An exploratory research of calorimetric and structural shape memory effect characteristics of Cu–Al–Sn alloy

Journal Pre-proof An Exploratory Research of Calorimetric and Structural Shape Memory Effect Characteristics of Cu-Al-Sn Alloy

Canan Aksu Canbay, Oktay Karaduman, Nihan Ünlü, İskender Özkul PII:

S0921-4526(19)30812-9

DOI:

https://doi.org/10.1016/j.physb.2019.411932

Reference:

PHYSB 411932

To appear in:

Physica B: Physics of Condensed Matter

Received Date:

31 October 2019

Accepted Date:

02 December 2019

Please cite this article as: Canan Aksu Canbay, Oktay Karaduman, Nihan Ünlü, İskender Özkul, An Exploratory Research of Calorimetric and Structural Shape Memory Effect Characteristics of Cu-AlSn Alloy, Physica B: Physics of Condensed Matter (2019), https://doi.org/10.1016/j.physb. 2019.411932

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An Exploratory Research of Calorimetric and Structural Shape Memory Effect Characteristics of Cu-Al-Sn Alloy 1Canan 2Mersin

Aksu Canbay,1Oktay Karaduman,1Nihan Ünlü,2İskender Özkul

1Firat University, Faculty of Science, Department of Physics, Elazig/TURKEY University, Faculty of Engineering, Department of Mechanical Engineering, Mersin/TURKEY

The ternary CuAlSn alloy was fabricated as cast ingot by arc melting method and the traditional homogenization and fast cooling (quenched in iced-brine water) SMA processes were carried out on small-cut samples of the ingot alloy. Then, the differential thermal and structural EDX, XRD measurements and analyses were made for this monotype alloy samples. The DSC thermograms graphed at different heating/cooling rates revealed the deep endo/exo peaks indicating martensitic phase transitions occurred in the alloy. The alloy’s behavior in high temperature region was elicited by DTA results. The thermodynamical parameters such as characteristic phase transformation temperatures, hysteresis, enthalpy and entropy changes, equilibrium temperature were determined either by taking directly from DSC data or by calculations made on them. XRD measurement made in room conditions showed the diffraction patterns belong to the existing martensite phase in the alloy, plus the crystallite size of the alloy was computed by using XRD data. Keywords:Cu-Al-Sn shape memory alloy, Martensite, Austenite, Shape memory effect, DSC, DTA

1. Introduction Shape memory alloys (SMAs) are characterised by their exceptional properties of shape memory effect (SME) and superelasticity (SE) which are their macroscopic responsive behaviors to the external physical forces like heat, stress, electrical or magnetic field [1, 2]. Their unique properties led these smart materials to be used in a wide range of modern industrial applications such as actuators, automotive, aerospace, medical, micro/nanoelectromechanical systems (M/NEMS) and so on [2, 3]. Among SMAs, Cu-rich SMAs are thought the low cost alternatives to superior NiTi SMAs. Their production processes are also easier than NiTi ones. But when compared with NiTi ones they have drawbacks such as lower shape recovery (a shape memory strain up to % 4.5, in NiTi ones it is % 10), brittlement, low strength or poor corrosion resistance [1-4]. Nevertheless, Cu-based SMAs which are alloyed as ternary or more elemental alloys on the binary CuAl, Cu-Zn and Cu-Sn base systems have also good shape recovery, excellent damping and much better electrical and thermal conductivity. So, in order to bring better shape memory effect property and enhance ductility by grain refinement or improve some different properties the binary Cu-based alloys are doped with minor amounts of a ternary or more additive elements such as Mn, Ni, Be, Sn, Ti, Al, Zn, Mg, Fe, Co, Zr, V, B, Ga, Si, etc. [2-9]. The binary Cu-Sn alloys which are more of an experimental and theoretical research interest rather than commercial purposes, do not generally exhibit ideal thermoelastic transformations and suffer from rapid loss of shape memory capacity by aging at even moderate temperatures, plus they are very brittle and their β phase region is very narrow [10]. However, the ternary Cu-Sn-Al , Cu-Zn-Sn and Cu-Sn-Mn alloys were previously studied [11-

15]. But, according to the available literature, the Cu-Al-Sn alloys doped with minor amounts of tin (also these alloys are named and classified in aluminum bronzes) have been only studied for their superior properties such as oxidation and corrosion resistance, excellent tribological and mechanical high strength and fatigue properties as compared to other bronzes used in a great number of engineering structures in applications such as shipbuilding and aerospace [16-18]. In this work, the novel Cu-10.6Al-1.26Sn (at%) shape memory alloy was produced by arc melting and thermokinetic and structural analyses were carried out to reveal and determine the remarkable shape memory features of this SMA. 2. Experimental details. In this research work, to fabricate the ternary Cu-10.6Al1.26Sn (at.%) SMA, at first the high purity (99.9 %) elements of Cu, Al and Sn powders were mixed by using a magnetic stirrer, pelletized under pressure and then melted under argon atmosphere by an Edmund Buehler Arc Melter and finally after the end of the melting process the alloy was obtained ascast ingot. In order to make proper test samples of alloy the small pieces (sized as ~35-50 mg and ~5x4x2 mm) of the alloy were cut from this as-cast ingot and to bring SMA properties (to form martensite phase) in these samples heattreatment was applied to all samples at 900 °C for 1h to homogenize the alloy texture at nano-scale and right after the samples were all quenched in the traditional iced-brine water to surpass the formation of hypoeutectoid precipitations by this lattice freezing rapid cooling, thus martensite phase was generated in the alloy samples. Then a series of differential calorimetry and microstructural characterization measurements and analyses were carried out on these martensitic Cu-Al-Sn samples. A Zeiss Evo MA10 model EDX (energy dispersive X-ray) instrument was used at room

temperature to detect the atomic fractions (at.%) of the Cu, Al and Sn elements in the alloy composition. By using a DSCJournal 60A instrument the differential scanning calorimetry (DSC) tests under inert argon gas flowing at constant rate of 100 ml/min were taken at different heating/cooling rates of 5, 15, 25, 35 and 45 °C/min to observe the characteristic exothermic and endothermic peaks of reversible martensitic phase transformations on the heating/cooling DSC curves (thermograms) and determine the functional thermokinetic SMA parameters of the alloy. In order to inspect the behavior of the alloy at high temperatures, the differential thermal analysis (DTA) measurement was conducted also in same argon atmosphere and at the only heating/cooling rate of 25 °C/min. A Rigaku RadB-DMAX II diffractometer with CuKα radiation was used at room temperature for the X-ray diffraction (XRD) analysis of the alloy to obtain the diffraction pattern which bears the characteristic diffraction peaks of atomic planes and their corresponding phases present in the martensitic alloy. Again at room temperature, the optical photomicrograph of the alloy was taken by using an OEM XJP-6A metal microscope to determine the phases formed on the alloy surface.

as a high temperature SMA (HTSMA) having an outstanding SME property. A minor amount of Sn addition Pre-proof into the binary Cu-Al base improved the SME property of this base alloy. The transformation temperatures strongly depend on alloy’s chemical composition and it was previously reported [20] that an increase in Al content in a Cu-Al-Ni alloy decreased the transformation temperatures but an Al content less than 12 wt.% (nearly 20 at%) increased the transformation temperatures [21] (actually this happens in Cu-rich SMAs because of that a relative increase in Cu content occurs instead of the lack occurred from a decrement of Al content). In addition, minor tin content used here broadened the hysteresis temperature gap [15] and also contributed to some raising of transformation temperatures [22].

3. Results and discussion: The multiple DSC thermograms, each obtained at different heating/cooling rates for the ternary shape memory alloy (with Cu-10.6Al-1.26Sn at% composition determined by EDX test) can be seen in Fig.1. As seen in this figure the characteristic downward endothermic peaks (on heating part) indicating forward martensite to austenite (M→A) phase transformations at around ~300 °C (at between 280.54 °C and 317.09 °C) and their corresponding backward A→M peaks on the cooling parts of the cycled colorful curves at between ~200-240 °C. In a recent study [19] which was carried out on a Cu-11Al-3Sn (wt%) alloy the transformation temperature region of M(β1')→A(β) phase transition has been reported as at about ~564 K (=290.85 °C) and this highly concurred with the M→A transition temperatures given in this work. The well seen endo/exo peaks at these high temperatures imply the Cu-Al-Sn alloy

Fig.1:DSC results of Cu-Al-Sn SMA sample as multiple heating/cooling curves at different heating/cooling rates.

The values of functional parameters i.e. the characteristic austenite and martensite phase start and finish temperatures; As, Af, Ms, Mf and Amax temperature parameters and enthalpy change (∆H) amounts expended during both transformations at every single different heating/cooling rate were directly taken from the DSC peak analysis data and the calculated Af-Ms hysteresis, equilibrium (T0) temperature and entropy change (∆S) values were all listed in Table 1.

Table 1: Transformation temperatures and kinetic parameters of Cu-Al-Sn alloy at different heating rates. Heating/ cooling rate (oC/min) 5 15 25 35 45

As (oC) 282.94 286.98 287.65 280.54 289.83

Af (oC) 298.80 300.32 307.33 305.61 317.09

Amax (oC) 291.79 295.21 297.86 294.00 302.83

Ms (oC) 241.21 242.43 241.15 240.14 238.51

Mf (oC) 225.69 216.60 211.76 207.14 203.47

The T0 equilibrium temperature takes place at between martensite and austenite phases where the Gibbs free energies of these two phases are equal and here T0 values were calculated by using T0=(Af+Ms)/2 equation [23]. Next, the ∆S amounts during these transformations were obtained by using ∆SA→M =∆HA→M /T0 relation [24] for backward transformations and similarly for forward ones by using the values of parameters with M→A indices.

As-Mf (oC) 57.25 70.38 75.89 73.40 86.36

T0 (oC) 270.01 271.38 274.24 272.88 277.80

ΔHM→A (J/g) 7.77 8.68 9.58 8.84 9.21

ΔHA→M (J/g) -3.85 -5.77 -5.63 -6.08 -6.34

ΔSM→A (J/goC) 0.02878 0.03199 0.03493 0.03240 0.03315

ΔSA→M (J/goC) -0.01426 -0.02126 -0.02053 -0.02228 -0.02282

The activation energy (Ea) parameter is a kinetic parameter of SMAs which determines martensitic phase transitions and crystallization behavior of the alloy. Here, the value of Ea parameter of the Cu-Al-Sn alloy was calculated by using the formula of Kissinger [25] as below;

d ln  Tm2   / d 1 Tm    Ea / R

(1)

Journal Pre-proof here the variables are; ϕ is heating/cooling rate, Tm is maximum austenite peak temperature (Amax) and R is the universal gas constant (R=8.314 J/mol.K). The left term in this equation was found as a slope value from by taking linear fit on the graph of ln(ϕ /Tm2) versus 1000/Tm shown in Fig.2. By substituting this negative slope value in the Eq.-1, the activation energy of Cu-Al-Sn alloy was found as 403 kJ/mol.

Ln(/T2m)(/Kmin)

-8,5

-9,0

-9,5

Fig.3:DTA curve of Cu-Al-Sn SMA sample at 25 °C/min of heating/cooling rate.

-10,0

-10,5

-11,0 1,74

1,75

1000/Tm (

1,76

1,77

oK-1)

Fig.2:The activation energy change graphic of Cu-Al-Sn alloy.

DTA curve of the alloy obtained at single heating/cooling rate of 25 °C/min from room temperature to 900°Cis can be seen in Fig.3. On the heating part of this cycle starting from far left, the Cu-Al-Sn alloy showed the peaks indicating a multiple phase transitions as; Martensite (β1′(or β1′′=β1′+γ1′)) → Austenite (β1;DO3) → β2(B2, disordered) → α+γ2 precipitating → eutectoid recomposition → β2(B2, ordered) → β(A2, disordered) and inversely on cooling part and this chain of transitions is found compatible with the previous works [24-30] in the literature. However, in the recent work of Ref.[30] it was reported that the β1′ martensite phase disordered to β1(A2) instead of converting to β1(DO3), and the hypoeutectoid precipitating reactions β→α+β→β + β1 instead of β2(disordered) → α+γ2(or γ1) → eutectoid recomposition → β2(B2, ordered). Nevertheless, the characteristic DTA curve of CuAlSn alloy here became compatible with the results revealed in these literature works referred above. Furthermore, here on cooling part of the DTA curve the backward eutectoid peak is seen as distorted like it would almost split. This semi-splitting of backward eutectoid peak (occurred as a result of by heating up to 900 °C and then cooling back at this slow 25 °C/min of cooling rate that is slower than the rate in the open room air) may be happened due to a little evaporation loss of tin content (tin element has a low melting point of 231.9 °C) from the regions near the alloy sample’s surface that led to different local composition domains which became to have slightly different eutectoid temperatures and also it was previously reported [31] that in Cu–Al–Sn alloys during thermal cycles at slow heating/cooling rates tin tends to segregate to grain boundaries and to enhance their decohesion.

In general, the conduction electron concentration per atom (average valence electron number) or briefly the electron/atom ratio (e/a) is a key parameter of SMAs to have SME property and the value of this parameter can give us a foreknowledge about the type of martensite phase which should dominantly exist in the alloy matrix and also the vibrational entropy change (ΔS) of the average periodic lattice formation that proceeds from the first order and diffusionless martensitic transformations driven by heat induced internal stresses is a function that is strongly depended on the e/a ratio of alloy [29, 32]. For β-phase shape memory alloys (e.g. Au-Cd, Ag-Cd, Cu-Al-Mn, Cu-Al-Ni, Cu-Zn-Al etc.) the value of e/a ratio is generally around ~1.5, at which bcc (body-centered cubic) or ordered bcc structure is stabilized (due to nesting at the Brillouin zone boundary) and the ordered bcc structures are mostly B2 type or DO3 type [33]. Furthermore, if the e/a value of an alloy is at the range between 1.45 and 1.49 or 1.50 then the percentages of both types of the 18R and 2H martensite are expected to be nearly equal, and the 18R structure becomes dominant over 2H by the e/a values below 1.45, and similarly the 2H structure gains dominancy by the e/a values above 1.50, as these were theoretically mentioned in the literature previously [28, 32, 34-36]. Here, the e/a value of the CuAlSn alloy was determined by using a custom-built formula [24, 37, 38] as written below;

𝑒

𝑎 = 𝑓𝐶𝑢𝑣𝐶𝑢 + 𝑓𝐴𝑙𝑣𝐴𝑙 + 𝑓𝑆𝑛𝑣𝑆𝑛

(4)

where; f refers to the atomic fractions (the EDX analysis %at data) of each element in the alloy composition (here; fCu=88.14 at%, fAl=10.6 at% and fSn=1.26 at%) and v refers to the correspondent valence electron number of these elements (vCu=1, vAl=3 and vSn=2). Thus, the e/a value of the CuAlSn alloy was calculated as 1.2246. Therefore, theoretically the 18R martensite forms should be dominant over 2H type martensite forms and this front suggestion was substantiated by the XRD results which revealed the peaks of X-rays diffracted from atomic planes of 18R martensite body of the alloy sample and also by the optical metallograph displaying the 18R dominancy on the surface

Journal Pre-proof

30

40

)

50

1'(042)

Cu-(2 00

1'(002) 1'(1210) 1'(2 012)

1'(122)

1'(0022)

Intensity ( a.u. )

morphology of the alloy. These XRD and optical microscopy results were given as below;

60

70

Fig.5:Optical micrograph of surface morphology of the Cu-AlSn alloy sample. 80

2 ( o )

Conclusions

Fig.4:XRD result of Cu-Al-Sn SMA sample.

The X-ray measurement result of the Cu-Sn-Al alloy sample which demonstrates the existence of martensite phases in the Cu-Al-Sn alloy sample at room temperature can be seen in Fig.4. As seen on this diffraction pattern the observed diffraction peaks of β1′(122), β1′(0022), β1′(1210) and β1′(2012) planes belong to 18R type of martensite, the peak of γ1′(002) plane belongs to 2H martensite and lastly a peak of Cu(200) plane belongs to α–Cu phase [24, 27, 28, 39-41]. Among these, the main (the highest) peak is the peak of β1′(0022) plane observed at the Bragg angle of 2θ=42.54° and this means the most powerful diffraction occurred from this martensitic atomic plane. Here from, the average crystallite size (D) of the alloy sample was calculated by substituting the FWHM data value of this highest peak in the following Debye-Scherrer formula [42] as below;

D

0.9 B1 2 cos

(2)

where; λ is the X-ray wavelength of the CuKα radiation (λ=0.15406 nm) used in this XRD measurement, B1/2 is full width at half maximum (FWHM) value of the highest peak and θ is the Bragg angle of diffraction. In this way, the value of average crystallite size of the Cu-Al-Sn alloy sample was found as 17.99 nm. The optical microscopy result of the alloy sample given in Fig.5 also confirmed the morphological martensite formation on the surface of Cu-Al-Sn alloy sample. On the figure the lamellar martensite of β1′ martensite plates, Vtype martensite plates and and the 2H(γ1′) martensite in lath shape can be seen on the surface of alloy sample, plus a few dribblets of dark coloured γ2 and lighter α-phase structures are also visible in this photomicrograph frame [26, 30, 43, 44].

In this work, the unprecedent Cu-10.6Al-1.26Sn (at.%) shape memory alloy was successfully produced by arc melting method. Thermokinetic and microstructural characterization measurements carried on this alloy revealed that the alloy has remarkable shape memory alloy properties according to alloy’s thermal and structural characteristics. The results of calorimetric DSC and DTA measurements demonstrated the peaks of reversible M↔A martensitic transformations in the temperature range of ~203-317 °C on heating and cooling parts of the thermal cycles. DTA cycle displayed a chain of multiple phase transitions of β1′ →β1(DO3) →disordered β1(B2) → precipitating → eutectoid dissolution → ordered B2 →disordered A2 on the heating part of this curve cycle and reversely on its cooling part. Also, a semi-splitting of eutectoid peak observed on the cooling part of DTA was presumably attributed to the slight local composition diversities occurred due to the movement of tin atoms toward grain borders and surface by the effect of the slow heating/cooling rate of DTA test. The existence of 18R martensite dominancy in the alloy at room temperature as theoretical pre-estimation based on the average valence electron/atom concentration value of the alloy (determined as 1.2246 lower than 1.45) was confirmed by X-ray and optical microscopy results. The X-ray and optical microscopy findings verified the major 18R martensite formation with very minor percentage of 2H martensite phases in the alloy. From all obtained results, it can be said that this new Cu-Al-Sn SMA system can be useful in a wide range of SMA related R&D applications.

Acknowledgment: This work is financially supported by Firat University Scientific Research Unit FUBAP under the project number of FUBAP: FF.18.12.

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Manuscript title: An Exploratory Research of Calorimetric and Structural Shape Memory Effect Characteristics of Cu-Al-Sn Alloy

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Declaration of interests ☒ The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. ☐The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: