CN115231901A - 一种均匀稳定的陶瓷前驱体溶胶制备方法 - Google Patents
一种均匀稳定的陶瓷前驱体溶胶制备方法 Download PDFInfo
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
本发明涉及一种均匀稳定的陶瓷前驱体溶胶制备方法,包括将可电离金属盐和金属醇盐加入到去离子水中,在超声和分层搅拌的协同作用下进行水解和缩聚反应,获得半透明溶胶;加热搅拌回流,使得进一步进行水解和缩聚反应,获得均相透明溶胶;加入水溶性聚合物粉末,加热搅拌,使其中水溶性聚合物完全溶解,获得稳定的透明前驱体溶胶;减压蒸馏,提高其粘度,然后进行真空脱泡处理,获得均一、稳定的可纺性前驱体溶胶。与现有技术相比,本发明制备的可纺性前驱体溶胶储存时间长、可规模化生产,可用于规模化的干法纺丝。
Description
技术领域
本发明涉及连续陶瓷长丝制备领域,尤其是涉及一种均匀稳定的陶瓷前驱体溶胶制备方法。
背景技术
陶瓷纤维具有高熔点、耐高温、高强度和高模量等特点,使陶瓷纤维在耐高温材料领域具有重要的地位。传统制备陶瓷长丝的方法是将硬质粘土、矿石等原料加热到其熔点以上,通过控制原料的组成和加热温度对可纺性熔体进行喷吹或甩丝成纤。对于熔点较高的原料,如氧化铝矿石,则难以采用熔融法制备长丝。
溶胶凝胶法在液相下将高化学活性的化合物均匀混合,通过水解、缩聚等化学反应,在溶液中形成透明溶胶体系,溶胶经过老化,在胶粒之间缓慢聚合,形成三维网络结构的凝胶。利用该方法制备的陶瓷纤维均匀度高,纤维的各组分之间均匀程度达到分子或原子水平;反应温度低,节约能源;烧结温度比传统制备方法低400~500℃。通过溶胶凝胶法制备的可纺性溶胶通过干法纺丝可获得连续陶瓷长丝,以连续陶瓷长丝为增强材料制备的聚合物基、金属基、陶瓷基复合材料可广泛应用于航空航天、军工国防、环境化工及耐高温绝热材料等领域。
目前,基于溶胶凝胶法制备连续陶瓷长丝存在以下技术难题:一是溶胶凝胶反应过程中存在许多的变量如原料的种类及配比、反应温度、搅拌速度、体系中的pH值等都会影响其物理化学特性,进而影响陶瓷长丝的成型;二是体系中含有大量的金属离子,破坏溶胶粒子的均一性和稳定性;三是凝胶长丝通常含有较多的水分,水分的挥发使凝胶长丝产生较大的收缩进而导致长丝开裂。为了克服这些问题,研究者相继做出大量的实验探索。
CN102465358A公开了一种多晶莫来石纤维的制备方法,将铝粉溶解于甲酸和乙酸的混合物中,加热回流,制得甲酸铝和乙酸铝混合溶胶,然后加入脱钠的酸性硅溶胶;混合均匀后加入助纺剂,在混合液中加入表面活性剂;在纺丝原液中加入酒石酸、柠檬酸或乳酸中的一种或几种,上述混合液在喷吹或甩丝条件下成纤,然后经热处理获得多晶莫来石纤维。纤维柔度高、韧性好和脆性指数低;但该制备方法中反应过程较为复杂,且制备得到的是短纤维,无法进行纺纱和编织等需求。
CN101381225A公开了一种连续氧化铝基陶瓷纤维的制备方法,用金属铝和铝盐制备氧化铝溶胶,利用有机硅酸酯碱性水解获得氧化硅溶胶,将氧化硅溶胶pH值调为酸性,然后将氧化硅溶胶和氧化铝溶胶混合获得双相溶胶,加入纺丝助剂后进行浓缩获得纺丝液,经过脱泡处理进行成纤、干燥、烧结,得到连续氧化铝基陶瓷长丝。但该制备过程较为复杂,制备的双相溶胶稳定性差,储存时间短。亟需开发出一种制备工艺简单、溶胶稳定和纺丝性优异的前驱体陶瓷溶胶的制备方法。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种均匀稳定的陶瓷前驱体溶胶制备方法,以本方法制备的可纺性前驱体溶胶储存时间长、可规模化生产,可用于规模化的干法纺丝。
本发明的目的可以通过以下技术方案来实现:
本发明的目的是保护一种均匀稳定的陶瓷前驱体溶胶制备方法,包括以下步骤:
S1:将可电离金属盐和金属醇盐加入到去离子水中,在超声和分层搅拌的协同作用下进行水解和缩聚反应,获得半透明溶胶;
S2:将S1中得到的半透明溶胶进行加热搅拌回流,使得进一步进行水解和缩聚反应,获得均相透明溶胶;
S3:将水溶性聚合物粉末加入到S2中得到的均相透明溶胶中,加热搅拌,使其中水溶性聚合物完全溶解,获得稳定的透明前驱体溶胶;
S4:将S3中得到的透明前驱体溶胶进行减压蒸馏,提高其粘度,然后进行真空脱泡处理,获得均一、稳定的可纺性前驱体溶胶。
进一步地,S1中,所述可电离金属盐质量占半透明溶胶质量的1~10%,所述金属醇盐质量占半透明溶胶质量的10~50%。
进一步地,S1中,所述可电离金属盐和金属醇盐的摩尔比为1:(1~5)。
进一步地,S1中,所述可电离金属盐选自硝酸铝、硝酸镧、硝酸铈、硝酸钇、氯化铝或氯化钇中的一种或多种组合;
S1中,所述金属醇盐选自正硅酸四乙酯、乙酸三甲基硅酯、四正丁氧基硅烷、异丙醇铝、正丁醇铝、仲丁醇铝、叔丁醇铝、正丙醇锆、异丙醇锆、正丁醇锆、异丁醇锆、异丙醇钛、正丁醇钛、四乙醇钛或叔丁醇钛中的一种或几种。
进一步地,S1中,所述水解和缩聚反应在恒温条件下进行,恒温条件为20~50℃,反应时间是2~12h;
S2中,加热搅拌回流在恒定温度和恒定搅拌条件下进行,温度条件为60~120℃,加热搅拌回流时间为3~10h;
S3中,加热搅拌温度条件为20~90℃,加热搅拌时间为1~4h。
进一步地,S1中,超声频率为20~100kHz;
S1中,所述分层搅拌为在反应釜中安装两个搅拌杆,两个搅拌杆旋转方向相反;
其中,以顺时针方向为正向搅拌杆,正向搅拌杆速度为100~1000rad/min,以逆时针方向为正向搅拌杆,逆向搅拌杆速度100~1000rad/min。
进一步地,S3中,所述水溶性聚合物选自聚乙烯醇、聚乙烯吡咯烷酮、聚氧化乙烯、聚乙二醇、羟甲基长丝素中的一种或几种;
S3中,所述水溶性聚合物加入量占陶瓷长丝质量的8~30%。
进一步地,S4中,减压蒸馏的条件为:在恒温搅拌和恒定真空度条件下进行,恒温条件为30~80℃。
进一步地,S4中,减压蒸馏过程中,两个搅拌杆速度差小于100rad/min,真空度条件为-1~-0.01MPa;
S4中,通过减压蒸馏使得透明前驱体溶胶粘度为30~100Pa·s。
进一步地,S4中,真空脱泡的条件为:在恒定温度和恒定真空度条件下进行,恒温条件为10~40℃,真空度条件为-1~-0.01MPa,脱泡时间为1~5h。
本发明的机理如下:
利用溶胶凝胶法合成材料是一个需要精确控制的湿化学过程,在制备过程中,体系中原料种类及配比、反应温度、搅拌速度、pH值等因素的调控,直接决定了胶体结构和性能的变化,从而对长丝的性能有非常重要的影响。
在形成溶胶过程中,水-金属盐体系发生溶剂化反应,金属盐电离出的金属离子会吸收水分子形成溶剂单元M(H2O)n x+(M为金属元素,x为M离子的电价数),为维持配位数有释放出H+的趋势。
如下所示,在水溶液中,金属离子通常会产生三种配体,分别是水(H2O)、羟基(OH)和氧基(=O)。
水-金属醇盐体系发生水解反应,金属醇盐不能电离,可以通过亲核取代反应,生成活性羟基,是发生缩聚反应的前提条件。如下所示,一般来说,金属原子的电负性越小,离子半径越大,配位数就越大,配位不饱和度也就越大,则金属醇盐水解的活性越强。
缩聚反应可以分为三种缩聚方式,分别是烷氧基化作用、氧桥合作用和羟桥合作用。如下所示。
烷氧基化作用
氧桥合作用
羟桥合作用
在本发明中,通过调控可电离金属盐和水的含量控制体系中pH值,精确控制金属醇盐、反应温度和搅拌速度进而控制体系中水解和缩聚反应速率,形成能够相互稳定存在的胶粒,获得均相透明的溶胶。基于上述参数的控制,本发明采用超声和分层搅拌混合溶液:一是使原料颗粒物加速溶解;二是提高原料之间的混合均匀性,有利于水解和缩聚反应的进行。
与现有技术相比,本发明具有以下技术优势:
(1)本发明中的前驱体透明溶胶制备工艺简单,原料来源广泛,反应条件温和,且能够大规模制备,透明前驱体溶胶可稳定储存2个月以上。
(2)本发明中的透明前驱体溶胶进行减压蒸馏和真空脱泡处理后,溶胶具有良好的纺丝性能,可利用干法纺丝制备连续陶瓷长丝。
附图说明
图1为采用实施例1中莫来石溶胶的粒径分布图;
图2为采用实施例3中铝锆溶胶的粒径分布图。
具体实施方式
本发明提供一种均匀、稳定的陶瓷前驱体溶胶制备方法,具体包括以下步骤:
第一步:将可电离金属盐和金属醇盐加入到去离子水中,在超声和分层搅拌的协同作用下进行水解和缩聚反应,获得半透明溶胶;其中,可电离金属盐质量占半透明溶胶质量的1~10%,金属醇盐质量占半透明溶胶质量的10~50%。
第二步:将上述半透明溶胶进行加热搅拌回流,原料之间进一步的进行水解和缩聚反应,获得均相透明溶胶;
第三步:将水溶性聚合物粉末加入到上述均相透明溶胶中,加热搅拌使其水溶性聚合物完全溶解,获得稳定的透明前驱体溶胶;
第四步:将透明前驱体溶胶进行减压蒸馏,提高其粘度;然后进行真空脱泡处理,获得均一、稳定的可纺性前驱体溶胶。
在本发明的一个实施方式中,第一步中,所述可电离金属盐选择硝酸铝、硝酸镧、硝酸铈、硝酸钇、氯化铝或氯化钇中的一种或多种组合。所述金属醇盐选择正硅酸四乙酯、乙酸三甲基硅酯、四正丁氧基硅烷、异丙醇铝、正丁醇铝、仲丁醇铝、叔丁醇铝、正丙醇锆、异丙醇锆、正丁醇锆、异丁醇锆、异丙醇钛、正丁醇钛、四乙醇钛或叔丁醇钛一种或几种。控制可电离金属盐和金属醇盐的摩尔比为1:(1~5)。
在本发明的一个实施方式中,第一步中,所述超声是指在溶液体系中放置一个超声波探头;其中,超声频率为20~100kHz。所述分层搅拌是指在反应釜中安装两个搅拌杆,两个搅拌杆旋转方向相反,其中,以顺时针方向为正向搅拌杆;所述正向搅拌杆速度为100~1000rad/min,逆向搅拌杆速度为100~1000rad/min。
在本发明的一个实施方式中,第一步中,水解和缩聚反应是在恒温条件下进行的,所述恒温条件是20~50℃,反应时间是2~12h。
在本发明的一个实施方式中,第二步中,所述加热搅拌回流是在恒定温度和恒定搅拌条件下进行的,所述温度条件为60~120℃,搅拌速度与第一步中一致,反应时间为3~10h。
在本发明的一个实施方式中,第三步中,所述加热搅拌是在恒定温度和恒定搅拌条件下进行的,所述温度条件为20~90℃,搅拌速度与第一步中一致,反应时间为1~4h。
在本发明的一个实施方式中,第三步中,所述水溶性聚合物选择聚乙烯醇、聚乙烯吡咯烷酮、聚氧化乙烯、聚乙二醇、羟甲基长丝素中的一种或几种。
在本发明的一个实施方式中,第三步中,所述水溶性聚合物加入量占陶瓷长丝质量的5~30%。
在本发明的一个实施方式中,第三步中,所述的透明前驱体溶胶稳定,在温度范围20~35℃条件下可存放2个月以上;当进行干法纺丝时,只需要在反应釜中对前驱体透明溶胶进行减压蒸馏和真空脱泡处理后即可纺丝。
在本发明的一个实施方式中,第四步中进行减压蒸馏的条件为:在恒温搅拌和恒定真空度条件下进行,所述恒温条件为30~80℃,两个搅拌杆速度差小于100rad/min,真空度条件为-1~-0.01MPa;所述溶胶粘度为1~150Pa·s,优选为30~100Pa·s。本发明中所称的粘度测定方法为标准“GB/T 10247-2008粘度测试方法”中的“4旋转法”。
在本发明的一个实施方式中,第四步中进行真空脱泡的条件为:在恒定温度和恒定真空度条件下进行,所述恒温条件为10~40℃,真空度条件为-1~-0.01MPa,脱泡时间为1~5h。
下面结合附图和具体实施例对本发明进行详细说明。本技术方案中如未明确说明的制备手段、材料、结构或组成配比等特征,均视为现有技术中公开的常见技术特征。
实施例1
本实施例中一种均匀、稳定的陶瓷前驱体溶胶制备方法,具体步骤如下:
第一步:将硝酸铝、仲丁醇铝和四正丁氧基硅烷依次加入到去离子水中,在30℃下,利用超声和分层搅拌的协同作用下进行反应3h,获得半透明溶胶;其中,超声频率选择为80kHz,正向搅拌速度为600rad/min,逆向搅拌速度为500rad/min,可电离金属盐质量占半透明溶胶质量的6%,金属醇盐质量占半透明溶胶质量的31%。
第二步:将上述半透明溶胶进行加热搅拌回流,获得均相透明溶胶;其中,加热时间为5h,加热温度为80℃,搅拌速度与上述第一步中一致;
第三步:将聚乙烯吡咯烷酮粉末加入到上述均相透明溶胶中,在60℃下以600rad/min转速进行搅拌2h,获得稳定的透明前驱体溶胶,可稳定存放时间为2个月以上。其中,聚乙烯吡咯烷酮的质量占陶瓷长丝质量的10%。
第四步:将透明前驱体溶胶在60℃下进行减压蒸馏,当溶胶粘度达到50Pa·s时停止减压蒸馏,然后进行真空脱泡4h后,获得均一、稳定的可纺性前驱体溶胶,直接用于干法纺丝。
本发明采用的透明前驱体溶胶制备工艺简单,原料来源广泛,反应条件温和,且能够大规模制备,可稳定储存2个月以上,同时粒径分布集中,粒径小(13nm),参见图1。
实施例2
本实施例中一种均匀、稳定的陶瓷前驱体溶胶制备方法,具体步骤如下:
第一步:将氯化铝、异丙醇铝和正硅酸四乙酯依次加入到去离子水中,在40℃下,利用超声和分层搅拌的协同作用下进行反应4h,获得半透明溶胶;其中,超声频率选择为60kHz,正向搅拌速度为550rad/min,逆向搅拌速度为450rad/min,可电离金属盐质量占半透明溶胶质量的4%,金属醇盐质量占半透明溶胶质量的35%。
第二步:将上述半透明溶胶进行加热搅拌回流,获得均相透明溶胶;其中,加热时间为6h,加热温度为85℃,搅拌速度与上述第一步中一致;
第三步:将聚氧化乙烯粉末加入到上述均相透明溶胶中,在80℃下以600rad/min转速进行搅拌2h,获得稳定的透明前驱体溶胶,可稳定存放时间为2个月以上。其中,聚氧化乙烯的质量占陶瓷长丝质量的8%。
第四步:将透明前驱体溶胶在50℃下进行减压蒸馏,当溶胶粘度达到35Pa·s时停止减压蒸馏,然后进行真空脱泡处理,获得均一、稳定的可纺性前驱体溶胶,直接用于干法纺丝。
本发明采用的透明前驱体溶胶制备工艺简单,原料来源广泛,反应条件温和,且能够大规模制备,可稳定储存2个月以上,同时粒径分布集中,粒径小(10nm)。
实施例3
本实施例中一种均匀、稳定的陶瓷前驱体溶胶制备方法,具体步骤如下:
第一步:将硝酸铝、正丙醇锆依次加入到去离子水中,在25℃下,利用超声和分层搅拌的协同作用下进行反应7h,获得半透明溶胶;其中,超声频率选择为100kHz,正向搅拌速度为500rad/min,逆向搅拌速度为400rad/min,可电离金属盐质量占半透明溶胶质量的4%,金属醇盐质量占半透明溶胶质量的38%。
第二步:将上述半透明溶胶进行加热搅拌回流,获得均相透明溶胶;其中,加热时间为9h,加热温度为70℃,搅拌速度与上述第一步中一致;
第三步:将聚乙烯醇粉末加入到上述均相透明溶胶中,在50℃下以500rad/min转速进行搅拌4h,获得稳定的透明前驱体溶胶,可稳定存放时间为2个月以上。其中,聚乙烯醇的质量占陶瓷长丝质量的15%。
第四步:将前驱体透明溶胶在40℃下进行减压蒸馏,当溶胶粘度达到50Pa·s时停止减压蒸馏,然后进行真空脱泡5h后,获得均一、稳定的可纺性前驱体溶胶,直接用于干法纺丝。
本发明采用的透明前驱体溶胶制备工艺简单,原料来源广泛,反应条件温和,且能够大规模制备,可稳定储存2个月以上,同时粒径分布集中,粒径小(11nm),参见图2。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (10)
1.一种均匀稳定的陶瓷前驱体溶胶制备方法,其特征在于,包括以下步骤:
S1:将可电离金属盐和金属醇盐加入到去离子水中,在超声和分层搅拌的协同作用下进行水解和缩聚反应,获得半透明溶胶;
S2:将S1中得到的半透明溶胶进行加热搅拌回流,使得进一步进行水解和缩聚反应,获得均相透明溶胶;
S3:将水溶性聚合物粉末加入到S2中得到的均相透明溶胶中,加热搅拌,使其中水溶性聚合物完全溶解,获得稳定的透明前驱体溶胶;
S4:将S3中得到的透明前驱体溶胶进行减压蒸馏,提高其粘度,然后进行真空脱泡处理,获得均一、稳定的可纺性前驱体溶胶。
2.根据权利要求1所述的一种均匀稳定的陶瓷前驱体溶胶制备方法,其特征在于,S1中,所述可电离金属盐质量占半透明溶胶质量的1~10%,所述金属醇盐质量占半透明溶胶质量的10~50%。
3.根据权利要求1所述的一种均匀稳定的陶瓷前驱体溶胶制备方法,其特征在于,S1中,所述可电离金属盐和金属醇盐的摩尔比为1:(1~5)。
4.根据权利要求1所述的一种均匀稳定的陶瓷前驱体溶胶制备方法,其特征在于,S1中,所述可电离金属盐选自硝酸铝、硝酸镧、硝酸铈、硝酸钇、氯化铝或氯化钇中的一种或多种组合;
S1中,所述金属醇盐选自正硅酸四乙酯、乙酸三甲基硅酯、四正丁氧基硅烷、异丙醇铝、正丁醇铝、仲丁醇铝、叔丁醇铝、正丙醇锆、异丙醇锆、正丁醇锆、异丁醇锆、异丙醇钛、正丁醇钛、四乙醇钛或叔丁醇钛中的一种或几种。
5.根据权利要求1所述的一种均匀稳定的陶瓷前驱体溶胶制备方法,其特征在于,S1中,所述水解和缩聚反应在恒温条件下进行,恒温条件为20~50℃,反应时间是2~12h;
S2中,加热搅拌回流在恒定温度和恒定搅拌条件下进行,温度条件为60~120℃,加热搅拌回流时间为3~10h;
S3中,加热搅拌温度条件为20~90℃,加热搅拌时间为1~4h。
6.根据权利要求1所述的一种均匀稳定的陶瓷前驱体溶胶制备方法,其特征在于,S1中,超声频率为20~100KHz;
S1中,所述分层搅拌为在反应釜中安装两个搅拌杆,两个搅拌杆旋转方向相反;
其中,以顺时针方向为正向搅拌杆,正向搅拌杆速度为100~1000rad/min,以逆时针方向为正向搅拌杆,逆向搅拌杆速度100~1000rad/min。
7.根据权利要求1所述的一种均匀稳定的陶瓷前驱体溶胶制备方法,其特征在于,S3中,所述水溶性聚合物选自聚乙烯醇、聚乙烯吡咯烷酮、聚氧化乙烯、聚乙二醇、羧甲基长丝素中的一种或几种;
S3中,所述水溶性聚合物加入量占陶瓷长丝质量的8~30%。
8.根据权利要求6所述的一种均匀稳定的陶瓷前驱体溶胶制备方法,其特征在于,S4中,减压蒸馏的条件为:在恒温搅拌和恒定真空度条件下进行,恒温条件为30~80℃。
9.根据权利要求6所述的一种均匀稳定的陶瓷前驱体溶胶制备方法,其特征在于,S4中,减压蒸馏过程中,两个搅拌杆速度差小于100rad/min,真空度条件为-1~-0.01MPa;
S4中,通过减压蒸馏使得透明前驱体溶胶粘度为30~100Pa·s。
10.根据权利要求1所述的一种均匀稳定的陶瓷前驱体溶胶制备方法,其特征在于,S4中,真空脱泡的条件为:在恒定温度和恒定真空度条件下进行,恒温条件为10~40℃,真空度条件为-1~-0.01MPa,脱泡时间为1~5h。
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