WO2018196524A1 - 一种基于微合金化与同步寄生钎焊的钼合金熔焊方法 - Google Patents

一种基于微合金化与同步寄生钎焊的钼合金熔焊方法 Download PDF

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WO2018196524A1
WO2018196524A1 PCT/CN2018/080433 CN2018080433W WO2018196524A1 WO 2018196524 A1 WO2018196524 A1 WO 2018196524A1 CN 2018080433 W CN2018080433 W CN 2018080433W WO 2018196524 A1 WO2018196524 A1 WO 2018196524A1
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welded
workpiece
welding
joint
molybdenum alloy
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French (fr)
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张林杰
白清林
宁杰
杨健楠
孙院军
安耿
朱琦
李思功
龚星
李锐
任啟森
刘彤
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Xian Jiaotong University
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Xian Jiaotong University
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    • 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
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
    • 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
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/20—Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating

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  • the invention belongs to the technical field of welding and relates to a method for welding a molybdenum alloy based on microalloying and synchronous parasitic brazing.
  • molybdenum melting point up to 2610 ° C, small neutron absorption cross section, low thermal expansion coefficient, excellent thermal conductivity, good mechanical properties at high temperature, good processability, when the temperature is lower than 500 ° C, molybdenum has good stability in air or water.
  • the above advantages make molybdenum and molybdenum alloys, especially high-performance molybdenum alloys, have important applications in metallurgy, aerospace, aerospace, nuclear energy, military and other fields.
  • the high-performance molybdenum alloy itself has excellent toughness, but once it is welded, its toughness advantage will be completely lost. Not only that, because the melting point of molybdenum is too high, it must be processed by powder metallurgy.
  • the density of the material cannot be compared with the molten metallurgy material, the gas content is high, and the weld porosity defects are serious; on the other hand, it is easy to Impurities such as O and N are introduced into the material, and the solubility of impurity elements such as O and N in molybdenum is extremely low at room temperature.
  • impurity elements such as O and N are easily segregated at the grain boundary, and the grain boundary is severely weakened. The mechanical properties of the joint are extremely poor.
  • the above problems severely restrict the application of molybdenum and molybdenum alloys as structural materials in critical applications such as nuclear power.
  • the object of the present invention is to overcome the above disadvantages of the prior art, and to provide a method for welding a molybdenum alloy based on microalloying and synchronous parasitic brazing, which can effectively improve the mechanical properties of a welded joint of a workpiece after welding.
  • the molybdenum alloy fusion welding method based on microalloying and synchronous parasitic brazing according to the present invention comprises the following steps:
  • pretreating the joint to be welded of the workpiece to be welded in step 1) is: grinding the combined area of the workpiece to be welded, alkali washing, acetone washing and drying;
  • the material to be welded is made of pure molybdenum, a molybdenum alloy having an alloy element content of 2 wt% or less, or a molybdenum alloy having a second phase dopant content of 2 wt% or less.
  • step 4 laser welding, electron beam welding, plasma beam welding or argon arc welding is used to complete the welding of the workpiece to be welded;
  • the welded joints of the workpiece after welding are in the form of pipe/bar casing joints, lap joints, butt joints with backing plates, backing joints, incompletely welded T-joints or incompletely welded cross joints.
  • the material of the intermediate layer metal is Ti, Ni, Zr or Al.
  • step 2) the intermediate layer metal is filled at the joint surface to be welded of the workpiece to be welded by directly filling the metal foil, sputter coating, electroplating, cold spraying or laser cladding.
  • the purity of the intermediate layer metal is greater than or equal to 99.99%.
  • the temperature for preheating in step 3) is from 400 ° C to 500 ° C.
  • the mating gap of the workpiece to be welded is less than or equal to 0.1 mm, the amount of misalignment of the joint of the workpiece to be welded is less than or equal to 10% of the thickness of the workpiece to be welded, and the joint of the workpiece to be welded is wrong.
  • the side amount is less than 0.5mm;
  • the gap of the overlap region of the workpiece to be welded filled with the intermediate layer metal is 0.05 mm or less.
  • the molybdenum alloy welding method based on microalloying and synchronous parasitic brazing fills the intermediate layer metal at the joint surface to be welded of the workpiece to be welded in a specific operation, wherein the melting point of the intermediate layer metal is lower than Welding the melting point of the workpiece, so that part of the intermediate layer metal enters the molten pool during the welding process, realizing the microalloying of the welded weld, and at the same time, the weld line is welded due to the high thermal conductivity of the molybdenum and molybdenum alloy.
  • the intermediate layer metal in a certain distance range is melted, thereby forming a brazing interface parasitic in the heat affected zone of the fusion welding, and the metallurgical bonding between the workpieces to be welded is realized through the brazing interface, and has obvious auxiliary bearing effect.
  • the micro-alloying effectively improves the mechanical properties of the welded weld
  • the auxiliary bearing of the welded joint is realized by synchronous parasitic brazing, and under the joint action of the two mechanisms, significant Improve the overall mechanical properties of the welded joints of molybdenum and molybdenum alloys.
  • Figure 1 is a binary equilibrium phase diagram of Ti-Mo
  • 2a is a schematic view showing the structure of the first embodiment without adding a Ti foil
  • 2b is a schematic structural view of the first embodiment when Ti is added only at the butt joint;
  • 2c is a schematic structural view of the first embodiment when Ti is added to the butt joint and the lap joint;
  • Figure 3a is a dimensional view of the molybdenum tube 1 of the first embodiment
  • Figure 3b is a dimensional view of the molybdenum alloy end plug 2 of the first embodiment
  • Figure 3c is a dimensional view of the intermediate layer metal 3 when only Ti is added at the butt joint in the first embodiment
  • Figure 3d is a dimensional view of the intermediate layer metal 3 when the Ti foil is applied to both the butt joint and the lap joint in the first embodiment;
  • Figure 4 is a cross-sectional view of the welded joint of the first embodiment and a composition analysis diagram of the brazing interface
  • Figure 5a is a microhardness distribution diagram of a welded joint in the first embodiment without a Ti foil
  • Figure 5b is a microhardness distribution diagram of the welded joint when the Ti foil is added at the butt joint and the lap joint in the first embodiment
  • Figure 6 is a tensile diagram of the first embodiment of the present invention.
  • 7a is a topographical view of the welded joint after tensile fracture in the first embodiment without the Ti foil;
  • Figure 7b is a top view showing the tensile fracture of the welded joint when the Ti foil is added at the butt joint and the lap joint in the first embodiment;
  • Figure 8a is a microscopic top view of the tensile fracture of the welded joint without the Ti foil in the first embodiment
  • Figure 8b is a microscopic top view of the tensile fracture of the welded joint when the Ti foil is added at the butt joint and the lap joint in the first embodiment;
  • Figure 9 is a cross-sectional top view of the welded joint of the second embodiment.
  • Figure 10 is a tensile diagram of the second embodiment
  • Figure 11 is a cross-sectional top view of the welded joint of the third embodiment
  • Figure 12 is a tensile diagram of the third embodiment
  • Figure 13 is a tensile diagram of the fourth embodiment
  • Figure 14 is a microscopic topographical view of a tensile fracture of a welded joint in the fourth embodiment.
  • 1 is a molybdenum tube
  • 2 is an end plug
  • 3 is an intermediate layer metal.
  • the molybdenum alloy fusion welding method based on microalloying and synchronous parasitic brazing according to the present invention comprises the following steps:
  • pretreating the joint to be welded of the workpiece to be welded in step 1) is: grinding the combined area of the workpiece to be welded, alkali washing, acetone washing and drying.
  • the material to be welded is made of pure molybdenum, a molybdenum alloy having an alloy element content of 2 wt% or less, or a molybdenum alloy having a second phase dopant content of 2 wt% or less.
  • step 4 the welding of the workpiece to be welded is completed by laser welding, electron beam welding, plasma beam welding or argon arc welding.
  • the welded joints of the workpiece after welding are in the form of tube/bar sleeve joints, lap joints, butt joints with backing plates, backing joints, incompletely welded T-joints or incompletely welded cross joints.
  • the material of the intermediate layer metal 3 is Ti, Ni, Zr or Al.
  • step 2) the intermediate layer metal 3 is filled at the joint surface to be welded of the workpiece to be welded by directly filling the metal foil, sputter coating, electroplating, cold spraying or laser cladding.
  • the intermediate layer metal 3 has a purity of 99.99% or more.
  • the temperature for preheating in step 3) is from 400 ° C to 500 ° C.
  • the mating gap of the workpiece to be welded is less than or equal to 0.1 mm, the amount of misalignment of the joint of the workpiece to be welded is less than or equal to 10% of the thickness of the workpiece to be welded, and the joint of the workpiece to be welded is wrong.
  • the side amount is less than 0.5mm;
  • the gap of the overlap region of the workpiece to be welded filled with the intermediate layer metal 3 is 0.05 mm or less.
  • Titanium is selected as the material of the intermediate layer metal 3, because Ti and Mo undergo a homogenization reaction during the transition from the liquid phase to the solid phase, as shown in Fig. 1, so that Ti and Mo are infinitely miscible with each other, and no brittle phase is formed.
  • Mo-Ti solid solution has a high melting point and good high temperature mechanical properties; Ti has a strong affinity for elements such as O at high temperature, and a trace amount of Ti in the weld pool reacts with O and Mo to form Mo x Ti
  • the second phase particles of the y O z composite oxide can eliminate the segregation of the impurity element grain boundaries and can enhance the second phase particles of the weld metal.
  • Fig. 2a, Fig. 2b and Fig. 2c three sets of molybdenum alloy thin-walled tube-end plug 2 casing joints are welded by laser welding, wherein the first group is directly assembled with the molybdenum tube 1 and the end plug 2, and the second group In order to fill the titanium foil at the abutment of the molybdenum tube 1 and the end plug 2, the third group is filled with titanium foil at the abutment and the lap joint of the molybdenum tube 1 and the end plug 2.
  • the test material is a high-performance molybdenum alloy doped with 0.25 wt% La 2 O 3 dispersion strengthening phase.
  • FIG. 4 A cross section of the welded joint of the sample filled with the titanium foil at the butt joint and the lap joint was observed (as shown in Fig. 4).
  • the titanium foil filled between the molybdenum tube 1 and the end plug 2 is melted and brazed, and the titanium foil and the molybdenum tube 1, the titanium foil and the end plug 2 are A parasitic brazing metallurgical bond is formed between them, and Mo and Ti are mutually soluble at the brazing interface.
  • the sample without titanium foil and the sample filled with titanium foil at the butt joint and the joint were respectively measured for the microhardness of the weld zone of the weld, and the measurement results are shown in Fig. 5a and Fig. 5b.
  • the microhardness of the molybdenum alloy base material used in the test is about 235 HV. It can be seen from Fig. 5a and Fig. 5b that the microhardness of the weld zone of the weld without the titanium foil is significantly lower than that of the base metal.
  • the microhardness of the sample weld filled with titanium foil at the butt joint and the lap joint is only about 15 HV lower than that of the base metal, so it is indicated that by incorporating Ti into the weld as an alloying element. Can improve the weld strength.
  • the tensile mechanical properties of the parent material of the molybdenum tube 1 and the three sets of welded joints were measured respectively.
  • the tensile curve is shown in Fig. 6.
  • the tensile strength of the parent material of the molybdenum tube 1 is 720 MPa, and the elongation at break is 10.6 mm.
  • the tensile strength of welded joints without titanium foil is only 124 MPa, and the elongation at break is only 0.6 mm; the tensile strength of welded joints with titanium foil at the joint of molybdenum tube 1 and end plug 2 is 606 MPa, reaching the mother
  • the tensile strength of the material is 84.2%, and the elongation at break is 3.1mm, which indicates that the incorporation of Ti into the weld as a microalloying element can significantly improve the tensile strength of the weld; at the same time, the joint between the molybdenum tube 1 and the end plug 2
  • the tensile strength of the welded joint with titanium foil at the joint and the lap joint reaches 688 MPa, which is as high as 95.6% of the tensile strength of the base metal, and the elongation at break reaches 9.8 mm, indicating that the weld is microalloyed while Ti is added.
  • the fusion-welding joint region parasitic in the heat-affected zone of the welded joint serves as an auxiliary load-bearing function, and the tensile strength of the welded joint is further improved, and the elongation of the welded joint is remarkably improved.
  • the former is broken in the weld seam, and the latter molybdenum tube 1 is necked significantly and starts to break from the molybdenum tube 1; as can be seen from Fig. 8a and Fig. 8b, the welded joint is not added when the titanium foil is added. Breaking in the weld, the fracture mode is mainly characterized by intergranular fracture; the welded joint filled with titanium foil at the joint and the joint is mainly broken in the base metal, only a small part of the fracture is in the weld and is located on the fracture of the weld.
  • the fracture morphology is mainly characterized by transgranular cleavage fracture.
  • Nickel is selected as the material of the intermediate layer metal 3, and the two sets of molybdenum alloy thin-walled tube-end plug 2 casing joints are the same as in the first embodiment, wherein the first group is the direct assembly of the molybdenum tube 1 and the end plug 2, and the second group is The joint surface of the molybdenum tube 1 and the end plug 2 is filled with a nickel foil.
  • the sample When welding, the sample is placed in a high-purity argon protective atmosphere, and then the joint is preheated. When the joint temperature reaches 500 °C, the IPG-4000 fiber laser is used to weld the power P to 1200 W, and the defocus amount f The laser welding ring welding of the molybdenum tube 1 and the end plug 2 is completed for the welding parameters of +1 mm and the rotating linear velocity v of 0.2 m/min. After welding, the welded joint is kept at 500 ° C for 30 s, and then slowly cooled to room temperature.
  • FIG. 9 The cross section of the welded joint of the sample filled with nickel foil is shown in Fig. 9.
  • Fig. 9 in the heat affected zone of the laser welded joint, the nickel foil filled between the molybdenum tube 1 and the end plug 2 melts and melts. Brazing, nickel foil and molybdenum tube 1, nickel foil and end plug 2 form a parasitic brazing metallurgical bond.
  • the tensile curve is shown in Fig. 10.
  • the tensile strength of the welded joint without nickel foil is only 124 MPa, and the elongation at break is only 0.6mm; the tensile strength of the welded joint filled with nickel foil at the joint surface of the molybdenum tube 1 and the end plug 2 is 624 MPa, reaching 86.7% of the tensile strength of the base material (about 720 MPa), and the elongation at break is 2.55.
  • Zirconium is selected as the intermediate layer filling metal material, and the size of the molybdenum alloy thin-walled tube-end plug 2 casing joint is the same as that of the first embodiment, wherein the first group is to directly assemble the molybdenum tube 1 and the end plug 2, and the second group is The joint surface of the molybdenum tube 1 and the end plug 2 is filled with zirconium foil.
  • the test material is a high performance molybdenum alloy doped with 0.25 wt% La 2 O 3 dispersion strengthening phase. The high performance molybdenum alloy thin wall tube and end plug 2 size used in the test. As shown in Fig. 3a and Fig.
  • the IPG-4000 fiber laser was used to have a welding power P of 1200 W, a defocus amount f of +1 mm, and a rotational linear velocity v. 0.2m / min to complete the welding parameters for laser welding a molybdenum tube 1 and the end plug weld ring 2, after the welded joint heat above 500 °C 30s, and then slowly cooled to room temperature.
  • the cross section of the welded joint of the sample filled with the zirconium foil was observed; as can be seen from Fig. 11, in the heat affected zone of the laser welded joint, the zirconium foil filled between the molybdenum tube 1 and the end plug 2 was melted. Zr and Mo interdiffused to form an intermetallic compound, and a metallurgical bond was formed between the zirconium foil and the molybdenum tube 1, the zirconium foil and the end plug 2.
  • the tensile strength of the welded joint without zirconium foil is 124 MPa, which is only the tensile strength of the base metal. 17.2% of about 720 MPa), the elongation at break is only 0.6 mm; the tensile strength of the welded joint filled with zirconium foil at the joint surface of the molybdenum tube 1 and the end plug 2 is 480 MPa, and the tensile strength of the base material is 66.7.
  • the elongation at break is 1.55mm, indicating that when laser welding is used to weld high-performance molybdenum alloy doped with 0.25wt% La 2 O 3 dispersion strengthening phase, micro-alloying and formation of weld metal is performed by filling zirconium foil
  • the strength and elongation of the welded joint can be significantly improved by the combination of two mechanisms of simultaneous parasitic brazing.
  • the material of aluminum is the material of the intermediate layer metal 3, and the size of the sleeve of the molybdenum alloy thin-wall tube-end plug 2 is the same as that of the first embodiment, wherein the first group is to directly assemble the molybdenum tube 1 and the end plug 2, and the second group is
  • the aluminum foil is filled at the joint surface of the molybdenum tube 1 and the end plug 2;
  • the test material is a high-performance molybdenum alloy doped with 0.25 wt% La 2 O 3 dispersion strengthening phase, and the high-performance molybdenum alloy thin-walled tube and the end plug 2 are used for the test.
  • the specific welding process is as follows: first, the contact portion of the molybdenum tube 1 and the end plug 2 is sanded with a sandpaper, then alkali washed with a dilute aqueous solution of sodium hydroxide, and then washed with water and acetone in turn. Drying; processing the aluminum foil with a thickness of 0.05 mm into the size shown in Figure 3d, washing it with a dilute aqueous solution of sodium hydroxide, washing it with water and acetone, then drying it; assembling the two sets of samples Then, the welding is carried out in turn, the sample is placed in a high-purity argon protective atmosphere, and the joint is preheated.
  • the IPG-4000 fiber laser is used to have a welding power P of 1200 W.
  • the welding parameters of the defocusing amount f is +1 mm and the rotating linear velocity v is 0.2 m/min.
  • the tensile curve is shown in Fig. 13.
  • the tensile strength of the welded joint without aluminum foil is 124 MPa, which is only the tensile strength of the base material (about 720 MPa). 17.2%, the elongation at break is only 0.6mm; the tensile strength of the welded joint filled with aluminum foil at the joint surface of the molybdenum tube 1 and the end plug 2 is 557 MPa, reaching 77.4% of the tensile strength of the base material, and elongation at break The amount is 1.8mm.
  • Figure 14 shows the tensile fracture morphology of the aluminum foil sample.
  • the fracture mode of the fracture is dominated by transgranular fracture, which indicates that the laser is used to weld high-performance molybdenum alloy doped with 0.25 wt% La 2 O 3 dispersion strengthening phase. Filled with aluminum foil, the strength and elongation of the welded joint can be significantly improved by the combined action of weld metal microalloying and simultaneous parasitic brazing.

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Abstract

一种基于微合金化与同步寄生钎焊的钼合金熔焊方法，包括以下步骤：1)对待焊接工件的待焊结合区域进行预处理，其中，所述待焊接工件的材质为钼或钼合金；2)在待焊接工件的待焊结合面处填充中间层金属，再完成待焊接工件的对接；3)将待焊接工件置于惰性气体保护的气氛中或真空环境中，再对待焊接工件的待焊结合区域进行预热；4)完成待焊接工件的熔焊焊接，得焊接后的工件；5)将焊接后工件的焊接接头进行保温，再将焊接后工件的焊接接头置于惰性气体保护气氛中或真空环境中冷却至室温，完成基于微合金化与同步寄生钎焊的钼合金熔焊。该熔焊方法能够有效提高焊接后工件焊接接头的力学性能。

Description

一种基于微合金化与同步寄生钎焊的钼合金熔焊方法 技术领域
本发明属于焊接技术领域，涉及一种基于微合金化与同步寄生钎焊的钼合金熔焊方法。
背景技术
钼，熔点高达2610℃，中子吸收截面小，热膨胀系数低，热传导性能优异，高温力学性能好，可加工性好，当温度低于500℃时，钼在空气或水中有良好的稳定性。上述优点使得钼及钼合金，尤其是高性能钼合金在冶金、航空、航天、核能、军事等领域有着重要应用。高性能钼合金自身强韧性优异，但一旦进行熔焊，其强韧性优势将完全丧失。不仅如此，由于钼的熔点太高，一般须采用粉末冶金的方式加工制备，一方面导致材料致密度无法和熔铸冶金材料相比、含气量较高，焊接气孔缺陷严重；另一方面，易将O、N等杂质引入材料中，而室温下O、N等杂质元素在钼中的溶解度极低，熔池凝固时O、N等杂质元素易在晶界处偏析，使晶界严重弱化，焊缝的力学性能极差，上述问题严重制约了钼及钼合金作为结构材料在核电等关键场合的应用。
发明内容
本发明的目的在于克服上述现有技术的缺点，提供了一种基于微合金化与同步寄生钎焊的钼合金熔焊方法，该方法能够有效提高焊接后工件焊接接头的力学性能。
为达到上述目的，本发明所述的基于微合金化与同步寄生钎焊的钼 合金熔焊方法包括以下步骤：
1)对待焊接工件的待焊结合区域进行预处理，其中，所述待焊接工件的材质为钼或钼合金；
2)在待焊接工件的待焊结合面处填充中间层金属，再完成待焊接工件的对接，其中，中间层金属的熔点低于待焊接工件的熔点，中间层金属的填充区域范围覆盖焊接过程中待焊接工件熔焊焊缝区域及熔焊的热影响区域；
3)将待焊接工件置于惰性气体保护的气氛中或真空环境中，再对待焊接工件的待焊结合区域进行预热；
4)完成待焊接工件的熔焊焊接，在熔焊焊接过程中，待焊接工件的接头位置及其附近区域的中间层金属发生融化，使中间层金属与待焊接工件的接头位置形成熔钎焊冶金结合；
5)将焊接后工件的焊接接头进行保温，再将焊接后工件的焊接接头置于惰性气体保护气氛中或真空环境中冷却至室温，完成基于微合金化与同步寄生钎焊的钼合金熔焊。
步骤1)中对待焊接工件的待焊结合区域进行预处理的具体操作为：将待焊接工件的待焊结合区域依次进行打磨、碱洗、丙酮清洗及烘干；
待焊接工件的材质为纯钼、合金元素含量小于等于2wt％的钼合金或第二相掺杂物含量小于等于2wt％的钼合金。
步骤4)中采用激光焊、电子束焊、等离子束焊或氩弧焊的方法完成待焊接工件的熔焊焊接；
焊接后工件的焊接接头形式为管/棒套管接头、搭接接头、带垫板的 对接接头、封底对接接头、不完全焊透的T型接头或不完全焊透的十字接头。
中间层金属的材质为Ti、Ni、Zr或Al。
步骤2)中通过直接填充金属箔材、溅射镀膜、电镀、冷喷涂或激光熔覆的方式在待焊接工件的待焊结合面处填充中间层金属。
中间层金属的纯度大于等于99.99％。
步骤3)中预热的温度为400℃-500℃。
步骤2)中待焊接工件的对接完成后，待焊接工件的对接间隙小于等于0.1mm，待焊接工件接合处的错边量小于等于待焊接工件厚度的10％，且待焊接工件接合处的错边量小于0.5mm；
填充有中间层金属的待焊接工件的搭接区域的间隙小于等于0.05mm。
本发明具有以下有益效果：
本发明所述的基于微合金化与同步寄生钎焊的钼合金熔焊方法在具体操作时，在待焊接工件的待焊结合面处填充中间层金属，其中，中间层金属的熔点低于待焊接工件的熔点，从而在熔焊过程中将部分中间层金属进入到熔池中，实现熔焊焊缝的微合金化，同时由于钼和钼合金的导热率较高，使距焊缝熔合线一定距离范围内的中间层金属发生熔化，从而形成寄生于熔焊热影响区的钎焊界面，通过该钎焊界面实现待焊工件之间的冶金结合，具有明显的辅助承载作用。需要说明的是，本发明一方面通过微合金化有效改善熔焊焊缝的力学性能，另一方面通过同步寄生钎焊实现对焊接接头的辅助承载，并在两种机制的共同作用下，显 著的改善钼及钼合金的熔焊接头的总体力学性能。
附图说明
图1为Ti-Mo二元平衡相图；
图2a为实施例一中不加Ti箔时的结构示意图；
图2b为实施例一中只在对接处加Ti时的结构示意图；
图2c为实施例一中在对接处和搭接处均加Ti箔时的结构示意图；
图3a为实施例一中钼管1的尺寸图；
图3b为实施例一中钼合金端塞2的尺寸图；
图3c为实施例一中只在对接处加Ti时中间层金属3的尺寸图；
图3d为实施例一中在对接处和搭接处均加Ti箔时中间层金属3的尺寸图；
图4为实施例一中焊接接头横截面形貌与钎焊界面成分分析图；
图5a为实施例一中不加Ti箔时焊接接头显微硬度分布图；
图5b为实施例一中在对接处及搭接处均加Ti箔时焊接接头显微硬度分布图；
图6是本发明实施例一中拉伸曲线图；
图7a为实施例一中不加Ti箔时焊接接头拉伸断裂后的形貌图；
图7b为实施例一中在对接处及搭接处均加Ti箔时焊接接头拉伸断裂后的形貌图；
图8a为实施例一中不加Ti箔时焊接接头拉伸断口的显微形貌图；
图8b为实施例一中在对接处及搭接处均加Ti箔时焊接接头拉伸断口的显微形貌图；
图9为实施例二中焊接接头的横截面形貌图；
图10为实施例二中的拉伸曲线图；
图11为实施例三中焊接接头的横截面形貌图；
图12为实施例三中的拉伸曲线图；
图13为实施例四中的拉伸曲线图；
图14为实施例四中焊接接头拉伸断口的显微形貌图。
其中，1为钼管、2为端塞、3为中间层金属。
具体实施方式
下面结合附图对本发明做进一步详细描述：
本发明所述的基于微合金化与同步寄生钎焊的钼合金熔焊方法包括以下步骤：
1)对待焊接工件的待焊结合区域进行预处理，其中，所述待焊接工件的材质为钼或钼合金；
2)在待焊接工件的待焊结合面处填充中间层金属3，再完成待焊接工件的对接，其中，中间层金属3的熔点低于待焊接工件的熔点，中间层金属3的填充区域范围覆盖焊接过程中待焊接工件熔焊焊缝区域及熔焊的热影响区域；
3)将待焊接工件置于惰性气体保护的气氛中或真空环境中，再对待焊接工件的待焊结合区域进行预热；
4)完成待焊接工件的熔焊焊接，在熔焊焊接过程中，待焊接工件的接头位置及其附近区域的中间层金属3发生融化，使中间层金属3与待焊接工件的接头位置形成熔钎焊冶金结合；
5)将焊接后工件的焊接接头进行保温，再将焊接后工件的焊接接头置于惰性气体保护气氛中或真空环境中冷却至室温，完成基于微合金化与同步寄生钎焊的钼合金熔焊。
步骤1)中对待焊接工件的待焊结合区域进行预处理的具体操作为：将待焊接工件的待焊结合区域依次进行打磨、碱洗、丙酮清洗及烘干。
待焊接工件的材质为纯钼、合金元素含量小于等于2wt％的钼合金或第二相掺杂物含量小于等于2wt％的钼合金。
步骤4)中采用激光焊、电子束焊、等离子束焊或氩弧焊的方法完成待焊接工件的熔焊焊接。
焊接后工件的焊接接头形式为管/棒套管接头、搭接接头、带垫板的对接接头、封底对接接头、不完全焊透的T型接头或不完全焊透的十字接头。
中间层金属3的材质为Ti、Ni、Zr或Al。
步骤2)中通过直接填充金属箔材、溅射镀膜、电镀、冷喷涂或激光熔覆的方式在待焊接工件的待焊结合面处填充中间层金属3。
中间层金属3的纯度大于等于99.99％。
步骤3)中预热的温度为400℃-500℃。
步骤2)中待焊接工件的对接完成后，待焊接工件的对接间隙小于等于0.1mm，待焊接工件接合处的错边量小于等于待焊接工件厚度的10％，且待焊接工件接合处的错边量小于0.5mm；
填充有中间层金属3的待焊接工件的搭接区域的间隙小于等于0.05mm。
实施例一
选用钛作为中间层金属3的材料，因为Ti与Mo在从液相到固相的转变过程中发生匀晶反应，如图1所示，从而使Ti与Mo无限互溶，且不会生成脆性相；Mo-Ti固溶体的熔点较高，并且有良好的高温力学性能；高温下Ti对O等元素有极强的亲和力，焊接熔池中的微量Ti元素与O及Mo发生反应，生成Mo xTi yO z复合氧化物的第二相粒子，在消除杂质元素晶界偏析的同时，能对焊缝金属起到第二相粒子强化的作用。
如图2a、图2b及图2c所示，采用激光焊焊接三组钼合金薄壁管-端塞2套管接头，其中，第一组为钼管1和端塞2直接装配，第二组为在钼管1与端塞2的对接处填充钛箔，第三组为在钼管1与端塞2的对接处和搭接处都填充钛箔。试验材料为掺有0.25wt％La 2O 3弥散强化相的高性能钼合金，试验所用高性能钼合金薄壁管、端塞2及钛箔的尺寸如图3a、图3b、图3c及图3d所示；具体操作为：先将钼管1及端塞2的接触部位用砂纸打磨，然后用稀氢氧化钠水溶液进行碱洗，再依次用清水和丙酮洗净后吹干；将厚度为0.05mm的TA1钛箔加工成如图3d所示尺寸，用由12mL的HNO 3、6mL的HF及82mL的H 2O配制而成的溶液进行酸洗，再依次用清水及丙酮洗净后吹干；将三组试样装配好，然后再依次焊接，焊接时将试样置于高纯氩气保护气氛中，再对接头进行预热，当接头温度达到500℃后，使用IPG-4000型光纤激光器以焊接功率P为1200W、离焦量f为+1mm、旋转线速度v为0.2m/min的焊接参数完成对钼管1和端塞2的激光焊环焊，焊后将焊接接头在500℃以上保温30s，之后再缓慢冷却至室温。
观察在对接处和搭接处都填充了钛箔的试样的焊接接头横截面(如图4所示)。从图4中可以看出，在激光焊接头的热影响区，钼管1与端塞2之间填充的钛箔熔化发生熔钎焊，钛箔与钼管1、钛箔与端塞2之间都形成了寄生钎焊冶金结合，Mo与Ti在钎焊界面处发生互溶。
选取不加钛箔的试样与在对接处和搭接处都填充了钛箔的试样，分别测量二者焊缝熔化区的显微硬度，测量结果如图5a及图5b所示。经测量，试验所用钼合金母材的显微硬度约为235HV，从图5a及图5b可以看出，不加钛箔试样焊缝熔化区的显微硬度相较于母材下降明显，降幅约为30HV；在对接处和搭接处都填充有钛箔的试样焊缝的显微硬度相较于母材只下降了约15HV，因此说明通过向焊缝中掺入Ti作为合金元素确能提高焊缝强度。
分别测量钼管1母材与三组焊接接头试样的拉伸力学性能，拉伸曲线如图6所示，钼管1母材的抗拉强度为720MPa，断裂时伸长量达到10.6mm；不加钛箔的焊接接头的抗拉强度仅有124MPa，断裂时伸长量仅为0.6mm；在钼管1与端塞2对接处加钛箔的焊接接头的抗拉强度为606MPa，达到母材抗拉强度的84.2％，断裂时伸长量为3.1mm，说明向焊缝中掺入Ti作为微合金化元素可以显著提高焊缝的抗拉强度；同时在钼管1和端塞2对接处和搭接处都加钛箔的焊接接头的抗拉强达到688MPa，高达母材抗拉强度的95.6％，断裂时伸长量达到9.8mm，说明在加Ti使焊缝微合金化的同时，寄生于熔焊接头热影响区的熔钎焊结合区起到了辅助承载作用，在进一步提高焊接接头抗拉强度的同时，显著改善焊接接头的延伸率。
由图7a及图7b可以看出，前者断在焊缝，而后者钼管1颈缩明显且从钼管1开始断裂；由图8a及图8b可以看出，不加钛箔时焊接接头全部断在焊缝，断裂模式主要表现为沿晶断裂；在对接处和搭接处都填充钛箔的焊接接头主要断在母材，只有一小部分断口在焊缝，且位于焊接的断口上的断裂形貌主要表现为穿晶解理断裂。
实施例二
选用镍作为中间层金属3的材料，两组钼合金薄壁管-端塞2套管接头与实施例一相同，其中，第一组是钼管1与端塞2直接装配，第二组在钼管1与端塞2的接合面填充镍箔。试验材料为掺有0.25wt％La 2O 3弥散强化相的高性能钼合金；具体熔焊焊接过程为：先将钼管1与端塞2的接触部位用砂纸打磨，然后用稀氢氧化钠水溶液进行碱洗，再依次用清水和丙酮洗净并吹干；将厚度为0.05mm的镍箔加工成如图3d所示尺寸，用由配比为HF:HNO 3:H 2O＝2:1:4.5的混合酸液进行酸洗，再依次用清水和丙酮洗净后吹干；将两组试样装配好，再依次进行熔焊焊接。焊接时将试样置于高纯氩气保护气氛中，再对对接头进行预热，当对接头温度达到500℃后，使用IPG-4000型光纤激光器以焊接功率P为1200W、离焦量f为+1mm、旋转线速度v为0.2m/min的焊接参数完成对钼管1与端塞2的激光焊环焊，焊后将焊接接头在500℃以上保温30s，然后再缓慢冷却至室温。
填充有镍箔的试样的焊接接头横截面如图9所示，从图9中可以看出，在激光焊接头的热影响区，钼管1与端塞2间填充的镍箔熔化发生熔钎焊，镍箔与钼管1、镍箔与端塞2之间都形成寄生钎焊冶金结合。
对比不加镍箔和加镍箔两组焊接接头的拉伸力学性能，拉伸曲线如图10所示，不加镍箔的焊接接头的抗拉强度仅有124MPa，断裂时伸长量仅为0.6mm；在钼管1和端塞2接合面处填充有镍箔的焊接接头的抗拉强度为624MPa，达到母材抗拉强度(约720MPa)的86.7％，且断裂时伸长量为2.55mm，说明在采用激光焊焊接掺有0.25wt％La 2O 3弥散强化相的高性能钼合金时，通过填充镍箔，在焊缝金属微合金化和形成同步寄生钎焊两种机制的共同作用下，焊接接头的强度和延伸率可以得到显著改善。
实施例三
选用锆作为中间层填充金属材料，钼合金薄壁管-端塞2套管接头的尺寸与实施例一相同，其中，第一组是将钼管1和端塞2直接装配，第二组在钼管1和端塞2的接合面处填充锆箔，试验材料为掺有0.25wt％La 2O 3弥散强化相的高性能钼合金，试验所用高性能钼合金薄壁管及端塞2尺寸如图3a及图3b所示，具体焊接过程为：将钼管1和端塞2的接触部位用砂纸打磨，然后用稀氢氧化钠水溶液进行碱洗，再依次用清水和丙酮洗净并吹干；将厚度为0.05mm的锆箔加工成如图3d所示尺寸，再用由配比为HF:HNO 3:H 2O＝3:45:52的混合酸液进行酸洗，然后再依次用清水和丙酮洗净后吹干；将两组试样装配好，依次进行焊接，焊接时将试样置于高纯氩气保护气氛中，再对接头进行预热，当接头温度达到500℃后，使用IPG-4000型光纤激光器以焊接功率P为1200W、离焦量f为+1mm、旋转线速度v为0.2m/min的焊接参数完成对钼管1和端塞2的激光焊环焊，焊后将焊接接头在500℃以上保温30s，然后再 缓慢冷却至室温。
如图11所示，观察填充有锆箔的试样的焊接接头横截面；从图11中可以看出，在激光焊接头的热影响区，钼管1和端塞2间填充的锆箔熔化，Zr与Mo相互扩散生成金属间化合物，锆箔与钼管1、锆箔与端塞2之间都形成冶金结合。
对比不加锆箔和加锆箔的两组焊接接头的拉伸力学性能，拉伸曲线如图12所示，不加锆箔焊接接头的抗拉强度为124MPa，仅为母材抗拉强度(约720MPa)的17.2％，断裂时伸长量仅为0.6mm；在钼管1和端塞2接合面处填充有锆箔的焊接接头的抗拉强度为480MPa，达到母材抗拉强度的66.7％，断裂时伸长量为1.55mm，说明在采用激光焊焊接掺有0.25wt％La 2O 3弥散强化相的高性能钼合金时，通过填充锆箔，在焊缝金属微合金化和形成同步寄生钎焊两种机制的共同作用下，焊接接头的强度和延伸率可以得到显著改善。
实施例四
选用铝为中间层金属3的材料，钼合金薄壁管-端塞2套管接头尺寸与实施例一相同，其中，第一组为将钼管1与端塞2直接装配，第二组为在钼管1与端塞2的接合面处填充铝箔；试验材料为掺有0.25wt％La 2O 3弥散强化相的高性能钼合金，试验所用高性能钼合金薄壁管及端塞2尺寸如图3a及图3b所示，具体焊接过程为：先将钼管1与端塞2的接触部位用砂纸打磨，然后用稀氢氧化钠水溶液进行碱洗，再依次用清水和丙酮洗净后吹干；将厚度为0.05mm的铝箔加工成如图3d所示尺寸，用稀氢氧化钠水溶液对其进行碱洗，再依次用清水和丙酮洗净后 吹干；将两组试样装配好，再依次进行焊接，焊接时将试样置于高纯氩气保护气氛中，再对接头进行预热，当接头温度达到500℃后，使用IPG-4000型光纤激光器以焊接功率P为1200W、离焦量f为+1mm、旋转线速度v为0.2m/min的焊接参数完成钼管1和端塞2的激光焊环焊；焊后让焊接接头在500℃以上保温30s，然后再缓慢冷却至室温。
对比不加铝箔和加铝箔两组焊接接头的拉伸力学性能，拉伸曲线如图13所示，不加铝箔焊接接头的抗拉强度为124MPa，仅为母材抗拉强度(约720MPa)的17.2％，断裂时伸长量仅为0.6mm；在钼管1和端塞2接合面处填充铝箔的焊接接头的抗拉强度为557MPa，达到母材抗拉强度的77.4％，断裂时伸长量为1.8mm。图14为加铝箔试样拉伸断口形貌，整个断口断裂模式以穿晶断裂为主，说明在采用激光焊焊接掺有0.25wt％La 2O 3弥散强化相的高性能钼合金时，通过填充铝箔，在焊缝金属微合金化和形成同步寄生钎焊两种机制的共同作用下，焊接接头的强度和延伸率可以得到显著改善。

Claims (10)

  1. 一种基于微合金化与同步寄生钎焊的钼合金熔焊方法，其特征在于，包括以下步骤：
    1)对待焊接工件的待焊结合区域进行预处理，其中，所述待焊接工件的材质为钼或钼合金；
    2)在待焊接工件的待焊结合面处填充中间层金属(3)，再完成待焊接工件的对接，其中，中间层金属(3)的熔点低于待焊接工件的熔点，中间层金属(3)的填充区域范围覆盖焊接过程中待焊接工件熔焊焊缝区域及熔焊的热影响区；
    3)将待焊接工件置于惰性气体保护的气氛中或真空环境中，再对待焊接工件的待焊结合区域进行预热；
    4)完成待焊接工件的熔焊焊接，在熔焊焊接过程中，待焊接工件的接头位置及其附近区域的中间层金属(3)发生融化，使中间层金属(3)与待焊接工件的接头位置形成熔钎焊冶金结合；
    5)将焊接后工件的焊接接头进行保温，再将焊接后工件的焊接接头置于惰性气体保护气氛中或真空环境中冷却至室温，完成基于微合金化与同步寄生钎焊的钼合金熔焊。
  2. 根据权利要求1所述的基于微合金化与同步寄生钎焊的钼合金熔焊方法，其特征在于，步骤1)中对待焊接工件的待焊结合区域进行预处理的具体操作为：将待焊接工件的待焊结合区域依次进行打磨、碱洗、丙酮清洗及烘干。
  3. 根据权利要求1所述的基于微合金化与同步寄生钎焊的钼合金熔焊方法，其特征在于，待焊接工件的材质为纯钼、合金元素含量小于等于2wt％的钼合金或第二相掺杂物含量小于等于2wt％的钼合金。
  4. 根据权利要求1所述的基于微合金化与同步寄生钎焊的钼合金熔焊方法，其特征在于，步骤4)中采用激光焊、电子束焊、等离子束焊或氩弧焊的方法完成待焊接工件的熔焊焊接。
  5. 根据权利要求1所述的基于微合金化与同步寄生钎焊的钼合金熔焊方法，其特征在于，焊接后工件的焊接接头形式为管/棒套管接头、搭接接头、带垫板的对接接头、封底对接接头、不完全焊透的T型接头或不完全焊透的十字接头。
  6. 根据权利要求1所述的基于微合金化与同步寄生钎焊的钼合金熔焊方法，其特征在于，中间层金属(3)的材质为Ti、Ni、Zr或Al。
  7. 根据权利要求1所述的基于微合金化与同步寄生钎焊的钼合金熔焊方法，其特征在于，步骤2)中通过直接填充金属箔材、溅射镀膜、电镀、冷喷涂或激光熔覆的方式在待焊接工件的待焊结合面处填充中间层金属(3)。
  8. 根据权利要求1所述的基于微合金化与同步寄生钎焊的钼合金熔焊方法，其特征在于，中间层金属(3)的纯度大于等于99.99％。
  9. 根据权利要求1所述的基于微合金化与同步寄生钎焊的钼合金熔焊方法，其特征在于，步骤3)中预热的温度为400℃-500℃。
  10. 根据权利要求1所述的基于微合金化与同步寄生钎焊的钼合金熔焊方法，其特征在于，步骤2)中待焊接工件的对接完成后，待焊接工件的对接间隙小于等于0.1mm，待焊接工件接合处的错边量小于等于待焊接工件厚度的10％，且待焊接工件接合处的错边量小于0.5mm。
PCT/CN2018/080433 2017-04-26 2018-03-26 一种基于微合金化与同步寄生钎焊的钼合金熔焊方法 Ceased WO2018196524A1 (zh)

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