Microstructure and properties of continuous casting Ag-28Cu-8Sn alloy fabricated by dieless drawing
来源期刊:Rare Metals2020年第3期
论文作者:Ji-Heng Fang Ming Xie Ji-Ming Zhang You-Cai Yang Yong-Tai Chen Song Wang Man-Men Liu Jie-Qiong Hu
文章页码:279 - 288
摘 要:Ag-28Cu-8Sn(wt%) alloy is a widely used brittle silver-based brazing filler metal.The wire of brazing filler metal was prepared by continuous casting process and dieless drawing technology.The phase structure was measured by X-ray diffraction(XRD),and the microstructure of wetting interface,cast states,processing states and fracture morphologies were characterized by the optical microscopy(OM) and scanning electron microscopy(SEM),respectively.The electrical conductivity,hardness,tensile strength and elongation rate were tested as well.Furthermore,the solid-liquid phase temperature was measured by a differential scanning calorimeter(DSC),and the wettability of brazing filler metal was tested by spreading method.The outcomes obtained show that the as-cast microstructure is a typical three-zone structure,including region of surface fine grain,zone of columnar grain and region of center equiaxed crystal.Ag-28Cu-8Sn alloy is mainly composed of Ag-rich a-phase,Cu-rich pphase and intermediate compounds.Grain refinement appears in the cross section,as for grains of the longitudinal section,the shape is changed from ribbon to fiber to form a silk texture.The strength and hardness improve with the increase in the true strain,while the conductivity and elongation are reduced.Furthermore,the solid-phase temperature is 605.9℃,and the liquid-phase temperature is 725.1℃.The spreading area of Ag-28Cu-8Sn brazing filler metal is 174 mm2,and the metallurgical bonding occurs between Ag-28Cu-8Sn brazing filler metal and Cu matrix.In addition,compared with cold drawing process,there are not any microcracks at the fracture morphology for the alloy fabricated by dieless drawing.The dieless drawing process overcomes some processing defects of traditional cold drawing,and the processing performance of Ag-28Cu-8Sn alloy is improved.
稀有金属(英文版) 2020,39(03),279-288
Ji-Heng Fang Ming Xie Ji-Ming Zhang You-Cai Yang Yong-Tai Chen Song Wang Man-Men Liu Jie-Qiong Hu
State Key Laboratory of Advanced Technologies for Comprehensive Utilization of Platinum Metal
作者简介:*Ming Xie,e-mail:powder@ipm.com.cn;
收稿日期:18 October 2017
基金:financially supported by the National Natural Science Foundation of China (Nos.U1602271 and U1302272);
Ji-Heng Fang Ming Xie Ji-Ming Zhang You-Cai Yang Yong-Tai Chen Song Wang Man-Men Liu Jie-Qiong Hu
State Key Laboratory of Advanced Technologies for Comprehensive Utilization of Platinum Metal
Abstract:
Ag-28Cu-8Sn(wt%) alloy is a widely used brittle silver-based brazing filler metal.The wire of brazing filler metal was prepared by continuous casting process and dieless drawing technology.The phase structure was measured by X-ray diffraction(XRD),and the microstructure of wetting interface,cast states,processing states and fracture morphologies were characterized by the optical microscopy(OM) and scanning electron microscopy(SEM),respectively.The electrical conductivity,hardness,tensile strength and elongation rate were tested as well.Furthermore,the solid-liquid phase temperature was measured by a differential scanning calorimeter(DSC),and the wettability of brazing filler metal was tested by spreading method.The outcomes obtained show that the as-cast microstructure is a typical three-zone structure,including region of surface fine grain,zone of columnar grain and region of center equiaxed crystal.Ag-28Cu-8Sn alloy is mainly composed of Ag-rich a-phase,Cu-rich pphase and intermediate compounds.Grain refinement appears in the cross section,as for grains of the longitudinal section,the shape is changed from ribbon to fiber to form a silk texture.The strength and hardness improve with the increase in the true strain,while the conductivity and elongation are reduced.Furthermore,the solid-phase temperature is 605.9℃,and the liquid-phase temperature is 725.1℃.The spreading area of Ag-28Cu-8Sn brazing filler metal is 174 mm2,and the metallurgical bonding occurs between Ag-28Cu-8Sn brazing filler metal and Cu matrix.In addition,compared with cold drawing process,there are not any microcracks at the fracture morphology for the alloy fabricated by dieless drawing.The dieless drawing process overcomes some processing defects of traditional cold drawing,and the processing performance of Ag-28Cu-8Sn alloy is improved.
Keyword:
Continuous casting; Cold drawing; Dieless drawing; Microstructure; Properties;
Received: 18 October 2017
1 Introduction
With the advantages of low vapor pressure,moderate melting point,high strength of solder joints and excellent wettability on copper,nickel,steel and Kovar alloy
Thus far,the domestic and foreign scholars have conducted numerous theoretical and experimental researches in the field of dieless drawing technology.Twohig et al.
In addition,compared with the ordinary casting techniques,the continuous casting technology remarkably enhances the quality of casting,increases yield of metal and achieves mechanical automation easily
2 Experimental
2.1 Processing of dieless drawing
Ag-28Cu-8Sn alloy bars (8 mm in diameter),obtained through continuous casting technology,were processed by vacuum annealing (400℃×1 h).Subsequently,the alloy bars were drawn to the target diameter (2 mm) on the intelligent dieless drawing equipment of the University of Science and Technology Beijing
Fig.1 Schematic diagram of continuous dieless drawing process
2.2 Observation and testing of phase,microstructure and mechanical properties
The phase was investigated by means of D/max-RC X-ray diffractometer (XRD).Subsequently,the analytical samples were etched by corrosion solution (10 ml hydrogen peroxide,20 ml ammonia and 30 ml water),and the micro structure of wetting interface,casting states,working states and fracture morphologies were characterized by MM-4XC optical microscope (OM) and HITACHI S-3400N scanning electron microscope (SEM),respectively.Hardness was measured on the HV-5 Vickers hardness tester;tensile strength and elongation rate were measured on the AG-X100KN universal electronic testing machine.Eventually,the resistance was measured by the ZY9987 digital micro-ohmmeter,and it was converted to the electrical conductivity with formulaη=17.24L/(S×R)
2.3 Testing of brazing properties
The solidus-liquidus temperature was measured using NETZSCH STA409 PG/PC differential scanning calorimetry (DSC).According to the national standard GB11364-2008,wettability of brazing filler metal was tested by spreading method,which was tested in a vacuum tube furnace,and the experimental parameter are as follows:Cu as matrix (40 mm×40 mm×1 mm),brazing temperature of 640℃,0.2 g Ag-28Cu-8Sn brazing filler metal and holding time of 5 min;besides,the spread samples were scanned by scanner,and the spreading area of brazing filler metals was measured by graphic software.
3 Results and discussion
3.1 As-cast microstructure and phase of continuous casting Ag-28Cu-8Sn alloy
3.1.1 As-cast microstructure of continuous casting Ag-28Cu-8Sn alloy
The as-cast microstructure of Ag-28Cu-8Sn alloy is illustrated in Fig.2,showing that the microstructure of casting states is typical three-zone structure,including region of surface fine grain,zone of columnar grain and region of center equiaxed crystal
Fig.2 As-cast microstructure of continuous casting Ag-28Cu-8Sn alloy:a simulation result of ProCAST software and b metallographic image
3.1.2 Phase of continuous casting Ag-28Cu-8Sn alloy
According to the phase diagram of Ag-Cu-Sn
XRD pattern of Ag-28Cu-8Sn alloy is illustrated in Fig.4.Ag-28Cu-8Sn alloy is mainly composed of Ag-richα-phase (fcc structure) and Cu-richβ-phase (complex structure).In addition,there are also Ag6.7Sn,Cu0.85Sn0.15,Cu3Sn and other intermediate compounds.Among them,α-phase is plastic phase,butβ-phase and intermediate compounds are brittle phases.Sn content has a direct impact on the quantity ofβ-phase and intermediate compounds,and the higher the Sn content is,the more the brittle phases are,which leads to the deterioration of processing performance
Fig.3 BSE image of Ag-28Cu-8Sn alloy by continuous casting
Table 1 EDS analysis results for component of marking points on microstructure of Ag-28Cu-8Sn alloy in Fig.3
Fig.4 XRD pattern of continuous casting Ag-28Cu-8Sn alloy
3.2 Effects of deformation on microstructure of continuous casting Ag-28Cu-8Sn alloy
Figure 5 shows the microstructures of Ag-28Cu-8Sn alloy under different deformations.Ag-28Cu-8Sn alloy presents clear morphology and homogeneous compositions,the white phase is Ag-richα-phase,and the black phase is Curichβ-phase.The phase size decreases gradually with true strain increasing on the cross section,which is attributed to the local slip and stress cracking of grain
Fig.5 SEM images of a-d cross section and e-h longitudinal section of continuous casting Ag-28Cu-8Sn alloy:a,eη=0.575;b,fη=1.380;c,gη=1.960;d,hη=2.770
3.3 Effects of deformation on properties of Ag-28Cu-8Sn alloy
3.3.1 Effect of deformation on hardness of Ag-28Cu-8Sn alloy
Figure 6a shows the curve of hardness,as far as the change of hardness is concerned.On the one hand,with the increase in cold-drawn deformation,the dislocation density increases,the interaction between the dislocations increases,and a large number of entanglement and fixed dislocations are formed
3.3.2 Effects of deformation on electrical conductivity of Ag-28Cu-8Sn alloy
Figure 6b shows the curve of electrical conductivity.The electrical conductivity gradually decreases with the increase in plastic deformation.In the first place,the lattice distortion,vacancy concentration and crystal defects increase as the deformation proceeds.These changes exacerbate the scattering of electromagnetic waves,which ultimately increases the resistivity
Fig.6 Properties curves of continuous casting Ag-28Cu-8Sn alloy:a hardness-strain curve,b electrical conductivity-strain curve,c strength-strain curve and d elongation rate-strain curve
3.3.3 Effects of deformation on tensile strength of Ag-28Cu-8Sn alloy
Figure 6c shows the curve of tensile strength.The increase in tensile strength can be explained by the following reasons.(1) The smaller grain size corresponds to the larger total grain boundary area,which refers to more complicated grain boundaries and more severe blocking effect on the crack growth
3.3.4 Effects of deformation on elongation rate of Ag-28 Cu-8Sn alloy
Figure 6d shows the curve of elongation rate.In the first place,the effect of work hardening weakens the plasticity and toughness,and elongation rate,therefore,decreases as the deformation proceeds.Furthermore,the energy of plastic deformation is distributed to the smaller grains after grain refining,which results in more uniform plastic deformation and smaller stress concentration,and elongation rate increases at last
3.4 Melting characteristics of Ag-28Cu-8Sn alloy
Figure 7 shows DSC curve of Ag-28Cu-8Sn brazing filler metal.The brazing filler metal has an endothermic peak at the position of 724.0℃.In addition to the main endothermic peak,there are several smaller endothermic peaks near the main endothermic peak.The presence of the smaller attached peaks indicates the generation of new phases,demonstrating the formation of intermediate compounds.The melting point of Ag-28Cu brazing filler metal is 780℃,and there is no temperature range for melting points
3.5 Brazing properties of Ag-28Cu-8Sn alloy
The average spread area of the five tests was taken as the final result value,and the spreading area of Ag-28Cu-8Sn brazing filler metal is 174 mm2.Under the same conditions,the spreading area of Ag-28Cu solder is 213 mm2,and the reason for the decrease in the spreading area of Ag-28Cu-8Sn brazing filler metal is as follows.(1) Ag6 7Sn,Cu0.85Sn0.15,Cu3Sn and other intermediate compounds are formed in the brazing filler metal,which hinders the diffusion of filler metal and reduces the fluidity of liquid brazing filler metal
Fig.7 DSC curve of Ag-28Cu-8Sn alloy
3.6 Fracture morphology of Ag-28Cu-8Sn alloy fabricated by cold drawing and dieless drawing process
Fracture morphology of Ag-28Cu-8Sn alloy fabricated by two processing methods is shown in Fig.9.First of all,for the fracture morphology of Ag-28Cu-8Sn alloy prepared by cold drawing,whenη=0.575,the alloy surface is very rough,dimple size is not uniform,and part of the equiaxed dimple size is large.The average diameter can reach16μm,and the three-dimensional tensile stress causes the shape of the partially equiaxed dimple to change from regular circle to oval or rectangle.In addition,several microcracks are scattered on the fracture of the alloy,the average length of the crack is about 10μm,and its position is close to the large equiaxed dimple.These cracks are initiated by the intermediate compounds of the Ag-28Cu-8Sn alloy;similar to the inclusions and the second phases,cracks appear first in these regions.Whenη=1.960,the microcracks still exist in the fracture.Compared with the true strain of 0.575,the shape of the large dimple is more regular,and the depth of the dimple is only half of the former,indicating that the plasticity of the alloy has declined.Whenη=2.770,the large dimple disappears,and the fracture is distributed with uniform equiaxed dimples.The smaller the dimple shape is,the shallower the depth is,and the lower the plasticity is
Fig.8 SEM image of wetting interface of Ag-28Cu-8Sn alloy with Cu matrix
Table 2 EDS analysis results for component of marking points on wetting interfaces in Fig.6b
In conclusion,as the deformation increases,the fracture morphology shows that the plasticity of the alloy decreases gradually.And the previous mechanical performance data also show that the alloy elongation decreases with the increase in the deformation.In addition,the alloy contains more micro-crack defects under cold drawing process,indicating the poor processing performance.
The fracture morphology of Ag-28Cu-8Sn alloy prepared by dieless drawing is similar to that of alloy prepared by cold drawing.But there are some differences:the microcracks are not found in the fracture surface;in addition,whenη=1.960 and 2.770,the average size of the dimples is larger than that of the alloy prepared by cold drawing.The above phenomenon can be attributed to the following reasons:dieless drawing is hot working with the increase of temperature;on the one hand,due to the increase in thermal motion,the diffusion ability of metal atoms in alloy is improved so that alloy elements near the second phase or intermediate compound are easy to expand,the stress distribution gradually becomes uniform,and microcracks are eventually reduced.On the other hand,the high-temperature activation can reduce the dislocation resistance and density of dislocation ring.The expansion rate of the small dimple is accelerated,and the small dimples connect to each other,which are easy to translate into larger dimples.Finally,the dimple size becomes larger,indicating that the deformation of materials becomes more complete,and plastic has improved.
Fig.9 SEM images of fracture morphologies of continuous casting Ag-28Cu-8Sn alloy under a-c cold drawing and d-f dieless drawing process:a,dη=0.575;b,eη=1.960;c,fη=2.770
In summary,the microcracks do not appear in the fracture morphology of the Ag-28Cu-8Sn alloy prepared by the dieless drawing,the size of the dimple increases,and the plasticity is enhanced.The results show that the dieless drawing technology improves the processability of the Ag-28Cu-8Sn alloy.
4 Conclusion
The as-cast micros truc ture of Ag-28Cu-8Sn alloy is a typical three-zone structure.Its phases contain Ag67Sn,Cu0.85Sn0.15,Cu3Sn and some other intermediate compounds,and these brittle intermediate compounds deteriorate the processing performance.The processing performance of Ag-28Cu-8Sn alloy is improved by the dieless drawing process,and the defects of the traditional cold drawing are overcome,such as serious work hardening,low drawing deformation rate,short service life of the mold,high frequency of broken wire,large energy consumption and other issues.Compared with Ag-28Cu brazing filler metal,the addition of Sn reduces the temperature of the solid-liquid phase at 100℃;this meets the lower-temperature requirements of the brazing filler metal.But it expands the temperature range of the solid-liquid phase at 119.2℃,which reduces the spreading area of the brazing filler metal at 39 mm2.The brazing filler metal and Cu matrix material can achieve better metallurgical bonding,which is conducive to the formation of a good welded joints.In addition,the strength and hardness improve with the increase in the true strain,while the conductivity and elongation are reduced.The processing micro structure and fracture morphology also change with the increase in deformation.The analysis of the microstructure and performance reveals the effect of dieless drawing process on the micros tructure and properties of brittle alloys,which fills the gaps in research at home and abroad in this area.Finally,in the follow-up work,the dieless drawing process can be applied to more brittle precious metal materials,to explore its feasibility to improve the processing performance of brittle brazing filler metal.
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