CN105948797B - 一种轻质多孔磷酸铝—铁铝尖晶石陶瓷球的制备方法 - Google Patents

一种轻质多孔磷酸铝—铁铝尖晶石陶瓷球的制备方法 Download PDF

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CN105948797B
CN105948797B CN201610283699.6A CN201610283699A CN105948797B CN 105948797 B CN105948797 B CN 105948797B CN 201610283699 A CN201610283699 A CN 201610283699A CN 105948797 B CN105948797 B CN 105948797B
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白佳海
高杰
杜庆洋
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Shandong University of Technology
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Abstract

一种轻质多孔磷酸铝—铁铝尖晶石陶瓷球的制备方法，其特征在于采用以下步骤：（1）把铁铝尖晶石粉末，氧化铝粉末，磷酸二氢铝粉末，熔块粉末按比例进行干混；（2）造粒、成型，制得圆柱状坯体；（3）在70℃干燥坯体5小时后，把坯体放到内底部为半圆球形的氧化铝坩埚内，在大气气氛下以5℃/min的速度加热升温到150℃并保温2小时，再以10‑20℃/min的速度加热升温到380℃并保温1个小时，然后以1℃/min的速度加热升温到680℃并保温2小时，最后在弱还原性气氛下以5℃/min的速度加热升温到1150℃并保温2个小时，随后自然冷却到室温，即制得轻质多孔磷酸铝—铁铝尖晶石陶瓷球。

Description

一种轻质多孔磷酸铝—铁铝尖晶石陶瓷球的制备方法
技术领域
本发明提供的是一种轻质多孔磷酸铝—铁铝尖晶石陶瓷球的制备方法，属于特种陶瓷材料制备技术领域。
背景技术
多孔磷酸铝（AlPO4）—铁铝尖晶石（FeAl2O4)陶瓷球在工业生产中的应用非常广泛，可以作为催化剂载体、化工填料、保温和耐火材料等。在作为光催化剂载体和其他液相反应催化剂载体，以及作为水中有毒物质的吸附剂时，为了保障具有高效的催化效果和（或）吸附效率，往往要求多孔陶瓷球在水中处于悬浮状态，这就需要制备一种轻质多孔陶瓷球。目前，国内外主要是采用易烧失的有机物制成的球体作为球形坯体的“芯”，然后通过烧成除去球形有机“芯”，从而制备一种可悬浮的多孔陶瓷空心球。该方法的缺点是：成型较困难，且在有机物烧失的过程中，易导致陶瓷开裂或破坏，降低产品的成品率；此外，这种工艺过程较复杂，成本较高，经济效益差，易污染环境。为了克服上述难题，本发明了提供了一种高效、简单、安全、可靠、易于操作、成本低廉的轻质多孔磷酸铝—铁铝尖晶石陶瓷球的制备方法。
发明内容
本发明技术提供一种高效、简单、安全、可靠、易于操作、成本低廉的轻质多孔磷酸铝—铁铝尖晶石陶瓷球的制备方法，其技术方案为：
一种轻质多孔磷酸铝—铁铝尖晶石陶瓷球的制备方法，其特征在于采用以下步骤：（1）把铁铝尖晶石粉末，氧化铝粉末，磷酸二氢铝粉末，熔块粉末按照质量比为2：1：3.11：0.03的比例进行干混；其中，熔块中含有50 wt%氧化锂、30 wt%的氧化钠和20 wt%的二氧化硅；（2）添加浓度为8 wt%的聚乙烯醇溶液作为粘结剂，粘结剂的添加量是坯料总质量的5%；然后造粒、成型，制得圆柱状坯体；（3）在70 ℃干燥坯体5小时后，把坯体放到内底部为半圆球形的氧化铝坩埚内，在大气气氛下以5 ℃/min的速度加热升温到150 ℃并保温2小时，再以10-20 ℃/min的速度加热升温到380 ℃并保温1个小时，然后以1 ℃/min的速度加热升温到680 ℃并保温2小时，最后在弱还原气氛下以5 ℃/min的速度加热升温到1150 ℃并保温2个小时，随后自然冷却到室温，即制得轻质多孔磷酸铝—铁铝尖晶石陶瓷球。
所述的一种轻质多孔磷酸铝—铁铝尖晶石陶瓷球的制备方法，其特征在于：步骤（1）中的铁铝尖晶石粉末和氧化粉末的平均粒径都为0.6微米，磷酸二氢铝粉末平均粒径为0.5微米，熔块粉末的平均粒径为0.7微米。
所述的一种轻质多孔磷酸铝—铁铝尖晶石陶瓷球的制备方法，其特征在于：步骤（2）中的成型指的是对粉体进行干压成型，成型压力为10-25MPa。
本技术发明的原理如下：
利用磷酸二氢铝在较低温度下可熔融为液体，然后在较高温度下又可凝固的性能，使得坯体在烧结过程中自发形成为球体，具体原理如下：把磷酸二氢铝加热到150 ℃、保温2小时后，磷酸二氢铝转变为为液态，然后快速加热到380 ℃并保温1小时，其目的是使各种原料在该温度下形成一种粘度很大的粘滞体。加入熔块的作用是一方面可以促进原料熔融为一种粘性很大的粘滞体，另一方面还可以增大表面张力，使得粘滞体能自发形成为球体。缓慢加热到680 ℃过程中，磷酸二氢铝逐渐凝固为固体；升温过程中，磷酸二氢铝会分解为磷酸铝、水蒸气和磷酸，生成的磷酸会和碳酸镁反应生成磷酸铝—铁铝尖晶石，而水蒸气和二氧化碳等具有成孔的作用，这样就可制备轻质多孔磷酸铝—铁铝尖晶石陶瓷。
具体实施方式
实施例1
把铁铝尖晶石粉末，氧化铝粉末，磷酸二氢铝粉末，熔块粉末按照质量比为2：1：3.11：0.03的比例进行干混；其中，熔块中含有50 wt%氧化锂、30 wt%的氧化钠和20 wt%的二氧化硅；控制铁铝尖晶石粉末和氧化粉末的平均粒径为0.6微米，磷酸二氢铝粉末平均粒径为0.5微米，熔块粉末的平均粒径为0.7微米；添加浓度为8 wt%的聚乙烯醇溶液作为粘结剂，粘结剂的添加量是坯料总质量的5%；然后造粒、用10MPa压力干压成型，制得圆柱状坯体；在70 ℃干燥坯体5小时后，把坯体放到内底部为半圆球形的氧化铝坩埚内，在大气气氛下以5 ℃/min的速度加热升温到150 ℃并保温2小时，再以10 ℃/min的速度加热升温到380 ℃并保温1个小时，然后以1 ℃/min的速度加热升温到680 ℃并保温2小时，最后在弱还原气氛下以5 ℃/min的速度加热升温到1150 ℃并保温2个小时，随后自然冷却到室温，即制得轻质多孔磷酸铝—铁铝尖晶石陶瓷球。用阿基米德法测得多孔陶瓷球的体积密度为0.93 g/cm3，开气孔率为38 %。用XRD分析测得陶瓷球的晶相为磷酸铝—铁铝尖晶石。
实施例2
铁铝尖晶石粉末，氧化铝粉末，磷酸二氢铝粉末，熔块粉末按照质量比为2：1：3.11：0.03的比例进行干混；其中，熔块中含有50 wt%氧化锂、30 wt%的氧化钠和20 wt%的二氧化硅；控制铁铝尖晶石粉末和氧化粉末的平均粒径为0.6微米，磷酸二氢铝粉末平均粒径为0.5微米，熔块粉末的平均粒径为0.7微米；添加浓度为8 wt%的聚乙烯醇溶液作为粘结剂，粘结剂的添加量是坯料总质量的5%；然后造粒、用20MPa压力干压成型，制得圆柱状坯体；在70 ℃干燥坯体5小时后，把坯体放到内底部为半圆球形的氧化铝坩埚内，在大气气氛下以5 ℃/min的速度加热升温到150 ℃并保温2小时，再以15 ℃/min的速度加热升温到380 ℃并保温1个小时，然后以1 ℃/min的速度加热升温到680 ℃并保温2小时，最后在弱还原气氛下以5 ℃/min的速度加热升温到1150 ℃并保温2个小时，随后自然冷却到室温，即制得轻质多孔磷酸铝—铁铝尖晶石陶瓷球。用阿基米德法测得多孔陶瓷球的体积密度为0.93 g/cm3，开气孔率为36 %。用XRD分析测得陶瓷球的晶相为磷酸铝—铁铝尖晶石。
实施例3
铁铝尖晶石粉末，氧化铝粉末，磷酸二氢铝粉末，熔块粉末按照质量比为2：1：3.11：0.03的比例进行干混；其中，熔块中含有50 wt%氧化锂、30 wt%的氧化钠和20 wt%的二氧化硅；控制铁铝尖晶石粉末和氧化粉末的平均粒径都为0.6微米，磷酸二氢铝粉末平均粒径为0.5微米，熔块粉末的平均粒径为0.7微米；添加浓度为8 wt%的聚乙烯醇溶液作为粘结剂，粘结剂的添加量是坯料总质量的5%；然后造粒、用25 MPa压力干压成型，制得圆柱状坯体；在70 ℃干燥坯体5小时后，把坯体放到内底部为半圆球形的氧化铝坩埚内，在大气气氛下以5 ℃/min的速度加热升温到150 ℃并保温2小时，再以20 ℃/min的速度加热升温到380 ℃并保温1个小时，然后以1 ℃/min的速度加热升温到680 ℃并保温2小时，最后在弱还原气氛下以5 ℃/min的速度加热升温到1150 ℃并保温2个小时，随后自然冷却到室温，即制得轻质多孔磷酸铝—铁铝尖晶石陶瓷球。用阿基米德法测得多孔陶瓷球的体积密度为0.95g/cm3，开气孔率为34 %。用XRD分析测得陶瓷球的晶相为磷酸铝—铁铝尖晶石。

Claims (2)

1.一种轻质多孔磷酸铝—铁铝尖晶石陶瓷球的制备方法，其特征在于采用以下步骤：（1）把铁铝尖晶石粉末，氧化铝粉末，磷酸二氢铝粉末，熔块粉末按照质量比为2：1：3.11：0.03的比例进行干混；其中，熔块中含有50 wt%氧化锂、30 wt%的氧化钠和20 wt%的二氧化硅；控制铁铝尖晶石粉末和氧化铝粉末的平均粒径都为0.6微米，磷酸二氢铝粉末平均粒径为0.5微米，熔块粉末的平均粒径为0.7微米; （2）添加浓度为8 wt%的聚乙烯醇溶液作为粘结剂，粘结剂的添加量是坯料总质量的5%；然后造粒、成型，制得圆柱状坯体；（3）在70 ℃干燥坯体5小时后，把坯体放到内底部为半圆球形的氧化铝坩埚内，在大气气氛下以5 ℃/min的速度加热升温到150 ℃并保温2小时，再以10-20 ℃/min的速度加热升温到380 ℃并保温1个小时，然后以1 ℃/min的速度加热升温到680 ℃并保温2小时，最后在弱还原性气氛下以5 ℃/min的速度加热升温到1150 ℃并保温2个小时，随后自然冷却到室温，即制得轻质多孔磷酸铝—铁铝尖晶石陶瓷球。
2.如权利要求1所述的一种轻质多孔磷酸铝—铁铝尖晶石陶瓷球的制备方法，其特征在于：步骤（2）中的成型指的是对粉体进行干压成型，成型压力为10-25MPa。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85100057A (zh) * 1985-04-01 1986-07-23 清华大学 高温应变粘结剂
US6022513A (en) * 1996-10-31 2000-02-08 Pecoraro; Theresa A. Aluminophosphates and their method of preparation
CN101242948A (zh) * 2005-06-27 2008-08-13 应用薄膜股份有限公司 基于磷酸铝的微球
CN104311109A (zh) * 2014-10-09 2015-01-28 山东理工大学 发泡注模、磷酸二氢铝胶结制备泡沫陶瓷的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85100057A (zh) * 1985-04-01 1986-07-23 清华大学 高温应变粘结剂
US6022513A (en) * 1996-10-31 2000-02-08 Pecoraro; Theresa A. Aluminophosphates and their method of preparation
CN101242948A (zh) * 2005-06-27 2008-08-13 应用薄膜股份有限公司 基于磷酸铝的微球
CN104311109A (zh) * 2014-10-09 2015-01-28 山东理工大学 发泡注模、磷酸二氢铝胶结制备泡沫陶瓷的方法

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