CN101421073A - 具有改良抗裂性的硬面堆焊合金 - Google Patents
具有改良抗裂性的硬面堆焊合金 Download PDFInfo
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- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
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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
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- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
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Abstract
通过控制基质晶粒尺寸并平衡钛和/或铌与碳和/或硼的含量,提供了一种具有改良的抗裂性、改良的耐磨性和改良的硬度的焊接熔敷物组合物。另外,显著减少粗的铬碳化物的出现以便减少龟裂裂纹的量。优选地,该焊接熔敷物由药芯或金属芯焊丝产生。该焊接熔敷物的特征包括具有细晶粒尺寸的基质、基质内细小的均匀分散的碳化物、和基质内少量的碳。
Description
技术领域
[0001]本发明涉及用于电弧焊的合金组合物,且更具体涉及适合用于硬面堆焊(hard surfacing)的焊接熔敷物(weld deposit)组合物,该组合物减少裂纹并增加耐磨性和硬度。
发明背景
[0002]本节中的描述仅仅提供与本发明相关的背景技术信息,并且可能并不构成现有技术。
[0003]硬面堆焊(hard-facing)通常涉及将硬质、耐磨的合金施用到基底(例如较软的金属)表面上的技术或方法,以便减少由磨蚀、侵蚀、腐蚀和加热、连同其它操作或环境条件引起的磨损。有多种方法可用于将耐磨合金施用到基底上,其中包括焊接,在焊接中焊丝被熔敷在基底表面来产生具有高耐磨性的焊接熔敷物。焊丝可以包括实心焊丝、金属芯焊丝或药芯焊丝,其中金属芯焊丝通常包含填充有粉末金属合金的金属外皮(sheath),而药芯焊丝通常包含粉末金属与焊剂成分的混合物。从而,由于除外皮提供的合金含量外可以在粉末金属芯中包含各种合金,因此药芯焊丝和金属芯焊丝提供了额外的多功能性。
[0004]一种公知的常用于硬面堆焊的焊丝材料包括铬碳化物。虽然常规的铬碳化物提供良好的耐磨性,但由碳化铬焊丝产生的焊接熔敷物可能在硬质焊接熔敷物表面上产生交叉龟裂图案(crosschecking pattern),由于该图案会产生增加的开裂敏感性,因此其是不希望的。另外,粗的铬碳化物会造成龟裂裂纹(check-cracking),该龟裂裂纹是垂直于焊缝方向发展并加速磨损的裂纹。
发明概述
[0005]总体而言,通过利用成核位置控制基质晶粒尺寸并通过平衡钛和/或铌与碳和/或硼的含量,提供了具有改良的抗裂性、改良的耐磨性和改良的硬度的焊接熔敷物。另外,显著降低粗铬碳化物的存在量以便减少龟裂裂纹的量。优选地,焊接熔敷物由药芯/金属芯焊丝产生,然而应当理解的是也可以使用其它类型的焊接耗材,例如实心焊丝或带涂层的保护金属电弧焊条。焊接熔敷物的特征包括具有细晶粒尺寸的基质、基质内细小的均匀分散碳化物、和基质内少量的碳。另外的合金化元素用以实现焊接熔敷物的期望性质,并且在这里对它们进行更加详细的描述。
[0006]在本发明的一个形式中,提供了由药芯或金属芯焊丝生产的焊接熔敷物组合物,该组合物按质量百分比计包含:约0.7%至约2.0%的碳、约0.2至约0.5%的锰、约0.5%至约1.1%的硅、约2.0%至约8.0%的铬、约2.0%至约6.0%的钼、约2.0%至约5.0%的钨、约2.0%至约8.0%的铌和钛、约1.0%至约2.5%的钒、约0.2%至约0.9%的硼、和余量的铁。在另外的形式中,碳占约1.1%、锰占约0.3%、硅占约0.8%、铬占约4.0%、钼占约4.0%、钨占约3.5%、铌和钛占约3.2%、钒占约1.8%、硼占约0.5%。
[0007]在另一个形式中,提供了由药芯或金属芯焊丝产生的焊接熔敷物组合物,该组合物按质量百分比计包含:约0.7%至约2.0%的碳、约0.1至约0.5%的锰、约0.7%至约1.4%的硅、约6.0%至约11.0%的铬、约0.5%至约2.0%的钼、约2.0%至约8.0%的铌和钛、约0.2%至约1.0%的钒、约0.2%至约0.9%的硼、约0.4%至约0.8%的铜、和余量的铁。在另外的形式中,碳占约1.1%、锰占约0.3%、硅占约0.8%、铬占约9.0%、钼占约0.8%、铌和钛占约3.5%、钒占约0.3%、硼占约0.5%、铜占约0.6%。
[0008]在本发明的其它形式中,通过本发明的指导提供了能够产生具有上述元素的焊接熔敷物的药芯或金属芯焊丝,以及具有含上述元素的焊接熔敷物的焊接结构。
[0009]根据这里提供的描述,其它适用性范围将变得显而易见,应当理解的是,描述和特定实施例仅仅是为了进行说明的目的,而并不意图限制本发明的范围。
附图说明
[0010]这里描述的附图仅仅用于说明的目的,并且在任何情况下并不意图限制本发明的范围。
[0011]图1是根据本发明的原理构造的药芯或金属芯焊丝的剖面图;
[0012]图2是根据本发明的原理构造的具有硬面堆焊表面的焊接结构的透视图;
[0013]图3是说明根据本发明的组合物与现有技术组合物相对比的试验结果的坐标图;
[0014]图4是具有粗铬碳化物的基质的现有技术碳化铬焊接熔敷物的显微照片;
[0015]图5a是根据本发明教导的具有细晶粒尺寸基质的焊接熔敷物的显微照片;
[0016]图5b是另一个根据本发明教导的具有细晶粒尺寸基质的焊接熔敷物的显微照片。
发明详述
[0017]下述说明在本质上仅仅是示例性的,而不意图用来限制当前的发明、应用或使用。应当理解的是在所有附图中,相应的附图标记表示相同或相应的部分和特征。
[0018]用于硬面堆焊应用中的焊接熔敷物产生改良的抗裂性,改良的耐磨性、和改良的硬度,所述焊接熔敷物是通过根据本发明的教导控制基质晶粒尺寸并平衡钛和/或铌与碳的含量提供的。另外,显著减少粗铬碳化物的存在以便减少龟裂裂纹的量。优选地,由药芯焊丝产生该焊接熔敷物,然而应当理解的是也可以使用其它类型的焊接耗材,如实心焊丝或带涂层的保护金属电弧焊条,这依然在本发明的范围内。该焊接熔敷物的特征包括具有细晶粒尺寸的基质、基质内细小的均匀分散碳化物、和基质内少量的碳。提供另外的合金化元素用以实现焊接熔敷物的各种性质,并且在这里对它们进行更加详细的描述。
[0019]参照图1,对根据本发明教导的能产生焊接熔敷物的药芯或金属芯焊丝进行说明,并将其用附图标记10概括表示。药芯/金属芯焊丝10包括低碳钢外皮12,该外皮填充有粉末金属合金芯14。如图2所示,当焊接到基底22上时,药芯/金属芯焊丝10产生硬面堆焊表面20,从而产生具有改良的抗裂性、耐磨性和硬度的焊接结构24。
[0020]现在将对根据本发明教导的焊接熔敷物中存在的特定合金元素和它们的量进行更详细的描述。
[0021]参考下表1,以“焊接熔敷物A”和“焊接熔敷物B”列出了根据本发明的两(2)种焊接熔敷物组合物(包括元素的目标百分数和百分数范围,均以重量计),为了对比同时列出典型的M7工具钢和马氏体硬面堆焊组合物。M7工具钢是非常频繁的用于涉及大磨损和冲击应用中的组合物。对该M7工具钢组合物进行组分改变得到焊接熔敷物A,在耐磨性方面存在显著的改善。马氏体硬面堆焊组合物是一种低成本的堆焊层(overlay),其在硬面堆焊工业中于要求中等耐磨性和耐冲击性的应用中具有广泛的使用。焊接熔敷物B是对该马氏体硬面堆焊组合物的改变,其在耐磨性方面产生显著的改善。
表1
M7工具钢 | 焊接熔敷物A,目标 | 焊接熔敷物A,范围 | 马氏体硬面堆焊 | 焊接熔敷物B,目标 | 焊接熔敷物B,范围 | |
C | 0.9 | 1.1 | 0.7-2.0 | 0.6 | 1.1 | 0.7-2.0 |
Mn | 0.4 | 0.3 | 0.2-0.5 | 1.5 | 0.2 | 0.1-0.5 |
Si | 0.8 | 0.8 | 0.5-1.1 | 1.3 | 1.0 | 0.7-1.4 |
Cr | 3.5 | 4.0 | 2.0-8.0 | 6.0 | 9.0 | 6.0-11.0 |
Mo | 8.0 | 4.0 | 2.0-6.0 | 0.7 | 0.8 | 0.5-2.0 |
W | 1.5 | 3.5 | 2.0-5.0 | 0 | 0 | 0 |
Fe | 余量 | 余量 | 余量 | 余量 | 余量 | 余量 |
Nb,Ti | 0 | 3.2 | 2.0-8.0 | 0 | 3.5 | 2.0-8.0 |
V | 1.6 | 1.8 | 1.0-2.5 | 0 | 0.3 | 0.2-1.0 |
B | 0 | 0.5 | 0.2-0.9 | 0 | 0.5 | 0.2-0.9 |
Cu | 0 | 0 | 0 | 0 | 0.6 | 0.4-0.8 |
[0022]现在更详细地描述每种元素及其对焊接熔敷物性能的作用。
[0023]碳(C)是一种改善硬度和强度的元素。对于焊接熔敷物A和焊接熔敷物B两者,优选的碳量为约0.7至2.0%,目标值为约1.1%。
[0024]锰(Mn)是一种改善硬度、韧性并且充当脱氧剂的元素,其中当细氧化物没有飘浮脱离金属时或者如果最终的晶界区域由于富硅锰共晶相的最终凝固而增大,该脱氧剂也充当晶粒细化剂。对于焊接熔敷物A,优选的锰量为约0.2至0.5%,目标值为约0.3%;对于焊接熔敷物B,优选的锰量为约0.1至0.5%,目标值为约0.2%。
[0025]硅(Si)是一种充当脱氧剂用以改善抗腐蚀性的元素,并且在当细氧化物没有飘浮脱离金属时或者如果最终晶界区域由于富硅锰共晶相的最终凝固而增大,其也充当晶粒细化剂。对于焊接熔敷物A,优选的硅量为约0.5至1.1%,目标值为约0.8%。对于焊接熔敷物B,优选的硅量为约0.7至1.4%,目标值为约1.0%。硅也被添加到焊接金属中用于改善流动性。
[0026]铬(Cr)是一种提供淬透性深度、抗腐蚀性、碳化物/硼化物形成、以及改善的高温蠕变强度的元素。对于焊接熔敷物A,优选的铬量为约2.0至约8.0%,目标值为约4.0%。对于焊接熔敷物B,优选的铬量为约6.0至约11.0%,目标值为约9.0%。
[0027]钼(Mo)是一种提供改善的焊接熔敷物抗拉强度的元素,以碳化物、硼化物或固溶强化体的形式。钨和钼充当固溶强化体。在许多情形中钨和钼可以相互替代,但是钼在增加基质强度和硬度方面更加有效。对于焊接熔敷物A,优选的钼量为约2.0至约6.0%,目标值为约4.0%。对于焊接熔敷物B,优选的钼量为约0.1至约2.0%,目标值为约0.8%。
[0028]钨(W)是一种提供改善的焊接熔敷物蠕变强度的元素。对于焊接熔敷物A,优选的钨量为约2.0至约5.0%,目标值为约3.5%。由于成本考虑以及钼的存在,因此焊接熔敷物B中不存在钨。
[0029]钛(Ti)和铌(Nb)充当晶粒细化剂、脱氧剂和初生碳化物/硼化物形成剂。如前所述,使钛和铌的量与碳/硼的量平衡,以便降低在焊接金属基质和晶界中的碳/硼的量,这降低开裂的可能性并改善硬面堆焊表面的韧性。这些元素的比例基于原子量和期望的金属间碳化物/硼化物的类型。钛通常4倍于碳的质量,铌通常8倍于碳的质量。任何过量的碳被留给次生碳化物形成剂和基质。对于硼化钛,钛与硼的比例为4.4,而对于二硼化钛,钛与硼的比例为2.2。对于硼化铌,铌/硼的比例为8.6,而对于二硼化铌,铌/硼的比例为4.3。钛/铌对和碳/硼对在本质上是可替代的,因而可以容许从这些比例的偏离,并应该认为落入了本发明的范围内。另外,这些元素的颗粒在非常高的温度下凝固,因此可以被看作初生碳化物/硼化物。
[0030]钒(V)为次生碳化物形成剂和晶粒细化剂,因而增加焊接熔敷物的韧性。对于焊接熔敷物A,钒的优选量为约1.0至约2.5%,目标值为约1.8%。对于焊接熔敷物B,钒的优选量为约0.2至约1.0%,目标值为约0.3%。
[0031]当与碳和/或硼结合时,钛和铌将充当晶粒细化剂来提供成核位置用于形成许多细小晶粒,这将带来改良的抗裂性。另外,这些细小晶粒通过如下方式改善延展性和减少热撕裂:增加晶界面积和减小晶粒必须相互滑移以适应由冷却引起的收缩导致的局部应变的平均距离。晶界滑移被称为切变,其通常导致晶界内的热撕裂。
[0032]硼(B)为一种在基质内提供填隙硬化、通过适应错配来强化晶界的元素,所述错配是由于相邻晶粒相对于公用晶界的晶格倾角引起的,并且硼元素本身或与碳联合,与钛和/或铌一起作为金属间化合物形成成核位置。对于焊接熔敷物A,硼的优选量为约0.2至约0.9%,目标值为约0.5%。对于焊接熔敷物B,硼的优选量为约0.2至约0.9%,目标值为约0.5%。
[0033]铜(Cu)为一种合金化元素,其可以用于钢中通过向分割/细化晶粒提供次生相或通过抑制奥氏体相的凝固点获得更短的凝固区间来改变钢的组织。由于热膨胀/收缩的系数,更短的凝固区间意味着施加到所述相上的更小的剪应变。实际上,因为奥氏体被冷却通过其正常凝固区间的仅仅一半,因此由冷却时发生的收缩引起的应变更小。由于奥氏体易于发生热撕裂,因此目标是使该相避免任何过大的剪切应力,这极大降低合金中的这种失效机制。对于焊接熔敷物B,铜的优选量为约0.4至约0.8%,目标值为约0.6%。优选地,在焊接熔敷物A中不存在铜。
[0034]已阐述了根据本发明教导的焊接熔敷物组合物,与其它马氏体和工具钢焊丝熔敷物相比,能够降低交叉龟裂的量,同时改善耐磨性。在示例性的试验中,与其它焊接熔敷物组合物相比时,焊接熔敷物A的组成表现出改良的硬度和重量损失,如下表2所示。
表2
组合物 | HRC硬度值 | ASTM G-65磨损试验重量损失 |
焊接熔敷物A | HRC 62至67 | 0.13克 |
典型的碳化铬 | HRC 55至63 | 0.15克 |
M7工具钢 | HRC 60至64 | 0.55克 |
马氏体熔敷物 | HRC 58至60 | 1.30克 |
焊接熔敷物B | HRC 63-65 | 0.21克 |
[0035]参照图3,示出了本发明的组合物的和现有技术组合物的耐磨性。与现有技术的合金相比,可以看出碳化铬硬面堆焊具有最好的耐磨性(在ASTM G65磨损试验中最低的重量损失)。然而,碳化铬熔敷物包含显著(relief)的龟裂裂纹,所述龟裂裂纹使得堆焊层较不适合用于同时涉及高冲击和高磨损的应用。对于根据焊接熔敷物A的组合物,耐磨性增强并且优于碳化铬熔敷物和M7工具钢,如图所示。类似地,与马氏体熔敷物相比,根据焊接熔敷物B的组合物导致显著更好的耐磨性。因而,焊接熔敷物B非常适合用于涉及中等冲击和磨损的应用中,且相比马氏体熔敷物在成本上仅略微增加。
[0036]通过控制基质晶粒尺寸并且平衡钛和/或铌与碳/硼的含量,根据本发明的教导产生具有改良抗裂性的焊接熔敷物。另外,根据本发明的焊接熔敷物不含粗的铬碳化物。不存在粗碳化铬相将会减少龟裂裂纹的出现。
[0037]作为例子,图4示出了现有技术的具有粗铬碳化物的焊接熔敷物基质,而图5a和5b示出了根据本发明的不具有这些粗铬碳化物的焊接熔敷物基质。如图所示,本发明的示例性焊接熔敷物在基质内表现出细晶粒尺寸,兼有细小且均匀分散的碳化物。该细晶粒尺寸和均匀分散的碳化物有助于改良的抗裂性和改良的耐磨性。
[0038]本发明的说明书在本质上仅仅为示例性的,因而不脱离本发明要点的变化被认为落入本发明的范围内。例如,根据本发明教导的焊接熔敷物可以由药芯/金属芯焊丝之外的焊丝类型产生,例如实心焊丝,然而依然处在本发明的范围内。这样的变化不被认为是脱离了本发明的主旨和范围。
Claims (24)
1.一种由药芯或金属芯焊丝产生的焊接熔敷物组合物,该焊接熔敷物组合物按质量百分比计包含:
约0.7%至约2.0%的碳;
约0.2%至约0.5%的锰;
约0.5%至约1.1%的硅;
约2.0%至约8.0%的铬;
约2.0%至约6.0%的钼;
约2.0%至约5.0%的钨;
约2.0%至约8.0%的铌和钛;
约1.0%至约2.5%的钒;
约0.2%至约0.9%的硼;和
余量的铁。
2.根据权利要求1所述的焊接熔敷物组合物,其中碳含量为约1.1%。
3.根据权利要求1所述的焊接熔敷物组合物,其中锰含量为约0.3%。
4.根据权利要求1所述的焊接熔敷物组合物,其中硅含量为约0.8%。
5.根据权利要求1所述的焊接熔敷物组合物,其中铬含量为约4.0%。
6.根据权利要求1所述的焊接熔敷物组合物,其中钼含量为约4.0%。
7.根据权利要求1所述的焊接熔敷物组合物,其中钨含量为约3.5%。
8.根据权利要求1所述的焊接熔敷物组合物,其中铌和钛的含量为约3.2%。
9.根据权利要求1所述的焊接熔敷物组合物,其中钒含量为约1.8%。
10.根据权利要求1所述的焊接熔敷物组合物,其中硼含量为约0.5%。
11.一种由药芯焊丝产生的焊接熔敷物组合物,该焊接熔敷物组合物按质量百分比计包含:
约0.7%至约2.0%的碳;
约0.1%至约0.5%的锰;
约0.7%至约1.4%的硅;
约6.0%至约11.0%的铬;
约0.5%至约2.0%的钼;
约2.0%至约8.0%的铌和钛;
约0.2%至约1.0%的钒;
约0.2%至约0.9%的硼;
约0.4%至约0.8%的铜;和
余量的铁。
12.根据权利要求11所述的焊接熔敷物组合物,其中碳含量为约1.1%。
13.根据权利要求11所述的焊接熔敷物组合物,其中锰含量为约0.3%。
14.根据权利要求11所述的焊接熔敷物组合物,其中硅含量为约0.8%。
15.根据权利要求11所述的焊接熔敷物组合物,其中铬含量为约9.0%。
16.根据权利要求11所述的焊接熔敷物组合物,其中钼含量为约0.8%。
17.根据权利要求11所述的焊接熔敷物组合物,其中铌和钛的含量为约3.5%。
18.根据权利要求11所述的焊接熔敷物组合物,其中钒含量为约0.3%。
19.根据权利要求11所述的焊接熔敷物组合物,其中硼含量为约0.5%。
20.根据权利要求11所述的焊接熔敷物组合物,其中铜含量为约0.6%。
21.一种能够产生包含如下成分的焊接熔敷物组合物的药芯焊丝,按质量百分比计:
约0.7%至约2.0%的碳;
约0.2%至约0.5%的锰;
约0.5%至约1.1%的硅;
约2.0%至约8.0%的铬;
约2.0%至约6.0%的钼;
约2.0%至约5.0%的钨;
约2.0%至约8.0%的铌和钛;
约1.0%至约2.5%的钒;
约0.2%至约0.9%的硼;和
余量的铁。
22.一种能够产生包含如下成分的焊接熔敷物组合物的药芯焊丝,按质量百分比计:
约0.7%至约2.0%的碳;
约0.1%至约0.5%的锰;
约0.7%至约1.4%的硅;
约6.0%至约11.0%的铬;
约0.5%至约2.0%的钼;
约2.0%至约8.0%的铌和钛;
约0.2%至约1.0%的钒;
约0.2%至约0.9%的硼;
约0.4%至约0.8%的铜;和
余量的铁。
23.包含至少一焊接熔敷物的焊接结构,所述焊接熔敷物具有包含如下成分的组成,按质量百分比计:
约0.7%至约2.0%的碳;
约0.2%至约0.5%的锰;
约0.5%至约1.1%的硅;
约2.0%至约8.0%的铬;
约2.0%至约6.0%的钼;
约2.0%至约5.0%的钨;
约2.0%至约8.0%的铌和钛;
约1.0%至约2.5%的钒;
约0.2%至约0.9%的硼;和
余量的铁。
24.包含至少一焊接熔敷物的焊接结构,所述焊接熔敷物具有包含如下成分的组成,按质量百分比计:
约0.7%至约2.0%的碳;
约0.1%至约0.5%的锰;
约0.7%至约1.4%的硅;
约6.0%至约11.0%的铬;
约0.5%至约2.0%的钼;
约2.0%至约8.0%的铌和钛;
约0.2%至约1.0%的钒;
约0.2%至约0.9%的硼;
约0.4%至约0.8%的铜;和
余量的铁。
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CN102848102A (zh) * | 2012-06-28 | 2013-01-02 | 北京工业大学 | 一种含超细硬质相铁基耐磨合金 |
CN102848102B (zh) * | 2012-06-28 | 2015-04-08 | 北京工业大学 | 一种含超细硬质相铁基耐磨合金 |
CN102962604A (zh) * | 2012-11-07 | 2013-03-13 | 北京奥邦焊业有限公司 | 一种焊丝及其制造方法 |
CN102962604B (zh) * | 2012-11-07 | 2015-07-15 | 北京奥邦焊业有限公司 | 一种焊丝 |
CN103111771A (zh) * | 2013-02-21 | 2013-05-22 | 北京工业大学 | 一种低硼低铬铁基耐磨堆焊药芯焊丝 |
CN103111771B (zh) * | 2013-02-21 | 2015-11-04 | 北京工业大学 | 一种低硼低铬铁基耐磨堆焊药芯焊丝 |
CN107201474A (zh) * | 2016-03-16 | 2017-09-26 | 优频科技材料股份有限公司 | 硬面合金材料 |
CN107201474B (zh) * | 2016-03-16 | 2022-05-06 | 优频科技材料股份有限公司 | 硬面合金材料 |
CN109226994A (zh) * | 2018-10-31 | 2019-01-18 | 首钢集团有限公司 | 一种硬面堆焊用药芯焊丝 |
CN110587179A (zh) * | 2019-09-03 | 2019-12-20 | 西安理工大学 | T2铜与304不锈钢焊接用自保护药芯焊丝及制备方法 |
CN110587179B (zh) * | 2019-09-03 | 2021-11-16 | 西安理工大学 | T2铜与304不锈钢焊接用自保护药芯焊丝及制备方法 |
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WO2007097946A2 (en) | 2007-08-30 |
CA2720307A1 (en) | 2007-08-30 |
CA2642767A1 (en) | 2007-08-30 |
CA2642767C (en) | 2015-03-24 |
AU2007217975A1 (en) | 2007-08-30 |
US20070187369A1 (en) | 2007-08-16 |
US8735776B2 (en) | 2014-05-27 |
US8669491B2 (en) | 2014-03-11 |
CA2720307C (en) | 2014-10-14 |
AU2010202463A1 (en) | 2010-07-01 |
AU2010202463B2 (en) | 2012-01-12 |
CN101421073B (zh) | 2014-03-26 |
WO2007097946A3 (en) | 2008-08-07 |
US20130294819A1 (en) | 2013-11-07 |
AU2007217975B2 (en) | 2010-07-01 |
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