CN105377474A - 新型粉末 - Google Patents

新型粉末 Download PDF

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CN105377474A
CN105377474A CN201480034266.6A CN201480034266A CN105377474A CN 105377474 A CN105377474 A CN 105377474A CN 201480034266 A CN201480034266 A CN 201480034266A CN 105377474 A CN105377474 A CN 105377474A
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coating
cast iron
powder
welding
metal dust
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P·奥尔塞里厄斯
B·马若里
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Hoganas AB
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • 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
    • B22F7/02—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 of composite layers
    • B22F7/04—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 of composite layers with one or more layers not made from powder, e.g. made from solid metal
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    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K10/00—Welding or cutting by means of a plasma
    • B23K10/02—Plasma welding
    • B23K10/027—Welding for purposes other than joining, e.g. build-up welding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/34—Laser welding for purposes other than joining
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0255—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in welding
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    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3033—Ni as the principal constituent
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    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3053—Fe as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
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    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3053—Fe as the principal constituent
    • B23K35/3066—Fe as the principal constituent with Ni as next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
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    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3053—Fe as the principal constituent
    • B23K35/308—Fe as the principal constituent with Cr as next major constituent
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    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3053—Fe as the principal constituent
    • B23K35/308—Fe as the principal constituent with Cr as next major constituent
    • B23K35/3086—Fe as the principal constituent with Cr as next major constituent containing Ni or Mn
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/011—Layered products comprising a layer of metal all layers being exclusively metallic all layers being formed of iron alloys or steels
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    • 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
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    • 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
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    • 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
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
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    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
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Abstract

本发明涉及可用于涂布铸铁零件的新型金属粉末。本发明还涉及使用该新型金属粉末涂布铸铁零件的方法。使用该金属粉末涂布玻璃模具表面的可能性尤其重要。本发明还涉及被该金属粉末涂布的金属零件，如铸铁零件或玻璃模具。

Description

新型粉末
发明领域
本发明涉及可用于涂布铸铁零件的新型金属粉末。本发明还涉及使用该新型金属粉末涂布铸铁零件的方法。使用该金属粉末涂布玻璃模具表面的可能性尤其重要。本发明还涉及被该金属粉末涂布的金属零件，如铸铁零件或玻璃模具。
背景
通过用耐磨和耐腐蚀表面涂布工具，可以延长在苛刻磨损和腐蚀条件下工作的金属工具的寿命。这样的金属工具存在于各种工业中并可以例如由低合金钢、青铜、不锈钢或铸铁制成。
许多工业具有经受磨损、腐蚀和热循环的铸铁零件。这些包括中空玻璃制造、汽车、船舶、接地工具等。其一个实例是用于制造玻璃瓶和罐的工具。为了改进该设备的寿命，用镍基自助熔粉末涂布关键零件(例如模具和导环(guidering)边缘、活塞(plunger)和颈环(neckring)表面)。使用不同的表面加硬方法：例如通过火焰喷涂接着熔结或HVOF接着熔结涂布活塞，而模具边缘、颈环、导环使用粉末焊接或等离子转移弧(PTA)-焊接涂布。
在两个步骤中进行玻璃成型：在所谓粗模(blnkmold)中进行的预成型，和在所谓最终模具中进行的最终成型。与模具接触的玻璃的温度在粗模中为大约1100℃，在最终模具中为700-800℃。模具的温度可以波动至550-600℃，但表面温度甚至可以短时间更高。此外，模具表面与化学活性玻璃接触。对模具的重要要求是良好的表面光洁度、良好的抗热冲击性、抗尺寸变化性、抗氧化和生长性。这造成三个关键问题：玻璃与模具表面的粘着/粘合和形成不平整(表面粗糙化)；模具的氧化；和模具的磨损/点蚀。
这些问题造成玻璃产品中的瑕疵并限制模具的使用寿命。
一般而言，自助熔合金被定义为含有与强碳化物和硼化物形成元素如W和/或Mo和/或Cr结合的0.5-5％硼、0.1-6％硅和最多3％碳的铁基、镍基、钴基或铜基合金。商业上最多使用的自助熔合金是含有超过1.5％的单独或结合的硼和硅的Ni基合金。硼和硅将熔点降低几百度；它们通过还原Ni、Co、Cr和Fe的氧化物促进润湿；它们形成轻质低熔点硼硅玻璃，其流向该沉积物的表面并防止其氧化。硼也是具有与镍、铬、钼、钨和铁硬质硼化物的潜在的硬化剂。在Ni基自助熔合金的情况下，根据可高达16％的铬含量，硼含量为1-3.5％。
各种工业中使用的基底材料可以是低合金钢、球墨铸铁或层状铸铁(lamellarcastiron)、青铜或不锈钢。对于一些用途，由于能实现更高生产率和更低成本的良好热导率，层状铸铁是优选的选择。通过层状铸铁的堆焊的表面加硬是困难的，因为铸铁由于石墨片层的低强度、低延性和接近0的热膨胀系数而对断裂敏感。在其它类型的基底，如青铜或不锈钢的表面加硬中也可能发生裂纹形成。目前，只有用镍基自助熔系列物(grade)进行铸铁零件的堆焊才能获得无裂纹涂层。
由于成本和环境和健康考虑，长期以来希望通过在粉末中引入更多Fe来降低合金成本，但这样做的尝试尚未成功，其造成在层状铸铁热影响区(HAZ)中的更多裂纹形成。
发明概述
本发明提供对上述问题的解决方案。本发明人已经表明，可以提高金属粉末的铁含量并将这种粉末用于由铸铁，例如层状铸铁制成的零件的堆焊，如PTA焊接，同时避免裂纹形成。
通过用相对高量的铁稀释镍基系列物，同时优化铬和镍的量并将这种合金粉末用于表面涂布金属基底，例如铸铁的PTA焊接，获得具有下列性质的涂层：类似于目前使用的镍基自助熔系列物的硬度；与目前使用的镍基系列物类似的焊接和机械加工性质；可以避免铸铁热影响区中的裂纹和/或减小至与镍基系列物相当的尺寸；比目前使用的镍基自助熔系列物中更少的孔隙和更少的游离石墨；较低材料成本；在操作和焊接过程中的较低环境影响和危害较低的工作条件。
可以优化Cr和镍的量以使铸铁热影响区中的裂纹总长度最小化，以使总裂纹长度为0至最多1100微米。
通过用镍稀释该铁基涂层，逐渐降低该涂层中的游离石墨量和孔隙率，在16％镍下，孔隙和游离石墨的量小于在常用Ni基材料中观察到的量。
本发明还具有使镍的用量最小化由此降低在粉末生产、操作和焊接过程中对健康和/或环境的潜在影响的优点。
详述
图例
图1.显示堆焊在层状铸铁上的样品I的横截面的LOM显微照片。显示涂层和基底之间的结合区。在铸铁HAZ中没有观察到裂纹。
图2.显示堆焊在层状铸铁上的对比例3的横截面的LOM显微照片。显示涂层和基底之间的结合。在铸铁HAZ中观察到从涂层边缘开始的裂纹。
图3.来自实施例8的表面涂布结果。
图4.来自实施例9的表面涂布结果。
图5.来自实施例10的表面涂布结果。
图6.来自实施例11的表面涂布结果。
在全文中，待覆盖或被覆盖的金属零件或部件(例如铸铁部件)被称作基底。
涂布基底表面的方法可以被称作“表面涂布”或“表面加硬”或堆焊。
本发明基于实现下述状况：具有相对较高Fe含量的金属粉末可用于表面涂布基底，例如铸铁、低合金碳钢、青铜或不锈钢零件，并在涂层和基底之间极少形成裂纹。用于表面涂布的方法可以是可在铸铁零件上沉积金属粉末的任何方法。这样的方法包括例如等离子转移弧(PTA)或激光熔覆(lasercladding)；热喷涂法，如HVOF或HVAF，火焰喷涂、等离子喷涂或冷喷涂。
根据本发明使用的金属粉末可通过雾化具有适量合金元素的熔体制造。气-气或气-水雾化是此类方法的实例。粒度的选择取决于用于表面涂布的沉积方法和所选设备并在技术人员的能力范围内。粒度可以为10至250微米，优选对于PTA为53至212微米，对于激光熔覆为45至150微米，对于火焰喷涂为36-125微米，和对于HVOF、HVAF、冷喷涂或等离子喷涂为53微米至10微米。
本发明提供；
1.适合通过热喷涂或包覆焊接表面涂布金属零件的金属粉末，其由5-20％Cr；0.5-5％Si；0.2-3.5％B；12-70％Ni；0-1.5％C、0-2％P构成；余量是Fe。
2.根据第1点的金属粉末，其由5-9％Cr；2-3％Si；0.2-2％B；16-55％Ni；0-1.5％C、0-2％P构成；余量是Fe。
3.根据第1或2点的金属粉末，其由5.5-8％Cr、2-3％Si；0.2-2％B、16-50％Ni；0-1.5％C、0-2％P构成；余量是Fe。
4.根据第1-3点任一项的金属粉末，其适合通过等离子转移弧焊或激光熔覆表面涂布。
5.根据第1-4点任一项的金属粉末，其适合表面涂布铸铁。
6.根据第1至5点任一项的金属粉末用于铸铁部件的等离子转移弧焊或激光熔覆的用途。
7.金属或铸铁部件，其具有使用根据第1-5点任一项的粉末制成的表面涂层。
该金属粉末可用于表面处理球墨铸铁和层状铸铁。
另一方面，本发明提供已使用该金属粉末涂布或表面处理的铸铁零件。
实施例
实施例1
下列实施例中所用的粉末通过传统气体雾化制造，然后在53-150微米之间筛分。各种粉末的含量显示在表1中。
注：所有量按重量％计。“++”是指比500微米短的总裂纹长度；“+”是指500至微米的裂纹；且“–”是指长于微米的裂纹。
实施例2
如下涂布具有90毫米直径和大约35毫米高度的层状铸铁圆盘(punk)。该圆盘在炉中在空气中在380℃下预加热。沿圆盘直径沉积一个大约1厘米宽的层。使用下列焊接参数：焊接电流90-105A、焊接速度6-7cm/min、进料速度28-30g/min、3.5l/min的进料气体、PTA束的振荡、1-2A的前导电流(pilotcurrent)。在焊接后，该样品在蛭石中冷却。
实施例3
如下激光熔覆具有90毫米直径和大约35毫米高度的层状铸铁圆盘。该圆盘在炉中在空气中在380℃下预加热。使用配有同轴粉末进料器的具有12x2mm的点的4kW直接二极管激光器(directdiodelaser)沿圆盘直径沉积一个大约1厘米宽的层。使用下列激光熔覆参数：2kW功率、4-5mm/sec的熔覆速度、粉末进料速率31g/min和保护气体10-11l/min。实现的结果显示在表2中。
样品 C B Si Cr Ni Fe 防止裂纹
V 0.0 1.5 2.8 7 50 39 ++
表2
实施例4
评估刚焊接的部件：使用模具渗透剂评估涂层中的裂纹形成。用经毛细作用吸入表面缺陷或裂纹的高渗透红色染料涂布样品。在一段时间后，从表面上除去过量染料，并施加白色显影剂。显影剂将渗透剂从对表面开放的缺陷中吸出并能看出是否存在与表面接触的裂纹。涂层无一表现出与表面接触的裂纹。
实施例5
来自基底材料的稀释。轻微研磨样品表面以除去表面氧化物并通过手持X射线荧光分析仪在2个各大约7平方毫米的区域中分析涂层的化学。然后评估平均涂层化学。已知该粉末和基底材料的化学组成，如下计算稀释：
稀释度＝ρc(Xc+s–Xc)/ρs(Xs-Xc+s)+ρc(Xc+s–Xc)
ρc＝熔融粉末合金的密度(kg/m3)
ρs＝基底材料的密度(kg/m3)
Xc+s＝沉积物中元素X的重量％
Xc＝粉末合金中元素X的重量％
Xs＝基底中元素X的重量％
进行的试验显示所有材料的稀释度为5-20％。
实施例6
在涂层表面用Buehler硬度计测量在30kgf载荷下的Vickers硬度(HV30)。在硬度测量前，用氧化铝石平面研磨涂层以实现与样品底部平行的平面。在平面研磨后用500，然后800目碳化硅纸细磨。在涂层表面上进行5次压印并计算平均硬度。
实施例7
微结构。在光学显微镜下分析样品。大致在涂层中部垂直于焊接方向切割用于金相研究的样品。将样品模制在酚醛树脂中，然后用Al2O3石和9μm布平面研磨。然后用3μm布，接着1μm布抛光样品以实现镜面表面。在刚抛光的状况下研究样品以评估与基底的粘合度、最长长度>100μm的孔隙数、游离石墨的存在、涂层和/或铸铁热影响区中的裂纹。在涂层中没有发现裂纹。在一些样品中，在铸铁HAZ中观察到在涂层边缘开始的裂纹。测量裂纹长度并将涂层边缘的总裂纹长度报道在PTA涂布样品的表1中和激光熔覆样品的表2中。在检查的横截面中最长长度>100μm的孔隙数为0-5并具有与对比例1-3中类似的量。
实施例8
通过火焰喷涂接着熔结在低合金碳钢上沉积粉末I。涂布20毫米直径的圆棒。该棒首先喷砂，然后用Metco5P-II枪喷涂。通过氧乙炔炬在空气中进行熔结。该棒在喷涂和熔结过程中都旋转。实现与基底的良好粘合和正常孔隙率。见图3。
实施例9
通过UniqueCoatTechnologiesM3HVAF枪在低合金碳钢上沉积粉末I。为该试验选择的粒度是25-37微米。涂布直径大约20毫米的硬币。在涂布前喷砂处理该样品。使用空气和丙烷作为燃烧气体，同时使用空气作为载气。进料速率为100g/min。涂层的概况显示在图4中。粘合区中的黑色粒子是来自喷砂步骤的氧化铝。
实施例10
在铝青铜基底类型SS5716-15(典型化学77-82％Cu、8.5-11％Al、4-6％Ni、2.5-5％Fe)上通过PTA焊接沉积粉末I。在具有大约920毫米直径和30毫米高度的圆盘上进行涂布。在涂布前，该圆盘在空气中在450℃下预加热。使用下列工艺参数effect90A、焊接速度7cm/min、进料速率25g/min。沉积一个层。可以实现与基底具有良好粘合的无裂纹涂层。图5。
实施例11
通过PTA焊接在不锈钢基底类型AISI316L上沉积粉末I。在尺寸为50x100x30mm的棒上进行涂布。为了涂布，使用下列工艺参数effect110A、焊接速度7cm/min、进料速率25g/min。沉积一个层。实现与基底具有良好粘合的无裂纹涂层。
实施例12
将50％的粉末I与50％球形铸造碳化钨WC/W2C混合。使用4kW二极管激光器激光熔覆该混合物。使用3kw的功率和5mm/sec的熔覆速度熔覆该混合物。涂层的横截面显示在图6中。

Claims (7)

1.适合通过热喷涂或包覆焊接表面涂布金属零件的金属粉末，其由5-20％Cr；0.5-5％Si；0.2-3.5％B；12-70％Ni；0-1.5％C、0-2％P构成；余量是Fe。
2.根据权利要求1的金属粉末，其由5-9％Cr；2-3％Si；0.2-2％B；16-55％Ni；0-1.5％C、0-2％P构成；余量是Fe。
3.根据权利要求1或2的金属粉末，其由5.5-8％Cr、2-3％Si；0.2-2％B、16-50％Ni；0-1.5％C、0-2％P构成；余量是Fe。
4.根据权利要求1-3任一项的金属粉末，其适合通过等离子转移弧焊或激光熔覆表面涂布。
5.根据权利要求1-4任一项的金属粉末，其适合表面涂布铸铁。
6.根据权利要求1至5任一项的金属粉末用于铸铁部件的等离子转移弧焊或激光熔覆的用途。
7.金属或铸铁部件，其具有使用根据权利要求1至5任一项的粉末制成的表面涂层。
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