CN109970464B - 一种多孔金属氧化物的制备方法 - Google Patents

一种多孔金属氧化物的制备方法 Download PDF

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CN109970464B
CN109970464B CN201910037156.XA CN201910037156A CN109970464B CN 109970464 B CN109970464 B CN 109970464B CN 201910037156 A CN201910037156 A CN 201910037156A CN 109970464 B CN109970464 B CN 109970464B
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ball milling
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方华婵
肖鹏
朱佳敏
李金伟
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Central South University
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Abstract

本发明涉及一种多孔金属氧化物的制备方法，属于金属粉末技术与金属材料表面处理交叉领域。其制备方法为：先通过将短碳纤维进行脱胶处理，再将脱胶处理的短碳纤维与金属粉末通过适当的球磨工艺得到超细碳颗粒嵌入的金属粉末，经压制后在保护气氛或真空中烧结，或直接松装烧结，最后在含氧空气中进行短时退火处理，在去除金属粉中碳颗粒的同时，金属颗粒表面部分氧化，得到表面部分氧化的多孔金属。本发明所制备的多孔金属氧化物表现出良好的储油、储氢、储石蜡、储锂性能，以及催化性能，且制备工艺简单，成本低。

Description

一种多孔金属氧化物的制备方法
技术领域
本发明涉及一种多孔金属氧化物的制备方法，属于金属粉末技术与金属材料表面处理交叉领域。
背景技术
多孔金属材料是一种在基体内含有大量连通或者闭合的孔隙的新型金属材料。同致密金属相比，多孔金属具有良好的可压缩性，泊松比在变形过程中会发生改变；同聚合物泡沫相比，具有高的刚度和高的使用温度，同时也不会被有机溶剂溶解；同泡沫陶瓷相比，具有良好的韧性、传热性能和导电性。由于其具有优良的性能，因此在汽车工业、航空航天、环保领域、建筑等领域具有广阔的前景。
多孔金属氧化物在催化领域中的地位很重要，它作为主催化剂、助催化剂和载体被广泛使用。就主催化剂而言，金属氧化物催化剂可分为过渡金属氧化物催化剂和主族金属氧化物催化剂，后者主要为固体酸碱催化剂(见酸碱催化作用)。孔径可调、比表面积可控、表面化学性质可调、具有高热稳定性、高校催化活性、高耐腐蚀性、高耐磨性的多孔材料是目前研发的重点。
多孔金属/金属氧化物的制备工艺主要包括水热法、溶胶-凝胶法、化学气相沉积法、模板法、粉末冶金、冷冻干燥法、阳极氧化法等。中国发明专利CN 106629836 B提供了一种多孔钛表面氧化制备多孔二氧化钛块体材料的方法，将造孔剂与钛粉以1：10～1：1的体积比进行配比，并进行机械混合，装入垫有碳纸的不锈钢模具中，将压好的坯料块体放置于真空干燥箱中造孔剂脱除；放置于可充入流动性气体的石英炉中，对多孔钛材料进行烧结，降温后向炉体中以100-200mL/s的速率充入脱氧处理后的水蒸气；在多孔钛表面生成纯金红石型二氧化钛层；反应完成后，关闭水蒸气入口，对炉体降温至室温。该方法采用石英加热炉同时进行材料的烧结与表面水蒸气反应，以获得不同表面晶型的多孔二氧化钛材料。该方法工艺简单、成本较低、制得的样品孔隙率高，但气泡大小和孔隙均匀度难以控制。制备金属颗粒尺寸、孔隙率大小和孔径尺寸可控的多孔金属粉的制备方法是当前的技术难题。
中国发明专利200910219978.6提出通过“电极感应熔化气体雾化法”制备纯钛或钛合金粉末，然后采用冷轧法将充分混合的钛或钛合金粉末和造孔剂成型，最后将成型后的粉末块体在1000℃～1400℃进行烧结而获得孔径为10μm～500μm，孔隙率为10％～50％大尺寸多孔钛或钛合金材料。通过控制钛或钛合金粉末和造孔剂颗粒的大小、轧制工艺等工艺参数来调节多孔材料的孔隙率及孔径大小，从而获得大尺寸钛或钛合金多孔材料。但该方法设备为常规轧制设备和粉末烧结设备，工艺简单，成本低，但只针对制备多孔钛基体材料，未提出在此基础上多孔二氧化钛材料的制备，且存在孔隙率偏低、造孔剂杂质残留等问题。
中国发明专利CN 107281997 A提供了一种多孔氧化物/二氧化钛微米球复合催化材料及其制备方法，适用于污水处理时使用。二氧化钛与氧化物的摩尔比为1/10～1/5复合形成异质结；微米球的直径在10～70μm之间，且微米球内部呈多孔结构；所述的微米球比表面积在20～90m2/g之间。采用喷雾的形式将金属铵盐和TiO2粉末混合浆料均匀的喷到液氮中，然后在低温低压环境中冷冻干燥，最后在空气气氛下烧结得到多孔的微米球。制备过程简单，易于工业化，所述的多孔微米球由金属氧化物纳米片及均匀分布在纳米片表面的TiO2堆积而成，比表面积大，光催化性能良好。
现有技术中，仅有微纳空心金属粉末的报道，通常采用模板法进行制备以胶体、乳状液滴等做模板，然后在其表面进行组装、吸附和化学沉积等反应，最后还需用溶解、煅烧、化学反应等方法去除模板。中国发明专利CN 102274975 A公开了一种金属微纳米空心球粉末制备方法，其主要内容是：工具电极与工件电极保持着火花放电所需间隙对应地浸入在工作液中，接通脉冲电源使工具电极与工件电极火花放电熔化、气化,同时在火花放电过程中对工具电极与工件电极之间的工作液实施超声频振动，使间隙内的工作液产生微气泡，工具电极与工件电极熔化、气化的金属材料附着沉积在微气泡表面，形成金属微纳米空心球。采用本发明的方法制得的金属微纳米空心球粉末，空心球中空程度高，粒径分布在20纳米到100微米之间，壁厚不大于1微米，空心球比例高。该制备方法不足的地方是工艺复杂、生产效率低、生产成本高、模板不易去除干净且易造成环境污染。目前为止，还未见采用高能球磨配合压制—烧结—氧化处理制备表面部分氧化的多孔金属的相关记载。
发明内容
为了解决上述技术问题，本发明的目的在于提供一种工艺简单，成本低、制备效率高的多孔金属氧化物的制备方法。
本发明一种多孔金属氧化物的制备方法，将脱胶短碳纤维和金属粉末进行高能球磨，先进行压制和非氧化气氛下烧结或直接在非氧化气氛下烧结，然后在氧化气氛下热处理，即得多孔金属氧化物。
所述脱胶短碳纤维的制备工艺为：将短碳纤维束在保护性气氛下，于650～800℃热处理20～90min即得。碳纤维表面包覆固化有机胶体层，经脱胶处理后去除碳纤维表面上浆剂，增加碳纤维表面的粗糙度，使得后续球磨处理可以解除上浆剂的“束缚/限制”，并去除碳纤维表面的杂质和活性官能团，提高了短碳纤维的破碎率。
所述保护性气氛为惰性气氛或者真空，例如氮气、氩气。
所述短碳纤维束直径为6～8μm、长度1～4mm。
短纤维过长，球磨时容易缠绕团聚，过短则不仅提高成本，而且实现其在金属粉体表面贯穿的难度增大，一旦无法在金属粉体表面形成贯穿和/或镶嵌，那么后期氧化的时候，就很难实现细小孔洞的形成，进而影响所得材料的孔隙率。
作为优选方案，所述脱胶短碳纤维与金属粉末的体积比为1～9：19～1、进一步优选为1～4：9～1、更进一步优选为1～4：4～1。
所述金属粉中，金属元素为零价，所述金属元素选自Ti、Fe、Cr、V、Co、Ni、Mo、Mn、Zr、Al、Mg、Zn、Ag中的至少一种。
作为优选方案，所述高能球磨的方式为行星球磨或振动球磨。
作为优选方案，所述高能球磨中脱胶短碳纤维和金属粉末的总质量与磨球的质量比为1:5～8。
所述高能球磨转速为220～350r/min，时间至少为6h。
根据权利要求1所述的制备方法，其特征在于：所述压制压力为10～300MPa，保压时间20s；所述烧结温度为基体金属熔点的0.55～0.85；保温时间为10～200min，优选为0.5～3h。
所述非氧化气氛为还原性气氛、惰性气氛或真空。
所述氧化气氛下热处理的条件：温度250～1000℃，时间10～60min。时间根据氧化程度和产品的需求做出调整而决定(其目的在于迫使镶嵌和/或贯穿金属粉体的碳完全氧化脱除，金属表面部分氧化或完全氧化，金属内部部分或完全氧化)。一般为10～60min。
所述氧化气氛下包括含氧气氛或纯氧气氛。所述含氧气氛优选为空气。、在工业上应用时，还可以通过鼓入含氧气体的方式，确保氧化程度以及孔隙程度。在本发明中，通过调整适当脱胶参数处理的碳纤维与金属粉体的质量比；通过球磨参数和压制工艺的配合以及氧化工艺的协同，可以控制好金属的氧化程度以及所得产品的孔隙率。这在本发明以前几乎没有报道过。
本发明一种多孔金属氧化物，通过调节碳纤维的加入量和球磨转速，以及后续压制或烧结处理工艺参数来调节金属粒子尺寸、孔隙率和孔径尺寸，孔隙度可达90％，通过后续的氧化处理工艺参数来调节金属的含氧层厚度。
本发明一种多孔金属氧化物；所述短碳纤维为脱胶处理短碳纤维。市面上现有的碳纤维表面包覆固化有机胶体层，必须通过脱胶处理，以去除碳纤维表面上浆剂，增加碳纤维表面的粗糙度，使得后续(磨碎)处理可以解除上浆剂的“束缚/限制”，并去除了碳纤维表面的杂质，否则破碎率很低。在本发明，严格控制原料短碳纤维的长度以及必须为脱胶处理后的产物，其目的在于配合本发明的球磨转速和研磨球及配比，可以很好的实现碳纤维的超细化和在金属颗粒中的均匀嵌入，以及金属颗粒尺寸的控制，获得超细碳颗粒嵌入金属粉末。
本发明进一步利用获得超细碳颗粒嵌入金属粉末，采用压制-烧结或粉末松装烧结处理，结合氧化处理，脱除金属内部的超细碳颗粒，并使多孔颗粒部分氧化或全部氧化，制备多孔金属氧化物块体。通过调节压制、烧结和氧化的工艺参数(压制压力、烧结方式、烧结和时间、氧化温度和时间等)，获得晶粒尺寸、孔隙率和孔径尺寸、氧化程度可控的多孔金属氧化物块体。
本发明所设计和制备的多孔金属氧化物的颗粒内部孔径对应超细碳颗粒的尺寸，仅为1～3μm，且分布相对而言比较均匀。这些贯穿和/或镶嵌的碳颗粒，在后期氧化后留下孔隙；其孔隙的大小也约等于碳颗粒的尺寸。这就就是为什么本发明所得产品孔隙大小比较均匀的主要原因之一。
现有技术中尚没有高能球磨配合压制-烧结-氧化处理制备多孔金属氧化物材料的相关报道。本发明首次尝试了，采用脱胶处理工艺制备的短碳纤维，通过适当球磨参数的高能球磨工艺，结合压制-烧结或粉末松装烧结，以及氧化处理，制备出多孔金属氧化物块体，节约了生产成本。
现有技术中所制备的多孔氧化物材料力学性能较差，氧化物多为沉积获得，故附着能力较差。本发明所制备的多孔金属氧化物的芯部根据工艺调控，可维持为未反应的金属，而表面是金属氧化物，且氧化物层直接由金属氧化生成，能够在满足金属氧化物催化领域使用要求的同时，满足较高的力学性能与氧化物的附着性能。
针对多晶型的金属氧化物(如Ti、Zr等)，本发明还可在通过调节氧化温度和时间制备不同表面晶型、不同氧化物厚度的多孔金属氧化物材料，使所制备的多孔金属氧化物满足不同催化条件的需要。
原理和优势：
(1)选择短碳纤维。由于碳纤维表面存在大量的活性官能团，因此直接以长碳纤维进行破碎，纤维间易团聚，无法破碎，因此选择短碳纤维，可避免此问题。
(2)短碳纤维的处理方法而言。首先采用脱胶工艺，这是由于市售的碳纤维表面包覆固化胶体层，必须通过脱胶处理，以去除碳纤维表面上浆剂，使得后续(磨碎)处理可以解除上浆剂的“束缚/限制”，并利用脱胶工艺去除了碳纤维表面的杂质和活性官能团，否则破碎率很低。其次选用球磨工艺，球磨转速和研磨球及配比的优化，可以很好的实现碳纤维的超细化，获得超细碳粉均匀嵌入的金属粉末。
(3)压制、烧结工艺及参数选择。通过压制压力、烧结温度和烧结时间的控制，获得孔隙度可控、高力学性能的金属块体，甚至可直接采用粉末松装烧结，获得高孔隙度的金属材料。
(4)氧化工艺及参数选择。为去除金属内部的碳颗粒，以及按产品需求氧化金属，选取氧化的温度和时间，获得氧化程度可控的多孔金属粉末。
总之，本发明具有制备工艺简单(仅脱胶、球磨、去碳-脱氧去杂退火即可)、成本低廉、所得多孔金属粉末性能优良且均匀，具有良好的市场前景。
附图说明
附图1为本发明提供的多孔金属氧化物的制备流程图；
附图2为直接将市售短碳纤维与金属粉末通过高能球磨得到的粉末SEM形貌；
附图3为将1000℃脱胶处理的短碳纤维与金属粉末通过高能球磨得到的粉末SEM形貌；
附图4为将700℃脱胶处理的短碳纤维与金属粉末通过过高(600r/min)或过低(150r/min)转速球磨得到的粉末SEM形貌；
附图5为本发明所制备的700℃脱胶处理的短碳纤维与金属粉末250r/min高能球磨法，结合压制-烧结-300℃空气退火处理制备的多孔金属氧化物材料SEM形貌。
附图6为本发明所制备的700℃脱胶处理的短碳纤维与金属粉末250r/min高能球磨法，结合压制-烧结-300℃空气退火处理制备的多孔金属氧化物材料内部孔隙金相组织。
附图7为本发明所制备的700℃脱胶处理的短碳纤维与金属粉末250r/min高能球磨法，结合压制-烧结-300℃空气退火处理制备的多孔金属氧化物材料的能谱分析。
从图1中可以看出本发明设计的多孔金属氧化物的制备流程，具体为：先通过将短碳纤维进行脱胶处理，再将脱胶处理的短碳纤维与金属粉末通过适当的球磨工艺得到超细碳颗粒嵌入的金属粉末，之后先进行压制和非氧化气氛下烧结或直接在非氧化气氛下松装烧结，最后在含氧空气中进行退火处理去除碳颗粒，并使多孔金属氧化，得到孔隙均匀且高度分散、氧化层厚度可控的多孔金属氧化物材料。
由图2至图4可知，短碳纤维不经过特殊碳化处理，或是碳化处理温度过高，或是高能球磨转速过快或过慢，都无法获得超细碳颗粒嵌入的金属粉末。
由图5～7可知，结合组织和能谱分析，通过脱胶处理结合合适的高能球磨工艺和压制-烧结-氧化退火工艺，获得了晶粒内孔径约为1～3μm的、孔隙均匀分布的多孔金属氧化物材料。
具体实施方式
下面结合本发明的附图，对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明所记载技术方案中的一部分实施例，而不是全部的实施例。基于本发明的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明的保护范围。
对比例1
本对比例1采用粒径为120μm的鳞片状石墨和粒径为120μm的电解铜粉为球磨原料，天然鳞片石墨体积百分比计20％，电解铜粉加入体积百分比计80％，将两者加入到球磨设备中进行高能球磨，转速为250r/min，球磨时间为6h，球料比为5:1。天然鳞片石墨自发团聚，并未发生破碎。经实施例1完全一样的后续处理后，未得到多孔金属粉末。压制烧结后，所得产品的孔隙率约为8～12％。
对比例2
本对比例2采用粒径为120μm的颗粒状石墨和粒径为120μm的电解铜粉为球磨原料，颗粒状石墨体积百分比计20％，电解铜粉加入体积百分比计80％，将两者加入到球磨设备中进行高能球磨，转速为250r/min，球磨时间为6h，球料比为5:1。颗粒状石墨部分被破碎，且并未明显嵌入铜粉中。经实施例1完全一样的后续处理后，未得到多孔金属粉末。压制烧结后，所得产品的孔隙率约为5～8％。
对比例3
本对比例3采用市售、不经过任何预处理的短碳纤维和粒径为120μm的电解铜粉为球磨原料，碳纤维体积百分比计20％，电解铜粉加入体积百分比计80％，短碳纤维的直径为8μm，长度2mm，将两者加入到球磨设备中进行高能球磨，转速为250r/min，球磨时间为6h，球料比为5:1。短碳纤维并未破碎，粘在球磨罐壁处，具体见图2所示。经实施例1完全一样的后续处理后，未得到碳颗粒嵌入金属粉末。压制烧结后，所得产品的孔隙率约为8～12％。
对比例4
本对比例4采用市售、1000℃脱胶处理的短碳纤维和粒径为120μm的电解铜粉为球磨原料，短碳纤维体积百分比计20％，电解镍粉加入体积百分比计80％，短碳纤维的直径为8μm，长度2mm，将两者加入到球磨设备中进行高能球磨，转速为250r/min，球磨时间为6h，球料比为5:1。短碳纤维并未明显破碎，具体见图3所示。经实施例1完全一样的后续处理后，未得到多孔金属粉末。压制烧结后，所得产品的孔隙率约为5～8％。
对比例5
本对比例5采用市售、700℃脱胶处理的短碳纤维和粒径为120μm的电解铜粉为球磨原料，短碳纤维体积百分比计20％，电解镍粉加入体积百分比计80％，短碳纤维的直径为12μm，长度2mm，将两者加入到球磨设备中进行高能球磨，转速为250r/min，球磨时间为6h，球料比为5:1。短碳纤维并未明显破碎，经实施例1完全一样的后续处理后，未得到多孔金属粉末。压制烧结后，所得产品的孔隙率约为8～12％。
对比例6
本对比例6采用市售、700℃脱胶处理的短碳纤维和粒径为120μm的电解镍粉为球磨原料，短碳纤维体积百分比计20％，电解镍粉加入体积百分比计80％，短碳纤维的直径为6μm，长度2mm，将两者加入到球磨设备中进行高能球磨，转速为600r/min，球磨时间为6h，球料比为6:1。短碳纤维并未明显破碎，大多数沉积球磨罐顶部盖子处，具体见图4所示。后续操作按照实施例2的条件进行；压制烧结后，所得产品的孔隙率约为18～25％。
对比例7
本对比例7采用市售、700℃脱胶处理的短碳纤维和粒径为120μm的电解镍粉为球磨原料，短碳纤维体积百分比计20％，电解镍粉加入体积百分比计80％，短碳纤维的直径为6μm，长度2mm，将两者加入到球磨设备中进行高能球磨，转速为100r/min，球磨时间为6h，球料比为6:1。短碳纤维并未明显破碎，经实施例2完全一样的后续处理后，未得到多孔金属粉末。后续操作按照实施例2的条件进行；压制烧结后，所得产品的孔隙率约为4～7％。
实施例1
本实施例1采用市售、700℃脱胶处理60min的短碳纤维和粒径为120μm的电解铜粉为球磨原料，短碳纤维体积百分比计10％，电解铜粉加入体积百分比计90％，短碳纤维的直径为6μm，长度2mm，将两者加入到球磨设备中进行高能球磨，转速为250r/min，球磨时间为6h，球料比为6:1。将所得混合粉在室温下进行冷压，压制压力为50MPa，保压时间为20s，制备的碳颗粒嵌入铜压坯在氢气气氛保护下烧结，在900℃烧结1h，炉子的升温速率与降温速率均为15℃/min，之后将烧结坯在空气中退火去碳氧化，退火温度为300℃，保温时间为20min，得到多孔氧化铜孔隙度达到9～14％，氧化铜含量为总质量的20％。多孔氧化铜材料的形貌见图5，内部组织见图6，材料的能谱分析见图7。
实施例2
本实施例2采用市售、750℃脱胶处理60min的短碳纤维和粒径为120μm的电解镍粉为球磨原料，短碳纤维体积百分比计25％，电解镍粉加入体积百分比计75％，短碳纤维的直径为6μm，长度2mm，将两者加入到球磨设备中进行高能球磨，转速为280r/min，球磨时间为7h，球料比为6:1。将所得混合粉料直接在氢气气氛保护下烧结，在850℃烧结1h，炉子的升温速率与降温速率均为15℃/min，之后将烧结坯在空气中退火去碳氧化，退火温度为500℃，保温时间为30min，得到多孔氧化镍孔隙度达到22～30％，氧化镍含量为总质量的90％。
实施例3
本实施例3采用市售、800℃脱胶处理60min的短碳纤维和粒径为150μm的还原铁粉为球磨原料，短碳纤维体积百分比计40％，还原铁粉加入体积百分比计60％，短碳纤维的直径为6μm，长度2mm，将两者加入到球磨设备中进行高能球磨，转速为300r/min，球磨时间为8h，球料比为6:1。将所得混合粉料直接在真空下烧结，在980℃烧结1h，炉子的升温速率与降温速率均为15℃/min，之后将烧结坯在空气中退火去碳氧化，退火温度为500℃，保温时间为60min，得到多孔氧化铁孔隙度达到40～48％，氧化铁含量为总质量的85％。
实施例4
本实施例4采用市售、750℃脱胶处理60min的短碳纤维和粒径为50μm的球形钛粉为球磨原料，短碳纤维体积百分比计55％，球形钛粉加入体积百分比计45％，短碳纤维的直径为7μm，长度2mm，将两者加入到球磨设备中进行高能球磨，转速为250r/min，球磨时间为10h，球料比为7:1。将所得混合粉料在室温下进行冷压，压制压力为250MPa，保压时间为20s，制备的碳颗粒嵌入钛压坯在真空下烧结，在1200℃烧结1h，炉子的升温速率与降温速率均为15℃/min，之后将烧结坯在空气中退火去碳氧化，退火温度为600℃，保温时间为10min，得到多孔氧化钛孔隙度达到50～60％，氧化钛含量为总质量的15％。
实施例5
本实施例5采用市售、800℃脱胶处理60min的短碳纤维和粒径为180μm的球形银粉为球磨原料，短碳纤维体积百分比计65％，球形银粉加入体积百分比计35％，短碳纤维的直径为8μm，长度2mm，将两者加入到球磨设备中进行高能球磨，转速为280r/min，球磨时间为8h，球料比为6:1。将所得混合粉料在室温下进行冷压，压制压力为60MPa，保压时间为20s，制备的碳颗粒嵌入银压坯在氢气下烧结，在400℃烧结1h，炉子的升温速率与降温速率均为15℃/min，之后将烧结坯在空气中退火去碳氧化，退火温度为300℃，保温时间为60min，得到多孔氧化银孔隙度达到65～72％，氧化银含量为总质量的100％。
实施例6
本实施例6采用市售、750℃脱胶处理30min的短碳纤维和粒径为100μm的高纯镁粉为球磨原料，短碳纤维体积百分比计70％，高纯镁粉加入体积百分比计30％，短碳纤维的直径为8μm，长度2mm，将两者加入到球磨设备中进行高能球磨，转速为250r/min，球磨时间为8h，球料比为7:1。所得混合粉料直接在真空下烧结，在500℃烧结1h，炉子的升温速率与降温速率均为15℃/min，之后将烧结坯在空气中退火去碳氧化，退火温度为400℃，保温时间为20min，得到多孔氧化镁孔隙度达到70～78％，氧化镁含量为总质量的70％。
实施例7
本实施例7采用市售、750℃脱胶处理60min的短碳纤维和粒径为150μm的球形钴粉为球磨原料，短碳纤维体积百分比计80％，球形钴粉加入体积百分比计20％，短碳纤维的直径为8μm，长度2mm，将两者加入到球磨设备中进行高能球磨，转速为280r/min，球磨时间为8h，球料比为6:1。所得混合粉料直接在真空下烧结，在1000℃烧结1h，炉子的升温速率与降温速率均为15℃/min，之后将烧结坯在空气中退火去碳氧化，退火温度为800℃，保温时间为40min，得到多孔氧化钴孔隙度达到72～84％，氧化钴含量为总质量的60wt％。
实施例8
本实施例8采用市售、750℃脱胶处理60min的短碳纤维和粒径为200μm的钼粉为球磨原料，短碳纤维体积百分比计90％，钼粉加入体积百分比计10％，短碳纤维的直径为8μm，长度2mm，将两者加入到球磨设备中进行高能球磨，转速为280r/min，球磨时间为10h，球料比为6:1。所得混合粉直接在氢气气氛下烧结，在1850℃烧结1h，炉子的升温速率与降温速率均为15℃/min，之后将烧结坯在空气中退火去碳氧化，退火温度为600℃，保温时间为30min，得到多孔氧化钼孔隙度达到82～90％，氧化钼含量为总质量的50％。
实施例9
本实施例9采用市售、750℃脱胶处理60min的短碳纤维和粒径为200μm的雾化铝粉为球磨原料，短碳纤维体积百分比计90％，钼粉加入体积百分比计10％，短碳纤维的直径为8μm，长度2mm，将两者加入到球磨设备中进行高能球磨，转速为280r/min，球磨时间为10h，球料比为7:1。所得混合粉料直接在氮气气氛下烧结，在500℃烧结1h，炉子的升温速率与降温速率均为15℃/min，之后将烧结坯在空气中退火去碳氧化，退火温度为300℃，保温时间为40min，得到多孔氧化铝孔隙度达到86～90％，氧化铝含量为总质量的100％。
(由于金属颗粒不仅内部镶嵌超细碳颗粒，其表面还有大量的碳颗粒，大颗粒的存在，阻止了金属之间的烧结，即使压制压力尽可能减少金属颗粒间的孔隙度(高压制压力下，通常压制孔隙度为10～15％)，但烧结时，金属间无法烧结致密，加上内部碳的氧化脱除，材料整体的孔隙度在10～15％上，还要叠加碳颗粒脱出后残留的孔隙)。

Claims (5)

1.一种多孔金属氧化物的制备方法，其特征在于：将脱胶短碳纤维和金属粉末进行高能球磨，先进行压制和非氧化气氛下烧结或直接在非氧化气氛下烧结，然后在氧化气氛下热处理，即得多孔金属氧化物；
所述脱胶短碳纤维的制备工艺为：将短碳纤维束在惰性气氛或真空条件下，于650~800℃热处理20~90min即得；
所述短碳纤维束直径为6~8 μm、长度1~4mm；
所述脱胶短碳纤维与金属粉末的体积比为1~9:19~1；
所述高能球磨中脱胶短碳纤维和金属粉末的总质量与磨球的质
量比为1: 5~8；
所述高能球磨转速为220~350r/min，时间至少为6h。
2.根据权利要求1所述的制备方法，其特征在于：所述金属粉末中金属元素为零价，所述金属元素选自Ti、Fe、Cr、V、Co、Ni、Mo、Mn、Zr、Al、Mg、Zn、Ag中的至少一种，且金属粉末与零价氧反应并生成氧化物。
3.根据权利要求1所述的制备方法，其特征在于：所述高能球磨的方式为行星球磨或振动球磨。
4.根据权利要求1所述的制备方法，其特征在于：所述压制压力为10~300MPa，保压时间20s；所述烧结温度为基体金属熔点的0.55~0.85；保温时间为10~200min。
5.根据权利要求1所述的制备方法，其特征在于：
所述非氧化气氛为还原性气氛、惰性气氛或真空气氛；
所述氧化气氛下热处理的条件：温度250~1000℃，时间10~60 min。
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