CN106699227B - 一种纳米线自增强多孔氮化硅陶瓷及其制备方法 - Google Patents

一种纳米线自增强多孔氮化硅陶瓷及其制备方法 Download PDF

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CN106699227B
CN106699227B CN201710024219.9A CN201710024219A CN106699227B CN 106699227 B CN106699227 B CN 106699227B CN 201710024219 A CN201710024219 A CN 201710024219A CN 106699227 B CN106699227 B CN 106699227B
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silicon nitride
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丁军
吴郑敏
邓承继
余超
祝洪喜
柴志南
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Wuhan University of Science and Engineering WUSE
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Abstract

本发明涉及一种纳米线自增强多孔氮化硅陶瓷及其制备方法。其技术方案是：以70~80wt%的硅粉、5~10wt%的催化剂和10~20wt%的氮源为原料，外加所述原料20~30wt%的去离子水，搅拌，得到陶瓷浆料；向所述陶瓷浆料加入所述原料10~20wt%的发泡剂制成的泡沫，持续搅拌30~60min，得到陶瓷泡沫浆料；将所述陶瓷泡沫浆料倒入模具中，于氮气环境中静置，干燥，脱模，得到陶瓷坯体；将所述陶瓷坯体在氮气气氛条件下，先升温至1100~1150℃，保温；再升温至1200~1600℃，保温；自然冷却，即得纳米线自增强多孔氮化硅陶瓷。本发明工艺简单、成本低廉、原料利用率高和过程易于控制，所制备的制品气孔大小均一、气孔分布均匀和机械强度高。

Description

一种纳米线自增强多孔氮化硅陶瓷及其制备方法
技术领域
本发明属于多孔氮化硅陶瓷技术领域。具体涉及一种纳米线自增强多孔氮化硅陶瓷及其制备方法。
背景技术
多孔氮化硅陶瓷是一种将氮化硅陶瓷的性能特征与多孔材料的结构特征相结合的高级耐火材料，被广泛应用于航空航天、化工、冶金等领域。目前多孔氮化硅陶瓷的制备方法主要有添加造孔剂法、冷冻干燥法、溶胶-凝胶法和碳热还原法等。
这些方法得到的多孔氮化硅陶瓷的气孔大小不均一和气孔分布不均匀，并且在反应过程中主要是通过氮气与硅粉直接接触发生反应生成氮化硅，使得多孔氮化硅陶瓷内部的硅粉无法与氮气充分接触，不仅降低了硅粉的利用率，残存的硅粉还会与氮化硅形成结构缺陷，影响产品的性能。
发明内容
本发明旨在克服现有技术缺陷，目的是提供一种工艺简单、成本低廉、原料利用率高和过程易于控制的纳米线自增强多孔氮化硅陶瓷制备方法，用该方法制备的纳米线自增强多孔氮化硅陶瓷气孔大小均一、气孔分布均匀和机械强度高。
为实现上述目的，本发明所采用的技术方案的具体步骤是：
步骤一、以70~80wt%的硅粉、5~10wt%的催化剂和10~20wt%的氮源为原料，外加所述原料20~30wt%的去离子水，搅拌30~60min，得到陶瓷浆料。
步骤二、在搅拌条件下，向所述陶瓷浆料加入所述原料10~20wt%的发泡剂制成的泡沫，所述泡沫加入完毕，再持续搅拌30~60min，得到陶瓷泡沫浆料；所述泡沫中发泡剂和去离子水的质量比为1∶（10~15）。
步骤三、将所述陶瓷泡沫浆料倒入模具中，在室温条件和氮气环境中静置1~48h；然后在60~110℃条件下干燥12~24h，脱模，得到陶瓷坯体。
步骤四、将所述陶瓷坯体置于真空管式炉内，在氮气气氛条件下，先以5~10℃/min的速率升温至1100~1150℃，保温1~2h；再以1~4℃/min的速率升温至1200~1600℃，保温3~6h；然后自然冷却至室温，即得纳米线自增强多孔氮化硅陶瓷。
所述硅粉的纯度为85~99.9wt%；硅粉粒度为1~200μm。
所述催化剂为铁粉、钴粉、镍粉中的一种，纯度为99wt%以上；所述催化剂粒度为2~100μm。
所述氮源为叠氮化钠和氯化铵中的一种以上；所述氮源的纯度为99.0~99.9wt%。
所述发泡剂为烷基酚聚氧乙烯醚、脂肪醇聚氧乙烯醚、羟甲基纤维素钠和羟乙基纤维素中的一种以上。
由于采用上述技术方案，本发明与现有技术相比具有如下积极效果：
本发明以硅粉、催化剂和氮源为原料，成本低廉；其制备工艺是在原料中加入泡沫，搅拌，浇注成型，干燥，脱模，高温烧成，即得纳米线自增强多孔氮化硅陶瓷，工艺简单和过程易于控制。
本发明采用发泡法将泡沫引入陶瓷浆料中，干燥后得到具有多孔结构的陶瓷坯体；外部通入的氮气与陶瓷坯体表面的硅粉接触发生反应生成氮化硅，同时外部通入的氮气通过气孔进入坯体内部与硅粉发生反应生成氮化硅。氮源在高温下分解产生氮气，使陶瓷坯体内部的氮气浓度提高，促进氮气与硅粉的接触，提高硅粉氮化率同时促进氮化硅形成，原料利用率高。烧成后的纳米线自增强多孔氮化硅陶瓷物相均为Si3N4，无硅粉残留。
另外，催化剂与硅粉形成活性中心，使氮气与硅粉能在较低的热处理温度下发生反应，在反应过程中，催化剂与硅粉形成小液滴，硅蒸气和氮气溶解在液滴中。随着氮化硅晶粒的生长，少量的含催化剂小液滴将被不断推动并最终产生氮化硅纳米线。热处理过程中不生成有害物质，节能环保。原位生成的氮化硅纳米线起桥连作用，提升了纳米线自增强多孔氮化硅陶瓷的机械强度。纳米线自增强多孔氮化硅陶瓷内部气孔由氮化硅纳米线连接。烧成后得到的纳米线自增强多孔氮化硅陶瓷气孔大小均一，气孔分布均匀，抗折强度为20~30MPa，耐压强度为50~70MPa。
因此，本发明具有工艺简单、成本低廉、原料利用率高和过程易于控制的特点，所制备的纳米线自增强多孔氮化硅陶瓷气孔大小均一、气孔分布均匀和机械强度高。
附图说明
图1为本发明制备的一种纳米线自增强多孔氮化硅陶瓷的XRD图谱；
图2为图1所示纳米线自增强多孔氮化硅陶瓷SEM图。
具体实施方案
下面结合附图和具体实施方式对本发明作进一步描述，并非对其保护范围的限制。实施例中所述原料及试剂均市售可得。
为避免重复，先将本具体实施方式的原料统一描述如下，实施例中不再赘述：
所述硅粉的纯度为85~99.9wt%；硅粉粒度为1~200μm。
所述催化剂的纯度为99wt%以上；所述催化剂粒度为2~100μm。
所述氮源的纯度为99.0~99.9wt%。
实施例1
一种纳米线自增强多孔氮化硅陶瓷及其制备方法。本实施例所述制备方法的步骤是：
步骤一、以70~76wt%的硅粉、5~10wt%的催化剂和14~20wt%的氮源为原料，外加所述原料20~26wt%的去离子水，搅拌30~60min，得到陶瓷浆料。
步骤二、在搅拌条件下，向所述陶瓷浆料加入所述原料10~16wt%的发泡剂制成的泡沫，所述泡沫加入完毕，再持续搅拌30~60min，得到陶瓷泡沫浆料；所述泡沫中发泡剂和去离子水的质量比为1∶（10~13）。
步骤三、将所述陶瓷泡沫浆料倒入模具中，在室温条件和氮气环境中静置1~24h；然后在60~110℃条件下干燥12~24h，脱模，得到陶瓷坯体。
步骤四、将所述陶瓷坯体置于真空管式炉内，在氮气气氛条件下，先以5~10℃/min的速率升温至1100~1150℃，保温1~2h；再以1~4℃/min的速率升温至1200~1400℃，保温3~6h；然后自然冷却至室温，即得纳米线自增强多孔氮化硅陶瓷。
所述催化剂为铁粉。
所述氮源为叠氮化钠。
所述发泡剂为烷基酚聚氧乙烯醚。
本实施例制备的纳米线自增强多孔氮化硅陶瓷经检测：抗折强度为20~26MPa；耐压强度为50~60MPa。
实施例2
一种纳米线自增强多孔氮化硅陶瓷及其制备方法。本实施例除发泡剂外，其余同实施例1。
本实施例所述发泡剂为烷基酚聚氧乙烯醚和脂肪醇聚氧乙烯醚的混合物。
本实施例制备的纳米线自增强多孔氮化硅陶瓷经检测：抗折强度为20~26MPa；耐压强度为50~60MPa。
实施例3
一种纳米线自增强多孔氮化硅陶瓷及其制备方法。本实施例除发泡剂外，其余同实施例1。
本实施例所述发泡剂为脂肪醇聚氧乙烯醚、羟甲基纤维素钠和羟乙基纤维素的混合物。
本实施例制备的纳米线自增强多孔氮化硅陶瓷经检测：抗折强度为20~26MPa；耐压强度为50~60MPa。
实施例4
一种纳米线自增强多孔氮化硅陶瓷及其制备方法。本实施例所述制备方法的步骤是：
步骤一、以72~78wt%的硅粉、5~10wt%的催化剂和12~18wt%的氮源为原料，外加所述原料22~28wt%的去离子水，搅拌30~60min，得到陶瓷浆料。
步骤二、在搅拌条件下，向所述陶瓷浆料加入所述原料12~18wt%的发泡剂制成的泡沫，所述泡沫加入完毕，再持续搅拌30~60min，得到陶瓷泡沫浆料；所述泡沫中发泡剂和去离子水的质量比为1∶（11~14）。
步骤三、将所述陶瓷泡沫浆料倒入模具中，在室温条件和氮气环境中静置12~36h；然后在60~110℃条件下干燥12~24h，脱模，得到陶瓷坯体。
步骤四、将所述陶瓷坯体置于真空管式炉内，在氮气气氛条件下，先以5~10℃/min的速率升温至1100~1150℃，保温1~2h；再以1~4℃/min的速率升温至1300~1500℃，保温3~6h；然后自然冷却至室温，即得纳米线自增强多孔氮化硅陶瓷。
所述催化剂为钴粉。
所述氮源为氯化铵。
所述发泡剂为脂肪醇聚氧乙烯醚。
本实施例制备的纳米线自增强多孔氮化硅陶瓷经检测：抗折强度为26~30MPa；耐压强度为60~70MPa。
实施例5
一种纳米线自增强多孔氮化硅陶瓷及其制备方法。本实施例除发泡剂外，其余同实施例4。
本实施例所述发泡剂为脂肪醇聚氧乙烯醚和羟甲基纤维素钠的混合物。
本实施例制备的纳米线自增强多孔氮化硅陶瓷经检测：抗折强度为26~30MPa；耐压强度为60~70MPa。
实施例6
一种纳米线自增强多孔氮化硅陶瓷及其制备方法。本实施例除发泡剂外，其余同实施例4。
本实施例所述发泡剂为烷基酚聚氧乙烯醚、羟甲基纤维素钠和羟乙基纤维素的混合物。
本实施例制备的纳米线自增强多孔氮化硅陶瓷经检测：抗折强度为26~30MPa；耐压强度为60~70MPa。
实施例7
一种纳米线自增强多孔氮化硅陶瓷及其制备方法。本实施例所述制备方法的步骤是：
步骤一、以74~80wt%的硅粉、5~10wt%的催化剂和10~16wt%的氮源为原料，外加所述原料24~30wt%的去离子水，搅拌30~60min，得到陶瓷浆料。
步骤二、在搅拌条件下，向所述陶瓷浆料加入所述原料14~20wt%的发泡剂制成的泡沫，所述泡沫加入完毕，再持续搅拌30~60min，得到陶瓷泡沫浆料；所述泡沫中发泡剂和去离子水的质量比为1∶（12~15）。
步骤三、将所述陶瓷泡沫浆料倒入模具中，在室温条件和氮气环境中静置24~48h；然后在60~110℃条件下干燥12~24h，脱模，得到陶瓷坯体。
步骤四、将所述陶瓷坯体置于真空管式炉内，在氮气气氛条件下，先以5~10℃/min的速率升温至1100~1150℃，保温1~2h；再以1~4℃/min的速率升温至1400~1600℃，保温3~6h；然后自然冷却至室温，即得纳米线自增强多孔氮化硅陶瓷。
所述催化剂为镍粉。
所述氮源为叠氮化钠和氯化铵的混合物。
所述发泡剂为羟甲基纤维素钠或为羟乙基纤维素。
本实施例制备的纳米线自增强多孔氮化硅陶瓷经检测：抗折强度为24~28MPa；耐压强度为55~65MPa。
实施例8
一种纳米线自增强多孔氮化硅陶瓷及其制备方法。本实施例除发泡剂外，其余同实施例7。
本实施例所述发泡剂为羟甲基纤维素钠和羟乙基纤维素的混合物。
本实施例制备的纳米线自增强多孔氮化硅陶瓷经检测：抗折强度为24~28MPa；耐压强度为55~65MPa。
实施例9
一种纳米线自增强多孔氮化硅陶瓷及其制备方法。本实施例除发泡剂外，其余同实施例7。
本实施例所述发泡剂为烷基酚聚氧乙烯醚、脂肪醇聚氧乙烯醚、羟甲基纤维素钠和羟乙基纤维素的混合物。
本实施例制备的纳米线自增强多孔氮化硅陶瓷经检测：抗折强度为24~28MPa；耐压强度为55~65MPa。
本具体实施方式与现有技术相比具有如下积极效果：
本具体实施方式以硅粉、催化剂和氮源为原料，成本低廉；其制备工艺是在原料中加入泡沫，搅拌，浇注成型，干燥，脱模，高温烧成，即得纳米线自增强多孔氮化硅陶瓷，工艺简单和过程易于控制。
本具体实施方式采用发泡法将泡沫引入陶瓷浆料中，干燥后得到具有多孔结构的陶瓷坯体；外部通入的氮气与陶瓷坯体表面的硅粉接触发生反应生成氮化硅，同时外部通入的氮气通过气孔进入坯体内部与硅粉发生反应生成氮化硅。氮源在高温下分解产生氮气，使陶瓷坯体内部的氮气浓度提高，促进氮气与硅粉的接触，提高硅粉氮化率同时促进氮化硅形成。图1为实施例1制备的一种纳米线自增强多孔氮化硅陶瓷的XRD图谱，由图1可知，烧成后的纳米线自增强多孔氮化硅陶瓷物相均为Si3N4，无硅粉残留。
另外，催化剂与硅粉形成活性中心，使氮气与硅粉能在较低的热处理温度下发生反应，在反应过程中，催化剂与硅粉形成小液滴，硅蒸气和氮气溶解在液滴中。随着氮化硅晶粒的生长，少量的含催化剂小液滴将被不断推动并最终产生氮化硅纳米线。热处理过程中不生成有害物质，节能环保。原位生成的氮化硅纳米线起桥连作用，提升了纳米线自增强多孔氮化硅陶瓷的机械强度。图2为图1所示纳米线自增强多孔氮化硅陶瓷SEM图，由图2可知，纳米线自增强多孔氮化硅陶瓷内部气孔由氮化硅纳米线连接。烧成后得到的纳米线自增强多孔氮化硅陶瓷气孔大小均一，气孔分布均匀，抗折强度为20~30MPa，耐压强度为50~70MPa。
因此，本具体实施方式具有工艺简单、成本低廉、原料利用率高和过程易于控制的特点，所制备的纳米线自增强多孔氮化硅陶瓷气孔大小均一、气孔分布均匀和机械强度高。

Claims (3)

1.一种纳米线自增强多孔氮化硅陶瓷的制备方法，其特征在于所述制备方法的步骤：
步骤一、以70～80wt％的硅粉、5～10wt％的催化剂和10～20wt％的氮源为原料，外加所述原料20～30wt％的去离子水，搅拌30～60min，得到陶瓷浆料；
步骤二、在搅拌条件下，向所述陶瓷浆料加入所述原料10～20wt％的发泡剂制成的泡沫，所述泡沫加入完毕，再持续搅拌30～60min，得到陶瓷泡沫浆料；所述泡沫中发泡剂和去离子水的质量比为1∶(10～15)；
步骤三、将所述陶瓷泡沫浆料倒入模具中，在室温条件和氮气环境中静置1～48h；然后在60～110℃条件下干燥12～24h，脱模，得到陶瓷坯体；
步骤四、将所述陶瓷坯体置于真空管式炉内，在氮气气氛条件下，先以5～10℃/min的速率升温至1100～1150℃，保温1～2h；再以1～4℃/min的速率升温至1200～1600℃，保温3～6h；然后自然冷却至室温，即得纳米线自增强多孔氮化硅陶瓷；
所述催化剂为铁粉、钴粉、镍粉中的一种，纯度为99wt％以上；所述催化剂粒度为2～100μm；
所述氮源为叠氮化钠和氯化铵中的一种以上；所述氮源的纯度为99.0～99.9wt％；
所述发泡剂为烷基酚聚氧乙烯醚、脂肪醇聚氧乙烯醚、羟甲基纤维素钠和羟乙基纤维素中的一种以上。
2.根据权利要求1所述纳米线自增强多孔氮化硅陶瓷的制备方法，其特征在于所述硅粉的纯度为85～99.9wt％；硅粉粒度为1～200μm。
3.一种纳米线自增强多孔氮化硅陶瓷，其特征在于所述纳米线自增强多孔氮化硅陶瓷是根据权利要求1～2项中任一项所述纳米线自增强多孔氮化硅陶瓷的制备方法所制备的纳米线自增强多孔氮化硅陶瓷。
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