 多孔碳化硅陶瓷材料及其制备方法 - Google Patents
多孔碳化硅陶瓷材料及其制备方法 Download PDFInfo
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 56
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 22
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- 238000000498 ball milling Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
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- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims abstract description 9
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Abstract
本公开提供了一种多孔碳化硅陶瓷材料及其制备方法。所述多孔碳化硅陶瓷为蜂窝状结构，多孔碳化硅陶瓷的孔隙呈立体网格状无序联通，孔隙分布均匀，孔隙的尺寸为20μm～30μm。所述多孔碳化硅陶瓷材料的制备方法包含：a.将基体原料碳化硅粉体、氢氧化铝粉体、氧化钇粉体加入容器中，然后再加入分散剂、去离子水，首次球磨，之后再加入粘结剂，二次球磨，得到均匀的浆料；b.将步骤a所制得的浆料倒入容器中真空除泡，之后将除泡后的浆料注入到冷冻模具中冷冻，得到冷冻生胚；c.将步骤b所制得的冷冻生胚在真空条件下干燥，得到多孔SiC胚体；d.将步骤c所制得的胚体放入保温箱干燥；e.将步骤d所得到的胚体烧结。本公开的制备工艺简单高效，操作易于控制。
Description
技术领域
本公开涉及陶瓷材料领域，具体涉及一种多孔碳化硅陶瓷材料及其制备方法。
背景技术
通过冷冻干燥法制备的多孔碳化硅，具有高孔隙率、高比表面积、优异的力学性能、稳定的化学性能、较高的导热率以及较低的热膨胀系数等性质，在催化剂载体材料方面具有巨大的应用价值。
目前通过冷冻干燥法制备的多孔碳化硅陶瓷，其孔隙结构多为具有高取向性的层状或树枝状。
国内外关于冷冻干燥制备多孔碳化硅材料的报道中，浆料的冷冻过程通常不伴随吞噬现象的发生，制备的孔隙结构普遍呈高取向性的层状或树枝状。例如，于2018年6月1公布的中国专利申请公布号为CN108101544A的中国专利申请公开了一种层片状梯度多孔碳化硅陶瓷及其制备方法，以碳化硅粉体为原料，以水作为冷冻介质，制备得到了在具有高度取向性的片层状孔隙结构。例如，于2011年11月30日公布的中国专利申请公布号为CN102260092的中国专利申请公开了一种多孔碳化硅陶瓷材料的制备方法，通过控制粘结剂加入量，制备了具有不同层厚与层间距的试样，其孔隙结构为高取向性的层状或树枝状。
然而，片层状与树枝状结构中的孔隙通道均较为平直，当反应物进入孔隙后无法获得足够的滞留时间以进行充分的催化反应，这使得冷冻干燥法制备的多孔碳化硅陶瓷在催化剂载体方面的应用受到了一定的限制。
上述的说明仅是提供背景技术，并未承认上文的“背景技术”构成本公开的现有技术。
发明内容
针对背景技术存在的问题，本公开的目的在于提供一种多孔碳化硅陶瓷材料及其制备方法。
在一些实施例中，本公开提供了一种多孔碳化硅陶瓷材料，本公开的多孔碳化硅陶瓷为蜂窝状结构，多孔碳化硅陶瓷的孔隙呈立体网格状无序联通，孔隙分布均匀，孔隙的尺寸为20μm～30μm。
在一些实施例中，本公开提供了一种多孔碳化硅陶瓷材料的制备方法，其用于制备本公开的蜂窝状多孔碳化硅陶瓷材料，包含步骤：
a.将基体原料碳化硅粉体、氢氧化铝粉体、氧化钇粉体加入容器中；然后再加入分散剂、去离子水，进行首次球磨，之后再加入粘结剂，进行二次球磨，得到均匀的浆料；
b.将步骤a所制得的浆料倒入容器中进行真空除泡，之后将除泡后的浆料注入到冷冻模具中进行冷冻，得到冷冻生胚；
c.将步骤b所制得的冷冻生胚在真空条件下进行干燥处理，得到多孔SiC胚体；
d.将步骤c所制得的胚体放入保温箱，进行干燥；
e.将步骤d所得到的胚体进行烧结，烧结后得到具有蜂窝结构的多孔碳化硅陶瓷材料。
本公开的有益效果如下：
本公开制备的多孔碳化硅陶瓷材料具有蜂窝状孔隙结构，并且具有孔隙率高、孔隙分布无序性高、孔隙尺寸分布集中、抗压强度高、比表面积高等特点。并且本公开的制备工艺简单高效，操作易于控制。
附图说明
图1为本公开的实施例1的多孔碳化硅陶瓷的一电镜图；
图2为本公开的实施例1的多孔碳化硅陶瓷的另一扫描电镜图。
具体实施方式
应理解的是，所公开的实施例仅是本公开的示例，本公开可以以各种形式实施，因此，本公开的具体细节不应被解释为限制，而是仅作为权利要求的基础且作为表示性的基础用于教导本领域普通技术人员以各种方式实施本公开。
在本公开的说明中，未明确说明的术语、专业用词均为本领域技术人员的公知常识，未明确说明的方法均为本领域技术人员公知的常规方法。
[多孔碳化硅陶瓷材料]
本公开的多孔碳化硅陶瓷为蜂窝状结构，多孔碳化硅陶瓷的孔隙呈立体网格状无序联通，孔隙分布均匀，孔隙的尺寸为20μm～30μm。
在一些实施例中，本公开的多孔碳化硅陶瓷材料的原料包含碳化硅、氢氧化铝以及氧化钇。在一些实施例中，碳化硅、氢氧化铝、氧化钇的质量比为(65～85):(10～30):(5～25)。
在一些实施例中，本公开的多孔碳化硅陶瓷的孔隙率为50％～80％。
在一些实施例中，本公开的多孔碳化硅陶瓷的抗压强度为4MPa～25MPa。
在一些实施例中，本公开的多孔碳化硅陶瓷的比表面积为4m2/g～18m2/g。
[多孔碳化硅陶瓷材料的制备方法]
本公开利用冷冻干燥技术制备本公开的多孔碳化硅陶瓷。在一些实施例中，本公开通过对冷冻温度的控制来制备本公开的多孔碳化硅陶瓷。在一些实施例中，本公开通过限定冷冻模具和/或冷冻容器的材质来制备本公开的多孔碳化硅陶瓷。
在一些实施例中，制备本公开的多孔碳化硅陶瓷的方法包含步骤：
a.将基体原料碳化硅粉体、氢氧化铝粉体、氧化钇粉体加入容器中；然后再加入分散剂、去离子水，进行首次球磨，之后再加入粘结剂，进行二次球磨，得到均匀的浆料；
b.将步骤a所制得的浆料倒入容器中进行真空除泡，之后将除泡后的浆料注入到冷冻模具中进行冷冻，得到冷冻生胚；
c.将步骤b所制得的冷冻生胚在真空条件下进行干燥处理，得到多孔SiC胚体；
d.将步骤c所制得的胚体放入保温箱，进行干燥；
e.将步骤d所得到的胚体进行烧结，烧结后得到具有蜂窝结构的多孔碳化硅陶瓷材料。
在步骤a中：在一些实施例中，碳化硅、氢氧化铝、氧化钇的质量比为(65～85):(10～30):(5～25)；在一些实施例中，分散剂选自四甲基氢氧化铵、硅酸钠以及聚丙烯酰胺中的至少一种；在一些实施例中，分散剂的加入量为基体原料质量的0.5％～1.5％；在一些实施例中，粘结剂选自聚乙二醇、聚乙烯醇以及羧甲基纤维素钠中的至少一种；在一些实施例中，所述粘结剂的加入量为基体原料质量的0.5％～1.5％；在一些实施例中，去离子水的加入量为基体原料质量的0.5倍～2.5倍；在一些实施例中，首次球磨的时间为2h～12h，二次球磨的时间为1h～6h。
在步骤b中：冷冻模具的底部材料为导热率在100-250W/mK的金属，在一些实施例中，所述底部材料为铝、铍或铝铍合金中的至少一种；所述冷冻模具的周边材料为导热率小于0.05W/mK的聚合物，在一些实施例中，所述周边材料为聚苯乙烯、聚四氟乙烯、硅橡胶中的至少一种；在一些实施例中，所述冷冻温度为-10℃～-20℃。
在步骤c中：在一些实施例中，真空条件为-5℃～-60℃的温度、4Pa～20Pa的真空度，所述干燥处理时间为20h～40h。
在步骤d中：在一些实施例中，干燥的温度为70℃～120℃，所述干燥的时间为2h～36h。
在步骤e中：在一些实施例中，烧结的温度为1400℃～1500℃。
下面结合实施例，进一步阐述本公开。应理解，这些实施例仅用于说明本公开而不用于限制本公开的范围。
在下述实施例、对比例中，所使用到的试剂、材料以及仪器如没有特殊的说明，均可商购获得或本领域中公知的方法制备获得。
实施例1
1)按照质量百分比在球磨罐中加入70％的碳化硅、25％的氢氧化铝、5％的氧化钇作为基体原料，再加入基体原料质量的0.6％的分散剂四甲基氢氧化铵，以及基体原料质量1.5倍的去离子水，然后开始球磨，球磨5h；之后再加入0.5％的聚乙烯醇，球磨1h，得到均匀的浆料；
2)将步骤1)所制得的浆料倒入容器中进行真空除泡，之后将浆料注入到底部为铝板、壁部为聚苯乙烯的冷冻模具中，在-15℃进行冷冻，得到冷冻生胚；
3)将步骤2)所制得的冷冻生胚在-5℃，4～20Pa的真空度下进行40h的干燥处理，得到多孔SiC胚体；
4)将步骤3)所制得到的胚体放入保温箱，在80℃下干燥12h；
5)将步骤4)所制得的生坯在1450℃下进行烧结，烧结后得到多孔碳化硅陶瓷。
实施例2
实施例2的多孔碳化硅陶瓷的制备和实施例1相同，区别在于：
步骤2)中的冷冻温度由-15℃改为-10℃进行冷冻。
实施例3
实施例3的多孔碳化硅陶瓷的制备和实施例1相同，区别在于：
步骤4)中的烧结温度由1450℃改成1500℃。
实施例4
实施例4的多孔碳化硅陶瓷的制备和实施例1相同，区别在于：
步骤1)中的去离子水添加量由1.5倍改成2.3倍。
实施例5
实施例5的多孔碳化硅陶瓷的制备和实施例1相同，区别在于：
步骤1)中的去离子水添加量由1.5倍改成1倍。
对比例1
1)按照质量百分比在球磨罐中加入70％的碳化硅、25％的氢氧化铝、5％的氧化钇作为基体原料，再加入基体原料质量的0.6％的分散剂四甲基氢氧化铵，9％的丙烯酰胺与0.5％的N，N-亚甲基双丙烯酰胺，以及基体原料质量1.5倍的去离子水，然后开始球磨，球磨5h；之后再加入引发剂过硫酸铵，球磨1h，得到均匀的浆料；
2)将步骤1)所制得的浆料倒入容器中进行真空除泡，倒入烧杯。之后向浆料中加入催化剂四甲基乙二胺诱发凝胶。待凝胶结束后，脱模得到生胚；
3)将步骤2)所制得的冷冻生胚在放入保温箱，在80℃下干燥12h；
5)将步骤4)所制得的生坯在1450℃下进行烧结，烧结后得到多孔碳化硅陶瓷。
对比例2
对比例2的多孔碳化硅陶瓷的制备和实施例1相同，区别在于：
步骤2)中的冷冻温度由-15℃改为-30℃进行冷冻。
对比例3
对比例3的多孔碳化硅陶瓷的制备和实施例1相同，区别在于：
步骤2)中，将底部为铝板、壁部聚苯乙烯的冷冻模具替换为玻璃烧杯。
对比例4
对比例4的多孔碳化硅陶瓷的制备和实施例1相同，区别在于：
步骤2)中，将底部为铝板、壁部为聚苯乙烯的冷冻模具替换为底部为高导热率的铜板、壁部为聚苯乙烯的冷冻模具。
最后说明实施例1-5和对比例1-4的测试过程。
(1)孔隙率的测试过程
采用阿基米德排水法测定试样的开孔隙率。将待测试样作好编号标记，在超声清洗器中清洗7-10分钟后，置于烘箱中在110℃的温度下烘干至恒重，冷至室温后，称取各试样在空气中的质量，记为W1。之后将试样放在烧杯中，以蒸馏水浸没试样后，把烧杯在小电炉上煮沸5min后连水冷却至室温，然后进行液体静力法称重：用饱和了浸渍蒸馏水的毛巾小心地轻拭去已浸渍试样表面多余的液体，注意不可将开孔中的液体吸出，并立即称量浸渍试样在空气中的质量W3。然后，用镊子小心地依次逐一把试样放在液体静力天平的盛物金属丝网中，注意在放样或取出样时切不可将水洒在天平的称量部位上，并确保试样和丝网浸没于水面下一定深度，且不与盛水容器的壁、底相碰；称量浸渍试样在水中的质量W2。将各试样测得的数据代入公式：开孔隙率＝(W3-W1)/(W3-W2)，计算试样开孔隙率。
(2)抗压强度的测试过程
采用万能力学试验仪测量试样抗压强度。首先，每组试样设置不少于5个的平行试样，测量每个的试样受压面的尺寸，计算出试样的面积。然后，将试样放置在试验机压板的中心部位，以2×102N/s的速度施加负荷，直至试样破坏，读出试样破坏时的最大负荷。将测试结果代入公式：抗压强度＝破坏负荷/试样受力面积，计算试样抗压强度。
(3)比表面积的测试过程
采用BET氮气吸附比表面积仪测量试样比表面积。测定吸附等温线之前，测量待测样品质量m，之后将试样置于盛样器，脱气除去样品表面的物理吸附物质。将已经加热脱气的盛样器与真空泵和管道隔离，若气压稳定不变，则脱气完成。脱气后，将盛样器冷却到测试温度-196℃，将已知量的吸附气体通样品室，在有限的固定溶剂中，样品开始吸附气体，气压下降，直至气压P不变，吸附达到平衡。在平衡压力下，测量平衡压力P、吸附气体饱和蒸汽压力P0与气体吸附量V。将上述数值代入BET方程：P/(V(P0-P))＝1/(CVm)+(C-1)/(CVmP/P0)，其中C为常数(其值取决于测试试样材料，取值范围为1.23-1.29，在本公开中取值为1.25)，计算得到试样吸附单层气体分子的气体体积Vm，通过SBET＝4.35×Vm/m计算得到试样比表面积SBET。
(4)孔隙尺寸的测试过程
采用扫描电镜测量孔隙尺寸。将待测试样置入真空干燥箱，于60℃真空干燥24h，取出后用导电双面胶将样品粘贴于扫描电镜铜板试样台上。对试样台上的试样在进行真空喷金处理，喷金时间为1-3min，预处理结束。将样品台放入扫描电镜开始观察，利用测试系统的测距功能对多个孔隙进行孔隙尺寸测量并分别记录为R1、R2…Rn(n≥30)。将上述数值代入公式：试样孔隙尺寸R＝ΣRi/n，其中i＝1,2…n，计算得到试样孔隙尺寸R。
实施例1-5和对比例1-4的多孔碳化硅陶瓷的测试结果如表1所示。
表1
对比例1通过凝胶注模法制备了多孔碳化硅陶瓷，虽然可以获得蜂窝状孔隙结构，但孔隙多为闭孔，且尺寸较大。对比例2的冷冻温度过低，对比例3中的模具的材质不满足本公开的要求，对比例4的模具底部导热率过高，都会导致冷冻过程中的吞噬现象较弱，进而无法获得具有蜂窝状结构、孔隙呈立体网格状无序联通的多孔碳化硅陶瓷。
由实施例1-2可以发现，冷冻温度越高，孔隙尺寸越大；由实施例1、4、5可以看出，固相含量与孔隙率呈现出明显的负相关关系。利用上述规律，可以对本公开的多孔碳化硅陶瓷产品的结构及性能进行有效调整。
Claims (3)
1.一种多孔碳化硅陶瓷材料的制备方法，其特征在于，包括步骤：
a.将基体原料碳化硅粉体、氢氧化铝粉体和氧化钇粉体以质量比(65～85):(10～30):(5～25)加入容器中；然后再加入分散剂、去离子水，去离子水的加入量为基体原料质量的0.5倍～2.5倍，进行首次球磨，之后再加入粘结剂，进行二次球磨，得到均匀的浆料；
b.将步骤a所制得的浆料倒入容器中进行真空除泡，之后将除泡后的浆料注入到冷冻模具中进行冷冻，冷冻温度为-10℃～-20℃，冷冻模具的底部为铝板、冷冻模具的壁部为聚苯乙烯，得到冷冻生胚；
c.将步骤b所制得的冷冻生胚在真空条件下进行干燥处理，真空条件为-5℃～-60℃的温度、4Pa～20Pa的真空度，干燥处理时间为20h～40h，得到多孔SiC胚体；
d.将步骤c所制得的胚体放入保温箱，进行干燥，干燥的温度为70℃～120℃，干燥的时间为2h～36h；
e.将步骤d所得到的胚体进行烧结，所述烧结的温度为1400℃～1500℃，烧结后得到具有蜂窝结构的多孔碳化硅陶瓷材料；
所述多孔碳化硅陶瓷的孔隙呈立体网格状无序联通，所述孔隙分布均匀，所述孔隙的尺寸为20μm～30μm；
所述多孔碳化硅陶瓷的孔隙率为50％～80％；
所述多孔碳化硅陶瓷的抗压强度为4MPa～25MPa；
所述多孔碳化硅陶瓷的比表面积为4m2/g～18m2/g。
2.根据权利要求1所述的多孔碳化硅陶瓷材料的制备方法，其特征在于，
步骤a中，所述分散剂选自四甲基氢氧化铵、硅酸钠以及聚丙烯酰胺中的至少一种，所述分散剂的加入量为基体原料质量的0.5％～1.5％；和/或
步骤a中，所述粘结剂选自聚乙二醇、聚乙烯醇以及羧甲基纤维素钠中的至少一种，所述粘结剂的加入量为基体原料质量的0.5％～1.5％。
3.根据权利要求1所述的多孔碳化硅陶瓷材料的制备方法，其特征在于，首次球磨的时间为2h～12h，二次球磨的时间为1h～6h。
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