CN115340365A - 一种杂化凝胶长丝的陶瓷化方法 - Google Patents
一种杂化凝胶长丝的陶瓷化方法 Download PDFInfo
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Abstract
本发明涉及一种杂化凝胶长丝的陶瓷化方法，包括以下步骤：S1：通过牵拉设备将连续杂化凝胶长丝引入热处理炉中，进行热交联处理，以此提升连续杂化凝胶长丝的强度、耐水性；S2：在牵拉设备的张力控制下，将S1中处理的连续杂化凝胶长丝引入多区段煅烧设备中，得到连续陶瓷化长丝，所述多区段煅烧设备中依次包括结合水去除区、有机物去除区、晶型转化区以及阶段降温区。与现有技术相比，本发明能够获得陶瓷化程度高，晶粒尺寸小，长丝直径均一的连续陶瓷长丝。
Description
技术领域
本发明涉及陶瓷长丝制备技术领域，尤其是涉及一种杂化凝胶长丝的陶瓷化方法。
背景技术
陶瓷长丝具有良好的耐高温，耐磨性，低热导率，抗热震性能好以及高强度，高模量，高韧性等优异的性能，使其能够广泛的应用于隔热材料，防护材料以及结构增强材料。目前，陶瓷长丝存在两种形式：短纤和连续长丝。短纤形式的陶瓷长丝主要应用在隔热，高温过滤器材等领域。连续长丝形式的陶瓷长丝主要作为结构增强材料，以改善陶瓷材料的脆性。连续陶瓷长丝主要采用溶胶-凝胶法以干法纺丝的方式制备，其纺丝液中除了溶胶外，还必须添加聚合物作为纺丝助剂以提高纺丝液的可纺性能。因此，为了获得连续陶瓷长丝，杂化凝胶长丝必须经历有机物和小分子的去除以及晶粒的成型过程。
国内相关单位对连续陶瓷长丝进行大量的研究，主要是针对溶胶-凝胶的可纺性，对连续杂化凝胶长丝的陶瓷化方法通常采取阶段式升温的简单方法。即在特定温度和时间的煅烧炉中进行煅烧。此方法存在生产效率低，所获得的陶瓷长丝产量低、晶粒尺寸不均一、强度弱的问题，无法应用到连续陶瓷长丝生产中。受限于连续杂化凝胶长丝陶瓷化本身特性，不同于无受力状态下的阶段式煅烧方法，连续杂化凝胶长丝的陶瓷化需采取处于受力状态下的悬浮煅烧方式。该方法存在长丝内部组织结构的变化导致长丝强度的变化，致使长丝在连续陶瓷化过程中容易出现断裂的现象。
因此，亟需开发连续杂化凝胶长丝在受力状态的悬浮煅烧方法，使得长丝内部组织结构变化的同时，长丝本身具有一定的拉伸强度，从而获得陶瓷化程度高，晶粒尺寸小，长丝直径均一的连续陶瓷长丝。
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杂化凝胶长丝的陶瓷化方法，能够以此获得陶瓷化程度高，晶粒尺寸小，长丝直径均一的连续陶瓷长丝。
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杂化凝胶长丝的陶瓷化方法，包括以下步骤：
S1：通过牵拉设备将连续杂化凝胶长丝引入热处理炉中，除去杂化凝胶长丝内部残留的自由水同时进行热交联处理，以此提升连续杂化凝胶长丝的强度、耐水性；
S2：在牵拉设备的张力控制下，将S1中处理的连续杂化凝胶长丝引入多区段煅烧设备中，得到陶瓷化长丝，所述多区段煅烧设备中依次包括结合水去除区、有机物去除区、晶型转化区以及阶段降温区。
进一步地，S1中，所述连续杂化凝胶长丝包括氧化铝凝胶长丝、氧化硅凝胶长丝、硅酸铝凝胶长丝、莫来石凝胶长丝、铝锆凝胶长丝、氧化锆凝胶长丝、硅酸锆凝胶长丝中的一种或多种组合。
进一步地，S1中，所述连续杂化凝胶长丝为丝束形态，丝束是由300～1500根丝组成。
进一步地，S1中，所述连续杂化凝胶长丝的单丝平均直径为10～100μm，所述连续杂化凝胶长丝由小分子和有机高分子聚合物组成，所述有机高分子聚合物占陶瓷长丝总质量的8～30wt％。
进一步地，S1中，所述连续杂化凝胶长丝中的有机高分子聚合物包括聚乙烯醇、聚乙烯吡咯烷酮、聚氧化乙烯、聚乙二醇、羧甲基长丝素、羟甲基长丝素中的一种或几种；
进一步地，S1中，所述热处理炉的温度为100～200℃，连续杂化凝胶长丝通过热处理炉的速度为0.1～10m/min，所述热交联的处理时间为10～30min。
进一步地，S1和S2中，所述牵拉设备为五辊牵拉设备，S1中牵拉设备对长丝的张力控制为0.01～5N；
S2中牵拉设备对长丝的张力控制为0.01～10N。
进一步地，S1中，所述煅烧区为空气氛围，其中结合水去除区温度为200～400℃，有机物去除区温度为400～600℃，晶型转化区的温度为800～1000℃；
连续杂化凝胶长丝在结合水去除区停留时间为5～20min，在有机物去除区停留时间为5～20min，在晶型转化区的停留时间为5～10min，在阶段降温区停留时间为10～20min。
进一步地，S1中，所述阶段降温区分为三段：降温区Ⅰ的温度为600～800℃，降温区Ⅱ的温度为400～500℃，降温区Ⅲ的温度为100～300℃；
长丝在降温区Ⅰ、Ⅱ、Ⅲ的停留时间相等。
进一步地，S2中得到陶瓷化长丝的平均直径为5～90μm，平均晶粒尺寸为5～50nm。
本发明机理介绍如下：
杂化凝胶长丝主要是由结合水，有机高分子，凝胶等组成，由于杂化凝胶长丝内部以范德华力和氢键作用力为主，其抗拉张力远远低于陶瓷长丝的抗拉张力，易在陶瓷化工艺中连续长丝发生断裂。因此在杂化凝胶长丝内部引入共价键连接的交联结构网络，大大提高杂化凝胶长丝的抗拉强度。本发明基于杂化凝胶长丝内部存在的水溶性有机高分子本身特性，利用热处理的方式使得烷烃分子链发生交联反应。
在连续陶瓷化过程中提出阶段式去除结合水和有机聚合物，目的在于尽可能地排除因结合水和有机聚合物的去除而留下的孔穴，使得杂化凝胶长丝细化，同时凝胶粒子上的羟基能够无阻碍的发生热缩聚反应，急剧地增加凝胶长丝的交联程度，从而弥补由于有机物的去除导致的弱抗拉强度，进一步保证杂化凝胶长丝的连续陶瓷化进程。
杂化凝胶长丝的陶瓷化过程就是长丝的细化和原子的重排，空气氛围给予凝胶长丝充分陶瓷化。由于陶瓷长丝在骤冷过程出现内应力而导致在外加张力的情况下出现断裂现象，本发明提供梯度降温过程以消除陶瓷长丝内部的内应力。
与现有技术相比，本发明具有以下技术优势：
(1)本发明中提供的连续杂化凝胶长丝的陶瓷化过程，极大地缩短传统阶段式升温陶瓷化时间；
(2)本发明中的热处理过程，分段式去除结合水和有机高分子以及梯度降温的设计为成功制备连续陶瓷长丝提供良好的条件，该工艺简单，具有较好的普适性，可实现大规模的工业生产推广。
(3)该方法制备的连续陶瓷长丝具有长丝陶瓷程度高，长丝直径均匀性好，晶粒尺寸小，使得产品品质显著提升。
附图说明
图1为本发明中连续杂化凝胶长丝的陶瓷化化过程示意图；
图2为实施例1中制备的莫来石长丝的SEM图；
图3为实施例1中制备的莫来石长丝的XRD图。
图4为实施例3中制备的氧化铝长丝的XRD图。
图5为实施例3中制备的氧化锆长丝的XRD图。
图1中：1、五辊设备，2、热处理炉，3-1、结合水去除区，3-2、有机物去除区，3-3、晶型转化区，3-4、降温区Ⅰ，3-5、降温区Ⅱ，3-6、降温区Ⅲ。
具体实施方式
针对目前缺乏连续杂化凝胶长丝煅烧技术以及在长丝煅烧过程中存在长丝易断裂的问题，本发明提供一种连续杂化凝胶长丝的陶瓷化方法，具体方案如下：
(1)将所获得的连续杂化凝胶长丝引入热处理炉中，除去杂化凝胶长丝内部残留的自由水同时进行热交联处理，以此提升连续杂化凝胶长丝的强度、耐水性；
(2)将上述获得的连续杂化凝胶长丝引入煅烧区中，采用五辊设备差速补偿张力，获得连续陶瓷长丝。煅烧区可分为结合水去除区、有机物去除区、晶型转化区以及阶段降温区；
在本发明的一个实施方法中，步骤(1)中，所述连续杂化凝胶长丝是丝束，丝束是由300～1500根丝组成；
在本发明的一个实施方法中，步骤(1)中，所述连续杂化凝胶长丝的单丝平均直径为10～100μm，组成连续杂化凝胶长丝为小分子和有机高分子聚合物，其中有机高分子聚合物占陶瓷长丝总质量的8～30wt％。
在本发明的一个实施方法中，步骤(1)中，所述连续杂化凝胶长丝包括氧化铝凝胶长丝、氧化硅凝胶长丝、硅酸铝凝胶长丝、莫来石凝胶长丝、铝锆凝胶长丝、氧化锆凝胶长丝、硅酸锆凝胶长丝中的一种或多种组合。
在本发明的一个实施方法中，步骤(1)中，所述连续杂化凝胶长丝中的有机聚合物包括聚乙烯醇、聚乙烯吡咯烷酮、聚氧化乙烯、聚乙二醇、羧甲基长丝素、羟甲基长丝素中的一种或几种；。
在本发明的一个实施方法中，步骤(1)中，所述热处理炉的温度为100～200℃，连续杂化凝胶长丝通过热处理炉的速度为0.1～10m/min，所述热交联处理时间为10～30min。
在本发明的一个实施方法中，步骤(1)中，所述五辊设备控制的张力为0.01～5N。
在本发明的一个实施方法中，步骤(2)中，所述煅烧区为空气氛围，结合水去除区温度为200～400℃，有机物去除区温度为400～600℃，晶型转化区的温度为800～1000℃。
在本发明的一个实施方法中，步骤(2)中，所述的阶段降温区分为三段；降温区Ⅰ的温度为600～800℃，降温区Ⅱ的温度为400～500℃，降温区Ⅲ的温度为100～300℃。
在本发明的一个实施方法中，步骤(2)中，所述的连续杂化凝胶长丝通过煅烧区的速度为0.1～10m/min，连续杂化凝胶长丝在结合水去除区停留时间为5～20min，有机物去除区停留时间为5～20min，晶型转化区的停留时间为5～10min，阶段降温区停留时间为10～20min。
在本发明的一个实施方法中，步骤(2)中，所述降温区Ⅰ、Ⅱ、Ⅲ停留时间一致。
在本发明的一个实施方法中，步骤(2)中，所述五辊设备控制的张力为0.01～10N。
在本发明的一个实施方法中，步骤(2)中，经过煅烧区获得陶瓷长丝平均直径为5～90μm，平均晶粒尺寸为5～50nm。
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结构/模块名称、控制模式、算法、工艺过程或组成配比等特征，均视为现有技术中公开的常见技术特征。
实施例1
本实施例中的连续杂化凝胶长丝的陶瓷化方法，具体步骤如下：
第一步：将所获得的平均直径为19μm的连续杂化凝胶长丝束(400根单丝，莫来石长丝)经过五辊设备(图1中的标号1)牵引入热处理炉(图1中的标号2)中，热处理炉温度设定为130℃，去除残留自由水的同时进行热交联处理，连续杂化凝胶长丝束行进速度为0.1m/min，在热处理炉中停留时间为8min。连续杂化凝胶长丝束所受张力为0.5N。获得具有一定强度、耐水性的连续杂化凝胶长丝。
第二步：将经过交联处理后的连续杂化凝胶长丝束通过五辊设备引入煅烧区(对应图1中分别为有机物去除区3-2、晶型转化区3-3、降温区Ⅰ3-4、降温区Ⅱ3-5、降温区Ⅲ3-6)，其中结合水去除区温度为200℃，有机物去除区温度为400℃，晶型转化区的温度为1000℃，阶段降温区Ⅰ、Ⅱ和Ⅲ温度分别是600℃、400℃和200℃。每段区停留时间依次是5min，10min，5min和15min。所获得陶瓷长丝平均直径为9μm，晶粒尺寸为10nm，晶型为莫来石晶型。图2为陶瓷化后莫来石长丝的SEM图，图3为莫来石晶型的XRD图。
实施例2
本实施例中连续杂化凝胶长丝的陶瓷化方法，具体步骤如下：
第一步：将所获得的平均直径为40μm的连续杂化凝胶长丝束(500根单丝，氧化铝长丝)经过五辊设备牵引入热处理炉中，热处理炉温度设定为140℃，去除残留自由水的同时进行热交联处理，连续杂化凝胶长丝束行进速度为0.15m/min，在热处理炉中停留时间为5min。连续杂化凝胶长丝束所受张力为0.5N。获得具有一定强度、耐水性的连续杂化凝胶长丝。
第二步：将经过交联处理后的连续杂化凝胶长丝束通过五辊设备引入煅烧区，其中结合水去除区温度为250℃，有机物去除区温度为500℃，晶型转化区的温度为1300℃或1400℃，阶段降温区Ⅰ、Ⅱ和Ⅲ温度分别是800℃、500℃和300℃。每段区停留时间依次是3min，6min，3min和10min。所获得陶瓷长丝平均直径为21μm，晶粒尺寸为30nm(1300℃)，晶型主要为α-Al2O3，还有少量的莫来石晶型。
实施例3
本实施例中连续杂化凝胶长丝的陶瓷化方法，具体步骤如下：
第一步：将所获得的平均直径为30μm的连续杂化凝胶长丝束(800根单丝，氧化锆长丝)经过五辊设备牵引入热处理炉中，热处理炉温度设定为140℃，去除残留自由水的同时进行热交联处理，连续杂化凝胶长丝束行进速度为0.2m/min，在热处理炉中停留时间为4min。连续杂化凝胶长丝束所受张力为0.15N。获得具有一定强度、耐水性的连续杂化凝胶长丝。
第二步：将经过交联处理后的连续杂化凝胶长丝束通过五辊设备引入煅烧区，其中结合水去除区温度为250℃，有机物去除区温度为500℃，细化区的温度为1100℃，阶段降温区Ⅰ、Ⅱ和Ⅲ温度分别是700℃、500℃和200℃。每段区停留时间依次是2min，5min，2min和7min。所获得陶瓷长丝平均直径为17μm，晶粒尺寸为15nm，晶型主要为t-ZrO2，还有少量的α-Al2O3(图4所示)。
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)
1.一种杂化凝胶长丝的陶瓷化方法，其特征在于，包括以下步骤：
S1：通过牵拉设备将连续杂化凝胶长丝引入热处理炉中，除去杂化凝胶长丝内部残留的自由水同时进行热交联处理，以此提升连续杂化凝胶长丝的抗拉强度和耐水性；
S2：在牵拉设备的张力控制下，将S1中处理的连续杂化凝胶长丝引入多区段煅烧设备中，得到陶瓷化长丝，所述多区段煅烧设备中依次包括结合水去除区、有机物去除区、晶型转化区以及阶段降温区。
2.根据权利要求1所述的一种杂化凝胶长丝的陶瓷化方法，其特征在于，S1中，所述连续杂化凝胶长丝包括氧化铝凝胶长丝、氧化硅凝胶长丝、硅酸铝凝胶长丝、莫来石凝胶长丝、铝锆凝胶长丝、氧化锆凝胶长丝、硅酸锆凝胶长丝中的一种或多种组合。
3.根据权利要求1所述的一种杂化凝胶长丝的陶瓷化方法，其特征在于，S1中，所述连续杂化凝胶长丝为丝束形态，丝束由300～1500根丝组成。
4.根据权利要求1所述的一种杂化凝胶长丝的陶瓷化方法，其特征在于，S1中，所述连续杂化凝胶长丝的单丝平均直径为10～100μm，所述连续杂化凝胶长丝由小分子和有机高分子聚合物组成，所述有机高分子聚合物占陶瓷长丝总质量的8～30wt％。
5.根据权利要求1所述的一种杂化凝胶长丝的陶瓷化方法，其特征在于，S1中，所述连续杂化凝胶长丝中的有机高分子聚合物包括聚乙烯醇、聚乙烯吡咯烷酮、聚氧化乙烯、聚乙二醇、羧甲基长丝素、羟甲基长丝素中的一种或几种。
6.根据权利要求1所述的一种杂化凝胶长丝的陶瓷化方法，其特征在于，S1中，S1中，所述热处理炉的温度为100～200℃，连续杂化凝胶长丝通过热处理炉的速度为0.1～10m/min，所述交联时间为10～30min。
7.根据权利要求1所述的一种杂化凝胶长丝的陶瓷化方法，其特征在于，S1中，S1和S2中，所述牵拉设备为五辊牵拉设备，S1中牵拉设备对长丝的张力控制为0.01～5N；
S2中牵拉设备对长丝的张力控制为0.01～10N。
8.根据权利要求1所述的一种杂化凝胶长丝的陶瓷化方法，其特征在于，S1中，所述煅烧区为空气氛围，其中结合水去除区温度为200～400℃，有机物去除区温度为400～600℃，晶型转化区的温度为800～1000℃；
连续杂化凝胶长丝在结合水去除区停留时间为5～20min，在有机物去除区停留时间为5～20min，在晶型转化区的停留时间为5～10min，在阶段降温区停留时间为10～20min。
9.根据权利要求8所述的一种杂化凝胶长丝的陶瓷化方法，其特征在于，S1中，所述阶段降温区分为三段：降温区Ⅰ的温度为600～800℃，降温区Ⅱ的温度为400～500℃，降温区Ⅲ的温度为100～300℃；
长丝在降温区Ⅰ、Ⅱ、Ⅲ的停留时间相等。
10.根据权利要求1所述的一种杂化凝胶长丝的陶瓷化方法，其特征在于，S1中，S2中得到陶瓷化长丝的平均直径为5～90μm，平均晶粒尺寸为5～50nm。
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