CN112028612B - 一种应用增强材料的镁碳砖 - Google Patents

一种应用增强材料的镁碳砖 Download PDF

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CN112028612B
CN112028612B CN202010911516.7A CN202010911516A CN112028612B CN 112028612 B CN112028612 B CN 112028612B CN 202010911516 A CN202010911516 A CN 202010911516A CN 112028612 B CN112028612 B CN 112028612B
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carbon brick
magnesia carbon
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曹丽云
龚育才
彭仁
俞晓东
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Jiangsu Sujia Group New Materials Co ltd
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Abstract

本发明公开了一种应用增强材料的镁碳砖，涉及镁碳砖技术领域，其配料含有A组分、B组分和C组分，所述A组分、B组分和C组分之间的含量比为3:1：0.5，所述A组分由电熔镁砂、鳞片状石墨、有机结合剂、抗氧化剂和单晶α‑Al2O3纤维组成，按含量比计，电熔镁砂：鳞片状石墨：有机结合剂：抗氧化剂：单晶α‑Al2O3纤维＝3:1：4：0.3：0.2，所述B组分由铜、铍和三氟甲基苯组成，按含量比计，铜：铍：三氟甲基苯＝1：1：1，所述C组分由活性氧化铝和吸水树脂组成，按含量比计，活性氧化铝：吸水树脂＝1:1。该应用增强材料的镁碳砖，添加有单晶α‑Al2O3纤维，在将单晶α‑Al2O3纤维应用于镁碳砖的生产制备上，极大地改善了镁碳砖的产品性能，提高了镁碳砖的强度。

Description

一种应用增强材料的镁碳砖
技术领域
本发明涉及镁碳砖技术领域，具体为一种应用增强材料的镁碳砖。
背景技术
镁碳砖的主要原料包括电熔镁砂或烧结镁砂、鳞片状石墨、有机结合剂以及抗氧化剂，生产镁碳砖常用的结合剂有煤焦油、煤沥青和石油沥青，以及特殊碳质树脂、多元醇、沥青变性酚醛树脂、合成树脂等，常见的抗氧化剂有Si、Al、Mg、Al-Si、Al-Mg、Al-Mg-Ca、Si-Mg-Ca、SiC、B4C、BN等添加剂。
镁碳砖具有良好的耐高温性能，抗渣能力强，抗热震性好，高温蠕变低，相比传统砖块产品而言，镁碳砖具有更好的市场优势。
现有的镁碳砖为增强强度，多选择在其中添加高性能无机纤维，如碳化硅、碳纤维、氧化铝等材料，这些非氧化物纤维在高温下虽然具有很好的抗蠕变性，但缺乏化学稳定性，如高硅氧纤维复合材料在800℃以上会出现二氧化硅-碳-氧相分解而造成材料缺陷，而碳基纤维在500℃以上会与氧发生反应，这些都是造成镁碳砖性能下降的关键性原因。
发明内容
针对现有技术的不足，本发明提供了一种应用增强材料的镁碳砖，解决了上述背景技术中提出的问题。
为实现以上目的，本发明通过以下技术方案予以实现：一种应用增强材料的镁碳砖，其配料含有A组分、B组分和C组分，所述A组分、B组分和C组分之间的含量比为3:1：0.5，所述A组分由电熔镁砂、鳞片状石墨、有机结合剂、抗氧化剂和单晶α-Al2O3纤维组成，按含量比计，电熔镁砂：鳞片状石墨：有机结合剂：抗氧化剂：单晶α-Al2O3纤维＝3:1：4：0.3：0.2，所述B组分由铜、铍和三氟甲基苯组成，按含量比计，铜：铍：三氟甲基苯＝1：1：1，所述C组分由活性氧化铝和吸水树脂组成，按含量比计，活性氧化铝：吸水树脂＝1:1。
可选的，所述A组分中，有机结合剂为沥青变性酚醛树脂和苯酚-甲醛合成树脂的混合体。
可选的，所述A组分中，抗氧化剂为Al-B-C、Al-SiC-C中的一种。
可选的，所述单晶α-Al2O3纤维的制备过程如下：
①将半埋于SiO2粉体(含有Ni作为催化剂)中的单质Al熔化蒸发形成Al蒸气，并与SiO2反应，生成Al和Si的氧化物；
②Al和Si的气相氧化物继续反应生成Al2O3和Si(l)；
③Si(l)形成能够溶解气态物质的液滴，并缓慢溶解含有Al和SiO2的气相，故液滴始终存在于纤维的顶端，维持纤维生长；
④反应过程中，最初的液滴沉积在反应的基底上，形成半球形，当液滴中Al2O3含量饱和时，Al2O3单晶开始形成，并逐渐析出；
⑤随着成核过程的发生，Al2O3继续发生外延生长，从而获得单晶α-Al2O3纤维。
可选的，所述B组分中，铜和铍均选用粉末态，且均过100目筛。
可选的，所述C组分的制取过程为：将活性氧化铝和吸水树脂进行搅拌混合，至混合均匀。
可选的，该应用增强材料的镁碳砖的制备包括下述工艺步骤：
①将A组分中，电熔镁砂、鳞片状石墨、有机结合剂和抗氧化剂混合均匀后，加入单晶α-Al2O3纤维，混合至均匀；
②将铜和铍分别加入到A组分中，搅拌混合；
③铜和铍完全加入后，边搅拌，便向空气中引入三氟甲基苯，使在镁砂表面上生成氟化镁保护膜；
④加入混合均匀的C组分，并搅拌混合，搅拌2h；
⑤上模具，开始板砖烧结。
本发明提供了一种应用增强材料的镁碳砖，具备以下有益效果：
1、该应用增强材料的镁碳砖，添加有单晶α-Al2O3纤维，单晶α-Al2O3纤维具有显著优于多晶氧化物纤维和其他无机纤维的优越性能，具有高硬度、高强度、优异的电学性能和机械性能，克服了多晶氧化铝纤维在高温下力学性能下降的缺点，可在1500℃以上的高温和强氧化、强还原、强腐蚀条件下使用，在将单晶α-Al2O3纤维应用于镁碳砖的生产制备上，极大地改善了镁碳砖的产品性能，提高了镁碳砖的强度。
2、该应用增强材料的镁碳砖，添加有铜、铍和三氟甲基苯，铜和铍均能使镁的氧化速度下降，铍的抗氧化效果更明显，它对镁、直到熔化温度，长期都有保护作用，故而铜和铍的加入能够保证镁的品质，同样的，三氟甲基苯的加入，也能有效降低镁的氧化速率。
3、该应用增强材料的镁碳砖，添加有活性氧化铝和吸水树脂，活性氧化铝和吸水树脂均具有吸水性，能够吸收掉镁碳砖生产过程中或成品中的水分，使得镁碳砖保持足够的干燥度，进而保证产品品质。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。
实施例1
一种应用增强材料的镁碳砖，其配料含有A组分、B组分和C组分，所述A组分、B组分和C组分之间的含量比为3:1：0.5，所述A组分由电熔镁砂、鳞片状石墨、有机结合剂、抗氧化剂和单晶α-Al2O3纤维组成，按含量比计，电熔镁砂：鳞片状石墨：有机结合剂：抗氧化剂：单晶α-Al2O3纤维＝3:1：4：0.3：0.2，所述B组分由铜、铍和三氟甲基苯组成，按含量比计，铜：铍：三氟甲基苯＝1：1：1，所述C组分由活性氧化铝和吸水树脂组成，按含量比计，活性氧化铝：吸水树脂＝1:1；
A组分中，有机结合剂为沥青变性酚醛树脂和苯酚-甲醛合成树脂的混合体；
A组分中，抗氧化剂为Al-B-C、Al-SiC-C中的一种；
单晶α-Al2O3纤维的制备过程为：①将半埋于SiO2粉体(含有Ni作为催化剂)中的单质Al熔化蒸发形成Al蒸气，并与SiO2反应，生成Al和Si的氧化物；②Al和Si的气相氧化物继续反应生成Al2O3和Si(l)；③Si(l)形成能够溶解气态物质的液滴，并缓慢溶解含有Al和SiO2的气相，故液滴始终存在于纤维的顶端，维持纤维生长；④反应过程中，最初的液滴沉积在反应的基底上，形成半球形，当液滴中Al2O3含量饱和时，Al2O3单晶开始形成，并逐渐析出；⑤随着成核过程的发生，Al2O3继续发生外延生长，从而获得单晶α-Al2O3纤维；
具体的，单晶α-Al2O3纤维具有显著优于多晶氧化物纤维和其他无机纤维的优越性能，具有高硬度、高强度、优异的电学性能和机械性能，克服了多晶氧化铝纤维在高温下力学性能下降的缺点，可在1500℃以上的高温和强氧化、强还原、强腐蚀条件下使用，在将单晶α-Al2O3纤维应用于镁碳砖的生产制备上，极大地改善了镁碳砖的产品性能，提高了镁碳砖的强度；
B组分中，铜和铍均选用粉末态，且均过100目筛；
铜和铍均能使镁的氧化速度下降，铍的抗氧化效果更明显，它对镁、直到熔化温度，长期都有保护作用，故而铜和铍的加入能够保证镁的品质，同样的，三氟甲基苯的加入，也能有效降低镁的氧化速率；
C组分的制取过程为：将活性氧化铝和吸水树脂进行搅拌混合，至混合均匀；
进一步地，活性氧化铝和吸水树脂均具有吸水性，能够吸收掉镁碳砖生产过程中或成品中的水分，使得镁碳砖保持足够的干燥度。
实施例2
一种应用增强材料的镁碳砖的制备包括下述工艺步骤：
①将A组分中，电熔镁砂、鳞片状石墨、有机结合剂和抗氧化剂混合均匀后，加入单晶α-Al2O3纤维，混合至均匀；
②将铜和铍分别加入到A组分中，搅拌混合；
③铜和铍完全加入后，边搅拌，便向空气中引入三氟甲基苯，使在镁砂表面上生成氟化镁保护膜；
④加入混合均匀的C组分，并搅拌混合，搅拌2h；
⑤上模具，开始板砖烧结。
综上，该应用增强材料的镁碳砖，添加有单晶α-Al2O3纤维，单晶α-Al2O3纤维具有显著优于多晶氧化物纤维和其他无机纤维的优越性能，具有高硬度、高强度、优异的电学性能和机械性能，克服了多晶氧化铝纤维在高温下力学性能下降的缺点，可在1500℃以上的高温和强氧化、强还原、强腐蚀条件下使用，在将单晶α-Al2O3纤维应用于镁碳砖的生产制备上，极大地改善了镁碳砖的产品性能，提高了镁碳砖的强度。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。

Claims (4)

1.一种应用增强材料的镁碳砖，其特征在于：应用增强材料的镁碳砖配料含有A组分、B组分和C组分，所述A组分、B组分和C组分之间的含量比为3:1:0.5，所述A组分由电熔镁砂、鳞片状石墨、有机结合剂、抗氧化剂和单晶
Figure 965532DEST_PATH_IMAGE001
纤维组成，按含量比计，电熔镁砂:鳞片状石墨:有机结合剂:抗氧化剂: 单晶
Figure 420784DEST_PATH_IMAGE002
纤维=3:1:4:0.3:0.2，所述B组分由铜、铍和三氟甲基苯组成，按含量比计，铜:铍:三氟甲基苯=1:1:1，所述C组分由活性氧化铝和吸水树脂组成，按含量比计，活性氧化铝:吸水树脂=1:1；
所述A组分中，有机结合剂为沥青变性酚醛树脂和苯酚-甲醛合成树脂的混合体；
所述A组分中，抗氧化剂为Al-B-C、Al-SiC-C中的一种；
该应用增强材料的镁碳砖的制备包括下述工艺步骤：
①A组分中，电熔镁砂、鳞片状石墨、有机结合剂和抗氧化剂混合均匀后，加入单晶
Figure 586186DEST_PATH_IMAGE003
纤维，混合至均匀；
②将铜和铍分别加入到A组分中，搅拌混合；
③铜和铍完全加入后，边搅拌，便向空气中引入三氟甲基苯，使在镁砂表面上生成氟化镁保护膜；
④加入混合均匀的C组分，并搅拌混合，搅拌2h；
⑤上模具，开始板砖烧结。
2.根据权利要求1所述的一种应用增强材料的镁碳砖，其特征在于：所述单晶
Figure 932723DEST_PATH_IMAGE004
纤维的制备过程如下：
①将半埋于
Figure 499970DEST_PATH_IMAGE005
粉体中的单质Al熔化蒸发形成Al蒸气，并与
Figure 126124DEST_PATH_IMAGE005
反应，生成Al和Si的氧化物，其中，所述
Figure 44401DEST_PATH_IMAGE005
粉体含有用着Ni，Ni作为催化剂；
②Al和Si的气相氧化物继续反应生成
Figure 679782DEST_PATH_IMAGE006
和Si（l）；
③Si（l）形成能够溶解气态物质的液滴，并缓慢溶解含有Al和
Figure 852268DEST_PATH_IMAGE007
的气相，故液滴始终存在于纤维的顶端，维持纤维生长；
④过程中，最初的液滴沉积在反应的基底上，形成半球形，当液滴中
Figure 914902DEST_PATH_IMAGE008
含量饱和时，
Figure 789317DEST_PATH_IMAGE008
单晶开始形成，并逐渐析出；
⑤随着成核过程的发生，
Figure 493968DEST_PATH_IMAGE008
继续发生外延生长，从而获得单晶
Figure 770229DEST_PATH_IMAGE009
纤维。
3.根据权利要求1所述的一种应用增强材料的镁碳砖，其特征在于：所述B组分中，铜和铍均选用粉末态，且均过100目筛。
4.根据权利要求1所述的一种应用增强材料的镁碳砖，其特征在于：所述C组分的制取过程为：将活性氧化铝和吸水树脂进行搅拌混合，至混合均匀。
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