Introduction
Selective laser melting (SLM) is a versatile additive manufacturing process. Parts are built layer by layer, which allows customizing their density and obtaining complex shapes 1 . A large number of processing parameters can be varied as laser power, scanning speed, spot size and overlapping of individual tracks (hatching) 1 . This makes necessary to investigate the best combination of parameters in order to produce samples with particular properties, as for example, high density and with a refined microstructure.
Introduction
This method was barely used to fabricate shape memory alloys (SMAs) 2, 3 . These alloys have the ability to recover their initial shape after plastic deformation by means of a structural transformation upon heating to a critical temperature. A low symmetry phase (martensite) undergoes a reverse martensitic transformation to a high-temperature phase (parent phase). SMAs are used in several applications including pipe couplings, orthodontic wires, micro-actuators, and a variety of biomedical devices 4 . The Cu-based SMAs have some advantages when compared with traditional TiNi-based SMAs because they have larger thermal and electrical conductivities, have a lower cost and are easier to process 5 . As a drawback, Cu-based SMAs have a reduced recoverable strain and a low ductility at room temperature due to intergranular cracking 5 , which is related to an abnormally high elastic anisotropy, particularly when large grains are present. The high cooling rate applied during the SLM process promotes a grain refinement, which could help to improve the ductility and fatigue behaviour 6 . Moreover, the performance of SMA components strongly depend on the microstructure, i.e. the phases present, their distribution and their respective sizes 7 . It is important to verify how the grain refinement and the non-equilibrium state promoted by the SLM process affect the properties of SMAs including their thermal stability and mechanical properties.
Introduction
The present work aims to investigate the correlation between phase formation, thermal stability and mechanical properties of a Cu-Al-Ni-Mn shape memory alloy produced using an innovative processing route that combines SLM and gas atomization.
Experimental Procedure
Gas-atomized powders of the Cu-11.85Al-3.2Ni-3Mn (wt%) alloy were prepared by nitrogen gas atomization. The parameters used and the description of the set up can be found elsewhere 8, 9 . Powders with size in the range 32 to 106 μm were used to produce rods with 3 mm in diameter and 10 mm in length on a Cu10%Sn substrate using a SLM device (SLM Solutions GmbH, model SLM 250 HL). Selective laser melting (SLM) is an additive manufacturing process used to produce parts with complex geometries layer by layer. This rapid solidification method allows fabricating samples in a non-equilibrium state and with refined microstructure. In this work, this method is used to fabricate 3 mm diameter rods of a Cu-based shape memory alloy. The phase formation, thermal stability and mechanical properties were investigated and correlated. Samples with a relative density higher than 92% and without cracks were obtained. A single monoclinic martensitic phase was formed with average grain size ranging between 28 to 36 μm. The samples exhibit a reverse martensitic transformation temperature around 106 ± 2 °C and a large plasticity in compression (around 15±1%) with a typical "double-yielding" behaviour.
Keywords: selective laser melting, shape memory alloys, Cu-based alloys, additive manufacturing
energy-dispersive X-ray spectroscopy (EDX). The processing was carried out in an inert argon atmosphere using a Laser Nd-YAG. The parameters used were previously optimized in order to have high relative densities 9 . The power, scanning speed and hatching used were 300 W, 500 mm/s and 50%, respectively.
Keywords: selective laser melting, shape memory alloys, Cu-based alloys, additive manufacturing
The structure of the rods was investigated by X-ray diffraction (XRD) in a Rigaku ME210GF2 with Cu-Kα radiation and in a STOE STADI P with Mo-Kα radiation and the microstructure was studied using a Philips XL 30 FEG and a Hitachi Tabletop Microscope TM-1000 scanning electron microscopes. The thermal stability of the samples was analyzed by differential scanning calorimetry (DSC) with a DSC 7 PerkinElmer using a heating rate of 10 K/min. The pores distribution was determined by X-ray tomography using a Phoenix Nanotom General Electrics. The density of the rods was also measured using the Archimedes principle.
Keywords: selective laser melting, shape memory alloys, Cu-based alloys, additive manufacturing
The mechanical properties of the rods were measured by compression tests using an INSTRON 5869. The samples have 3 mm in diameter and 6 mm in length and the strain rate used was 0.001 s
Results and Discussion
The morphology of the powder used can be seen in Figure 1 . There is a mix of particles with spherical and non-spherical shape. The particles with non-spherical shape probably solidified only when their movement was interrupted by the atomization chamber, which modifies the shape from spherical to more ellipsoidal. The XRD result (inset Figure 1) proves that only the β'-martensite (a = 0.443 nm, b = 0.530 nm, c = 1.278 nm and β = 95.8°, with space group P21/m [10] ) was formed in the powder. The powder selected to be used has particles size < 106 μm, with 60% in the range 75 -106 μm.
Results and Discussion
The powder was then used to produce 3 mm diameter rods (inset Figure 2a) by SLM. The rods exhibit a similar XRD pattern to the powders (inset Figure 1) with only the β'-martensite being detected. No cracks were observed in the rods but they exhibited a poor surface quality (inset Figure 2a) , which is probably related to the large particles size used (< 106 μm). The rods microstructure was investigated using SEM and the results are shown in Figure 2 . Grains where S is the area of a certain circle defined at a micrograph and N is the effective number of grains inside this circle. The grains exhibit an elongated morphology at the longitudinal section of the rod, following the direction of heat extraction from top to bottom (Figure 2b) . The martensite formed in the samples exhibits the zigzag morphology typical of the β' martensite (Figure 2c ), which corroborates with the XRD results, and consists of fine martensite laths with thickness varying from 50 to 200 nm. The density measured by the Archimedes method was 6,826 g/cm 3 , which correspond to 92.4% of the theoretical density (7,390 g/cm 3 ). The relative low density is attributed to the large amount of pores formed in the samples (Figure 2c ). Their formation was favored by the non-spherical morphology of the powder used (Figure 1) , which probably did not allow a good densification of the powder layer. The pores size varies from 15 to 25 μm and they are homogeneously distributed in the rod as can be seen in the X-ray tomography image shown in the inset of Figure 3 .
Results and Discussion
The mechanical behaviour of the rods was investigated in compression and the results are shown in Figure 3 . The rod shows average fracture strain, yield strength and ultimate tensile strength of 15±1%, 113±38 MPa and 1086±30 MPa, respectively. A large work hardening was observed with the ultimate tensile strength almost 10 times larger than the yield strength. A typical "double yielding" behaviour was observed with the presence of two inflection points (indicated by arrows), which correspond to the beginning of martensite reorientation and its plastic deformation, respectively 12 . The relative large plasticity observed is attributed to the microstructural refinement promoted by the selective laser melting processing.
Results and Discussion
It was observed that some monocrystalline Cu-based SMAs with a martensitic structure can exhibit a superelastic (or pseudoelasticity) behaviour 10 , which is a large strain recovery (up to 18%) after unloading 12 . It was performed different load-unload tests in order to investigate the superelastic behaviour of the rods nevertheless, this was not observed probably because they are polycrystals. The grain boundaries usually inhibits this behaviour 12 . Some Cu-based SMAs also exhibit phase transformations during deformation as the Cu-14,0Al-4,2Ni (wt.%) alloy, in which the γ 1 ' martensite undergoes transformation to the β 1 " martensite during loading 5 . The deformed rods were also checked by XRD but no phase transformation occurred.
Results and Discussion
It is also important to verify the influence of the microstructural refinement in the thermal stability of the alloy. This study was carried out by differential scanning calorimetry and the results are shown in Figure 4 . Only a single transformation peak is observed and it corresponds to the martensitic transformation (cubic P2mm structure to monoclinic β'-martensite) as could be inferred by in-situ XRD analyses. The martensitic transformation occurs around 106 ± 2 °C during the reverse (martensite → austenite) transformation. Similar transformation temperatures were observed during three different thermal cycles.
Results and Discussion
The fracture surface of a rod after compression is shown in Figure 5 . The fracture occurs around 45° (inset Figure 5) to the loading direction, in the direction of maximum shear stress. Dimples were seen at the fracture surface ( Figure 5 ), which shows that the samples deformed considerably before fracture.
Conclusion
The results obtained showed that is possible to produce samples of Cu-based shape memory alloys by the combination of atomization and selective laser melting. The samples exhibited a relative density around 92%, showing a considerable amount of pores as inferred by SEM and X-ray tomography. The large porosity is attributed to the irregular morphology of the powder used and its larger size. Although the rods produced by SLM exhibits a large amount of pores, a large fracture strain was observed in compression, which is related to the small grain size obtained in the rods.

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