CN112095045B - 增材制造用粉末以及模铸模具部件 - Google Patents
增材制造用粉末以及模铸模具部件 Download PDFInfo
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Abstract
本发明涉及一种增材制造用粉末,以质量%计,其组成由以下元素构成:0.25<C<0.40,0.001≤Si≤0.15,0.30≤Mn≤0.45,5.0≤Cr≤5.5,1.0≤Mo≤1.5,0.35≤V≤0.45,0.01≤N≤0.05,0.01≤O≤0.04,以及任选地,P<0.10,Cu<0.20,Ni<0.20,Al<0.05,Zr<0.05,S<0.20,Pb<0.20,Bi<0.20,Nb<0.20,Ti<0.20,B<0.10和Co<0.20,余量为Fe和不可避免的杂质,其中增材制造用粉末的表面被覆有氧化物膜,并且氧化物膜的厚度为3nm以上30nm以下。
Description
技术领域
本发明涉及增材制造用粉末以及模铸模具部件,并且特别涉及能够在增材制造设备中平稳传送的增材制造用粉末,以及通过对增材制造用粉末进行增材制造而获得的模铸模具部件。
背景技术
“模铸”是一种将熔融金属压装入模具中,并在模具中凝固从而制作铸件的方法。模铸具有可以在短时间内大量制作精密铸件的优点。
用于模铸的典型模具在内部具有冷却水回路,使得压装入模具中的熔融金属可以在短时间内凝固。通常通过诸如切削之类的机械加工形成冷却水回路。此外,在模铸期间,反复加热和冷却模具。
因此,用于模铸模具的钢材需要具有(a)高机械加工性,使得可以通过切削形成冷却水回路,(b)高耐久性,以抵抗由使用时的热历程引起的损伤(热裂纹),以及(c)高热导率,使得可以在短循环内压装入熔融金属并且使熔融金属凝固。
为了满足这些要求,通常将诸如JIS SKD61之类的热加工用工具钢用于模铸模具。
然而,通过切削形成的冷却水回路局限为类似直线的回路。因此,通过切削形成的冷却水回路不适合功能性地冷却复杂形状。
此外,SKD61中为了确保机械加工性而包含的约0.9质量%的Si会导致钢的热导率降低。因此,使用诸如SKD61之类的背景技术中的热加工用工具钢的模铸模具具有有限的冷却性能。
为了解决该问题,已经提出了各种建议。
例如,专利文献1公开了一种使用具有预定组成的钢粉末从而进行模铸模具的部件的增材制造的方法。
该文献建议(a)可以通过使用增材制造方法容易地形成因过于复杂以至于不能通过切削制作的冷却回路,以及(b)可以优化钢粉末的组成以提高冷却效率,抑制热裂纹并防止水冷却孔开裂。
“增材制造方法”是一种将类似于薄片的层彼此层叠以制造三维结构的方法,其中薄片对应于水平切割成圆形切片的三维结构。用于层叠类似于薄片的层的方法的实例包括(a)重复进行形成由金属粉末制成的薄层的步骤、以及用诸如激光束或电子束之类的能量束照射粉末层从而使粉末层局部熔融并凝固的步骤的方法,以及(b)将具有预定形状的薄片置于其他薄片的顶部,并通过扩散与其他薄片结合的方法。
在这些方法中,使用金属粉末的增材制造方法具有这样的优点,
即,仅通过改变能量束的照射位置就可以形成各种三维形状。因此,当将该方法应用于制造模铸模具时,可以有利地在模具中设置非线性冷却水回路或三维冷却水回路。
为了通过利用这种使用金属粉末的增材制造方法有效地制造各种构件,需要将金属粉末平稳地传送到制造区域。然而,由于聚集,在背景技术中通常难以传送金属粉末。
专利文献1:JP-A-2016-145407
发明内容
本发明的目的是提供一种增材制造用粉末,其不易于聚集,而是可以通过增材制造设备平稳地传送。
本发明的另一目的是提供一种通过对增材制造用粉末进行增材制造而获得的模铸模具部件。
也就是说,本发明涉及以下构成(1)至(4)。
(1)一种增材制造用粉末,以质量%计,该增材制造用粉末的组成由以下元素构成:
0.25<C<0.40,
0.001≤Si≤0.15,
0.30≤Mn≤0.45,
5.0≤Cr≤5.5,
1.0≤Mo≤1.5,
0.35≤V≤0.45,
0.01≤N≤0.05,
0.01≤O≤0.04,以及
任选地,
P<0.10,
Cu<0.20,
Ni<0.20,
Al<0.05,
Zr<0.05,
S<0.20,
Pb<0.20,
Bi<0.20,
Nb<0.20,
Ti<0.20,
B<0.10和
Co<0.20,
余量为Fe和不可避免的杂质,
其中增材制造用粉末的表面被覆有氧化物膜,并且
氧化物膜的厚度为3nm以上30nm以下。
(2)根据(1)所述的增材制造用粉末,以质量%计,包含选自由以下元素组成的组中的至少一种元素:
0.001<Al<0.05,和
0.001<Zr<0.05。
(3)根据(1)或(2)所述的增材制造用粉末,以质量%计,包含选自由以下元素组成的组中的至少一种元素:
0.001<S<0.20,
0.001<Pb<0.20,和
0.001<Bi<0.20。
(4)一种模铸模具部件,其通过对根据(1)至(3)中任一项所述的增材制造用粉末进行增材制造而获得。
根据增材制造方法,可以将构件制造成近终型(near net shape),使得与背景技术相比,可降低加工量。因此,即使Si含量降低,也可以抑制由机械加工性的劣化引起的缺点,并且由于Si含量的降低,反而可以提高热导率。
此外,金属粉末局部地熔融并凝固,从而在凝固时基本上已经淬火。由于这种状态,可以省略对增材制造制品进行淬火的步骤。此外,由于不需要淬火步骤,因此不需要在结构体中形成VC(碳化钒),其中在背景技术中,认为VC是防止淬火期间的晶粒粗大化所需的。
此外,当组分已调节为具有预定组成的金属粉末的表面被覆有氧化物膜时,可以抑制粉末聚集。在用这种粉末进行增材制造时,除了上述效果以外,还可以平稳地传送粉末。
具体实施方式
以下将详细描述本发明的实施方案。
[1.增材制造用粉末]
[1.1.成分]
[1.1.1.主要组成元素]
根据本发明的增材制造用粉末包含以下元素,余量为Fe和不可避免的杂质。以下将对添加元素的种类、元素的组成范围以及限定该范围的原因进行描述。除非另外说明,在本说明书中,各化学成分的值以质量%表示。
(1)0.25<C<0.40
C为具有提高增材制造制品的硬度并改善耐热裂纹性的效果的元素。C含量必须超过0.25质量%以实现高耐热裂纹性。C含量优选为0.28质量%以上。
另一方面,当C含量过高时,增材制造制品的韧性降低。因此,C含量必须低于0.40质量%。C含量优选为0.38质量%以下。
(2)0.001≤Si≤0.15
Si为具有降低增材制造制品的热导率的效果的元素。为了获得高热导率,Si含量必须为0.15质量%以下。
另一方面,Si也作为脱氧剂。当Si含量过低时,脱氧不充分。因此,Si含量必须为0.001质量%以上。Si含量优选为0.03质量%以上。
(3)0.30≤Mn≤0.45
Mn为具有改善硬化性的效果的元素。为了获得高硬化性,Mn含量必须为0.30质量%以上。Mn含量优选为0.33质量%以上。
另一方面,由于熔化和凝固的区域非常小,所以在增材制造制品中熔化区域具有相对较快的冷却速率。也就是说,增材制造制品在凝固时基本上已经淬火。因此,即使添加多于所需量的Mn,也不能获得更多的效果。多于所需量的Mn无实际用途。因此,Mn含量必须为0.45质量%以下。Mn含量优选为0.42质量%以下。
(4)5.0≤Cr≤5.5
Cr为具有改善冷却水回路的表面的耐锈蚀性的效果的元素。为了获得高耐锈蚀性,Cr含量必须为5.0质量%以上。Cr含量优选为5.2质量%以上。
另一方面,当Cr含量过高时,增材制造制品的热导率降低。因此,Cr含量必须为5.5质量%以下。Cr含量优选为5.4质量%以下。
(5)1.0≤Mo≤1.5
Mo为具有改善耐高温性的效果的元素。为了获得高耐高温性,Mo含量必须为1.0质量%以上。Mo含量优选为1.1质量%以上。
另一方面,当Mo含量过高时,韧性可能降低至足以使得在冷却水回路的拐角部分处产生裂纹。因此,Mo含量必须为1.5质量%以下。Mo含量优选为1.3质量%以下。
(6)0.35≤V≤0.45
V为当在高温下使增材制造制品回火时具有二次硬化增材制造制品的效果的元素。为了获得高硬度,V含量必须为0.35质量%以上。
另一方面,当V含量过高时,易于在增材制造制品凝固时形成粗碳化物。粗碳化物易于作为裂纹的起点。因此,V含量必须为0.45质量%以下。V含量优选为0.42质量%以下。
(7)0.01质量%≤N≤0.05质量%
N为不可避免地包含的元素。在固溶体中,N为以与C同样的方式有助于提高硬度的元素。为了获得这样的效果,N含量必须为0.01质量%以上。
另一方面,当N含量过高时,易于形成粗碳氮化物。粗碳氮化物易于作为裂纹的起点。因此,N含量必须为0.05质量%以下。
(8)0.01≤O≤0.04
O为具有在粉末的表面形成氧化物从而抑制粉末的聚集的效果(即,改善增材制造设备的粉末传送性能的效果)的元素。为了获得这样的效果,O含量必须为0.01质量%以上。
另一方面,当O含量过高时,氧化物层具有过大的厚度。厚的氧化物层易于在增材制造制品中形成氧化物,从而作为裂纹的起点。因此,O含量必须为0.04质量%以下。
[1.1.2.任选的组成元素]
根据本发明的增材制造用粉末可以进一步包含如下的一种或多种元素。以下将对添加元素的种类、元素的组成范围以及限定该范围的原因进行描述。
(9)P<0.10;
(10)Cu<0.20;以及
(11)Ni<0.20
这些元素为包含在原料废料中的元素。可以包含这些元素,只要这些元素分别低于上述含量即可。
(12)0.001<Al<0.05;以及
(13)0.001<Zr<0.05
Al和Zr各自具有在粉末的表面形成致密氧化物膜的效果。为了获得这样的效果,Al含量和Zr含量各自优选高于0.001质量%。
另一方面,即使当过量添加这些元素时,包含的这些元素相对于氧的比例增加,从而对氧化物膜的形成没有影响。因此,Al含量和Zr含量各自优选低于0.05质量%。
(14)0.001<S<0.20;
(15)0.001<Pb<0.20;以及
(16)0.001<Bi<0.20
可以添加这些元素以改善可自由切削性(free cuttability)。为了获得这样的效果,S含量、Pb含量和Bi含量各自优选为高于0.001质量%。
另一方面,当这些元素的含量过高时,韧性降低。因此,S含量、Pb含量和Bi含量各自优选为低于0.20质量%。
(17)Nb<0.20;
(18)Ti<0.20;
(19)B<0.10;以及
(20)Co<0.20
这些元素为原料废料中包含的杂质。可以包含这些元素中的每一种,只要这些元素的含量低于上述含量即可。
[1.2.氧化物膜]
根据本发明的增材制造用粉末的表面被覆有氧化物膜。这是与背景技术不同之处。粉末的表面中的氧化物膜的厚度对粉末的传送性能和增材制造制品的韧性产生影响。
在本文中,“氧化物膜的厚度”对应于通过俄歇能谱测量的深度,并且可通过该深度估计所形成的氧化物。形成氧化物的主要氧化物通常为金属氧化物,例如SiO2。当添加Al时,主要氧化物为Al2O3。由SiO2标准试样或Al2O3标准试样的溅射时间和深度之间的关系来计算深度。
当氧化物膜的厚度太薄时,粉末易于聚集,从而降低粉末的传送性能。因此,氧化物膜的厚度优选为3nm以上。
另一方面,当氧化物膜的厚度太厚时,粗氧化物残留在增材制造制品中,使得氧化物易于作为裂纹的起点。因此,氧化物膜的厚度优选为30nm以下。
[1.3.平均粒径]
增材制造用粉末的平均粒径不受特别地限制,但是可以根据目的选择最佳值。最佳平均粒径取决于增材制造设备的规格。增材制造用粉末的平均粒径通常为约1μm至200μm。平均粒径优选为约15μm至45μm。
[2.增材制造用粉末的制造方法]
可以(例如)通过如下方法制造根据本发明的增材制造用粉末,这些方法为:(a)雾化法,其中将空气、水、惰性气体等的射流喷射到熔融金属上;(b)通过机械方式将铸块形成为粉末的方法;等等。
可以通过考虑在随后的分级等步骤中将获得的氧的量(即,考虑到将形成的天然氧化物)来调节熔融金属中的氧含量,从而获得具有所需厚度的氧化物膜。此外,通过在具有一定氧分压的气氛中加热粉末,也可以获得氧化物膜。
[3.模铸模具部件]
根据本发明的模铸模具部件包括通过对根据本发明的增材制造用粉末进行增材制造而获得的制品。
这种模铸模具部件的实例包括嵌套、芯型栓、芯部等。
此外,通过使用这种模铸模具部件制造的模铸部件的实例包括发动机组、变速箱、悬挂塔架等。
具体而言,可以通过重复步骤(a)和步骤(b),从而制造根据本发明的模铸模具部件,其中步骤(a)为形成包含根据本发明的增材制造用粉末的薄粉末层的步骤,步骤(b)为用诸如激光束或电子束之类的能量束照射粉末层,从而局部熔化粉末层并使粉末层凝固的步骤。
此外,如果需要,可将如此获得的模铸模具部件在500℃至700℃进行回火。
增材制造设备的种类、用于增材制造的条件和关于回火的其他条件不受特别地限制,但是可以根据目的进行最佳选择。
[4.效果]
该增材制造方法可以将构件制造为近终型,使得与背景技术相比,可降低加工量。因此,即使降低Si含量,也可以抑制由机械加工性的劣化引起的缺点,并且由于Si含量的降低,反而可以提高热导率。
此外,金属粉末局部地熔融并凝固,从而在凝固时基本上已经淬火。由于这种状态,可以省略对增材制造制品进行淬火的步骤。此外,由于不需要淬火步骤,因此不需要在结构体中形成VC,其中在背景技术中,认为VC是防止淬火期间的晶粒粗大化所需的。
此外,当成分已调节为具有预定组成的金属粉末的表面被覆有氧化物膜时,可以抑制粉末聚集。在使用这种粉末的增材制造中,除了上述效果以外,还可以平稳地传送粉末。
例子
(实施例1至20以及比较例1至5)
[1.试样的制造]
[1.1.增材制造用粉末的制造]
使用通过共混而具有预定组成的原料,通过雾化法制造粉末。接下来,除比较例1以外,对如此获得的粉末进行氧化处理,以在粉末的表面形成具有预定厚度的氧化物膜。表1示出了获得的增材制造用粉末各自的组成(余量为Fe和不可避免的杂质)。
表1
[1.2.增材制造制品的制造]
通过使用增材制造用粉末制造增材制造制品。将由Concept Laser GmbH制造的M2用作增材制造设备。
[2.试验方法]
[2.1.铺展性]
对于增材制造,在用激光束照射之前,将金属粉末铺展于增材制造区域中。目视评价所铺展的金属粉末的均匀性。“A”表示粉末层的表面中不存在凹凸的状态。“B”表示粉末层的表面由于聚集的粉末而升高或由于粉末的不充分供给而下降的状态。
[2.2.制品的硬度]
通过洛氏硬度C标尺测定增材制造制品(未回火)的硬度。
[2.3.冲击值]
由增材制造制品(未回火)制作具有2mm的U形缺口的Charpy冲击试验片。通过使用获得的试验片测定冲击值。在室温的测定条件下使用根据JIS B 7722:2018的测定试验仪。
[2.4.耐热裂纹性]
由增材制造制品(未回火)制造直径为70mm的柱状试验片。重复进行利用高频加热将试验片的平坦表面加热到580℃的步骤以及水冷却步骤,直至在试验片的表面产生裂纹为止。将产生裂纹时的重复次数视为耐热裂纹性的指标。
[2.5.热导率]
从增材制造制品(未回火)上切出尺寸为10mm(直径)×(2mm)的试验片。使用获得的试验片通过激光闪光法测定热导率。用激光照射密度已知的黑化试验片,并且在温度升高时测定比热和热扩散率。由此,计算热导率。在室温的条件下进行测定。
[2.6.氧化物膜厚度]
对于各种粉末,通过俄歇能谱测量氧化物膜厚度。
[3.结果]
表2示出了结果。从表2中,可以推断出如下这些事实。(1)比较例1的铺展性较低。认为这是因为粉末表面的氧化物膜的厚度较薄以至于使粉末聚集。(2)在比较例2中,制品的硬度较低,并且耐热裂纹性也较低。认为这是因为C含量较低。(3)比较例3的冲击值较低。认为这是因为V量过高以至于使得生成了粗碳化物。
(4)在比较例4中,热导率较低。认为这是因为Si量过高。(5)在比较例5中,冲击值较低。认为这是因为O量过高(即,在粉末的表面形成过多的氧化物膜)。(6)实施例1至20中各自的铺展性良好,制品的硬度较高,耐热裂纹性优异,冲击值较高,并且热导率较高。
表2
尽管对本发明的实施方案进行了以上描述,但本发明并不限定于上述实施方案。在不脱离本发明的主旨的情况下,可以对本发明进行各种修改。
本申请基于在2019年6月18日提交的日本专利申请No.2019-112613以及在2020年3月12日提交的日本专利申请No.2020-043541,并且该申请的内容通过引用并入本文。
工业实用性
根据本发明的增材制造用粉末可用于模铸模具部件的增材制造。
Claims (4)
1.一种增材制造用粉末,以质量%计,所述增材制造用粉末的组成由以下元素构成:
0.25<C<0.40,
0.001≤Si≤0.15,
0.30≤Mn≤0.45,
5.0≤Cr≤5.5,
1.0≤Mo≤1.5,
0.35≤V≤0.45,
0.01≤N≤0.05,
0.01≤O≤0.04,以及
任选地,
P<0.10,
Cu<0.20,
Ni<0.20,
Nb<0.20,
Ti<0.20,
B<0.10和
Co<0.20,
余量为Fe和不可避免的杂质,
其中所述增材制造用粉末的表面被覆有氧化物膜,并且
所述氧化物膜的厚度为3nm以上30nm以下。
2.根据权利要求1所述的增材制造用粉末,以质量%计,包含选自由以下元素组成的组中的至少一种元素:
0.001<Al<0.05,和
0.001<Zr<0.05。
3.根据权利要求1或2所述的增材制造用粉末,以质量%计,包含选自由以下元素组成的组中的至少一种元素:
0.001<S<0.20,
0.001<Pb<0.20,和
0.001<Bi<0.20。
4.一种模铸模具部件,其通过对根据权利要求1至3中任一项所述的增材制造用粉末进行增材制造而获得。
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