CN103341291B - 烧结多孔材料及应用该多孔材料的过滤元件 - Google Patents
烧结多孔材料及应用该多孔材料的过滤元件 Download PDFInfo
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Abstract
本发明公开了一种具有较强耐腐蚀性的烧结多孔材料以及应用该多孔材料的过滤元件。本申请的烧结多孔材料具有如下特征:a)它主要由Ti、Si、C三种元素组成,这三种元素的重量之和占该烧结多孔材料重量的90%以上,其中,Ti为Ti、Si、C总重量的60~75%,Si为Ti、Si、C总重量的10~20%;b)该烧结多孔材料中的C主要是以Ti3SiC2三元MAX相化合物的形式存在,且在该多孔材料中大致上均匀分布;c)它的孔隙率为30~60%,平均孔径为0.5~50μm,抗拉强度≥23MPa,厚度≤5mm的烧结多孔材料在0.05MPa的过滤压差下测得纯水的过滤通量≥1t/m2·h,且在5wt%的盐酸溶液中室温浸泡48天后的失重率在1.5%以下。本发明的烧结多孔材料具有非常优异的耐腐蚀性能。
Description
技术领域
本发明涉及一种多孔材料及应用该多孔材料的过滤元件,具体涉及一种通过粉末冶金法制备的烧结多孔材料及应用该多孔材料的过滤元件。
背景技术
目前对烧结多孔材料的研究主要集中在制备工艺的优化、成孔机理的探讨、材料性能的改善和应用范围的扩大几个方面。其中,就成孔机理而言,已应用在烧结多孔材料制备方法中的成孔方式主要有:第一,通过化学反应成孔,其原理是基于不同元素本征扩散系数的较大差异所引起的偏扩散效应,使得材料中产生Kirkendall孔隙;第二,通过原料粒子物理堆积成孔;第三,通过添加成分脱出成孔。上述几种成孔方式的选择和组合不可避免的会对多孔材料的孔结构造成直接的影响。而多孔材料的孔结构又会进一步的决定多孔材料的性能。因此,基于不同成孔方式所生成的烧结多孔材料往往具有差异化的孔结构和使用性能,通过对它们的认识和测量,可使得这些多孔材料能够更清楚的被识别和表征。目前,为了充分的表征多孔材料,本领域通常采用:1)原料成分和含量;2)孔结构,主要包括孔隙率、孔径等;3)材料性能参数,包括渗透性能,力学强度和化学稳定性,其中,渗透性能常用流体渗透法测量,力学强度通常用抗拉强度表示,化学稳定性主要用耐酸和/或碱性能表示。
Ti-Al金属间化合物多孔材料是一种介于高温合金与陶瓷之间的烧结无机多孔材料。由于其按照金属键和共价键共同结合,兼有金属材料和陶瓷材料的共同优点,因此,Ti-Al金属间化合物多孔材料作为过滤材料具有广阔的应用前景。尽管Ti-Al金属间化合物多孔材料公认具有优异的性能,但其在强酸条件下的耐腐蚀性能依然有待提高。比如,Al含量为35wt%的Ti-Al金属间化合物多孔材料在90℃的恒温条件下,当pH值从3下降到2时,样品的质量损失和开孔隙率均显著增大,表明材料的耐腐蚀性能下降较明显。因此,针对一些特殊的应用场合,还需进一步提高材料的耐腐蚀性。在本申请的申请日以前,还未找到一种类似于Ti-Al金属间化合物多孔材料这种兼有金属材料和陶瓷材料的共同特点,同时又具有更强耐腐蚀性的烧结多孔材料。
发明内容
本申请所要解决的技术问题是提供一种具有较强耐腐蚀性的烧结多孔材料以及应用该多孔材料的过滤元件。
本申请的烧结多孔材料具有如下特征:
a)它主要由Ti、Si、C三种元素组成,这三种元素的重量之和占该烧结多孔材料重量的90%以上,其中,Ti为Ti、Si、C总重量的60~75%,Si为Ti、Si、C总重量的10~20%;
b)该烧结多孔材料中的C主要是以Ti3SiC2三元MAX相化合物的形式存在,且在该多孔材料中大致上均匀分布;
c)它的孔隙率为30~60%,平均孔径为0.5~50μm,抗拉强度≥23MPa,厚度≤5mm的烧结多孔材料在0.05MPa的过滤压差下测得纯水的过滤通量≥1t/m2·h,且在5wt%的盐酸溶液中室温浸泡48天后的失重率在1.5%以下。
上述的烧结多孔材料可以仅由Ti、Si、C三种元素组成,也可以在不超过烧结多孔材料总重量10%的范围内添加除Ti、Si、C以外的其他物质,例如Cr、Mo、V、Nb、Al、W中一种或几种元素。目前建议将该多孔材料中Ti、Si、C三种元素的重量之和控制在多孔材料重量的95%、97%、98%或者99%以上,从而保证烧结多孔材料的性能,同时也可简化原料种类,便于生产。
当烧结多孔材料由Ti、Si、C三种元素组成时,最好通过控制Ti、Si、C的比例使材料烧结后的结晶相由Ti3SiC2三元MAX相化合物组成,从而获得最佳的耐腐蚀性。
本申请的烧结多孔材料具有如下有益的技术效果:
一、具有非常优异的耐腐蚀性能;
二、尤其令人惊讶的是,由于原料中的C与Ti反应而改善了孔结构,使得三维贯通孔的曲折因子变小,降低了过滤介质的通过阻力,可获得更理想的过滤通量;
三、当烧结多孔材料的结晶相由Ti3SiC2三元MAX相化合物组成,材料的耐腐蚀性能更好。
具体实施方式
下面通过实验对烧结多孔材料的制备方法和由这些方法得到的烧结多孔材料进行具体说明。通过这些说明,本领域技术人员能够清楚认识到本申请的烧结多孔材料所具有的突出特点。以下涉及的实验例的编号与对应“压坯”、“试样”的编号一致。
为说明本申请的烧结多孔材料及其制备,共准备了以下10组实验例。其中,通过实验例1至5分别制备得到的试样1至5均属于本申请权利要求1所要保护的烧结多孔材料的范围之内。实验例6至10作为体现实验例1至5实质性特点和技术效果的对比实验,其编号上用“*”标出,以便区分。实验例6具体是在实验例2的基础上增加了原料中Ti粉和C粉的含量,并将由此制备的试样6与试样2进行比较。实验例7具体是在实验例2的基础上,将原料C粉原料改为TiC粉(C含量不变),并将由此制备的试样7与试样2进行比较。实验例8直接使用Ti3SiC2粉为原料来制备多孔材料。实验例9和实验例10则分别实施了一种现有的烧结Ti-Al基合金多孔材料制备方法。具体如下。
一、材料制备工艺
实验例1至10的原料成分及含量(以重量百分比计)见表1。为便于比较,统一采用粒径为-400目的Ti粉和TiC粉,粒径为-325目的TiH2粉,粒径为10~15μm的Si粉,粒径为3~5μm的C粉、粒径为15~20μm的Ti3SiC2粉以及粒径为-100目的NH4HCO3(造孔剂)。当然,在实际生产中,本领域技术人员也可根据其所要获得的多孔材料的孔径,对各原料的粒径进行有针对性的调整。
表1:实验例1至10所用原料的成分及含量
如表1所列,实验例9和实验例10的原料由造孔剂(具体采用了NH4HCO3)、TiH2粉、TiC粉、Al粉组成;实验例9中,NH4HCO3、TiH2粉、TiC粉以及Si的含量(原子百分比)分别为15%、35%、35%、15%,换算为重量百分比分别约为21.72%、32.08%、38.50%和7.70%;实验例12中,NH4HCO3、TiH2粉、TiC粉以及Si的含量(原子百分比)分别为5%、35%、50%、10%,换算为重量百分比分别为7.28%、32.26%、55.30%和5.16%(见表1)。
按表1所列,分别对实验例1至10的原料进行混合。充分混合后,考虑到实验例1至6的原料中均掺有重量较轻的C粉,容易引起偏析,因此,还需对实验例1至6的粉料进行造粒,造粒后再进行干燥,干燥温度设定为55℃,干燥时间设定为6小时。而实验例7至10不含有C粉,因而无需进行造粒即可进入下一步成型工序。由于造粒干燥只是为了避免偏析,此外并不会对材料的最终结构和性能造成影响,故不会影响实验对比的准确性。
之后,分别将实验例1至10的粉料装入统一规格的等静压成型模具中,然后将这些模具分别置于冷等静压成型机,在250MPa成型压力下保压30秒,脱模后即制成编号为1至10的管状压坯。然后,将这些压坯分别装入烧结舟,再把这些烧结舟置于烧结炉内进行烧结,烧结后随炉冷却,最后再从各烧结舟中取得试样1至10。
1.1实验例1至7的烧结制度
实验例1至7的烧结制度可分为五个阶段,其中第一阶段是将烧结温度从室温逐渐升至450℃,升温速率控制在1~25℃/min,该阶段的总烧结时间为30~600分钟;第二阶段是将烧结温度从450℃逐渐升至900℃,升温速率控制在1~20℃/min,该阶段的总烧结时间为180~1000分钟;第三阶段是将烧结温度从900℃逐渐升至1000℃,升温速率控制在1~20℃/min,该阶段的总烧结时间为30~1000分钟;第四阶段是将烧结温度从1000℃逐渐升至1200℃,升温速率控制在1~20℃/min,该阶段的总烧结时间为30~600分钟;第五阶段是将烧结温度从1200℃逐渐升至1450℃,升温速率控制在1~20℃/min,该阶段的总烧结时间为60~600分钟,且在第五阶段中,应在1300~1400℃的温度区间内保温2~3小时。上述第一阶段的主要目的在于脱脂;第二阶段的主要目的在于TiH2脱氢造孔的(试验例1、3除外),并促成Ti和C反应造孔生成TiC;第三阶段的主要目的在于进一步促成Ti和C反应造孔生成TiC;第四的主要目的在于生成液相Si,第五阶段的主要目的在于促成Ti、液相Si和TiC反应最终生成Ti3SiC2三元MAX相化合物。第五阶段中在1300~1400℃的温度区间内保温2~3小时可提高Ti3SiC2三元MAX相化合物的结晶化程度,从而保证材料的抗拉强度。
实验例1至7的烧结工艺中五个阶段的烧结工艺参数具体如表2所示。表2中升温速率的单位为℃/min,烧结时间的单位为分钟。
表2:实验例1至6的烧结制度
1.2实验例8至10的烧结制度
实验例8的烧结制度相对比较简单,其具体是将烧结温度从室温逐渐升至1300℃,升温速率控制在15℃/min,总烧结时间为180分钟。
实验例9的烧结制度分为四个阶段,其中第一阶段是将烧结温度从室温逐渐升至150℃,升温速率控制在3℃/min,然后保温30分钟,完成NH4HCO3的分解造孔;第二阶段是将烧结温度从150℃逐渐升至480℃,升温速率控制在8℃/min,然后保温120分钟,完成TiH2脱氢造孔;第三阶段是将烧结温度从480℃逐渐升至620℃,升温速率控制在2℃/min,然后保温240分钟,完成Ti和Si的反应造孔,生成Ti-Si二元金属间化合物;第四阶段是将烧结温度从620℃逐渐升至1300℃,升温速率控制在5℃/min,然后保温300分钟,促成Ti-Si二元金属间化合物与TiC反应最终生成Ti3SiC2三元MAX相化合物。
实验例12的烧结制度分为四个阶段,其中第一阶段是将烧结温度从室温逐渐升至350℃,升温速率控制在5℃/min,然后保温60分钟,完成NH4HCO3的分解造孔;第二阶段是将烧结温度从350℃逐渐升至560℃,升温速率控制在10℃/min,然后保温60分钟,完成TiH2脱氢造孔;第三阶段是将烧结温度从560℃逐渐升至950℃,升温速率控制在1℃/min,然后保温360分钟,完成Ti和Si的反应造孔,生成Ti-Si二元金属间化合物;第四阶段是将烧结温度从950℃逐渐升至1400℃,升温速率控制在3℃/min,然后保温420分钟,促成Ti-Si二元金属间化合物与TiC反应最终生成Ti3SiC2三元MAX相化合物。
二、材料的相组成及其性能参数
为更清楚表征试样1至10对应的烧结多孔材料,以下将对试样1至10的相组成及材料性能参数进行说明。其中,由于实验例4和5都是为了研究掺入除Ti、Si、C外的其他物质对材料最终性能的影响,因此,在说明材料相组成时,仅选择了试样4为例。
通过XRD对分别试样1至4、试样6至10进行检测,其结果如表3所示。
表3:试样1至6、试样8至10的相组成
试样编号 | 相组成 |
1 | Ti3SiC2、SiC、少量的C |
2 | Ti3SiC2 |
3 | Ti3SiC2、TiC、TiSix |
4 | Ti3SiC2、Ti3SixAl1-xC2固溶体 |
6* | Ti3SiC2、TiC |
7* | Ti3SiC2 |
8* | Ti3SiC2 |
9* | Ti3SiC2、TiC |
10* | Ti3SiC2、TiC |
试样1至10的性能测试如表4。其中,材料孔隙率和平均孔径的测试采用汽泡法,过滤通量具体为在0.05MPa的过滤压差下纯水的过滤通量,材料抗拉强度的测试是将试样1至10按中国国家标准GB7963-87加工为标准试样后通过拉伸机测得,材料耐腐蚀性采用在5wt%(即质量百分数为5)的盐酸溶液中室温浸泡48天后的失重率来表征。
表4:试样1至10的性能测试结果
三、试验结果分析
1)参见表4,试样1至5的抗拉强度度均≥23MPa,在0.05MPa的过滤压差下纯水的过滤通量均≥1t/m2·h,在5wt%的盐酸溶液中室温浸泡48天后的失重率均在1.5%以下(而TiAl金属间化合物多孔材料则高达2.8%左右)。其中,试样1的抗拉强度为25MPa,接近下限值23MPa;而从试样2开始,材料的抗拉强度显著增大,试样2至5中除试样3外,其余试样的抗拉强度均≥30MPa,并以试样4的抗拉强度最高。试样1至5中除试样1、3外,其余试样的过滤通量均>2t/m2·h。试样6至10在5wt%的盐酸溶液中室温浸泡48天后的失重率同样均在1.5%以下,但是,试样6至10中均无能同时达到抗拉强度度≥23MPa、且在0.05MPa的过滤压差下纯水的过滤通量≥1t/m2·h者。
2)关于材料的抗拉强度。结合表3来看,试样1至5中,随着TiC相的生成,材料的抗拉强度产生一定程度的下降(试样3)。试样6相比于试样2,Ti和C的含量更高,而Si的含量相对较少,故生成较多的TiC相,故对试样6的抗拉强度产生了明显的不利的影响。试样10的烧结过程无反应相变,导致材料的抗拉强度也不高。试样9和试样10均使用NH4HCO3作造孔剂故得到较高的孔隙率,加之生成较多的TiC相,因此材料的抗拉强度同样未能达到23MPa。
3)关于材料的渗透性。从试样1至10的过滤通量来看,可认为:由于原料中的C与Ti反应而改善了孔结构,使得三维贯通孔的曲折因子变小,降低了过滤介质的通过阻力,可获得更理想的过滤通量。尽管实验例9和实验例10均使用了造孔剂使得试样9和试样10的孔隙率达到甚至超过了试样2至5的孔隙率,在平均孔径基本相同的情况下试样9和试样10的过滤通量依然达到甚至低于试样2至5的过滤通量,进一步佐证了C与Ti反应造孔对改善三维贯通孔曲折因子的作用。
Claims (6)
1.烧结多孔材料,其特征在于:
a)它主要由Ti、Si、C三种元素组成,这三种元素的重量之和占该烧结多孔材料重量的90%以上,其中,Ti为Ti、Si、C总重量的60~75%,Si为Ti、Si、C总重量的10~20%;
b)该烧结多孔材料中的C主要是以Ti3SiC2三元MAX相化合物的形式存在,且在该多孔材料中大致上均匀分布,烧结时所述C先与Ti反应造孔生成TiC,TiC再与Ti、Si反应生成Ti3SiC2三元MAX相化合物;
c)它的孔隙率为30~60%,平均孔径为0.5~50μm,抗拉强度≥23MPa,厚度≤5mm的烧结多孔材料在0.05MPa的过滤压差下测得纯水的过滤通量≥1t/m2·h,且在5wt%的盐酸溶液中室温浸泡48天后的失重率在1.5%以下。
2.如权利要求1所述的烧结多孔材料,其特征在于:所述烧结多孔材料中Ti、Si、C三种元素的重量之和占该烧结多孔材料重量的95%以上。
3.如权利要求2所述的烧结多孔材料,其特征在于:所述烧结多孔材料由Ti、Si、C三种元素组成;其结晶相由Ti3SiC2三元MAX相化合物组成。
4.如权利要求1所述的烧结多孔材料,其特征在于:所述烧结多孔材料的平均孔径为1~20μm。
5.如权利要求1所述的烧结多孔材料,其特征在于:所述烧结多孔材料中还含有Cr、Mo、V、Nb、Al、W元素中的至少一种。
6.一种过滤元件,其特征在于:该过滤元件含有权利要求1至5中任意一项权利要求所述的烧结多孔材料。
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