CN110511032A - 一种提高氮化物结合碳化硅材料抗氧化性能的烧结方法 - Google Patents

一种提高氮化物结合碳化硅材料抗氧化性能的烧结方法 Download PDF

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CN110511032A
CN110511032A CN201910891154.7A CN201910891154A CN110511032A CN 110511032 A CN110511032 A CN 110511032A CN 201910891154 A CN201910891154 A CN 201910891154A CN 110511032 A CN110511032 A CN 110511032A
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silicon carbide
carbide material
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combined silicon
nitride
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王佳平
黄志刚
王文武
李�杰
吴吉光
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Sinosteel Luoyang Institute of Refractories Research Co Ltd
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Abstract

本发明提供一种提高氮化物结合碳化硅材料抗氧化性能的烧结方法，属于耐火材料技术领域，其方法为：在氮化物结合碳化硅材料完成氮化烧结后，在1100℃~1400℃温度范围内，先通入纯O2/H2O混合气体，并保温1~15小时进行“湿氧”保护性氧化，之后，开始通入纯O2气体，并保温1~10小时进行“干氧”保护性氧化，氧化过程中炉内保持正压。本发明所述提高氮化物结合碳化硅材料抗氧化性能的烧结方法，工艺设计简单，工艺过程易于控制，且该方法是在氮化物/氮氧化物结合碳化硅材料完成氮化烧结以后直接进行保护性氧化，属于一次完成制品的烧结，节省能源，适用于工业化生产。

Description

一种提高氮化物结合碳化硅材料抗氧化性能的烧结方法
技术领域
本发明涉及一种提高氮化物结合碳化硅材料抗氧化性能的烧结方法，尤其是涉及一种通过控制气氛，并使氮化、保护性氧化连续一次完成的高抗氧化性氮化物结合碳化硅材料烧结方法。
背景技术
氮化物结合碳化硅材料因其具有热导率大、线膨胀系数小、常温和高温强度高、抗热震性好、耐化学腐蚀和高温耐磨性优良等优异性能，在钢铁、有色冶金、化学、电力、陶瓷和垃圾焚烧发电等领域均有广泛应用。
氮化物结合碳化硅材料属于非氧化物耐火材料，易氧化，因此上述材料的烧结过程必须是采用非氧化烧结气氛，目前在耐火材料工业中普遍采用金属硅和碳化硅为原料的氮化反应烧结法，但仅通过氮化反应烧结法生产出来的氮化物结合碳化硅材料在高温使用的过程中经常遇到氧化损毁的问题，尤其是在水蒸气含量较高的工况环境中，氧化损坏的情况更明显，损毁速度更快。因此，如何提高氮化物结合碳化硅材料的抗氧化性能，尤其是抗高温水蒸气氧化性能，一直是行业亟待解决的问题。美国专利US8003557B2中报道通过添加硼化物的方法来提高氮化物/氮氧化物结合碳化硅材料的抗高温水蒸气氧化性能，专利中介绍的烧结气氛为氮气气氛或氧气和氮气的混合气氛。
然而，在氮化物结合碳化硅材料完成烧结以后，再采用“湿氧-干氧”气氛（湿氧即氧气和水蒸气的混合气体）来提高氮化物结合碳化硅材料抗氧化性能的方法却十分少见。为了便于理解上述方法，下面简要分析该方法的原理和可行性。氮化物结合碳化硅材料在使用过程中氧化损坏主要是由于Si3N4、Si2N2O、SiC分别与O2、H2O (g)发生了以下反应：
Si3N4(s) + 3O2 (g) = 3SiO2(s) + 2N2 (g)
Si2N2O(s) +1.5 O2 (g) = 2SiO2(s) + N2 (g)
SiC (s) + 2 O2 (g) = SiO2(s) +CO2 (g)
Si3N4(s) + 6H2O (g) =3SiO2(s) + 6H2 (g) + 2N2 (g)
Si2N2O(s) + 3H2O (g) =2SiO2(s) + 3H2 (g) + N2 (g)
SiC(s) + 3H2O (g) =SiO2(s) + CO (g)+3H2(g)
从上述反应中可以看到SiO2在高氧高水蒸气含量的环境中是稳定相，之所以在高温使用过程中氧化产物SiO2未能对材料形成保护，主要原因是在于生成的SiO2不是连续的，而且在高温使用过程中，有时候会因为冲刷等原因不断的产生剥落。
发明内容
如果氮化物结合碳化硅材料在使用之前就在材料的表面覆盖上一层连续的、合适厚度的SiO2氧化膜层，在高温使用过程中就能有效的阻碍氧气和水蒸气对氮化物结合碳化硅材料的氧化破坏。但如何能使氮化物结合碳化硅材料的表面生成连续的、合适厚度的SiO2氧化膜层：在集成电路半导体行业，就是利用二氧化硅的掩蔽作用来实现部件的绝缘，工艺上对硅片进行热氧化，即在硅片的表面形成一层结构致密、厚度合适的二氧化硅层，为了兼顾效率和质量，通常采用“干氧-湿氧-干氧”氧化相结合的工艺方式。Si3N4、Si2N2O、SiC的氧化和Si的氧化原理相通。
本发明的目的是提出一种提高氮化物结合碳化硅材料抗氧化性能的烧结方法，通过控制气氛，采用“湿氧-干氧”相结合方式来提高氮化物结合碳化硅材料抗氧化性能的方法，且该方法是在氮化物结合碳化硅材料完成氮化烧结以后直接进行保护性氧化，无须重复从常温加热。
本发明提出了一种提高氮化物结合碳化硅材料抗氧化性能的烧结方法，包括在氮化物结合碳化硅材料完成氮化烧结后，向装有氮化物结合碳化硅材料的窑炉内，通入纯O2/H2O混合气体或纯O2气体经历“湿氧-干氧”过程进行保护性氧化，用流量计控制气体的流量以及混合气体的比例，同时观测U型管内水柱高度差，确保窑内处于正压状态，其烧结过程如下：在氮化物结合碳化硅材料完成氮化烧结后，在1100℃~1400℃温度范围内，先通入纯O2/H2O混合气体，并保温1~15小时进行“湿氧”保护性氧化，之后，开始通入纯O2气体，并保温1~10小时进行“干氧”保护性氧化，其中所述纯O2气体是指O2含量≥99%的干氧气体；所述纯O2/H2O混合气体中，按体积百分数计算，纯O2（O2含量≥99%）2~98%，H2O（g）2~98%；所述正压力范围在10~30毫米水柱。
本发明所述的提高氮化物结合碳化硅材料抗氧化性能烧结方法，其中所述正压力范围在15~25毫米水柱，所述纯O2/H2O混合气体中，按体积百分数计算，纯O2（O2含量≥99%）5~95%，H2O（g）5~95%；
本发明所述提高氮化物结合碳化硅材料抗氧化性能的烧结方法，工艺设计简单，工艺过程易于控制，且该方法是在氮化物结合碳化硅材料完成氮化烧结以后直接进行保护性氧化，属于一次完成材料的烧结，节省能源，适用于工业化生产。
附图说明
图1是本发明的高抗氧化性氮化物结合碳化硅材料烧结设备示意图。
图中：1：空气流量计、2：水蒸气流量计，3：气体混合装置，4：窑炉，5：氮化物结合碳化硅材料，6： U型管，7：水柱。
具体实施方式
下面结合图1，对本发明所述的烧结方法在实施例中进行详细描述。其中本发明所述的氮化物结合碳化硅材料不限于实施例中提到的几种物质，只要该材料中以氮化物或氮氧化物或氮化物/氮氧化物为结合相，碳化硅含量≥50%（按百分比重量计），都属于本发明所述的氮化物结合碳化硅材料，都属于本发明的保护范围。
实施例1
氮化物结合碳化硅材料选用的原料及原料组成（按百分比重量计）为：SiC颗粒75%，SiC细粉10%，Si粉15%，经压制成型后装入窑炉内，经1300℃氮化烧结后，待炉内温度降到1100℃，经过流量计控制，向窑内通入2%纯O2和98%H2O(g)的混合气体，观察U型管内水柱高度差，使窑内压力保持在10mm水柱，在1100℃保温15小时进行“湿氧”保护性氧化，随后通入纯O2气体，观察U型管内水柱高度差，使窑内压力保持在10mm水柱，在1100℃保温10小时进行“干氧”保护性氧化。比较例1为相同试样仅经1300℃氮化烧结、不经历保护性氧化处理过程，比较例1氮化过程与实施例1保持一致。
从实施例1和比较例1烧成后的材料上各切取3个尺寸为165×114×22mm的试样，测试试样的体积和质量，然后放入试验炉。按照ASTM-C863标准升温至1000℃，以32kg/(m3.h)的速率通入水蒸汽，保温500小时。待停炉降温后，取出试样测试其氧化后体积和质量，计算体积变化率和质量变化率，取平均值。以测试前后试样的体积变化率作为评判材料抗氧化性能的标准，体积变化率越小，其抗氧化性能越好，测试前后试样的重量变化率仅为参考指标。结果见表1。
实施例2
氮化物结合碳化硅材料选用的原料及原料组成（按百分比重量计）为：SiC颗粒70%，SiC细粉11.5%，Si粉16%，SiO2微粉2.5%，经压制成型后装入电炉窑内，经1350℃氮化烧结后，待炉内温度降到1100℃，经过流量计控制，向窑内通入60%纯O2和40%H2O(g)的混合气体，观察U型管内水柱高度差，使窑内压力保持在20mm水柱，在1100℃保温8小时进行“湿氧”保护性氧化，随后停止通气将炉内温度升高至1300℃，通入纯O2气体，观察U型管内水柱高度差，使窑内压力保持在25mm水柱，在1300℃保温6小时进行“干氧”保护性氧化。比较例2为相同试样仅经1350℃氮化烧结、不经历保护性氧化处理过程，比较例2氮化过程与实施例2保持一致。
从实施例2和比较例2烧成后的材料上各切取3个尺寸为165×114×22mm的试样，测试试样的体积和质量，然后放入试验炉。按照ASTM-C863标准升温至1000℃，以32kg/(m3.h)的速率通入水蒸汽，保温500小时。待停炉降温后，取出试样测试其氧化后体积和质量，计算体积变化率和质量变化率，取平均值。以测试前后试样的体积变化率作为评判材料抗氧化性能的标准，体积变化率越小，其抗氧化性能越好，测试前后试样的重量变化率仅为参考指标。结果见表2。
实施例3
氮化物结合碳化硅材料选用的原料及原料组成（按百分比重量计）为：SiC颗粒70%，SiC细粉22%，Si粉6%，SiO2微粉2%，经压制成型后装入电炉窑内，经1420℃氮化烧结后，待炉内温度降到1400℃，经过流量计控制，向窑内通入70%纯O2和30%H2O(g)的混合气体，观察U型管内水柱高度差，使窑内压力保持在15mm水柱，在1400℃保温1小时进行“湿氧”保护性氧化，随后通入纯O2气体，观察U型管内水柱高度差，使窑内压力保持在15mm水柱，在1400℃保温1小时进行“干氧”保护性氧化。比较例3为相同试样仅经1420℃氮化烧结、不经历保护性氧化处理过程，比较例3氮化过程与实施例3保持一致。
从实施例3和比较例3烧成后的材料上各切取3个尺寸为165×114×22mm的试样，测试试样的体积和质量，然后放入试验炉。按照ASTM-C863标准升温至1000℃，以32kg/(m3.h)的速率通入水蒸汽，保温500小时。待停炉降温后，取出试样测试其氧化后体积和质量，计算体积变化率和质量变化率，取平均值。以测试前后试样的体积变化率作为评判材料抗氧化性能的标准，体积变化率越小，其抗氧化性能越好，测试前后试样的重量变化率仅为参考指标。结果见表3。
实施例4
氮化物结合碳化硅材料选用的原料及原料组成（按百分比重量计）为：SiC颗粒65%，SiC细粉10%，Si粉20%，SiO2微粉5%，经压制成型后装入电炉窑内，经1350℃氮化烧结后，待炉内温度将至1200℃，经过流量计控制，向窑内通入98%纯O2和2%H2O(g)的混合气体，观察U型管内水柱高度差，使窑内压力保持在30mm水柱，在1200℃保温10小时进行“湿氧”保护性氧化，随后通入纯O2气体，观察U型管内水柱高度差，使窑内压力保持在30mm水柱，在1200℃保温6小时进行“干氧”保护性氧化。比较例4为相同试样仅经1350℃氮化烧结、不经历保护性氧化处理过程，比较例4氮化过程与实施例4保持一致。
从实施例4和比较例4烧成后的材料上各切取3个尺寸为165×114×22mm的试样，测试试样的体积和质量，然后放入试验炉。按照ASTM-C863标准升温至1000℃，以32kg/(m3.h)的速率通入水蒸汽，保温500小时。待停炉降温后，取出试样测试其氧化后体积和质量，计算体积变化率和质量变化率，取平均值。以测试前后试样的体积变化率作为评判材料抗氧化性能的标准，体积变化率越小，其抗氧化性能越好，测试前后试样的重量变化率仅为参考指标。结果见表4。
实施例5
氮化物结合碳化硅材料选用的原料及原料组成（按百分比重量计）为：SiC颗粒60%，SiC细粉20%，Si粉15%，SiO2微粉5%，经压制成型后装入电炉窑内，经1380℃氮化烧结后，待温度降至1300℃，经过流量计控制，向窑内通入50%纯O2和50%H2O(g)的混合气体，观察U型管内水柱高度差，使窑内压力保持在25mm水柱，在1300℃保温6小时进行“湿氧”保护性氧化，随后通入纯O2气体，观察U型管内水柱高度差，使窑内压力保持在20mm水柱，在1300℃保温8小时进行“干氧”保护性氧化。比较例5为相同试样仅经1380℃氮化烧结、不经历保护性氧化处理过程，比较例5氮化过程与实施例5保持一致。
从实施例5和比较例5烧成后的材料上各切取3个尺寸为165×114×22mm的试样，测试试样的体积和质量，然后放入试验炉。按照ASTM-C863标准升温至1000℃，以32kg/(m3.h)的速率通入水蒸汽，保温500小时。待停炉降温后，取出试样测试其氧化后体积和质量，计算体积变化率和质量变化率，取平均值。以测试前后试样的体积变化率作为评判材料抗氧化性能的标准，体积变化率越小，其抗氧化性能越好，测试前后试样的重量变化率仅为参考指标。结果见表5。
从以上5个实施例检测结果可以看出，相同的碳化硅材料，经过本发明所提供的烧结方法处理后，其抗氧化性能明显提高。

Claims (4)

1.一种提高氮化物结合碳化硅材料抗氧化性能的烧结方法，其特征在于：在氮化物结合碳化硅材料完成氮化烧结后，向装有氮化物结合碳化硅材料的窑炉内，通入纯O2/H2O混合气体或纯O2气体经历“湿氧-干氧”过程进行保护性氧化，用流量计控制气体的流量以及混合气体的比例，同时观测U型管内水柱高度差，确保窑内处于正压状态，其烧结过程如下：在氮化物结合碳化硅材料完成氮化烧结后，在1100℃~1400℃温度范围内，先通入纯O2/H2O混合气体，并保温1~15小时进行“湿氧”保护性氧化，之后，开始通入纯O2气体，并保温1~10小时进行“干氧”保护性氧化，其中所述纯O2气体是指O2含量≥99%的干氧气体；所述纯O2/H2O混合气体中，按体积百分数计算，纯O2 2~98%，H2O（g）2~98%；所述正压状态的压力范围在10~30毫米水柱。
2.如权利要求1所述一种提高氮化物结合碳化硅材料抗氧化性能的烧结方法，其特征在于：所述氮化物结合碳化硅材料，包括所有以氮化物或氮氧化物或氮化物/氮氧化物为结合相，碳化硅含量≥50%（按百分比重量计）的材料。
3.如权利要求1所述一种提高氮化物结合碳化硅材料抗氧化性能的烧结方法，其特征在于：所述正压状态的压力范围在15~25毫米水柱。
4.如权利要求1所述一种提高氮化物结合碳化硅材料抗氧化性能的烧结方法，其特征在于：所述纯O2/H2O混合气体中，按体积百分数计算，纯O2 （O2含量≥99%）5~95%，H2O（g）5~95%。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111781086A (zh) * 2020-08-11 2020-10-16 中钢集团洛阳耐火材料研究院有限公司 一种快速检测碳化硅耐火材料高温抗氧化性的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101555161A (zh) * 2008-04-11 2009-10-14 中国科学院金属研究所 一种提高碳化硅泡沫陶瓷高温抗氧化性能的表面改性方法
KR20150030872A (ko) * 2013-09-13 2015-03-23 한국기계연구원 나노급 금속, 탄화물 또는 질화물 분말의 산화를 방지하거나 산소와의 반응을 방지하기 위한 분말 처리방법
CN107602153A (zh) * 2017-08-03 2018-01-19 彩虹（合肥）液晶玻璃有限公司 一种SiC板表面氧化层快速增厚的方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
HUE029210T2 (en) 2008-06-13 2017-02-28 Saint-Gobain Ceram & Plastics Inc Volume Resistant Silicon Oxynitride Bound Silicon Carbide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101555161A (zh) * 2008-04-11 2009-10-14 中国科学院金属研究所 一种提高碳化硅泡沫陶瓷高温抗氧化性能的表面改性方法
KR20150030872A (ko) * 2013-09-13 2015-03-23 한국기계연구원 나노급 금속, 탄화물 또는 질화물 분말의 산화를 방지하거나 산소와의 반응을 방지하기 위한 분말 처리방법
CN107602153A (zh) * 2017-08-03 2018-01-19 彩虹（合肥）液晶玻璃有限公司 一种SiC板表面氧化层快速增厚的方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王黎 等: "Si3N4结合SiC复相材料的高温氧化行为", 《兵器材料科学与工程》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111781086A (zh) * 2020-08-11 2020-10-16 中钢集团洛阳耐火材料研究院有限公司 一种快速检测碳化硅耐火材料高温抗氧化性的方法

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