CN108863338B - 一种锰锌功率铁氧体的六段气氛控制方法 - Google Patents
一种锰锌功率铁氧体的六段气氛控制方法 Download PDFInfo
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- 239000012298 atmosphere Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 35
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 10
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 40
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005245 sintering Methods 0.000 claims abstract description 29
- 238000004321 preservation Methods 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 2
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- 238000002156 mixing Methods 0.000 description 10
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- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 description 7
- JIYIUPFAJUGHNL-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] JIYIUPFAJUGHNL-UHFFFAOYSA-N 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000001238 wet grinding Methods 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
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- 239000000696 magnetic material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
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- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
本发明公开了一种锰锌功率铁氧体的六段气氛控制方法，其主要内容是：在二次配料时，添加适量的掺杂元素；将烧结过程分为6段保温保压平台。首先在1150℃‑1250℃的区间内保温2‑5小时，控制0.25％‑1％的低氧气氛；随后在1080℃‑1120℃之间保温1‑2小时，控制2.5％‑4％的高氧气氛；然后分别为990℃‑1020℃，900℃‑950℃，750‑800℃，保温时间30‑60min，并保持平衡气氛；最后在500℃‑600℃，保温时间为1‑2小时。本发明的创新性在于通过六次保温和控制氧分压，能够有效阻止Fe2+的迁移和获得高电阻率晶界，有效降低涡流损耗，同时降低了材料的内应力，从而得到优秀的高频交流磁性能。
Description
技术领域
本发明涉及一种锰锌功率铁氧体的六段气氛控制方法，属于锰锌铁氧体烧结技术领域。
背景技术
近年来，随着整机电子产品核心和关键技术正迅速向元器件转移，轻、薄、短、小，高性能、高可靠、高环境适应性的应用需求推动电子元件向小型化、微型化、片式化和集成化方向发展。为了满足应用需求和提高竞争力，功率铁氧体应进一步向高频化、低损耗、宽温、高磁导率方向发展。
研究表明，锰锌铁氧体的烧结工艺对于控制产品的功耗及其功耗最低温度具有显著的影响。中国专利申请CN 106747393 A公布了一种适用于高频领域的烧结气氛控制方法，主要内容是通过升温段空气烧结、保温段低氧烧结和降温段无氧烧结步骤，减少了烧结过程中的锌挥发和Fe2+氧化程度，获得了较低的功率损耗。中国专利申请CN 1276897C公布了一种锰锌铁氧体软磁烧结方法，其烧结过程的降温阶段期间再经历至少一次重新升温和保温的步骤，使得锰锌铁氧体功耗最低温度的调整较为简便，而且功耗较低。关于MnZn铁氧体烧结制度的专利仍虽然繁多，但大多数专利对于保温及降温制度对掺杂离子分布产生的影响。为解决上述问题，本发明提出一种六段烧结气氛控制方法，该方法能够与掺杂离子的作用形成良好配合，从而明显降低材料的损耗。
发明内容
本发明的目的在于一种锰锌功率铁氧体的六段气氛控制方法，目的是通过在保温和降温阶段的温度和气氛控制，阻止Fe2+的迁移和获得高电阻率晶界层，降低材料的内应力，从而提高材料的高频磁性能。
本发明通过以下技术方案实现：
(1)掺杂过程：在预烧料中掺杂含Ca、Si、Zr、V、Nb、Sn或同类元素的氧化物。按照其作用方式，可将掺杂的氧化物分为四类：
第一类：CaO:500-3000ppm,SiO2:200-1000ppm；
第二类：,Nb2O5:100-500ppm,SnO2:100-500ppm，TiO2:200-800ppm
第三类：Co2O3:50-300ppm，NiO:100-500ppm，K2CO3：50-200ppm；
第四类：ZrO2：200-500ppm，V2O5:300-1000ppm；
注：ppm表示各掺杂物质占预烧料的质量分数。
其中，第一类和第四类氧化物主要分布在晶界处，用于形成高电阻层；第二类和第三类元素进入晶格，用于阻止Fe2+迁移，并改善材料的内禀磁性能。在掺杂时，必须加入CaO，同时保证每类掺杂元素至少加入一种，四类掺杂元素的总质量分数不应超过0.5％。
(2)升温过程：首先在空气气氛下将温度升至250℃-500℃进行排胶，随后按2-5℃/min的速率继续升温，当温度达到900-1000℃时，将空气气氛转换为低氧气氛，氧分压控制在低于1％。
作为优选，一般使用2-3℃/min的速度将温度升至300℃-400℃，适当降低升温速率有助于聚乙烯醇更为充分地分解和挥发，避免由于该类物质的残留造成的开裂现象。随后在900℃-950℃范围内开始使用低氧气氛，优选的氧分压为0.1％-0.5％之间，使用较低的氧分压可以促进烧结固相反应的进行和密度的提高，有利于获得纯度和密度较高的铁氧体。
(3)六段气氛控制过程：首先在1150℃-1250℃的区间内保温2-5h，控制0.25％-1％的低氧气氛；随后在20min-40min之内将温度降至1080℃-1120℃，保温1-2h，保温时控制2.5％-4％的高氧气氛。采用高温低氧气氛和低温高氧气氛的配合，能够使得Fe2+的迁移被尽可能地阻止，从而提高材料晶粒内部的电阻率，获得较低的损耗。继续降温，控制降温速率为2-5℃/min，分别在990℃-1020℃，900℃-950℃，750-800℃的温度区间内保温30-60min，并采用平衡气氛，选用的平衡气氛公式为
通过在适当温度下保温，能够促进第一类和第四类元素的析出过程，以便在晶界形成高电阻率层，减少材料的涡流损耗。然后继续降温，控制降温速率为2-5℃/min，当温度降至500-600℃时执行保温，保温时间为1-2h，随后逐渐冷却至室温。
本发明的积极效果在于：传统烧结方法一般较多关注材料的组织和Fe2+的变化，忽略了烧结过程对掺杂物质分布的影响。本发明在烧结保温和降温过程中采用六段保温保压控制方法，适当的温度和烧结气氛的配合，能够在保持磁导率的同时降低材料的微观涡流损耗和宏观涡流损耗，从而改善材料的高频磁性能。
具体实施方式
以下对本发明的优选实施例进行说明，需要理解的是，此处所描述的优选实施例仅用于解释和说明本发明的特点，目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并没有对本发明的保护范围作出任何限定。
实施案例1：
选用原料的主成分以摩尔分数记为：55.1mol％Fe2O3、40mol％MnO2、4.9mol％ZnO。将主成分混合进行湿磨，球磨时间为4h，将干燥后的粉末投入预烧，在950℃和空气气氛中烧结2h，随后炉冷。将烧结后的粉末与500ppmCaO、300ppmV2O5、300ppmZrO2、100ppmNb2O5、200ppmCo2O3混合，湿磨8h后干燥，此时粉末的平均粒度在1um以下。造粒时，添加2wt％的浓度为10wt％的聚乙烯醇溶液和微量硬脂酸锌，以获得粒度在50-100um的大颗粒。随后将粉料压制成型，保证生坯密度在2.8-3.0g/cm3之间。将生坯投入烧结，先按2℃/min的升温速率升温至400℃并保温2h，保证排胶完全。保持升温速率为3.5℃/min，在900℃时将空气气氛转变成低氧气氛，相应氧分压为0.2％。保温过程分两步进行，首先升温至1180℃处保温3h，氧分压0.5％，随后用20min将温度降至1100℃保温1h，相应氧分压控制为2.5％；降温时，分别在990℃保温30min，相应氧分压为0.06％；900℃保温30min，相应氧分压为0.008％；750℃保温30mim，保持氮气气氛；500℃保温1h，保持氮气气氛；最后冷却至室温，得到烧结锰锌铁氧体材料。整个过程的降温速率为4℃/min，控制氧分压随温度变化的关系式为
使用SY-8258型B-H分析仪测量材料的起始磁导率和高频磁损耗。材料的起始磁导率为800,；在1MHZ、30mT、100℃的测量条件下，产品的功率损耗为206KW/m3；在3MHZ、10mT、100℃的测量条件下，产品的功率损耗为160KW/m3；在5MHZ、10mT、100℃的测量条件下，产品的功率损耗为535KW/m3.
对比例1：保温之前的步骤与实施例1完全相同。将材料升温至1150℃并保温3h，随后以3℃/min的速率降温至室温，整个过程中氧分压随温度变化的关系式为
所得到的材料的起始磁导率为780,1MHZ、30mT、100℃的磁损耗为257KW/m3,3MHZ、10mT、100℃的磁损耗为197KW/m3，5MHZ、10mT、100℃的磁损耗为682KW/m3.
实施例1相比于对比例1而言，所得到的材料的磁导率略高，而磁损耗则显著降低，上述三种测量条件下，磁损耗降低幅度至少超过15％。这表明，高温低氧气氛和低温高氧气氛的配合有效地加强了高价离子和Fe2+之间的配对，同时降温段的保温保压过程使得晶界变得更加均匀厚重，其叠加效果使得材料的涡流损耗显著降低。
实施案例2：
选用原料的主成分以摩尔分数记为：54.5mol％Fe2O3、38.0mol％MnO2、7.5mol％ZnO。将主成分混合进行湿磨，球磨时间为2h，将干燥后的粉末投入预烧，在920℃和空气气氛中烧结2h，随后炉冷。将烧结后的粉末与2000ppmCaO、500ppmSiO2、200ppmSnO2、200ppmNb2O5、300ppmNiO、300ppmZrO2混合，湿磨10h后干燥，此时粉末的平均粒度在1um以下。造粒时，添加2wt％的浓度为10wt％的聚乙烯醇溶液和微量硬脂酸锌，以获得粒度在50-100um的大颗粒。随后将粉料压制成型，保证生坯密度在2.8-3.0g/cm3之间。将生坯投入烧结，先按3℃/min的升温速率升温至300℃并保温3h，保证排胶完全。保持升温速率为4℃/min，在950℃时将空气气氛转变成低氧气氛，氧分压为0.5％。保温过程分两步进行，首先升温至1200℃处保温2h，氧分压为0.5％，随后用30min将温度降至1100℃并保温2h，相应氧分压控制为4％；降温时，分别在1020℃保温20min，相应氧分压为0.036％；930℃保温40min，相应氧分压为0.005％；800℃保温40mim，保持氮气气氛；550℃保温1h，保持氮气气氛；最后冷却至室温，得到烧结锰锌铁氧体材料。整个过程的降温速率为3℃/min，控制氧分压随温度变化的关系式为
使用SY-8258型B-H分析仪测量材料的起始磁导率和高频磁损耗。材料的起始磁导率为630；在1MHZ、30mT、100℃的测量条件下，产品的功率损耗为283KW/m3；在3MHZ、10mT、100℃的测量条件下，产品的功率损耗为202KW/m3；在5MHZ、10mT、100℃的测量条件下，产品的功率损耗为627KW/m3.
对比例2：保温之前的步骤与实施例2完全相同。将材料升温至1200℃并保温2h，随后以3℃/min的速率降温至室温，整个过程中氧分压随温度变化的关系式为
所得到的材料的起始磁导率为615,1MHZ、30mT、100℃的磁损耗为326KW/m3,3MHZ、10mT、100℃的磁损耗为247KW/m3，5MHZ、10mT、100℃的磁损耗为761KW/m3.
实施案例3：
选用原料的主成分以摩尔分数记为：55.5mol％Fe2O3、36.0mol％MnO2、6.5mol％ZnO。将主成分混合进行湿磨，球磨时间为5h，将干燥后的粉末投入预烧，在1000℃和空气气氛中烧结3h，随后炉冷。将烧结后的粉末与2000ppmCaO、500ppmSiO2、500ppmSnO2、500ppmNb2O5、200ppmZrO2、400ppm V2O5、100ppmK2CO3混合，湿磨6h后干燥，此时粉末的平均粒度在1um以下。造粒时，添加2wt％的浓度为10wt％的聚乙烯醇溶液和微量硬脂酸锌，以获得粒度在50-100um的大颗粒。随后将粉料压制成型，保证生坯密度在2.8-3.0g/cm3之间。将生坯投入烧结，先按3℃/min的升温速率升温至400℃并保温2h，保证排胶完全。保持升温速率为4℃/min，在900℃时将空气气氛转变成低氧气氛，控制氧分压为0.1％。保温过程分两步进行，首先升温至1250℃处保温3h，氧分压为1％，随后用30min将温度降至1080℃并保温1h，相应氧分压控制为3％；降温时，分别在1020℃保温30min，相应氧分压为0.057％；950℃保温30min相应氧分压为0.013％；780℃保温30mim，保持氮气气氛；550℃保温1h，保持氮气气氛；最后冷却至室温，得到烧结锰锌铁氧体材料。整个过程的降温速率为3℃/min，控制氧分压随温度变化的关系式为
使用SY-8258型B-H分析仪测量材料的起始磁导率和高频磁损耗。材料的起始磁导率为750；在1MHZ、30mT、100℃的测量条件下，产品的功率损耗为254KW/m3；在3MHZ、10mT、100℃的测量条件下，产品的功率损耗为188KW/m3；在5MHZ、10mT、100℃的测量条件下，产品的功率损耗为574KW/m3.
通过对比以上实施例1、2、3和对比例1、2，可以发现，对于不同的原始组分，不同的制备工艺，本发明提供的烧结六段保温控制方法均能够显著降低材料的磁损耗，同时并不降低材料的磁导率，证明该种方法的效果对于高频锰锌功率铁氧体而言具备普适性。
Claims (1)
1.一种锰锌功率铁氧体的六段气氛控制方法，其特征在于包括如下步骤：
（1）掺杂过程：将掺杂的氧化物分为四大类，在预烧料中进行掺杂；
所述四大类氧化物，其分类和相对于预烧料的加入质量分数分别如下：
第一类：CaO:500-3000ppm, SiO2:200-1000ppm；
第二类： Nb2O5:100-500ppm, SnO2:100-500ppm，TiO2:200-800ppm
第三类：Co2O3:50-300ppm，NiO:100-500ppm，K2CO3：50-200ppm；
第四类：ZrO2：200-500ppm，V2O5:300-1000ppm；
且保证每一类至少加入一种氧化物，掺杂氧化物的总质量不应超过预烧料质量分数的0.5%;
（2）升温过程：在250℃-500℃温度范围内排胶后，按照2-5℃/min的速率继续升温，当温度达到900-1000℃时，将空气气氛转换为低氧气氛，氧分压控制在低于1%；
（3）六段气氛控制过程：首先在1150℃-1250℃的区间内保温2-5h，控制0.25%-1%的低氧气氛；随后在20min-40min之内将温度降至1080℃-1120℃，保温1-2h，保温时控制2.5%-4%的高氧气氛；继续降温，控制降温速率为2-5℃/min，分别在990℃-1020℃，900℃-950℃，750-800℃的温度区间内保温30-60min，并采用平衡气氛，选用的平衡气氛公式为
；然后继续降温，控制降温速率为2-5℃/min，当温度降至500-600℃时执行保温，保温时间为1-2h，随后逐渐冷却至室温。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103482986A (zh) * | 2013-09-13 | 2014-01-01 | 苏州天源磁业有限公司 | 一种低损耗MnZn铁氧体材料的烧结方法 |
| CN103693952A (zh) * | 2013-12-04 | 2014-04-02 | 江门安磁电子有限公司 | 一种超低损耗MnZn功率铁氧体材料的制造方法 |
| CN107555984A (zh) * | 2017-10-10 | 2018-01-09 | 浙江大学 | 一种高频宽温低损耗MnZn铁氧体的烧结过程气氛控制方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN101620908A (zh) * | 2009-06-05 | 2010-01-06 | 南京精研磁性技术有限公司 | 宽温宽频高居里点低损耗锰锌铁氧体材料及其制备方法 |
| CN103482986A (zh) * | 2013-09-13 | 2014-01-01 | 苏州天源磁业有限公司 | 一种低损耗MnZn铁氧体材料的烧结方法 |
| CN103693952A (zh) * | 2013-12-04 | 2014-04-02 | 江门安磁电子有限公司 | 一种超低损耗MnZn功率铁氧体材料的制造方法 |
| CN107555984A (zh) * | 2017-10-10 | 2018-01-09 | 浙江大学 | 一种高频宽温低损耗MnZn铁氧体的烧结过程气氛控制方法 |
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