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**in (Ni,Pt)Ti shape memory alloys
**

Y. Gao

a

, N. Zhou

a

, F. Yang

a

, Y. Cui

a,1

, L. Kovarik

a,2

, N. Hatcher

b

, R. Noebe

c

,

M.J. Mills

a

, Y. Wang

a,⇑

a

Ohio State University, Department of Materials Science and Engineering, 2041 College Road, 477 Watts Hall, Columbus, OH 43210, USA

b

Interdisciplinary Centre for Advanced Materials Simulations, Ruhr-Universita¨ t Bochum, Germany

c

NASA Glen Research Center, 21000 Brookpark Road, Cleveland, OH 44135, USA

Received 26 August 2011; received in revised form 18 November 2011; accepted 19 November 2011

Abstract

A new precipitate phase named P-phase has recently been identiﬁed in (Ni,Pt)Ti high temperature shape memory alloys. In order to

understand the roles played by the ﬁne coherent P-phase precipitates in determining the martensitic transformation temperature (M

s

),

strength of the B2 matrix phase, dimensional stability and shape memory eﬀect of the alloys, a phase ﬁeld model of P-phase precipitation

is developed. Model inputs, including lattice parameters, precipitate–matrix orientation relationship, elastic constants and free energy

data, are obtained from experimental characterization, ab initio calculations and thermodynamic databases. Through computer simu-

lations, the shape and spatial distribution of the P-phase precipitates, as well as the compositional and stress ﬁelds around them, are

quantitatively determined. On this basis, the elastic interaction energy between the P-phase precipitates and a martenstic nucleus is cal-

culated. It is found that both the chemical non-uniformity and stress ﬁeld associated with the P-phase precipitates are in favor of the

martensitic transformation. Their relative contributions to the increase in M

s

temperature are quantiﬁed as a function of aging time

and the result seems to agree with the experimental measurements. The shape and spatial distribution of the P-phase precipitates pre-

dicted by the simulations also agree well with experimental observations.

Ó 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Coherent precipitate; Elastic interaction; Nucleation; Aging eﬀect; Phase ﬁeld simulation

1. Introduction

Recent work has shown that the new class of high tem-

perature shape memory alloys (HTSMAs) (i.e. NiTi with

ternary additions such as Pt, Pd, replacing Ni or Hf and

Zr replacing Ti) have several important advantages relative

to the conventional NiTi binary shape memory alloys

(SMAs) – relatively high transformation temperatures

and good dimensional stability [1]. A unique microstruc-

tural feature of these HTSMAs is the presence of ﬁne

coherent precipitates. For example, recent experimental

characterization of (Ni,Pt)Ti alloys [2] has shown ﬁne pre-

cipitates of an intermetallic phase named “P-phase” after

aging at $600 °C for 100 h (Fig. 1). These precipitates have

a monoclinic structure and are fully coherent with the

matrix phase. Their shapes are more or less cuboidal, with

edge length 200–400 nm and faces nearly parallel to {100}.

Spatial alignment of the precipitates along h100i directions

is also obvious from Fig. 1. Previous studies [3–6] have

shown that the precipitates not only strengthen the matrix

but also increase martensitic transformation temperature

M

s

. In addition, SMAs stabilized by ﬁne precipitates exhi-

bit minimal accumulation of non-recoverable strain during

thermomechanical cycling [1,5,6]. However, the mecha-

1359-6454/$36.00 Ó 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

doi:10.1016/j.actamat.2011.11.043

⇑

Corresponding author. Tel.: +1 614 292 0682; fax: +1 614 292 1537.

E-mail address: wang.363@osu.edu (Y. Wang).

1

Present address: IMDEA Materials, Science Park of the University

Carlos III of Madrid Mediterranean Avenue, No. 22, 28918 Leganes,

Spain.

2

Present address: EMSL, Paciﬁc Northwest National Laboratory,

Richland, WA 99301, USA.

www.elsevier.com/locate/actamat

Available online at www.sciencedirect.com

Acta Materialia 60 (2012) 1514–1527

nisms by which the precipitates inﬂuence the martensitic

transformation and dislocation plasticity in the B2 matrix

phase in these HTSMAs have not been investigated.

Phase ﬁeld modeling and simulation have been used

widely to treat both diﬀusional and displacive phase transfor-

mations, as well as dislocation–precipitate interactions

[7–16]. In this study, we formulate a phase ﬁeld model to

study P-phase precipitation and its eﬀect on martensite nucle-

ation. In particular, we document through systematic com-

puter simulations (a) the shape and spatial distribution of

coherent P-phase precipitates and (b) the stress and concen-

tration ﬁelds around a P-phase precipitate and their eﬀects on

the B2 ! B19 martensitic transformation. Interaction of the

precipitates with dislocations and its eﬀects on transforma-

tion induced plasticity in the B2 matrix and on dimensional

stability of the alloy will be reported in a separate paper.

The concentration and stress ﬁelds surrounding a coher-

ent precipitate are determined by the interplay between

chemical free energy and coherency elastic strain energy.

In this study, the chemical free energy models for the

matrix and precipitate phases in Ni–Pt–Ti are formulated

based on existing thermodynamic databases [17–19], while

the coherency elastic strain energy is formulated using

Khachaturyan and Shatalov’s microelasticity theory [20].

In the following sections, thermodynamic modeling and

transformation strain calculation are ﬁrst presented (Sec-

tions 2 and 3), followed by descriptions of the phase ﬁeld

model (Section 4). Simulation results and their implications

are presented and discussed respectively in Sections 5 and

6. The major ﬁndings are summarized in Section 7.

2. Thermodynamic modeling of B2 phase in Ti–Ni–Pt

The accuracy of phase ﬁeld simulations and predictions

relies on the accuracy of available thermodynamic dat-

abases, especially the free energy of the B2 matrix phase

in the case of NiTi based SMAs [9]. Because of the limited

amount of thermodynamic data for the Ti–Ni–Pt ternary

system, the assessment of the B2 phase chemical free energy

is ﬁrst carried out via the CALPHAD method utilizing

available experimental data from the literature [17–19].

The B2 phase in Ti–Ni–Pt can be described by a two-sub-

lattice model (Ni,Pt,Ti)

1

(Ni,Pt,Ti)

2

:

G

B2

y

1

Ni

; y

1

Pt

; y

1

Ti

; y

2

Ni

; y

2

Pt

; y

2

Ti

_ _

¼y

1

Ni

y

2

Ni

G

0

Ni;Ni

þy

2

Pt

G

0

Ni;Pt

þy

2

Ti

G

0

Ni;Ti

_ _

þy

1

Pt

y

2

Ni

G

0

Pt;Ni

þy

2

Pt

G

0

Pt;Pt

þy

2

Ti

G

0

Pt;Ti

_ _

þy

1

Ti

y

2

Ni

G

0

Ti;Ni

þy

2

Pt

G

0

Ti;Pt

þy

2

Ti

G

0

Ti;Ti

_ _

þRT y

1

Ni

lny

1

Ni

þy

1

Pt

lny

1

Pt

þy

1

Ti

lny

1

Ti

_ _

þRT y

2

Ni

lny

2

Ni

þy

2

Pt

lny

2

Pt

þy

2

Ti

lny

2

Ti

_ _

þy

1

Ni

y

1

Ti

y

2

Ni

i

L

i

NiTi;Ni

y

1

Ni

Ày

1

Ti

_ _

i

þy

2

Pt

i

L

i

NiTi;Pt

y

1

Ni

Ày

1

Ti

_ _

i

_

þy

2

Ti

i

L

i

NiTi;Ti

y

1

Ni

Ày

1

Ti

_ _

i

_

þy

1

Ni

y

1

Pt

y

2

Ni

i

L

i

NiPt;Ni

y

1

Ni

Ày

1

Pt

_ _

i

þy

2

Pt

i

L

i

NiPt;Pt

y

1

Ni

Ày

1

Pt

_ _

i

_

þy

2

Ti

i

L

i

NiPt;Ti

y

1

Ni

Ày

1

Pt

_ _

i

_

þy

1

Ti

y

1

Pt

y

2

Ni

i

L

i

TiPt;Ni

y

1

Ti

Ày

1

Pt

_ _

i

þy

2

Pt

i

L

i

TiPt;Pt

y

1

Ti

Ày

1

Pt

_ _

i

_

þy

2

Ti

i

L

i

TiPt;Ti

y

1

Ti

Ày

1

Pt

_ _

i

_

þy

2

Ni

y

2

Ti

y

1

Ni

i

L

i

Ni;NiTi

y

2

Ni

Ày

2

Ti

_ _

i

þy

1

Pt

i

L

i

Pt;NiTi

y

2

Ni

Ày

2

Ti

_ _

i

_

þy

1

Ti

i

L

i

Ti;NiTi

y

2

Ni

Ày

2

Ti

_ _

i

_

þy

2

Ni

y

2

Pt

y

1

Ni

i

L

i

Ni;NiPt

y

2

Ni

Ày

2

Pt

_ _

i

þy

1

Pt

i

L

i

Pt;NiPt

y

2

Ni

Ày

2

Pt

_ _

i

_

þy

1

Ti

i

L

i

Ti;NiPt

y

2

Ni

Ày

2

Pt

_ _

i

_

þy

2

Pt

y

2

Ti

y

1

Ni

i

L

i

Ni;PtTi

y

2

Pt

Ày

2

Ti

_ _

i

þy

1

Pt

i

L

i

Pt;PtTi

y

2

Pt

Ày

2

Ti

_ _

i

_

þy

1

Ti

i

L

i

Ti;PtTi

y

2

Pt

Ày

2

Ti

_ _

i

_

ð1Þ

Fig. 1. TEM images of the P-phase precipitates aged at 600 °C for 100 h.

Y. Gao et al. / Acta Materialia 60 (2012) 1514–1527 1515

where y

1

Ni

; y

1

Pt

; y

1

Ti

; y

2

Ni

; y

2

Pt

and y

2

Ti

are the site fractions,

representing mole fractions of elements Ni, Pt and Ti on

the two sublattices (the superscript) with

0:5y

1

Ni

þ 0:5y

2

Ni

¼ x

Ni

ð2aÞ

0:5y

1

Pt

þ 0:5y

2

Pt

¼ x

Pt

ð2bÞ

0:5y

1

Ti

þ 0:5y

2

Ti

¼ x

Ti

ð2cÞ

y

1

Ni

þ y

1

Pt

þ y

1

Ti

¼ 1 ð2dÞ

y

2

Ni

þ y

2

Pt

þ y

2

Ti

¼ 1 ð2eÞ

where x is the mole fraction of each species in the crystal. The

ﬁrst three terms in the expression describe the contributions

from the Gibbs free energies of the so-called end member

phases in which each sublattice is occupied by only one kind

of species. The fourth and ﬁfth term describe the contribu-

tions from mixing on each sublattice. The other terms are

the excess Gibbs free energy that describes the interactions be-

tween atoms on the same sublattice, as in a regular solution

model. At any given temperature and initial composition,

the phases must also be at internal equilibrium determined

by

@G

B2

@y

¼ 0 for all site fractions (y = y

1

Ni

; y

1

Pt

; y

1

Ti

; y

2

Ni

;

y

2

Pt

or y

2

Ti

). The free energy model and the assessed param-

eters used in Eq. (1) are given in Appendix A.

3. Crystallography of B2 to P-phase transformation

3.1. Crystal structure of the P-phase and its orientation

relationship with the B2 matrix

The P-phase has a monoclinic crystal structure with

a

p

= 0.745 nm, b

p

= 1.292 nm, c

p

= 1.422 nm and b =

100.45

**[2]. The lattice parameter of the B2 matrix is
**

a

B2

= 0.3087 nm [2,21]. Each monoclinic unit cell of the P-

phase (Fig. 2a) includes 96 atoms in16 layers that are parallel

to the (111) plane of the B2 matrix phase. The P-phase has a

stoichiometry of Ti

44

Ni

36

Pt

16

, which indicates an excess of

Ni and a deﬁciency of Ti in the structure as compared to

the B2 structure. The 16 Pt atoms forman ordered structure

on the Ni sublattice and Ni substitutes for four sites (Wyck-

oﬀ notation 4e) on the Ti sublattice [2].

According to the orientation relationship between the

B2 phase and the P-phase observed in the experiment [2]

(½100

p

==½11

2

B2

; ½010

p

==½1

10

B2

; ½001

p

==½

3

3

2

B2

), the

following lattice correspondence has been proposed by

Kovarik et al. [2]: ½100

p

! ½11

2

B2

; ½010

p

! ½3

30

B2

and

½001

p

! ½

3

3

2

B2

. This lattice correspondence is schemati-

cally shown in Fig. 3. The space group of the B2 structure

and the monoclinic P-phase are Pm

**3m and C2/c, respec-
**

tively. Rotations in the point group of B2 structure include

three fourfold (h100i), four threefold (h111i), and six

twofold (h110i) rotation axes, totaling 24 elements com-

bining with identity. Meanwhile, there are only two rota-

tion elements for the P-phase, which are one twofold

rotation and its identity. Their intersection group contains

two common symmetry elements and thus there are 12

crystallographic equivalent variants for the P-phase, which

can be divided into four groups (see Table 1). It has been

observed that within each group, three variants stack into

a layered structure along h111i (Fig. 4).

3.2. Coherency of P-phase/B2 matrix interface

It is diﬃcult to directly observe the structure of P-phase/

B2 matrix interfaces since at room temperature, where the

high resolution STEM investigations have been carried

Fig. 2. (a) Ni sublattice (001)

P

planes in the P-phase (Ti sublattice planes

are not included). (b) The arrangement of Pt atoms in the (001)

P

Pt rich

planes. Each of these planes contain four Pt atoms and two Ni atoms [2].

Fig. 3. (a) Non-periodical arrangement of the three variants of the

monoclinic P-phase within a single P-phase particle. (b) A monoclinic unit

cell of the P-phase and its OR with the B2 parent phase [2].

Table 1

Symmetry related orientation variants of the P-phase.

Variant no. a b c a Â b

1 ½

211 ½03

3 ½

2

3

3 ð111Þ

2 ½211 ½03

3 ½2

3

3 ð

111Þ

3 ½21

1 ½033 ½2

33 ð1

11Þ

4 ½2

11 ½033 ½23

3 ð11

1Þ

5 ½1

21 ½

303 ½

3

2

3 ð111Þ

6 ½121 ½

303 ½

32

3 ð1

11Þ

7 ½12

1 ½303 ½

323 ð

111Þ

8 ½

121 ½303 ½32

3 ð11

1Þ

9 ½11

2 ½3

30 ½

3

3

2 ð111Þ

10 ½112 ½3

30 ½

3

32 ð11

1Þ

11 ½1

12 ½330 ½

332 ð

111Þ

12 ½

112 ½330 ½3

32 ð1

11Þ

1516 Y. Gao et al. / Acta Materialia 60 (2012) 1514–1527

out, the matrix has already transformed to B19 martensitie.

The martensite adjacent to the P-phase particles is often not

in an orientation suitable for high resolution imaging. How-

ever, on occasion this is not the case, as shown in the high

angle annular dark ﬁeld (HAADF) image in Fig. 5. This

HAADF image was obtained with a FEI Titan 80–300 with

C

s

-correction on the electron probe, and operated at

300 kV. In the image the precipitate is being viewed along

the ½0

**10 zone (i.e. a h110i orientation relative to the B2
**

matrix [2]). The key observation is that there are no inter-

face or misﬁt dislocations present at the interface, indicating

that the interface between the precipitate and the martensite

is fully coherent. This same result has been obtained for

other selected regions of particle/matrix interface that have

been suitable for imaging. Based on these observations we

assume in this study that the precipitate/B2 matrix interface

is also fully coherent because if the interface contains misﬁt

dislocations, one would expect that the dislocation content

will be inherited as the B2 matrix transforms to martensite.

STEM observations during in situ heating experiments

above the M

s

temperature are required in order to directly

observe the precipitate/B2 matrix interfaces, which is

beyond the scope of this study.

3.3. Calculation of stress-free transformation strain

According to the lattice correspondence described

above, the transformations of the three non-parallel lattice

vectors during B2 to P-phase transition are calculated as:

e

B2

1

¼ a

B2

0

Á

1

1

À2

_

¸

_

_

¸

_; e

B2

2

¼ a

B2

0

Á

3

À3

0

_

¸

_

_

¸

_;

e

B2

3

¼ a

B2

0

Á

À3

À3

À2

_

¸

_

_

¸

_ ð3aÞ

e

P

1

¼

a

P

ﬃﬃﬃ

6

p

1

1

À2

_

¸

_

_

¸

_; e

P

2

¼

b

P

ﬃﬃﬃﬃﬃ

18

p

3

À3

0

_

¸

_

_

¸

_;

e

P

2

¼

b

P

ﬃﬃﬃﬃﬃ

22

p

À

ﬃﬃﬃﬃﬃ

11

p

cosðb À arcsin

2

3

Þ

À

ﬃﬃﬃﬃﬃ

11

p

cosðb À arcsin

2

3

Þ

À

ﬃﬃﬃﬃﬃ

22

p

sinðb Àarcsin

2

3

Þ

_

¸

¸

_

_

¸

¸

_

ð3bÞ

Thus, the deformation gradient matrix, which corresponds

to variant 9 in Table 1, can be calculated with constrains

T

9

e

B2

i

¼ e

P

i

; ði ¼ 1–3Þ as:

T

9

¼

0:9860 À0:0005 0:0001

À0:0005 0:9860 0:0001

À0:0047 À0:0047 0:9806

_

¸

_

_

¸

_ ð4Þ

According to the experimental observations (Fig. 4) [2], all

P-phase particles consist of three orientation variants

belonging to the same group (Table 1), with each individual

variant forming {111}

B2

plates in a randomly layered

structure. The three variants are rotated 120° with respect

to each other and have almost equal volume fraction,

which minimizes the strain energy because there is a small

lattice mismatch between two adjacent variants [2]. In or-

der to describe the lattice misﬁt between the precipitate

and the matrix phases at the particle level, the stress-free

transformation strain (SFTS) is calculated by averaging

the three variants in a single P-phase particle, i.e. coarse-

graining the multi-layers into a homogenous structure as

shown in Fig. 6.

The SFTS of the coarse-grained P-phase particles can be

calculated as:

T

ð111Þ

¼

1

3

ðT

1

þT

5

þT

9

Þ ¼

0:9860 À0:0016 À0:0016

À0:0016 0:9860 À0:0017

À0:0016 À0:0016 0:9806

_

¸

_

_

¸

_

ð5aÞ

Fig. 4. High-angle annular dark ﬁeld image of the precipitate along the

zone axis directions h112i [2].

Fig. 5. HAADF image of an interface between the P-phase precipitate

(along a ½0

**10 zone, which is equivalent to a h110i zone of the B2 matrix)
**

and the B19 martensite. The continuity of lattice fringes from the

martensite to the precipitate indicates that the precipitate is coherent with

respect to the matrix.

Y. Gao et al. / Acta Materialia 60 (2012) 1514–1527 1517

e

T

ð111Þ

¼

T

T

ð111Þ

T

ð111Þ

À I

2

%

1

3

ðe

1

þ e

5

þ e

9

Þ

¼

À0:0157 À0:0016 À0:0016

À0:0016 À0:0157 À0:0016

À0:0016 À0:0016 À0:0157

_

¸

_

_

¸

_ ð5bÞ

e

T

ð

111Þ

¼

1

3

ðe

2

þ e

7

þ e

11

Þ ¼

À0:0157 0:0016 0:0016

0:0016 À0:0157 À0:0016

0:0016 À0:0016 À0:0157

_

¸

_

_

¸

_

ð5cÞ

e

T

ð1

11Þ

¼

1

3

ðe

3

þ e

6

þ e

12

Þ ¼

À0:0157 0:0016 À0:0016

0:0016 À0:0157 0:0016

À0:0016 0:0016 À0:0157

_

¸

_

_

¸

_

ð5dÞ

e

T

ð11

1Þ

¼

1

3

ðe

4

þ e

8

þ e

10

Þ ¼

À0:0157 À0:0016 0:0016

À0:0016 À0:0157 0:0016

0:0016 0:0016 À0:0157

_

¸

_

_

¸

_

ð5eÞ

where T

(111)

is the averaged deformation gradient matrix

for the three variants within the (111) group and e

(111)

is

the averaged SFTS. I is the identity matrix. Such a

coarse-graining process reduces the 12 variants down to

four, characterized by the SFTS given above. Correspond-

ingly, four order parameters instead of 12 are used in the

phase ﬁeld simulations, which will be described in the next

section.

4. Phase ﬁeld model

4.1. Energy formulation

According to Landau’s theory of phase transformations,

a set of four order parameters, {g

1

, g

2

, g

3

, g

4

}, is introduced

to characterize the B2 to P-phase transformation, with

{g

1

= g

2

= g

3

= g

4

= 0} representing the B2 phase and

{g

i

= 1, g

j–i

= 0} (where i = 1–4 and j = 1–4) representing

the four coarse-grained P-phase variants. In addition, an

interpolation function hðg

i

Þ ¼ g

3

i

ð10 À15g

i

þ 6g

2

i

Þ is used

to connect the equilibrium free energy functions of the

two phases through the order parameters. The ﬁnal form

of the chemical free energy density in the phase ﬁeld model

(in a unit of J m

–3

) can be expressed as:

f ðx

Ni

; x

Pt

; fg

p

; p ¼ 1–4gÞ

¼ V

À1

m

G

B2

ð1 À

4

p¼1

hðg

p

ÞÞ þ G

p

4

p¼1

hðg

p

Þ

_ _

ð6Þ

where x

Ni

and x

Pt

are mole fractions of Ni and Pt respec-

tively, V

m

is the molar volume and G

B2

and G

p

are the equi-

librium Gibbs free energies of the B2 matrix and P-phase.

G

B2

at 873 K is ﬁtted to available thermodynamic data

(see Section 2) (in a unit of 10

6

J mol

–1

):

G

B2

¼ 0:4493 À2:2897x

Ni

À 1:6992x

Pt

þ 3:4637x

2

Ni

þ 1:0x

Ni

x

Pt

þ 3:1846x

2

Pt

ð7Þ

and G

p

could be approximated as a second order polyno-

mial function of Ni and Pt concentrations [22]:

G

p

¼ 0:4781 À 2:3586x

Ni

À 1:0980x

Pt

þ 3:0x

2

Ni

þ 3:0x

2

Pt

ð8Þ

where the constants are determined by two conditions: (a) a

common tangent plane going through the equilibrium B2

matrix concentration and the equilibrium P-phase concen-

tration determined from experimental characterization; (b)

the curvature of the polynomial at the equilibrium concen-

tration of the P-phase yielding the desired interfacial energy

between the two phases for the gradient energy coeﬃcient

chosen. The two equilibrium free energy functions (Eqs.

(7) and (8)) are plotted in Fig. 7. For an alloy of Ni

0.3

Pt

0.2-

Ti

0.5

, the equilibrium Ni and Pt concentrations determined

by the common-tangent construction are x

B2

Ni

¼ 0:285;

x

B2

Pt

¼ 0:207 and x

P

Ni

¼ 0:375; x

P

Pt

¼ 0:167, which are close to

the equilibrium concentrations determined by experiment

at 873 K [2].

Assuming that the lattice misﬁt between the two coexis-

ting phases is associated with both chemical and structural

non-uniformities, the SFTS ﬁeld is formulated as a function

of both concentrations and structural order parameters:

e

T

ij

ðrÞ ¼ v

B2

Ni

d

ij

g

1

ðx

Ni

Þ þ v

B2

Pt

d

ij

g

2

ðx

Pt

Þ þ

4

p¼1

e

ij

ðpÞhðg

p

Þ ð9Þ

where v

B2

Ni

¼

@a

B2

@x

Ni

1

a

B2

and v

B2

Pt

¼

@a

B2

@x

Pt

1

a

B2

are the lattice expan-

sion coeﬃcients of the B2 phase, d

ij

is the Kronecker delta

function, and g

1

and g

2

are two hyperbolic tangent functions,

which are used to describe the concentration dependence of

the B2 lattice parameters:

g

1

ðx

Ni

Þ ¼

2

x

B2

Ni

À x

0

Ni

tanh

x

B2

Ni

À x

0

Ni

2

x

Ni

À x

0

Ni

_ _

_ _

g

2

ðx

Pt

Þ ¼

2

x

B2

Pt

À x

0

Pt

tanh

x

B2

Pt

À x

0

Pt

2

x

Pt

À x

0

Pt

_ _

_ _

:

Based on theoretical calculations of the concentration

dependence of the B2 lattice parameter [23,24], the lattice

constants for Ni

0.5

Pt

0.5

, Ni

0.5

Ti

0.5

and Pt

0.5

Ti

0.5

are 0.2995

nm, 0.3015 nm and 0.3137 nm respectively. By linear inter-

polation, the lattice expansioncoeﬃcients can be determined

as: v

B2

Ni

¼ À0:092, v

B2

Pt

¼ À0:013. The initial composition

Fig. 6. Schematic drawing of the coarse graining assumption.

1518 Y. Gao et al. / Acta Materialia 60 (2012) 1514–1527

(x

0

Ni

¼ 0:3; x

0

Pt

¼ 0:2) is chosen as a reference state for the

strain calculations.

The structural dependence of the SFTS, e

ij

(p), in Eq. (9)

can be expressed as:

e

ij

ð1Þ ¼ e

T

ð111Þ

À v

B2

Ni

½x

P

Ni

À x

0

Ni

d

ij

À v

B2

Pt

½x

P

Pt

À x

0

Pt

d

ij

¼

À0:0126 À0:0016 À0:0016

À0:0016 À0:0126 À0:0016

À0:0016 À0:0016 À0:0126

_

¸

_

_

¸

_ ð10aÞ

e

ij

ð2Þ ¼ e

T

ð

111Þ

À v

B2

Ni

½x

P

Ni

À x

0

Ni

d

ij

À v

B2

Pt

½x

P

Pt

À x

0

Pt

d

ij

¼

À0:0126 0:0016 0:0016

0:0016 À0:0126 À0:0016

0:0016 À0:0016 À0:0126

_

¸

_

_

¸

_ ð10bÞ

e

ij

ð3Þ ¼ e

T

ð1

11Þ

À v

B2

Ni

½x

P

Ni

À x

0

Ni

d

ij

À v

B2

Pt

½x

P

Pt

À x

0

Pt

d

ij

¼

À0:0126 0:0016 À0:0016

0:0016 À0:0126 0:0016

À0:0016 0:0016 À0:0126

_

¸

_

_

¸

_ ð10cÞ

e

ij

ð4Þ ¼ e

T

ð11

1Þ

À v

B2

Ni

½x

P

Ni

À x

0

Ni

d

ij

À v

B2

Pt

½x

P

Pt

À x

0

Pt

d

ij

¼

À0:0126 À0:0016 0:0016

À0:0016 À0:0126 0:0016

0:0016 0:0016 À0:0126

_

¸

_

_

¸

_ ð10dÞ

The total elastic energy can then be formulated following

the Khachaturyan–Shatalov microelasticity theory [20]:

E

elastic

¼

1

2

4

p;q¼1

_

--

d

3

k

ð2pÞ

3

B

pq

ð~nÞf~g

p

g

k

f~g

q

g

Ã

k

ð11Þ

where the integral is taken in the reciprocal space,

~

k, and~n is

a unit vector in the reciprocal space. Note that

~

k ¼ 0 is to be

excluded from the integration, which deﬁnes the principle

value of the integral. f~g

p

g

k

is the Fourier transform of

g. The asterisk denotes a complex conjugate. Considering

a system having free external boundaries, B

pq

ð~nÞ can be

expressed as:

B

pq

ð~nÞ ¼

0 ~n ¼ 0

C

ijkl

e

ij

ðpÞe

kl

ðqÞ À n

i

r

p

ij

X

jk

r

q

kl

n

l

~n–0

_

ð12Þ

where X

À1

ij

¼ C

iklj

n

k

n

l

, r

p

ij

¼ C

ijkl

e

kl

ðpÞ

After incorporating the gradient terms, the total free

energy of the system becomes:

F ¼

_

d

3

r Á f x

Ni

; x

Pt

; fg

p

g

_ _

þ

j

Ni

2

rx

Ni

ð Þ

2

þ

j

Pt

2

rx

Pt

ð Þ

2

_

þ

4

p¼1

j

g

2

rg

p

_ _

2

_

þ E

elastic

ð13Þ

where j

Ni

, j

Pt

and j

g

are the gradient energy coeﬃcients

respectively for the Ni and Pt concentrations and the order

parameters.

4.2. Kinetic equations

The Cahn–Hilliard equation and the time-dependent

Ginsburg–Landau (or Allen–Cahn equation) are used to

describe the time evolution of the concentration and order

parameter ﬁelds [9,16,25]:

1

V

2

m

@x

Ni

@t

¼ r M

Ni

r

dF

dx

Ni

_ _ _ _

1

V

2

m

@x

Pt

@t

¼ r M

Pt

r

dF

dx

Pt

_ _ _ _

ð14Þ

@g

p

@t

¼ ÀL

dF

dg

p

; p ¼ 1–4

where M

Ni

and M

Pt

are the chemical mobilities of Ni and

Pt, and L is the kinetic coeﬃcient characterizing time

evolution of the order parameters.

Fig. 7. Gibbs free energies for B2 phase and P-phase as functions of Ni, Pt compositions in a NiTiPt ternary system.

Y. Gao et al. / Acta Materialia 60 (2012) 1514–1527 1519

5. Simulation results

As discussed earlier, interfaces between the B2 matrix

and the P-phase precipitates are assumed to be fully coher-

ent in this study. Correspondingly, the interfacial energy is

assumed to be 200 mJ m

–2

, which yields a grid size of

l

0

= 1.687 nmin the phase ﬁeld simulations. Thus, a compu-

tation cell of 128l

0

Â 128l

0

Â 128l

0

grids represents a phys-

ical system of edge length 216 nm. The elastic constants

used in the simulations for the B2 Ni

30

Pt

20

Ti

50

are:

c

11

= 183 GPa, c

12

= 146 GPa and c

44

= 46 GPa [21]. All

dimensionless parameters used in the simulations are listed

in Appendix B.

5.1. Equilibrium shape of a P-phase precipitate

The equilibrium shape of an isolated P-phase precipitate

obtained from the simulation is shown in Fig. 8. It can be

seen that the precipitate has a slightly distorted cube shape

with smoothly curved edges and corners. Because the elas-

tic constants of the B2 matrix phase have a Zener anisot-

ropy factor (c

11

À c

12

)/(2c

44

) = 2.5, and the three normal

strains (the diagonal terms) in the transformation strain

tensor are equal and far greater than the shear components

(oﬀ diagonal terms), the predicted habit plane of the pre-

cipitate is {11,1,1}, nearly parallel to {100}, as the elastic

soft directions lie along h100i. Because of the presence of

the shear components in the SFTS, the habit plane normal

deviates from that of {100} by $7°.

5.2. Multi-particle correlation

In phase ﬁeld simulations, nucleation can be simulated

by using either the Langevin noise terms [26,27] or the

explicit nucleation algorithm [28,29]. In this study the

Langevin noise terms are used to generate microstructures

consisting of multi-particles in the simulations [30]. An

example is shown in Fig. 9. The spatial alignment is caused

by elastic interactions among the precipitates during nucle-

ation and growth, i.e. preferred nucleation and growth

along the elastically soft h100i directions [30]. Both the

shape and spatial alignment of the precipitates predicted

by the simulations agree well with the TEM images of

the P-phase precipitates shown in Fig. 1.

5.3. Concentration ﬁeld around a P-phase particle

The equal-concentration contours around a P-phase parti-

cle (on a (001) center cross-section) obtained from the phase

ﬁeld simulation are shown in Fig. 10. Comparing to the initial

composition of Ni

0.3

Pt

0.2

Ti

0.5

, the precipitation of P-phase

particles that have a composition of Ni

0.375

Pt

0.167

Ti

0.458

will

leave the matrix with lower Ni and higher Pt concentrations.

As shown clearly in Fig. 10a and b, the B2 matrix is depleted

in Ni and enriched in Pt near a growing P-phase particle.

When the particle reaches its equilibrium volume fraction,

the Ni and Pt concentrations in the B2 matrix become more

or less uniform(Fig. 10c and d). However, noticeable Ni con-

centration non-uniformity exists as shown in Fig. 10c. This is

caused by the elastic interaction between Ni atoms and the

coherency stress associated with the precipitates. Since the

principal SFTSs of the P-phase are all negative and the lattice

expansion coeﬃcients of the B2 phase are v

B2

Ni

¼ À0:092 and

v

B2

Pt

¼ À0:013; higher Ni and Pt concentrations around a P-

phase particle, in particular along the elastically soft direc-

tions, are expected as compared to the equilibriumconcentra-

tions of the B2 phase predicted by the thermodynamic

database. Because of the relatively small lattice mismatch

between the precipitate and matrix phases, concentration

non-uniformity caused by the elastic interactions around an

equilibrium precipitate, $0.01% for Ni and 60.001% for Pt,

are negligible as compared to Ni depletion and Pt enrichment

in the matrix associated with precipitate nucleation and

growth (Fig. 10a and b).

The maximum Pt concentration in the B2 matrix near a

growing P-phase precipitate is monitored as a function of

aging time (Fig. 11). The initial microstructure of the simula-

tion consists of a supercritical particle of $10 nm diameter.

The location of the maximum Pt concentration is found to

be near the corner of the cube-like precipitate. As one can

see from Fig. 11, the maximum Pt concentration in the B2

matrix increases with aging time with a decreasing rate, and

slowly approaches the equilibrium concentration. Note that

the Gibbs–Thompsoneﬀect, under the assumptionof a spher-

ical particle with similar size, will change the equilibrium Pt

concentration from 0.207 (given by the common-tangent

construction of the free energy surfaces in Fig. 7) to 0.2067.

5.4. Stress ﬁeld around a P-phase particle

Since the three principal SFTSs of a P-phase particle are

all negative, there are both compressive and tensile stresses

around the particle and mostly tensile stresses inside the

particle. Fig. 12 shows the variation of diﬀerent stress com-

ponents around a P-phase particle. Since the stress compo-

nents r

13

and r

23

are orders of magnitude smaller than the

others, they are not included in Fig. 12. Signiﬁcant elastic

eﬀects of P-phase precipitate on the martensitic transfor-

mation in the B2 matrix phase will be discussed below.

6. Discussion

6.1. Eﬀect of Pt concentration in B2 on martensitic

transformation

The change of concentration in the B2 matrix caused by

P-phase precipitation (which depletes Ni while enriching Pt

in the matrix) shown in Figs. 10 and 11 may have a pro-

found impact on the M

s

temperature. Based on experimen-

tal measurements, the M

s

temperatures of non-aged

Ni

0.3

Pt

0.2

Ti

0.5

and Ni

0.2

Pt

0.3

Ti

0.5

are 259 °C and 530 °C,

respectively [3,31,32]. Within this temperature range, the

M

s

temperature increases almost linearly with Pt concen-

tration [33]. Thus a 0.1 at.% diﬀerence in Pt concentration

1520 Y. Gao et al. / Acta Materialia 60 (2012) 1514–1527

Fig. 8. Three-dimensional views of the equilibrium shape of a P-phase particle (variant 1) obtained by the phase ﬁeld simulation.

Fig. 9. Multi-particle simulation results generated by Langevin noise induced nucleation in an initially supersaturated matrix.

Fig. 10. Concentration ﬁelds (in atomic fractions) around a P-phase particle along its central (100) cross-section. (a) Ni contour around a growing

precipitate; (b) Pt contour around a growing precipitate; (c) Ni contour around an equilibrium precipitate; (d) Pt contour around an equilibrium

precipitate.

Y. Gao et al. / Acta Materialia 60 (2012) 1514–1527 1521

could lead to a 2.7 °C change in M

s

temperature. As a

result, the M

s

temperature for a B2 matrix with 20.7 at.%

Pt is estimated to be $278 °C.

6.2. Eﬀect of stress ﬁelds on martensitic transformation

Like any other stress-carrying defects such as disloca-

tions, the stress ﬁeld associated with the coherent P-phase

precipitates may aﬀect the martensitic transformation of

the B2 matrix phase as well [9,34–40]. To investigate this

eﬀect, the elastic interaction energy between the P-phase

precipitate and a nucleating martensitic particle is calcu-

lated according to the following equation:

E

int

¼ Àr

ij

e

M

ij

ðpÞ ð15Þ

where r

ij

is the stress ﬁeld generated by the coherent P-

phase precipitates and e

M

ij

ðpÞ is the SFTS of martensitic var-

iant p. A negative value of the interaction energy means

that the formation of martensite is favored by the presence

of the P-phase precipitates.

Since the space groups of B2 and B19 are Pm

3m and

Pmma, respectively, there are three twofold rotation axes

and identity elements in the intersection group. As a result,

six orientation variants of the martenstic phase can be gener-

ated after the transition. The lattice parameters of the B19

martensitic phases from experimental measurement and ab

initio calculations [4,21] are a

B19

= 0.470 nm,

b

B19

= 0.444 nm and c

B19

= 0.275 nm. The lattice corre-

spondence between the B2 and B19 phases has been pro-

posed as the following [33,41]: ½100

B19

! ½0

1

1

B2

; ½010

B19

! ½01

1

B2

; ½001

B19

! ½100

B2

. As a result, the SFTS can

be calculated as:

e

M

ð1Þ ¼

0:0507 0 À0:0313

0 À0:1014 0

À0:0313 0 0:0507

_

¸

_

_

¸

_; e

M

ð2Þ ¼

0:0507 0 0:0313

0 À0:1014 0

0:0313 0 0:0507

_

¸

_

_

¸

_;

e

M

ð3Þ ¼

0:0507 À0:0313 0

À0:0313 0:0507 0

0 0 À0:1014

_

¸

_

_

¸

_; e

M

ð4Þ ¼

0:0507 0:0313 0

0:0313 0:0507 0

0 0 À0:1014

_

¸

_

_

¸

_;

e

M

ð5Þ ¼

À0:1014 0 0

0 0:0507 À0:0313

0 À0:0313 0:0507

_

¸

_

_

¸

_; e

M

ð6Þ ¼

À0:1014 0 0

0 0:0507 0:0313

0 0:0313 0:0507

_

¸

_

_

¸

_:

ð16Þ

The calculation results of the interaction energy are plotted

in Fig. 13. The locations with the most negative interaction

energy ($À0.138 J mm

–3

or À1.22 kJ mol

–1

) are near the

edges of a cube-like shaped precipitate with edge length

of $116 nm. Based on ab initio calculations [21] of the

formation energy of B2 and B19 in (Ni,Pt)Ti system, the

enthalpy change of B2 to B19 transformation in Ni

0.3

Pt

0.2-

Ti

0.5

at 0 K is DH = À6 kJ mol

À1

.

By assuming that both enthalpy change DH and entropy

change DS do not depend on temperature and the increase

in M

s

is the same as that in T

0

, at which temperature the

driving force of the martensitic transformation is zero,

the change of M

s

temperature by the elastic interaction

of a martensite nucleus with an existing P-phase particle

can be estimated using the data of M

s

(532 K) and A

s

(511 K) from experimental measurements [3]:

T

0

¼

MsþAs

2

¼ 522 K

DS ¼

DH

T

0

¼ À0:0115 kJ=ðK molÞ

T

new

0

¼

DHÀ1:22

DS

¼ 627K

M

new

s

% M

s

þ ðT

new

0

À T

0

Þ ¼ 637 K

ð17Þ

where M

new

s

is the martensitic transformation start temper-

ature with pre-existing P-phase particles. Comparing with

the chemical driving force for B2 to B19 transformation,

the maximum elastic interaction energy is nearly one-ﬁfth

of DH. As a result, the coherency stress of P-phase precip-

itates could make a major contribution to the driving force

for the B2 to B19 martensitic transformation. The M

s

tem-

perature could increase as much as 100 K.

From Fig. 13 it is seen that the edges of the cube-like

shaped particle are the most preferred sites for martensite

nucleation and diﬀerent martensitic variants (indicated by

diﬀerent colors online) are favored at diﬀerent edges. How-

ever, since internally twinned martensitic plates are usually

formed in shape memory alloys, it is expected that internally

twinned martensitic particles consisting of large fractions of

the most favored variant will develop via an autocatalytic

eﬀect [42,43].

Considering the relative contributions from the chemical

non-uniformity and stress ﬁeld associated with P-phase

precipitation, the most favorable nucleation site for the

martensitic phase should be located somewhere near the

edge center of the cuboidal P-phase particle. Correspond-

ing NEB calculations [42] for determining the nucleation

site, critical nucleus conﬁguration and activation energy

are underway.

6.3. Eﬀect of aging on M

s

temperature

As compared to the Ni–Ti binary system where the

eﬀects of Ni

4

Ti

3

precipitates on martensitic transforma-

tions have been investigated extensively [9,33,44,45], the

ternary element addition oﬀers the opportunity to alter

the type, shape, spatial distribution and stress state of pre-

cipitates and hence their eﬀects on the strength of the B2

matrix and the behavior of the martensitic transformation.

0.2

0.201

0.202

0.203

0.204

0.205

0.206

0.207

0 500 1000 1500 2000 2500 3000 3500 4000

reduced time

m

a

x

i

m

u

m

P

t

c

o

n

c

e

n

t

r

a

t

i

o

n

Fig. 11. Simulation results of maximum Pt concentration around a P-

phase particle during growth.

1522 Y. Gao et al. / Acta Materialia 60 (2012) 1514–1527

From experimental observations, the M

s

temperature of

Ti–Ni–Pt alloys increases signiﬁcantly with aging time.

As shown in Fig. 14, the M

s

temperature for a nominal

Ni

0.3

Pt

0.2

Ti

0.5

alloy has a strong and highly non-linear

dependence on the aging time, with a sharp increase at

the initial stage of aging. The above simulation results

and analysis could provide some insight into the physical

origin of such a dependence of M

s

on aging time.

The phase ﬁeld simulation results show that both the

chemical non-uniformity (enrichment in Pt) and elastic

stress ﬁeld in the B2 matrix generated by P-phase precipita-

tion alter the driving force for the martensitic transforma-

tion and hence alter the M

s

temperature. As shown in

Fig. 11, the Pt concentration in the B2 matrix increases

monotonically as the precipitates grow, reaching a maxi-

mum when the precipitate phase reaches its equilibrium

volume fraction. Meanwhile, as the formation of 0.2% (vol-

ume fraction) martensite is usually deﬁned as the incubation

period [46,47], the 0.2% fraction of the matrix phase with

the lowest elastic interaction energy has been monitored

in our simulation and its cut-oﬀ energy is used in the corre-

sponding M

s

temperature calculations. As the P-phase par-

ticles grow, their elastic interaction energy (magnitude) with

martensite nuclei increases sharply at the beginning and

then continues to increase but at a much slower rate, as

shown in Figs. 15 and 16, where the change of the cut-oﬀ

elastic interaction energy in the B2 matrix phase is plotted

as a function of particle volume and aging time,

respectively.

Based on the calculated Pt concentration (Fig. 11) and

elastic interaction energy (Fig. 16) around a growing

P-phase particle as a function of aging time, the change

Fig. 12. Stress ﬁelds around a P-phase particle: (a) r

11

, (b) r

22

, (c) r

33

and (d) r

12

. Axis 1 is along [100]

B2

; axis 2 is along [010]

B2

and axis-3 is along

[001]

B2

.

Fig. 13. Three-dimensional elastic interaction energy iso-surface (À0.1 J mm

–3

or –0.886 kJ mol

–1

) between a P-phase precipitate and martensite nucleus.

Y. Gao et al. / Acta Materialia 60 (2012) 1514–1527 1523

of M

s

temperature can be determined. The result is plotted

in Fig. 17. Since the diﬀusivity data for this ternary system

are not available, the time scale of our phase ﬁeld simula-

tions is in a reduced unit. Therefore, only qualitative com-

parison with the experimental results can be made. By

comparing Fig. 17 with Fig. 14, it is readily seen that the

general trend of M

s

variation with aging time predicted

by the phase ﬁeld simulation agrees well with the experi-

mental measurement. This also indicates that the elastic

interaction between the P-phase precipitates and martens-

itic nuclei may dominate the aging eﬀect on M

s

in this ter-

nary alloy system.

The eﬀects of the P-phase precipitates on the martensitic

transformation found in this ternary alloy are similar to

that found in the NiTi binary system [9,44]. For example,

when coherent Ni

4

Ti

3

particles start to precipitate out, a

jump in M

s

was also observed and M

s

was found to

increase with aging temperature within a certain tempera-

ture range [44].

Comparing the magnitudes of the M

s

changes, the calcu-

lations slightly overestimate the aging eﬀect primarily at

the earliest time increments. This could be due to the fact

that the data used for elastic constants and transformation

enthalpy are obtained from ab initio calculations at 0 K,

which is a rough approximation for the actual values at

the aging temperature. Comparing to the elastic constants

of NiTi binary alloy measured from experiments at room

temperature (C

11

= 162 GPa, C

12

= 129 GPa,

C

44

= 34 GPa) [48], the elastic constants calculated at 0 K

are already signiﬁcantly higher. Since the M

s

temperature

is much higher than room temperature, the elastic moduli

may further soften at the transformation temperature. This

will lead to an overestimation of the elastic interaction

energy.

6.4. Limitations of the model

As mentioned above, a homogeneous modulus approx-

imation is used in our simulations for simplicity, which

assumes both the parent and product phases have the same

elastic constants. However, based on the ab initio calcula-

tion results listed in Table 2 [21], the C

11

of the B2 and B19

phases in Ni

31

Pt

19

Ti

50

are signiﬁcantly diﬀerent. The ab ini-

tio calculations were performed using the full-potential lin-

earized augmented plane wave method (FLAPW) [49] and

converged with respect to both k-point mesh and repeated-

cell size. A system size of 16 atoms was found to be

suﬃcient in determining the elastic properties. However,

Fig. 14. Experimental result of the eﬀect of aging time at 500 °C on the M

s

temperature of a nominal Ni

30

Pt

20

Ti

50

alloy.

Fig. 15. Simulation results of the lowest interaction energies around a

particle with diﬀerent volume.

Fig. 16. Simulation results of the lowest interaction energy around a P-

phase particle as a function of reduced aging time.

0

20

40

60

80

100

120

0 500 1000 1500 2000 2500 3000 3500

reduced time

c

h

a

n

g

e

o

f

M

s

t

e

m

p

e

r

a

t

u

r

e

(

K

)

Fig. 17. Change of M

s

temperature as a function of reduced time

estimated from phase ﬁeld simulation results.

1524 Y. Gao et al. / Acta Materialia 60 (2012) 1514–1527

the ground state C

0

elastic constant of the B2 structure was

found to be unstable while the B19 structure exhibited

comparable elastic constants to that of the binary alloy.

In future work, a more accurate model [50–52], includ-

ing elastic modulus inhomogeneity, will be applied to cal-

culate the stress ﬁeld provided that the elastic constants

of both B2 phase and P-phase at high temperature are

known.

In the present calculation of the SFTS for the P-phase, a

coarse-graining assumption has been made in which the

SFTSs of three monoclinic variants are averaged. To

document the eﬀect of such coarse-graining in SFTS calcu-

lations on the coherency stress ﬁeld around a precipitate,

parallel simulations have been carried out using respectively

the averaged SFTS of three variants and the individual

SFTS of the three variants in a layered structure (Fig. 18).

The results show similar stress ﬁeld distributions around

the P-phase precipitate in the two cases. Slight diﬀerences

can be seen near the P-phase interface which is due to the

laminate structure. Considering the fact that the layer thick-

ness in the P-phase particle is only $1.4 nm and the typical

dimension of the P-phase particles ($200 nm) far exceeds

the layer thickness, the eﬀect of such coarse-graining may

be neglected. However, if the particle size is comparable

to the layer thickness, then the coarse-graining may result

in larger errors.

7. Summary

A phase ﬁeld model that describes P-phase precipitation

in Ti(Ni,Pt) ternary high temperature shape memory alloys

is developed. The major model inputs such as lattice param-

eters, precipitate–matrix orientation relationship, elastic

constants and free energy data are determined based on

experimental characterization, ab initio calculations and

thermodynamic databases. The dilatational components

of the stress-free transformation strain (SFTS) of the P-

phase precipitates are found to be À1.57% and the shear

components to be 0.16%. Under the assumption of isotropic

interfacial energy, the simulation results show that the P-

phase particles have slightly distorted cuboidal shapes and

are aligned along the elastically soft h100i directions. The

predicted particle shape and spatial alignment agree well

with experimental observations.

The concentration non-uniformity around both a grow-

ing precipitate and an equilibrium one has been determined

quantitatively. Around a growing P-phase particle, the

enrichment in Pt and depletion in Ni in the B2 matrix could

lead to an increase in the M

s

temperature up to $19 °C.

The coherency stress ﬁelds caused by the P-phase precip-

itates are calculated and their eﬀects on the B2 to B19

martensitic transformation are investigated by calculating

the elastic interaction energy between a B19 martensite

nucleus and the existing P-phase precipitates. It is shown

that the elastic interaction could contribute as much as

1.22 kJ mol

–1

to the driving force for the B2 to B19 transfor-

mation, by which the M

s

temperature could increase as

much as 100 °C.

Considering both the chemical and mechanical eﬀects

analyzed above, the variation of M

s

temperature during

aging is obtained. It is found that the magnitude of the

elastic interaction energy between the ﬁne P-phase precipi-

tates and martensite nucleus increases sharply at early

stages of precipitation, which may be responsible for the

experimentally observed sharp increase in M

s

temperature

at the initial stage of aging.

In conclusion, ﬁne coherent precipitates could be

utilized in practice as an eﬃcient way of increasing the

M

s

temperature in shape memory alloys. This is indeed

the case in the recently developed high temperature shape

memory alloy NiTiPt [3,4], and may also have relevance

for NiTi with ternary additions of Pd and Hf [5,6,53–55].

Table 2

Elastic constants of NiTiPt (GPa) [21].

NiTi-B2 Ni

31

Pt

19

Ti

50

-B2 Ni

31

Pt

19

Ti

50

-B19

C

11

183 167 242

C

12

146 168 163

C

44

46 53 51

Fig. 18. Stress ﬁelds (r

11

) around a P-phase particle calculated using (a) an averaged stress-free transformation strain (SFTS) and (b) SFTSs of individual

variants having a laminate structure.

Y. Gao et al. / Acta Materialia 60 (2012) 1514–1527 1525

Acknowledgements

This work was supported by the NASA Fundamental

Aeronautics Program, Supersonics Project (Dale Hopkins,

API), NSF under grant DMR1008349 (YW) and US

Department of Energy, Oﬃce of Basic Energy Sciences un-

der grant DE-SC0001258 (YG, FY and MJM).

Appendix A. Free energy model and parameters of the B2

phase in Ti–Ni–Pt

The assessed parameters are as listed (unit: J mol

–1

,

298 K < T < 1728 K) below.

G

0

Ni;Ni

¼16645:85þ228:596T À44:192T lnT À0:0096814T

2

G

0

Pt;Pt

¼26256:138þ243:976552T À49:1052T ln

T À0:00496494T

2

À4:0276Â10

À8

T

3

þ15948T

À1

G

0

Ti;Ti

¼23195:712þ2:197944T À3:167T lnT þ0:00822826T

2

G

0

Ni;Pt

¼9961:694þ236:286276T À46:6486T ln

T À0:00732367T

2

À2:0138Â10

À8

T

3

þ7974T

À1

G

0

Ni;Ti

¼À71442:08þ257:929208T À46:0893T ln

T À0:009618675T

2

þ1:06716Â10

À7

T

3

þ72636T

À1

G

0

Pt;Ti

¼63428:5þ13:001T

G

0

Pt;Ni

¼9961:694þ236:286276T À46:6486T ln

T À0:00732367T

2

À2:0138Â10

À8

T

3

þ7974T

À1

G

0

Ti;Ni

¼À71442:08þ257:929208T À46:0893T ln

T À0:009618675T

2

þ1:06716Â10

À7

T

3

þ72636T

À1

G

0

Ti;Pt

¼À89500:675þ129:232248T À26:1361T

lnT þ0:00163116T

2

À2:0138Â10

À8

T

3

þ7974T

À1

L

0

NiTi;Ni

¼ À103000 þ 32T

L

1

NiTi;Ni

¼ 23000

L

0

Ni;NiTi

¼ À103000 þ 32T

L

1

Ni;NiTi

¼ 23000

L

0

Ni;NiPt

¼ À45000

L

0

Pt;NiTi

¼ À45000

L

0

Ti;NiTi

¼ 100000

L

0

PtTi;Pt

¼ À125052:7 þ 39:631T

L

0

Pt;PtTi

¼ À34135:1 þ 24:302T

L

0

Ti;PtTi

¼ À34:135:1 þ 24:302T

L

0

NiTi;Ti

¼ 100000

L

0

PtTi;Ti

¼ À125052:7 þ 39:631T

Appendix B. Dimensionless parameters used in simulations

G

B2

¼0:8986À4:5794x

Ni

À3:3984x

Pt

þ6:9273x

2

Ni

þ2:0x

Ni

x

Pt

þ6:3692x

2

Pt

G

p

¼0:9561À4:7172x

Ni

À2:1960x

Pt

þ6:0x

2

Ni

þ6:0x

2

Pt

j

Ni

¼ 20

j

Pt

¼ 20

j

g

¼ 0:2

c

11

¼ 91:084

c

12

¼ 72:668

c

44

¼ 22:895

V

2

m

Á M

Ni

¼ 1:0

V

2

m

Á M

Pt

¼ 1:0

L ¼ 5:0

References

[1] Ronald Noebe, Glen Bigelow, Darrell Gaydosh et al. In: Grummon

DS, Mitchell MR, Mertmann M, editors. SMST 2010: proceedings of

the international conference on shape memory and superelastic

technology, Paciﬁc Grove, California. New York: Springer; 2010.

[2] Kovarik L, Yang F, Garg A, Diercks D, Kaufman M, Noebe RD,

et al. Acta Mater 2010;58:4660.

[3] Noebe R, Draper S, Gaydosh D, Garg A, Lerch B, Penney N,

et al. In: Berg B, Mitchell MR. Proft J, editors. SMST 2006:

proceedings of the international conference on shape memory and

superelastic technologies. Materials Park (OH): ASM International;

2008. p. 409.

[4] Noebe R, Gaydosh D, Padula II S, Garg A, Biles T, Nathal M, et al.

In: Armstrong WD, editor. Smart structures and materials 2005:

active materials: behavior and mechanics, SPIE proceedings, vol.

5761. Bellingham (WA): SPIE; 2005.

[5] Sasaki TT, Hornbuckle BC, Thompson GB, Weaver ML, Noebe RD,

et al. IFES 2010 - 52nd International Field Emission Symposium,

Sydney, Australia: Imaging & Microscopy; 2010.

[6] Bigelow GS, Garg A, Padula SA, et al. Scripta Mater 2011;64:725.

[7] Wang YZ, Chen LQ. Simulation of microstructural evolution using

the ﬁeld method. New York: Wiley; 2000.

[8] Wang YZ, Li J. Acta Mater 2010;58:1212.

[9] Zhou N, Shen C, Wagner M, Eggeler G, Mills MJ, Wang Y, et al.

Acta Mater 2010;58:6685.

[10] Boettinger WJ et al. Annu Rev Mater Res 2002;32:163.

[11] Chen LQ. Annu Rev Mater Res 2002;32:113.

[12] Moelans N, Blanpain B, Wollants P. Calphad- Comput Coupl Phase

Diagrams Thermochem 2008;32:268.

[13] Steinbach I. Modell Simul Mater Sci Eng 2009;17:073001.

[14] Zhou N, Shen C, Mills MJ, Li J, Wang Y, et al. Acta Mater

2011;59:3484.

[15] Zhou N, Shen C, Mills MJ, Wang Y, et al. Acta Mater 2007;55:5369.

[16] Cahn JW, Hillard J. J Chem Phys 1958;28:258.

[17] Bellen P, Kumar KCH, Wollants P, et al. Z Metall 1996;87:972.

[18] Mei Li, Hana Wei, Changrong L, et al. J Alloys Compd 2008;461:189.

[19] Lu XG, Sundman B, Agren J, et al. Calphad – Comput Coupl Phase

Diagrams Thermochem 2009;33:450.

[20] Khachaturyan AG. Theory of structural transformations in sol-

ids. New York: Wiley-Interscience; 1983.

[21] Hatcher N, Kontsevoi OY, Freeman AJ, et al. In: ESOMAT 2009:

proceedings of the 8th European symposium on martensitic trans-

formations. Prague: EDP Science; 2009.

[22] Hu SY, Murray J, Weiland H, et al. Comput Coupl Phase Diagrams

Thermochem 2007;31:303.

[23] Che XL, Li JH, Dai Y, et al. Sci China Ser E – Technol Sci

2009;52:2681.

[24] Bozzolo G, Mosca H, del Grosso M, et al. Intermetallics 2008;16:668.

[25] Wang Y, Banerjee D, Su CC, et al. Acta Mater 1998;46:2983.

[26] Wang Y, Wang HY, Chen LQ, Khachaturyan AG, et al. J Am Ceram

Soc 1995;78:657.

1526 Y. Gao et al. / Acta Materialia 60 (2012) 1514–1527

[27] Shen C, Wang Y, in: Furrer DU, Semiatin SL, editors. ASM

handbook, vol. 22A. Fundamentals of modeling for materials

processing. Materials Park (OH): ASM International; 2010.

[28] Simmons JP, Shen C, Wang Y, et al. Scripta Mater 2000;43:935.

[29] Simmons JP, Wen YH, Shen C, Wang Y, et al. Mater Sci Eng A

2004;365:136.

[30] Wang Y, Khachaturyan AG. Philos Mag A 1995;72:1161.

[31] Rios O, Noebe R, Biles T, Garg A, Palczer A, Scheiman D, et al. In:

Armstrong WD, editor. Smart structures and materials 2005: active

materials: behavior and mechanics, SPIE proceedings, vol. 5761.

Bellingham (WA): SPIE; 2005.

[32] Zarinejad M, Liu Y, Tong Y, et al. Intermetallics 2009;17:914.

[33] Otsuka K, Ren X. Prog Mater Sci 2005;50:511.

[34] Khalil-Allaﬁ J, Dlouhy A, Eggeler G. Acta Mater 2002;50:4255.

[35] Gall K, Sehitoglu H, Chumlyakov YI, Kireeva IV, Maier HJ. J Eng

Mater Technol – Trans ASME 1999;121:19.

[36] Gall K, Sehitoglu H, Chumlyakov YI, Kireeva IV, Maier HJ. J Eng

Mater Technol – Trans ASME 1999;121:28.

[37] Tirry W, Schryvers D. Nat Mater 2009;8:752.

[38] Tirry W, Schryvers D. Acta Mater 2005;53:1041.

[39] Ke C, Ma X, Zhang XP, et al. Acta Mater Sin 2010;46:921.

[40] Wang QY, Zheng YF, Liu Y. Mater Lett 2011;65:74.

[41] Huang XY, Ackland GJ, Rabe KM, et al. Nat Mater 2003;2:307.

[42] Shen C, Li J, Wang Y, et al. Metall Mater Trans A 2008;39A:976.

[43] Wang Y, Khachaturyan AG. Mater Sci Eng A – Struct Mater Prop

Microstruct Process 2006;438:55.

[44] Zheng Y, Jiang F, Li L, et al. Acta Mater 2008:56;736.

[45] Guo W et al. Acta Mater 2011;59:3287.

[46] Entwisle AR. Metall Mater Trans B 1971;2:2395.

[47] Shih CH, Averbach BL, Cohen M, et al. J Metals Trans AIME

1955;203:709.

[48] Mercier O, Melton KN, Gremaud G, Hagi J, et al. J Appl Phys

1980;51:1833.

[49] Wimmer E, Krakauer H, Weinert M, et al. Phys Rev B 1981;24:864.

[50] Wang YU, Jin YM, Khachaturyan AG, et al. J Appl Phys

2002;92:1351.

[51] Shen Y, Li Y, Li Z, et al. Scripta Mater 2009;60:901.

[52] Zhou N, Shen C, Mills MJ, et al. Acta Mater 2008;56:6156.

[53] Bigelow GS, Padula SA, Garg A, et al. Metall Mater Trans A

2010;41A:3065.

[54] Shimizu S, Xu Y, Okunishi E, Tanaka S, Otsuka K, Mitose K, et al.

Mater Lett 1998;34:23.

[55] Meng XL, Cai W, Zheng YF, Zhao LC, et al. Mater Sci Eng – Struct

Mater Prop Microstruct Process 2006;438:666.

Y. Gao et al. / Acta Materialia 60 (2012) 1514–1527 1527

Pt. In the following sections. Simulation results and their implications are presented and discussed respectively in Sections 5 and 6.NiTi y 2 À y 2 Ni Ti Pt Ni Ti Ái À y2 Ti ) i LiTi. while the coherency elastic strain energy is formulated using Khachaturyan and Shatalov’s microelasticity theory [20].Ni y 1 À y 1 þ y 2 LiTiPt.Pt y 1 À y 1 Ti Pt Pt Ti Pt Ái À y1 Pt ) i LiTiPt. Thermodynamic modeling of B2 phase in Ti–Ni–Pt The accuracy of phase ﬁeld simulations and predictions relies on the accuracy of available thermodynamic databases.NiPt y 2 À y 2 þ y 1 LiPt. we document through systematic computer simulations (a) the shape and spatial distribution of coherent P-phase precipitates and (b) the stress and concentration ﬁelds around a P-phase precipitate and their eﬀects on the B2 ! B19 martensitic transformation.Pt. 1. nisms by which the precipitates inﬂuence the martensitic transformation and dislocation plasticity in the B2 matrix phase in these HTSMAs have not been investigated.Ni y 1 À y 1 þ y 2 LiNiPt.y 1 .NiTi y1 Ni À y2 Ni ( þ y2 y2 Ni Pt þy 1 Ti X i X i X À Ái À Ái LiNi. we formulate a phase ﬁeld model to study P-phase precipitation and its eﬀect on martensite nucleation.Pt y 1 À y 1 Ni Pt Pt Ni Pt Ái ) i LiNiPt.Y. In particular. y 2 . In this study.Ti y1 Ni À y1 Ti ( þ y2 y2 Ni Ti þy 1 Ti X i X i X À Ái À Ái LiNi. TEM images of the P-phase precipitates aged at 600 °C for 100 h.Ni y 1 À y 1 þ y 2 LiNiTi.Ti À Á þ RT y 1 ln y 1 þ y 1 ln y 1 þ y 1 lny 1 Ni Ni Pt Pt Ti Ti À 2 Á þ RT y Ni ln y 2 þ y 2 ln y 2 þ y 2 lny 2 Ni Pt Pt Ti Ti ( X X À Ái À Ái LiNiTi.NiTi y 2 À y 2 þ y 1 LiPt.y 2 Ni Pt Ti Ni Pt Ti ¼ y 1 y 2 G0 þ y 2 G0 þ y 2 G0 Ni Ni Ni.Ti)1(Ni.Ti y 1 À y 1 Ni Pt X i À ( þ y1 y1 y2 Ti Pt Ni þy 2 Ti X i X À Ái À Ái LiTiPt.PtTi y 2 À y 2 Pt Ti Pt Pt Ti Ái À y2 Ti ) i LiTi. especially the free energy of the B2 matrix phase in the case of NiTi based SMAs [9].PtTi À y2 Pt ð1Þ .PtTi y 2 À y 2 þ y 1 LiPt. y 2 . followed by descriptions of the phase ﬁeld model (Section 4).Ti À y1 Ni Ái À y1 Ti ) i ( þ y1 y1 y2 Ni Pt Ni þy 2 Ti X i X i X À Ái À Ái LiNiPt.NiPt y1 Ni À y2 Ni ( þ y2 y2 Pt Ti þy 1 Ti X i X i X À Ái À Ái LiNi. the assessment of the B2 phase chemical free energy is ﬁrst carried out via the CALPHAD method utilizing available experimental data from the literature [17–19].Ti)2: À Á GB2 y 1 . 2. Gao et al. Phase ﬁeld modeling and simulation have been used widely to treat both diﬀusional and displacive phase transformations.Ni Pt Ni. The major ﬁndings are summarized in Section 7. The concentration and stress ﬁelds surrounding a coherent precipitate are determined by the interplay between chemical free energy and coherency elastic strain energy. Because of the limited amount of thermodynamic data for the Ti–Ni–Pt ternary system. / Acta Materialia 60 (2012) 1514–1527 1515 Fig. as well as dislocation–precipitate interactions [7–16]. Interaction of the precipitates with dislocations and its eﬀects on transformation induced plasticity in the B2 matrix and on dimensional stability of the alloy will be reported in a separate paper.Pt y 1 À y 1 þ y1 y1 y2 Ni Ti Ni Ni Ti Pt Ni Ti i þy 2 Ti X i LiNiTi.Ti þ y 1 y 2 G0 þ y 2 G0 þ y 2 G0 Ti Ni Ti. In this study.Ti þ y 1 y 2 G0 þ y 2 G0 þ y 2 G0 Pt Ni Pt.Pt Ti Ti.Pt Ti Pt. the chemical free energy models for the matrix and precipitate phases in Ni–Pt–Ti are formulated based on existing thermodynamic databases [17–19].y 1 .Pt Ti Ni.NiPt y 2 À y 2 Ni Pt Pt Ni Pt Ái À y2 Pt ) i LiTi. thermodynamic modeling and transformation strain calculation are ﬁrst presented (Sections 2 and 3).Ni Pt Ti.Ni Pt Pt. The B2 phase in Ti–Ni–Pt can be described by a two-sublattice model (Ni.

Crystal structure of the P-phase and its orientation relationship with the B2 matrix The P-phase has a monoclinic crystal structure with ap = 0. y 2 and y 2 are the site fractions. y 1 . 4). y 2 . y 1 . 2. y 1 . According to the orientation relationship between the B2 phase and the P-phase observed in the experiment [2] 2 1 3 3 2 the (½1 0 0p ==½1 1 B2 . cp = 1.45 [2]. Ni Pt Ti Ni @y y 2 or y 2 ).422 nm and b = 100. bp = 1. The space group of the B2 structure and the monoclinic P-phase are Pm and C2/c. 1 2 3 4 5 6 7 8 9 10 11 12 a ½ 1 1 2 ½2 1 1 ½2 1 1 ½2 1 1 ½1 1 2 ½1 2 1 ½1 2 1 ½ 2 1 1 ½1 1 2 ½1 1 2 ½1 2 1 ½ 1 2 1 b ½0 3 3 ½0 3 3 ½0 3 3 ½0 3 3 ½ 0 3 3 ½ 0 3 3 ½3 0 3 ½3 0 3 ½3 0 3 ½3 0 3 ½3 3 0 ½3 3 0 c 3 3 ½2 ½2 3 3 ½2 3 3 ½2 3 3 ½ 3 2 3 ½ 2 3 3 ½ 2 3 3 ½32 3 ½332 ½ 2 33 ½3 3 2 ½3 2 3 aÂb ð1 1 1Þ ð1 1 1Þ ð1 1Þ 1 ð1 1 1Þ ð1 1 1Þ ð1 1Þ 1 ð 1 1Þ 1 ð1 1 1Þ ð1 1 1Þ ð1 1 1Þ ð 1 1Þ 1 ð1 1Þ 1 Fig. . The lattice parameter of the B2 matrix is aB2 = 0. The other terms are the excess Gibbs free energy that describes the interactions between atoms on the same sublattice. Ni Pt Ti Ni Pt Ti representing mole fractions of elements Ni. as in a regular solution model. which are one twofold rotation and its identity. four threefold (h1 1 1i). y 2 . The ﬁrst three terms in the expression describe the contributions from the Gibbs free energies of the so-called end member phases in which each sublattice is occupied by only one kind of species. (a) Non-periodical arrangement of the three variants of the monoclinic P-phase within a single P-phase particle. three variants stack into a layered structure along h1 1 1i (Fig. Variant no. there are only two rotation elements for the P-phase. and six twofold (h1 1 0i) rotation axes.21]. 3. The free energy model and the assessed paramPt Ti eters used in Eq. 2a) includes 96 atoms in 16 layers that are parallel to the (1 1 1) plane of the B2 matrix phase. (b) The arrangement of Pt atoms in the (0 0 1)P Pt rich planes. respec3m tively. This lattice correspondence is schemati3 3 2 cally shown in Fig. ½0 1 0p ! ½3 0B2 and 2 3 ½0 0 1p ! ½ B2 . [2]: ½1 0 0p ! ½1 1 B2 . Their intersection group contains two common symmetry elements and thus there are 12 crystallographic equivalent variants for the P-phase. The 16 Pt atoms form an ordered structure on the Ni sublattice and Ni substitutes for four sites (Wyckoﬀ notation 4e) on the Ti sublattice [2]. Each of these planes contain four Pt atoms and two Ni atoms [2]. Gao et al. where the high resolution STEM investigations have been carried Fig. (b) A monoclinic unit cell of the P-phase and its OR with the B2 parent phase [2]. Meanwhile. Pt and Ti on the two sublattices (the superscript) with 0:5y 1 þ 0:5y 2 ¼ xNi Ni Ni 0:5y 1 Pt y1 Ni y2 Ni þ þ þ y1 Pt y2 Pt 0:5y 2 Pt þ þ y1 Ti y2 Ti ¼ xPt ¼1 ¼1 0:5y 1 þ 0:5y 2 ¼ xTi Ti Ti ð2aÞ ð2bÞ ð2cÞ ð2dÞ ð2eÞ where x is the mole fraction of each species in the crystal. Table 1 Symmetry related orientation variants of the P-phase. 3. Each monoclinic unit cell of the Pphase (Fig. Rotations in the point group of B2 structure include three fourfold (h1 0 0i). (a) Ni sublattice (0 0 1)P planes in the P-phase (Ti sublattice planes are not included). 3. / Acta Materialia 60 (2012) 1514–1527 where y 1 . y 1 . ½0 1 0p ==½1 0B2 . which can be divided into four groups (see Table 1).745 nm. the phases must also be at internal equilibrium determined B2 by @G ¼ 0 for all site fractions (y = y 1 .1. totaling 24 elements combining with identity. (1) are given in Appendix A. At any given temperature and initial composition. 3.1516 Y. The fourth and ﬁfth term describe the contributions from mixing on each sublattice. It has been observed that within each group. which indicates an excess of Ni and a deﬁciency of Ti in the structure as compared to the B2 structure. Coherency of P-phase/B2 matrix interface It is diﬃcult to directly observe the structure of P-phase/ B2 matrix interfaces since at room temperature.2. ½0 0 1p ==½ B2 ).292 nm.3087 nm [2. following lattice correspondence has been proposed by Kovarik et al. Crystallography of B2 to P-phase transformation 3. The P-phase has a stoichiometry of Ti44Ni36Pt16.

e. The martensite adjacent to the P-phase particles is often not in an orientation suitable for high resolution imaging. ð3bÞ Fig. the matrix has already transformed to B19 martensitie. However. Thus. The SFTS of the coarse-grained P-phase particles can be calculated as: 2 3 0:9860 À0:0016 À0:0016 1 6 7 T ð111Þ ¼ ðT 1 þ T 5 þ T 9 Þ ¼ 4 À0:0016 0:9860 À0:0017 5 3 À0:0016 À0:0016 0:9806 ð5aÞ out. HAADF image of an interface between the P-phase precipitate (along a ½0 0 zone. Gao et al. In the image the precipitate is being viewed along the ½0 1 0 zone (i. 1 0 2 0 À3 6 7 ¼ Á 4 À3 5 À2 2 3 2 3 1 3 P P a 6 b 6 7 7 eP ¼ pﬃﬃﬃ 4 1 5. the stress-free transformation strain (SFTS) is calculated by averaging the three variants in a single P-phase particle. on occasion this is not the case. with each individual variant forming {1 1 1}B2 plates in a randomly layered structure. 3. as shown in the high angle annular dark ﬁeld (HAADF) image in Fig.e. STEM observations during in situ heating experiments above the Ms temperature are required in order to directly observe the precipitate/B2 matrix interfaces. The three variants are rotated 120° with respect to each other and have almost equal volume fraction. eP ¼ pﬃﬃﬃﬃﬃ 4 À3 5. In order to describe the lattice misﬁt between the precipitate and the matrix phases at the particle level. which is beyond the scope of this study. Calculation of stress-free transformation strain According to the lattice correspondence described above. the transformations of the three non-parallel lattice vectors during B2 to P-phase transition are calculated as: 2 3 2 3 1 3 6 7 6 7 eB2 ¼ aB2 Á 4 1 5. i. The continuity of lattice fringes from the martensite to the precipitate indicates that the precipitate is coherent with respect to the matrix. / Acta Materialia 60 (2012) 1514–1527 1517 will be inherited as the B2 matrix transforms to martensite. 4) [2]. coarsegraining the multi-layers into a homogenous structure as shown in Fig. a h1 1 0i orientation relative to the B2 matrix [2]). which corresponds to variant 9 in Table 1. 5. 4. 6. Based on these observations we assume in this study that the precipitate/B2 matrix interface is also fully coherent because if the interface contains misﬁt dislocations.Y.3. ði ¼ 1–3Þ as: i i 2 3 0:9860 À0:0005 0:0001 6 7 ð4Þ T 9 ¼ 4 À0:0005 0:9860 0:0001 5 À0:0047 À0:0047 0:9806 According to the experimental observations (Fig. which is equivalent to a h1 1 0i zone of the B2 matrix) 1 and the B19 martensite. High-angle annular dark ﬁeld image of the precipitate along the zone axis directions h1 1 2i [2]. which minimizes the strain energy because there is a small lattice mismatch between two adjacent variants [2]. This HAADF image was obtained with a FEI Titan 80–300 with Cs-correction on the electron probe. indicating that the interface between the precipitate and the martensite is fully coherent. can be calculated with constrains T 9 eB2 ¼ eP . one would expect that the dislocation content . 1 2 6 18 À2 0 2 pﬃﬃﬃﬃﬃ 3 À 11 cosðb À arcsin 2Þ 3 7 bP 6 pﬃﬃﬃﬃﬃ eP ¼ pﬃﬃﬃﬃﬃ 6 À 11 cosðb À arcsin 2Þ 7 2 4 3 5 22 pﬃﬃﬃﬃﬃ À 22 sinðb À arcsin 2Þ 3 aB2 0 2 À2 3 0 ð3aÞ eB2 3 Fig. all P-phase particles consist of three orientation variants belonging to the same group (Table 1). 5. eB2 ¼ aB2 Á 4 À3 5. the deformation gradient matrix. and operated at 300 kV. This same result has been obtained for other selected regions of particle/matrix interface that have been suitable for imaging. The key observation is that there are no interface or misﬁt dislocations present at the interface.

the SFTS ﬁeld is formulated as a function of both concentrations and structural order parameters: eT ðrÞ ¼ vB2 dij g1 ðxNi Þ þ vB2 dij g2 ðxPt Þ þ ij Ni Pt 4 X p¼1 eij ðpÞhðgp Þ ð9Þ where vB2 ¼ @aB2 a1 and vB2 ¼ @aB2 a1 are the lattice expanNi Pt @xNi B2 @xPt B2 sion coeﬃcients of the B2 phase. g3. the lattice expansion coeﬃcients can be determined as: vB2 ¼ À0:092.5Ti0. The two equilibrium free energy functions (Eqs. fgp . Ni xB2 ¼ 0:207 and xP ¼ 0:375. 0. 7. For an alloy of Ni0. which are close to Pt Ni Pt the equilibrium concentrations determined by experiment at 873 K [2]. Assuming that the lattice misﬁt between the two coexisting phases is associated with both chemical and structural non-uniformities. Correspondingly. dij is the Kronecker delta function.5. a set of four order parameters. Such a coarse-graining process reduces the 12 variants down to four.5Ti0. xP ¼ 0:167.1.3015 nm and 0. (7) and (8)) are plotted in Fig.5 are 0.1518 Y.3Pt0. / Acta Materialia 60 (2012) 1514–1527 eT ¼ ð111Þ T T T ð111Þ À I ð111Þ 2 2 À0:0157 6 ¼ 4 À0:0016 À0:0016 1 % ðe1 þ e5 þ e9 Þ 3 3 À0:0016 À0:0016 7 À0:0157 À0:0016 5 f ðxNi . 4. g4}. The initial composition Ni Pt Fig.5. Energy formulation According to Landau’s theory of phase transformations. the lattice constants for Ni0. and g1 and g2 are two hyperbolic tangent functions. which are used to describe the concentration dependence of the B2 lattice parameters: B2 Á 2 xNi À x0 À 0 Ni g1 ðxNi Þ ¼ B2 xNi À xNi tanh 2 xNi À x0 Ni B2 Á 2 xPt À x0 À 0 Pt xPt À xPt : tanh g2 ðxPt Þ ¼ B2 2 xPt À x0 Pt Based on theoretical calculations of the concentration dependence of the B2 lattice parameter [23. characterized by the SFTS given above.5Pt0. the equilibrium Ni and Pt concentrations determined by the common-tangent construction are xB2 ¼ 0:285. GB2 at 873 K is ﬁtted to available thermodynamic data (see Section 2) (in a unit of 106 J mol–1): GB2 ¼ 0:4493 À 2:2897xNi À 1:6992xPt þ 3:4637x2 Ni þ 1:0xNi xPt þ 3:1846x2 Pt ð7Þ and Gp could be approximated as a second order polynomial function of Ni and Pt concentrations [22]: Gp ¼ 0:4781 À 2:3586xNi À 1:0980xPt þ 3:0x2 þ 3:0x2 Ni Pt ð8Þ eT ð111Þ eT ð111Þ where T(111) is the averaged deformation gradient matrix for the three variants within the (1 1 1) group and e(111) is the averaged SFTS. which will be described in the next section. an interpolation function hðgi Þ ¼ g3 ð10 À 15gi þ 6g2 Þ is used i i to connect the equilibrium free energy functions of the two phases through the order parameters. 6. In addition. Vm is the molar volume and GB2 and Gp are the equilibrium Gibbs free energies of the B2 matrix and P-phase.5 and Pt0. Ni0. with {g1 = g2 = g3 = g4 = 0} representing the B2 phase and {gi = 1. I is the identity matrix. p ¼ 1–4gÞ " ¼V ð5bÞ À1 m GB2 ð1 À 4 X p¼1 hðgp ÞÞ þ Gp 4 X p¼1 # hðgp Þ ð6Þ eT ð111Þ À0:0016 À0:0157 2 3 À0:0157 0:0016 0:0016 1 6 7 ¼ ðe2 þ e7 þ e11 Þ ¼ 4 0:0016 À0:0157 À0:0016 5 3 0:0016 À0:0016 À0:0157 À0:0157 1 6 ¼ ðe3 þ e6 þ e12 Þ ¼ 4 0:0016 3 À0:0016 À0:0157 1 6 ¼ ðe4 þ e8 þ e10 Þ ¼ 4 À0:0016 3 0:0016 2 2 ð5cÞ 3 0:0016 À0:0016 7 À0:0157 0:0016 5 0:0016 À0:0016 À0:0157 0:0016 À0:0157 ð5dÞ 3 0:0016 7 0:0016 5 À0:0157 ð5eÞ where xNi and xPt are mole fractions of Ni and Pt respectively.2995 nm. g2. .24].2Ti0.3137 nm respectively. The ﬁnal form of the chemical free energy density in the phase ﬁeld model (in a unit of J m–3) can be expressed as: where the constants are determined by two conditions: (a) a common tangent plane going through the equilibrium B2 matrix concentration and the equilibrium P-phase concentration determined from experimental characterization. Gao et al. {g1. gj–i = 0} (where i = 1–4 and j = 1–4) representing the four coarse-grained P-phase variants. is introduced to characterize the B2 to P-phase transformation. xPt . (b) the curvature of the polynomial at the equilibrium concentration of the P-phase yielding the desired interfacial energy between the two phases for the gradient energy coeﬃcient chosen. Phase ﬁeld model 4. Schematic drawing of the coarse graining assumption. By linear interpolation. four order parameters instead of 12 are used in the phase ﬁeld simulations. vB2 ¼ À0:013.

Bpq ð~ can be expressed as: ( ~¼ 0 0 n Bpq ð~ ¼ nÞ ð12Þ p q C ijkl eij ðpÞekl ðqÞ À ni rij Xjk rkl nl ~ n–0 where XÀ1 ¼ C iklj nk nl . in Eq. 7. xPt . ~ and ~ is k. / Acta Materialia 60 (2012) 1514–1527 1519 (x0 ¼ 0:3.16. n a unit vector in the reciprocal space. Note that ~ ¼ 0 is to be k excluded from the integration. Fig. f~p gk is the Fourier transform of g g. jPt and jg are the gradient energy coeﬃcients respectively for the Ni and Pt concentrations and the order parameters.Y. The asterisk denotes a complex conjugate. Gibbs free energies for B2 phase and P-phase as functions of Ni. x0 ¼ 0:2) is chosen as a reference state for the Ni Pt strain calculations. eij(p). Kinetic equations The Cahn–Hilliard equation and the time-dependent Ginsburg–Landau (or Allen–Cahn equation) are used to describe the time evolution of the concentration and order parameter ﬁelds [9. which deﬁnes the principle value of the integral. rp ¼ C ijkl ekl ðpÞ ij ij After incorporating the gradient terms.q¼1 ð2pÞ3 where the integral is taken in the reciprocal space. The structural dependence of the SFTS.25]: & 1 @xNi ¼ r M Ni r V 2 @t m & 1 @xPt ¼ r M Pt r V 2 @t m @gp dF ¼ ÀL . the total free energy of the system becomes: Z h À Á jNi jPt 2 2 F ¼ d 3 r Á f xNi . (9) can be expressed as: eij ð1Þ ¼ eT À vB2 ½xP À x0 dij À vB2 ½xP À x0 dij ð111Þ Ni Ni Ni Pt Pt Pt 2 3 À0:0126 À0:0016 À0:0016 6 7 ¼ 4 À0:0016 À0:0126 À0:0016 5 À0:0016 eij ð2Þ ¼ À0:0126 6 ¼ 4 0:0016 0:0016 2 eT ð111Þ À À0:0016 À0:0126 À x0 dij À vB2 ½xP À x0 dij Ni Pt Pt Pt 3 0:0016 0:0016 7 À0:0126 À0:0016 5 À0:0016 À0:0126 vB2 ½xP Ni Ni nÞ a system having free external boundaries. ð10aÞ ð10bÞ eij ð3Þ ¼ eT À vB2 ½xP À x0 dij À vB2 ½xP À x0 dij Ni Ni Ni Pt Pt Pt ð111Þ 2 3 À0:0126 0:0016 À0:0016 6 7 ¼ 4 0:0016 À0:0126 0:0016 5 À0:0016 0:0016 À0:0126 eij ð4Þ ¼ eT À vB2 ½xP À x0 dij À vB2 ½xP À x0 dij Ni Ni Ni Pt Pt Pt ð111Þ 2 3 À0:0126 À0:0016 0:0016 6 7 ¼ 4 À0:0016 À0:0126 0:0016 5 0:0016 0:0016 À0:0126 ð10cÞ 4. Pt compositions in a NiTiPt ternary system. Gao et al. dgp @t !' dF dxNi !' dF dxPt ð10dÞ The total elastic energy can then be formulated following the Khachaturyan–Shatalov microelasticity theory [20]: 4 Z 1 X d 3k Eelastic ¼ Bpq ð~ gp gk f~q gÃ nÞf~ g k ð11Þ 2 p. Considering ð14Þ p ¼ 1–4 where MNi and MPt are the chemical mobilities of Ni and Pt. fgp g þ ðrxNi Þ þ ðrxPt Þ 2 2 # 4 X jg À Á2 rgp ð13Þ þ þ Eelastic 2 p¼1 where jNi.2. and L is the kinetic coeﬃcient characterizing time evolution of the order parameters. .

Since the stress components r13 and r23 are orders of magnitude smaller than the others. in particular along the elastically soft directions.2Ti0. Simulation results As discussed earlier. Note that the Gibbs–Thompson eﬀect. The maximum Pt concentration in the B2 matrix near a growing P-phase precipitate is monitored as a function of aging time (Fig.5 and Ni0. there are both compressive and tensile stresses around the particle and mostly tensile stresses inside the particle. The initial microstructure of the simulation consists of a supercritical particle of $10 nm diameter. 10c and d). Because the elastic constants of the B2 matrix phase have a Zener anisotropy factor (c11 À c12)/(2c44) = 2. they are not included in Fig. respectively [3. Signiﬁcant elastic eﬀects of P-phase precipitate on the martensitic transformation in the B2 matrix phase will be discussed below.3. the Ni and Pt concentrations in the B2 matrix become more Since the three principal SFTSs of a P-phase particle are all negative.29]. Based on experimental measurements. 9. the B2 matrix is depleted in Ni and enriched in Pt near a growing P-phase particle. As shown clearly in Fig.1.3Ti0. In this study the Langevin noise terms are used to generate microstructures consisting of multi-particles in the simulations [30]. However. interfaces between the B2 matrix and the P-phase precipitates are assumed to be fully coherent in this study. 5. concentration non-uniformity caused by the elastic interactions around an equilibrium precipitate.2. Because of the relatively small lattice mismatch between the precipitate and matrix phases.458 will leave the matrix with lower Ni and higher Pt concentrations.2Ti0. 10 and 11 may have a profound impact on the Ms temperature. This is caused by the elastic interaction between Ni atoms and the coherency stress associated with the precipitates. 10a and b). The location of the maximum Pt concentration is found to be near the corner of the cube-like precipitate.1.31. 5. 12 shows the variation of diﬀerent stress components around a P-phase particle. All dimensionless parameters used in the simulations are listed in Appendix B. Fig. higher Ni and Pt concentrations around a PPt phase particle. the Ms temperatures of non-aged Ni0. the predicted habit plane of the precipitate is {11. nearly parallel to {1 0 0}.27] or the explicit nucleation algorithm [28. preferred nucleation and growth along the elastically soft h1 0 0i directions [30]. a computation cell of 128l0 Â 128l0 Â 128l0 grids represents a physical system of edge length 216 nm.207 (given by the common-tangent construction of the free energy surfaces in Fig. $0. c12 = 146 GPa and c44 = 46 GPa [21]. 10c. will change the equilibrium Pt concentration from 0. 1.5.5. 5. Concentration ﬁeld around a P-phase particle The equal-concentration contours around a P-phase particle (on a (0 0 1) center cross-section) obtained from the phase ﬁeld simulation are shown in Fig. the Ms temperature increases almost linearly with Pt concentration [33]. 10a and b. 6. Discussion 6. Equilibrium shape of a P-phase precipitate The equilibrium shape of an isolated P-phase precipitate obtained from the simulation is shown in Fig. An example is shown in Fig. noticeable Ni concentration non-uniformity exists as shown in Fig.1 at. Since the principal SFTSs of the P-phase are all negative and the lattice expansion coeﬃcients of the B2 phase are vB2 ¼ À0:092 and Ni vB2 ¼ À0:013. It can be seen that the precipitate has a slightly distorted cube shape with smoothly curved edges and corners. 7) to 0. and the three normal strains (the diagonal terms) in the transformation strain tensor are equal and far greater than the shear components (oﬀ diagonal terms). Thus.2067.3Pt0. are expected as compared to the equilibrium concentrations of the B2 phase predicted by the thermodynamic database. i. the precipitation of P-phase particles that have a composition of Ni0. Comparing to the initial composition of Ni0.2Pt0.4.001% for Pt.32]. which yields a grid size of l0 = 1. the interfacial energy is assumed to be 200 mJ m–2. 8.01% for Ni and 60. As one can see from Fig. 11). When the particle reaches its equilibrium volume fraction. 11. Stress ﬁeld around a P-phase particle In phase ﬁeld simulations. Because of the presence of the shear components in the SFTS.3Pt0. 5.e. Gao et al.1. and slowly approaches the equilibrium concentration. 12. Eﬀect of Pt concentration in B2 on martensitic transformation The change of concentration in the B2 matrix caused by P-phase precipitation (which depletes Ni while enriching Pt in the matrix) shown in Figs.1}. nucleation can be simulated by using either the Langevin noise terms [26. 10. Within this temperature range.167Ti0. The elastic constants used in the simulations for the B2 Ni30Pt20Ti50 are: c11 = 183 GPa.375Pt0. as the elastic soft directions lie along h1 0 0i. Multi-particle correlation or less uniform (Fig.% diﬀerence in Pt concentration . Correspondingly. Both the shape and spatial alignment of the precipitates predicted by the simulations agree well with the TEM images of the P-phase precipitates shown in Fig. The spatial alignment is caused by elastic interactions among the precipitates during nucleation and growth. are negligible as compared to Ni depletion and Pt enrichment in the matrix associated with precipitate nucleation and growth (Fig.5 are 259 °C and 530 °C. / Acta Materialia 60 (2012) 1514–1527 5. the habit plane normal deviates from that of {1 0 0} by $7°. the maximum Pt concentration in the B2 matrix increases with aging time with a decreasing rate.687 nm in the phase ﬁeld simulations.1520 Y. under the assumption of a spherical particle with similar size. Thus a 0.

Multi-particle simulation results generated by Langevin noise induced nucleation in an initially supersaturated matrix. Three-dimensional views of the equilibrium shape of a P-phase particle (variant 1) obtained by the phase ﬁeld simulation. (d) Pt contour around an equilibrium precipitate. (a) Ni contour around a growing precipitate. Gao et al. / Acta Materialia 60 (2012) 1514–1527 1521 Fig. Fig. 9. 8. 10. Concentration ﬁelds (in atomic fractions) around a P-phase particle along its central (1 0 0) cross-section. (c) Ni contour around an equilibrium precipitate.Y. (b) Pt contour around a growing precipitate. . Fig.

41]: ½1 0 0B19 ! ½0 B2 . ½0 0 1B19 ! ½1 0 0B2 . the stress ﬁeld associated with the coherent P-phase precipitates may aﬀect the martensitic transformation of the B2 matrix phase as well [9. Based on ab initio calculations [21] of the formation energy of B2 and B19 in (Ni.33. As a result.43].138 J mm–3 or À1. Comparing with the chemical driving force for B2 to B19 transformation. Eﬀect of aging on Ms temperature As compared to the Ni–Ti binary system where the eﬀects of Ni4Ti3 precipitates on martensitic transformations have been investigated extensively [9. As a result. ½0 1 0B19 1 1 ! ½0 1 1B2 . e ð4Þ ¼ 4 0:0313 0:0507 5.201 0. Eﬀect of stress ﬁelds on martensitic transformation Like any other stress-carrying defects such as dislocations.% Pt is estimated to be $278 °C. 13. the ternary element addition oﬀers the opportunity to alter the type. shape. 3 where M new is the martensitic transformation start tempers ature with pre-existing P-phase particles. The lattice correspondence between the B2 and B19 phases has been proposed as the following [33. 6. critical nucleus conﬁguration and activation energy are underway.202 0. / Acta Materialia 60 (2012) 1514–1527 0. e ð2Þ ¼ 4 3 2 0:0507 0 0:0313 0 À0:1014 0 0:0313 0 0:0507 0 3 7 5. since internally twinned martensitic plates are usually formed in shape memory alloys.2 0 500 1000 1500 2000 2500 3000 3500 4000 reduced time Fig. The locations with the most negative interaction energy ($À0. the change of Ms temperature by the elastic interaction of a martensite nucleus with an existing P-phase particle can be estimated using the data of Ms (532 K) and As (511 K) from experimental measurements [3]: þA T 0 ¼ M s 2 s ¼ 522 K maximum Pt concentration DS ¼ DH ¼ À0:0115 kJ=ðK molÞ T0 À1:22 T new ¼ DHDS ¼ 627K 0 M new % M s þ ðT new À T 0 Þ ¼ 637 K s 0 ð17Þ where rij is the stress ﬁeld generated by the coherent Pphase precipitates and eM ðpÞ is the SFTS of martensitic varij iant p.3Pt0. The lattice parameters of the B19 martensitic phases from experimental measurement and ab initio calculations [4. Considering the relative contributions from the chemical non-uniformity and stress ﬁeld associated with P-phase precipitation.7 at. the SFTS can be calculated as: 2 6 eM ð1Þ ¼ 4 2 0:0507 0 À0:0313 0 À0:1014 0 À0:0313 0 0:0507 0 0 3 2 7 M 6 5. respectively. 11.204 0. could lead to a 2.21] are aB19 = 0.444 nm and cB19 = 0. at which temperature the driving force of the martensitic transformation is zero. the enthalpy change of B2 to B19 transformation in Ni0.34–40]. 7 M 7 6 0 5. spatial distribution and stress state of precipitates and hence their eﬀects on the strength of the B2 matrix and the behavior of the martensitic transformation. Since the space groups of B2 and B19 are Pm and 3m Pmma. To investigate this eﬀect.7 °C change in Ms temperature.207 Y. By assuming that both enthalpy change DH and entropy change DS do not depend on temperature and the increase in Ms is the same as that in T0. 6. the most favorable nucleation site for the martensitic phase should be located somewhere near the edge center of the cuboidal P-phase particle. The Ms temperature could increase as much as 100 K.44. Simulation results of maximum Pt concentration around a Pphase particle during growth. the elastic interaction energy between the P-phase precipitate and a nucleating martensitic particle is calculated according to the following equation: Eint ¼ Àrij eM ðpÞ ij ð15Þ The calculation results of the interaction energy are plotted in Fig.Pt)Ti system.206 0. Gao et al. bB19 = 0. there are three twofold rotation axes and identity elements in the intersection group. it is expected that internally twinned martensitic particles consisting of large fractions of the most favored variant will develop via an autocatalytic eﬀect [42.275 nm.3. As a result. the coherency stress of P-phase precipitates could make a major contribution to the driving force for the B2 to B19 martensitic transformation. A negative value of the interaction energy means that the formation of martensite is favored by the presence of the P-phase precipitates. 13 it is seen that the edges of the cube-like shaped particle are the most preferred sites for martensite nucleation and diﬀerent martensitic variants (indicated by diﬀerent colors online) are favored at diﬀerent edges. 0 0 À0:1014 0 0 À0:1014 3 3 2 2 À0:1014 0 0 À0:1014 0 0 7 M 7 6 6 M e ð5Þ ¼ 4 0 0:0507 À0:0313 5.2Ti0.22 kJ mol–1) are near the edges of a cube-like shaped precipitate with edge length of $116 nm.1522 0.2. six orientation variants of the martenstic phase can be generated after the transition. e ð6Þ ¼ 4 0 0:0507 0:0313 5: 0 À0:0313 0:0507 0 0:0313 0:0507 6 eM ð3Þ ¼ 4 À0:0313 0:0507 0:0507 À0:0313 0:0507 0:0313 ð16Þ . As a result. However.5 at 0 K is DH = À6 kJ molÀ1. the Ms temperature for a B2 matrix with 20.203 0. From Fig.470 nm. the maximum elastic interaction energy is nearly one-ﬁfth of DH.205 0.45]. Corresponding NEB calculations [42] for determining the nucleation site.

Based on the calculated Pt concentration (Fig. 11. As shown in Fig. axis 2 is along [0 1 0]B2 and axis-3 is along [0 0 1]B2. their elastic interaction energy (magnitude) with martensite nuclei increases sharply at the beginning and then continues to increase but at a much slower rate. 13. As the P-phase particles grow. Meanwhile. the Pt concentration in the B2 matrix increases monotonically as the precipitates grow. Gao et al. 14. 15 and 16.2% fraction of the matrix phase with the lowest elastic interaction energy has been monitored in our simulation and its cut-oﬀ energy is used in the corresponding Ms temperature calculations. 11) and elastic interaction energy (Fig. As shown in Fig.886 kJ mol–1) between a P-phase precipitate and martensite nucleus. Fig. The above simulation results and analysis could provide some insight into the physical origin of such a dependence of Ms on aging time.3Pt0. Three-dimensional elastic interaction energy iso-surface (À0.2% (volume fraction) martensite is usually deﬁned as the incubation period [46.1 J mm–3 or –0.5 alloy has a strong and highly non-linear dependence on the aging time. (b) r22. the Ms temperature of Ti–Ni–Pt alloys increases signiﬁcantly with aging time. Axis 1 is along [1 0 0]B2. respectively. reaching a maximum when the precipitate phase reaches its equilibrium volume fraction. (c) r33 and (d) r12.Y.47]. as the formation of 0. where the change of the cut-oﬀ elastic interaction energy in the B2 matrix phase is plotted as a function of particle volume and aging time.2Ti0. Stress ﬁelds around a P-phase particle: (a) r11. / Acta Materialia 60 (2012) 1514–1527 1523 Fig. 12. the change . the 0. the Ms temperature for a nominal Ni0. The phase ﬁeld simulation results show that both the chemical non-uniformity (enrichment in Pt) and elastic stress ﬁeld in the B2 matrix generated by P-phase precipitation alter the driving force for the martensitic transformation and hence alter the Ms temperature. 16) around a growing P-phase particle as a function of aging time. From experimental observations. as shown in Figs. with a sharp increase at the initial stage of aging.

by the phase ﬁeld simulation agrees well with the experimental measurement. 17. This could be due to the fact that the data used for elastic constants and transformation enthalpy are obtained from ab initio calculations at 0 K. However. 14. The ab initio calculations were performed using the full-potential linearized augmented plane wave method (FLAPW) [49] and converged with respect to both k-point mesh and repeatedcell size. a jump in Ms was also observed and Ms was found to increase with aging temperature within a certain temperature range [44].4. Fig. a homogeneous modulus approximation is used in our simulations for simplicity. Change of Ms temperature as a function of reduced time estimated from phase ﬁeld simulation results. C12 = 129 GPa. Comparing to the elastic constants of NiTi binary alloy measured from experiments at room temperature (C11 = 162 GPa. Comparing the magnitudes of the Ms changes. Since the Ms temperature is much higher than room temperature. C44 = 34 GPa) [48]. 6. / Acta Materialia 60 (2012) 1514–1527 change of Ms temperature (K) 120 100 80 60 40 20 0 0 500 1000 1500 2000 2500 3000 3500 reduced time Fig. 14. This also indicates that the elastic interaction between the P-phase precipitates and martensitic nuclei may dominate the aging eﬀect on Ms in this ternary alloy system. it is readily seen that the general trend of Ms variation with aging time predicted As mentioned above. Simulation results of the lowest interaction energies around a particle with diﬀerent volume. the calculations slightly overestimate the aging eﬀect primarily at the earliest time increments.44]. This will lead to an overestimation of the elastic interaction energy.1524 Y. when coherent Ni4Ti3 particles start to precipitate out. However. 17 with Fig. Simulation results of the lowest interaction energy around a Pphase particle as a function of reduced aging time. 15. Gao et al. 16. 17. the elastic moduli may further soften at the transformation temperature. A system size of 16 atoms was found to be suﬃcient in determining the elastic properties. . which is a rough approximation for the actual values at the aging temperature. the time scale of our phase ﬁeld simulations is in a reduced unit. Since the diﬀusivity data for this ternary system are not available. For example. Therefore. The eﬀects of the P-phase precipitates on the martensitic transformation found in this ternary alloy are similar to that found in the NiTi binary system [9. The result is plotted in Fig. only qualitative comparison with the experimental results can be made. By comparing Fig. the elastic constants calculated at 0 K are already signiﬁcantly higher. of Ms temperature can be determined. which assumes both the parent and product phases have the same elastic constants. based on the ab initio calculation results listed in Table 2 [21]. Experimental result of the eﬀect of aging time at 500 °C on the Ms temperature of a nominal Ni30Pt20Ti50 alloy. the C11 of the B2 and B19 phases in Ni31Pt19Ti50 are signiﬁcantly diﬀerent. Limitations of the model Fig. Fig.

Stress ﬁelds (r11 ) around a P-phase particle calculated using (a) an averaged stress-free transformation strain (SFTS) and (b) SFTSs of individual variants having a laminate structure. 18.Pt) ternary high temperature shape memory alloys is developed. In future work. The dilatational components of the stress-free transformation strain (SFTS) of the Pphase precipitates are found to be À1. Under the assumption of isotropic interfacial energy. The results show similar stress ﬁeld distributions around the P-phase precipitate in the two cases. The predicted particle shape and spatial alignment agree well with experimental observations. ab initio calculations and thermodynamic databases.Y.6. / Acta Materialia 60 (2012) 1514–1527 Table 2 Elastic constants of NiTiPt (GPa) [21]. Gao et al. This is indeed the case in the recently developed high temperature shape memory alloy NiTiPt [3.16%.22 kJ mol–1 to the driving force for the B2 to B19 transformation. precipitate–matrix orientation relationship. the enrichment in Pt and depletion in Ni in the B2 matrix could lead to an increase in the Ms temperature up to $19 °C. . Fig.4 nm and the typical dimension of the P-phase particles ($200 nm) far exceeds the layer thickness. Considering both the chemical and mechanical eﬀects analyzed above. ﬁne coherent precipitates could be utilized in practice as an eﬃcient way of increasing the Ms temperature in shape memory alloys. It is shown that the elastic interaction could contribute as much as 1. The concentration non-uniformity around both a growing precipitate and an equilibrium one has been determined quantitatively. However. To document the eﬀect of such coarse-graining in SFTS calculations on the coherency stress ﬁeld around a precipitate. and may also have relevance for NiTi with ternary additions of Pd and Hf [5. which may be responsible for the experimentally observed sharp increase in Ms temperature at the initial stage of aging.4]. including elastic modulus inhomogeneity. parallel simulations have been carried out using respectively the averaged SFTS of three variants and the individual SFTS of the three variants in a layered structure (Fig. a coarse-graining assumption has been made in which the SFTSs of three monoclinic variants are averaged. the variation of Ms temperature during aging is obtained. a more accurate model [50–52]. NiTi-B2 C11 C12 C44 183 146 46 Ni31Pt19Ti50-B2 167 168 53 Ni31Pt19Ti50-B19 242 163 51 1525 the ground state C0 elastic constant of the B2 structure was found to be unstable while the B19 structure exhibited comparable elastic constants to that of the binary alloy. It is found that the magnitude of the elastic interaction energy between the ﬁne P-phase precipitates and martensite nucleus increases sharply at early stages of precipitation. then the coarse-graining may result in larger errors. The major model inputs such as lattice param- eters.53–55]. the simulation results show that the Pphase particles have slightly distorted cuboidal shapes and are aligned along the elastically soft h1 0 0i directions. In the present calculation of the SFTS for the P-phase. if the particle size is comparable to the layer thickness. elastic constants and free energy data are determined based on experimental characterization. Considering the fact that the layer thickness in the P-phase particle is only $1. 18). Around a growing P-phase particle. The coherency stress ﬁelds caused by the P-phase precipitates are calculated and their eﬀects on the B2 to B19 martensitic transformation are investigated by calculating the elastic interaction energy between a B19 martensite nucleus and the existing P-phase precipitates. Summary A phase ﬁeld model that describes P-phase precipitation in Ti(Ni. by which the Ms temperature could increase as much as 100 °C. the eﬀect of such coarse-graining may be neglected.57% and the shear components to be 0. will be applied to calculate the stress ﬁeld provided that the elastic constants of both B2 phase and P-phase at high temperature are known. 7. In conclusion. Slight diﬀerences can be seen near the P-phase interface which is due to the laminate structure.

In: Berg B. J Alloys Compd 2008.NiPt ¼ À45000 L0 Pt. Simulation of microstructural evolution using the ﬁeld method. New York: Wiley-Interscience. 2005.32:113. Lerch B. et al. [19] Lu XG. Su CC. 1983. Mosca H. Intermetallics 2008.59:3484.Ni ¼ 23000 L0 Ni. [23] Che XL. IFES 2010 . Garg A. 2010. Chen LQ. [18] Mei Li.32:163. 2010. [10] Boettinger WJ et al. Dimensionless parameters used in simulations GB2 ¼ 0:8986 À 4:5794xNi À 3:3984xPt þ 6:9273x2 þ 2:0xNi xPt Ni þ6:3692x2 Pt Gp ¼ 0:9561 À 4:7172xNi À 2:1960xPt þ 6:0x2 þ 6:0x2 Ni Pt . [22] Hu SY. Sundman B. T À 0:00732367T À 2:0138 Â 10À8 T 3 þ 7974T À1 ¼ À71442:08 þ 257:929208T À 46:0893T ln T À 0:009618675T 2 þ 1:06716 Â 10À7 T 3 þ 72636T À1 G0 ¼ À89500:675 þ 129:232248T À 26:1361T Ti. G0 ¼ 16645:85 þ 228:596T À 44:192T ln T À 0:0096814T 2 Ni. Proft J. p. Murray J. Khachaturyan AG. Li J. Penney N. Acta Mater 2010. API). Mitchell MR.Ni G0 Pt. [14] Zhou N. Shen C. vol. Mitchell MR. 298 K < T < 1728 K) below. et al. Free energy model and parameters of the B2 phase in Ti–Ni–Pt The assessed parameters are as listed (unit: J mol–1. [16] Cahn JW.16:668. Eggeler G.Ti G0 ¼ 9961:694 þ 236:286276T Pt. Annu Rev Mater Res 2002. 2000. Oﬃce of Basic Energy Sciences under grant DE-SC0001258 (YG.Pt ¼ 26256:138 þ 243:976552T À 49:1052T ln T À 0:00496494T 2 À 4:0276 Â 10À8 T 3 þ 15948T À1 G0 ¼ 23195:712 þ 2:197944T À 3:167T ln T þ 0:00822826T 2 Ti. et al.461:189. Wang Y. Li J. Acta Mater 2010. et al.PtTi ¼ À34:135:1 þ 24:302T L0 NiTi. Hornbuckle BC. 2008. Wang HY. Freeman AJ. Acta Mater 2010. SMST 2010: proceedings of the international conference on shape memory and superelastic technology. Chen LQ. J Chem Phys 1958. 2009.Pt T À 0:00732367T 2 À 2:0138 Â 10À8 T 3 þ 7974T À1 G0 ¼ À71442:08 þ 257:929208T À 46:0893T ln Ni. In: ESOMAT 2009: proceedings of the 8th European symposium on martensitic transformations. editors. Padula II S. Sci China Ser E – Technol Sci 2009.Ti ¼ À125052:7 þ 39:631T Appendix B. In: Armstrong WD. [8] Wang YZ.32:268. Calphad. Wollants P. In: Grummon DS. [15] Zhou N. et al. et al. et al. [6] Bigelow GS. Hillard J. et al. [25] Wang Y.58:4660. Mertmann M. Weiland H. Noebe RD. Scripta Mater 2011. 5761. et al. Prague: EDP Science.NiTi ¼ 23000 L0 Ni. Comput Coupl Phase Diagrams Thermochem 2007. Garg A. Garg A.52nd International Field Emission Symposium. Mills MJ. [2] Kovarik L.64:725. editors.PtTi ¼ À34135:1 þ 24:302T L0 Ti. [13] Steinbach I. Gaydosh D. del Grosso M.Ti T À 0:009618675T 2 þ 1:06716 Â 10À7 T 3 þ 72636T À1 G0 ¼ 63428:5 þ 13:001T Pt. Blanpain B. Nathal M. Biles T. Australia: Imaging & Microscopy. Annu Rev Mater Res 2002. et al.Ti ¼ 100000 L0 PtTi. Acta Mater 2011. Kaufman M. Li JH. Thompson GB. Materials Park (OH): ASM International. Wollants P. FY and MJM). Bellingham (WA): SPIE.28:258. Shen C. et al. Gao et al. New York: Springer.55:5369. [3] Noebe R.Ni À 46:6486T ln jNi ¼ 20 jPt ¼ 20 jg ¼ 0:2 c11 ¼ 91:084 c12 ¼ 72:668 c44 ¼ 22:895 V 2 Á M Ni ¼ 1:0 m V 2 Á M Pt ¼ 1:0 m L ¼ 5:0 References [1] Ronald Noebe. Yang F.NiTi ¼ À45000 L0 Ti. Glen Bigelow. Garg A.17:073001. Sydney. et al. New York: Wiley. Mills MJ. Wang Y. editor. J Am Ceram Soc 1995. Changrong L. [17] Bellen P. Gaydosh D. Mills MJ.Pt ln T þ 0:00163116T 2 À 2:0138 Â 10À8 T 3 þ 7974T À1 L0 NiTi. [21] Hatcher N. Z Metall 1996. Agren J. Appendix A.Pt ¼ À125052:7 þ 39:631T L0 Pt. et al. 409. Supersonics Project (Dale Hopkins. Kontsevoi OY. et al. Padula SA. [7] Wang YZ. [26] Wang Y. et al. / Acta Materialia 60 (2012) 1514–1527 Acknowledgements This work was supported by the NASA Fundamental Aeronautics Program. Acta Mater 2007. et al. Darrell Gaydosh et al. Wang Y. Diercks D. Calphad – Comput Coupl Phase Diagrams Thermochem 2009. Banerjee D. Smart structures and materials 2005: active materials: behavior and mechanics. Paciﬁc Grove. Dai Y. NSF under grant DMR1008349 (YW) and US Department of Energy. [9] Zhou N. [20] Khachaturyan AG. Wagner M. SPIE proceedings.33:450. [24] Bozzolo G.78:657.58:1212.NiTi ¼ 100000 L0 PtTi. Acta Mater 1998. [4] Noebe R. Weaver ML. SMST 2006: proceedings of the international conference on shape memory and superelastic technologies. et al.87:972. [11] Chen LQ. Theory of structural transformations in solids. Hana Wei. Modell Simul Mater Sci Eng 2009.1526 Y.Ni ¼ À103000 þ 32T L1 NiTi. [12] Moelans N. Noebe RD. Shen C.NiTi ¼ À103000 þ 32T L1 Ni.Ti G0 ¼ 9961:694 þ 236:286276T À 46:6486T ln Ni.58:6685.46:2983. Draper S. California.52:2681. Kumar KCH.31:303.Ni 2 G0 Ti.Comput Coupl Phase Diagrams Thermochem 2008. [5] Sasaki TT.

Hagi J. [47] Shih CH. J Appl Phys 2002. et al.50:511. Wang Y. [30] Wang Y. Metall Mater Trans B 1971. et al. Li Z. 2005. [54] Shimizu S. Fundamentals of modeling for materials processing.438:666. [38] Tirry W. Chumlyakov YI. J Eng Mater Technol – Trans ASME 1999. [31] Rios O. et al. Otsuka K. Prog Mater Sci 2005. Zhao LC. Melton KN. Padula SA.365:136. vol. ASM handbook. [53] Bigelow GS. J Metals Trans AIME 1955. [51] Shen Y.24:864. et al. Ma X. Khachaturyan AG. Li J.203:709. Bellingham (WA): SPIE. Okunishi E. [34] Khalil-Allaﬁ J.51:1833.39A:976. Scheiman D. Maier HJ. [35] Gall K. Zhang XP. Mills MJ. Smart structures and materials 2005: active materials: behavior and mechanics.2:307. Li Y. vol. Acta Mater Sin 2010. [52] Zhou N. 22A. Acta Mater 2002. Mitose K. Li L.92:1351. [42] Shen C. [44] Zheng Y.59:3287. [32] Zarinejad M. [49] Wimmer E. Khachaturyan AG. [45] Guo W et al. [48] Mercier O. Garg A. Sehitoglu H. et al. Acta Mater 2005.60:901. Cohen M.65:74. [37] Tirry W. et al. editors. J Appl Phys 1980. Schryvers D. et al. et al. Eggeler G. / Acta Materialia 60 (2012) 1514–1527 [27] Shen C. Zheng YF. Palczer A.121:19. Ackland GJ. Dlouhy A. Garg A. in: Furrer DU. Tanaka S. Acta Mater 2008:56. Sehitoglu H. Kireeva IV. et al. J Eng Mater Technol – Trans ASME 1999. [29] Simmons JP. Gao et al. . Acta Mater 2008. Cai W. Wang Y. Metall Mater Trans A 2010.2:2395. [55] Meng XL. [46] Entwisle AR. Zheng YF.736. Khachaturyan AG. Jin YM. et al.46:921. et al. Scripta Mater 2009.53:1041. Mater Sci Eng – Struct Mater Prop Microstruct Process 2006. Mater Sci Eng A – Struct Mater Prop Microstruct Process 2006. Mater Lett 1998. Jiang F. Liu Y. Ren X.Y.43:935. Metall Mater Trans A 2008. Phys Rev B 1981. et al. Krakauer H. [50] Wang YU. Weinert M. Materials Park (OH): ASM International. Tong Y. et al. Chumlyakov YI. editor.438:55. Biles T. 1527 [41] Huang XY.121:28. Liu Y. et al. Noebe R. [40] Wang QY. Wang Y. Shen C. In: Armstrong WD. 2010. Shen C. Mater Sci Eng A 2004. [36] Gall K. Intermetallics 2009.34:23.8:752. SPIE proceedings. Nat Mater 2009. Scripta Mater 2000. Maier HJ.41A:3065. Kireeva IV. et al. Wen YH. [39] Ke C. Xu Y. Shen C. Rabe KM. Gremaud G. Semiatin SL.72:1161. Averbach BL. et al. Acta Mater 2011. 5761. Schryvers D. Nat Mater 2003. Wang Y. [33] Otsuka K.50:4255. Mater Lett 2011.17:914.56:6156. et al. [28] Simmons JP. Philos Mag A 1995. [43] Wang Y.

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