CN116219326B - 一种制备高Fe含量非晶纳米晶软磁合金的过冷凝固方法 - Google Patents
一种制备高Fe含量非晶纳米晶软磁合金的过冷凝固方法Info
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Abstract
本发明提供一种制备高Fe含量非晶纳米晶软磁合金的过冷凝固方法及适用的非晶纳米晶成分。所述过冷凝固通过玻璃净化结合循环过热或者电磁悬浮熔炼实现。过冷凝固合金通过熔体快淬或雾化制成非晶带材或粉体,并可经热处理制备成纳米晶合金。所述适用的非晶纳米晶化学式为FeSiBM,其特征在于M为P、C、Nb、Mo、Zr、Hf、Mo、Y、Cu、Co中的一种或多种,各合金元素原子百分比总和为100%,满足以下元素含量:Fe为80.0~89.0at%,Si为1.0~9.0at%,B为3.0~12.0at%,P为0~5.0at%,C为0~5.0at%,Nb为0~3.0at%,Zr为0~3.0at%,Hf为0~3.0at%,Mo为0~3.0at%,Y为0~5.0at%,Cu为0~2.0at%,Co为0~16.0at%。利用过冷非平衡凝固制备得非晶纳米晶合金非晶形成能力高,具有高饱和磁化强度、低矫顽力的特点。
Description
技术领域
本发明涉及一种通过过冷凝固制备高Fe含量非晶纳米晶软磁合金的方法,属于金属软磁材料领域。
背景技术
Fe基非晶纳米晶软磁合金由于其特殊的显微组织结构,与晶态软磁合金相比,具有矫顽力低、电阻率高等显著优势。然而,Fe基非晶纳米晶合金中由于大量非晶形成元素的存在,降低了饱和磁化强度,限制了相关软磁器件的高功率和小型化发展。经典非晶软磁合金(国际牌号Metglas 2605SA1、我国牌号1K101)的饱和磁化强度约为1.55T,而经典纳米晶软磁合金(国际牌号Finemet、我国牌号1K107)的饱和磁化强度约为1.24T,均远低于硅钢的饱和磁化强度(约2.12T)。
为了充分发挥非晶纳米晶软磁合金在各类电力电子设备的应用潜力,亟需提高Fe基非晶纳米晶合金中以Fe为主的磁性元素含量及饱和磁化强度。制备高Fe含量非晶纳米晶软磁合金的挑战在于获得非晶基体的要求较为苛刻,熔融合金冷却速度需达到约105℃/s以上。依据Inoue非晶原则,合金中往往需要添加约20at%的非磁性元素以促进非晶结构的形成。纳米晶软磁合金由非晶合金经晶化退火而成,往往还需要添加形核及抑制晶粒长大的非磁性元素。这些元素的引入极大限制了非晶纳米晶软磁合金中铁磁性元素的含量,故难以获得高饱和磁化强度。
目前,提高Fe基非晶纳米晶软磁合金饱和磁化强度的方法主要集中于成分调控方面。一是通过添加Co元素增强合金中铁磁交换强度以提高合金饱和磁化强度,如专利ZL201410728540.1公开了一种FeaCobNbcBdCue合金,通过添加6~20at%的Co提高纳米晶合金饱和磁化强度至1.80T,矫顽力在10~35A/m范围内。二是调整类金属元素如Si、B、C、P元素的添加量,如专利ZL200510066862.5公开了一种FeaSibBcCd合金,当c在12~18at%范围内,且满足b≤(0.5×a-36)×d1/3条件时,铁基非晶带材的饱和磁化强度可达1.60T以上。此外,ZL201410285976.8公开了一种FeaSibBcCdPe合金,通过调节类金属元素添加比例,获得的Fe84.3Si2.3B9.7C0.9P2.8合金具有最高的饱和磁化强度为1.69T。这类方法一方面依据Inoue非晶原则,调节类金属添加比例影响合金混合焓、原子尺寸差异,以提高合金非晶形成能力,进而提高铁磁性元素含量;另一方面由于类金属元素的2p电子能够对Fe的3d电子产生影响,影响Fe原子磁矩大小,从而调控合金饱和磁化强度。由上述专利可知,通过调节类金属元素含量的方法,需要精确控制不同元素的比例关系,且铁磁性元素添加量的提高仍有限,限制了饱和磁化强度的进一步提升。
本专利通过玻璃净化结合循环过热或者电磁悬浮熔炼实现Fe基非晶纳米晶合金过冷凝固,减少合金中非磁性元素的添加量,能有效提高合金中铁磁性元素添加量,增大合金饱和磁化强度并保持低矫顽力。
发明内容
本发明目的在于克服现有Fe基非晶纳米晶软磁合金制备技术中的不足,通过过冷非平衡凝固方法,减少合金中非晶形成元素的添加量,实现了高Fe含量非晶纳米晶软磁合金的制备,进而拓宽Fe基非晶纳米晶软磁合金成分设计范围,提高合金饱和磁化强度。
本发明是通过以下技术方案实现的:
一种制备高Fe含量非晶纳米晶软磁合金的过冷凝固方法,采用熔融玻璃净化结合循环过热或者电磁悬浮熔炼的方法,使合金过冷凝固,减少Fe基非晶纳米晶软磁合金中非晶形成元素的添加量,提高Fe元素的占比,实现提高饱和磁化强度、降低矫顽力的目标。
优选地,所述熔融玻璃净化结合循环过热的方法包括以下步骤:
第一步,所述的非晶纳米晶合金化学表达式为FeSiBM,其中M为P、C、Nb、Mo、Zr、Hf、Mo、Y、Cu、Co中的一种或多种元素。去除合金原料氧化皮后清洗,按照一定的质量比称量原料。将称量后的原料在真空感应熔炼炉或真空电弧熔炼炉内,抽真空至少达到10-3Pa后,充惰性气体保护进行熔炼,反复熔炼4~6次得到合金锭子;
第二步,将合金锭子放入坩埚中,并在其上下表面覆盖一定质量配比的玻璃净化剂,使玻璃净化剂完全包覆合金锭子;
第三步,抽真空至少达到10-2Pa后,充惰性气体保护并加热合金至熔化,之后升温至1200~1500℃,保温1~10分钟,关闭加热电源,使合金自然冷却;
第四步,进行“加热-保温-凝固”循环处理3~6次,使合金获得所需过冷度;
第五步,将过冷凝固合金通过熔体快淬或雾化方式凝固成带材或粉体;
第六步,将获得的带材或粉体通过去应力退火获得Fe基非晶合金,或者通过晶化退火获得Fe基纳米晶合金。
优选地,所述的惰性气体为纯度不低于99.9vol%的氩气或氮气。
优选地,所述的坩埚耐热温度不低于1400℃。
优选地,所述熔融玻璃净化结合循环过热制备高Fe含量非晶纳米晶软磁合金的方法,其特征在于,所述玻璃净化剂制备过程包括:称取纯度不低于98%的粉末状Na2B4O7和B2O3分别置于高纯刚玉坩埚中,于400~600℃烧制1~8小时,再于800~1000℃熔融烧制2~16小时。将烧制后的Na2B4O7和B2O3混合得到净化剂,两者质量比=1:1~20。
优选地,所述的玻璃净化剂与合金锭子的质量比为1:1~5。
优选地,所述电磁悬浮熔炼的方法包括以下步骤:
第一步,所述的非晶纳米晶合金化学表达式为FeSiBM,其中M为P、C、Nb、Mo、Zr、Hf、Mo、Y、Cu、Co中的一种或多种元素。去除合金原料氧化皮后清洗,按照一定的质量比称量原料。将称量后的原料在真空感应熔炼炉或真空电弧熔炼炉内,抽真空至少达到10-3Pa后,充惰性气体保护进行熔炼,反复熔炼4~6次得到合金锭子;
第二步,抽真空至少达到10-3Pa后,充惰性气体保护,将合金铸锭送至悬浮线圈下方,依靠电磁场和感应电流间相互作用形成的洛伦兹力将母合金的稳定悬浮于加热线圈中心;
第三步,利用加热线圈感应加热合金至熔化,之后升温至1200~1500℃,保温1~10分钟,保温后,关闭加热电源,使合金自然冷却;
第四步,进行“加热-保温-凝固”循环处理3~6次,使合金获得所需过冷度;
第五步,将过冷凝固合金通过熔体快淬或雾化方式凝固成带材或粉体;
第六步,将获得的带材或粉体通过去应力退火获得Fe基非晶合金,或者通过晶化退火获得Fe基纳米晶合金。
优选地,所述的高Fe含量非晶纳米晶软磁合金化学表达式为FeSiBM,其特征在于M为P、C、Nb、Mo、Zr、Hf、Mo、Y、Cu、Co中的一种或多种元素,各合金元素原子百分比总和为100%,满足以下元素含量:Fe为80.0~89.0at%,Si为1.0~9.0at%,B为3.0~12.0at%,P为0~5.0at%,C为0~5.0at%,Nb为0~3.0at%,Zr为0~3.0at%,Hf为0~3.0at%,Mo为0~3.0at%,Y为0~5.0at%,Cu为0~2.0at%,Co为0~16.0at%。
优选地,所述的惰性气体为纯度不低于99.9vol%的氩气或氮气。
优选地,所述的非晶合金退火在晶化温度以下50~100℃温度区间内,纳米晶退火温度在晶化温度以上0~100℃温度区间内。
优选地,所述的退火在惰性气体气氛或者真空度优于10-1Pa环境中进行。
利用上述非平衡凝固方法制备的非晶纳米晶软磁合金具有高非晶形成能力,利于减少合金中非晶形成元素的添加量,增大铁磁性元素Fe的含量。由所述方式制备的高Fe含量非晶纳米晶合金具有高饱和磁化强度、低矫顽力的软磁特性。
具体实施方式
下面对本发明的实施例作详细说明,通过调控合金成分和过冷度,获得具有高饱和磁化强度的高Fe含量非晶纳米晶软磁合金。
实施例1
过冷凝固制备FeSiB非晶合金
制备FeSiB体系合金,其中合金1中Fe含量为83.0at%,Si含量为8.0at%,B含量为9.0at%;合金2中Fe含量为85.0at%,Si含量为7.0at%,B含量为8.0at%;合金3中Fe含量为88.0at%,Si含量为3.0at%,B含量为9.0at%;
第一步,去除合金原料氧化皮后清洗,按照一定的质量比称量原料。将称量后的原料在真空电弧熔炼炉内,抽真空达到8×10-4Pa后,充纯度为99.9vol%氩气保护进行熔炼,反复熔炼5次得到合金锭子;
第二步,将合金锭子放入坩埚中,并在其上下表面覆盖Na2B4O7和B2O3两者混合的净化玻璃,两者质量比=1:5,使玻璃净化剂完全包覆合金锭子;
第三步,抽真空达到5×10-3Pa后,充纯度为99.9vol%氩气保护并加热合金至熔化,之后升温至1350℃,保温2分钟,关闭加热电源,使合金自然冷却;
第四步,分别进行“加热-保温-凝固”循环处理4次和6次,使合金获得约190℃和260℃的过冷度;
第五步,将过冷凝固合金通过熔体快淬凝固成带材;
第六步,将获得的带材在300℃去应力退火,获得Fe基非晶合金;
不同过冷度下合金的饱和磁化强度、矫顽力如下表所示:
表1不同过冷度FeSiB系非晶合金的饱和磁化强度及矫顽力
实施例2
过冷凝固制备FeSiBPC非晶合金
制备FeSiBPC体系合金,其中合金1中Fe含量为84.0at%,Si含量为2.0at%,B含量为8.0at%,P含量为5.0at%,C含量为1.0at%;合金2中Fe含量为84.0at%,Si含量为2.0at%,B含量为8.0at%,P含量为1.0at%,C含量为5.0at%;合金3中Fe含量为89.0at%,Si含量为2.0at%,B含量为8.0at%,P含量为0.5at%,C含量为0.5at%;
第一步,去除合金原料氧化皮后清洗,按照一定的质量比称量原料。将称量后的原料在真空电弧熔炼炉内,抽真空达到7×10-4Pa后,充纯度为99.9vol%氮气保护进行熔炼,反复熔炼6次得到合金锭子;
第二步,将合金锭子放入坩埚中,并在其上下表面覆盖Na2B4O7和B2O3两者混合的净化玻璃,两者质量比=1:4,使玻璃净化剂完全包覆合金锭子;
第三步,抽真空达到4×10-3Pa后,充纯度为99.9vol%氮气保护并加热合金至熔化,之后升温至1400℃,保温3分钟,关闭加热电源,使合金自然冷却;
第四步,分别进行“加热-保温-凝固”循环处理4次和6次,使合金获得约160℃和255℃的过冷度;
第五步,将过冷凝固合金通过熔体快淬凝固成带材;
第六步,将获得的带材在300℃去应力退火,获得Fe基非晶合金;
不同过冷度下合金的饱和磁化强度、矫顽力如下表所示:
表2不同过冷度FeSiBPC系非晶合金的饱和磁化强度及矫顽力
实施例3
过冷凝固制备FeSiBC非晶合金
制备FeSiBC体系合金,其中合金1中Fe含量为84.0at%,Si含量为2.0at%,B含量为8.0at%,C含量为6.0at%;合金2中Fe含量为85.0at%,Si含量为2.0at%,B含量为8.0at%,C含量为5.0at%;合金3中Fe含量为89.0at%,Si含量为2.0at%,B含量为8.0at%,C含量为1.0at%;
第一步,去除合金原料氧化皮后清洗,按照一定的质量比称量原料。将称量后的原料在真空感应熔炼炉或真空电弧熔炼炉内,抽真空达到8×10-4Pa后,充惰性气体保护进行熔炼,反复熔炼6次得到合金锭子;
第二步,抽真空达到4×10-3Pa后,充纯度为99.9vol%氮气保护,将合金铸锭送至悬浮线圈下方,依靠电磁场和感应电流间相互作用形成的洛伦兹力将母合金的稳定悬浮于加热线圈中心;
第三步,利用加热线圈感应加热合金至熔化,之后升温至1500℃,保温5分钟,保温后,关闭加热电源,使合金自然冷却;
第四步,分别进行“加热-保温-凝固”循环处理3次和5次,使合金获得约150℃和225℃的过冷度;
第五步,将过冷凝固合金通过熔体快淬凝固成带材;
第六步,将获得的带材在300℃去应力退火,获得Fe基非晶合金;
不同过冷度下合金的饱和磁化强度、矫顽力如下表所示:
表3不同过冷度FeSiBC系非晶合金的饱和磁化强度及矫顽力
实施例4
过冷凝固制备FeSiBCu纳米晶合金
制备FeSiBCu体系合金,合金1中Fe含量为80.5at%,Si含量为7.0at%,B含量为12.0at%,Cu含量为0.5at%;合金2中Fe含量为85.0at%,Si含量为2.5at%,B含量为12.0at%,Cu含量为0.5at%;合金3中Fe含量为85.0at%,Si含量为1.2at%,B含量为12.0at%,Cu含量为1.8at%;
第一步,去除合金原料氧化皮后清洗,按照一定的质量比称量原料。将称量后的原料在真空感应熔炼炉内,抽真空达到9×10-4Pa后,充纯度为99.9vol%氩气保护进行熔炼,反复熔炼4次得到合金锭子;
第二步,将合金锭子放入坩埚中,并在其上下表面覆盖Na2B4O7和B2O3两者混合的净化玻璃,两者质量比=1:20,使玻璃净化剂完全包覆合金锭子;
第三步,抽真空达到5×10-3Pa后,充纯度为99.9vol%氩气保护并加热合金至熔化,之后升温至1320℃,保温5分钟,关闭加热电源,使合金自然冷却;
第四步,分别进行“加热-保温-凝固”循环处理3次和4次,使合金获得约205℃和255℃的过冷度;
第五步,将过冷凝固合金通过熔体快淬凝固成带材;
第六步,将获得的带材在450℃晶化退火,获得Fe基纳米晶合金;
不同过冷度下合金的饱和磁化强度、矫顽力如下表所示:
表4不同过冷度FeSiBCu系纳米晶合金的饱和磁化强度及矫顽力
实施例5
过冷凝固制备FeSiBNbCu纳米晶合金
制备FeSiBNbCu体系合金,其中合金1中Fe含量为80.0at%,Si含量为7.0at%,B含量为9.0at%,Nb含量为3.0at%,Cu含量为1.0at%;合金2中Fe含量为82.0at%,Si含量为6.0at%,B含量为9.0at%,Nb含量为2.0at%,Cu含量为1.0at%;合金3中Fe含量为85.0at%,Si含量为4.5at%,B含量为9.0at%,Nb含量为0.5at%,Cu含量为1.0at%;
第一步,去除合金原料氧化皮后清洗,按照一定的质量比称量原料。将称量后的原料在真空电弧熔炼炉内,抽真空达到8×10-4Pa后,充纯度为99.9vol%氩气保护进行熔炼,反复熔炼6次得到合金锭子;
第二步,将合金锭子放入坩埚中,并在其上下表面覆盖Na2B4O7和B2O3两者混合的净化玻璃,两者质量比=1:10,使玻璃净化剂完全包覆合金锭子;
第三步,抽真空达到8×10-3Pa后,充纯度为99.9vol%氮气保护并加热合金至熔化,之后升温至1380℃,保温1分钟,关闭加热电源,使合金自然冷却;
第四步,分别进行“加热-保温-凝固”循环处理5次和6次,使合金获得约190℃和225℃的过冷度;
第五步,将过冷凝固合金通过熔体快淬凝固成带材;
第六步,将获得的带材在550℃晶化退火,获得Fe基纳米晶合金;
不同过冷度下合金的饱和磁化强度、矫顽力如下表所示:
表5不同过冷度FeSiBNbCu系纳米晶合金的饱和磁化强度及矫顽力
实施例6
过冷凝固制备FeSiBMoCu纳米晶合金
制备FeSiBMoCu体系合金,其中合金1中Fe含量为80.0at%,Si含量为7.0at%,B含量为9.0at%,Mo含量为3.0at%,Cu含量为1.0at%;合金2中Fe含量为82.0at%,Si含量为6.0at%,B含量为9.0at%,Mo含量为2.0at%,Cu含量为1.0at%;合金3中Fe含量为83.3at%,Si含量为5.0at%,B含量为9.0at%,Mo含量为0.7at%,Cu含量为1.0at%;
第一步,去除合金原料氧化皮后清洗,按照一定的质量比称量原料。将称量后的原料在真空感应熔炼炉内,抽真空达到8×10-4Pa后,充纯度为99.9vol%氩气保护进行熔炼,反复熔炼4次得到合金锭子;
第二步,将合金锭子放入坩埚中,并在其上下表面覆盖Na2B4O7和B2O3两者混合的净化玻璃,两者质量比=1:1,使玻璃净化剂完全包覆合金锭子;
第三步,抽真空达到1×10-2Pa后,充纯度为99.9vol%氩气保护并加热合金至熔化,之后升温至1370℃,保温6分钟,关闭加热电源,使合金自然冷却;
第四步,分别进行“加热-保温-凝固”循环处理3次和5次,使合金获得约175℃和255℃的过冷度;
第五步,将过冷凝固合金通过熔体快淬凝固成带材;
第六步,将获得的带材在500℃晶化退火,获得Fe基纳米晶合金;
不同过冷度下合金的饱和磁化强度、矫顽力如下表所示:
表6不同过冷度FeSiBMoCu系纳米晶合金的饱和磁化强度及矫顽力
实施例7
过冷凝固制备FeCoSiBCCu纳米晶晶合金
制备FeCoSiBCCu体系合金,其中合金1中Fe含量为80.0at%,Co含量为5.0at%,Si含量为1.5at%,B含量为9.0at%,C含量为3.0at.%,Cu含量为1.5at%;合金2中Fe含量为75.0at%,Co含量为10.0at%,Si含量为1.5at%,B含量为9.0at%,C含量为3.0at%,Cu含量为1.5at%;合金3中Fe含量为70.0at%,Co含量为15.0at%,Si含量为1.5at%,B含量为9.0at%,C含量为3.0at%,Cu含量为1.5at%;
第一步,去除合金原料氧化皮后清洗,按照一定的质量比称量原料。将称量后的原料在真空电弧熔炼炉内,抽真空达到8×10-4Pa后,充纯度为99.9vol%氩气保护进行熔炼,反复熔炼5次得到合金锭子;
第二步,将合金锭子放入坩埚中,并在其上下表面覆盖Na2B4O7和B2O3两者混合的净化玻璃,两者质量比=1:3,使玻璃净化剂完全包覆合金锭子;
第三步,抽真空达到8×10-3Pa后,充纯度为99.9vol%氮气保护并加热合金至熔化,之后升温至1350℃,保温8分钟,关闭加热电源,使合金自然冷却;
第四步,分别进行“加热-保温-凝固”循环处理3次和6次,使合金获得约150℃和265℃的过冷度;
第五步,将过冷凝固合金通过熔体快淬凝固成带材;
第六步,将获得的带材在400℃晶化退火,获得Fe基纳米晶合金;
不同过冷度下合金的饱和磁化强度、矫顽力如下表所示:
表7不同过冷度FeCoSiBCCu系纳米晶合金的饱和磁化强度及矫顽力
实施例8
过冷凝固制备FeSiBZrHfCu纳米晶晶合金
制备FeSiBZrHfCu体系合金,其中合金1中Fe含量为80.0at%,Si含量为6at%,B含量为9.0at%,Zr含量为3.0at%,Hf含量为1.0at%,Cu含量为1.0at%;合金2中Fe含量为80.0at%,Si含量为6.0at%,B含量为9.0at%,Zr含量为1.0at%,Hf含量为3.0at%,Cu含量为1.0at%;合金3中Fe含量为87.0at%,Si含量为2.0at%,B含量为9.0at%,Zr含量为0.5at%,Hf含量为0.5at%,Cu含量为1.0at%;
第一步,去除合金原料氧化皮后清洗,按照一定的质量比称量原料。将称量后的原料在真空感应熔炼炉或真空电弧熔炼炉内,抽真空达到8×10-4Pa后,充惰性气体保护进行熔炼,反复熔炼6次得到合金锭子;
第二步,抽真空达到4×10-3Pa后,充纯度为99.9vol%氮气保护,将合金铸锭送至悬浮线圈下方,依靠电磁场和感应电流间相互作用形成的洛伦兹力将母合金的稳定悬浮于加热线圈中心;
第三步,利用加热线圈感应加热合金至熔化,之后升温至1400℃,保温10分钟,保温后,关闭加热电源,使合金自然冷却;
第四步,分别进行“加热-保温-凝固”循环处理4次和6次,使合金获得约210℃和270℃的过冷度;
第五步,将过冷凝固合金通过熔体快淬凝固成带材;
第六步,将获得的带材在550℃晶化退火,获得Fe基纳米晶合金;
不同过冷度下合金的饱和磁化强度、矫顽力如下表所示:
表8不同过冷度FeSiBZrHfCu系纳米晶合金的饱和磁化强度及矫顽力
实施例9
过冷凝固制备FeSiBYCu纳米晶晶合金
制备FeSiBYCu体系合金,其中合金1中Fe含量为81.0at%,Si含量为4.0at%,B含量为9.0at%,Y含量为5.0at%,Cu含量为1.0at%;合金2中Fe含量为84.0at%,Si含量为4.0at%,B含量为9.0at%,Y含量为2.0at%,Cu含量为1.0at%;合金3中Fe含量为87.0at%,Si含量为2.0at%,B含量为9.0at%,Y含量为1.0at%,Cu含量为1.0at%;
第一步,去除合金原料氧化皮后清洗,按照一定的质量比称量原料。将称量后的原料在真空电弧熔炼炉内,抽真空达到8×10-4Pa后,充惰性气体保护进行熔炼,反复熔炼4次得到合金锭子;
第二步,抽真空达到5×10-3Pa后,充纯度为99.9vol%氩气保护,将合金铸锭送至悬浮线圈下方,依靠电磁场和感应电流间相互作用形成的洛伦兹力将母合金的稳定悬浮于加热线圈中心;
第三步,利用加热线圈感应加热合金至熔化,之后升温至1500℃,保温3分钟,保温后,关闭加热电源,使合金自然冷却;
第四步,分别进行“加热-保温-凝固”循环处理3次和6次,使合金获得约180℃和255℃的过冷度;
第五步,将过冷凝固合金通过熔体快淬凝固成带材;
第六步,将获得的带材在500℃晶化退火,获得Fe基纳米晶合金;
不同过冷度下合金的饱和磁化强度、矫顽力如下表所示:
表9不同过冷度FeSiBYCu系纳米晶合金的饱和磁化强度及矫顽力
综上,本发明的技术效果为通过玻璃净化结合循环过热或者电磁悬浮熔炼,提高Fe基合金的非晶形成能力,实现降低非晶形成元素含量,提高铁磁性元素含量的目标,获得兼具饱和磁化强度和低矫顽力的非晶纳米晶软磁合金。取得该技术效果的原理为:在玻璃净化结合循环过热的过程中,不仅熔融玻璃能够吸附熔融合金中的异质形核点,过热及升温-保温-降温的冷热循环过程亦能够使异质形核点在高温下热分解,并在内部与表面热对流的过程中产生物质交换,有效减少合金内部的异质形核点。在电磁悬浮熔炼过程中,通过无容器熔炼,有效避免合金在熔炼过程中引入杂质,并且通过高温过热,使合金内部异质形核点热分解。这两种方式均能够减少或避免晶化现象,提高非晶形成能力。一方面,减少异质形核点能够优化合金微观组织结构,减弱对磁交换耦合作用的破坏作用,增大合金饱和磁化强度。另一方面,合金非晶形成能力的提高,利于形成更加无序的非晶结构,有效消除磁晶各向异性,也减少或避免异质形核点对磁反转的阻碍作用,获得低矫顽力。
Claims (6)
1.一种制备高Fe含量非晶纳米晶软磁合金的过冷凝固方法,其特征在于:采用熔融玻璃净化结合循环过热,使合金过冷凝固,减少Fe基非晶纳米晶软磁合金中非晶形成元素的添加量,提高Fe元素的占比,实现提高饱和磁化强度、降低矫顽力的目标;
高Fe含量非晶纳米晶软磁合金化学表达式为FeSiBM,M为P、C、Nb、Mo、Zr、Hf、Mo、Y、Cu、Co中的一种或多种元素,各合金元素原子百分比总和为100%,满足以下元素含量:Fe为80.0~89.0at%,Si为1.0~9.0at%,B为3.0~12.0at%,P为0~5.0at%,C为0~5.0at%,Nb为0~3.0at%,Zr为0~3.0at%,Hf为0~3.0at%,Mo为0~3.0at%,Y为0~5.0at%,Cu为0~2.0at%,Co为0~16.0at%;
熔融玻璃净化过程中采用的玻璃净化剂的制备过程包括:称取纯度不低于98%的粉末状Na2B4O7和B2O3分别置于高纯刚玉坩埚中,于400~600℃烧制1~8小时,再于800~1000℃熔融烧制2~16小时,将烧制后的Na2B4O7和B2O3混合得到净化剂,两者质量比=1:1~20。
2.根据权利要求1所述一种制备高Fe含量非晶纳米晶软磁合金的过冷凝固方法,其特征在于,所述熔融玻璃净化结合循环过热的方法包括以下步骤:
第一步,去除合金原料氧化皮后清洗,称量原料,将称量后的原料在真空感应熔炼炉或真空电弧熔炼炉内,抽真空至少达到10-3Pa后,充惰性气体保护进行熔炼,反复熔炼4~6次得到合金锭子;
第二步,将合金锭子放入坩埚中,并在其上下表面覆盖玻璃净化剂,使玻璃净化剂完全包覆合金锭子,玻璃净化剂与合金锭子的质量比为1:1~5;
第三步,抽真空至少达到10-2Pa后,充惰性气体保护并加热合金至熔化,之后升温至1200~1500℃,保温1~10分钟,关闭加热电源,使合金自然冷却;
第四步,进行“加热-保温-凝固”循环处理3~6次,使合金获得所需过冷度;
第五步,将过冷凝固后的合金通过熔体快淬或雾化方式快速凝固成带材或粉体;
第六步,将获得的带材或粉体通过去应力退火获得Fe基非晶合金,或者通过晶化退火获得Fe基纳米晶合金。
3.根据权利要求2所述的一种制备高Fe含量非晶纳米晶软磁合金的过冷凝固方法,其特征在于,惰性气体为纯度不低于99.9vol%的氩气或氮气。
4.根据权利要求2所述一种制备高Fe含量非晶纳米晶软磁合金的过冷凝固方法,其特征在于,坩埚耐热温度不低于1400℃。
5.根据权利要求2所述的一种制备高Fe含量非晶纳米晶软磁合金的过冷凝固方法,其特征在于,非晶合金退火在晶化温度以下50~100℃温度区间内,纳米晶退火温度在晶化温度以上0~100℃温度区间内。
6.根据权利要求5所述的一种制备高Fe含量非晶纳米晶软磁合金的过冷凝固方法,其特征在于,退火在惰性气体气氛环境中进行。
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