CN110303165B - 一种浸渍型氧化钪掺杂铼钨多相混合基扩散阴极及制备方法 - Google Patents
一种浸渍型氧化钪掺杂铼钨多相混合基扩散阴极及制备方法 Download PDFInfo
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Abstract
一种浸渍型氧化钪掺杂铼钨多相混合基扩散阴极及制备方法，属于难熔金属阴极技术领域。阴极基体是氧化钪掺杂的铼与钨形成的多相合金粉通过粉末冶金的方法制备而成的多孔体，之后向基体中浸渍活性盐并对阴极表面后处理形成具有电子发射能力的阴极。该方法所制备的阴极具有发射电流密度大，可重复性好等特点，适用于对电流密度要求较高的电真空器件以及电子束源。
Description
技术领域
本发明属于稀土难熔金属与电子发射材料领域，一种浸渍型氧化钪掺杂钨铼合金基扩散阴极的制备方法。
背景技术
阴极是电真空器件的电子源，被誉为器件的心脏。近年来，随着电真空器件的不断发展，器件对阴极的电子发射能力要求不断提高，尤其是现在处于研究热点的大功率太赫兹辐射源、微焦点X射线管等对未来科技有着重要意义的器件都对阴极的电子发射能力提出了极其高的要求。
浸渍型氧化钪掺杂钨基阴极是一类具有优异电子发射能力的阴极，尤其是氧化钪掺杂钨基阴极是热阴极中目前电子发射能力最强的阴极。但是由于该阴极存在诸多的不确定性导致其一直无法在实际应用中得到广泛的推广。
铼作为添加元素对钨的机械加工性能、高温强度等很多方面性能都有着明显的提升，因此铼钨合金在科技、工业中有着广泛的应用。将铼添加到钨中制备而成的合金阴极较纯钨的电子发射能力也有着明显的提升。部分研究表明将铼添加的钨基扩散阴极中形成钨铼基扩散阴极其电子发射能力也会有明显的提升。但是目前对于将铼添加到浸渍型氧化钪掺杂钨基阴极中的作用的研究尚不充分，仅有研究表明通过覆膜的方式在含钪阴极表层制备发射活性层对阴极发射性能性能的提高有着非常明显的作用，但是该方法可重复性非常差，无法稳定的制备出高性能的阴极。
综上所述，将铼添加在钨基阴极中对阴极发射性能的提升有着积极作用，通过改进其添加方式获得电子发射能力杰出的阴极对于整个真空电子器件的性能有着非常重要的意义。
发明内容
本发明提供了一种浸渍型氧化钪掺杂钨铼多相混合基扩散阴极的制备方法，使用固液、固固、液固、浆化等混合方式将铼钨以及氧化钪原料进行混合，采用分步热还原方法得到氧化钪掺杂钨铼多相合金粉体，之后通过粉末冶金的方法获得稀氧化钪掺杂钨铼多相合金基体，最后通过浸渍活性钡盐以及表面处理获得氧化钪掺杂铼钨多相合金基扩散阴极。目前尚未见该材料以及该方法的研究报道。
本发明一种浸渍型氧化钪掺杂铼钨多相混合基扩散阴极，其特征在于，钨与铼形成多种不同比例的合金相，铼元素在基体中的质量含量占比为0.5％-99％，氧化钪的质量占比为0.05％-15％，钨元素质量占比为0.45-99％；浸渍物质为活性盐，活性盐质量占比为0.1％-25％。
钨和铼以钨单质、铼单质、钨铼固溶体、钨铼金属间化合物等至少两种形式存在于粉体中；如选ReW、ReW3、Re3W、W、Re等。一般钨单质、铼单质不同时存在。
活性盐主要包括氧化钡、氧化钙、氧化锶等碱土族氧化物与氧化铝、氧化锆、氧化硅、氧化钨中的一种或几种经过高温烧制而成的活性盐，此为常规技术。
具体制备过程包括如下步骤：
步骤一：制备氧化钪掺杂钨铼多相合金粉末；
步骤二：将步骤一粉末进行压制成型和烧结，制备产生具有孔隙的阴极基体，其中通孔占阴极基体体积大小为1％-30％；
步骤三：将步骤二制备的阴极基体浸渍发射活性盐；
步骤四：根据阴极表面洁净度不同对阴极表面进行处理，处理方式为水洗、酸洗、碱洗等清洗方式，或机械加工等物理处理方法；然后进行退火处理。
进一步优选步骤一：氧化钪掺杂钨铼多相合金粉末的制备，包括以下步骤：将分析纯的含有钨元素的铵盐、含有铼元素的铵盐、硝酸钪进行机械混合，分别使用去离子水、乙醇、乙二醇等液体作为调和剂，将固体原料制成浆液并进行充分搅拌，并不断调节调和剂添加量以此提高原料的混合均匀性；将浆液在100-200℃烘干之后，进行氢气气氛的分解和还原。分解和还原采用多步进行处理，第一步为150-450℃，保温0.1-10小时。第二步为550-850℃，保温0.5-5小时，第三步为970-1700℃，保温0.5-5小时，最终获得氧化钪掺杂铼钨多相混合。
进一步优选步骤二烧结温度为1300-1800℃，时间为1分钟-5小时。
进一步优选步骤四退火的温度为850-1700℃，时间为10分钟-2小时。
本发明专利制备方法简单，可操作性强，制备样品强度高，适合大规模工业制备，且制备阴极发射性能优异，其电子发射性能超过了目前现有的扩散阴极数倍，能够在器件中以更低的温度工作，极大的延长了器件使用寿命，适用于对电流密度要求较高的高频、大功率电真空器件以及电子束源。
附图说明
为了更详实地表述该发明实施例的技术方案，以下对实施例描述中所使用的附图作简单介绍。显然，以下描述中的附图仅为本发明的一些实施例的附图，对于该领域普通技术人员来讲，在未付诸创造性劳动的前提下，还可依据此类附图获得其它的附图。
图1阴极制备工艺路线图；
图2氧化钪掺杂钨铼多相混合基阴极表面形貌；
图3氧化钪掺杂钨铼多相混合基阴极发射性能曲线，氧化钪掺杂钨铼多相混合基阴极900℃发射性能。
具体实施方法
下面结合实施例对本发明进行进一步说明，但本发明不限于以下实施示例。
实施例1：分别将107.96g高铼酸铵，33.51g偏钨酸铵和13.4g硝酸钪进行固相机械混合，向混合粉末中添加100ml去离子水和50ml乙醇，搅拌成浆状，将浆化粉末置于200℃烘干，制成混合前驱粉。将前驱粉末在氢气气氛中分解还原。第一步温度为450℃，保温2h；第二步还原温度为800℃，保温2h，第三步还原温度为1100℃，保温时间2h，获得氧化钪含量为4％的铼钨合金混合合金粉末，如图2所示为获得粉体XRD。采用模压方式将粉体压制成型，压力为700Mpa，保压时间为120秒。将压制坯体进行烧结成阴极基体，烧结温度为1550℃，保温3小时，最终基体空隙率为35％。对基体浸渍铝酸钡钙411盐，活性盐浸渍量为19％。清洗阴极表面残盐，进行退火处理，退火温度为1200℃，时间1小时，如图2所示为获得阴极表面SEM，图3所示为该阴极以及后续实施事例所制备阴极的电子发射性能。
实施例2：分别将107.96g高铼酸铵，33.51g偏钨酸铵和16.75g硝酸钪在去离子水中溶解成溶液，采用溶胶凝胶方法制备获得前驱粉。将前驱粉末在氢气气氛中分解还原。第一步温度为450℃，保温2h；第二步还原温度为700℃，保温2h，第三步还原温度为1300℃，保温时间2h，获得氧化钪含量为5％的铼钨合金混合粉末。采用等静压方法将粉体压制成型，压力为600Mpa，保压时间为300秒。将压制坯体进行烧结成阴极基体，烧结温度为1700℃，，时间20分钟，最终基体空隙率为33％。对基体浸渍铝酸钡钙612盐，活性盐浸渍量为15％。清洗阴极表面残盐，进行退火处理，退火温度为1200℃，时间0.5小时，发射性能见图3。
实施例3：分别将62.43g七氧化二铼，60.54g三氧化钨和13.4g硝酸钪进行固相机械混合，之后加水将粉体制成膏状并加入脱水剂，加热脱水。将得到的前驱粉末在氢气气氛中分解还原。第一步温度为250℃，保温2h；第二步还原温度为600℃，保温2h，第三步还原温度为1100℃，保温时间2h，获得氧化钪含量为1％的钨铼合金粉。对粉体进行压制烧结，等静压压力为800Mpa，烧结温度1500℃，烧结时间为2小时，浸渍铝酸钡钙411盐，浸渍量为9％。清洗阴极表面残盐，进行退火处理，退火温度为1000℃，时间1小时。发射性能见图3。
Claims (4)
1.一种浸渍型氧化钪掺杂铼钨多相混合基扩散阴极的制备方法，其特征在于，钨与铼形成多种不同比例的合金相，铼元素在基体中的质量含量占比为0.5%-99%，氧化钪的质量占比为0.05%-15%，钨元素质量占比为0.45-99%；浸渍物质为活性盐，活性盐质量占比为0.1%-25%；
其制备方法，包括以下步骤：
步骤一：制备氧化钪掺杂铼钨多相合金粉末；
步骤二：将步骤一粉末进行压制成型和烧结，制备产生具有孔隙的阴极基体，其中通孔占阴极基体体积大小为1%-30%；
步骤三：将步骤二制备的阴极基体浸渍发射活性盐；
步骤四：根据阴极表面洁净度不同对阴极表面进行处理，处理方式为水洗、酸洗、碱洗的清洗方式，或机械加工的物理处理方法；然后进行退火处理；
其中步骤一：氧化钪掺杂铼钨多相合金粉末的制备，包括以下步骤：将分析纯的含有钨元素的铵盐、含有铼元素的铵盐、硝酸钪进行机械混合，分别使用去离子水、乙醇、乙二醇液体作为调和剂，将固体原料制成浆液并进行充分搅拌，并不断调节调和剂添加量以此提高原料的混合均匀性；将浆液在100-200℃烘干之后，进行氢气气氛的分解和还原；分解和还原采用多步进行处理，第一步为150-450 ℃，保温0.1-10小时；第二步为550-850℃，保温0.5-5小时，第三步为970-1700℃，保温0.5-5小时，最终获得氧化钪掺杂铼钨多相合金粉体。
2.按照权利要求1所述的一种浸渍型氧化钪掺杂铼钨多相混合基扩散阴极的制备方法，其特征在于，活性盐主要包括氧化钡、氧化钙、氧化锶与氧化铝、氧化锆、氧化硅、氧化钨中的一种或几种经过高温烧制而成的活性盐。
3.按照权利要求1所述的一种浸渍型氧化钪掺杂铼钨多相混合基扩散阴极的制备方法，其特征在于，步骤二烧结温度为1300-1800℃，时间为10分钟-3小时。
4.按照权利要求1所述的方法，其特征在于，步骤四退火的温度为850-1700℃，时间为10分钟-2小时。
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