CN103998164A - 用于高速氧燃料喷涂的新材料和由其制成的产品 - Google Patents

用于高速氧燃料喷涂的新材料和由其制成的产品 Download PDF

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CN103998164A
CN103998164A CN201280059829.8A CN201280059829A CN103998164A CN 103998164 A CN103998164 A CN 103998164A CN 201280059829 A CN201280059829 A CN 201280059829A CN 103998164 A CN103998164 A CN 103998164A
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scorification
powder
alloy
spraying
plunger
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L·尼尔松
P·奥尔塞里厄斯
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Hoganas AB
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/115—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by spraying molten metal, i.e. spray sintering, spray casting
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/008—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression characterised by the composition
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0433—Nickel- or cobalt-based alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/08—Metallic material containing only metal elements

Abstract

本发明人已经开发出了可用于基底(例如玻璃制造中所用的柱塞)的HVOF喷涂的新合金。在用所述合金涂布时，这些部件表现出高的抗磨性和因此较长的寿命。

Description

用于高速氧燃料喷涂的新材料和由其制成的产品
背景技术
使用自熔镍基合金的热堆焊在玻璃容器工业中的工具的抗磨损保护中起到重要作用。瓶机床在非常严峻的条件下工作，经受磨损、腐蚀和快速热循环。
自熔镍基合金的主要性质是在高温下良好的抗磨性和良好的抗腐蚀性。这导致镍合金广泛用于堆焊玻璃瓶制造工业中的铸铁部件。利用粉末焊接、火焰喷涂、高速氧燃料(HVOF)喷涂和PTA焊接的表面硬化法在新模具、柱塞(plungers)、挡板、颈环、板等的制造中以及在修复和维护中使用自熔粉末。
自熔合金中的基本元素是硅(Si)和硼(B)。这两种元素对液相线温度具有非常强的影响。纯镍(Ni)的熔融温度为1455℃。可通过Si和B的提高的浓度将合金液相线降至1000℃以下。通过固相线和液相线限定熔融温度范围(图2a/2b)。自熔合金的低熔点非常有利，因为这些可以在不烧熔的情况下涂布到基底金属上。合金通常含有铬(Cr)、铁(Fe)和碳(C)，有时也加入钼(Mo)、钨(W)和铜(Cu)。用Si和B溶解的其它金属氧化物(例如Fe和Ni氧化物)具有形成硅酸盐的能力。这在镍基合金的施加过程中是重要的，因为Si-B熔渣充当助焊剂。这防止新的金属表面氧化并确保对熔融金属的更好的可润湿性。
Ni-Cr-Si-B-合金的微结构是含有各种量的硬粒子的相对延性的富Ni基质。提高合金元素的量会提高硬粒子的数量并因此提高合金的硬度。提高的硬度也使该材料更难机械加工。在具有低Si、B和Cr浓度的软合金中，主要的硬相是Ni3B。
希望制造具有延长的寿命的模具、柱塞、挡板、颈环和板，因此需要开发可实现这一点的新合金。
发明概述
在玻璃模具工业中，HVOF(High Velocity Oxy-Fuel，高速氧燃料)喷涂常用于细颈柱塞上的涂层，并在有限程度上用于压吹柱塞。
本发明人已经开发出可用于HVOF(高速氧燃料喷涂)-玻璃制造中所用的基底(例如柱塞)的处理-的新合金。在用所述合金处理时，这些部件表现出高抗磨性和因此较长的寿命。
该合金中包括的组分可以以粉末形式供应。
使用HVOF喷涂法使所述粉末沉积在基底上。
发明详述
本发明的一个目的是提供可用于HVOF喷涂法的镍基粉末，所述粉末由(所有百分比按重量％计)碳2.2-2.85、硅2.1-2.7、硼1.2-1.7、铁1.3-2.6、铬5.7-8.5、钨32.4-33.6、钴4.4-5.2、余量的镍构成。
在另一实施方案中，该粉末由(所有百分比按重量％计)碳2.3-2.7、硅2.15-2.6、硼1.4-1.6、铁1.5-2.05、铬7.3-7.5、钨32.4-33.6、钴4.4-5.2、余量的镍构成。
在一个实施方案中，该粉末包括两种类型的粉末；合金1是软合金，合金2是硬合金。在本文中，术语“软合金”和“硬合金”是指两种合金，一种比另一种软。这两种不同的合金具有下述组成：
合金 C Si B Fe Cr Ni
1 0.25％ 3.5 1.6 2.5 7.5 余量
2 0.75％ 4.3 3.1 3.7 14.8 余量
在一个实施方案中，该粉末具有12-58微米或15-53微米或20-53微米的通过筛析测得的粒度。
本发明的另一目的是提供由该镍基粉末制成的合金。
本发明的另一目的是提供用所述合金涂布、优选通过HVOF(高速氧燃料喷涂)涂布的部件。
用于涂布玻璃柱塞的HVOF法由两个步骤构成：用喷枪喷涂，并用烧熔喷灯(fusing torch)烧熔沉积物。通过注射将该粉末送入氧-乙炔或氧-氢枪，并高速射向基底材料。热粒子在撞击下压平并与基底材料互锁和互相互锁，以形成机械结合。
需要烧熔处理以获得喷涂层的致密并充分粘结的涂层。将该涂层加热至其固相线与液相线之间的温度—通常大约1000℃。在最佳温度下，该材料是熔融粒子与固体粒子的混合物。在烧熔过程中在熔体填充粒子间隙时发生15-20％的收缩。
根据气体类型和喷枪的品牌，可以使用细粉和粗粉。HVOF喷涂设备的市面上最常见的类型是Metco Diamond Jet、Tafa JP5000或TafaJP8000。都非常适用于使用宽泛的材料选择和最高生产率(以千克喷涂的粉末/小时计)的这种作业类型。
应该正确地调节粉末流速。如果流速太低，其造成过热，如果太高，粒子的加热不足－在这两种情况下这都会造成含孔隙或氧化物的较差的层品质。将该柱塞的最粗部分预热至200-300℃。然后喷涂数层粉末。喷枪通常在机器人装置中使用，且喷枪应以平稳均匀的动作移动并且一定不能停住不动，因为这会造成涂层过热。应该考虑到该层在随后烧熔过程中收缩大约20％。烧熔后的正常厚度为0.6-0.8毫米。
在喷涂后，必须烧熔沉积物。使用适当尺寸的烧熔喷灯，即对于小柱塞，1,000l/min喷灯容量，对于大柱塞，高达4,000l/min。如果喷灯太小，这可能导致过长的烧熔时间，以产生氧化层。用太大的喷灯烧熔会使该层过热并造成孔隙或不均匀性。应该将该柱塞加热至大约900℃。然后应将火焰调节至乙炔气体过量－所谓的“软火焰”。距顶部大约30毫米开始烧熔。当涂层看起来像镜子一样发光时，将火焰移向柱塞点并先烧熔这一段。回到起点并完成柱塞的烧熔。推荐将深色焊接玻璃磨损，以正确看见该发光。如果烧熔温度太低，则熔融的材料不足。在喷涂后，必须烧熔沉积物。使用适当尺寸的烧熔喷灯，即对于小柱塞，1,000l/min喷灯容量，对于大柱塞，高达4,000l/min。如果喷灯太小，这可能导致过长的烧熔时间，以产生氧化层。用太大的喷灯烧熔会使该层过热并造成孔隙或不均匀性。这导致差的粘合性质和高孔隙率。太热会造成例如沉积物流挂、稀释、基底材料变形和过度烧熔之类的破坏，这造成过量熔渣并使沉积物太软。在喷涂直径小于25毫米的柱塞时，在喷枪上使用附加气帽更经济。这使粉末流集中在柱塞的小面积区域上。因此降低喷涂时间并提高沉积效率。
在烧熔后，将柱塞在旋转下冷却至大约600℃。此后，可以使其在空气中缓慢冷却。如果使用硬合金(50-60HRC)，推荐将该零件置于隔热材料如蛭石中。这会减慢冷却以防止裂纹。
细颈柱塞具有小于25毫米的直径并需要硬的致密涂层。因此使用HVOF法更经济。这具有比火焰喷涂更集中的火焰并由于粉末粒子的高速度而产生更致密的涂层。HVOF需要比火焰喷涂细的粉末。最常见的解决方案是具有20-53微米粒度范围的粉末。一些HVOF系统需要更细的粉末，例如15-45微米。大多数HVOF涂层可以在不烧熔的情况下使用。在细颈柱塞的情况中，通常要求烧熔该涂层。
实施例
实施例1
制备三种粉末混合物，它们具有下述组成(余量为镍)：
元素 样品1 样品2 参考
C 2.2-2.7 2.30-2.85 1.95-2.50
Si 2.1-2.6 2.15-2.7 2.30-3.00
B 1.2-1.5 1.50-1.70 1.50-1.90
Fe 1.30-2.05 1.50-2.60 1.40-2.70
Cr 5.7-7.5 7.30-8.50 7.10-8.70
W 32.-33.6 32.4-33.6 26.80-28.10
Co 4.4-5.2 4.4-5.2 3.60-4.40
实施例2
可用所述粉末涂布盘，然后将其用于磨损试验(所谓的销对盘试验，显示在实施例3中)。使用HVOF喷涂法涂布该盘。
HVOF喷涂法通常在一个步骤中进行。但是，对于柱塞，进行两个步骤：用HVOF喷枪喷涂，并用烧熔喷灯(fusing torch)烧熔沉积物。使用氩气作为载体将该粉末从粉末进料斗送入喷枪。
在此实施例中可以使用市面上常见类型的HVOF喷涂设备，例如Metco Diamond Jet、Tafa JP5000、Tafa JP8000等。
在该盘(或如果适当，柱塞)上喷涂数层粉末。喷枪应以平稳均匀的动作移动并且一定不能停住不动，因为这会造成涂层过热。
此后用烧熔喷灯将该涂层加热至其固相线与液相线之间的温度，大约1000℃。使用适当尺寸的烧熔喷灯，即对于小柱塞，1,000l/min喷灯容量，对于大柱塞，高达4,000l/min。如果喷灯太小，这可能导致过长的烧熔时间，以产生氧化层。用太大的喷灯烧熔会使该层过热并造成孔隙或不均匀性。应该将该盘加热至大约900℃。然后可以将火焰调节至乙炔气体过量－所谓的“软火焰(soft flame)”。距顶部大约30毫米开始烧熔。当涂层看起来像镜子一样发光时，开始烧熔。回到起点并完成该盘的烧熔。推荐将深色焊接玻璃磨损，以正确看见该发光。如果烧熔温度太低，则熔融的材料不足。在喷涂后，烧熔沉积物。使用适当尺寸的烧熔喷灯，即对于小柱塞，1,000l/min喷灯容量，对于大柱塞，高达4,000l/min。如果喷灯太小，这可能导致过长的烧熔时间，以产生氧化层。
在烧熔后，将柱塞在旋转下冷却至大约600℃。此后，可以使其在空气中缓慢冷却。如果使用硬合金(50-60HRC)，推荐将该零件置于隔热材料(例如蛭石)中。这会减慢冷却以防止裂纹。
实施例3
对该HVOF涂布的盘施以“销对盘”磨损试验。该试验根据标准ASTMG65在500℃至550℃的温度下进行，在该球上存在2小时持续压力。由本发明样品制成的涂层的磨损系数低至参考材料的大约1/3。这表明比参考材料高的抗磨损性。

Claims (5)

1.适用于HVOF喷涂法的金属粉末，以重量％计，所述粉末由碳2.2-2.85、硅2.1-2.7、硼1.2-1.7、铁1.3-2.6、铬5.7-8.5、钨32.4-33.6、钴4.4-5.2和余量的镍构成。
2.根据权利要求1的金属粉末，所述粉末由碳2.3-2.7、硅2.15-2.6、硼1.4-1.6、铁1.5-2.05、铬7.3-7.5、钨32.4-33.6、钴4.4-5.2和余量的镍构成。
3.根据权利要求1或2的金属粉末，所述粉末具有20-53微米的通过筛析测得的粒度。
4.通过高速氧燃料喷涂涂布表面的方法，其中使用根据前述权利要求任一项的粉末。
5.通过根据权利要求4的方法制成的部件。
CN201280059829.8A 2011-12-05 2012-12-05 用于高速氧燃料喷涂的新材料和由其制成的产品 Pending CN103998164A (zh)

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EP11191917 2011-12-05
EP11191917.1 2011-12-05
PCT/EP2012/074432 WO2013083599A1 (en) 2011-12-05 2012-12-05 New material for high velocity oxy fuel spraying, and products made therefrom

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