effect of niobium addition on the martensitic

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Effect of niobium addition on the martensitic transformation and magnetocaloric effect in low hysteresis NiCoMnSn magnetic shape memory alloys Baris Emre, Nickolaus M. Bruno, Suheyla Yuce Emre, and Ibrahim Karaman Citation: Applied Physics Letters 105, 231910 (2014); doi: 10.1063/1.4903494 View online: http://dx.doi.org/10.1063/1.4903494 View Table of Contents: http://scitation.aip.org/content/aip/journal/apl/105/23?ver=pdfcov Published by the AIP Publishing Articles you may be interested in Large reversible entropy change at the inverse magnetocaloric effect in Ni-Co-Mn-Ga-In magnetic shape memory alloys J. Appl. Phys. 113, 213905 (2013); 10.1063/1.4808340 Elastocaloric and magnetocaloric effects in Ni-Mn-Sn(Cu) shape-memory alloy J. Appl. Phys. 113, 053506 (2013); 10.1063/1.4790140 The martensitic transformation, magnetocaloric effect, and magnetoresistance in high-Mn content Mn 47 + x Ni 43 − x Sn 10 ferromagnetic shape memory alloys J. Appl. Phys. 108, 103920 (2010); 10.1063/1.3511748 Mössbauer study on martensite phase in Ni 50 Mn 36.5 Fe 0.5 57 Sn 13 metamagnetic shape memory alloy Appl. Phys. Lett. 93, 042509 (2008); 10.1063/1.2960551 Boron’s effect on martensitic transformation and magnetocaloric effect in Ni 43 Mn 46 Sn 11 B x alloys Appl. Phys. Lett. 92, 102503 (2008); 10.1063/1.2895645 This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP: 165.91.74.118 On: Wed, 02 Sep 2015 21:34:00

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Page 1: Effect of niobium addition on the martensitic

Effect of niobium addition on the martensitic transformation and magnetocaloric effectin low hysteresis NiCoMnSn magnetic shape memory alloysBaris Emre, Nickolaus M. Bruno, Suheyla Yuce Emre, and Ibrahim Karaman Citation: Applied Physics Letters 105, 231910 (2014); doi: 10.1063/1.4903494 View online: http://dx.doi.org/10.1063/1.4903494 View Table of Contents: http://scitation.aip.org/content/aip/journal/apl/105/23?ver=pdfcov Published by the AIP Publishing Articles you may be interested in Large reversible entropy change at the inverse magnetocaloric effect in Ni-Co-Mn-Ga-In magnetic shapememory alloys J. Appl. Phys. 113, 213905 (2013); 10.1063/1.4808340 Elastocaloric and magnetocaloric effects in Ni-Mn-Sn(Cu) shape-memory alloy J. Appl. Phys. 113, 053506 (2013); 10.1063/1.4790140 The martensitic transformation, magnetocaloric effect, and magnetoresistance in high-Mn content Mn 47 + x Ni43 − x Sn 10 ferromagnetic shape memory alloys J. Appl. Phys. 108, 103920 (2010); 10.1063/1.3511748 Mössbauer study on martensite phase in Ni 50 Mn 36.5 Fe 0.5 57 Sn 13 metamagnetic shape memory alloy Appl. Phys. Lett. 93, 042509 (2008); 10.1063/1.2960551 Boron’s effect on martensitic transformation and magnetocaloric effect in Ni 43 Mn 46 Sn 11 B x alloys Appl. Phys. Lett. 92, 102503 (2008); 10.1063/1.2895645

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Page 2: Effect of niobium addition on the martensitic

Effect of niobium addition on the martensitic transformationand magnetocaloric effect in low hysteresis NiCoMnSnmagnetic shape memory alloys

Baris Emre,1 Nickolaus M. Bruno,2 Suheyla Yuce Emre,3 and Ibrahim Karaman2,4,a)

1Department of Engineering Physics, Ankara University, 06100 Ankara, Turkey2Department of Mechanical Engineering, Texas A&M University, College Station, Texas 77843, USA3Department of Physics, Ondokuz Mayis University, 55139 Samsun, Turkey4Department of Materials Science and Engineering, Texas A&M University, College Station,Texas 77843, USA

(Received 25 October 2014; accepted 17 November 2014; published online 11 December 2014)

The effect of Nb substitution for Ni in Ni45Co5Mn40Sn10 magnetic shape memory alloys on their

magnetic properties, martensitic transformation characteristics, transformation hysteresis, and

magnetocaloric properties was studied using wavelength-dispersive X-ray spectroscopy, differen-

tial scanning calorimetry, and the temperature and field dependence of the magnetization.

Ni45Co5Mn40Sn10 alloy has a very low transformation hysteresis; however, the martensitic transfor-

mation temperatures are notably above room temperature, which is not desirable for magnetic re-

frigeration applications. In this study, small quantities of Nb substitution were shown to drastically

shift the transformation temperatures to lower temperatures, at a rate of 68 K/at. % Nb, which is

needed for household refrigeration. The austenite Curie temperature also decreased with increasing

Nb content. However, a decrease in the latent heat of the martensitic transition was observed, which

negatively affects the magnetic field-induced adiabatic temperature change capability. Still, the rel-

atively large transformation entropy and the low transformation hysteresis make the Nb-doped

Ni45Co5Mn40Sn10 alloys potential candidates for solid state refrigeration near room temperature.VC 2014 AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4903494]

Magnetic shape memory alloys (MSMAs) have attracted

considerable interest as a new type of functional materials

due to their promising features for actuation and sensing.

Since the discovery of large magnetic field induced strain

(MFIS) in Ni2MnGa,1 extensive research has been conducted

on the magnetic field-induced martensitic transition

(MT).2–14 These alloys undergo a first-order magnetic transi-

tion from a high symmetry phase (austenite) to a low symme-

try phase (martensite) upon cooling. This transition is

associated with sharp changes in magnetization.15 Due to the

strong coupling between the crystallographic structure and

magnetism, these Ni-Mn based MSMAs show other attractive

properties such as magnetocaloric effect (MCE) and magne-

toresistance (MR).6–11

The MCE is defined as a temperature change that

occurs when a magnetic field is applied to a material. This

principle can be used in solid state refrigeration schemes.

Magnetocaloric materials (MCM) are classified as conven-

tional MCM and inverse MCM. Conventional MCM heats

up with the application of magnetic field and cools down

when magnetic field is removed. The most well-known con-

ventional MCM are Gd5Si2Ge2,16 LaFe13�xSixH,17,18 and

MnFeP (As,Ge).19,20 Among the inverse MCM, the most

well-known materials are Heusler type Ni-Mn-(In, Sn, Sb)-

based MSMAs.2,21–24 Due to the strong magneto-structural

coupling, a magnetic field can induce a simultaneous

change of magnetic and lattice entropies; therefore, one can

observe the so called “giant MCE” (GMCE) in these mate-

rials. Studies up to now have revealed that the maximum

MCE is obtained when the structural and magnetic transi-

tion temperatures overlap.15 It is reported8 that there are at

least three important characteristics while evaluating a

magnetocaloric material: (1) the effect must occur near

room temperature for room temperature applications, (2)

the MCE and refrigeration capacity (RC) must be signifi-

cant at reasonable applied magnetic field levels, and (3) the

process must be reversible with respect to changing/revers-

ing magnetic field and show low hysteresis loss. In addition

to improving the achievable MCE in NiMn-(In,Sn,Sb)

alloys, it is a well-known fact that low transformation hys-

teresis also promotes cyclic reversibility.25,26 Therefore, it

is important to explore the behavior of MSMAs that exhibit

low hysteresis.

Ni45Co5Mn40Sn10 was reported to exhibit low thermal

hysteresis while also exhibiting one of the highest magnet-

ization changes across the martensitic transformation (DM)

among the Ni-Co-Mn-Sn alloy family.25 However, this par-

ticular alloy has a major drawback for MCE applications,

that is, the large magnetization change, and MT occurs well

above room temperature, i.e., �400 K.25 From the practical

point of view, the material should exhibit the structural tran-

sition around room temperature.

Many investigations have been conducted on the effect

of 3d transition-metal doping on the structural phase

transitions, magnetic, and magnetocaloric characteristics

of Ni-Mn-Sn based MSMAs.27–33 However, the effect of

4d-transition-metal substitution has not yet been widely

a)Author to whom correspondence should be addressed. Electronic mail:

[email protected].

0003-6951/2014/105(23)/231910/5/$30.00 VC 2014 AIP Publishing LLC105, 231910-1

APPLIED PHYSICS LETTERS 105, 231910 (2014)

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Page 3: Effect of niobium addition on the martensitic

studied with the exception of the work in Ref. 34. In the

present work, we report that the doping of 4d-transition

metal substitutions (Nb in this case) is an effective way for

moving attractive high temperature properties (i.e., low hys-

teresis and high magnetization difference (DM) between the

austenite and martensite phases upon martensitic transforma-

tion) closer to room temperature.

Polycrystalline Ni45�xNbxCo5Mn40Sn10 (x¼ 1 and 1.5)

alloys were arc-melted on a water-cooled copper hearth from

high-purity elements with the appropriate amounts of Ni,

Nb, Mn, Co, and Sn under argon protection, after purging

the chamber several times under vacuum. After fabrication,

these alloys were then sealed in quartz tubes under Ar and

annealed at 1173 K for 24 h followed by water quenching.

Polycrystalline samples were cut from the ingots using a

low-speed diamond saw and used as samples for differential

scanning calorimetry (DSC) and magnetization measure-

ments. The compositions of the alloys were determined using

wavelength-dispersive X-ray spectroscopy (WDS) at 3 loca-

tions within 4 different grains after homogenization. The

compositions (in at. %) of the samples were determined as

Ni43.660.2Mn39.460.16Co560.1Sn10.860.1Nb1.060.02 (denoted as

Nb1) and Ni43.460.1Mn39.360.3Co560.05Sn10.760.2Nb1.660.03

(denoted as Nb1.5). Microstructure observations performed

to identify the room temperature phases of the alloys are pre-

sented in Fig. 1. Both alloys show a mixture of the martens-

ite and austenite at room temperature (Figs. 1(a) and 1(b)).

The DSC curves for Nb1 and Nb1.5 alloys are shown in

the lower insets of Figs. 2(a) and 2(d), respectively. Both for-

ward and reverse martensitic transitions are accompanied by

well-defined peaks, arising from the latent heat of the

transformation. The characteristic temperatures for the mar-

tensitic transition are determined to be Ms¼ 351 K,

Mf¼ 335 K, As¼ 347 K, and Af¼ 361 K for the Nb1 sample,

and Ms¼ 304 K, Mf¼ 290 K, As¼ 305 K, and Af¼ 318 K for

the Nb1.5 sample. Here, Ms is the martensite start, Mf is the

martensite finish, As is the austenite start, and Af is the aus-

tenite finish temperatures. The Curie temperature of the aus-

tenite, TAC, is also observed in the DSC curve for the Nb1.5

sample (Fig. 2(f)). However, the intense peaks of the forward

and reverse transformation mask the TAC of the Nb1 sample.

The thermal hysteresis defined as (Af�Ms) and reported as

6 K for Ni45Co5Mn40Sn10 (parent alloy).25 We observed ther-

mal hysteresis as 10 K for Nb1 and 14 K for Nb1.5 from the

DSC results. Still, the thermal hysteresis of the Nb1 and

Nb1.5 samples is one of the lowest among the other studied

compositions of the NiCoMnSn system.25 In addition, the

TAC was not observed in DSC curves in the parent alloy, but

from M(T) data it was observed to be around 445 K.25 The

addition of Nb causes a decrease in the martensitic transfor-

mation temperatures with the rate of about 68 K/at. %Nb.

The temperature dependence of magnetization at several

magnetic fields for Nb1 and Nb1.5 is shown in Figs. 2(a) and

2(b) and Figs. 2(d) and 2(e), respectively. The characteristic

temperatures for the martensitic transition from DSC meas-

urements indicated as arrows in Figs. 2(b) and 2(d). In all

M(T) measurements, the field heated (FH) data do not retrace

the field cooled (FC) data but show a hysteresis, which is the

fingerprint of a first-order structural transition, as found in

the DSC results. As in the parent alloy, the samples show

multiple transitions upon cooling: (i) from the paramagnetic

(PM) austenite phase to a ferromagnetic (FM) austenite

FIG. 1. Backscattered electron (BSE)

images of the microstructure for

Ni45�xNbxMn40Co5Sn10 (a) x¼ 1 and

(b) x¼ 1.5, showing a mixture of

the austenite and martensite phases.

The images were taken at room

temperature.

FIG. 2. Magnetization (M(T)) curves

of Ni45�xNbxMn40Co5Sn10 alloys

under the magnetic fields of 1 T, 3 T,

5 T, and 7 T for x¼ 1 (a) and x¼ 1.5

(d). The upper insets show M(T) at

50 mT for x¼ 1 (b) and x¼ 1.5 (e).

The lower insets show DSC curves of

Nb1 (c) and Nb1.5 (f).

231910-2 Emre et al. Appl. Phys. Lett. 105, 231910 (2014)

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Page 4: Effect of niobium addition on the martensitic

phase at TAC; and (ii) from the FM austenite phase to the low

magnetic state (PM or antiferromagnetic (AF)35) martensite

at the martensitic transition temperature. For both alloys, the

martensite has a low magnetization, leading to a large DMacross the martensitic transition. The magnetization

increases abruptly at TAC� 355 K and 345 K during cooling

for the Nb1 and Nb1.5 samples, respectively. Due to the for-

ward and reverse martensitic transformation, magnetization

shows abrupt decrease/increase at 340 K/345 K for the Nb1

sample and at 300 K/306 K for the Nb1.5 sample. The width

of the hysteresis of the Nb1 and Nb1.5 samples from M(T)

measurements is found to be around 5 K and 6 K in 50 mT,

respectively. This is almost constant under higher magnetic

fields.

Figure 3(a) shows the transformation entropy (DS) and

the As temperature change as a function of Nb composition.

As has a linear dependency to the Nb content, whereas the

transformation entropy shows a non-linear trend. In Fig. 3(b),

the martensitic transformation temperatures under several

magnetic fields are also plotted. With increasing magnetic

field, the martensitic transitions shift toward lower tempera-

tures, in agreement with the magnetic field stabilization of fer-

romagnetic austenite phase. The characteristic temperatures,

Mf and As, linearly decrease with the field at a rate of

dMf /dH¼�2.5 K T�1 and dAs/dH¼�2.0 K T�1 for the

Nb1.5 sample and dMf/dH¼�1.1 K T�1 and dAs/dH

¼�0.9 K T�1 for the Nb1 sample, which are close to those

reported in Ref. 25 (�2.6 K/T). The transformation ranges

(Ms�Mf and Af�As) are less than 7 K for the Nb1 sample

and less than 22 K for the Nb1.5 sample. These transition

ranges are an indication of the difficulty of phase front motion

between the martensite and austenite. Large transition ranges

indicate large stored elastic energy within the crystal lattice,

and highly compatible austenite and martensite phases exhibit

sharp transitions. The shift in the transition temperature with

magnetic field is accounted for by the Claussius-Clapeyron

equation: DT � DMDS

� �DH, where DM and DS are the differ-

ences in the magnetization and entropy between the austenite

and martensite phases, respectively. DSs of the Nb1 and

Nb1.5 samples are calculated from the enthalpy data obtained

by DSC as DS¼ 41.4 J/kg K and 34 J/kg K, respectively.

Using the equation above with DH¼ 7 T and DM for the Nb1

and Nb1.5 samples as 60 emu/g and 70 emu/g, respectively,

DTs are calculated as 10.1 K and as 14.4 K, respectively.

Figures 4(a) and 4(c) show M(H) curves of Nb1 and

Nb1.5, respectively, at several temperatures. The measure-

ment is done by following the procedure reported in Ref. 36.

The M(H) curves of Fig. 4(a) at 325–341 K exhibit typical

magnetic behavior of austenite, and the curves at

344 K–353 K temperature interval clearly indicate magnetic

field-induced phase transformation for the Nb1 sample. In

this sample, the maximum magnetic hysteresis of �2.4 T is

observed at 347 K. In the case of the Nb1.5 sample, the M(H)

(Fig. 4(c)) curves exhibit metamagnetic transition almost for

all temperatures, but it is more clear for the temperature inter-

val of 287 K–312 K. However, the magnetic hysteresis is not

as clear as that for the Nb1 sample. The M(H) results are in

line with M(T) curves shown in Figs. 2(a) and 2(d).

We have estimated the field induced entropy change

(DS) around the martensitic transformation for both samples

using the relationship DSðTK; 0! HÞ ¼ 1DTk½ÐH

0MTkþ1

dH �ÐH0

MTkdH� numerically from the M(H) isotherms. The tem-

perature dependence of the DS is plotted in Figs. 4(b) and

4(d), for Nb1 and Nb1.5, respectively. For both samples, the

sign of DS is positive in the range of MT. However, DS is

negative for temperatures close to TAC since @M

@T < 0 for this

case. The inverse nature of the magnetocaloric effect is con-

sistent with the magnetic field stabilization of the cubic

phase. The maxima DS in a magnetic field of 5 T are about

48 J K�1 kg�1 for Nb1 and 10 J K�1 kg�1for Nb1.5 around

MT. Such a large MCE is comparable to those of

Ni44Mn43Cu2Sn11, Ni43Mn43Co4Sn11, and Ni50Mn34Co2Sn14,

which exhibit DS of approximately 50 J kg�1 K�1 for a field

change of 0–5 T, thus makes Nb1 a good candidate for MCE.

The values of DS around TAC are smaller since the magnetic

transition is second-order and magnetization changes over a

broader temperature range than the first-order martensitic trans-

formation. The measured values of DS for the Nb1 sample are

larger than those for Nb1.5 since the Nb1 sample shows almost

complete reversible martensitic transformation under 5 T field

loading, while the Nb1.5 sample only partially transforms

reversibly at all temperatures when employing the discontinu-

ous heating protocol.21 The width of the DS vs. T peaks for the

Nb1 sample also increases with increasing magnetic field

thereby leading to an increase in the refrigerant capacity.21

In conclusion, the magnetic and martensitic transforma-

tion behavior of Ni45�xNbxCo5Mn40Sn10 (x¼ 1 and 1.5)

alloys were investigated. It was found that the addition of

small amount of Nb leads to a sharp decrease in martensitic

transformation and TAC temperatures. Namely, the

FIG. 3. (a) Changes in the transformation entropy of the forward martensitic

transformation and As temperature as a function of Nb composition. (b) The

martensitic transformation temperatures determined from the M(T) curves

(open symbols for the Nb1.5 sample and closed symbols for the Nb1 sam-

ple). Lines correspond to linear regression to the data.

231910-3 Emre et al. Appl. Phys. Lett. 105, 231910 (2014)

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Page 5: Effect of niobium addition on the martensitic

transformation temperatures decrease approximately with a

rate of 68 K/at. %Nb. Furthermore, the martensite finish

temperature Mf linearly decreases with the field at a rate

dMf /dH¼�1.1 K T�1 and �2.5 K T�1 for the Nb1 and

Nb1.5 samples, respectively. Application of magnetic field

induces a decrease in martensitic transformation temperatures

and the magnetic field-induced phase transformation from

martensite to austenite was confirmed. The detrimental effect

on the transformation hysteresis and the reversibility of the

magnetocaloric effect were relatively minor due to very low

hysteresis. The large magnetization and low hysteresis make

the Nb1 sample a potential candidate for magnetic shape

memory, energy conversion, and solid-state refrigeration.

This work was supported by the U.S. National Science

Foundation, Division of Materials Research, Metals and

Metallic Nanostructures Program, Grant No. 1108396, under

the umbrella of the Materials World Network Initiative.

Additional support was received from the U.S. National

Science Foundation under Grant No. DMR 08-44082, which

supports the International Materials Institute for Multi-

functional Materials for Energy Conversion (IIMEC) at

Texas A&M University.

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FIG. 4. M(H) curves for Nb1 (a) and

Nb1.5 (c). Magnetic field induced en-

tropy change (magnetocaloric effect)

as a function of temperature for

selected values of the magnetic field

(1, 2, 3, 4, 5, 6, and 7 T) of Nb1 (b)

and Nb1.5 (d).

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