CN106927808A - 一种钇铝石榴石连续纤维的制备方法 - Google Patents

一种钇铝石榴石连续纤维的制备方法 Download PDF

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CN106927808A
CN106927808A CN201710228775.8A CN201710228775A CN106927808A CN 106927808 A CN106927808 A CN 106927808A CN 201710228775 A CN201710228775 A CN 201710228775A CN 106927808 A CN106927808 A CN 106927808A
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aluminium
yttrium
continuous fiber
preparation
garnet
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CN106927808B (zh
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陈代荣
孟强
贾玉娜
焦秀玲
朱超
柴鲁宁
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Shandong University
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Abstract

本发明涉及一种钇铝石榴石连续纤维的制备方法，该方法利用含Al13胶粒的氧化铝溶胶、γ‑AlOOH纳米分散液、氧化钇溶胶、冰醋酸和聚乙烯吡咯烷酮(PVP)制备可纺性前驱体溶胶，采用干法纺丝技术制备凝胶连续纤维，再经过热处理得到直径6‑12μm的钇铝石榴石连续纤维。本发明采用溶胶‑凝胶法制备的前驱体溶胶均匀稳定，可长时间存放。采用干法纺丝制备的凝胶连续纤维长度可达3000米，热处理后的纤维表面光滑，内部结构紧密，强度高，且有很好的柔韧性，在高温使用过程中，高温蠕变小，可广泛用于航空航天等工业的复合材料及热防护材料。本发明工艺简单，生产周期短，易于实现工业化。

Description

一种钇铝石榴石连续纤维的制备方法
技术领域
本发明涉及一种钇铝石榴石(YAG)连续纤维的制备方法，属于无机非金属材料领域。
背景技术
氧化铝纤维是高性能无机陶瓷纤维的一种，其主要成分为氧化铝，有的还添加有氧化硅、氧化硼、氧化锆等非金属氧化物和金属氧化物组分。按形态可分为短纤维、连续纤维、晶须等不同类型，其中连续纤维的直径一般在10μm左右，长度可达几千米。钇铝石榴石连续纤维属于氧化铝纤维中的一种，是Al2O3和Y2O3的复合氧化物，其熔点高达1970℃，化学性质稳定。钇铝石榴石纤维不仅具有高强度、高模量、耐高温等优良性能，还具有优异的抗高温蠕变性能，可广泛用作绝热耐火材料和结构增强材料。
目前制备钇铝石榴石纤维的方法有熔融法和化学法，熔融法一般采用铝和钇的氧化物为主要原料，通过高温加热获取熔融液，再将熔融液纺丝成纤(参见：硅酸盐通报2009,28,132)；Mileiko等按化学计量比混合Al2O3和Y2O3熔融液，将熔融液浸润到具有连续圆柱状通道的钼基模具中，熔融液在通道内冷却结晶后形成纤维，将纤维和模具分离后即可获得钇铝石榴石纤维，该纤维的弯曲强度最高可达1GPa，在1100℃下抗蠕变强度为169MPa(参见：J.Eur.Ceram.Soc.2002,22,1831)；Maston等按比例混合Al2O3和Y2O3后熔融，然后从特制的设备中直接拉制出Al2O3/YAG共晶纤维(参见：J.Eur.Ceram.Soc.1999,19,2487)。然而，由于YAG熔点较高，采用熔融法制备YAG纤维需要耐高温设备，且生产工艺难度大，成本高，这限制了YAG纤维的发展和应用。
化学法主要是采用溶胶-凝胶法，溶胶-凝胶法就是将含高化学活性组分的化合物经过溶液、溶胶、凝胶而固化，再经热处理而成的氧化物或其它化合物固体的方法。Towata等以异丙醇铝和异丙醇钇为前驱体原料，辅助加入水、盐酸、纳米氧化铝粉、粘度调节剂合成了YAG纺丝原液，凝胶纤维高温烧结获得钇铝石榴石晶体纤维和YAG/Al2O3共晶纤维(参见：Composites Part A 2001,32,1127)，由于金属醇盐的价格比较昂贵，成本太高，限制了利用金属醇盐制备YAG材料的发展；Pullar等采用Al(NO3)3、YCl3或Y(NO3)3为主要原料，氨水为沉淀剂，硝酸为胶溶剂，通过溶胶-凝胶法制备出YAG纤维，该方法采用喷吹纺丝技术，得到的是短纤维(参见：Mater.Lett.1999,39,173)；Shojaie-Bahaabad等采用铝粉、氯化铝、盐酸和氧化钇为原料，通过溶胶-凝胶法制备了YAG/Al2O3复合纤维，经1400℃热处理后纤维的晶粒尺寸在100-200nm，该方法只对前驱体凝胶的流变性能和纺丝性能进行了详细的分析，但没有探讨纤维的强度等其它性能(参见：Ceram.Int.2007,7,32)；US005217933A公开了一种钇铝石榴石纤维的制备方法，采用氯化铝、铝粉、甲酸、乙酸、乳酸，硝酸等原料，按氧化钇和与氧化铝不同的摩尔比例制备出钇铝石榴石陶瓷纤维，该方法加入了大量有机酸，导致溶胶合成反应较为复杂。
李呈顺等以廉价的铝粉、工业盐酸和醋酸钇为主要原料，制备了高性能的多晶钇铝石榴石纤维，纤维经热处理到900℃时可获得纯相的钇铝石榴石晶体。经1550℃热处理后，所得到的多晶钇铝石榴石纤维的平均粒径约200nm，拉伸强度为485MPa(参见：硅酸盐学报2009,37,1165)；CN105002601A公开了一种多晶Al2O3-YAG复相纤维或纯YAG纤维的制备方法，采用氯化铝、铝微粉、硝酸钇、醋酸钇、醋酸为原料制备前驱体溶胶，经离心纺丝后制得钇铝石榴石凝胶纤维，干燥、热处理后得到多晶Al2O3-YAG复相纤维或纯YAG纤维，但是，上述文献描述的纤维是采用离心甩丝技术制得的短纤维，不可进行2维或3维编织。CN102011215A公开了一种溶胶-凝胶法制备钇铝石榴石连续纤维的方法，采用无机铝盐、金属铝、氧化钇、醋酸为原料，加入一定量的纺丝助剂，浓缩纺丝后即可得到钇铝石榴石基纤维原丝，将凝胶纤维干燥、烧结后得到钇铝石榴石基连续纤维。但是，此方法没有对纤维长度进行探讨，且在纺丝原液制备过程中耗时太大，若进行工业化生产，则生产效率较低。
发明内容
针对现有技术的不足，本发明提供了一种操作工艺简单可控，生产周期短，成本低，易于实现工业化的钇铝石榴石连续纤维的制备方法。
本发明以含有Al13胶粒的氧化铝溶胶、γ-AlOOH(水合氧化铝)纳米分散液和氧化钇溶胶为原料，按比例加入冰醋酸和稀硝酸，并以聚乙烯吡咯烷酮(PVP)做纺丝助剂，通过溶胶-凝胶结合干法纺丝制得钇铝石榴石凝胶纤维，经煅烧后形成YAG连续纤维。
本发明的技术方案如下：
一种钇铝石榴石连续纤维的制备方法，包括步骤如下：
(1)可纺性前驱体溶胶的制备
将含有Al13胶粒的氧化铝溶胶和γ-AlOOH纳米分散液混合并加入氧化钇溶胶，30-40℃水浴搅拌，搅拌过程中加入冰醋酸，然后加入稀硝酸调节pH值至1-3，加入纺丝助剂PVP，搅拌混合均匀，设定老化温度为25-80℃，将纺丝液老化至黏度为400-600Pa·s，得到前驱体可纺性溶胶；
所述含有Al13胶粒的氧化铝溶胶中氧化铝含量为15-35wt％，氧化钇溶胶的固含量为10-30wt％，γ-AlOOH纳米分散液的固含量为8.5-15wt％，氧化钇与冰醋酸的摩尔比为1:(1-2)，PVP加入量为总固含量的0.5-5wt％；含有Al13胶粒的氧化铝溶胶和γ-AlOOH纳米分散液的主要成分以氧化铝计，氧化钇和氧化铝的摩尔比为1:(1-2)；
(2)干法纺丝制备YAG凝胶纤维
将步骤(1)制备的前驱体可纺性溶胶进行干法纺丝，得到YAG凝胶纤维，干法纺丝工艺条件：喷丝板孔数为15-800个，喷丝板孔径为0.06-0.15mm，收丝速度为60-180m/min，空气温度为18-40℃，空气湿度为20-70％；
(3)YAG凝胶纤维陶瓷化
将步骤(2)制得的YAG凝胶纤维陶瓷化，以0.5-3℃/min的速度升温至450-600℃，在此温度保温0.5-2h，再以3-10℃/min的速度升温至900-1400℃，在此温度保温0.5-2h，即得钇铝石榴石连续纤维。
根据本发明，优选的，步骤(1)中含有Al13胶粒的氧化铝溶胶中Al13胶粒的质量含量为20-25wt％，γ-AlOOH纳米分散液的固含量为10-15wt％，氧化钇溶胶固含量为15wt％，纺丝助剂PVP的加入量为总固含量的1wt％；
根据本发明，优选的，含有Al13胶粒的氧化铝溶胶和γ-AlOOH纳米分散液中氧化铝含量的质量比为(3-9)：1。
根据本发明，优选的，步骤(1)中老化温度为35-50℃，老化至黏度为450-550Pa·s。
根据本发明，优选的，步骤(1)中老化过程在真空度为0.095MPa条件下进行。
根据本发明，优选的，步骤(1)中氧化钇与冰醋酸的摩尔比为1:(1.1-1.5)。
根据本发明，优选的，加入稀硝酸调节pH值至1.5-2.5。
根据本发明，优选的，步骤(1)中所述的含Al13胶粒的氧化铝溶胶按以下方法制备：
以铝粉和铝盐溶液为原料，铝盐和铝粉的摩尔比为1:(1-5)，加热回流反应至铝粉完全反应，冷却、过滤，即得到含Al13胶粒的氧化铝溶胶，胶粒粒径≤5nm。优选的，所述的铝盐为氯化铝、硝酸铝或硫酸铝。
根据本发明，优选的，步骤(2)中喷丝板孔径为0.06-0.10mm，收丝速度为80-140m/min。
根据本发明，优选的，步骤(2)中空气温度为25-35℃，空气湿度为30-45％。
根据本发明，优选的，步骤(3)中YAG凝胶纤维以0.8-1℃/min的速度升温至450-600℃，在此温度保温1-2h；再以3-5℃/min的速度升温至900-1400℃，在此温度保温1-2h。
本发明方法制备的钇铝石榴石连续纤维属于立方晶系，具有石榴石晶体结构；纤维直径为6-12μm，无渣球，纤维长度可达数千米；纤维表面光滑且内部结构致密，有很好的柔韧性，强度高。
本发明的原理：
本发明可纺性前驱体溶胶制备过程是几种金属无机盐溶胶的混合，可以很好的控制前驱体溶胶的均匀性，且反应原料通过水解、缩聚容易得到线性粒子，从而有利于少支链高聚链状胶粒的产生；前驱体溶胶中加入冰醋酸，有利于提高溶胶的纺丝性能。这可能是由于：醋酸水解产生的醋酸根离子与金属离子结合，形成络合物，从而分子之间形成链状或网状结构，有利于溶胶的纺丝性能。
本发明采用干法纺丝技术制备YAG连续纤维，其中喷丝板孔数在15-800之间，孔径为0.06-0.15mm，由特种合金钢制成。纺丝原液从喷丝板孔眼中被压出进入纺丝甬道，与通入甬道中的热空气流进行换热，原液细流中的溶剂快速挥发并被热空气流带走。在逐步脱去溶剂的同时，原液细流发生固化，并在收丝机卷绕拉力的作用下伸长变细而形成初生纤维，缠绕于收丝辊上。纺丝速度主要取决于溶胶的性质和溶剂的挥发速度。与其它方法相比，此方法更易制得连续纤维。
本发明的技术特点及优良效果如下：
1)本发明制备的钇铝石榴石连续纤维直径均匀，无渣球，纤维长度可达数千米，纤维表面光滑且内部结构紧密，不易断裂，有很好的柔韧性。此外，纤维的热稳定性好，力学性质稳定，经1200热处理后的纤维单丝拉伸强度平均可达1GPa，具有良好的抗高温蠕变性。
2)本发明前驱体制备过程操作简单，可大大减少可纺性前驱体溶胶的制备时间，生产周期短，易于实现工业化。
3)本发明采用溶胶-凝胶方法制备YAG连续纤维，所制备的前驱体溶胶性质稳定，可长时间存放。
4)本发明老化过程在真空度0.095MPa条件下进行，大大减少了溶胶老化时间，可进行工业化生产。
5)本发明采用干法纺丝，纺丝速度较高且所得纤维的结构较致密，与其它方法比较更易制得连续纤维，本发明所制得的YAG连续纤维长度可达数千米，可利用收丝设备将纤维缠绕于收丝辊上。
附图说明：
图1是本发明实施例1不同温度烧结所得YAG连续纤维的XRD谱图。
图2是本发明实施例1所得的YAG连续凝胶纤维的光学照片。
图3是本发明实施例1所得YAG连续纤维的SEM照片。
图4是本发明实施例1所得YAG连续纤维高倍放大的SEM照片。
图5是本发明实施例1所得YAG连续纤维截面高倍放大的SEM照片。
具体实施方式：
下面结合实施例对本发明做进一步说明，但不限于此。
实施例中所述的含Al13胶粒的氧化铝溶胶按以下方法制备得到：
以铝粉和铝盐溶液为原料，铝盐和铝粉的摩尔比为1:(1-5)，加热回流反应至铝粉完全反应，冷却、过滤，即得到含Al13胶粒的氧化铝溶胶，Al13胶粒的质量含量为20-25wt％，胶粒粒径≤5nm，所述的铝盐为氯化铝、硝酸铝、硫酸铝。
实施例1
一种钇铝石榴石连续纤维的制备方法，包括步骤如下：
(1)可纺性前驱体溶胶的制备
将925.2g含有Al13胶粒的氧化铝溶胶(固含量为22.04wt％)和419.6gγ-AlOOH纳米分散液(固含量为12.15wt％)混合，利用分散机搅拌至均匀，按n(Al2O3):n(Y2O3)＝5:3的计量组成加入2258.1g氧化钇溶胶(固含量为15wt％)，35℃水浴搅拌，搅拌过程中加入450g冰醋酸，其中氧化钇与冰醋酸的摩尔比为1:1.25，然后加入173g稀硝酸调节pH值至2.0，加入39.6g PVP溶液，搅拌混合均匀。
设定老化温度为40℃，老化过程在真空度为0.095MPa条件下进行，将混合溶胶老化至黏度为500Pa·s，得到前驱体可纺性溶胶。
(2)干法纺丝制备凝胶纤维
将步骤(1)制备的前驱体溶胶进行干法纺丝，得到YAG凝胶纤维，工艺条件：喷丝板孔径为0.06mm，收丝速度为100m/min，空气温度为25-30℃，空气湿度为30-40％，如图2所示，纤维长度可达数千米。
(3)YAG凝胶纤维陶瓷化
将步骤(2)制备的YAG凝胶纤维陶瓷化，工艺条件：以1℃/min的速度升温至500℃，在此温度保温1h，再以5℃/min的速度升温至1200℃，在此温度保温2h，得到YAG连续纤维。所得钇铝石榴石连续纤维直径为7.7-8.5μm，纤维收缩率约为30％，纤维表面光滑，内部结构致密，XRD测试纤维晶相为钇铝石榴石晶相，纤维单丝拉伸强度平均为932MPa。
本实施例步骤(3)YAG凝胶纤维陶瓷化过程中，选择最终的烧结温度分别为700℃、800℃、900℃、1000℃，得到的钇铝石榴石连续纤维的XRD谱图如图1所示，烧结温度为800℃时得到的YAG纤维开始石榴石化，当烧结温度为1000℃时，已全部转化为钇铝石榴石晶相。
本实施例制得的钇铝石榴石连续纤维的SEM照片如图3所示，高倍放大的SEM照片如图4所示，纤维截面高倍放大的SEM照片如图5所示。由图3、4、5可知，纤维直径均匀，无渣球且表面光滑；纤维内部结构紧密，晶粒间气孔数量少，有利于纤维机械强度的提高。
对比例1
一种钇铝石榴石连续纤维的制备方法，包括步骤如下：
(1)可纺性前驱体溶胶的制备
按n(Al2O3):n(Y2O3)＝5:3的计量比将1156.5g含有Al13胶粒的氧化铝溶胶(固含量为22.04wt％)和2258.1g氧化钇溶胶(固含量为15wt％)混合，35℃水浴搅拌，搅拌过程中加入450g冰醋酸，其中氧化钇与冰醋酸的摩尔比为1:1.25，然后加入138g稀硝酸调节pH值至2.0，加入98.9g PVP溶液，搅拌混合均匀。
设定老化温度为40℃，老化过程在真空度为0.095MPa条件下进行，将混合溶胶老化至黏度为513Pa·s，得到前驱体可纺性溶胶。
(2)干法纺丝制备凝胶纤维
将步骤(1)制备的前驱体溶胶进行干法纺丝，得到YAG凝胶纤维，工艺条件：喷丝板孔径为0.06mm，收丝速度为80m/min，空气温度为25-30℃，空气湿度为30-40％。
步骤(3)同实施例1。
所得钇铝石榴石连续纤维直径为9.5-10.2μm，纺丝过程中凝胶纤维易断且直径较粗，纤维收缩率约为33％；纤维表面有渣球且内部结构不致密，XRD测试纤维晶相为钇铝石榴石晶相，纤维单丝拉伸强度平均为494MPa。可见单独采用含有Al13胶粒的氧化铝溶胶作为氧化铝源，严重影响钇铝石榴石连续纤维的单丝拉伸强度。
实施例2
一种钇铝石榴石连续纤维的制备方法，包括步骤如下：
(1)可纺性前驱体溶胶的制备
将925.2g含有Al13胶粒的氧化铝溶胶(固含量为22.04wt％)和419.6gγ-AlOOH纳米分散液(固含量为12.15wt％)混合，利用分散机搅拌至均匀，按n(Al2O3):n(Y2O3)＝5:3的计量组成加入2258.1g氧化钇溶胶(固含量为15wt％)，35℃水浴搅拌，搅拌过程中加入450g冰醋酸，其中氧化钇与冰醋酸的摩尔比为1:1.25，此时pH值为3.8，加入98.9g PVP溶液，搅拌混合均匀。
设定老化温度为40℃，老化过程在真空度为0.095MPa条件下进行，老化过程在真空度为0.095MPa条件下进行，将混合溶胶老化至黏度为496Pa·s，得到前驱体可纺性溶胶。
步骤(2)同实施例1。
步骤(3)同实施例1。
所得钇铝石榴石连续纤维直径为7.8-9.0μm；纤维收缩率约为32％，纤维表面较光滑但晶粒间气孔数量较多，XRD测试纤维晶相为钇铝石榴石晶相，纤维单丝拉伸强度平均为583MPa。
实施例3
一种钇铝石榴石连续纤维的制备方法，包括步骤如下：
(1)可纺性前驱体溶胶的制备
将925.2g含有Al13胶粒的氧化铝溶胶(固含量为22.04wt％)和419.6gγ-AlOOH纳米分散液(固含量为12.15wt％)混合，利用分散机搅拌至均匀，按n(Al2O3):n(Y2O3)＝5:3的计量组成加入2258.1g氧化钇溶胶(固含量为15wt％)，35℃水浴搅拌，搅拌过程中加入486g冰醋酸，其中氧化钇与冰醋酸的摩尔比为1:1.35，然后加入195g稀硝酸调节pH值至1.8，加入98.9g PVP溶液，搅拌混合均匀。
设定老化温度为40℃，老化过程在真空度为0.095MPa条件下进行，将混合溶胶老化至黏度为520Pa·s，得到前驱体可纺性溶胶。
步骤(2)同实施例1。
步骤(3)同实施例1。
所得钇铝石榴石连续纤维直径为7.8-9.0μm；纤维收缩率约为32％，纤维表面光滑，内部结构致密，XRD测试纤维晶相为钇铝石榴石晶相，纤维单丝拉伸强度平均为913MPa。
实施例4
一种钇铝石榴石连续纤维的制备方法，包括步骤如下：
(1)可纺性前驱体溶胶的制备
将925.2g含有Al13胶粒的氧化铝溶胶(固含量为22.04wt％)和419.6gγ-AlOOH纳米分散液(固含量为12.15wt％)混合，利用分散机搅拌至均匀，按n(Al2O3):n(Y2O3)＝5:3的计量组成加入2258.1g氧化钇溶胶(固含量为15wt％)，35℃水浴搅拌，搅拌过程中加入720g冰醋酸，其中氧化钇与冰醋酸的摩尔比为1:2，然后加入159g稀硝酸调节pH值至1.8，加入98.9g PVP溶液，搅拌混合均匀。
设定老化温度为40℃，老化过程在真空度为0.095MPa条件下进行，将混合溶胶老化至黏度为515Pa·s，得到前驱体可纺性溶胶。
(2)干法纺丝制备凝胶纤维
将步骤(1)制备的前驱体溶胶进行干法纺丝，得到YAG凝胶纤维，工艺条件：喷丝板孔径为0.06mm，收丝速度为80m/min，空气温度为25-30℃，空气湿度为30-40％，如图2所示，纤维长度可达数千米。
步骤(3)同实施例1。
所得钇铝石榴石连续纤维直径为8.5-9.5μm，纺丝过程中凝胶纤维易断且直径较粗；纤维收缩率约为34％，纤维表面较光滑，晶粒间气孔数量较多，XRD测试纤维晶相为钇铝石榴石晶相，纤维单丝拉伸强度平均为700MPa。
实施例5
一种钇铝石榴石连续纤维的制备方法，包括步骤如下：
步骤(1)同实施例1。
(2)干法纺丝制备凝胶纤维
将步骤(1)制备的前驱体溶胶进行干法纺丝，得到YAG凝胶纤维，工艺条件：喷丝板孔径为0.1mm，收丝速度为120m/min，空气温度为30-35℃，空气湿度为30-40％。
(3)YAG凝胶纤维陶瓷化
将步骤(2)制备的YAG凝胶纤维陶瓷化，工艺条件：以0.8℃/min的速度升温至500℃，在此温度保温1h，再以4℃/min的速度升温至1200℃，在此温度保温2h，得到YAG连续纤维。
所得钇铝石榴石连续纤维直径为8.5-9.8μm，纤维收缩率约为30％，纤维表面光滑，内部结构致密，XRD测试纤维晶相为钇铝石榴石晶相，纤维单丝拉伸强度平均为826MPa。
实施例6
一种钇铝石榴石连续纤维的制备方法，包括步骤如下：
(1)可纺性前驱体溶胶的制备
将809.6g含有Al13胶粒的氧化铝溶胶(固含量为22.04wt％)和629.4gγ-AlOOH纳米分散液(固含量为12.15wt％)混合，利用分散机搅拌至均匀，按n(Al2O3):n(Y2O3)＝5:3的计量组成加入2258.1g氧化钇溶胶(固含量为15wt％)，35℃水浴搅拌，搅拌过程中加入450g冰醋酸，其中氧化钇与冰醋酸的摩尔比为1:1.25，然后加入173g稀硝酸调节pH值至2.0，加入39.6g PVP溶液，搅拌混合均匀。
设定老化温度为40℃，老化过程在真空度为0.095MPa条件下进行，将纺丝液老化至黏度为485Pa·s，得到前驱体可纺性溶胶。
步骤(2)同实施例1。
步骤(3)同实施例1。
所得钇铝石榴石连续纤维直径为7.1-8.5μm，纤维收缩率约30％，纤维表面光滑，内部结构致密，XRD测试纤维晶相为钇铝石榴石晶相，纤维单丝拉伸强度平均为809MPa。
实施例7
一种钇铝石榴石连续纤维的制备方法，包括步骤如下：
(1)可纺性前驱体溶胶的制备
将925.2g含有Al13胶粒的氧化铝溶胶(固含量为22.04wt％)和419.6gγ-AlOOH纳米分散液(固含量为12.15wt％)混合，利用分散机搅拌至均匀，按n(Al2O3):n(Y2O3)＝5:3的计量组成加入2258.1g氧化钇溶胶(固含量为15wt％)，然后加入固含量为22％的醋酸锆54.9g，35℃水浴搅拌，搅拌过程中加入450g冰醋酸，其中氧化钇与冰醋酸的摩尔比为1:1.25，最后加入173g稀硝酸调节pH值至2.0，加入40.4g PVP溶液，搅拌混合均匀。
设定老化温度为40℃，老化过程在真空度为0.095MPa条件下进行，将纺丝液老化至黏度为500Pa·s，得到前驱体可纺性溶胶。
步骤(2)同实施例1。
步骤(3)同实施例1。
所得钇铝石榴石连续纤维直径为6.7-8.5μm，纤维收缩率约为29％，纤维表面光滑，内部结构致密，XRD测试纤维主晶相为钇铝石榴石晶相，纤维单丝拉伸强度平均为950MPa。
实施例8
一种钇铝石榴石连续纤维的制备方法，包括步骤如下：
(1)可纺性前驱体溶胶的制备
将1184.3g含有Al13胶粒的氧化铝溶胶(固含量为22.04wt％)和537.1gγ-AlOOH纳米分散液(固含量为12.15wt％)混合，利用分散机搅拌至均匀，按n(Al2O3):n(Y2O3)＝2:1的计量组成加入2408.6g氧化钇溶胶(固含量为15wt％)，35℃水浴搅拌，搅拌过程中加入450g冰醋酸，其中氧化钇与冰醋酸的摩尔比为1:1.25，然后加入206g稀硝酸调节pH值至2.0，加入45.8g PVP溶液，搅拌混合均匀。
设定老化温度为40℃，老化过程在真空度为0.095MPa条件下进行，将纺丝液老化至黏度为515Pa·s，得到前驱体可纺性溶胶。
(2)干法纺丝制备凝胶纤维
将步骤(1)制备的前驱体溶胶进行干法纺丝，得到YAG凝胶纤维，工艺条件：喷丝板孔径为0.06mm，收丝速度为100m/min，空气温度为25-30℃，空气湿度为25-35％。
(3)YAG凝胶纤维陶瓷化
将步骤(2)制备的YAG凝胶纤维陶瓷化，工艺条件：以1℃/min的速度升温至450℃，在此温度保温1h，再以5℃/min的速度升温至1200℃，在此温度保温2h，得到YAG连续纤维。
所得钇铝石榴石连续纤维直径约为7.5-8.4μm，纤维收缩率约为33％，纤维表面光滑，内部结构致密，XRD测试纤维主晶相为钇铝石榴石晶相，纤维单丝拉伸强度平均为1077MPa。

Claims (10)

1.一种钇铝石榴石连续纤维的制备方法，包括步骤如下：
(1)可纺性前驱体溶胶的制备
将含有Al13胶粒的氧化铝溶胶和γ-AlOOH纳米分散液混合并加入氧化钇溶胶，30-40℃水浴搅拌，搅拌过程中加入冰醋酸，然后加入稀硝酸调节pH值至1-3，加入纺丝助剂PVP，搅拌混合均匀，设定老化温度为25-80℃，将纺丝液老化至黏度为400-600Pa·s，得到前驱体可纺性溶胶；
所述含有Al13胶粒的氧化铝溶胶中氧化铝含量为15-35wt％，氧化钇溶胶的固含量为10-30wt％，γ-AlOOH纳米分散液的固含量为8.5-15wt％，氧化钇与冰醋酸的摩尔比为1:(1-2)，PVP加入量为总固含量的0.5-5wt％；含有Al13胶粒的氧化铝溶胶和γ-AlOOH纳米分散液的主要成分以氧化铝计，氧化钇和氧化铝的摩尔比为1:(1-2)；
(2)干法纺丝制备YAG凝胶纤维
将步骤(1)制备的前驱体可纺性溶胶进行干法纺丝，得到YAG凝胶纤维，干法纺丝工艺条件：喷丝板孔数为15-800个，喷丝板孔径为0.06-0.15mm，收丝速度为60-180m/min，空气温度为18-40℃，空气湿度为20-70％；
(3)YAG凝胶纤维陶瓷化
将步骤(2)制得的YAG凝胶纤维陶瓷化，以0.5-3℃/min的速度升温至450-600℃，在此温度保温0.5-2h，再以3-10℃/min的速度升温至900-1400℃，在此温度保温0.5-2h，即得钇铝石榴石连续纤维。
2.根据权利要求1所述的钇铝石榴石连续纤维的制备方法，其特征在于，步骤(1)中含有Al13胶粒的氧化铝溶胶中Al13胶粒的质量含量为20-25wt％，γ-AlOOH纳米分散液的固含量为10-15wt％，氧化钇溶胶固含量为15wt％，纺丝助剂PVP的加入量为总固含量的1wt％。
3.根据权利要求1所述的钇铝石榴石连续纤维的制备方法，其特征在于，含有Al13胶粒的氧化铝溶胶和γ-AlOOH纳米分散液中氧化铝含量的质量比为(3-9)：1。
4.根据权利要求1所述的钇铝石榴石连续纤维的制备方法，其特征在于，步骤(1)中老化温度为35-50℃，老化至黏度为450-550Pa·s。
5.根据权利要求1所述的钇铝石榴石连续纤维的制备方法，其特征在于，步骤(1)中老化过程在真空度为0.095MPa条件下进行。
6.根据权利要求1所述的钇铝石榴石连续纤维的制备方法，其特征在于，步骤(1)中氧化钇与冰醋酸的摩尔比为1:(1.1-1.5)。
7.根据权利要求1所述的钇铝石榴石连续纤维的制备方法，其特征在于，加入稀硝酸调节pH值至1.5-2.5。
8.根据权利要求1所述的钇铝石榴石连续纤维的制备方法，其特征在于，步骤(2)中喷丝板孔径为0.06-0.10mm，收丝速度为80-140m/min。
9.根据权利要求1所述的钇铝石榴石连续纤维的制备方法，其特征在于，步骤(2)中空气温度为25-35℃，空气湿度为30-45％。
10.根据权利要求1所述的钇铝石榴石连续纤维的制备方法，其特征在于，步骤(3)中YAG凝胶纤维以0.8-1℃/min的速度升温至450-600℃，在此温度保温1-2h；再以3-5℃/min的速度升温至900-1400℃，在此温度保温1-2h。
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CN115852528B (zh) * 2022-06-27 2024-05-31 东华大学 一种规模化生产连续钇铝石榴石长丝的方法
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