CN115255349A - 一种激光增材制造用低镍奥氏体不锈钢合金粉及其制备方法和应用 - Google Patents
一种激光增材制造用低镍奥氏体不锈钢合金粉及其制备方法和应用 Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 72
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910000963 austenitic stainless steel Inorganic materials 0.000 title claims abstract description 50
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 50
- 239000000654 additive Substances 0.000 title claims abstract description 37
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- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
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- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
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- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 claims abstract description 4
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- 229910052751 metal Inorganic materials 0.000 claims description 27
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 claims description 3
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- 229910001566 austenite Inorganic materials 0.000 description 4
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 4
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种激光增材制造用低镍奥氏体不锈钢合金粉及其制备方法和应用。本发明属于低镍奥氏体不锈钢激光增材制造领域。本发明的目的是为了解决目前适用于传统铸造的低镍奥氏体不锈钢组分设计无法满足SLM技术的要求,最终导致所得低镍奥氏体不锈钢构件存在带状偏析、等向性差以及裂纹缺陷的技术问题。本发明的合金粉按质量分数由镁粉:0.5%‑1%、电解锰:22%‑25%、硅铁:0.5%‑1%、铬粉:10%‑12%、镍粉:8%‑10%、钼铁:0.5%‑1%、铜粉:5%‑10%、钴粉:1%‑2%、钛粉:0.5%‑1%、铋粉:0.5%‑1%和余量氮化铬铁粉制备而成。方法:将原料粉混合均匀后进行高温熔炼,然后对熔融状态的合金进行二次搅拌混合,再进行气雾化制粉。本发明的合金粉用于选区激光熔化3D打印低镍奥氏体不锈钢构件。
Description
技术领域
本发明属于低镍奥氏体不锈钢激光增材制造领域,具体涉及一种激光增材制造用低镍奥氏体不锈钢合金粉及其制备方法和应用。
背景技术
低镍奥氏体不锈钢是一种使用N元素代替价格昂贵的Ni元素作为主要奥氏体化元素的强度高、韧性好、耐腐蚀性能优良的资源节约型不锈钢,由于固溶在钢中的N元素有着较高的层错能,可优化材料微观组织、大幅提高材料综合性能,近年来在海工装备、热交换器、建筑装饰、管道及压力容器等行业受到广泛关注。
激光增材制造技术有别于传统弧焊熔覆工艺,近年来得到了快速发展。激光增材制造技术有多种形式,其中选区激光熔化技术(Selective laser melting,SLM)在3D打印精密零件和复杂构件领域应用最为广泛。SLM技术选用金属粉末作为原料,通过逐层铺粉和扫描熔化得到最终所需的零件结构。选区激光熔化过程中形成的微熔池具有极快的冷却速率(106K/s~107K/s),在这种非平衡凝固的工艺中,元素扩散行为可以被有效抑制,从而可以降低宏观偏析程度,并且晶粒可以大幅得到细化,最终获得组织、性能、结构均匀良好的成形件。因此,激光增材制造技术解决了复杂金属零件成形困难等一系列问题,节约了85%以上的昂贵原材料,还能节省大量的再加工时间,从而应用前景广阔。
通过SLM技术进行低镍奥氏体不锈钢粉的扫描熔化,得到所需的耐腐蚀、强度高的不锈钢零件或堆覆层,从而可以显著降低耐腐蚀金属构件的生产成本,提高生产效率,因此,开发一种低镍奥氏体不锈钢激光增材制造用金属粉具有重要的实际应用意义。由于传统铸造方法与SLM技术工艺参数的巨大差异导致适用于传统铸造的低镍奥氏体不锈钢组分设计无法满足SLM技术的要求,最终导致所得低镍奥氏体不锈钢构件存在带状偏析和等向性差以及裂纹等缺陷。
发明内容
本发明的目的是为了解决目前适用于传统铸造的低镍奥氏体不锈钢组分设计无法满足SLM技术的要求,最终导致所得低镍奥氏体不锈钢构件存在带状偏析、等向性差以及裂纹缺陷的技术问题,而提供一种激光增材制造用低镍奥氏体不锈钢合金粉及其制备方法和应用。
本发明的一种激光增材制造用低镍奥氏体不锈钢合金粉按质量分数由镁粉:0.5%-1%、电解锰:22%-25%、硅铁:0.5%-1%、铬粉:10%-12%、镍粉:8%-10%、钼铁:0.5%-1%、铜粉:5%-10%、钴粉:1%-2%、钛粉:0.5%-1%、铋粉:0.5%-1%和余量氮化铬铁粉制备而成。
进一步限定,氮化铬铁粉的氮含量为:8%-10%。
进一步限定,镁粉、电解锰、硅铁的粒度为80-200目,其余金属粉粒度均为80目以下。
本发明的一种激光增材制造用低镍奥氏体不锈钢合金粉的制备方法按以下步骤进行:
将原料粉混合均匀后进行高温熔炼,然后对熔融状态的合金进行二次搅拌混合,再进行气雾化制粉。
进一步限定,高温熔炼温度为1750-1930℃。
进一步限定,熔炼过程中采用氦气保护,气流量为30L/min-40L/min。
进一步限定,二次搅拌混合时间为30min-40min。
进一步限定,气雾化制粉得到的合金粉粒径为50μm-150μm。
本发明的一种激光增材制造用低镍奥氏体不锈钢合金粉用于选区激光熔化3D打印低镍奥氏体不锈钢构件。
进一步限定,选区激光熔化3D打印低镍奥氏体不锈钢构件熔敷金属化学成分及含量为:C:0.05%-0.07%、Si:0.45%-0.50%、Mn:4.45%-4.90%、Ni:4.50%-5.25%、Mo:0.25%-0.30%、Cu:2.25%-2.50%、Cr:15.1%-19.5%、N:0.40%-0.59%、S≤0.001、P≤0.010、Co:0.25%-0.33%、Ti:0.15%-0.21%、Bi:0.12%-0.18%、Mg:0.15%-0.20%、余量为Fe。
本发明与现有技术相比具有的显著效果:
本发明通过成分设计获得适用于选区激光熔化3D打印的合金粉,通过合金粉中各元素在选区激光熔化3D打印工艺参数下的协同增效作用促进了低熔点共晶的形成,降低了增材制造产生的残余热应力,消除构件在成形时所产生的微裂纹及宏观开裂问题,提高了构件的致密度,从而进一步提升低镍奥氏体不锈钢构件的高温力学性能。本发明在现有低镍奥氏体不锈钢增材制造打印成形过程中,其制件中均无微裂纹及宏观裂纹存在,成形制件高温力学性能优异。具体优点如下:
1)本发明通过控制Mo粉和Mg粉含量,使经选区激光熔化3D打印的低镍奥氏体不锈钢增材金属中的铁素体含量应控制在5%-8%之间,在此含量下,可以打乱奥氏体柱状晶的方向一致性,并使奥氏体贯穿于晶粒之间形成腐蚀介质的运输通道,从而降低焊缝金属产生热裂纹的倾向,提高焊缝的耐晶间腐蚀性能,但铁素体含量不宜过高,若铁素体含量过高,不仅会在某些介质中引起选择性腐蚀,而且会使堆焊层的铁素体发生δ-σ相的转变,造成堆焊层的脆化,因此,控制低镍不锈钢金属粉增材制造打印金属中Mo:0.20%-0.30%、Mg:0.15%-0.20%之间。
2)低镍奥氏体不锈钢金属粉中,含量在2.25%~2.50%范围内的Cu可以在不锈钢中形成一定含量且弥散分布的金属间化合物,可以提高增材金属层的耐腐蚀性能和塑性,而过多含量的Cu则会形成过多的金属间化合物,大幅降低增材金属层的结合强度。进一步地,本发明采用Cu元素与Ni元素含量协同调控的方式,将Cu元素的添加量限定为Ni元素含量的一半左右,一方面,避免了随着熔点相对较低Cu在激光高温下形成的液态富铜相渗透到不锈钢晶界中而导致的晶间裂纹的产生,还可以有效避免产生“热脆性”的现象。另一方面,通过Cu元素与Ni元素含量的协同调控使Cu在不锈钢中的溶解度提高,进而使富铜相的熔点升高,从而有效抑制液态富铜相沿着晶界形成裂纹。因此,本发明中的各金属成分的合理配比不会在激光增材制造后产生裂纹,并改善了焊缝成形、提高了层间结合力的同时也增加了致密度。
3)低镍奥氏体不锈钢金属粉中,Cr是保证低镍不锈钢耐蚀性的主要因素,Ni是不锈钢奥氏体化的最关键元素,并可提高不锈钢焊接接头的塑韧性和液态熔池金属的流动性,在保证上述作用的同时,综合考虑生产成本,增材金属中的Cr控制在15.1%-19.5%,Ni控制在4.50%-5.25%之间。
4)低镍奥氏体不锈钢金属粉中,Ti是强碳化物形成元素,易与不锈钢中的C和N形成稳定的金属间化合物,高温下也不易分解,起到了稳定Cr的作用,保证了不锈钢的耐蚀性,但是过多的Ti会严重影响液态高温液态金属的流动铺展性,易产生未熔合、气孔等缺陷。
5)低镍奥氏体不锈钢金属粉中,Si有一定的脱氧作用,含量0.40%以上的Si可以增加奥氏体不锈钢增材制造金属的纯净度,减少缺陷发生概率,但Si含量超过0.50%以上焊接凝固裂纹敏感性就增强。
6)低镍奥氏体不锈钢金属粉中,Mn同样是良好的脱氧元素且能抑制作为杂质的S在奥氏体不锈钢中造成的加工脆性,但Mn含量超过5%时会导致奥氏体不锈钢在高温时延展性、韧性下降。
7)低镍奥氏体不锈钢金属粉中,Co是一种奥氏体形成元素,在钢中不形成碳化物,但对碳化物的形核和长大有影响。Co的存在提高了碳的活度和扩散系数,从而促进了含铬碳化物的析出,增加了晶间腐蚀倾向。但是Co可使不锈钢中奥氏体晶粒尺寸减小,会提高增材制造层的屈服强度和硬度。因此,为保证增材制造层的综合性能,Co的含量应控制在0.25%-0.33%之间。
8)低镍奥氏体不锈钢金属粉中,N元素可以代替价格昂贵的Ni元素,作为主要奥氏体化元素,具有提高强度、韧性和耐腐蚀性等作用,同时固溶在不锈钢中的N元素有着较高的层错能,可优化材料微观组织、大幅提高材料综合性能。而过多的N无法有效固溶于不锈钢中,并且在增材制造过程中很容易逸出或产生析出相,不但增加了制造成本也存在恶化性能的隐患。
附图说明
图1为实施例1中增材制造层微观形貌照片;
图2为实施例2中增材制造层微观形貌照片。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。
下述实施例中所使用的实验方法如无特殊说明均为常规方法。所用材料、试剂、方法和仪器,未经特殊说明,均为本领域常规材料、试剂、方法和仪器,本领域技术人员均可通过商业渠道获得。
实施例1、本实施例的一种激光增材制造用低镍奥氏体不锈钢合金粉按质量分数由镁粉:0.5%、电解锰:22%、硅铁:0.5%、铬粉:10%、镍粉:8%、钼铁:0.5%、铜粉:5%、钴粉:1%、钛粉:0.5%、铋粉:0.5%和余量氮化铬铁粉制备而成,其中所述氮化铬铁粉的氮含量为:8%,所述镁粉、电解锰、硅铁的粒度均为80-200目,除了镁粉、电解锰、硅铁之外的其余金属粉粒度均为80目以下。
制备激光增材制造用低镍奥氏体不锈钢合金粉的方法按以下步骤进行:
将镁粉、电解锰、硅铁、铬粉、镍粉、钼铁、铜粉、钴粉、钛粉、铋粉和氮化铬铁粉在混粉器内混合均匀,然后送入坩埚,在1750℃下进行高温熔炼,熔炼过程中采用氦气保护,气流量为30L/min,然后用搅拌装置对熔融状态的合金二次搅拌混合30min,再进行气雾化制粉,气雾化制粉得到的合金粉粒径为50μm。
将上述激光增材制造用低镍奥氏体不锈钢金属粉用于选区激光熔化3D打印低镍奥氏体不锈钢构件;
所述选区激光熔化3D打印工艺参数如表1所示:
表1选区激光熔化3D打印工艺参数
选区激光熔化3D打印低镍奥氏体不锈钢构件的熔敷金属化学成分及含量为:C:0.05%、Si:0.45%、Mn:4.45%、Ni:4.50%、Mo:0.25%、Cu:2.25%、Cr:15.1%、N:0.40%、S≤0.001、P≤0.010、Co:0.25%、Ti:0.15%、Bi:0.12%、Mg:0.15%、余量为Fe。
熔覆层的微观形貌如图1所示,从图1可以看出,微观组织中未发现气孔、裂纹、熔合不良等缺陷,同时组织较均匀且细化。
实施例2、本实施例的一种激光增材制造用低镍奥氏体不锈钢合金粉按质量分数由镁粉:1%、电解锰:25%、硅铁:1%、铬粉:12%、镍粉:10%、钼铁:1%、铜粉:10%、钴粉:2%、钛粉:1%、铋粉:1%和余量氮化铬铁粉制备而成,其中所述氮化铬铁粉的氮含量为:10%,所述镁粉、电解锰、硅铁的粒度均为80-200目,除了镁粉、电解锰、硅铁之外的其余金属粉粒度均为80目以下。
制备激光增材制造用低镍奥氏体不锈钢合金粉的方法按以下步骤进行:
将镁粉、电解锰、硅铁、铬粉、镍粉、钼铁、铜粉、钴粉、钛粉、铋粉和氮化铬铁粉在混粉器内混合均匀,然后送入坩埚,在1930℃下进行高温熔炼,熔炼过程中采用氦气保护,气流量为40L/min,然后用搅拌装置对熔融状态的合金二次搅拌混合40min,再进行气雾化制粉,气雾化制粉得到的合金粉粒径为150μm。
将上述激光增材制造用低镍奥氏体不锈钢金属粉用于选区激光熔化3D打印低镍奥氏体不锈钢构件;
所述选区激光熔化3D打印工艺参数如表2所示:
表2选区激光熔化3D打印工艺参数
选区激光熔化3D打印低镍奥氏体不锈钢构件的熔敷金属化学成分及含量为:C:0.07%、Si:0.50%、Mn:4.90%、Ni:5.25%、Mo:0.30%、Cu:2.50%、Cr:19.5%、N:0.59%、S≤0.001、P≤0.010、Co:0.33%、Ti:0.21%、Bi:0.18%、Mg:0.20%、余量为Fe。
熔覆层的微观形貌如图2所示,从图2可以看出,微观组织中未发现气孔、裂纹、熔合不良等缺陷,同时组织较均匀且细化。
Claims (10)
1.一种激光增材制造用低镍奥氏体不锈钢合金粉,其特征在于,合金粉按质量分数由镁粉:0.5%-1%、电解锰:22%-25%、硅铁:0.5%-1%、铬粉:10%-12%、镍粉:8%-10%、钼铁:0.5%-1%、铜粉:5%-10%、钴粉:1%-2%、钛粉:0.5%-1%、铋粉:0.5%-1%和余量氮化铬铁粉制备而成。
2.根据权利要求1所述的一种激光增材制造用低镍奥氏体不锈钢合金粉,其特征在于,氮化铬铁粉的氮含量为:8%-10%。
3.根据权利要求1所述的一种激光增材制造用低镍奥氏体不锈钢合金粉,其特征在于,镁粉、电解锰、硅铁的粒度为80-200目,其余金属粉粒度均为80目以下。
4.权利要求1-3任意一项所述的一种激光增材制造用低镍奥氏体不锈钢合金粉的制备方法,其特征在于,该方法按以下步骤进行:
将原料粉混合均匀后进行高温熔炼,然后对熔融状态的合金进行二次搅拌混合,再进行气雾化制粉。
5.根据权利要求4所述的方法,其特征在于,高温熔炼温度为1750-1930℃。
6.根据权利要求4所述的方法,其特征在于,熔炼过程中采用氦气保护,气流量为30L/min-40L/min。
7.根据权利要求4所述的方法,其特征在于,二次搅拌混合时间为30min-40min。
8.根据权利要求4所述的方法,其特征在于,气雾化制粉得到的合金粉粒径为50μm-150μm。
9.权利要求1-3任意一项所述的一种激光增材制造用低镍奥氏体不锈钢合金粉用于选区激光熔化3D打印低镍奥氏体不锈钢构件。
10.根据权利要求9所述的应用,其特征在于,选区激光熔化3D打印低镍奥氏体不锈钢构件熔敷金属化学成分及含量为:C:0.05%-0.07%、Si:0.45%-0.50%、Mn:4.45%-4.90%、Ni:4.50%-5.25%、Mo:0.25%-0.30%、Cu:2.25%-2.50%、Cr:15.1%-19.5%、N:0.40%-0.59%、S≤0.001、P≤0.010、Co:0.25%-0.33%、Ti:0.15%-0.21%、Bi:0.12%-0.18%、Mg:0.15%-0.20%、余量为Fe。
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