CN110526702B - 一种碳复合锰锌铁氧体宽频吸波材料的制备方法 - Google Patents

一种碳复合锰锌铁氧体宽频吸波材料的制备方法 Download PDF

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CN110526702B
CN110526702B CN201910966802.0A CN201910966802A CN110526702B CN 110526702 B CN110526702 B CN 110526702B CN 201910966802 A CN201910966802 A CN 201910966802A CN 110526702 B CN110526702 B CN 110526702B
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manganese
zinc ferrite
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汪嘉恒
杨标
张勇
吴玉程
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Hefei University of Technology
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Abstract

本发明公开了一种碳复合锰锌铁氧体宽频吸波材料的制备方法，通过对热处理气氛以及原料成分和配比进行优化，增强尖晶石结构微波磁性能的同时，使粉体成型工艺中必须的聚合物造粒剂碳化，碳在锰锌铁氧体晶界位置的复合大幅提升了吸波材料的介电性能和阻抗匹配，降低了晶界空气隙密度，从而增强了吸波性能和有效频宽。本发明制备的碳复合锰锌铁氧体吸波材料适用于9kHz～42.5GHz超宽频段的吸波应用，通过0～10cm的吸波体厚度调节可以实现该范围内不同频带的有效电磁波吸收。

Description

一种碳复合锰锌铁氧体宽频吸波材料的制备方法
技术领域
本发明涉及一种具有宽频带电磁波吸收性能的碳复合锰锌铁氧体宽频吸波材料的制备方法，属于电磁功能材料领域。
背景技术
电磁兼容(EMC)认证已经成为目前世界各国电子电气产品上市的强制标准，满足EMC标准的产品，不仅需要具有极小的电磁干扰(EMI)，而且应具备一定的电磁抗扰度(EMS)。因此，在合理的电气设计基础上，电磁波吸收材料在产品中的有效集成已经成为解决电磁兼容问题的主要方案。随着智能装备、新能源汽车、电子通讯、移动互联等行业的飞速发展，以及军事雷达和电磁对抗等技术的提升，传统的单组分吸波材料和电磁吸收体早已不适用于更宽应用频带的爆发性拓展所带来的电磁屏蔽和电磁兼容需要，开发适合目前生产环境又兼顾宽频带电磁波吸收的复合吸波材料已经成为行业的焦点。
铁氧体一直是VLF–UHF频段的主流吸波材料，广泛应用于大型设备、通讯产品、微波暗室等环境和器件在该频段的电磁屏蔽和抗电磁干扰。镍锌铁氧体在铁氧体吸波材料中性能一直占据主体地位，但因其原料成本过高而成为难以普及的瓶颈，而且也因其单一的损耗机制，难以覆盖目前无线充电、物联网、智能产品等在kHz–GHz频段的应用和拓展。锰锌铁氧体常用于低损耗和高导等软磁磁芯，在微波频段的磁导率与镍锌铁氧体相当，但其微波介电特性较差。因此，基于提升锰锌铁氧体介电性能，改善电磁阻抗匹配，从而增强吸波性能的方案无疑具有更大的开发潜力和应用价值，且考虑到锰锌铁氧体原料成本较低，更适合大规模应用量产。
目前，锰锌铁氧体在微波吸收方面产品的市场占有率仍然较少，通过改善阻抗匹配提升吸波性能的方案可分为两类：一类是金属元素的掺杂，即通过晶格畸变引入本征介电偶极，增强介电损耗性能。但该种方案往往需引入一些昂贵的稀土元素导致成本增加，同时畸变会削弱尖晶石铁氧体的超交换作用引起磁损耗下降；另一类是通过在锰锌铁氧体基体中加入介电材料复合进行性能的叠加，但添加成分与基体在热处理过程中的共同生长往往会产生气孔、裂纹等缺陷，影响吸波材料的力学性能。因此，如何通过合理的元素组合选择，结合介电材料的界面复合工艺设计，有效改善吸波体的磁损耗、介电损耗和电磁阻抗，已经成为锰锌铁氧体在吸波材料领域研究和应用的热点。
发明内容
本发明旨在提供一种碳复合锰锌铁氧体宽频吸波材料的制备方法，通过合理的元素掺杂增强了锰锌铁氧体的磁损耗性能；同时，通过热处理过程中气氛的控制，使粉体成型工艺中必须的聚合物造粒剂碳化，碳在锰锌铁氧体晶界位置的复合大幅提升了吸波材料的介电损耗性能和阻抗匹配，降低了晶界空气隙密度，从而增强了吸波性能和有效频宽。
本发明使用的原料成本低廉，工艺简单，常规设备即可完成，可以广泛应用于吸波贴片、磁瓦、隔磁片、涂层、涂料、柔性或复合吸波材料等领域。
本发明碳复合锰锌铁氧体宽频吸波材料的制备方法，包括如下步骤：
步骤1：称取铁氧化物、锰氧化物以及锌氧化物作为锰锌铁氧体的主料，各主料的配比按质量百分比构成如下：铁氧化物62.5～73％，锰氧化物11.5～22％，锌氧化物9.5～21.7％；
其中，所述铁氧化物为Fe2O3、Fe3O4中的一种或两种的复合，所述锰氧化物为MnO、Mn3O4中的一种或两种的复合，所述锌氧化物为ZnO。
步骤2：称取掺杂元素的氧化物作为锰锌铁氧体的辅料；所述掺杂元素的氧化物选自以下化合物中的一种或几种：P2O5、Co2O3、MgO、V2O5、Al2O3、CaO、SrO、Nb2O5、CeO2、Eu2O3、Cr2O3、SiO2。辅料添加的质量占主料质量的百分比不超过5％。
上述各掺杂元素的氧化物的添加比例(占主料的质量百分比)为：
P2O5 0.005～0.025％，Co2O3 0.01～0.8％，MgO 0.05～0.36％，V2O5 0.015～0.55％，Al2O3 0.03～0.15％，CaO 0.01～0.75％，SrO 0.01～0.55％，Nb2O5 0.005～0.35％，CeO2 0.015～0.065％，Eu2O3 0.05～0.55％，Cr2O3 0.03～0.35％，SiO2 0.02～0.85％。
步骤3：将主料和辅料充分混合，并以100～500rpm的速率进行3～20h的球磨，直至原料混合均匀，获得混合生料；
步骤4：将步骤3获得的混合生料放入箱式炉中，以3～10℃的升温速率升至800～1300℃，并保温0.5～5h进行预烧处理；
步骤5：将步骤4预烧处理后的混合生料再次以100～350rpm的速率进行3～10h的球磨，直至粒径均匀，获得前驱熟料；
步骤6：将步骤5获得的前驱熟料与0.5～10％的聚合物造粒剂进行均匀混合并造粒，使用筛网进行分选；所述聚合物造粒剂为聚乙烯醇、聚乙二醇、聚丙烯酸中的一种或几种。
步骤7：将步骤6造粒后的熟料颗粒放入模具中，以0.5～5T/cm2的压力进行压制成型，获得吸波材料的生胚；
步骤8：将步骤7获得的生胚放入气氛炉中，在一定气氛下以1～10℃/min的速率升温至1100～1450℃，并保温热处理2～10h，继续保持气氛直至冷却至室温，即获得碳复合锰锌铁氧体吸波材料。
所述一定气氛是指将气氛炉的炉腔抽至真空，或者持续通入高纯氮气或氩气与氧气的混合气体，氧气含量为0～7％。在气氛炉热处理的过程中，始终保持气氛气流畅通。
与现有技术相比，本发明的有益效果是：
1、本发明使用缺氧和无氧热处理方式，通过碳化成型工艺中必须的聚合物造粒剂，使其在锰锌铁氧体晶界位置形成有效的复合，从而改善吸波体的介电性能和电磁阻抗，进而提升其吸波性能和有效频带。
2、本发明方法仅对热处理气氛和原料成分进行优化，无需改变传统的工艺和手段，可广泛适用于传统的粉料成型生产设备。
3、本发明制备的碳复合锰锌铁氧体吸波材料适用于9kHz～42.5GHz的超宽频段吸波应用，通过0～10cm的吸波体厚度调节可以实现该范围内不同频带的有效电磁波吸收。
4、本发明中碳的复合进一步降低了锰锌铁氧体吸波材料的密度，可广泛应用于块体、贴片、角锥、涂层、薄膜等产品中，以及许多需要轻薄和微纳米集成吸波材料等领域。
附图说明
图1为碳复合锰锌铁氧体吸波材料的制备流程图，主要为一次球磨、预烧、二次球磨、造粒过筛、压制生胚、热处理等六个步骤。
图2为实施例1条件下制备的碳复合锰锌铁氧体吸波材料在10MHz～1GHz和2mm厚度时的反射损耗(RL)。吸收体的RL值在全频段均超过了-20dB，在100-858MHz频段超过-30dB，在f为107MHz时，RL达到了峰值-52.6dB。
图3为实施例2条件下制备的碳复合锰锌铁氧体吸波材料在10MHz～1GHz和2mm厚度时的反射损耗(RL)。吸收体的RL值在全频段均超过了-20dB，在100-564MHz频段超过-30dB，在f为100MHz时，RL达到了最小值-47.9dB。
图4为实施例3条件下制备的碳复合锰锌铁氧体吸波材料在10MHz～1GHz和2mm厚度时的反射损耗(RL)。吸收体的RL值在全频段均超过了-20dB，在100-772MHz频段超过-30dB，在f为100MHz时，RL达到了最小值-50.4dB。
具体实施方式
实施例1：
本实例制备的碳复合锰锌铁氧体吸波材料，原料的质量百分比如下：主料为Fe2O360％、MnO 19％、ZnO 21％，辅料为Co2O3 0.04％、P2O5 0.025％、Nb2O5 0.3％、SiO2 0.26％，辅料占主料的质量百分比低于1％。经过球磨、预烧、二次球磨、造粒分选、压制成型、气氛烧结等步骤获得碳/锰锌铁氧体复合吸波材料，具体包括如下步骤：
(1)准确称取9.6g Fe2O3、3.04g Mn3O4、3.36g ZnO，以及0.1g Co2O3、P2O5、Nb2O5、SiO2的按上述比例的混合辅料，然后将其倒入500ml的球磨罐中，并加入适量的球磨珠和水，使用球磨机以200rpm的速率进行8h的球磨直至成分混合均匀；
(2)将步骤(1)中获得的均匀混合生料放入烘箱中在70℃干燥24h，以除去其中的水。将干燥后的生料放入箱式炉中，在空气气氛下，以10℃/min的升温速率升至1100℃，并保温2h进行预处理；
(3)将经步骤(2)预处理后的生料再次装入球磨罐中，同样加入适量的水和球磨珠，并以200rpm的速率进行2h的球磨，获得前驱熟料；
(4)取步骤(3)获得的前驱熟料放入烘箱中在90℃干燥24h，以除去其中的水。取2g干燥后的熟料与0.5ml 10vol.％的聚乙烯醇(PVA)进行均匀混合造粒，并依次经过50目、100目、150目的筛网进行两次的分选，得到造粒的粉体；
(5)将经过步骤(4)造粒的熟料颗粒放入模具中，以1.5T/cm2的压力进行压制成型，获得吸波材料的生胚；
(6)步骤(5)获得的生胚放入管式炉中，持续通入高纯氮气；
(7)保持气氛气流畅通，将气氛炉以5℃/min的速率升温至1420℃，并保温热处理8h，继续保持气氛直至冷却至室温，获得碳/锰锌铁氧体吸波体材料。
实施例2：
本实例制备的碳复合锰锌铁氧体吸波材料，原料的质量百分比如下：主料为Fe2O365％、Mn3O4 15％、ZnO 20％，辅料为MgO 0.25％、Al2O3 0.08％、Nb2O5 0.26％、Eu2O30.35％，辅料占主料的质量百分比低于1％。经过球磨、预烧、二次球磨、造粒分选、压制成型、气氛烧结等步骤获得碳/锰锌铁氧体复合吸波材料，具体包括如下步骤：
(1)准确称取10.4g Fe2O3、2.4g Mn3O4、3.2g ZnO，以及0.15g MgO、Al2O3、Nb2O5、Eu2O3的按上述比例的混合辅料，然后将其倒入500ml的球磨罐中，并加入适量的球磨珠和水，使用球磨机以200rpm的速率进行8h的球磨直至成分混合均匀；
(2)将步骤(1)中获得的均匀混合生料放入烘箱中在70℃干燥24h，以除去其中的水。将干燥后的生料放入箱式炉中，在空气气氛下，以10℃/min的升温速率升至1100℃，并保温2h进行预处理；
(3)将经步骤(2)预处理后的生料再次装入球磨罐中，同样加入适量的水和球磨珠，并以200rpm的速率进行2h的球磨，获得前驱熟料；
(4)取步骤(3)获得的前驱熟料放入烘箱中在90℃干燥24h，以除去其中的水。取2g干燥后的熟料与0.5ml 10vol.％的聚乙烯醇(PVA)进行均匀混合造粒，并依次经过50目、100目、150目的筛网进行两次的分选，得到造粒的粉体；
(5)将经过步骤(4)造粒的熟料颗粒放入模具中，以1.5T/cm2的压力进行压制成型，获得吸波材料的生胚；
(6)步骤(5)获得的生胚放入管式炉中，持续通入氧含量为7％的氮气混合气体；
(7)保持气氛气流畅通，将气氛炉以5℃/min的速率升温至1400℃，并保温热处理5h，继续保持气氛直至冷却至室温，获得碳/锰锌铁氧体吸波体材料。
实施例3：
本实例制备的碳复合锰锌铁氧体吸波材料，原料的质量百分比如下：主料为Fe2O368％、Mn3O4 16％、ZnO 16％，辅料为V2O5 0.08％、CaO 0.06％、Nb2O5 0.32％、SrO 0.25％，辅料占主料的质量百分比低于1％。经过球磨、预烧、二次球磨、造粒分选、压制成型、气氛烧结等步骤获得碳/锰锌铁氧体复合吸波材料，具体包括如下步骤：
(1)准确称取10.88g Fe2O3、2.56g Mn3O4、2.56g ZnO，以及0.11g V2O5、CaO、Nb2O5、SrO的按上述比例的混合辅料，然后将其倒入500ml的球磨罐中，并加入适量的球磨珠和水，使用球磨机以200rpm的速率进行8h的球磨直至成分混合均匀；
(2)将步骤(1)中获得的均匀混合生料放入烘箱中在70℃干燥24h，以除去其中的水。将干燥后的生料放入箱式炉中，在空气气氛下，以10℃/min的升温速率升至1100℃，并保温2h进行预处理；
(3)将经步骤(2)预处理后的生料再次装入球磨罐中，同样加入适量的水和球磨珠，并以200rpm的速率进行2h的球磨，获得前驱熟料；
(4)取步骤(3)获得的前驱熟料放入烘箱中在90℃干燥24h，以除去其中的水。取2g干燥后的熟料与0.5ml 10vol.％的聚乙烯醇(PVA)进行均匀混合造粒，并依次经过50目、100目、150目的筛网进行两次的分选，得到造粒的粉体；
(5)将经过步骤(4)造粒的熟料颗粒放入模具中，以1.5T/cm2的压力进行压制成型，获得吸波材料的生胚；
(6)步骤(5)获得的生胚放入管式炉中，持续通入氧含量为2％的氮气混合气体；
(7)保持气氛气流畅通，将气氛炉以5℃/min的速率升温至1380℃，并保温热处理10h，继续保持气氛直至冷却至室温，获得碳/锰锌铁氧体吸波体材料。

Claims (3)

1.一种碳复合锰锌铁氧体宽频吸波材料的制备方法，其特征在于：
通过对热处理气氛以及原料成分和配比进行优化，增强尖晶石结构微波磁性能的同时，使粉体成型工艺中必须的聚合物造粒剂碳化，碳在锰锌铁氧体晶界位置的复合大幅提升了吸波材料的介电性能和阻抗匹配，降低了晶界空气隙密度，从而增强了吸波性能和有效频宽；包括如下步骤：
步骤1：称取铁氧化物、锰氧化物以及锌氧化物作为锰锌铁氧体的主料，各主料的配比按质量百分比构成如下：铁氧化物62.5~73%，锰氧化物11.5~22%，锌氧化物9.5~21.7%；
步骤2：称取掺杂元素的氧化物作为锰锌铁氧体的辅料；所述掺杂元素的氧化物选自以下化合物中的一种或几种：P2O5、Co2O3、MgO、V2O5、Al2O3、CaO、SrO、Nb2O5、CeO2、Eu2O3、Cr2O3、SiO2；
步骤3：将主料和辅料充分混合，并以100~500 rpm的速率进行3~20h的球磨，直至原料混合均匀，获得混合生料；
步骤4：将步骤3获得的混合生料放入箱式炉中，以3~10℃的升温速率升至800~1300℃，并保温0.5~5 h进行预烧处理；
步骤5：将步骤4预烧处理后的混合生料再次以100~350rpm的速率进行3~10 h的球磨，直至粒径均匀，获得前驱熟料；
步骤6：将步骤5获得的前驱熟料与0.5~10%的聚合物造粒剂进行均匀混合并造粒，使用筛网进行分选；所述聚合物造粒剂为聚乙烯醇、聚乙二醇、聚丙烯酸中的一种或几种；
步骤7：将步骤6造粒后的熟料颗粒放入模具中，以0.5~5 T/cm2的压力进行压制成型，获得吸波材料的生胚；
步骤8：将步骤7获得的生胚放入气氛炉中，在一定气氛下以1~10℃/min的速率升温至1100~1450℃，并保温热处理2~10 h，继续保持气氛直至冷却至室温，即获得碳复合锰锌铁氧体吸波材料；所得碳复合锰锌铁氧体吸波材料适用于9 kHz~42.5 GHz的超宽频段吸波应用；
步骤1中，所述铁氧化物为Fe2O3、Fe3O4中的一种或两种的复合，所述锰氧化物为MnO、Mn3O4中的一种或两种的复合，所述锌氧化物为ZnO；
步骤8中，所述一定气氛是指将气氛炉的炉腔抽至真空，或者持续通入高纯氮气或氩气与氧气的混合气体，氧气含量为0~7%。
2.根据权利要求1所述的制备方法，其特征在于：
步骤2中，各掺杂元素的氧化物的添加比例为：
P2O5 0.005~0.025%，Co2O3 0.01~0.8%，MgO 0.05~0.36%，V2O5 0.015~0.55%，Al2O3 0.03~0.15%，CaO 0.01~0.75%，SrO 0.01~0.55%，Nb2O5 0.005~0.35%，CeO2 0.015~0.065%，Eu2O30.05~0.55%，Cr2O3 0.03~0.35%，SiO2 0.02~0.85%。
3.根据权利要求1或2所述的制备方法，其特征在于：
辅料添加的质量占主料质量的百分比不超过5%。
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