CN111995422B - 一种蜂窝状陶瓷材料的制备方法 - Google Patents
一种蜂窝状陶瓷材料的制备方法 Download PDFInfo
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Abstract
本发明提供了一种蜂窝状陶瓷材料的制备方法,包括以下步骤:A)将粘结剂、陶瓷前驱体和水混合,得到分散液;B)将所述分散液进行取向冷冻;C)将步骤B)得到的块材与交联剂、不良溶剂进行溶剂置换、原位交联,得到的块材烘干后高温烧结,得到蜂窝状陶瓷材料。本发明提供了一种工艺简单、成本低廉的常压干燥制备蜂窝状陶瓷材料的方法,利用该方法同样可以得到性能优异、具有微纳米级孔道的蜂窝状陶瓷材料,且蜂窝状陶瓷的结构、密度和力学强度均可调控。
Description
技术领域
本发明涉及化学建材技术领域,尤其涉及一种蜂窝状陶瓷材料的制备方法。
背景技术
蜂窝材料是一类各向异性的多孔复合材料,其内部往往具有形状相似的孔道结构,天然的木头因为具有取向孔道也可理想化成为蜂窝材料。这类材料在工程上有着广泛的应用领域和巨大的应用前景,渗透到国防军工、航空航天、交通运输、生物医学、建筑工程等各个领域。蜂窝陶瓷在轻质高强材料、催化剂载体以及热交换器方面发挥着极其重要的作用。目前工业上蜂窝陶瓷块材的孔径基本都在毫米级别,这对进一步拓展材料的使用范围、提高材料的性能,都是极大的限制。例如,孔径的减小有利于提高蜂窝陶瓷的抗热冲击性能,也有利于负载更多的催化剂。因此,如何突破传统工业技术的限制,利用纳米技术制造出微米甚至纳米尺度的蜂窝陶瓷块材,已经成为人们亟待解决的问题。
取向冷冻技术作为一种制备微纳米尺度蜂窝状材料的简便技术手段,广泛应用于生物医学、仿生学和材料科学上。例如美国《美国陶瓷会志》(Journal of the AmericanCeramic Society,2001年84期230页)首次报道了一种利用取向冷冻技术,将氧化铝粉末和分散剂混合浆料取向冻干,高温1550℃烧结,制备了~20μm蜂窝孔道、孔隙率36%的氧化铝陶瓷材料。最近,美国《科学进展》(Science Advances,2018年4期eaat7233页)报道了一种利用取向冷冻,将海藻酸钠和陶瓷混合溶液取向冷冻,经过冷冻干燥、热固化,制备轻而强蜂窝状陶瓷材料的方法。
上述冷冻干燥又称升华干燥,是将含水物料冷冻到冰点以下,使水转变为冰,然后在较高真空下将冰转变为蒸气而除去的干燥方法。该方法干燥所得材料虽然几乎不变形,但是成本太高,最主要的成本来源于冷冻干燥,不仅需要专业昂贵的机器、耗时耗能的冻干过程,而且样品的尺寸受机器大小的影响,需要密闭的生产环境,难以实现连续、低成本、规模化生产,只能生产应用于高附加值的行业(如食品、制药业)。因此,这种取向冷冻铸造蜂窝状孔道的方法虽然简单,但是后续的冷冻干燥过程耗时耗能,同时由于处于密封环境,难以实现工业上的连续化生产,对后续拓展产品类型、提高产能,都是极大的限制。取向冷冻制备陶瓷材料已经发展了数十年,但是还未见有通用的常压干燥技术的报道。
发明内容
本发明解决的技术问题在于提供一种蜂窝状陶瓷材料的制备方法,本申请提供的蜂窝状陶瓷材料的制备方法条件温和、方法简单,可处于敞开系统中连续生产,且可得到性能优异、具有微纳米级孔道的蜂窝状陶瓷材料。
有鉴于此,本申请提供了一种蜂窝状陶瓷材料的制备方法,包括以下步骤:
A)将粘结剂、陶瓷前驱体和水混合,得到分散液;
B)将所述分散液进行取向冷冻;
C)将步骤B)得到的块材与交联剂、不良溶剂进行溶剂置换、原位交联,得到的块材烘干后高温烧结,得到蜂窝状陶瓷材料。
优选的,所述粘结剂、陶瓷前驱体和水的质量比为(0.5~4):(1~50):(50~100)。
优选的,所述粘结剂选自海藻酸钠、羟甲基纤维素钠、聚乙烯吡咯烷酮和聚乙烯醇中的一种或多种,所述陶瓷前驱体选自氧化铝、氧化锆、高岭土、羟基磷灰石、氧化硅和偏硅酸钠中的一种或多种。
优选的,步骤B)中,所述取向冷冻的温度为-10~-50℃。
优选的,步骤C)中,所述交联剂选自氯化钙、硝酸钙、氯化铜、氯化铁、氯化锌、氯化钴和氯化镉中的一种或多种,所述不良溶剂为乙醇或丙酮。
优选的,所述交联剂在所述不良溶剂中的浓度为0.01~1.0mol/L。
优选的,所述溶剂置换的温度为-5~-20℃,所述溶剂置换、原位交联的总时间为12~72h。
优选的,步骤C)中,所述烘干的温度为40~80℃,时间为0.1~4h。
优选的,所述高温烧结的温度为600~1600℃,时间为1~4h。
本申请提供了一种蜂窝状陶瓷材料的制备方法,其首先将粘结剂、陶瓷前驱体和水混合,得到分散液,将分散液取向冷冻后与交联剂、不良溶剂进行溶剂置换、原位交联,最后得到的块材烘干后高温烧结,即得到蜂窝状陶瓷材料;在上述制备过程中,本申请首先将含有粘结剂、陶瓷前驱体和水的分散液取向冷冻,以得到含有冰晶和粘结剂的冷冻块材,再将该冷冻块材与交联剂、不良溶剂混合,不良溶剂溶解冰晶,同时交联剂中的金属离子渗透进粘结剂,形成离子交联网络,最后高温烧结,即得到蜂窝状陶瓷材料。上述制备蜂窝状陶瓷材料的过程中采用常压干燥即可制备微纳米蜂窝状陶瓷材料,无需采用冷冻干燥机和冻干机,而使得方法简单、条件温和,且整个过程处于敞开系统,而无需密闭独立系统中进行,提高了本申请蜂窝状陶瓷材料的适应性。进一步的,本申请可以通过调控取向冷冻过程中的参数和高温烧结的温度,来调控材料的结构、密度和力学强度等性能。
附图说明
图1为本发明实施例1制备不同海藻酸钠浓度的收缩情况实物照片;
图2为本发明实施例1制备蜂窝状海藻酸钠横截面的扫描电镜图片;
图3为本发明实施例1制备蜂窝状海藻酸钠纵截面的扫描电镜图片;
图4为本发明实施例2制备不同金属离子交联的海藻酸钠的实物照片;
图5为本发明实施例2制备不同金属离子交联的抑制收缩图;
图6为本发明实施例3制备蜂窝状氧化铝的实物照片;
图7为本发明实施例3制备蜂窝状氧化铝横截面的扫描电镜图片;
图8为本发明实施例3制备蜂窝状氧化铝纵截面的扫描电镜图片;
图9为本发明实施例3制备蜂窝状氧化铝垂直孔道方向的弯曲测试应力应变曲线;
图10为本发明实施例4制备蜂窝状氧化锆的实物照片;
图11为本发明实施例4制备蜂窝状氧化锆横截面的扫描电镜图片;
图12为本发明对比例1制备的陶瓷颗粒静置前后分散性对比照片。
具体实施方式
为了进一步理解本发明,下面结合实施例对本发明优选实施方案进行描述,但是应当理解,这些描述只是为进一步说明本发明的特征和优点,而不是对本发明权利要求的限制。
针对蜂窝陶瓷材料中,取向冷冻需要在专用冷冻机、冻干机、密闭环境进行的问题,本申请提供了一种蜂窝状陶瓷材料的制备方法,该方法首次实现常压干燥制备蜂窝状陶瓷材料,且方法简单、环境友好、条件温和、节约能耗。具体的,本发明实施例公开了一种蜂窝状陶瓷材料的制备方法,包括以下步骤:
A)将粘结剂、陶瓷前驱体和水混合,得到分散液;
B)将所述分散液进行取向冷冻;
C)将步骤B)得到的块材与交联剂、不良溶剂进行溶剂置换、原位交联,得到的块材烘干后高温烧结,得到蜂窝状陶瓷材料。
按照本发明,首先将粘结剂、陶瓷前驱体和水混合,即得到分散液;在此过程中,仅仅是粘结剂、陶瓷前驱体和水混合的过程,以获得均匀的分散液。所述粘结剂用于辅助陶瓷粉体成型,其具体可选自海藻酸钠、羟甲基纤维素钠、聚乙烯吡咯烷酮和聚乙烯醇中的一种或多种,在具体实施例中,所述粘结剂选自海藻酸钠;所述陶瓷前驱体选自氧化铝、氧化锆、高岭土、羟基磷灰石、氧化硅和偏硅酸钠中的一种或多种。在本申请中,如果没有粘结剂或者粘结剂较少,在浸泡不良溶剂的时候,冷冻后的块材会坍塌,无法保持形状;如果粘结剂过多,会导致整个体系粘度太大,不方便实际操作,同时也会影响陶瓷的烧结,所以粘结剂的浓度是在一个范围内的;陶瓷前驱体影响的烧结后样品的物理性能(如密度、强度、孔隙率等);这三者的比例需要整体考虑,是一个完整的体系;因此,所述粘结剂、所述陶瓷前驱体和水的质量比为(0.5~4):(1~50):(50~100),更具体地,所述粘结剂、所述陶瓷前驱体和所述水的质量比为(1~3):(10~40):(80~100)。
本申请然后将分散液进行取向冷冻,以得到块材。所述取向冷冻为本领域技术人员熟知的技术手段,具体是将金属平台底面浸入液氮槽中,金属平台表面粘结热电偶,通过改变液氮加入量来控制金属平台表面温度;该方法可以将金属平台表面温度的误差控制在3℃以内。本发明中,制备的材料大小、形状由大小不同、形状不同的模具控制,所述模具的材料优选为硅橡胶、聚二甲基硅氧烷、聚四氟乙烯,更优选为硅橡胶、聚二甲基硅氧烷。取向冷冻过程时,将金属平台温度控制在所需冷冻温度,放上模具,灌入本发明所述分散液。所述取向冷冻的温度为-10~-50℃,更具体地,所述取向冷冻的温度为-20~-40℃。
在取向冷冻之后,则将得到的块材与交联剂、不良溶剂进行溶剂置换、原位交联;在此过程中,上述取向冷冻得到的含有冰晶和粘结剂的冷冻块材在低温不良溶剂和交联剂的作用下,不良溶剂溶解冰晶,且交联剂中的金属离子渗透进粘结剂,形成离子交联网络;上述过程在低温下持续进行,直至冰冻块材中的冰晶完全融化,实现溶剂置换(具体如图12所示)。本申请中,所述交联剂选自氯化钙、硝酸钙、氯化铜、氯化锌、氯化钴和氯化镉中的一种或多种,所述不良溶剂为乙醇或丙酮。所述交联剂在所述不良溶剂中的浓度为0.01~1.0mol/L,更具体地,所述交联剂在所述不良溶剂中的浓度为0.1~0.8mol/L;所述交联剂在不良溶剂的浓度太低则无法充分交联、粘结剂形成的骨架不够强,导致样品在后续的烘干阶段会收缩;同时,过高或过低的浓度会降低渗透速率,使得置换过程延长。所述溶剂置换的温度为溶剂置换的温度为-5~-20℃,所述溶剂置换、原位交联的时间为12~72h;更具体地,所述溶剂置换的温度为-10~-15℃,所述溶剂置换、原位交联的时间为24~36h。在上述溶剂置换的过程中置换的温度要低于溶液(即粘结剂水溶液)的凝固点,否则来不及置换冷冻的块材内部就会融化,而过低的温度,会延长置换时间、增加能耗;置换时间根据样品大小和不同的体系而定,如果时间太短,块材中央渗透不进去,烘干过程内部就会融化,从而失去蜂窝状结构。
本申请然后将上述得到的块材烘干后高温烧结,即得到蜂窝状陶瓷材料;所述烘干为本领域技术人员熟知的烘干手段,可在烘箱中进行,所述烘干的温度为40~80℃,时间为0.1~4h,更具体地,所述烘干的温度为50~70℃,时间为1~3h。所述高温烧结以利于上述得到的离子交联网络结构去除其中的溶剂、粘结剂,最终得到蜂窝状陶瓷材料;所述高温烧结的温度为600~1600℃,时间为1~4h,更具体地,所述高温烧结的温度为1000~1500℃,时间为2~3h;烧结的温度和时间影响材料的最终性能,如烧结前后样品的收缩率,孔隙率、密度、强度等;过低温度陶瓷粉末无法烧结成一个整体,晶粒无法熔融;过高温度,陶瓷会发生晶型变化,甚至会分解,影响最终性能。
本发明首次实现常压干燥制备微纳米蜂窝状陶瓷材料,方法简单(传统方法需要使用冷冻干燥机),条件温和(传统冻干机需要-50℃甚至更低,本方法仅需-5℃),节约能耗(不需要真空泵,真空泵在传统冻干法中是必须的),处于敞开系统方便连续化生产(传统冻干法属于密闭独立系统);采用的原材料为商业陶瓷和绿色安全的粘结剂,整个生产流程无毒无害,完全无污染:商业陶瓷合成技术成熟,简单易得,工业化程度高;粘结剂如海藻酸钠作为重要的生物产品,来源广泛,绿色环保;两者均价格低廉,可以有效降低生产成本,非常适合商业化生产。本发明采用取向冷冻法制备材料,工艺简单,技术成熟,可以规模化生产;同时,可以通过调控取向冷冻过程参数和固化温度,来调控材料结构、密度、力学强度等。调控过程简单可行,可以满足不同密度与强度需求。
为了进一步理解本发明,下面结合实施例对本发明提供的蜂窝状陶瓷材料的制备方法进行详细说明,本发明的保护范围不受以下实施例的限制。
本发明实施例中采用的化学试剂和设备均从市场上购得。
实施例1
依次将1、2、3、4g海藻酸钠(上海国药集团)分散在100ml去离子水中,搅拌过夜,获得无色透明海藻酸钠溶液,待用;
将连接热电偶的金属平台放置在塑料泡沫容器中,将液氮倒入塑料泡沫容器,控制液氮倒入量使金属平台温度稳定在-20℃;将含有长宽高1.5cm*1.5cm*1.5cm的贯通孔道的模具,平整放置在低温金属平台表面;将所述的不同浓度的溶液倒入不同模具中,通过加入液氮的量控制金属平台温度稳定在-20℃左右,约20分钟后,样块全部冷冻完毕;将样块从模具中取出,依次放入-10℃下1.0mol/mL的氯化钙无水乙醇中,置换一天后取出,放置于60℃烘箱中1h,得到蜂窝状海藻酸钠。实物照片如图1所示,可以看到随着海藻酸钠浓度增加,收缩情况逐渐好转。4%质量分数的海藻酸钠烘干后样品的横纵截面扫描电镜图分别如图2和图3所示。
实施例2
将4g海藻酸钠(上海国药集团)分散在100ml去离子水中,搅拌过夜,获得无色透明海藻酸钠溶液,待用;
将连接热电偶的金属平台放置在塑料泡沫容器中,将液氮倒入塑料泡沫容器,控制液氮倒入量使金属平台温度稳定在-20℃;将长宽高为1.5cm*1.5cm*1.5cm的贯通的聚四氟小块作为模具,平整放置在低温金属平台表面;将所述的不同浓度的溶液倒入不同模具中,通过加入液氮的量控制金属平台温度稳定在-20℃左右,约20分钟后,样块全部冷冻完毕;将样块从模具中取出,依次放入-10℃下1.0mol/mL的氯化钙、氯化钴、氯化镍、氯化铜、氯化锌、氯化镉的无水乙醇中,置换一天后取出,放置于60℃烘箱中1h。得到不同金属离子交联的蜂窝状海藻酸钠。实物照片如图4所示,自左至右,依次为Ca2+、Co2+、Ni2+、Cu2+、Zn2+、Cd2+交联的蜂窝状海藻酸钠,可以看到不同金属离子都可以交联以实现常压干燥。不同离子抑制收缩情况如图5所示,有些甚至已经优于传统的冷冻干燥法。
实施例3
将1g海藻酸钠(上海国药集团)分散在100ml去离子水中,搅拌过夜,获得无色透明海藻酸钠溶液,待用;
取80g所述海藻酸钠溶液至球磨罐中,加入20g氧化铝陶瓷粉末,球磨12h后,超声除去分散液内的气泡,待用;
利用和实施例1中的相同制备方法,金属平台温度稳定在-20℃;将含有3cm*3cm*0.4cm通孔硅胶模具平整放置在低温金属平台表面;将所述的混合分散液倒入模具中,通过加入液氮的量控制金属平台温度稳定在-20℃左右,约20分钟后,样块全部冷冻完毕;将样块从模具中取出,放入-10℃下的0.1mol/L氯化钙无水乙醇中,置换一天后取出,放置于60℃烘箱中1h;干燥完毕后取出,放置于马弗炉中,在空气氛围下1600℃烧结2h,得到蜂窝状氧化铝。测试得出,样品的密度约为1.3g/cm3,垂直孔道方向的弯曲强度约为60MPa,杨氏模量约4GPa。蜂窝状氧化铝的照片如图6所示,蜂窝状氧化铝的横、纵截面扫描电镜图分别如图7、8所示。蜂窝状氧化铝的垂直孔道方向的弯曲力学测试如图9所示。
实施例4
将0.5g海藻酸钠(上海国药集团)分散在100ml去离子水中,搅拌过夜,获得无色透明海藻酸钠溶液,待用;
取80g所述海藻酸钠溶液至球磨罐中,加入20g氧化锆粉末,球磨12h后,超声除去分散液内的气泡,待用;
利用和实施例3中的相同制备方法,金属平台温度稳定在-20℃;将上述硅胶模具平整放置在低温金属平台表面;将所述的混合溶液倒入模具中,通过加入液氮的量控制金属平台温度稳定在-20℃左右,约20分钟后,样块全部冷冻完毕;将样块从模具中取出,放入-10℃下的0.1mol/L氯化钙无水乙醇中,置换一天后取出,放置于60℃烘箱中1h;干燥完毕后取出,放置于马弗炉中,在空气氛围下1500℃烧结2h,得到蜂窝状氧化锆。蜂窝状氧化锆的照片如图10所示,横截面扫描电镜图如图11所示。
对比例1
将0.25g海藻酸钠(上海国药集团)分散在100ml去离子水中,搅拌过夜,获得无色透明海藻酸钠溶液,待用;取80g所述海藻酸钠溶液至球磨罐中,加入20g氧化铝陶瓷粉末,球磨12h后,超声除去分散液内的气泡,静置12h;静置前后陶瓷颗粒分散性对比照片如图12所示,由图可知,海藻酸钠的含量过低而使得氧化铝陶瓷颗粒分散液制备不成功。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。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,还可以对本发明进行若干改进和修饰,这些改进和修饰也落入本发明权利要求的保护范围内。
对所公开的实施例的上述说明,使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下,在其它实施例中实现。因此,本发明将不会被限制于本文所示的这些实施例,而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
Claims (6)
1.一种蜂窝状陶瓷材料的制备方法,包括以下步骤:
A)将粘结剂、陶瓷前驱体和水混合,得到分散液;
B)将所述分散液进行取向冷冻;
C)将步骤B)得到的块材与交联剂、不良溶剂进行溶剂置换、原位交联,得到的块材烘干后高温烧结,得到蜂窝状陶瓷材料;
所述交联剂选自氯化钙、硝酸钙、氯化铜、氯化铁、氯化锌、氯化钴和氯化镉中的一种或多种;
所述交联剂在所述不良溶剂中的浓度为0.01~1.0mol/L;
所述溶剂置换的温度为-5~-20℃,所述溶剂置换、原位交联的总时间为12~72h;
所述取向冷冻的温度为-10~-50℃。
2.根据权利要求1所述的制备方法,其特征在于,所述粘结剂、陶瓷前驱体和水的质量比为(0.5~4):(1~50):(50~100)。
3.根据权利要求1所述的制备方法,其特征在于,所述粘结剂选自海藻酸钠、羟甲基纤维素钠、聚乙烯吡咯烷酮和聚乙烯醇中的一种或多种,所述陶瓷前驱体选自氧化铝、氧化锆、高岭土、羟基磷灰石、氧化硅和偏硅酸钠中的一种或多种。
4.根据权利要求1所述的制备方法,其特征在于,步骤C)中,所述不良溶剂为乙醇或丙酮。
5.根据权利要求1所述的制备方法,其特征在于,步骤C)中,所述烘干的温度为40~80℃,时间为0.1~4h。
6.根据权利要求1所述的制备方法,其特征在于,所述高温烧结的温度为600~1600℃,时间为1~4h。
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