Metal Matrix Composites Focus On Alloys and Lattice Dynamics - Suzanne N. Fitzgerald

MATERIALS SCIENCE AND TECHNOLOGIES
METAL MATRIX COMPOSITES
FOCUS ON ALLOYS AND LATTICE

DYNAMICS
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MATERIALS SCIENCE AND TECHNOLOGIES
METAL MATRIX COMPOSITES
FOCUS ON ALLOYS AND LATTICE

DYNAMICS
SUZANNE N. FITZGERALD
EDITOR
Nova Science Publishers, Inc.

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Library of Congress Cataloging-in-Publication Data

Metal matrix composites : focus on alloys and lattice dynamics / editor, Suzanne N. Fitzgerald.
p. cm.
Includes bibliographical references and index.
ISBN: (eBook) Metallic composites. I. Fitzgerald, Suzanne N.
TA481.M4465 2011
620.1'6--dc23
2011012844
Published by Nova Science Publishers, Inc. †New York

CONTENTS
Preface vii
Chapter 1 Generation and Validation of Failure Assessment
Diagrams for High Strength Alloys Utilizing
the Inherent Flaw Model 1
S. Rajakumar and T. Christopher
Chapter 2 Effect of Applied Load on the Characteristics of Reversible
Martensitic Transformation during Thermal Cycling
Treatment of a Monocrystalline Cu-13.5Al-4Ni Alloy 19
E. C. Pereira, L. A. Matlakhova, A. N. Matlakhov,
S. N. Monteiro and R. J. S. Rodríguez
Chapter 3 Lattice Dynamics of Equiatomic Alkali Binary Alloys 47
Aditya M. Vora
Chapter 4 Lattice Dynamics of Liquid Alloys 71
Aditya M. Vora
Chapter 5 Lattice Dynamics of Liquid Metals 89
Aditya M. Vora
Chapter 6 Lattice Dynamics of Solid Metallic Elements 103
Aditya M. Vora
Index 123
PREFACE
This book presents current research in the study of metal matrix

composites, with a particular focus on alloys and lattice dynamics. Topics
discussed include lattice dynamics of equiatomic alkali binary alloys and
liquid alloys; lattice dynamics of liquid alloys, liquid metals and solid metallic
elements; generation and validation of failure assessment diagrams for high
strength alloys utilizing the inherent flaw model and the effect of applied load
on the characteristics of reversible martensitic transformation during thermal
cycling treatment of a monocrystalline Cu-13.5Al-4Ni alloy.
Chapter 1 - Modifications are made in the inherent flaw model of
Waddoups, Eisenman and Kaminski (known as the WEK model) to improve
fracture strength evaluation of cracked bodies. A relation is proposed for the
generation of failure assessment diagram and validated by comparing with the
test data of different high strength alloys.
Chapter 2 - The changes in the characteristics of the reversible martensitic
transformation (RMT), caused by different applied loads during thermal
cycling treatments under load (TCL) were investigated in a monocrystalline
Cu-13.5wt.%Al-4.0wt.%Ni alloy. The TCL was performed by an
accumulation of 300 cycles in the temperature interval between 0 oC (shortly
below the Mf) and 90 oC (just above Af). These treatments were conducted
both load-free and under three different applied load of 0.1, 0.2 and 0.5 kg,
corresponding to 0.056, 0.112 and 0.280 MPa, respectively. After each distinct
treatment condition, the alloy specimen was characterized by X-ray
diffraction, optical microscopy, differential calorimetry and microhardness. It
was found that the TCL promotes significant changes that are related to the
resulting structures and characteristics of the RMT. An increase in the applied
load causes a sensible decrease in the critical temperature interval associated
viii Suzanne N. Fitzgerald
with the RMT. Moreover, a decrease in both, the thermal hysteresis and the
enthalpy, as well as an increase in the microhardness were also observed with
applied load. This behavior is not only a consequence of a decrease in the
martensitic variants but also related to the greater stability of an intermediate
state, which facilitates the transformation mechanism.
Chapter 3 - The computations of the lattice dynamics of equiatomic alkali
binary alloys to second order in local model potential is discussed in terms of
real-space sum of Born von Karman central force constants. The local field
correlation functions due to Hartree (H) and Ichimaru-Utsumi (IU) are used to
investigate influence of the screening effects on the aforesaid properties.
Results for the lattice constants i.e. C11 , C12 , C 44 , C12  C44 , C12 C44 and
bulk modulus B obtained using the H-local field correction function have
higher values in comparison with the results obtained for the same properties
using IU local field correction function. The results for the Shear modulus (
C  ), deviation from Cauchy‟s relation, Poisson‟s ratio  , Young modulus
Y , propagation velocity of elastic waves, phonon dispersion curves and
degree of anisotropy A are highly appreciable for equiatomic alkali binary
alloys.
Chapter 4 - In the present chapter, the lattice dynamical properties of some
equiatomic liquid alkali binary alloys are reported in second order approach
through the equation given by Hubbard and Beeby (HB). The pair correlation
function is directly computed from the interatomic pair potential, which
is used in the present computation. Two different forms of local field
correction functions proposed by Hartree (H) and Ichimaru-Utsumi (IU) are
used in the present study the screening dependence of the phonon frequencies
in the equiatomic liquid alkali binary alloys. Thermodynamic and elastic
properties of equiatomic liquid alkali binary alloys are reported from the long
wave length limits of the phonon dispersion curves (PDC). The pseudo-alloy-
atom (PAA) model is applied for the first time for the alloying elements.
Chapter 5 - In the present chapter, the lattice dynamical properties of some
alkali metals are reported in second order approach through the equation given
by Hubbard and Beeby (HB). The pair correlation function is directly
computed from the interatomic pair potential, which is used in the present
computation. Two different forms of local field correction functions proposed
by Hartree (H) and Ichimaru-Utsumi (IU) are used in the present study the
screening dependence of the phonon frequencies in the metallic elements.
Preface ix
Thermodynamic and elastic properties of alkali metals are reported from the
long wave length limits of the phonon dispersion curves (PDC).
Chapter 6 - The computations of the lattice dynamics of solid metallic
elements to second order in local model potential is discussed in terms of real-
space sum of Born von Karman central force constants. The local field
correlation functions due to Hartree (H) and Ichimaru-Utsumi (IU) are used to
investigate influence of the screening effects on the aforesaid properties.
Results for the lattice constants i.e. C11 , C12 , C 44 , C12  C44 , C12 C44 and
bulk modulus B obtained using the H-local field correction function have
higher values in comparison with the results obtained for the same properties
using IU local field correction function. The results for the Shear modulus
( C  ), deviation from Cauchy‟s relation, Poisson‟s ratio  , Young modulus
Y , propagation velocity of elastic waves, phonon dispersion curves and
degree of anisotropy A are highly appreciable for metallic elements.
In: Metal Matrix Composites ISBN: 978-1-61324-483-8
Editor: Suzanne N. Fitzgerald © 2012 Nova Science Publishers, Inc.
Chapter 1
GENERATION AND VALIDATION OF FAILURE

ASSESSMENT DIAGRAMS FOR HIGH
STRENGTH ALLOYS UTILIZING
THE INHERENT FLAW MODEL
S. Rajakumar and T. Christopher

Faculty of Mechanical Engineering, Government College of Engineering,
Perumalpuram, Tirunelveli-627 007, India
ABSTRACT
Modifications are made in the inherent flaw model of Waddoups,

Eisenman and Kaminski (known as the WEK model) to improve fracture
strength evaluation of cracked bodies. A relation is proposed for the
generation of failure assessment diagram and validated by comparing
with the test data of different high strength alloys.
Keywords: High strength alloys, center crack tensile specimen, inherent flaw
model, failure assessment diagram, fracture strength

Corresponding author: E-mail: [email protected]
2 S. Rajakumar and T. Christopher
NOMENCLATURE
a ci Damage zone size
c Half crack length
K F , m, p Fracture parameters in equation (1)
KIFM,  aci Fracture parameters in equation (8)

K Q   NC

c  Parameter in Failure assessment diagram
t Specimen thickness
W Specimen width
Y Finite width correction factor
 Applied far field stress
 NC

Fracture strength of a wide specimen
 NC Fracture strength of finite width specimen
o Ultimate tensile strength (unnotched strength)
1. INTRODUCTION
Aerospace industry recognized two types of failure criteria: yielding and

fracture. Failure due to yielding is applied to a criterion in which some
functional of the stress or strain is exceeded and fracture is applied to a
criterion in which an already existing crack extends according to an energy
balance hypothesis. Experimentation with a variety of materials would show
that the theory works well for certain materials but not for others. The safety
assessment of structures without a fracture mechanics analysis is insufficient
and may cause an unexpected reduction in the load carrying capacity of an
actual structure due to the presence of unavoidable crack-like defects not being
taken into consideration. The extraordinary success of fracture mechanics lies
in its ability to combine a theoretical framework with experimentally measured
critical quantities.
Several fracture analysis methods [1] were described to predict the
fracture behavior of flawed structural components. None of these methods
correlated well with the test data of all structural materials. Gordon [2] has
reviewed several fracture-mechanics-based fitness-for-service concepts. In the
Generation and Validation of Failure Assessment Diagrams … 3
failure assessment diagram or the R6 method [3], the integrity of the structure
is assessed and represented in a two-dimensional way: a function of the failure
strength pursuant to linear elastic fracture mechanics (LEFM) is plotted as
ordinate and that pursuant to plastic collapse as abscissa. The Dugdale model
[4] established the stress limits for any transitional stages between linear
elastic failure and plastic collapse. Experiments largely proved these limits to
be conservative. The two-parameter fracture criterion of Newman [1, 5] too,
applies relations derived within the scope of LEFM. In this criterion, the two
fracture parameters take account of the deviation of the stress-to-failure from
the stress calculated pursuant to LEFM principles. These parameters have to
be determined earlier in pretests, so-called base-line tests, conducted under
identical conditions of the material. Keller, Junker and Merker [6] have carried
out fracture analysis of surface cracks in cylindrical vessels applying the two-
parameter fracture criterion. It was neither possible to determine satisfactorily
the failure stresses of vessels by means of fracture parameters obtained from
fracture mechanics specimens, nor to predict the loads to failure of the
specimens by means of the vessels‟ fracture parameters. Zerbst et al. [7] have
applied the recently developed European flaw assessment procedure SINTAP
(Structural Integrity Assessment Procedures for European Industry) to the
published fracture data [8] on steel pipes having through-wall and surface
cracks subjected to internal pressure. The SINTAP procedure offers a CDF
(Crack Driving Force) and a FAD (Failure Assessment Diagram) route. Both
are complementary and give identical results. In the CDF route the
determination of the crack tip loading in the component and its comparison
with the fracture resistance of the material are two separate steps. In contrast to
this philosophy, in the FAD route, a failure line is constructed by normalizing
the crack tip loading with the material‟s fracture resistance. The assessment of
the component is then based on the relative location of an assessment point
with respect to this failure line.
For cracked configurations, a relation between the stress intensity factor
(Kmax) and the corresponding stress ( f) at failure is suggested as [9-12]:
  f   
p

K max  K F 1  m    1  m  f   (1)
  u   u  
where,  f is the failure stress normal to the direction of the crack in a body
and  u is the nominal stress required to produce a plastic hinge on the net
section. For the pressurized cylinders,  f is the hoop stress at the failure
pressure of the flawed cylinder, and  u is the hoop stress at the failure
pressure of an unflawed cylinder. For the determination of three fracture
parameters (KF, m and p), test results of simple laboratory specimens like
compact tension specimens, center crack specimens etc. can be utilized. For
fracture strength evaluation of any other structural configuration, the stress
intensity factor corresponding to that geometry is to be used in equation (1) to
develop the necessary fracture strength equation. If the values of applied stress
and corresponding stress intensity factor for the specified crack size in a
structure lie below the Kmax -  f curve of the failure assessment diagram, the
structure for that loading condition is safe.
Fracture data [13] have been compiled for selected high strength alloys
(viz., steels, aluminium and titanium alloys) useful for aircraft applications.
This article utilizes an improved inherent flaw model for tensile fracture
strength evaluation of high strength alloys.
2. MODIFIED INHERENT FLAW MODEL
The stress intensity factor for a wide tensile specimen having a centre
crack is expressed as
K I   c (2)
where σ is the applied stress and c is half crack length. Similar to Irwin‟s
plastic zone correction, the assumption of the existence of an intense energy
region of length a ci (Figure1) results in the following equation for a wide
centre crack tensile specimen at failure:
KQ  NC (c  a ci ) (3a)


Here  NC is the fracture strength of the wide tensile specimen having a
centre crack of length 2c; a ci is the crack- tip damage size at failure. In other
words c  a ci  is an effective half crack length. For the case of unflawed
specimens, the fracture strength equals the ultimate tensile strength (  o ) and
equation (3a) becomes
KQ  o  a ci (3b)
Figure 1. The characteristic length (aci) in a center-crack wide tensile panel.
Thus, a ci can be considered equivalent to the half crack length of an

inherent flaw in the unflawed tensile specimen. Accordingly, this model is
known as “the inherent flaw model (IFM)”or “the WEK model”[14].
From equations (3a) and (3b), one can express
0
 NC  (4)
c
1
a ci
The unknown characteristic length a ci  is to be obtained from the test

data of a finite width tensile cracked specimen. The fracture Strength (  NC

)
of the center crack wide tensile specimen is obtained from that of a finite
width specimen (  NC ) as
 NC

=  NC Y (5)
where the finite width correction factor [15] is,
 c 
Y  sec  (6)
W
where „c‟ is half the crack length and W is the specimen width.
Using  NC

,  0 and c, the unknown characteristic a ci  is found from
equation (4) as
c
aci  2
(7)
 0 
    1
  NC 
Knowing the characteristic length a ci  , equation (4) gives the fracture

strength (  NC

) for the specified crack length (2c). Fracture strength (  NC ) of
the finite width plate is obtained from equation (5) or dividing (  NC

) with the
correction factor (Y). It is well known fact that the fracture strength decreases
with increase in the crack size. Equation (7) indicates that the characteristic
length a ci  need not be a material constant. This calls for a modification in
the inherent flaw model.
A relation between a ci  and (  NC

) in the non-dimensional form is
proposed as
 o a ci  NC
 1   aci (8)
K IFM o
To determine the parameters (KIFM and  aci ) in equation (8), two cracked
specimen tests in addition to an unflawed specimen test are required. Normally
more tests are performed to take into account the scatter in test results. The
parameters KIFM and  aci in equation (8) are determined by a least square
 N C
curve fit to the data for aci and .It should be noted that  aci = 0 in
0
equation (8) represents the constant damage size. When  aci >1 and  NC   0 ,

 0 aci
equation (8) results  0 . Hence, 0   aci  1. Whenever  aci is
K IFM
found to be greater than unity, the parameter  aci is truncated to 1 by suitably
modifying the parameter KIFM with the fracture data. If  aci is found to be less
than zero, the parameter  aci is truncated to zero and the average of
 0  aci values from the fracture data yields the parameter KIFM. Using
equations (7) and (8), one can write the following nonlinear equation for the
fracture strength (  NC

) after eliminating the characteristic length a ci  as
1  K IFM
2
   
2

   NC 
2

  1   aci  NC  1    c (9)
       
NC        
  

This non-linear fracture strength equation (9) is solved using the Newton–
Raphson iterative scheme to obtain (  NC

) for the specified crack size. The
fracture strength (  NC ) of the finite width plate is obtained by dividing (  NC

) with the correction factor (Y).
   NC


A relation between K Q    c and is obtained from
NC
o
equation (9) as
2
     
KQ  K IFM 1   aci NC  1  
 
NC 

(10)
  0   0 
Equation (10) represents a failure assessment diagram useful for fracture

strength evaluation of different cracked configurations. The fracture strength
 NC versus crack size 2c curves can be generated from equation (9) by
specifying 0 <  NC <  0 useful for evaluation of  NC to any specific crack
size. Applying the correction factor Y to  NC , the fracture strength (  NC ) can
be found.
3. RESULTS AND DISCUSSION
Fracture data [13] on high strength alloys useful for aircraft applications is
utilized in the present study to verify the validity of the fracture criterion. The
unnotched strength (  0 ) data in Table 1 are categorized by material, alloy,
temper and / or heat treatment, bare or clad and thickness. Specimen
identification is made by lettering LT or TL while generating the plane-stress
and transitional fracture toughness data. The first letter indicates the
orientation of material of the specimen relative to the direction of stressing and
the second, the direction of crack / damage propagation. Average strength
value of the multiple test results is considered in the analysis.
A standard error (SE) between analytical and test results is obtained from
2
1 N  AnalysisRe sult 
SE =  1 
N i 1 

Test Re sult  i
(11)
where N is the number of test specimens.

The relative error (%) is computed as
 Analysis Re sult 
Relative error (%) = 100 1  
Test Re sult 
(12)


Table 1. Fracture toughness parameters (KIFM and aci ) evaluated from
the test results [13] of centre crack tension specimens made of various
metallic alloys
Alloy Specification Temp., Material Un- Specimen N* Fracture

K orientation notched thickness, Parameters
strength, t (mm) in equation ( 8 )
o KIFM
(MPa) (M Pa√m)  aci

Steel- 295 LT 1961 3.2 3 165.9 0.064
300(AMS6434)
Steel- 295 LT 1882 9.5 7 85.9 0.0
300(AMS6434)
Ti-6Al-4V 295 LT 988 1.3 3 212.3 0.0
Ti-6Al-4V 295 LT 996 1.0 4 212.3 0.0
Ti-6Al-4V 295 LT 945 6.3 5 259.1 0.0
Ti-6Al-4V 295 LT 955 5.1 3 259.1 0.0
Ti-8Al-1Mo-1V 295 TL 1029 1.3 4 194.1 0.0
Ti-8Al-1Mo-1V 295 LT 1048 1.3 9 194.1 0.0
Ti-5Al-2.5Sn 20 LT 1556 0.5 8 135.0 0.0
Ti-5Al-2.5Sn 20 LT 1538 2.5 7 99.7 0.0
Inconel-718 295 - 1585 0.6 3 221.9 0.0
Inconel-718 77 - 2013 0.6 3 221.9 0.0
Inconel-718 20 - 2131 0.6 3 221.9 0.0
7475-T61 295 TL CLAD 522.6 1.6 3 107.3 0.0
aluminium
7475-T61 295 LT CLAD 532.0 1.6 3 107.3 0.0
aluminium
7475-T61 295 LT 550.2 1.6 5 107.3 0.0
aluminium
7475-T61 295 TL 557.1 1.6 5 107.3 0.0
aluminium
7075-T6 aluminium 295 LT CLAD 496.4 2.3 7 76.5 0.0
7075-T6 aluminium 295 LT CLAD 539.2 2.0 17 76.5 0.0
7075-T6 aluminium 295 LT 555.0 2.5 4 76.5 0.0
7075-T6 aluminium 295 LT 572.2 2.5 11 76.5 0.0
7075-T6 aluminium 295 LT 573.7 2.3 15 76.5 0.0
*N- Number of Specimens.
Fracture analysis has been carried out considering the ultimate tensile
strength values and the fracture data of various metallic alloys (viz, Steel-300,
7075-T6, Ti-6Al-4V, 7475-T61) generated from center–crack tensile
specimens having different thicknesses. From the fracture strength (  NC ) data
of the finite width center-crack tension specimens, the fracture strength (  NC

)
for wide tensile specimens is obtained from equation (5). Substituting the
crack length (2c), the unnotched strength (  0 ) and the notched strength (  NC

) in equation (7), the characteristic length (aci) is obtained. Values of aci ,  NC


and  0 from fracture data are fitted in equation (8) to obtain the fracture
parameters ( K IFM and  aci ). Table 1 gives the determined fracture
parameters ( K IFM and  aci ) from the test data of different materials. When
δaci= 0, the characteristic length becomes constant and the fracture strength (
 NC

) is obtained for the crack size (2c) from equation (4). The fracture
strength (  NC ) for the finite width plate is obtained by dividing  NC

with the
correction factor (Y). When  aci >0, one can generate fracture strength (  NC

)
versus the crack size (2c) curves from equation (9) by specifying the values of
 NC

from 0 to  0 . From this curve, one can find easily the fracture strength (
 NC

) for the crack size. Then applying the finite width correction factor (Y) to
 NC

, the fracture strength (  NC ) for the finite width plate can be estimated.
In the present study, the non-linear fracture strength equation (9) is solved
using the Newton-Raphson iterative method. Tables 2 to 6 give the
comparison of fracture strength estimations with the test results.
The standard error (SE) is found to be less than 0.1, which indicates that
the fracture strength estimations utilizing the fracture parameters ( K IFM and
 aci ) can be expected within ±10% of the test results. Figures 2 to 5 show the
failure assessment diagrams including the fracture data of the materials. It can
be seen from Figure-6 that most of the fracture strength estimations are within
±10% of the test results.
Table 2(a). Comparison of analytical and test results of center crack

tension specimens made of Steel-300 (AMS 6434) alloy (t = 3.2 mm, KIFM
=165.9 MPa√m,  aci =0.064)
Specimen Dimensions (mm) Un-notched Fracture strength, Relative Error

strength, NC (MPa) (%)
o (MPa)
Width, W Crack length, Test [13] Analysis
2c
127 29.7 1961 679.8 676.6 0.5
127 47.7 1961 490.2 518.2 -5.7
127 64.3 1961 436.5 415.8 4.7
Standard error = 0.043
Table 2(b). Comparison of analytical and test results of center crack

tension specimens made of Steel-300 (AMS 6434) alloy (t = 9.5 mm, KIFM
=85.9 MPa√m,  aci = 0)
Specimen Dimensions Un-notched Fracture strength, NC Relative Error

(mm) strength, (MPa) (%)
o (MPa)
Width, W Crack length, Test [13] Analysis
2c
127 33.3 1882 322.7 352.6 -9.3
127 62.7 1882 228.9 228.6 0.1
127 31.5 1882 361.3 363.6 -0.6
127 43.4 1882 305.5 300.2 1.7
127 64.0 1882 206.2 224.6 -8.9
127 26.7 1882 428.0 398.1 7.0
127 57.9 1882 264.1 244.5 7.4
Table 3. Comparison of analytical and test results of center crack tension

specimens made of Ti-6Al-4Valloy ( KIFM = 212.3 MPa√m,  aci = 0)
Specimen Dimensions (mm) Un-notched Fracturestrength, Relative

strength, NC(MPa) Error (%)
o (MPa)
Thick- Width, Crack
ness, t W length, Test [13] Analysis
1.0 203.2 2c
12.2 995.7 868.8 833.3 4.1
1.0 203.2 24.1 995.7 746.7 728.7 2.4
1.0 203.2 51.3 995.7 542.0 574.1 -5.9
1.0 203.2 77.0 995.7 422.0 473.6 -12.2
1.3 611.1 76.2 988.0 543.3 516.1 5.0
1.3 610.6 152.4 988.0 352.9 381.9 -8.2
1.3 611.4 254 988.0 286.8 283.5 1.1

specimens made of Ti-6Al-4Valloy ( KIFM = 259.1 MPa√m,  aci = 0)
Specimen Dimensions (mm) Un-notched Fracture strength, Relative

strength, NC (MPa) Error (%)
o (MPa)
Thick Width Crack Test
ness, t W length, [13] Analysis
2c
5.1 611.4 76.4 955.0 641.9 583.0 9.2
5.1 611.4 152.4 955.0 524.0 445.2 15.0
5.1 611.4 254 955.0 381.3 335.9 11.9
6.3 244.6 48.8 944.6 589.8 648.4 -9.9
6.3 409.5 101.4 944.6 465.4 514.6 -10.6
6.3 409.5 203.7 944.6 311.0 347.2 -11.6
6.3 816.6 204.2 944.6 394.0 395.6 -0.4
6.3 816.6 487.7 944.6 180.6 217.1 -20.2

specimens made of Ti-8Al-1Mo-1Valloy
(t = 1.3 mm, KIFM = 194.1 MPa√m,  aci = 0)
Specimen Dimensions (mm) Un-notched Fracture strength, Relative

strength, NC(MPa) Error (%)
o (MPa)
Width, Crack length, Test [13] Analysis
W 2c
203.2 25.4 1028.7 724.0 699.5 3.4

203.2 38.6 1028.7 633.0 611.5 3.4
203.2 51.3 1028.7 552.3 546.7 1.0
203.2 74.7 1028.7 427.5 454.3 -6.3
203.2 25.9 1048.0 724.0 701.4 3.1
203.2 38.1 1048.0 603.3 618.7 -2.5
203.2 50.5 1048.0 546.1 553.4 -1.3
508.0 51.8 1048.0 563.0 566.8 -0.7
508.0 95.5 1048.0 481.3 442.1 8.1
508.0 108.2 1048.0 406.1 417.3 -2.7
508.0 153.4 1048.0 328.2 348.9 -6.3
508.0 203.7 1048.0 294.4 293.1 0.5
508.0 253.0 1048.0 230.6 248.8 -7.9
CONCLUDING REMARKS
A relation for the characteristic length in the inherent flaw model is
proposed for accurate evaluation of fracture strength of cracked bodies. The
procedure is validated considering the fracture data of various high strength
alloys of center crack tension specimens. Failure assessment diagrams were
generated and showed the fracture data close to the failure boundary. Fracture
strength of any other cracked configurations can be evaluated from the present
fracture criterion. The correction factor (Y) of the cracked body and the
strength of the unflawed body are essential to carry out the fracture analysis.

specimens made of Inconel-718 alloy
(t = 0.6 mm, KIFM = 221.9 MPa√m,  aci = 0)
Specimen Dimensions (mm) Un-notched Fracture Relative

strength, strength,NC(MPa) Error (%)
o (MPa)
Width,W Crack Test [13] Analysis
length,2c
101.6 19.0 2130.6 1137.7 1074.5 5.5
101.6 32.5 2130.6 788.8 834.4 -5.8
101.6 44.4 2130.6 621.9 686.6 -10.4
101.6 18.5 2013.3 1184.2 1069.4 9.7
101.6 32.5 2013.3 848.1 825.8 2.6
101.6 43.9 2013.3 627.7 686.6 -9.4
101.6 32.3 1585.0 770.0 784.2 -1.8
101.6 18.5 1585.0 981.8 984.3 -0.2
457.2 139.2 1585.0 436.2 428.3 1.8
Figure 2. Failure assessment diagram for Ti-8Al-1Mo-1V alloy with test data [13].
Figure 3. Failure assessment diagrams for Ti-5Al-2.5Sn alloy with test data [13].
Figure 4. Failure assessment diagram for 7475-T61 Aluminium alloy with test data
[13].
Figure 5. Failure assessment diagrams for 7075-T6 Aluminium alloy with test data
[13].
Figure 6. Comparison of fracture strength of different high strength Alloys.

REFERENCES
[1] J.C. Newmann, Jr., “An evaluation of fracture analysis methods”, ASTM
– STP –896 (1985) pp 5-96.
[2] J.R. Gordon, “A review of fracture assessment procedures and their
applicability to welded structures”, Canadian Metallurgical Quarterly,
Vol.32, pp.195-203 (1993).
[3] Milne and G.G. Chell, “Evaluation of flaw tolerance during stable crack
growth”, Institute of Mechanical Engineers, C18, pp.85-91 (1980).
[4] D.S. Dugdale, “Yielding of steel sheets containing slits”, Journal of the
Mechanics and Physics of Solids, Vol.8, pp.100-108 (1960).
[5] J.C. Newmann, Jr., “The merging of fatigue and fracture mechanics
concepts: a historical perspective”, Progress in Aerospace Sciences, Vol.
34, pp. 347–390 (1998).
[6] H.P. Keller, G. Junker, and W. Merker, “Fracture analysis of surface
cracks in cylindrical pressure vessels applying the two parameter
fracture criterion (TPFC)”, International Journal of Pressure Vessels
and Piping, Vol. 29, pp. 113-153 (1987).
[7] U. Zerbst, R. Hamann and A. Wohlschlegel, “Application of The
European Flaw Assesment Procedure SINTAP to Pipes”, International
Journal of Pressure Vessels and Piping, Vol.77, pp. 697 – 702 (2000).
[8] J.F. Kiefner, W.A. Maxey, R.J. Eiber and A.R. Duffy, “Failure Stress
Levels of Flaws in Pressurized Cylinders”, Progress in Flaw Growth
and Fracture Toughness Testing, ASTM STP 536, pp. 461 - 481 (1973).
[9] P.K. Govindan Potti, B. Nageswara Rao and V.K. Srivatsava, “Residual
Strength of Aluminum–Lithium Alloy Center Surface Crack Tension
Specimens at Cryogenic Temperatures”, Cryogenics, Vol.40, pp. 789 –
795 (2000).
[10] T. Christopher, K. Sankaranarayanasamy and B. Nageswara Rao,
“Fracture strength of flawed cylindrical pressure vessels under cryogenic
temperatures”, International Journal of Cryogenics, Vol. 42, pp. 661–
673 (2002).
“Fracture behavior of maraging steel tensile specimens and pressurized
cylindrical vessels” Fatigue, Fracture of Engineering Materials and
Structures, Vol. 27, pp.177-186 (2004).
“Failure assessment on tensile cracked specimens of aluminum alloys”,
Trans. ASME Journal of Pressure Vessels Technology, Vol. 126, pp.

404–406 (2004).
[13] “Damage Tolerant Design Handbook: A compilation of Fracture and
Crack Growth Data for High Strength Alloys”, Metals and Ceramics
Information Center, Battelle, Columbus Laboratories, Ohio. Report No.
MCIC – HB – 01 (January 1975).
[14] M.E.Waddoups, J.R.Eisenman and B.E.Kaminski, “Macroscopic
fracture mechanics of advanced composite materials”, Journal of
Composite Materials, Vol.5, pp. 446 – 451(1971).
[15] Y. Murakami, “Stress Intensity Factors Handbook”, Pergamon Press,
New York (1987).
Reviewed by
Dr. B. Nageswara Rao
Scientist / Engineer
Structural Analysis and Testing Group
Vikram Sarabhai Space Centre
Trivandrum – 695 022, India.
Chapter 2
EFFECT OF APPLIED LOAD ON THE

CHARACTERISTICS OF REVERSIBLE
MARTENSITIC TRANSFORMATION DURING
THERMAL CYCLING TREATMENT
OF A MONOCRYSTALLINE CU-13.5AL-4NI
ALLOY
E. C. Pereira, L. A. Matlakhova, A. N. Matlakhov,

S. N. Monteiro and R. J. S. Rodríguez
State University of the Northern Rio de Janeiro, Advanced Materials
Laboratory
Av. Alberto Lamego 2000, Parque Califórnia, Campos dos Goytacazes, RJ,
CEP: 28015-620, Brazil
ABSTRACT
The changes in the characteristics of the reversible martensitic
transformation (RMT), caused by different applied loads during thermal
cycling treatments under load (TCL) were investigated in a

E-mail: [email protected]
20 E. C. Pereira, L. A. Matlakhova, A. N. Matlakhov et al.
monocrystalline Cu-13.5wt.%Al-4.0wt.%Ni alloy. The TCL was

performed by an accumulation of 300 cycles in the temperature interval
between 0 oC (shortly below the Mf) and 90 oC (just above Af). These
treatments were conducted both load-free and under three different
applied load of 0.1, 0.2 and 0.5 kg, corresponding to 0.056, 0.112 and
0.280 MPa, respectively. After each distinct treatment condition, the alloy
specimen was characterized by X-ray diffraction, optical microscopy,
differential calorimetry and microhardness. It was found that the TCL
promotes significant changes that are related to the resulting structures
and characteristics of the RMT. An increase in the applied load causes a
sensible decrease in the critical temperature interval associated with the
RMT. Moreover, a decrease in both, the thermal hysteresis and the
enthalpy, as well as an increase in the microhardness were also observed
with applied load. This behavior is not only a consequence of a decrease
in the martensitic variants but also related to the greater stability of an
intermediate state, which facilitates the transformation mechanism.
Keywords: Monocrystalline Cu-13.5Al-4Ni alloy; reversible martensitic

transformation; thermal cycling treatment; structure; critical temperatures
1. INTRODUCTION
The discovery of reversible martensitic transformation (RMT) in several
metallic alloys permitted to successfully explain the nature of anomalous non-
elastic behaviors such as the shape memory effect (SME) and the
superelasticity (SE) [1-7]. Some of the alloys that present these effects are
already being used in many engineering and medicine applications as special
actuator devices. In addition to SME and SE, these alloys also show superior
mechanical properties and corrosion resistance as well as biocompatibility in
their specific application [8-12].
In particular, Cu-Al-Ni alloys that present SME are gaining attention as a
more advantageous alternative for industrial application in comparison with
other alloys such as Ti-Ni, Cu-Zn and Cu-Zn-Al [13-16]. The Cu-Al-Ni alloy
advantages are related to better thermal and electrical conductivities as well as
low cost, especially in relation to the traditionally used Ti-Ni alloys [17-20].
Another point worth mentioning is that, in confront with the polycrystalline
alloys, the monocrystalline Cu-Al-Ni alloys display more attractive
thermoelastic and mechanical properties. In addition, these monocrystalline
alloys do not suffer grain boundary embrittlement, which translates into
Effect of Applied Load on the Characteristics … 21
superior plasticity and formability as well as resistance to the accumulation of

structural defects during thermal cycling treatments [19-23].
In terms of crystalline structure, the Cu-Al-Ni alloys that present SME and
are based on the intermetallic Cu3Al, posses different structures depending on
the temperature, composition, heat treatment and mechanical constraints. At
elevated temperatures, these alloys consist of a stable  phase, which is body
centered cubic (bcc). Below 565 oC, an ordering transformation occurs,
changing the stable  to an ordered 1 phase with a cubic structure of the type
DO3 [1,2,24]. With further cooling, and depending on the aluminum content,
the ordered 1 transforms into either a 1 martensite, with type Cu3Ti ordered
structure, or a 1 martensite with type 18R ordered structure [1,2,20,24]. The
monocrystalline Cu-Al-Ni alloys, in addition to the above mentioned phases,
may also show an intermetallic Al7Cu4Ni with an ordered R-3m rhombohedral
structure [25]. In the present work, as in previous ones [26-27], this
intermetallic is hereafter called as the R phase.
Thermal cycling is an important functional condition for these SME
alloys. In fact, in industrial applications the alloy is usually submitted to
multiple heating and cooling cycles in temperature intervals that cover the
RMT range MsMf, for cooling, and AsAf, for heating. Each cycle is
associated with a short hysteresis, in which the interface between the two
participant phases, 1 (austenite) and 1 (martensite), remains coherent or
semi-coherent. The hysteresis‟s magnitude can be evaluated as the
temperature difference for 50% of the alloy to be transformed to the austenite
(1) phase on heating and 50% of the martensite (1) on cooling [5,6-28,29].
In practice, one relevant limitation for the use of SME alloys is the change
in the operational behavior after a number of thermal cycling [21,23]. It is well
known that a thermal cycling treatment promotes alterations not only in the
structure and phase composition of the alloy but also modifies its physical and
mechanical properties [20,23,30]. After each cycle, additional defects are
created and they interfere with the RMT characteristics. As a consequence,
variations in the critical temperatures and changes in the thermal hysteresis
occur [31].
In addition to the thermal cycling effects, the RMT may also take place
under an applied load, which is the typical case of mechanically driven
actuator type devices. In this case, the applied load generates not only stress
and deformation but also phase transformations that may alter the structure of
the alloy in a complex manner [26-31,32]. These aspects however, have
received a limited attention regarding the SME Cu-Al-Ni alloys.
Therefore the objective of this work was to investigate the changes in the
structure and RMT characteristics in a Cu-13.5wt.%Al-4wt.%Ni alloy
subjected to thermal cycling treatments free of load and under different
applied compressive loads. For this specific alloy it was found [23] that during
heating a 11 reverse transformation occurred in the interval of +9 oC (As)
to +52 oC (Af) in association with an endothermic process. While, during
cooling a 11 direct transformation occurred in the interval of +25 oC (Ms)
to 9 oC (Mf). This exothermic transformation develops more intensively
between +19 oC and +0.5 oC.
2. EXPERIMENTAL PROCEDURE
The basic material investigated was a high purity monocrystalline Cu-
13.5wt.%Al-4wt.%Ni, that will be referred as Cu-13.5Al-4Ni, obtained as a 5
mm in diameter cylindrical bar from the Memory Crystals Group, of the
Technical University of Saint Petersburg, Russia [33]. Specimens with
approximately 5 mm in thickness were sectioned out, perpendicular to the bar
axis, by means of a Miniton cutter. For microstructure characterization, the
specimens were polished to a mirror appearance by means of to 0.1 m
alumina paste. No chemical attack was used since the surface transformation
relief was enough to reveal the phases. A previous thermal analysis by
differential scanning calorimetry (DSC) revealed the critical temperatures
associated with the RMT [23]. The results of this thermal analysis served as a
reference for the critical RMT temperatures necessary for conducting the
thermal cycling treatment under load (TCL) of the present work.
Specimens were submitted to 300 continuous thermal cycles, each one
associated with a heating up to 90 oC (above Af) followed by cooling to 0 oC
(close to Mf). These 300 thermal cycles were carried out on different modes:
without an applied load and under a constant load, TCL. Three separate load
levels were considered: 0.1, 0.2 and 0.5 kg, corresponding respectively to
stress of 0.056, 0.112 and 0.280 MPa. The load was applied simultaneously to
the thermal cycles using an apparatus specially developed for this purpose
[26]. After 300 cycles, the structural characteristics of the alloy were analyzed
by X-ray diffraction and surface metallography. This characterization was
conducted at room temperature (RT) by finishing the treatment: (a) with a half
cooling cycle to 0 oC, then up to RT and (b) with a half heating cycle to 90 oC,
then down to RT, as schematically illustrated in Figure 1.
The alloy phasic structure was determined at RT by X-ray diffraction

(XRD) in a model DRON-3M diffractometer using Cu-K radiation, covering
2 angles from 25o to 75o at scanning steps of 0.03o/3 s. A semi-quantitative
analysis of the crystalline phase was performed by associating the intensity of
the diffraction peaks with the volume fraction of corresponding phases. The
surface morphological relief caused by the phase transformation and the
contribution of deformation related defects, were observed by optical
microscopy in a Neophot-32 microscope with polarized light. Vickers
microhardness tests were conducted by means of a MHP-100 device coupled
to the Neophot-32 microscope.
Figure 1. Schematic diagram indicating the thermal cycling treatment of the

monocrystalline alloy Cu-13.5Al-4Ni by finishing: (a) with a half cooling cycle; (b)
with a half heating cycle.
The RMT critical temperatures as well as its intervals of temperature and

associated thermal effects after the TCL, were determined by differential
scanning calorimetry (DSC), in a model DSC-2010 TA Instrument. The
thermal tests were conducted in the range of temperature from -50 oC to +100
o
C at a heating rate of 10 oC/min, under inert atmosphere. Cooling was carried
out using liquid nitrogen.
3. RESULTS
The 300 thermal cycling results, load-free and under three different
applied loads, for the monocrystalline Cu-13.5Al-4Ni alloy are now presented.
3.1. X-Ray Diffraction after 300 TCL Finishing with a Half

Cooling Cycle
Figure 2 shows the X-ray patterns of 300 cycles thermal treatment

finishing with a half cooling cycle to 0 oC and then up to RT for the: (a) load-
free, (b) 0.1, (c) 0.2 and (d) 0.5 kg of applied load. Similar X-ray result for the
same alloy in its as received initial state was presented elsewhere [23]. The
load-free pattern Figure 2(a), displays peaks corresponding to the high
temperature 1 phase, type DO3 ordered body centered cubic structure,
martensitic 1 phase, type Cu3Ti ordered (2H) structure, and R phase, type R-
3m ordered Al7Cu4Ni intermetallic [25,34-36]. Among these peaks, some of
the 1 martensite and 1 high temperature stable phase coincide at the same
angular position with R phase peaks.
It has been suggested [25-27,34-36] that such R|1 and R|1 peaks are due
to the fact that R is an intermediate phase, which appears stable at RT during
the X-ray analysis. The R phase also has unique, very intense, (107)R and
(2014)R peaks, while both 1, with (011)1 and (022)1, and 1, with (331)1,
also have their exclusive peaks with medium intensity. The coherent peaks
(200)1|(018)R, (400)1|(1025)R and (111)1|(0015)R can be clearly seen in
Figure 2(a). It is worth mentioning that the load-free patterns in Figure 2(a)
display relatively broader peaks. Moreover, the 1 phase peaks are displaced
from the original position in the as received condition [23]. Once again, this
confirm the presence of an intermediate structure associated with the R phase,
which is formed during the RMT (11). It is suggested that lattice defects,
such as dislocations, accumulated during the cycling treatment can not only
retard the RMT but also stabilize this intermediate phase. After 300 TCL
under 0.1 kg, Figure 2(b), the (107)R and (2014)R peaks corresponding solely
to the R phase decrease in intensity, which contributes to a more prominent
participation of the coherent (200)1|(018)R and (400)1|(1025)R intermediate
peaks. The martensitic 1 phase, however, is only detected by a lower
intensity (011)1 peak. After 300 TCL under 0.2 kg, Figure 2(c), the peaks
Figure 2. X-ray patterns of the Cu-13.5Al-4Ni alloy after of 300 cycles thermal
treatment finishing with a half cooling cycle for the: (a) load-free and (b) 0.1 kg; (c)
0.2 kg; (d) 0.5 kg of applied load.
with higher intensities are the coherent (111)1|(0015)R and (222)1|(027)R,

which has not yet been observed, while both 1 and 1 peaks are seen with
lower intensities. No solely R peaks were detected. After 300 TCL under 0.5
kg, Figure 2(d), the unique (2014)R, with the highest intensity, and (107)R
peaks are seen again. The coherent (111)1|(0015)R peak is still present with
lower intensity as well as the 1 and 1 peaks. The reason for the return of the
sole R phase with increasing applied load is not yet clear.
Figure 3 shows a semi-quantitative analysis, based on the X-ray peak
intensity in Figure 2, for the volume fraction of the existing phases after 300
TCL finishing with a half cooling cycle as a function of the applied load.
Figure 3. Semi-quantitative analysis for the volume fraction of the existing phases after
300 cycles thermal treatment finishing with a half cooling cycle as a function of the
applied load.
In this figure one can see that the sole R phase peak decreases up to 0.2 kg
and then increases to a fraction higher than that corresponding to the load-free
cycling treatment. By contrast, the intermediate peak phase with coherent 1|R
plane significantly increases, more than 80% vol., up to 0.1 kg followed by a
marked decrease to 0% vol. at 0.5 kg. Both the high temperature stable 1
peaks and the martensitic 1 phase peaks are in relatively low amounts after
the load-free and the load-applied cycling treatments. The important fact in
Figure 3 is the higher stability of the R phase peak at the expenses of the
coherent 1|R peak at 0.5 kg.
3.2. X-Ray Diffraction after 300 TCL Finishing with a Half

Heating Cycle
Figure 4 presents the X-ray patterns of 300 TCL, finishing with a half
heating cycle, up to 90 oC and then back to RT, for the (a) load-free, (b) 0.1,
(c) 0.2 and (d) 0.5 kg of applied load.
Figure 4. Continued.
Figure 4. X-ray patterns of the Cu-13.5Al-4Ni alloy after of 300 cycles thermal
treatment finishing with a half heating cycle for the: (a) load-free and (b) 0.1 kg; (c)
0.2 kg; (d) 0.5 kg of applied load.
After a load-free 300 TCL, Figure 4(a), the higher intensity peaks are the
coherent (200)1|(018)R and the (331)1 corresponding solely to the high
temperature stable 1 phase. A medium intensity (111)1|(0015)R peak as well
as small intensity 1 martensitic (022)1 peak are observed. Furthermore, a
faint (107)R peak can also be detected. After 300 TCL under 0.1 kg, Figure
4(b), peaks corresponding solely to the R phase, (107)R and (2014)R, have
grown in intensity while the 1 peak disappeared. The coherent (200)1|(018)R
peak still shows the highest intensity. Another 1 martensitic peak (011)1
shows up in addition to the (111)1.
After 300 TCL under 0.2 kg, Figure 4(c), only a large coherent
(222)1|(027)R dominates the pattern, which is associated with a high
background. A faint (107)R peak apparently exists.
After 300 TCL under 0.5 kg, Figure 4(d), the most intense peaks,
(200)1|(018)R and (400)1|(1025)R, are those associated with the coherent
planes simultaneously belonging to both 1 and R phases. The 1 martensitic
phase is back, determined with its medium intensity (011)1 and (022)1 peaks.
The high temperature stable 1 phase as well as the sole R phase could again
be detected by faint (331)1, (107)R and (2014)R peaks.
Figure 5 shows a semi-quantitative analysis, based on X-ray peak intensity
in Figure 4, for the volume fraction of the observed phases after 300 TCL
finishing with a half heating cycle as a function of the applied load. The
diffractograms reveal an intermediate state, such the R phase, whenever one
phase is transformed into another by the RMT mechanism. Consequently,
certain crystallographic planes associated with the participant phases, are
coherent while others are not owing to the way the transformation occurs and
the difference between phases. In this respect, 1 is coherent while R and 1
are semi-coherent. In this figure one can see that the main result is a
significant increase in the coherent 1|R peak, which reaches a volume fraction
above 50% vol., with the applied load.
Figure 5. Semi-quantitative analysis for the volume fraction of the existing phases after
300 cycles thermal treatment finishing with a half heating cycle as a function of the
applied load.
3.3. Morphological Aspects after 300 TCL
Figure 6 presents the morphological aspects of the initially polished

surface of the alloys, which was then submitted to 300 TCL: (a,b) load-free
and (c,d) under 0.1 kg load. The observation was performed at RT after
finishing with a half: (a,c) cooling cycle (to 0 oC and back to RT) and (b,d)
heating cycle (up to 90 oC and back to RT).
Figure 6. Optical micrographs of a transversal section of the Cu-13.5Al-4Ni alloy after

of 300 cycles thermal treatment finishing (a,c) with a half cooling cycle and (b,d) with
a half heating cycle for the (a,b) load-free and (c,d) 0.1 kg of applied load.
In comparison with the as received state of the alloy [23] the martensite
variants are no longer limited by a central and four peripheric blocks. Still,
some straight edge shadows of what could have originally been a central
square block can be clearly seen in all pictures in Figure 6. In the load-free
TCL, finishing with a half cooling cycle, Figure 6(a), V-shaped crossing plates
can be attributed to the 1 martensite [2,20]. This result is in agreement with
the X-ray analysis in Figure 2(a) and Figure 3. In the load-free TCL, finishing
with a half heating cycle micrograph, Figure. 6(b), some plates and needles
observed in Fig. 6(a) tend to disappear. This is apparently a consequence of

the type of transformation originally denominated by Kurdiumov and Handros
[2] as “thermoelastic martensitic transformation” and currently known as
“reversible martensitic transformation” (RMT).
After 300 TCL under the smaller applied load of 0.1 kg finishing with a
half cooling cycle, Figure 6(c), the initially observed martensitic plates and
needles in Figure 6(a), tend to be replaced by deep slip lines. This suggested
that the 1 martensite characteristics have been largely reduced, in agreement
with the X-ray analysis in Figure 2(b) and Figure 3. The half heating cycle
micrograph, Figure 6(d), indicated that a possible stress relief of the deformed
structure is responsible for an apparent microscopic distortion in the peripheric
blocks, specially the one up in the right side of the picture, that were well
defined in the as received condition [23].
Figure 7 shows the morphological aspect of the alloy submitted to 300
TCL under loads of 0.2 kg (a,b) and 0.5 kg (c,d) finishing with a half cooling
cycle (a,c), and a half heating cycle (b,d).
Figure 7. Optical micrographs of a transversal section of the Cu-13.5Al-4Ni alloy after

of 300 cycles thermal treatment finishing (a,c) with a half cooling cycle and (b,d) with
a half heating cycle for the (a,b) 0.2 kg and (c,d) 0.5 kg of applied load.
In particular, Figure 7(a) shows two relatively large martensite needles

extending from the peripheric left side of the sample. These needles are
evidence of coherent planes between the R and 1 phases as revealed in the
XRD pattern in Figure 2(c). With subsequent heating, Figure 7(b), the needles
tend to disappear, which could be associated with 1|R coherent planes in
Figure 4(c). The upper dark region in Figure 7(b) is apparently related to a
deformation band caused by stress relief due to SME occurring as
consequence of the cycling treatment under load.
The main feature of the alloy microstructure after 300 TCL under 0.5 kg
finishing with a half cooling cycle, Figure 7(c), is a wide dark band crossing
the sample. This band, next to a martensitic twinning, is probably associated
with an intermediate state between the martensitic and the rhombohedric
phases shown in the XRD peaks in Figure 2(d). With subsequent heating,
Figure 7(d), the dark band deformation of Figure 7(c) decrease owing to the
SME in association with the R1 reaction evidenced by the XRD peaks in
Figure 4(d). A new martensite needle can be observed in the left side of Figure
7(d), which apparently confirms the participation of the 1 phase also
observed as peaks in Figure 4(d).
3.4. DSC Analysis after 300 TCL
Figures 8 and 9 present the DSC curves for the Cu-13.5Al-4Ni alloy after
300 TCL respectively for load-free and under load conditions. The critical
RMT temperatures determined by the tangent method [20] are displayed in
Table 1.
For the load-free condition, Figure 8(a), the DSC curves show that on
heating the 11 transformation occurs within the interval +3 oC (As) to
+46.3 oC (Af) through an endothermic process with a phase transformation
enthalpy of 8.33 J/g. This process develops in an on-set mode begin at +21.6
o
C (Ao) up to an extreme at +27.9 oC (Ae) corresponding to a maximum heat
flow. The off-set mode, which ends this process, occurs at an approximate
temperature of +38 oC (Aof). On cooling upper curve, Figure 8(a), the 11
martensitic transformation starts at +40 oC (Ms) and ends at 19.8 oC (Mf) with
an on-set temperature of +18.3 oC (Mo), extreme temperature of +6.9 oC (Me)
and off-set temperature of 7.5 oC (Mof) associated with an exothermic
enthalpy of 11.08 J/g, Table 1.
Figure 8. Heating and cooling DSC curves for the Cu-13.5Al-4Ni alloy after 300
cycles thermal treatment for the (a) load-free and (b) 0.1 kg of applied load.
Figure 9. Heating and cooling DSC curves for the Cu-13.5Al-4Ni alloy after 300
cycles thermal treatment for the (a) 0.2 kg and (b) 0.5 kg of applied load.
Table 1. Critical temperatures of RMT obtained by DSC as a function of

the applied
load after 300 cycles thermal treatment of the Cu-13.5Al-4Ni alloy
Figure 10. Continued on next page.

Figure 10. Critical temperatures of RMT obtained by DSC as a function of the applied
load upon (a) cooling and (b) heating of a Cu-13.5Al-4Ni alloy.
The influence of the 300 TCL on the RMT was evaluated by comparing
the displacement of the critical temperatures during cooling and heating of the
alloy for the load-free and under load conditions, as shown in Figures 8, 9 and
10. It was found that an increase in applied load promotes sensible variations
in the RMT temperatures. This corresponds to a tendency in decreasing the
critical transformation intervals the greater is the applied load mainly for the
reverse RMT temperatures.
The MsMf and AsAf intervals for the load-free 300 TCT were found to
be 59.8 oC and 43.3 oC, respectively, Tab. 1. Under 0.5 kg of load, these
intervals were determined as 50.3 oC and 37.6 oC. Furthermore, the intensive
transformation intervals MoMe and MoMof after the load-free treatment,
were determined as 11.4 oC and 25.8 oC. Likewise AoAe and AoAof were
found to be 6.3 oC and 16.4 oC respectively. After 300 TCL under 0.5 kg the
same intervals are reduced to 4.1 oC (MoMe), 16.3 oC (MoMof), 2.2 oC
(AoAe) and 7.5 oC (AoAof) as seen in Figures 9 and 10.
Figure 11. Values for the thermal hysteresis (a) and enthalpy (b) of the RMT in the Cu-
13.5Al-4Ni alloy as a function of the applied load.
The thermal hysteresis developed as a function of the applied load during

the 300 TCL is presented in Figure 11(a). A considerable decrease occurred in
the value of thermal hysteresis, from 21 oC for the load-free treatment to 13 oC
for the treatment under 0.5 kg. Figure 11(b) presents the RMT, both direct and
reverses, enthalpies as a function of the applied load for the 300 TCL. With
increasing applied load a marked decrease in these enthalpies is observed.
In fact, for the load-free treatment it was found enthalpy values of 11.1
J/g, corresponding to the MsMf an 8.3 J/g to the AsAf intervals. Under 0.5
kg, Figure 11(b), the enthalpy value has decreased to 6.2 J/g (MsMf) and 5.9
J/g (AsAf). Here it is important to notice that for the treatment under this
highest applied load, 0.5 kg, the difference in the enthalpies for both direct and
reverse RMT, is relatively small as a consequence of the corresponding
smallest hysteresis attained.
3.5. Microhardness after 300 TCL
Figure 12 shows the mean value and standard deviation for the alloy
Vickers microhardness as a function of the 300 TCL treatment applied load. A
slight tendency of increasing the microhardness with the applied load can be
noted. This is apparently a consequence of the more deformed alloy structure
related to the applied load. The load action during the thermal cycling
treatment tends to accumulate the crystalline imperfection, such as dislocations
introduced after each cycle [26,30,31].
Figure 12. Values for the Vickers microhardness in the Cu-13.5Al-4Ni alloy as a
function of the applied load.
In Figure 12 it is interesting to note that the 300 TCL under 0.5 kg,
displays a greater standard deviation, i.e., a larger variation in the statistical
error. This can be attributed not only to the amount of accumulated defects
owing to the nature of the RMT, but also to the characteristic correlation
between preferred crystalline planes and directions associate with the
martensitic transformation, which results in different dislocation densities.
DISCUSSION
It is well known the fact that an applied load at temperatures within the
interval of temperatures associated with the existence of the austenitic phase,
but below the critical Md temperature, promotes stress/strain induced
martensite in RMT related alloys. This is a direct martensitic transformation
[6,20,37]. Wasilewski [37-39] also suggested the possibility of a reverse
martensite to austenite transformation to occur by an applied stress or strain on
a RMT alloy. Although still under discussion, this phenomenon was reported
by Matlakhova et al. [20] in TiNi based alloys. The authors indicated that by
mechanically deforming the martensitic state in these alloys, the R phase,
intermediate between the B19 martensite and the B2 high temperature
austenitic phase, was revealed. More lately, this phenomenon was discovered
by Matlakhova et al. [40] in Cu-Al-Ni monocrystalline alloy. The
phenomenon was also investigated based on a specific behavior of the elastic
modulus, which is characteristic of all SME alloys [41-43].
In the present work is this feasible that the applied load during the 300
TCL, would promote the reverse 1R1 transformation, at lower
temperatures, during heating from 0 oC. Moreover, the direct 1R1
martensitic transformation probably is occurring, at more elevated
temperatures, during cooling from 90 oC. Therefore, by finishing the 300 TCL
with a half cooling cycle to 0 oC and then up to RT, one should expect that the
Cu-13.5Al-4Ni alloy would suffer a stress induced reverse transformation
towards 1. However, upon unload at RT, the alloy may undergo a relaxation
process followed by the direct transformation, back to 1, since the stressed
structure is not thermodynamically stable.
In principle one should expect that the 300 TCL under the higher 0.5 kg
load, to be associated with a more pronounced stress induced transformation,
especially when compared to the load-free condition. The accumulated
defects, mainly dislocations during the load-free thermal cycling treatment,
[20,23,26,30,31] however, could retard the complete transformation process
expected to occur during relaxation (0 oCRT). Thus the R phase is allowed

to predominate as found in the X-ray patterns in Figure 2.
The decrease in the critical temperatures for the reverse transformation
AsAf, observed with the increase in applied load, Figure 10, can justify the
displacement of the Ao value towards RT, the temperature in which the
diffractometric analysis were performed. This displacement favored the
stability of the intermediate R phase, coherent with the high temperature stable
1 phase. The predominance of R|1 peaks in the X-ray pattern, Figure 4(d),
corresponding to the 300 TCL under load 0.5 kg, finishing with a half heating
cycle (90 oCRT) is an evidence of this stability.
The results in this work are in agreement with others reported in the
literature [20,23,26,30,31]. In general the evolution of the RMT during a
thermal cycling treatment promotes changes in the critical transformation
temperatures, like those shown in Figure 10, with a tendency to decrease with
the number of cycles.
It is conceivable that the internal elastic stress field developed in the alloy
structure during the 300 TCL under 0.2 kg helps to promote the 1R1
reaction at elevated temperatures. This could then be responsible for the
widening of the MsMf interval of direct transformation by displacing the
value of Ms to higher temperatures. On the other hand, the plastic deformation
associated with the introduced crystalline defects, makes it difficult the
finishing of the transformation and thus displaces Mf to lower temperatures.
With greater applied load during the treatment, a decrease in the critical
interval of MsMf for direct RMT is again observed due to a more stable
intermediate structure as revealed in the XRD pattern in Figure 2(d).
It is known that thermal cycling treatment promotes accumulation of
crystalline imperfections in SME Cu-Al-Ni alloys, which could retard the
RMT process [20,30,31]. Additionally, it is also shown that multiple
crystalline orientations can be obtained for the martensite in a RMT process
[1,5,6,20,21]. Whenever, SME alloys are submitted to deformation and
multiple RMT process, the morphological changes among the martensitic
variants and tend to cause cancellation of one with respect to another. As a
result, a relatively small macroscopic deformation is produced [5,7,20].
One may then suppose that an applied load during a thermal cycling
treatment, contributes to the decrease in the number of martensitic variants
acting in association with the RMT. This apparently facilitates the
development of the transformation. In the present work XRD evidences
suggest that this behavior can be correlated to an intermediate state of higher
stability, which corresponds to the R phase semi- coherent with both, the high
temperature 1 or the low temperature 1, Figures 2 and 4. As a consequence,
significant decrease in the thermal hysteresis and the transformation enthalpy
occurred with increasing applied load in association with narrower critical
intervals for RMT.
CONCLUSIONS
1. The increase in the value of a mechanical load constantly applied to a

monocrystalline Cu-13.5%Al-4%Ni alloy during a 300 thermal
cycling treatment, within the interval of critical temperatures
associated with reversible martensitic transformation (RMT), revealed
significant changes in the alloy behavior.
2. The reverse martensitic transformation 1R1 after a last half
cycle of cooling to 0oC (finishing at RT) occurs at lower temperatures
while the direct transformation 1R1 after a last half cycle of
heating to 90 oC (finishing at RT) occurs at higher temperatures with
increasing applied load.
3. With increasing applied load a decrease in the RMT characteristics
such as the critical intervals of temperature (MoMof, AoAof, MsMf,
AsAf), the thermal hysteresis and the transformation enthalpy was
observed.
4. The Vickers microhardness of the alloy measured after the treatment
increases with applied load. This is attributed to the accumulation of
crystalline defects.
5. All changes in the alloy characteristics and structural behavior could
be associated to microstructural re-orientation of the martensitic
structure and be explained by the stabilization of the R phase semi-
coherent with both the low temperature 1 and the higher temperature
1.
ACKNOWLEDGMENTS
The authors thank the Brazilian agencies CNPq, CAPES and FAPERJ for
supporting this work. It is also acknowledge the collaboration of I. Viahhi, R.
Toledo, T. Castilló and G. Lubman.
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Chapter 3
LATTICE DYNAMICS OF EQUIATOMIC

ALKALI BINARY ALLOYS
Aditya M. Vora*
Humanities and Social Science Department,
S.T.B.S. College of Diploma Engineering, Opp. Spinning Mill,
Varachha Road, Surat 395 006, Gujarat, India
ABSTRACT
The computations of the lattice dynamics of equiatomic alkali binary
alloys to second order in local model potential is discussed in terms of
real-space sum of Born von Karman central force constants. The local
field correlation functions due to Hartree (H) and Ichimaru-Utsumi (IU)
are used to investigate influence of the screening effects on the aforesaid
properties. Results for the lattice constants i.e.
C11 , C12 , C 44 ,
C12  C44 , C12 C44 and bulk modulus B obtained using the H-local
field correction function have higher values in comparison with the
results obtained for the same properties using IU local field correction
function. The results for the Shear modulus ( C  ), deviation from
Cauchy‟s relation, Poisson‟s ratio  , Young modulus Y , propagation
*
Corresponding address: Tel. : +91-2832-256424, E-mail address : [email protected].,
Parmeshwari 165, Vijaynagar Area, Hospital Road, Bhuj–Kutch, 370 001, Gujarat, INDIA
48 Aditya M. Vora
velocity of elastic waves, phonon dispersion curves and degree of

anisotropy A are highly appreciable for equiatomic alkali binary alloys.
Keywords: Lattice dynamics; equiatomic alkali binary alloys; Phonon

dispersion curves (PDC)
1. INTRODUCTION
In the study of various properties of solids, one frequently requires the
knowledge of interaction energy between the ions or atoms. The studies of a
pair-effective interionic interaction in simple metals have long history and
originally they were not systematized and were concerned with individual
metals on groups of metals. In recent years, considerable attention has been
devoted to the theoretical study of the nature of effective interaction between
constituent atom or ion in simple metals [1-8]. The bcc equiatomic A0.5 B0.5
alkali binary alloy systems forms substitutional solid solution for the entire
region of concentration „ X ‟of the second component, and the crystal binding
of the solid solution is unchanged compared with that of the pure alkali metals.
Theoretical studies about the lattice dynamics of the alloy systems have been
devoted to equiatomic alkali binary systems since the lattice dynamics of the
pure alkalis has been investigated in detail. But the work on the
comprehensive study of lattice dynamical properties of their binary alloys is
almost negligible [1-9]. Only Soma et al. [10] have studied the phonon
dispersion curves of Cs0.7K0.3, Cs0.7Rb0.3, Cs0.3Rb0.7 and Rb0.71Cs0.29 alloys.
Very recently we have reported the static and vibrational properties of alkali
metals and their equiatomic Na-based binary alloys using model potential
formalism [1-5]. Also, Gajjar et al. [6] have studied the lattice dynamics of bcc
Cs0.3K0.7 alloy. Experimentally, Kamitakahara and Copley [11] have studied
the lattice dynamics of Rb1 X K X alloys with X = 0.06, 0.18 and 0.29 by
neutron scattering. Recently, Chushak and Baumketner [12] have reported the
dynamical properties of liquid Cs0.3K0.7 alloy. Most of the earlier theoretical
studies are used various types of local as well as non-local model potential
with older local field correction function. Lattice dynamics of Rb71K29 binary
alloys has been studied by Jacucci et al. [13] using MD technique. Also, the
equiatomic alloys of alkali metals contain equal amount of volume, valence
and the Fermi energy, which is reflected the nature of the alloying behaviour.
Lattice Dynamics of Equiatomic Alkali Binary Alloys 49
As a consequence of the disorder, the phonon spectra of alloys can differ

considerable in character from those of the pure metals. Localized vibrational
modes may be present, and all phonons acquire a broadening and shift in
frequency. Besides their importance for the thermodynamic properties, the
lattice vibrations in alloy systems provide an ideal testing ground for any
theory of elementary excitations in disordered systems because the energy
wave vector relationship can be measured directly by either the coherence
inelastic neutron scattering experimentally or by the many theoretical models.
Once the phonon spectrum of the alloy is known, the calculation of the
vibrational contribution to the thermodynamic functions is straightforward
[14].
Therefore, in the present article, we have decided to work on equiatomic
alkali binary alloys with PAA model [1-6]. Well known single parametric
local model potential of Gajjar et al. [1, 2, 6] is used to describe the electron-
ion interaction. For the first time an advanced and more recent local field
correlation functions due to Ichimaru-Utsumi (IU) [15] has been employed in
such investigations. This helps in identifying the influence of exchange and
correlation effects in the static form of Hartree (H) dielectric function [16].
2. THEORETICAL METHODOLOGY
The phonon frequencies can be obtained by solving the standard secular
determinantal equation [1-8]
det D q   4 2 2 M    0 ,
(1)
D q 
where, M is the ionic mass,  the phonon frequency and the
dynamical matrix in which the force between two ions depends only upon the
distance between them is given by,
  ddrdrr 
2
D q   1 e iqr ,
n   r r
n
(2)
where r  is the interionic pair potential, and r and  are  and 
r th th
th
Cartesian components of the position vector of n ion, respectively. T
50 Aditya M. Vora
The interionic pair potential r  is computed from the well known
relation [7, 8]
Z 2e2 0
 2  F q 
sin qr
(r )  dq .
r  qr (3)
Where F q  is the energy wave number characteristic given by [7, 8]
F (q) 
0 q 2
WB ( q )
2  H (q)  1 .
8 e 2
1   H (q) 1 1  f q  (4)
 , W q ,  q 
With O B H and f q  are the atomic volume, bare-ion
pseudopotential, static Hartree dielectric function and local field correlation
function, respectively.
The bare-ion pseudopotential due to Gajjar et al. is given by [1, 2, 6]
 8Z  qrC 2 
W B q    cosqrC   
O q 2 
 
1  qrC 
2
 
. (5)
r
here, Z and C are the valence and parameter of the model potential,
respectively. The details of the model potential are narrated in the literature [1,
2, 6]. In the present investigation, the local field correction functions due to H
[15], IU [16] and S [17] are incorporated to see the impact of exchange and
correlation effects. The details of all the local field corrections are below.
Table 1. Input parameters and constants for equiatomic alkali binary

alloys
Metal Z kF (au) O (au)3 rC (au)

Li 1 0.5890 144.9 0.7738
Na 1 0.4882 254.5 1.0765
K 1 0.3947 481.4 1.3880
Rb 1 0.3693 587.9 1.4837
Cs 1 0.3412 745.5 1.9108
The H-screening function [15] is purely static, and it does not include the
exchange and correlation effects. The expression of it is,
f X   0 . (6)
The Ichimaru-Utsumi (IU)-local field correction function [16] is a fitting

formula for the dielectric screening function of the degenerate electron liquids
at metallic and lower densities, which accurately reproduces the Monte-Carlo
results as well as it also, satisfies the self consistency condition in the
compressibility sum rule and short range correlations. The fitting formula is
  8A   4  Q2 2  Q 
f  X   AIU Q 4  BIU Q 2  CIU   AIU Q 4   BIU  IU Q 2  C IU   ln 
  3    4Q 2Q 
(7)
Where Q  2 X . The parameters IU , IU and

A B C
IU are the atomic
volume dependent parameters of IU local field correction functions. The

mathematical expressions of these parameters are narrated in the respective
papers of the local field correction function [16].
The dynamical matrix element used in the present calculation finally takes
the form,
 
  r r
D q    1  e iqr  K t  2 K r  K t  ,
n  r  (8)
Here K t and K r are the force constants between a pair of ions interacting
through a central interaction and n specifies shell index.
1 dr 
Kt 
r dr
Z 2e2    sinqr  
  3  2 0 2  F q  q 2 cos qr  
q r 
dq .
r  r 0  (9)
52 Aditya M. Vora
d 2
Kr 
dr 2
q  q 2  2 sinqr   2 cosqr   qr sinqr  dq

2 Z e2 0 
  F .
r 3
 r
2 2
0  qr 
(10)
Table 2. Lattice dynamical properties of Li0.5Na0.5 alloy
Expt.
Properties H IU
[17]
C11 in 1010 dyne.cm-2 20.63 11.70 1.2320
C12 in 1010 dyne.cm-2 19.44 10.52 1.0335
C44 in 1010 dyne.cm-2 6.65 6.74 0.9100
C  in 1010 dyne.cm-2 5.94 5.90 0.0990
10 -2
B in 10 dyne.cm 19.84 10.92 1.1000
(C12-C44) in 1010 dyne.cm-2 12.78 3.78 0.1250
Cauchy‟s ratio (C11/C44) 2.92 1.56 1.1318
 0.49 0.47 0.4553
Y in 109 dyne.cm-2 1.77 1.74 2.7555
vL[100] in 105 cm. sec-1 4.95 3.73 4.1750
vT[100] in 105 cm. sec-1 2.81 2.83 3.5882
vL[110] in 105 cm. sec-1 5.63 4.61 5.3762
vT1[110] in 105 cm. sec-1 2.91 2.83 3.7958
vT2[110] in 105 cm. sec-1 0.84 0.84 1.1839
vL[111] in 105 cm. sec-1 5.85 4.87 5.7208
vT[111] in 105 cm. sec-1 1.76 1.77 2.2863
Y1 in 1010 dyne.cm-2 4.04 3.00 4.6839
Y2 0.089 0.087 0.1108
A 11.20 11.42 9.0514
Using these atomic force constants, we can generate inter atomic force
K 
constants which can then be employed to investigate the elastic constants
d 2 (r )
K  
dr dr
 r r  r r
    2  Kt  2 Kr .
 r  r
(11)
Under the long-wave phonon method, the elastic constants are studied by
[1-8]
C11 
1
 
 N (n) x 2 K xxn  y 2 K yyn  z 2 K zzn ,
12a n (12)
C44 
1

24a n
   2
 
N (n) y 2  z 2 K xxn  z 2  x 2 K yyn  z 2 K zzn ,
(13)
C12  C44 
1

6a n

N (n) yzK yzn  zxK zxn  xy K xyn . 
(14)
Where “ a ” is the lattice constant and N n  is the number of atoms at the

n th neighbour separation. The shear modulus C  and bulk modulus B are
given by [1-8]
 C  C12 
C '   11  .
 2  (15)
and
 C  2C12 
B   11 .
 3  (16)
The extent to which the interatomic forces are non-pair wise can be
obtained by investigating the breakdown of the Cauchy relation. The Cauchy‟s
ratio is obtained by C12 C44 .
54 Aditya M. Vora
Poisson‟s ratio  is the second independent elastic parameter and is

given as [1-8],
C12
  .
C11  C12  (17)
From the calculated values of the bulk modulus and Poisson‟s ratio, Young
modulus Y is derived as [1-8],
Y  3B(1 2 ) . (18)
7.0
Li0.5Na0.5 [100] [111] [110]
6.0
Phonon Frequncy (THZ)
5.0
4.0
3.0
2.0
H
1.0 IU
Expt. (PAA)
0.0
0.0 0.5 1.0 0.5 0.0 0.5
Reduced wave vector
Figure 1. Phonon dispersion curves of Li0.5Na0.5 alloy.
In the cubic system the propagation velocity of longitudinal and transverse

waves in [100], [110] and [111] directions are given as [1-8]
1
C  2
v L [100]   11  .
   (19)
1
 (C  C12  2C44 )  2
v L [110]   11  .
 2  (20)
1
 (C  2C 12  4C 44 )  2
v L [111]   11  .
 3  (21)
1
C  2
v T [100]  v T 1[110]   44  .
   (22)
1
 (C11 - C12)  2
v T2 [110]    .
 2  (23)
1
 (C11  C12  2C 44 )  2
v T [111]    .
 3  (24)
Table 3. Lattice dynamical properties of Li0.5K0.5 alloy
Properties H IU Expt. [17]

C11 in 10 dyne.cm-2
10
9.75 15.21 0.9935
C12 in 1010 dyne.cm-2 9.21 13.99 0.8350
C44 in 1010 dyne.cm-2 3.53 3.57 0.7230
C  in 1010 dyne.cm-2 2.69 6.07 0.0795
10 -2
B in 10 dyne.cm 9.39 10.43 0.8880
(C12-C44) in 1010 dyne.cm-2 5.68 10.43 0.1270
Cauchy‟s ratio (C11/C44) 2.61 3.92 1.1689
 4.86 4.79 0.4543
Y in 109 dyne.cm-2 0.80 1.80 2.1730
vL[100] in 105 cm. sec-1 3.44 4.29 3.7604
vT[100] in 105 cm. sec-1 2.07 2.08 3.1962
vL[110] in 105 cm. sec-1 3.97 4.68 4.8202
vT1[110] in 105 cm. sec-1 2.07 2.08 3.1992
vT2[110] in 105 cm. sec-1 0.57 0.86 1.0677
vL[111] in 105 cm. sec-1 4.14 4.81 5.1250
vT[111] in 105 cm. sec-1 1.28 1.39 2.0430
Y1 in 1010 dyne.cm-2 2.04 2.79 4.1375
Y2 0.08 0.17 0.1177
A 13.11 5.87 8.6066
56 Aditya M. Vora
The behavior of phonon frequencies in the limit independent of direction

is given by [1-5]
i2 (q)  (C  2C 44 ) 
Y1  lim    11 ,
q 0
i q 2
   (25)
and
 C - C12 
2
 
Y2  lim  T1    11  .
q 0
  T2   2C 44  (26)
The degree of elastic anisotropy A is the inverse of Y2 , i.e. [1-8],
 2C44 
A .
 C11  C12  (27)
The value of A is unity when the material is elastically isotropic and

differs from unity otherwise.
6.0
Li0.5K0.5 [100] [111] [110]
5.0
4.0
3.0
2.0
H
1.0
IU
Expt. (PAA)
0.0
0.0 0.5 1.0 0.5 0.0 0.5
Reduced wave vector
Figure 2. Phonon dispersion curves of Li0.5K0.5 alloy.

6.0
H [100] Li0.5Rb0.5 [111] [110]
IU
5.0
Expt. (PAA)
4.0
3.0
2.0
1.0
0.0
0.0 0.5 1.0 0.5 0.0 0.5
Reduced wave vector
Figure 3. Phonon dispersion curves of Li0.5Rb0.5 alloy.
Table 4. Lattice dynamical properties of Li0.5Rb0.5 alloy

C11 in 10 dyne.cm-2
10
10.98 8.01 0.9435
C12 in 1010 dyne.cm-2 10.26 7.17 0.7930
C44 in 1010 dyne.cm-2 3.63 3.89 0.6855
C  in 1010 dyne.cm-2 3.61 4.21 0.0755
10 -2
B in 10 dyne.cm 10.50 7.44 0.8435
(C12-C44) in 1010 dyne.cm-2 6.63 3.27 0.1180
Cauchy‟s ratio (C11/C44) 2.82 1.84 1.1818
 0.48 0.47 0.4533
Y in 109 dyne.cm-2 1.07 1.24 2.0572
vL[100] in 105 cm. sec-1 2.79 2.38 3.3891
5 -1
vT[100] in 10 cm. sec 1.60 1.66 2.8830
vL[110] in 105 cm. sec-1 3.17 2.85 4.3447
vT1[110] in 105 cm. sec-1 1.60 1.66 2.8830
vT2[110] in 105 cm. sec-1 0.51 0.55 0.9599
vL[111] in 105 cm. sec-1 3.29 2.99 4.6195
vT[111] in 105 cm. sec-1 1.01 1.06 1.8404
Y1 in 1010 dyne.cm-2 12.90 11.17 3.8236
Y2 0.10 0.11 0.1220
A 10.05 9.23 8.3698
58 Aditya M. Vora
H [100] Li0.5Cs0.5 [111] [110]
6.0 IU
Expt. (PAA)
4.0
2.0
0.0
0.0 0.5 1.0 0.5 0.0 0.5
Reduced wave vector
Figure 4. Phonon dispersion curves of Li0.5Cs0.5 alloy
4.0
Na0.5K0.5 [100] [111] [110]
3.0
2.0
1.0 H
IU
Expt. (PAA)
0.0
0.0 0.5 1.0 0.5 0.0 0.5
Reduced wave vector
Figure 5. Phonon dispersion curves of Na0.5K0.5 alloy.

Constants and parameters employed for the present computational study
are listed in Table 1. In evaluating integration in Eqs. (10) and (11) the upper
limit of integral is taken as 40 kF so that, a complete convergence of the model

potential is achieved at higher momentum transfer and it covers all the
oscillations of the form factor. Therefore, any artificial/fictitious cut-off in the
present computations is avoided. In the present computation, the error
6
associated will be of the order of 10 k F 2 . We have performed the real space
sum analysis in r-space of 33 sets of nearest neighbours, which are found
sufficient for computing the elastic constants and bulk modulus using
interatomic force constants and for considering a long-range character for
proper convergence of the calculation and to achieve desired accuracy. The
present model is valid for both ordered and disordered alloys [1-8].
Table 5. Lattice dynamical properties of Li0.5Cs0.5 alloy.

C11 in 1010 dyne.cm-2 8.01 6.73 0.9155
C12 in 1010 dyne.cm-2 7.33 5.61 0.7725
C44 in 1010 dyne.cm-2 2.99 3.76 0.6600
C  in 1010 dyne.cm-2 3.40 5.56 0.0715
10 -2
B in 10 dyne.cm 7.56 5.99 0.8205
(C12-C44) in 1010 dyne.cm-
2 4.34 1.86 0.1125
Cauchy‟s ratio (C11/C44) 2.45 1.49 1.2478

 0.48 0.45 0.4559
Y in 109 dyne.cm-2 1.00 1.62 1.9497
vL[100] in 105 cm. sec-1 2.13 1.95 3.1411
vT[100] in 105 cm. sec-1 1.30 1.46 2.7642
vL[110] in 105 cm. sec-1 2.46 2.37 4.1773
vT1[110] in 105 cm. sec-1 1.30 1.46 2.7619
vT2[110] in 105 cm. sec-1 0.44 0.56 0.9133
vL[111] in 105 cm. sec-1 2.56 2.50 4.4401
vT[111] in 105 cm. sec-1 0.83 0.96 1.7608
Y1 in 1010 dyne.cm-2 7.95 8.09 3.7428
Y2 0.11 0.15 0.1209
A 8.81 6.76 8.4297
60 Aditya M. Vora
Table 6. Lattice dynamical properties of Na0.5K0.5 alloy.

C11 in 1010 dyne.cm-2 10.11 6.36 0.6545
C12 in 1010 dyne.cm-2 9.40 5.51 0.5395
C44 in 1010 dyne.cm-2 3.27 3.42 0.4730
C  in 10 10
dyne.cm -2 3.56 4.28 0.0575
B in 1010 dyne.cm-2 9.63 5.79 0.5780
10 -2
(C12-C44) in 10 dyne.cm 6.12 2.09 0.0830
Cauchy‟s ratio (C11/C44) 2.87 1.61 1.1552
 0.48 0.46 0.4514
Y in 109 dyne.cm-2 1.05 1.25 1.6695
vL[100] in 105 cm. sec-1 3.27 2.59 2.5447
vT[100] in 105 cm. sec-1 1.86 1.90 2.1522
vL[110] in 105 cm. sec-1 3.71 3.14 3.2481
vT1[110] in 105 cm. sec-1 1.86 1.90 2.3628
vT2[110] in 105 cm. sec-1 0.61 0.67 0.7556
vL[111] in 105 cm. sec-1 3.85 3.31 3.4508
vT[111] in 105 cm. sec-1 1.19 1.23 1.3889
Y1 in 1010 dyne.cm-2 17.61 13.96 1.6240
Y2 0.11 0.13 0.1242
A 9.17 7.99 8.0713
In the present computation, the bcc crystal structure considered for all the
solid solutions. The lattice constants „ a ‟ are obtained from the well known
relation
2O  . Tables 2-11 display the computed values of some static and
13
vibrational properties of equiatomic alkali binary alloys. It is noted in Tables

2-11 that our results for C11 , C12 , C 44 , C12  C44 , C12 C44 and bulk
modulus B from H-local field correction function give values higher than
those obtained for the IU-local field correction functions. There is a good
agreement for the calculated values of the Shear modulus C  , deviation from
velocity of elastic waves, phonon dispersion curves (PDC) and degree of
anisotropy A using H, IU and S-local field correction functions. The
experimental data of most of the alloys are not available in the literature, but in
the present case we have computed them through PAA model using the
experimental data of pure metallic elements. The comparison of the presently

computed values and PAA experimental data shows large discrepancies, but
they are found in qualitative agreement with experimental data [17]. Same
trends of the results are observed for alloys.
Table 7. Lattice dynamical properties of Na0.5Rb0.5 alloy

C11 in 1010 dyne.cm-2 8.00 4.98 0.6045
C12 in 1010 dyne.cm-2 7.45 4.30 0.4975
C44 in 1010 dyne.cm-2 2.73 2.87 0.4355
C  in 1010 dyne.cm-2 2.78 3.43 0.0535
10 -2
B in 10 dyne.cm 7.63 4.53 0.5335
(C12-C44) in 1010
4.72 1.42 0.0740
dyne.cm-2
Cauchy‟s ratio
2.73 1.49 1.1680
(C11/C44)
 0.48 0.46 0.4504
Y in 109 dyne.cm-2 0.82 1.00 1.5537
vL[100] in 105 cm. sec-
1 2.35 1.86 2.1735
vT[100] in 105 cm. sec-

1 1.38 1.41 1.8390
vL[110] in 105 cm. sec-

1 2.69 2.28 2.7726
vT1[110] in 105 cm.

1.38 1.41 2.0466
sec-1
vT2[110] in 105 cm.
0.44 0.49 0.6478
sec-1
vL[111] in 105 cm. sec-
1 2.79 2.41 2.9453
vT[111] in 105 cm. sec-

1 0.87 0.91 1.1864
Y1 in 1010 dyne.cm-2 9.33 7.43 1.3100

Y2 0.10 0.12 0.1286
A 9.83 8.39 7.8345
62 Aditya M. Vora
3.0
Na0.5Rb0.5 [100] [111] [110]
2.5
2.0
1.5
1.0
H
0.5
IU
Expt. (PAA)
0.0
0.0 0.5 1.0 0.5 0.0 0.5
Reduced wave vector
Figure 6. Phonon dispersion curves of Na0.5Rb0.5 alloy.
2.5
Na0.5Cs0.5 [100] [111] [110]
2.0
1.5
1.0
H
0.5
IU
Expt. (PAA)
0.0
0.0 0.5 1.0 0.5 0.0 0.5
Reduced wave vector
Figure 7. Phonon dispersion curves of Na0.5Cs0.5 alloy.

2.5
H [100] K0.5Rb0.5 [111] [110]
IU
2.0
Expt. (PAA)
1.5
1.0
0.5
0.0
0.0 0.5 1.0 0.5 0.0 0.5
Reduced wave vector
Figure 8. Phonon dispersion curves of K0.5Rb0.5 alloy.
The phonon dispersion curves (PDC) of equiatomic alkali binary alloys

along [100], [110] and [111] directions of high symmetry, which are shown in
Figures 1-10 with available experimental findings [17]. The present results of
pure alkali elements are found in qualitative agreement with the experimental
data [17]. We have found that the phonon frequencies in the longitudinal
branch are more sensitive to the exchange and correlation effects in
comparison with the transverse branches. The frequencies in the longitudinal
branch are suppressed due to IU-screening function than the frequencies due to
static H-screening function. While in the transverse branch effect of exchange
and correlation enhances slightly the phonon modes. It is found that at the
zone boundaries of [100] and [111] directions, i.e., for the larger momentum
transfer the effect of local field correlation is almost negligible. These
dispersion curves are not showing any abnormality in the three regions of high
symmetry directions and exhibiting qualitative behaviour like metallic
elements. From the Figures 1-10, we observe that, when we move from
Li0.5Na0.5 → Rb0.5Cs0.5 alloys, the phonon frequency decreases with increase in
the average volume of the solid alloys. The phonon dispersion curves (PDC)
are seen to be quite unsatisfactory except near the small k -regions (k < 0.6 or
so) because of the average data of the pure metallic elements. For some
equiatomic alkali binary alloys, present results deviate more from the
experimental points. The results for equiatomic alkali binary alloys can be
improved by fitting the parameters of the potential to the phonon frequency.
64 Aditya M. Vora
But present study is independent of such fitting hence in some cases the
discrepancy is observed. The experimental phonon frequencies of such alloys
are not available, but the experimental values of phonon frequency are
estimated from the pure metallic components [17], which are shown in Figures
1-10. This comparison favours and confirms our formulation of pseudo-alloy-
atom (PAA) of equiatomic alkali binary alloys. Also, in the absence of
experimental information such calculations may be considered as one of the
guidelines for further investigations either theoretical or experimental. Hence,
such study could be extended for the other types of the solid binary alloys.
2.0
H [100] K0.5Cs0.5 [111] [110]
IU
Expt. (PAA)
1.5
1.0
0.5
0.0
0.0 0.5 1.0 0.5 0.0 0.5
Reduced wave vector
Figure 9. Phonon dispersion curves of K0.5Cs0.5 alloy.
Table 8. Lattice dynamical properties of Na0.5Cs0.5 alloy

C11 in 1010 dyne.cm-2 8.15 5.87 0.5765
C12 in 1010 dyne.cm-2 7.53 5.09 0.4770
C44 in 1010 dyne.cm-2 2.44 2.38 0.4100
C  in 1010 dyne.cm-2 3.08 3.96 0.0495
10 -2
B in 10 dyne.cm 7.74 5.36 0.5105
(C12-C44) in 1010 dyne.cm-2 5.09 2.72 0.0685
Cauchy‟s ratio (C11/C44) 3.08 2.14 1.2340
 0.48 0.46 0.4530
Y in 109 dyne.cm-2 0.91 1.16 1.4462
vL[100] in 105 cm. sec-1 2.16 1.84 1.9255
Table 8. (Continued)

vT[100] in 105 cm. sec-1 1.18 1.17 1.7202
vL[110] in 105 cm. sec-1 2.43 2.12 2.6052
vT1[110] in 105 cm. sec-1 1.18 1.17 1.9255
vT2[110] in 105 cm. sec-1 0.42 0.48 0.6012
vL[111] in 105 cm. sec-1 2.51 2.21 2.7659
vT[111] in 105 cm. sec-1 0.76 0.78 1.1067
Y1 in 1010 dyne.cm-2 7.46 6.09 1.2293
Y2 0.13 0.17 0.1274
A 7.93 6.00 7.8944
Table 9. Lattice dynamical properties of K0.5Rb0.5 alloy

C11 in 1010 dyne.cm-2 6.14 6.13 0.3660
C12 in 1010 dyne.cm-2 5.50 5.50 0.2990
C44 in 1010 dyne.cm-2 2.36 2.36 0.2485
C  in 1010 dyne.cm-2 3.15 3.13 0.0340
10 -2
B in 10 dyne.cm 5.71 5.71 0.3215
(C12-C44) in 1010 dyne.cm-2 3.14 3.14 0.0760
Cauchy‟s ratio (C11/C44) 2.33 2.33 1.2051
 0.47 0.47 0.4494
Y in 109 dyne.cm-2 0.93 0.92 0.9712
vL[100] in 105 cm. sec-1 2.17 2.17 1.7588
vT[100] in 105 cm. sec-1 1.35 1.34 1.4470
vL[110] in 105 cm. sec-1 2.50 2.50 2.2166
vT1[110] in 105 cm. sec-1 1.35 1.34 1.4500
vT2[110] in 105 cm. sec-1 0.49 0.49 0.5317
vL[111] in 105 cm. sec-1 2.61 2.60 2.3495
vT[111] in 105 cm. sec-1 0.87 0.87 0.9430
Y1 in 1010 dyne.cm-2 8.32 8.31 0.7636
Y2 0.13 0.13 0.1354
A 7.49 7.53 7.3898
66 Aditya M. Vora
Figure 10. Phonon dispersion curves of Rb0.5Cs0.5 alloy.
Table 10. Lattice dynamical properties of K0.5Cs0.5 alloy

C11 in 10 dyne.cm-2
10
6.87 4.92 0.3380
C12 in 1010 dyne.cm-2 6.35 4.33 0.2785
C44 in 1010 dyne.cm-2 1.95 1.96 0.2230
C  in 1010 dyne.cm-2 2.61 2.93 0.0300
10 -2
B in 10 dyne.cm 6.52 4.53 0.2985
(C12-C44) in 1010 dyne.cm-2 4.40 2.38 0.0705
Cauchy‟s ratio (C11/C44) 3.26 2.21 1.2711
 0.48 0.47 0.4520
Y in 109 dyne.cm-2 0.77 0.86 0.8637
vL[100] in 105 cm. sec-1 2.09 1.77 1.5108
vT[100] in 105 cm. sec-1 1.11 1.12 1.3282
vL[110] in 105 cm. sec-1 2.33 2.05 2.0492
vT1[110] in 105 cm. sec-1 1.11 1.12 1.3289
vT2[110] in 105 cm. sec-1 0.41 0.43 0.4850
vL[111] in 105 cm. sec-1 2.41 2.13 2.1701
vT[111] in 105 cm. sec-1 0.72 0.73 0.8634
Y1 in 1010 dyne.cm-2 6.85 5.62 0.6829
Y2 0.13 0.15 0.1343
A 7.47 6.66 7.4496
Table 11. Lattice dynamical properties of Rb0.5Cs0.5 alloy

C11 in 1010 dyne.cm-2 6.04 4.26 0.2880
C12 in 1010 dyne.cm-2 5.59 3.77 0.2365
C44 in 1010 dyne.cm-2 1.74 1.77 0.1855
C  in 1010 dyne.cm-2 2.26 2.43 0.0260
10 -2
B in 10 dyne.cm 5.74 3.93 0.2540
(C12-C44) in 1010 dyne.cm-2 3.84 2.00 0.0615
Cauchy‟s ratio (C11/C44) 3.20 2.13 1.2840
 0.48 0.47 0.4511
Y in 109 dyne.cm-2 0.67 0.71 0.7480
vL[100] in 105 cm. sec-1 1.81 1.52 1.1396
vT[100] in 105 cm. sec-1 0.97 0.98 1.0151
vL[110] in 105 cm. sec-1 2.03 1.77 1.5737
vT1[110] in 105 cm. sec-1 0.97 0.98 1.0127
vT2[110] in 105 cm. sec-1 0.35 0.36 0.3772
vL[111] in 105 cm. sec-1 2.10 1.86 1.6646
vT[111] in 105 cm. sec-1 0.63 0.64 0.6608
Y1 in 1010 dyne.cm-2 5.19 4.24 0.3689
Y2 0.13 0.14 0.1386
A 7.73 7.29 7.2128
A good description of Cs or Rb is rather more complicated than that of the

other alkali elements. The problem stems from the fact that at pure Cs or Rb
density the compressibility of the electron gas is close to zero, and is
conceivably negative. Hence, the normal pseudopotential perturbation
approach based on the electron gas as the zero order approximation is rather
dubious. This is because one is starting with a thermodynamically unstable
system to provide a description of one which is thermodynamically stable. The
way out of this dilemma, was used to scale the electron gas density parameter
r *
i.e. the Wigner-Seitz radius S by the band structure effective mass m ,
which then meant that one was dealing with an effective density for which the
electron gas compressibility was large and positive. The physical meaning of
this approach was not clear, but it bears a close resembles to that the effect of
large core polarization of Cs or Rb could be taken into account by a suitable
rS
scaling of , also in the direction of large, positive compressibility. But, in
68 Aditya M. Vora
the present results of the lattice dynamics of the equiatomic alkali binary
alloys, we have made straightforward computation without any assumptions.
The relativistic effect of the heavier alkali element like Cs to other alkali
elements is significant, but in the case of equiatomic alkali binary alloys, this
effect is comparatively small. Therefore, we have ignored relativistic effects of
the heavier atom for the sake of simplicity.
CONCLUSIONS
We conclude that the present model is successful in explaining the lattice
dynamical properties of equiatomic alkali binary alloys and hence, it could be
explored for predicting the behavior of other such solid solutions. The
comparison of present theoretical findings helps us to note that the binding of
equiatomic alkali binary alloys is comparable to the pure metals, and hence,
behaves like a solid metallic alloy. This can be confirmed by investigating its
total crystal energy and heat of solution. Such study is under progress and the
results will be reported in due course of the time. From the present experience,
we also conclude that it should be interesting to apply other local
pseudopotentials for such comprehensive study to judge and confirm the wider
applicability of the potential.
REFERENCES
[1] Aditya M. Vora, J. Phys. Chem. Sol. 68 (2007) 1725
[2] Aditya M. Vora, Chinese Phys. Lett. 25 (2008) 654.
[3] Aditya M. Vora, Front. Mater. Sci. China 2 (2008) 311.
[4] Aditya M. Vora, Moroccan J. Conden. Matter 10 (2008) 7.
[5] Aditya M. Vora, Fizika A17 (2008) 87; Digest J. Nanomater. Biostruct.
4 (2009) 113.
[6] Gajjar, P. N., Patel, M. H., Thakore, B. Y. and Jani, A. R. Commun. of
Phys. 12 (2002) 81.
[7] Gajjar, P. N., Thakore, B. Y., Patel, H. K. and Jani, A. R. Acta Phys.
Pol. A88 (1995) 489.
[8] Gajjar, P. N., Thakore, B. Y., Luhar, J. S. and Jani, A. R. Physica B 215
(1995) 293.
[9] Wallis, R. F., Maradudin, A. A., Eguiluz, A. G., Quong, A. A.,
Franchini, A. and Santara, G. Phys. Rev. B 48 (1993) 6043.
[10] Soma, T., Ohsugi, H. and Matsuo Kagaya, H. Phys. State. Sol. (b) 124
(1984) 525.
[11] Kamitakahara, W. A. and Copley, J. R. D. Phys. Rev. B18 (1978) 3772.
[12] Chushak, Y. A. and Baumketner, A. Euro. Phys. J. B7 (1999) 129.
[13] Jacussi, G., Klein, M. L. and Taylor, R., Phys. Rev. B18 (1978) 3782.
[14] Hafner, J. From Hamiltonians to Phase Diagrams, (Sringer-Verlag,
Heidelberg, 1987).
[15] Ichimaru, S. and Utsumi, K. Phys. Rev. B24 (1981) 7385.
[16] Harrison, W. Elementary Electronic Structure, (World Scientific,
Singapore,1999).
[17] Shimada, K. Phys. State. Sol. (b) 61 (1974) 325.
Chapter 4
LATTICE DYNAMICS OF LIQUID ALLOYS
Aditya M. Vora*
ABSTRACT
In the present article, the lattice dynamical properties of some
equiatomic liquid alkali binary alloys are reported in second order
approach through the equation given by Hubbard and Beeby (HB). The
pair correlation function is directly computed from the interatomic
pair potential, which is used in the present computation. Two different
forms of local field correction functions proposed by Hartree (H) and
Ichimaru-Utsumi (IU) are used in the present study the screening
dependence of the phonon frequencies in the equiatomic liquid alkali
binary alloys. Thermodynamic and elastic properties of equiatomic liquid
alkali binary alloys are reported from the long wave length limits of the
phonon dispersion curves (PDC). The pseudo-alloy-atom (PAA) model is
applied for the first time for the alloying elements.
*
72 Aditya M. Vora
Keywords: Pseudopotential, equiatomic liquid alkali binary alloys, lattice

dynamical properties, phonon dispersion curves (PDC), thermodynamic
and elastic properties.
1. INTRODUCTION
The problem of an appropriate description of the structure and related
properties of liquids arise from their intermediate situation between ideal gases
and solids. It is well known that crystalline solids having long range order are
completely characterized by their symmetry properties whereas liquids having
no such periodicity and can be characterized only by distribution or correlation
functions. In liquids the interpretation of neutron inelastic scattering
measurements is more complicated than it is in the case of solids, largely
because there is no long range order, neither in space nor in time. At low
frequencies, the liquids behave as a viscous medium but at higher frequencies
its response is elastic, the system behaves like a solid and transverse
excitations are supported [1-10].
Collective excitations in fluids have been studied experimentally,
theoretically and by computer simulations for almost several decades. Lot of
effort has been put to study the dynamical properties of liquid metals [1-10]
both theoretically and experimentally. The investigation of collective modes in
liquid alloys has comparatively received less attention. Some few researchers
[1-8] have reported the phonon dispersion curves of simple liquid metals. It
was found that the maximum deviation takes place in the vicinity of the first
spherical Brillouin zone. This region lies nearly at the half distance of the first
peak in the structure factor . Thus, the choice of structure factor
also plays a vital role in the study of lattice dynamics of liquid metals. In the
present work we have used the pair correlation function instead of
structure factor calculated using the interatomic pair potential to give the
calculation a flavour model potential.
The present article deals with the computation of the lattice dynamical
properties of equiatomic liquid alkali binary alloys with the aim to explore the
applications of model potential of Gajjar et al. [11] for the first time. The
choice of the model potential form factor is certainly an important factor in the
study of metallic properties and its actual form is much more sensitive to the
choice of the local field correction functions of the electron gas. Hence, the
purpose of the present article is not only to study the lattice dynamical
Lattice Dynamics of Liquid Alloys 73
properties, but also to see the influence of the various local field correction
functions in the screening. Therefore, we have adopted here two different
types of local field correlation functions viz. Hartree (H) [12] and Ichimaru-
Utsumi (IU) [13]. Also, we have used here Hubbard and Beeby (HB) [14]
approach for studying the lattice dynamical properties of equiatomic liquid
alkali binary alloys.
From a theoretical point of view, A1 X BX is a good system to study. Both
constituents are the members of the different substances of the periodic table
which, because of their relatively simple band structure, are generally least
complicated of all metallic systems to deal with. Assuming, then, that a good
description of both A and B metals can be utilized, a study of the alloy
systems will shed a great deal of the light on the general usefulness of the
technique employed. One such technique that has been used successfully by us
is the pseudo-alloy-atom (PAA) model [15, 16]. It is well known that the
pseudo-alloy-atom (PAA) is a more meaningful approach to explain such kind
of interactions in binary systems [15, 16]. In the PAA approach a hypothetical
monoatomic crystal is supposed to be composed of pseudo-alloy-atoms, which
occupy the lattice sites and form a perfect lattice in the same way as pure
metals. In this model the hypothetical crystal made up of PAA is supposed to
have the same properties as the actual disordered alloy material and the
pseudopotential theory is then applied to studying various properties of an
alloy and metallic glass [15, 16]. The complete miscibility in the alloy systems
is considered as a rare case. Therefore, in such binary systems the atomic
matrix elements in the pure states are affected by the characteristics of alloys
such as lattice distortion effects and charging effects. In the PAA model, such
effects are involved implicitly. In addition to this it also takes into account the
self-consistent treatment implicitly [15, 16]. Looking to the advantage of the
PAA model, we propose a use of PAA model to investigate the lattice
dynamical properties of binary systems.
2. COMPUTATIONAL METHODOLOGY
The interatomic pair potential r  is calculated from the relation given
by [15, 16],
74 Aditya M. Vora
 Z 2 e 2  O  Sinqr   2
r     F q  
 r  2   qr 
 q dq
  . (1)
Where, and are the valence and atomic volume of the equiatomic
liquid alkali binary alloys, respectively. The energy wave number
characteristics appearing in the Eqs. (1) is written as [15, 16],
F q  
 O q 2
WB q 
2  H q   1
16 1   H q   11 f q  . (2)
Here WB q  ,  H q  , f q  are the bare ion potential, the Hartree

dielectric response function and the local field correction functions to
introduce the exchange and correlation effects, respectively.
The Hartree (H) screening function [12] is purely static, and it does not
include the exchange and correlation effects. The expression of it is,
f q   0 . (3)
The Ichimaru-Utsumi (IU) local field correction function [13] is a fitting

  q 2  q 
4    2    
4
q
2
q  q  4
8 A  q 
2
  k 
f q   AIU    BIU    CIU   AIU     BIU  IU     CIU    F  ln  kF  

  F   3   kF     q 
 F  F   4 
k k k q
2   
  k F  k  
 F
 .
(4)
A B C
The parameters IU , IU and IU are the atomic volume dependent
parameters of IU local field correction functions. The mathematical
expressions of these parameters are narrated in the respective papers of the
local field correction function [13].
The bare-ion pseudopotential due to Gajjar et al. [11] is given by
 8Z  qrC 2 
W B q    cosqrC   
O q 2 
 
1  qrC 
2
 
. (5)
r
respectively. The details of the model potential are narrated in the literature
[11].
To compute the phonon dispersion relations of liquid metals, which are
also applicable to liquid binary alloys, the most frequently used approach of
Hubbard and Beeby (HB) [14] is adopted. With the physical argument that the
product of the static pair correlation function and the second derivative
of the interatomic pair potential r  is peaked near the hard sphere diameter
, Hubbard and Beeby (HB) [14] have derived the expressions for the
longitudinal phonon frequencies L(q) and the transverse phonon frequencies
T(q) as [14],
 sin q  6 cosq  6 sin q  

 L2 q    E2 1    
 q q 2 q 3  , (6)
and
 3 cosq  3 sin q  

T2 q    E2 1   
 q 2
q 3  . (7)

 4 
    g r  r  r dr
2 2
E
with  3M 0 is the maximum frequency.
Where, and r  are the number density, atomic mass, pair
correlation function and interatomic pair potential of the element, respectively.
The fundamental ingredient, which goes into the calculation of the lattice
dynamics of equiatomic liquid alkali binary alloys, is the interatomic pair
potential r  . In the present study, the interatomic pair potential r  is
computed from Eqs. (1). A quantity which is equally important as the
76 Aditya M. Vora
interatomic pair potential (r) while studying a disorder system is the pair
correlation function (PCF) g r  . It provides the statistical description of the
structure of the system under investigation. The complete information of the
precise position and momentum of each particle at each instant of time is
contained in this function. The function g r  can be obtained either
experimentally by X-ray diffraction and neutron diffraction technique [17] or
computed theoretically from the interatomic pair potential r  [17]. Instead
of using experimentally available g r  , here the pair correlation function for
all disordered systems are generated from presently obtained interatomic pair
potential r  . The function g r  is presently calculated using the
expression [17],
 V r 
g r   exp   1
 kB T  . (8)
Here k B is the Boltzmann‟s constant and T the room temperature of the

system under investigation.
Figure 1. Phonon dispersion curves of liquid Li0.5Na0.5 alloy.

In the case of disordered materials, it is convenient to discuss density

fluctuations in q -space and obtain macroscopic properties by taking q  0
limit (in low frequency region). The introduction of the elastic model is a good
example of the same, because the stress can be written most conveniently in q
-space. Elastic behaviour of the system is in general given by the response of it
to the propagation of the density fluctuations in the wavelength limit.
Therefore, the dispersion relations prove to be useful in deriving the elastic as
well as thermodynamic properties of disordered materials.
Figure 2. Phonon dispersion curves of liquid Li0.5K0.5 alloy.

78 Aditya M. Vora
Figure 3. Phonon dispersion curves of liquid Li0.5Rb0.5 alloy.
The present study include some elastic properties such as the isothermal
bulk modulus BT , modulus of rigidity G , Poisson‟s ratio  and Young‟s
modulus Y and some thermodynamic properties such as longitudinal sound
velocity  L , transverse sound velocity T and Debye temperature  D for the
disordered materials. In the long wavelength limit of the frequency spectrum,
both the frequencies i.e. transverse and longitudinal are proportional to the
wave vectors and obey the relationships [14-16],
 L  q and T  q ,
  L  L q and T T q . (9)
Where  L and T are the longitudinal and transverse sound velocities in

the disordered materials, respectively.
Figure 4. Phonon dispersion curves of liquid Li0.5Cs0.5 alloy.

80 Aditya M. Vora
Figure 5. Phonon dispersion curves of liquid Na0.5K0.5 alloy.
For HB approach the formulations for  L and T are given by [14]
3 2
 L HB    E
10 , (10)
and
2
T HB    E
10 . (11)
Where  E is calculated from the equation (7).
The isothermal bulk modulus BT , modulus of rigidity G , Poisson‟s ratio

 and Young‟s modulus Y are found using the expressions [14, 15],
 4 
BT   M  L2  T2 
 3 , (12)
G   M  T2 . (13)
With  M is the isotropic number density of the disordered materials.
  T2 
1  2 2 
  L 
  T2 
2  2 2 
L  , (14)
and
Y  2G  1 . (15)
The Debye temperature is given in terms of both the velocities as [14, 15],
1 13 
 D   9  eff  3
1 2
D   2    3  3
kB kB  4   L T  , (16)
here k B the Boltzmann‟s constant and  D the Debye frequency, respectively.

82 Aditya M. Vora
Table 1. Constants and parameters for equiatomic liquid alkali binary

alloys

Li 1 0.5890 144.9 0.7738
Na 1 0.4882 254.5 1.0765
K 1 0.3947 481.4 1.3880
Rb 1 0.3693 587.9 1.4837
Cs 1 0.3412 745.5 1.9108

The constants and parameters used in the present computations of the
phonon dispersion curves of the liquid alkali metals are tabulated in Table 1.
Moreover, instead of taking the concentration average of pure metallic
elements, we have treated here A1 X BX as a pseudo-alloy-atom (PAA), which
is more meaningful approach [15, 16]. Following definitions for the
parameters of alloy A1 X BX is adopted for making the computations of the
lattice dynamics of equiatomic binary alloys [15, 16].
rC  (1  X ) rC  A   X rC  B 
, (17)
Z  (1  X ) Z  A  X Z  B 
, (18)
O  (1  X ) O A  X  O B 
, (19)
M  (1  X ) M  A  X M  B 
, (20)
k F  (1  X ) k F  A  X k F  B 
. (21)
The computed phonon dispersion curves of equiatomic liquid alkali binary

alloys are displayed in Figures 1-10. Here, also it may be seen that the
dispersion of the longitudinal phonon exhibits oscillatory behaviour extending
to the large wave vector transfer region. But in the case of transverse phonon,
the oscillatory behaviour seems quite insignificant for high q value. This
indicates that the transverse phonon undergoes larger thermal modulation than
the longitudinal phonon, which may be connected with the instability of

transverse phonons in liquids. The q curves for transverse phonons attain
maxima at a high q value than the longitudinal phonon curve. The influence of
the exchange and correlated motion of electron through various local field
correction functions lowers the phonon modes more than those due to static
Hartree (H) effect. The inclusion of local field correction does not affect the
position of the maxima, minima and the crossing of L and T modes, very
significantly. The position of the first minimum roughly coincides with the
first peak in the structure factor of the respective systems. The computer
simulations and analytical calculations have demonstrated that this minimum
arises from a process analogous to the Umklapp scattering in the crystalline
solids. This sharp first maximum in the static structure factor acts like a
smeared-out reciprocal lattice vector. The experimental or theoretical data of
most of the equiatomic liquid alkali binary alloys are not available in the
literature. But, the behaviour of the present results does not show any
abnormality. From the Figures 1-10, it can be noted that when we go from
Li0.5Na0.5 → Rb0.5Cs0.5 alloys, the peak of the phonon dispersion curves
reduces.
Figure 6. Phonon dispersion curves of liquid Na0.5Rb0.5 alloy.

84 Aditya M. Vora
Figure 7. Phonon dispersion curves of liquid Na0.5Cs0.5 alloy.
Figure 8. Phonon dispersion curves of liquid K0.5Rb0.5 alloy.

Figure 9. Phonon dispersion curves of liquid K0.5Cs0.5 alloy.
The thermodynamic and elastic properties of equiatomic liquid alkali

binary alloys computed from the long wavelength limit of the frequency
spectrum are tabulated in Table 2. From the Table 2, it is seen that, the present
results obtained from H-local field correction function show higher values in
comparison with IU-local field correction function for most of the alkali
metals. The experimental or theoretical data for most of the metallic
complexes are not available for further comparison. Thus, in the absence of
experimental results such calculations may be considered as one of the
guidelines for further theoretical or experimental investigations. This is very
much essential for obtaining concrete conclusions. Finally, we conclude that
the model potential along with H and IU local filed correction functions is
capable of explaining the lattice dynamical properties of equiatomic liquid
alkali binary alloys.
Table 2. Thermodynamic and elastic properties of equiatomic liquid alkali binary alloys
Metallic
vL x105 vT x105 BT x1011 G x1011  Y x1011  D (K)
cm/sec cm/sec dyne/cm 2 dyne/cm2
dyne/cm2
complexes
H IU H IU H IU H IU H IU H IU H IU
Li0.5Na0.5 11.5187 11.1662 6.6503 6.4468 6.1879 5.8013 3.7127 3.4808 0.25 0.25 9.2818 8.7020 710.99 689.23
Li0.5K0.5 9.6640 9.3244 5.5795 5.3834 3.6230 3.3729 2.1738 2.0237 0.25 0.25 5.4346 5.0593 513.44 495.40
Li0.5Rb0.5 6.1746 5.9436 3.5649 3.4315 2.9922 2.7724 1.7953 1.6635 0.25 0.25 4.4883 4.1587 311.32 299.67
Li0.5Cs0.5 5.0093 4.8559 2.8921 2.8036 2.4528 2.3049 1.4717 1.3829 0.25 0.25 3.6792 3.4573 236.69 229.44
Na0.5K0.5 8.1088 7.8576 4.6816 4.5366 3.0634 2.8765 1.8380 1.7259 0.25 0.25 4.5950 4.3147 408.27 395.62
Na0.5Rb0.5 5.6935 5.5098 3.2871 3.1811 2.5974 2.4325 1.5585 1.4595 0.25 0.25 3.8961 3.6488 274.03 265.19
Na0.5Cs0.5 4.7389 4.6076 2.7360 2.6602 2.1789 2.0598 1.3073 1.2359 0.25 0.25 3.2683 3.0898 215.41 209.45
K0.5Rb0.5 5.3659 5.5098 3.0980 3.1811 1.9702 2.4325 1.1821 1.4595 0.25 0.25 2.9553 3.6488 238.53 265.19
K0.5Cs0.5 4.5289 4.4044 2.6148 2.5429 1.7168 1.6237 1.0301 0.9742 0.25 0.25 2.5752 2.4356 192.30 187.02
Rb0.5Cs0.5 3.9024 3.7947 2.2531 2.1908 1.5522 1.4677 0.9313 0.8806 0.25 0.25 2.3283 2.2015 161.17 156.72
Figure 10. Phonon dispersion curves of liquid Rb0.5Cs0.5 alloy.
CONCLUSIONS
At the end, we conclude that the presently computed results of the lattice
dynamical properties of equiatomic liquid alkali binary alloys are showing
consistent nature. The experimental or theoretical data for most of the
equiatomic liquid alkali binary alloys are not available for further comparison.
Thus, in the absence of experimental results such calculations may be
considered as one of the guidelines for further theoretical or experimental
investigations. This is very much essential for obtaining concrete conclusions.
Also, the model potential along with H and IU local filed correction functions
is capable of explaining the lattice dynamical properties of equiatomic liquid
alkali binary alloys. From the present experience, we also conclude that it
should be interesting to apply other local pseudopotentials for such
comprehensive study to judge and confirm the wider applicability of the
potential.
88 Aditya M. Vora
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[6] Thakor, P. B., Gajjar, P. N. and Jani, A. R. Pramana –J. Phys. 72 (2009)
1045.
[7] Srivastava, S. K., J. Phys. Chem. Solids 36 (1975) 993.
[8] Srivastava, S. K. and Ram Dawar, Ind. J. Pure Appl. Phys. 31 (1993)
520.
[9] Suck, J. -B. Experimental Investigations of Collective Excitations in
Disordered matter, In: Collective dynamics of nonlinear and disordered
systems Eds. G. Radons, P. Haussler, W. Just, Springer Berlin,
Heidelberg (2005).
[10] Balucani, U. and Zoppi, M. Dynamics of the liquid state. Oxford
University Press Inc., New York (1994).
[11] Gajjar, P. N., Patel, M. H., Thakore, B. Y. and Jani, A. R. Commun.
Phys. 12 (2002) 81.
[12] Harrison, W. Elementary Electronic Structure, World Scientific,
Singapore (1999).
[14] Hubbard, J. and Beeby, L. J. Phys. C2 (1969) 556.
[15] Vora, A. M., Romanian J. Phys. 533 (2008) 517.
[16] Vora, A. M., J. Mater. Sci. 42 (2007) 935.
[17] Faber, T. E. Introduction to the Theory of Liquid Metals, Cambridge
Uni. Press, London (1972).
Chapter 5
LATTICE DYNAMICS OF LIQUID METALS
Aditya M. Vora*
ABSTRACT
In the present article, the lattice dynamical properties of some alkali
metals are reported in second order approach through the equation given
by Hubbard and Beeby (HB). The pair correlation function is
directly computed from the interatomic pair potential, which is used in
the present computation. Two different forms of local field correction
functions proposed by Hartree (H) and Ichimaru-Utsumi (IU) are used in
the present study the screening dependence of the phonon frequencies in
the metallic elements. Thermodynamic and elastic properties of alkali
metals are reported from the long wave length limits of the phonon
dispersion curves (PDC).
Keywords : Pseudopotential, liquid alkali metals, lattice dynamical properties,

phonon dispersion curves (PDC), thermodynamic and elastic properties
*
90 Aditya M. Vora
1. INTRODUCTION
The problem of an appropriate description of the structure and related
properties of liquids arise from their intermediate situation between ideal gases
and solids. It is well known that crystalline solids having long range order are
completely characterized by their symmetry properties whereas liquids having
no such periodicity and can be characterized only by distribution or correlation
functions. In liquids the interpretation of neutron inelastic scattering
measurements is more complicated than it is in the case of solids, largely
because there is no long range order, neither in space nor in time. At low
frequencies, the liquids behave as a viscous medium but at higher frequencies
its response is elastic, the system behaves like a solid and transverse
excitations are supported [1-10].
Collective excitations in fluids have been studied experimentally,
theoretically and by computer simulations for almost several decades. Lot of
effort has been put to study the dynamical properties of liquid metals [1-10]
both theoretically and experimentally. The investigation of collective modes in
liquids has comparatively received less attention. Some few researchers [1-8]
have reported the phonon dispersion curves of simple liquid metals. It was
found that the maximum deviation takes place in the vicinity of the first
spherical Brillouin zone. This region lies nearly at the half distance of the first
peak in the structure factor . Thus, the choice of structure factor
also plays a vital role in the study of lattice dynamics of liquid metals. In the
present work we have used the pair correlation function instead of
structure factor calculated using the interatomic pair potential to give the
calculation a flavour model potential.
The present article deals with the computation of the lattice dynamical
properties of alkali metals with the aim to explore the applications of model
potential of Gajjar et al. [11] for the first time. The choice of the model
potential form factor is certainly an important factor in the study of metallic
properties and its actual form is much more sensitive to the choice of the local
field correction functions of the electron gas. Hence, the purpose of the present
article is not only to study the lattice dynamical properties, but also to see the
influence of the various local field correction functions in the screening.
Therefore, we have adopted here two different types of local field correlation
functions viz. Hartree (H) [12] and Ichimaru-Utsumi (IU) [13]. Also, we have
used here Hubbard and Beeby (HB) [14] approach for studying the lattice
dynamical properties of liquid alkali metals.
Lattice Dynamics of Liquid Metals 91
2. COMPUTATIONAL METHODOLOGY
The interatomic pair potential r  is calculated from the relation given
by [15, 16],
 Z 2 e2  O  Sinqr   2
r     F q  
 r  2   qr 
 q dq
  . (1)
Where, and are the valence and atomic volume of the metallic
elements, respectively. The energy wave number characteristics appearing in
the Eqs. (1) is written as [15, 16],
F q  
 O q 2
WB q 
2  H q   1
16 1   H q   11 f q  . (2)
Here WB q  ,  H q  , f q  are the bare ion potential, the Hartree

dielectric response function and the local field correction functions to
introduce the exchange and correlation effects, respectively.
The Hartree (H) screening function [12] is purely static, and it does not
include the exchange and correlation effects. The expression of it is,
f q   0 . (3)

  q 2  q 
 4    2    
q
4
q
2
 4
q  8 A  q 
2
 
f q   AIU    BIU    CIU   AIU     BIU  IU     CIU    F  ln
k  kF  

   q 
 F  F   F    F    4 
k k k 3 k q
2   
  k F  k  
 F
 .
(4)
92 Aditya M. Vora
A B C
The parameters IU , IU and IU are the atomic volume dependent
parameters of IU local field correction functions. The mathematical
expressions of these parameters are narrated in the respective papers of the
local field correction function [13].
The bare-ion pseudopotential due to Gajjar et al. [11] is given by
 8Z  qrC 2 
W B q    cosqrC   
O q 2 
 
1  qrC 
2
 
. (5)
r
respectively. The details of the model potential are narrated in the literature
[11].
To compute the phonon dispersion relations of liquid metals, the most
frequently used approach of Hubbard and Beeby (HB) [14] is adopted. With
the physical argument that the product of the static pair correlation function
and the second derivative of the interatomic pair potential r  is
peaked near the hard sphere diameter , Hubbard and Beeby (HB) [14] have
derived the expressions for the longitudinal phonon frequencies L(q) and the
transverse phonon frequencies T(q) as [14],
 sin q  6 cosq  6 sin q  

 L2 q    E2 1    
 q q 2 q 3  , (6)
and
 3 cosq  3 sin q  

T2 q    E2 1   
 q 2
q 3  . (7)

 4 
 E2     g r  r  r dr
2
with  3M 0 is the maximum frequency.

Where, and r  are the number density, atomic mass, pair
correlation function and interatomic pair potential of the element, respectively.
The fundamental ingredient, which goes into the calculation of the lattice
dynamics of liquid metals, is the interatomic pair potential r  . In the
present study, the interatomic pair potential r  is computed from Eqs. (1). A
quantity which is equally important as the interatomic pair potential (r) while
studying a disorder system is the pair correlation function (PCF) g r  . It
provides the statistical description of the structure of the system under
investigation. The complete information of the precise position and
momentum of each particle at each instant of time is contained in this function.
The function g r  can be obtained either experimentally by X-ray diffraction
and neutron diffraction technique [17] or computed theoretically from the
interatomic pair potential r  [17]. Instead of using experimentally available
g r  , here the pair correlation function for all disordered systems are
generated from presently obtained interatomic pair potential r  . The
function g r  is presently calculated using the expression [17],
V r 
g r   exp   1
 kB T  . (8)
Here k B is the Boltzmann‟s constant and T the room temperature of the

system under investigation.
In the case of disordered materials, it is convenient to discuss density
fluctuations in q -space and obtain macroscopic properties by taking q  0
limit (in low frequency region). The introduction of the elastic model is a good
example of the same, because the stress can be written most conveniently in q
-space. Elastic behaviour of the system is in general given by the response of it
to the propagation of the density fluctuations in the wavelength limit.
Therefore, the dispersion relations prove to be useful in deriving the elastic as
well as thermodynamic properties of disordered materials.
The present study include some elastic properties such as the isothermal
bulk modulus BT , modulus of rigidity G , Poisson‟s ratio  and Young‟s
94 Aditya M. Vora
modulus Y and some thermodynamic properties such as longitudinal sound

velocity  L , transverse sound velocity T and Debye temperature  D for the
disordered materials. In the long wavelength limit of the frequency spectrum,
both the frequencies i.e. transverse and longitudinal are proportional to the
wave vectors and obey the relationships [14-16],
 L  q and T  q ,
  L  L q and T T q . (9)
Where  L and T are the longitudinal and transverse sound velocities in

the disordered materials, respectively.
For HB approach the formulations for  L and T are given by [14]
3 2
 L HB    E
10 , (10)
and
2
T HB    E
10 . (11)
Where  E is calculated from the equation (7).

The isothermal bulk modulus BT , modulus of rigidity G , Poisson‟s ratio
 and Young‟s modulus Y are found using the expressions [14, 15],
 4 
BT   M  L2   T2 
 3 , (12)
G   M  T2 . (13)
Table 1. Constants and parameters for alkali metals.

Li 1 0.5890 144.9 0.7738
Na 1 0.4882 254.5 1.0765
K 1 0.3947 481.4 1.3880
Rb 1 0.3693 587.9 1.4837
Cs 1 0.3412 745.5 1.9108
Table 2. Thermodynamic and elastic properties of liquid metals.
Metallic vL x105 vT x105 BT x1011 G x1011  Y x1011  D (K)

comple- cm/sec cm/sec dyne/cm2 dyne/cm 2
dyne/cm2
xes
H IU H IU H IU H IU H IU H IU H IU
Li 17.2113 16.6441 9.9369 9.6095 8.8298 8.2575 5.2979 4.9545 0.25 0.25 13.2447 12.3862 1182.24 1143.29
Na 9.1894 8.9183 5.3055 5.1490 4.7474 4.4714 2.8485 2.6829 0.25 0.25 7.1212 6.7072 523.17 507.73
K 7.3426 7.1183 4.2392 4.1098 2.2373 2.1028 1.3424 1.2617 0.25 0.25 3.3560 3.1541 338.01 327.69
Rb 4.4068 4.2680 2.5443 2.4641 1.7571 1.6481 1.0542 0.9889 0.25 0.25 2.6356 2.4722 189.79 183.81
Cs 4.4068 3.4238 2.5443 1.9767 1.7571 1.3006 1.0542 0.7804 0.25 0.25 2.6356 1.9509 189.79 136.23
96 Aditya M. Vora
With  M is the isotropic number density of the disordered materials.
 2 
1  2 T2 
  L 
 2 
2  2 T2 
L  , (14)
and
Y  2G  1 . (15)
The Debye temperature is given in terms of both the velocities as [14, 15],
1 13 
 D   9  eff  3
1 2
D   2    3  3
kB kB  4   L T  , (16)
here k B the Boltzmann‟s constant and  D the Debye frequency, respectively.
Figure 1. Phonon dispersion curves of liquid Li.

Figure 2. Phonon dispersion curves of liquid Na.

The constants and parameters used in the present computations of the
phonon dispersion curves of the liquid alkali metals are tabulated in Table 1.
The computed phonon dispersion curves of liquid alkali metals are displayed
in Figures 1-5. Here, also it may be seen that the dispersion of the longitudinal
phonon exhibits oscillatory behaviour extending to the large wave vector
transfer region. But in the case of transverse phonon, the oscillatory behaviour
seems quite insignificant for high q value. This indicates that the transverse
phonon undergoes larger thermal modulation than the longitudinal phonon,
which may be connected with the instability of transverse phonons in liquids.
The q curves for transverse phonons attain maxima at a high q value than
the longitudinal phonon curve. The influence of the exchange and correlated
motion of electron through various local field correction functions lowers the
phonon modes more than those due to static Hartree (H) effect. The inclusion
of local field correction does not affect the position of the maxima, minima
and the crossing of L and T modes, very significantly. The position of the
98 Aditya M. Vora
first minimum roughly coincides with the first peak in the structure factor of
the respective systems. The computer simulations and analytical calculations
have demonstrated that this minimum arises from a process analogous to the
Umklapp scattering in the crystalline solids. This sharp first maximum in the
static structure factor acts like a smeared-out reciprocal lattice vector. The
experimental or theoretical data of most of the alkali metals are not available
in the literature. But, the behaviour of the present results does not show any
abnormality. From the Figures 1-5, it can be noted that when we go from
LiCs, the peak of the phonon dispersion curves reduces.
Figure 3. Phonon dispersion curves of liquid K.
The thermodynamic and elastic properties of liquid alkalis computed from

the long wavelength limit of the frequency spectrum are tabulated in Table 2.
From the Table 2, it is seen that, the present results obtained from H-local field
correction function show higher values in comparison with IU-local field
correction function for most of the alkali metals. The experimental or
theoretical data for most of the metallic complexes are not available for further
comparison. Thus, in the absence of experimental results such calculations
may be considered as one of the guidelines for further theoretical or
experimental investigations. This is very much essential for obtaining concrete
conclusions. Finally, we conclude that the model potential along with H and
IU local filed correction functions is capable of explaining the lattice

dynamical properties of liquid metals.
Figure 4. Phonon dispersion curves of liquid Rb.
Figure 5. Phonon dispersion curves of liquid Cs.

100 Aditya M. Vora
CONCLUSIONS
dynamical properties of liquid alkali elements are showing consistent nature.
The experimental or theoretical data for most of the liquid metals are not
available for further comparison. Thus, in the absence of experimental results
such calculations may be considered as one of the guidelines for further
theoretical or experimental investigations. This is very much essential for
obtaining concrete conclusions. Also, the model potential along with H and IU
local filed correction functions is capable of explaining the lattice dynamical
properties of liquid alkali metals. From the present experience, we also
conclude that it should be interesting to apply other local pseudopotentials for
such comprehensive study to judge and confirm the wider applicability of the
potential.
REFERENCES
[1] Desai, R. C. and Nelkin, M. Phys. Rev. Lett. 16 (1966) 839.
[2] Copley, J. R. D. and Lovesy, S. W. Rep. Prog. Phys. 38 (1975) 461.
[3] Gartrell-Mills, P. R., McGreevy, R. L. and van der Lugt, W. Physica
B154 (1988) 1.
[4] Balucani, U., Ruocco, G., Torcini, A. and Vallauri, R. Phys. Rev. E47
(1993) 1677.
[5] Pratap, A., Lad, K. N. and Raval, K. G. Pramana-J. Phys. 63 (2004)
431.
[6] Thakor, P. B., Gajjar, P. N. and Jani, A. R. Pramana –J. Phys. 72 (2009)
1045.
[7] Srivastava, S. K., J. Phys. Chem. Solids 36 (1975) 993.
[8] Srivastava, S. K. and Ram Dawar, Ind. J. Pure Appl. Phys. 31 (1993)
520.
[9] Suck, J. -B. Experimental Investigations of Collective Excitations in
Disordered matter, In: Collective dynamics of nonlinear and disordered
systems Eds. G. Radons, P. Haussler, W. Just, Springer Berlin,
Heidelberg (2005).
[10] Balucani, U. and Zoppi, M. Dynamics of the liquid state. Oxford
University Press Inc., New York (1994).
Phys. 12 (2002) 81.
[12] Harrison, W. Elementary Electronic Structure, World Scientific,

Singapore (1999).
[14] Hubbard, J. and Beeby, L. J. Phys. C2 (1969) 556.
[15] Vora, A. M., Romanian J. Phys. 533 (2008) 517.
[16] Vora, A. M., J. Mater. Sci. 42 (2007) 935.
[17] Faber, T. E. Introduction to the Theory of Liquid Metals, Cambridge
Uni. Press, London (1972).
Chapter 6
LATTICE DYNAMICS OF SOLID METALLIC

ELEMENTS
Aditya M. Vora*
ABSTRACT
The computations of the lattice dynamics of solid metallic elements
to second order in local model potential is discussed in terms of real-
space sum of Born von Karman central force constants. The local field
correlation functions due to Hartree (H) and Ichimaru-Utsumi (IU) are
used to investigate influence of the screening effects on the aforesaid
properties. Results for the lattice constants i.e.
C11 , C12 , C 44 ,
C12  C44 , C12 C44 and bulk modulus B obtained using the H-local
field correction function have higher values in comparison with the
results obtained for the same properties using IU local field correction
function. The results for the Shear modulus ( C  ), deviation from
*
104 Aditya M. Vora
velocity of elastic waves, phonon dispersion curves and degree of

anisotropy A are highly appreciable for metallic elements
Keywords : Lattice dynamics; metallic elements; Phonon dispersion curves

(PDC)
1. INTRODUCTION
A crystal is described as a perfect periodic three-dimensional array of
atoms. However, the atoms are not static at their lattice sites but vibrate about
their mean positions with energies governed by the temperature of the solid.
The collective motions of atoms in solids form traveling waves (called lattice
vibrations), which are quantized in terms of “phonons”. The study of lattice
vibrations is of considerable interest because several physical properties of
crystals like their specific heat, thermal expansion, phase transitions are related
to the vibrations of atoms in solids [1-14].
The experimental studies of lattice vibrations are carried out using
techniques like Raman spectroscopy, infrared absorption (IR), inelastic
neutron scattering, inelastic X-ray scattering, etc. Unlike Raman and infrared
studies which probe only the long wavelength excitations in one phonon
scattering, inelastic neutron and X-ray scattering can directly probe the
phonons in the entire Brillouin zone. While inelastic neutron scattering is
widely used for such measurements, inelastic X-ray scattering has also been
recently used at intense synchrotrons sources for the study of phonons in a few
materials. Experimental studies at high pressures and temperatures are often
limited and accurate models for the compounds are of utmost importance. A
major goal of research therefore has been theoretical predictions of the
thermodynamic properties. The success of the models in predicting
thermodynamic properties depends crucially on their ability to explain a
variety of microscopic and macroscopic dynamical properties. These include
an understanding of the crystal structure, elastic constants, equation of state,
phonon frequencies, dispersion relations, density of states and thermodynamic
quantities like the specific heat and thermal expansion. The experimental
neutron and long wavelength optical data are used to test and validate models
of interatomic potentials, which in turn have been used to predict
thermodynamic properties at high pressures and temperatures [1-14].
While in the case of liquid metals and metallic glasses, it was found that
the maximum deviation takes place in the vicinity of the first spherical
Lattice Dynamics of Solid Metallic Elements 105
Brillouin zone. This region lies nearly at half the distance of the first peak in
the structure factor. Thus the choice of the structure factor also plays a vital
role in the study of phonon dispersion curves of liquid metals. It was also
observed that generally people have used the hard sphere reference system to
describe the structural information, which is independent of the model
potential [1-6].
As a consequence of the disorder, the phonon spectra of alloys can differ
considerable in character from those of the pure metals. Localized vibrational
modes may be present, and all phonons acquire a broadening and shift in
frequency. Besides their importance for the thermodynamic properties, the
lattice vibrations in alloy systems provide an ideal testing ground for any
theory of elementary excitations in disordered systems because the energy
wave vector relationship can be measured directly by either the coherence
inelastic neutron scattering experimentally or by the many theoretical models.
Once the phonon spectrum of the alloy is known, the calculation of the
vibrational contribution to the thermodynamic functions is straightforward
[14].
Therefore, in the present article, the lattice dynamics of alkali metals in
solid phase are reported. The well recognized model potential of Gajjar et al.
[1-6] is used with more advanced and recent local field correlation function
due to Ichimaru-Utsumi (IU) [15] has been employed in such investigations.
This helps in identifying the influence of exchange and correlation effects in
the static form of Hartree (H) (only static) dielectric function [16]. For solid
metallic complexes, the lattice dynamical studies are performed from in terms
of real-space sum of Born von Karman central force constants
2. THEORETICAL METHODOLOGY
The phonon frequencies can be obtained by solving the standard secular
determinantal equation [1-8]
det D q   4 2 2 M    0 ,
(1)
D q 
where, M is the ionic mass,  the phonon frequency and the
dynamical matrix in which the force between two ions depends only upon the
distance between them is given by,
106 Aditya M. Vora
  ddrdrr 
2
D q   1 e iqr ,
n   r r
n
(2)
where r  is the interionic pair potential, and r and  are  and 
r th th
th
Cartesian components of the position vector of n ion, respectively T.
The interionic pair potential r  is computed from the well known
relation [1-8]
Z 2e2 0
 2  F q 
sin qr
(r )  dq .
r  qr (3)
Where F q  is the energy wave number characteristic given by

[1-8]
F (q) 
0 q 2
WB ( q )
2  H (q)  1 .
8 e 2
1   H (q) 1 1  f q  (4)
 O , W B q ,  H q 
With and f q  are the atomic volume, bare-ion
pseudopotential, static Hartree dielectric function and local field correlation
function, respectively.
The bare-ion pseudopotential due to Gajjar et al. is given by [1-6]
 8Z  qrC 2 
W B q    cosqrC   
O q 2 
 
1  qrC 
2
 
. (5)
r
respectively. The details of the model potential are narrated in the literature [1-
6]. In the present investigation, the local field correction functions due to H
[15] and IU [16] are incorporated to see the impact of exchange and
correlation effects. The details of all the local field corrections are below.
The H-screening function [15] is purely static, and it does not include the
exchange and correlation effects. The expression of it is,
f X   0 . (6)

  8A   4  Q2 2  Q 
f  X   AIU Q 4  BIU Q 2  CIU   AIU Q 4   BIU  IU Q 2  C IU   ln 
  3    4Q 2Q 
.
(7)
Where Q  2 X . The parameters IU , IU and

A B C
IU are the atomic
volume dependent parameters of IU local field correction functions. The

mathematical expressions of these parameters are narrated in the respective
papers of the local field correction function [16].
The dynamical matrix element used in the present calculation finally takes
the form,
 
 
r r
D q    1  e iqr  K t  2 K r  K t  ,
n  r  (8)
Here K t and K r are the force constants between a pair of ions interacting
through a central interaction and n specifies shell index.
1 dr 
Kt 
r dr
Z 2e2    sinqr  
  3  2 0 2  F q  q 2 cos qr  
q r 
dq .
r  r 0  (9)
108 Aditya M. Vora
d 2
Kr 
dr 2
q  q 2  2 sinqr   2 cosqr   qr sinqr  dq

2 Z e2 0 
  F .
r 3
 r
2 2
0  qr  (10)
Table 1. Input parameters and constants for alkali metals.

Li 1 0.5890 144.9 0.7738
Na 1 0.4882 254.5 1.0765
K 1 0.3947 481.4 1.3880
Rb 1 0.3693 587.9 1.4837
Cs 1 0.3412 745.5 1.9108
Table 2. Dynamical elastic constants (in 1011 dyne/cm2) for Li
Present results Expt. Others

Prop.
H IU [17] [18-25]
C11 2.9026 1.4462 1.571 1.51, 2.023, 1.62, 1.84, 1.77, 3.762, 1.543, 1.570, 2.050,
1.437, 6.000, 1.68, 1.57, 1.472, 2.361, 1.539, 1.532, 1.40,
1.712, 4.465, 4.83, 1.388, 1.567, 2.072, 1.610, 1.530,
1.548
C12 2.7686 1.3481 1.329 1.274, 1.877, 1.44, 3.401, 1.173, 1.379, 1.284, 1.29, 3.395,
1.293, 1.39, 1.43, 1.853, 1.555, 1.274, 1.272, 1.57, 1.982,
1.556, 1.40, 4.070, 1.212, 1.283, 1.291, 1.279, 1.59, 1.639
C44 0.9338 0.9185 1.16 1.050, 0.937, 1.07, 1.336, 7.794, 1.390, 1.15, 0.904, 2.654,
1.079, 1.11, 1.08, 1.257, 1.371, 1.106, 1.17, 1.22, 1.128,
1.115, 1.10, 1.233, 1.191, 1.380, 1.053, 1.231, 1.544
C‟ 0.0670 0.0490 0.121 1.118, 0.703, 1.20, 0.072, 0.089, 0.77, 0.532
B 2.8133 1.3808 1.410 1.353, 1.926, 3.756, 1.349, 2.1081, 3.71, 1.183, 1.324,
1.341, 1.917, 1.248, 1.442, 1.783, 1.262, 1.297, 1.608,
1.246, 1.626, 3.517, 1.373, 1.246
Using these atomic force constants, we can generate inter atomic force
K 
constants which can then be employed to investigate the elastic constants
d 2 (r )
K  
dr dr
 r r  r r
    2  Kt  2 Kr .
 r  r
(11)
Under the long-wave phonon method, the elastic constants are studied by
[1-8]
C11 
1
 
 N (n) x 2 K xxn  y 2 K yyn  z 2 K zzn ,
12a n (12)
C44 
1

24a n
   2
 
N (n) y 2  z 2 K xxn  z 2  x 2 K yyn  z 2 K zzn ,
(13)
C12  C44 
1

6a n

N (n) yzK yzn  zxK zxn  xy K xyn . 
(14)
Where “ a ” is the lattice constant and N n  is the number of atoms at the

n th neighbour separation. The shear modulus C  and bulk modulus B are
given by [1-8]
 C  C12 
C '   11  .
 2  (15)
and
 C  2C12 
B   11 .
 3  (16)
110 Aditya M. Vora
Li [100] [111] [110]

Phonon Frequncy (THZ) 10.0
8.0
6.0
4.0
H
2.0 IU
Expt.
0.0
0.0 0.5 1.0 0.5 0.0 0.5
Reduced wave vector
Figure 1. Phonon dispersion curves of Li.
6.0
Na [100] [111] [110]
5.0
4.0
3.0
2.0
H
1.0 IU
Expt.
0.0
0.0 0.5 1.0 0.5 0.0 0.5
Reduced wave vector
Figure 2. Phonon dispersion curves of Na.
The extent to which the interatomic forces are non-pair wise can be
obtained by investigating the breakdown of the Cauchy relation. The Cauchy‟s
ratio is obtained by C12 C44 .
Poisson‟s ratio  is the second independent elastic parameter and is
given as [1-8],
C12
  .
C11  C12  (17)
From the calculated values of the bulk modulus an Poisson‟s ratio, Young
modulus Y is derived as [1-8],
Y  3B(1 2 ) . (18)
Table 3. Dynamical elastic constants (in 1011 dyne/cm2) for Na.

Prop.
H IU [17] [18-25]
C11 2.3897 1.7361 0.893, 1.049, 1.201, 0.98, 0.810, .0168, 1.064, 0.808, 0.816,
0.857, 0.814, 0.866, 1.020, 0.116, 0.891, 1.069, 0.821, 0.910,
0.85 0.740, 0.792, 0.786, 0.912, 1.657, 1.220, 1.260, 0.924,
1.100, 1.014, 0.616, 1.010, 0.810, 0.832, 0.546, 0.958,
1.120, 1.280
C12 2.2264 1.5695 0.738, 0.894, 1.001, 0.860, 0.644, 0.059, 0.742, 0.420, 0.799,
0.711, 0.827, 0.990, 1.070, 1.044, 0.737, 0.873, 0.686, 0.740,
0.704 0.630, 0.693, 0.688, 0.705, 0.672, 0.850, 0.830, 0.955,
0.838, 0.910, 0.085, 0.475, 0.692, 0.789, 1.502, 0.777,
0.683, 1.050, 0.880
C44 0.6062 0.6134 0.66, 0.594, 0.529, 0.590, 0.690, 0.520, 0.711, 0.550, 0.663,
0.63, 0.735, 0.573, 0.587, 0.553, 0.66, 0.595, 0.654, 0.580,
0.588 0.068, 0.680, 0.067, 0.775, 0.539, 0.579, 0.630, 0.055,
0.028, 0.610, 0.064, 0.068, 0.067, 0.549, 0.558
C‟ 0.0802 0.0833 0.077, 0.077, 0.100, 0.081, 0.077, 0.098, 0.043, 0.083
0.073
B 2.2798 1.6250 0.79, 0.946, 1.068, 0.699, 0.736, 0.730, 0.760, 0.718, 0.746,
0.76 0.742, 0.788, 0.938, 0.728, 0.830, 1.554, 0.807, 0.699,
0.743, 1.009, 0.866, 0.903, 0.773, 0.474, 0.851, 0.794,
0.766, 0.753, 0.722
In the cubic system the propagation velocity of longitudinal and transverse

waves in [100], [110] and [111] directions are given as [1-8]
1
C  2
v L [100]   11  .
   (19)
112 Aditya M. Vora
1
 (C  C12  2C44 )  2
v L [110]   11  .
 2  (20)
1
 (C  2C 12  4C 44 )  2
v L [111]   11  .
 3  (21)
1
C  2
v T [100]  v T 1[110]   44  .
   (22)
1
 (C11 - C12)  2
v T 2 [110]    .
 2  (23)
1
 (C11  C12  2C 44 )  2
v T [111]    .
 3  (24)
Table 4. Dynamical elastic constants (in 1011 dyne/cm2) for K.

Prop.
H IU [17] [18-25]
C11 0.7582 0.5088 0.416 0.499, 0.555, 0.410, 0.399, 0.420, 0.510, 0.402, 0.425, 0.304,
0.495, 0.530, 0.434, 0.481, 0.421, 0.50, 0.592, 0.616, 0.409,
0.395, 0.327, 0.480, 0.530, 0.503, 0.450, 0.478, 0.390, 0.565,
0.384, 0.394, 0.482, 0.466, 0.460
C12 0.7175 0.4331 0.341 0.441, 0.465, 0.35, 0.322, 0.35, 0.406, 0.332, 0.381, 0.240,
0.429, 0.44, 0.360, 0.415, 0.344, 0.41, 0.541, 0.491, 0.346,
0.324, 0.327, 0.42, 0.439, 0.37, 0.401, 0.34, 0.519, 0.325,
0.035, 0.411, 0.410, 0.10
C44 0.2461 0.2567 0.286 0.254, 0.259, 0.26, 0.34, 0.256, 0.263, 0.253, 0.29, 0.26,
0.251, 0.260, 0.288, 0.346, 0.269, 0.276, 0.28, 0.29, 0.264,
0.255, 0.27, 0.286, 0.359, 0.272, 0.269, 0.29, 0.25, 0.259
C‟ 0.0325 0.0379 0.038 0.029, 0.045, 0.023, 0.037, 0.033, 0.032, 0.038
B 0.7392 0.4583 0.366 0.460, 0.495, 0.106, 0.263, 0.451, 0.358, 0.368, 0.315, 0.534,
0.385, 0.437, 0.349, 0.349, 0.385, 0.348, 0.378, 0.427, 0.460,
0.366, 0.435, 0.424, 0.395, 0.376, 0.366, 0.348
The behavior of phonon frequencies in the limit independent of direction

is given by [1-5]
i2 (q)  (C  2C 44 ) 
Y1  lim    11 ,
q 0
i q 2
   (25)
and
 C - C12  
2
 
Y2  lim  T 1    11  .
q 0
 T2   2C 44  (26)
The degree of elastic anisotropy A is the inverse of Y2 , i.e. [1-8],
 2C44 
A .

 11
C  C 
12  (27)
The value of A is unity when the material is elastically isotropic and

differs from unity otherwise.

In evaluating integrations in Eqs. (10) and (11), the upper limit of integrals
is taken 40kF so that, a complete convergence of the model potential is
achieved at higher momentum transfer and it covers all the oscillations of the
form factor. Therefore, any artificial/fictitious cut-off in the present
computations is avoided. We have performed the real space sum analysis up to
33 sets of nearest neighbours in r -space, which are found sufficient for
computing the elastic constants and bulk modulus using interatomic force
constants, to consider a long-range character for proper convergence of the
calculation and to achieve desired accuracy.
114 Aditya M. Vora
3.0
K [100] [111] [110]
2.5
2.0
1.5
1.0
H
0.5 IU
Expt.
0.0
0.0 0.5 1.0 0.5 0.0 0.5
Reduced wave vector
Figure 3. Phonon dispersion curves of K.
Rb [100] [111] [110]

2.0
1.5
1.0
H
0.5
IU
Expt.
0.0
0.0 0.5 1.0 0.5 0.0 0.5
Reduced wave vector
Figure 4. Phonon dispersion curves of Rb.
The input parameters and other constants used in the present computation
of the lattice dynamics of metallic element and their alloys are narrated in
Table 1. In the present computation, the bcc crystal structure considered for all
alkali metals. The lattice constants „ a ‟ are obtained from the well known
relation O 2 1 3
. Tables 2-8 display the computed values of some static and
vibrational properties of alkali metals. It is noted from the Tables 2-8 that, our
results calculated for C11 , C12 , C 44 , C12  C44 , C12 C44 and bulk modulus
B from H-local field correction function give higher values than those
obtained for the IU-local field correction functions. There is a good agreement
for the calculated values of the Shear modulus C  , deviation from Cauchy‟s
relation, Poisson‟s ratio  , Young modulus Y , propagation velocity of
elastic waves, phonon dispersion curves (PDC) and degree of anisotropy A
using H and IU-local field correction functions. The present results are
compared with the experimentally [17] or theoretically [18-25] available data
and found in qualitative agreement with them. It is noticed from the present
study that, the percentile influence of the IU-local field correction function
with respect to the static H-local field correction function on the vibrational
properties of Li, Na, K, Rb and Cs is found 0.82%-76.59%, 0.59%-40.99%,
2.12%-62.58%, 3.72%-52.74% and 3.23%-36.41%, respectively. This clearly
indicates that the local field correlations play a very effective role in
explaining correctly the static and dynamic properties of such solid solutions.
The calculated results of the vibrational properties of Li, Na, K, Rb and Cs
alkali metals deviate in the range of 6.55%-985.68%, 2.06%-1900.12%,
0.26%-454.59%, 0.28%-868.06% and 0.45%-680.79% from the highest
experimental findings [17], respectively. The present results of the vibrational
properties are found in qualitative agreement with the other such available
experimental [17] or theoretical [18-25] data.
Table 5. Dynamical elastic constants (in 1011 dyne/cm2) for Rb

Prop.
H IU [17] [18-25]
C11 0.9292 0.6861 0.316, 0.333, 0.311, 0.332, 0.42, 0.372, 0.35, 0.33, 0.453, 0.379,
0.342 0.33, 0.305, 0.431, 0.318, 0.31, 0.29, 0.445, 0.410, 0.31,
0.318, 0.518, 0.322, 0.38, 0.30
C12 0.8692 0.6497 0.257, 0.267, 0.273, 0.271, 0.34, 0.319, 0.30, 0.28, 0.420, 0.355,
0.288 0.27, 0.256, 0.34, 0.263, 0.26, 0.24, 0.413, 0.33, 0.26,
0.269, 0.415, 0.263, 0.31, 0.25
C44 0.2206 0.2045 0.211, 0.193, 0.195, 0.220, 0.278, 0.207, 0.20, 0.19, 0.285, 0.20,
0.221 0.172, 0.198, 0.20, 0.197, 0.279, 0.209, 0.22, 0.19, 0.278,
0.22, 0.173, 0.200, 0.20, 0.27, 0.240, 0.21, 0.20, 0.172,
0.21, 0.20
C‟ 0.0300 0.0182 0.030, 0.020, 0.037, 0.016, 0.024, 0.038, 0.012, 0.026
0.027
B 0.8892 0.6618 0.277, 0.289, 0.264, 0.322, 0.261, 0.285, 0.311, 0.272, 0.363,
0.306 0.290, 0.283, 0.424, 0.306, 0.285, 0.359, 0.282, 0.285
116 Aditya M. Vora
Table 6. Dynamical elastic constants (in 1011 dyne/cm2) for Cs

Prop.
H IU [17] [18-25]
0.6423 0.4667 0.260 0.282, 0.23, 0.235, 0.27, 0.26, 0.351, 0.306, 0.22, 0.271,
C11
0.24, 0.21, 0.365, 0.239, 0.258, 0.16, 0.28, 0.22
0.5990 0.4392 0.216 0.264, 0.19, 0.196, 0.23, 0.22, 0.235, 0.232, 0.22, 0.232,
C12
0.20, 0.17, 0.327, 0.209, 0.290, 0.099, 0.24, 0.18
0.1617 0.1514 0.160 0.146, 0.144, 0.166, 0.15, 0.13, 0.13, 0.147, 0.15, 0.146,
C44
0.16, 0.14, 0.144, 0.14, 0.16, 0.15, 0.124
C‟ 0.0217 0.0138 0.022 0.009, 0.019, 0.037, 0.019, 0.015
0.6135 0.4483 0.231 0.270, 0.209, 0.340, 0.239, 0.213, 0.257, 0.245, 0.266,
B
0.245, 0.243, 0.219, 0.2174, 0.282, 0.217
1.5
Cs [100] [111] [110]
1.0
0.5
H
IU
Expt.
0.0
0.0 0.5 1.0 0.5 0.0 0.5
Reduced wave vector
Figure 5. Phonon dispersion curves of Cs.
Table 7. Deviation from Cauchy relation (1011 dynes/cm2), Cauchy’s ratio,

Poisson ratio and Young’s modulus (1011 dynes/cm2), Degree of
anisotropy, phonon frequencies limit for alkali metals

Prop.
H IU [17, 18] [18-25]
Li
C12-C44 1.8348 0.4296 0.1690 −
C12/C44 2.9648 1.4678 1.1456, 1.3000 3.43
σ 0.4882 0.4825 0.4582 −
Y 0.1994 0.1454 3.5290 −
Prop.
H IU [17, 18] [18-25]
Li
A 13.9355 18.7296 − −
Y1 8.8839 6.1142 − −
Y2 0.0718 0.0534 − −
Na
C12-C44 1.6201 0.9560 0.0810, 0.0780 −
1.4800, 1.1181,
C12/C44 3.6734 2.5584 3.05
1.1285
0.4524, 0.4534,
σ 0.4826 0.4748 0.49
0.4300
Y 0.2377 0.2457 2.2520, 2.1220 −
A 7.5618 7.3672 − −
Y1 3.5544 2.9261 − −
Y2 0.1322 0.1358 − −
K
C12-C44 0.4714 0.1764 0.0850 −
C12/C44 2.9152 1.6872 1.1923, 1.6700 2.72
σ 0.4783 0.4598 0.4504 −
Y 0.0960 0.1106 1.087 −
A 7.5787 6.7739 − −
Y1 1.4001 1.1228 − −
Y2 0.1319 0.1476 − −
Rb
C12-C44 0.6486 0.4451 0.067, 0.046 −
C12/C44 3.9395 3.1764 1.2180, 1.3031 −
σ 0.4833 0.4864 0.4485, 0.4571 −
Y 0.0890 0.0541 0.8555, 0.7868 −
A 7.3534 11.2317 − −
Y1 0.8410 0.6720 − −
Y2 0.1360 0.0890 − −
Cs
C12-C44 0.4373 0.2878 0.0560 −
C12/C44 3.7041 2.9000 1.3500 −
σ 0.4826 0.4848 0.4567 −
Y 0.0642 0.0409 0.6405 −
A 7.4703 11.0032 − −
Y1 0.4833 0.3851 − −
Y2 0.1339 0.0909 − −
118 Aditya M. Vora
Table 8. Propagation velocities (105 cm/sec) of elastic waves in alkali

metals
Present results Expt.

Prop.
H IU [17]
Li
VL(100) 7.3524 5.1897 5.3907
VT(100) 4.1702 4.1358 4.6322
VL(110) 8.3786 6.5669 6.9483
VT1(110) 4.1702 4.1358 4.6322
VT2(110) 1.1171 0.9556 1.4960
VL(111) 8.6937 6.9657 7.3950
VT(111) 2.5747 2.5121 2.9401
Na
VL(100) 4.8549 4.1406 2.9594, 2.8991
VT(100) 2.4468 2.4613 2.5442, 2.4857
VL(110) 5.3633 4.7308 3.8041, 3.7240
VT1(110) 2.4468 2.4613 2.9594, 2.8991
VT2(110) 0.8898 0.9071 0.8718, 0.8461
VL(111) 5.5224 4.9117 4.0466, 3.9609
VT(111) 1.5886 1.6024 1.6323, 1.5927
K
VL(100) 2.9316 2.3641 2.1301
VT(100) 1.6442 1.6791 1.7602
VL(110) 3.3077 2.8270 2.6922
VT1(110) 1.6442 1.6791 1.7662
VT1(110) 1.6442 1.6791 1.7662
VT2(110) 0.5973 0.6451 0.6395
VL(111) 3.4239 2.9653 2.8550
VT(111) 1.0672 1.1033 1.1456
Rb
VL(100) 2.3879 2.0519 1.3876, 1.4436
VT(100) 1.1636 1.1203 1.1339, 1.1604
VL(110) 2.6214 2.3138 1.7411, 1.8072
VT1(110) 1.1636 1.1203 1.1339, 1.1604
VT2(110) 0.4291 0.3343 0.4239, 0.4056
VL(111) 2.6948 2.3947 1.8440, 1.9132
VT(111) 0.7577 0.7020 0.7405, 0.7336
Present results Expt.

Prop.
H IU [17]
Cs
VL(100) 1.7928 1.5282 1.1366
VT(100) 0.8996 0.8705 0.8916
VL(110) 1.9784 1.7391 1.4063
VT1(110) 0.8996 0.8705 0.8916
VT2(110) 0.3291 0.2624 0.3306
VL(111) 2.0368 1.8039 1.4853
VT(111) 0.5848 0.5464 0.5812
The phonon dispersion curves (PDC) of five alkali metals viz. Li, Na, K,
Rb and Cs along [100], [110] and [111] directions of high symmetry, which
are shown in Figures 1-5 with available experimental findings [26-29]. The
present results of pure alkali elements are found in qualitative agreement with
the experimental data [26-29]. We have found that the phonon frequencies in
the longitudinal branch are more sensitive to the exchange and correlation
effects in comparison with the transverse branches. The frequencies in the
longitudinal branch are suppressed due to IU-screening function than the
frequencies due to static H-screening function. While in the transverse branch
effect of exchange and correlation enhances slightly the phonon modes. It is
found that at the zone boundaries of [100] and [111] directions, i.e., for the
larger momentum transfer the effect of local field correlation is almost
negligible. These dispersion curves are not showing any abnormality in the
three regions of high symmetry directions and exhibiting qualitative behaviour
like metallic elements. From the Figures 1-5, we observe that, when we move
from Li → Cs, the phonon frequency decreases with increase in the average
volume of the metallic elements. The phonon dispersion curves (PDC) are
seen to be quite unsatisfactory except near the small k -regions (k < 0.6 or so)
because of the average data of the pure metallic elements. For some
equiatomic binary alloys, present results deviate more from the experimental
points. But present study is independent of such fitting hence in some cases the
discrepancy is observed.
A good description of Cs or Rb is rather more complicated than that of the
other alkali elements. The problem stems from the fact that at pure Cs or Rb
density the compressibility of the electron gas is close to zero, and is
conceivably negative. Hence, the normal pseudopotential perturbation
120 Aditya M. Vora
approach based on the electron gas as the zero order approximation is rather
dubious. This is because one is starting with a thermodynamically unstable
system to provide a description of one which is thermodynamically stable. The
way out of this dilemma, was used to scale the electron gas density parameter
r *
i.e. the Wigner-Seitz radius S by the band structure effective mass m ,
which then meant that one was dealing with an effective density for which the
electron gas compressibility was large and positive. The physical meaning of
this approach was not clear, but it bears a close resembles to that the effect of
large core polarization of Cs or Rb could be taken into account by a suitable
r
scaling of S , also in the direction of large, positive compressibility. But, in
the present results of the lattice dynamics of the alkali metals, we have made
straightforward computation without any assumptions. The relativistic effect
of the heavier alkali element like Cs to other alkali elements is significant,
which is comparatively very small. Therefore, we have ignored relativistic
effects of the heavier atom for the sake of simplicity.
CONCLUSIONS
dynamical properties of pure alkali elements are found in qualitative
agreement with the experimental or theoretical data. From the present
experience, we also conclude that it should be interesting to apply other local
pseudopotentials for such comprehensive study to judge and confirm the wider
applicability of the potential.
REFERENCES
[1] Aditya M. Vora, J. Phys. Chem. Sol. 68 (2007) 1725
[2] Aditya M. Vora, Chinese Phys. Lett. 25 (2008) 654.
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INDEX
Born von Karman central force XE "force"

A constants, viii, ix, 47, 101, 103
breakdown, 53, 108
accurate models, 102
bulk modulus, viii, ix, 47, 53, 54, 59, 60, 77,
agencies, 42
80, 92, 93, 101, 107, 109, 111, 113
alloy specimen, vii, 20
alloys, 1, 4, 8, 9, 10, 13, 17, 20, 21, 30, 39,
40, 42, 43 C
alternative, 20
alumin(i)um, 4, 9, 17, 21 cadmium, 42
AMS, 11 calorimetry, vii, 20, 22, 23
anisotropy, viii, ix, 48, 56, 60, 102, 111, ceramics, 18
113, 114 chemical, 22
anomalous, 20 composites, vii
Asia, 43 composition, 21, 42
assessment, vii, 1, 2, 3, 4, 8, 10, 13, 14, 15, compounds, 102
16, 17 compressibility, 51, 67, 73, 90, 105, 117
assessment procedures, 17 compression, 45
ASTM, 17 computation, viii, 59, 60, 68, 70, 71, 88, 89,
atmosphere, 23 112, 118
atomic force, 52, 106 computer, 71, 82, 89, 97
atoms, 48, 53, 72, 102, 107 computer simulations, 71, 82, 89, 97
computing, 59, 111
configuration, 4
B constant load, 22
constituents, 72
back, 27, 29, 30, 39
constraints, 21
behavior(s), viii, 2, 17, 20, 21, 39, 40, 41,
convergence, 59, 111
44
cooling, 21, 22, 23, 24, 25, 26, 30, 31, 32,
biocompatibility, 20
33, 34, 36, 39, 41
blocks, 30, 31
124 Index
correlation(s), viii, ix, 39, 47, 49, 50, 51, 63, 96, 97, 98, 102, 103, 108, 112, 113, 114,
70, 71, 72, 73, 74, 75, 88, 89, 90, 91, 92, 117
101, 103, 104, 105, 113, 117 displacement, 36, 40
correlation function, viii, ix, 47, 49, 50, 70, distinct treatment XE "treatment"
71, 72, 74, 75, 88, 89, 91, 92, 101, 103, condition, vii, 20
104 distribution, 71, 89
crack(s), 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, DSC, 22, 23, 32, 33, 34, 35, 36
13, 14, 17 dynamical properties, viii, 48, 52, 55, 57,
cracked bodies, vii, 1, 13 59, 60, 61, 64, 65, 66, 67, 68, 70, 71, 72,
critical temperature, vii, 20, 21, 22, 23, 36, 84, 86, 88, 89, 98, 99, 102, 118
40, 41
crystal structure, 60, 102, 112
crystalline, 21, 23, 38, 39, 40, 41, 71, 82, E
89, 97
crystalline solids, 71, 82, 89, 97 elastic fracture, 3
crystals, 102 elastic waves, viii, ix, 48, 60, 102, 113, 116
cubic system, 54, 109 electron, 49, 51, 67, 71, 73, 82, 89, 90, 96,
cybernetics, 44 105, 117
cycles, vii, 20, 21, 22, 24, 25, 26, 28, 29, 30, elongation, 45
31, 33, 34, 35, 40 energy, 2, 4, 48, 49, 50, 68, 73, 90, 103, 104
cycling, vii, 19, 20, 21, 22, 23, 24, 26, 27, equiatomic alkali binary alloys, vii, viii, 47,
28, 29, 30, 31, 32, 36, 37, 38, 39, 40, 41, 48, 49, 50, 60, 63, 68
44 equiatomic liquid alkali binary alloys, viii,
70, 71, 73, 74, 81, 84, 85, 86
equilibrium, 42
D evidence, 32, 40
evolution, 40
defects, 2, 21, 23, 24, 39, 40, 41
deformation, 21, 23, 32, 40, 42, 44, 45
degenerate, 51, 73, 90, 105 F
degree of anisotropy, viii, ix, 48, 60, 102,
113 fabrication, 43
density fluctuations, 76, 92 FAD, 3
deviation, viii, ix, 3, 38, 39, 47, 60, 71, 89, failure, vii, 1, 2, 3, 4, 5, 8, 10, 13
101, 102, 113 fluctuations, 76, 92
differential scanning, 22, 23 force, viii, ix, 47, 49, 51, 52, 59, 101, 103,
differential scanning calorimetry, 22, 23 105, 106, 111
diffraction, vii, 20, 22, 23, 75, 92 force constants, viii, ix, 47, 51, 52, 59, 101,
diffusion, 42 103, 105, 106, 111
dislocation, 39 formation, 45
disorder, 49, 75, 92, 103 formula, 51, 73, 90, 105
disordered systems, 49, 75, 87, 92, 99, 103 fracture, vii, 1, 2, 4, 5, 6, 7, 8, 10, 13, 16,
dispersion, viii, ix, 48, 54, 56, 57, 58, 60, 17, 18, 44
62, 63, 64, 66, 70, 71, 74, 75, 76, 77, 78, fracture resistance, 3
79, 81, 82, 83, 84, 86, 88, 89, 91, 92, 95, fracture strength evaluation, vii, 1, 4, 8
fracture toughness, 8
Index 125
integrity, 3
G interface, 21
interval, vii, 20, 22, 32, 39, 40, 41
generation, vii, 1
ions, 48, 49, 51, 103, 105
generation of failure assessment diagram,
vii, 1
geometry, 4 L
glasses, 102
gold, 42 lattice, 24
grain, 20 lattice dynamical properties, viii, 48, 68, 70,
guidelines, 64, 84, 86, 97, 99 71, 72, 84, 86, 88, 89, 98, 99, 118
light, 23, 72
limitation, 21
H limitations, 43
linear, 3, 7, 10
Hartree (H), viii, ix, 47, 49, 70, 72, 73, 82,
liquid nitrogen, 23
88, 89, 90, 96, 101, 103
liquids, 51, 71, 73, 82, 89, 90, 96, 105
heat, 8, 21, 32
Lithium, 17
heating, 21, 22, 23, 27, 28, 29, 30, 31, 32,
loading, 3, 4
36, 39, 40, 41
local model potential, viii, ix, 47, 48, 49,
heating rate, 23
101
high strength, vii, 1, 4, 8, 13, 16
high strength alloys, vii, 1, 4, 8, 13
high temperature, 24, 26, 28, 29, 39, 40, 41 M
H-local field correction function, viii, ix, 47,
60, 84, 97, 101, 113 magnitude, 21
Hubbard and Beeby (HB), viii, 18, 70, 72, mass, 49, 67, 74, 91, 103, 118
74, 79, 88, 89, 91, 93 materials, 2, 10, 18, 76, 77, 78, 80, 92, 93,
hypothesis, 2 95, 102
hysteresis, viii, 20, 21, 37, 38, 41 matrix, vii, 49, 51, 72, 103, 105
matter, iv, 87, 99
MD technique, 48
I measurements, 71, 89, 102
mechanical properties, 20, 21
Ichimaru-Utsumi (IU), viii, ix, 47, 49, 50,
memory, 20, 42, 43, 44, 45
51, 52, 55, 57, 59, 60, 61, 63, 64, 65, 66,
metallography, 22
67, 70, 72, 73, 84, 85, 86, 88, 89, 90, 91,
metals, vii, viii, 42, 48, 49, 68, 71, 72, 74,
94, 97, 99, 101, 103, 104, 105, 106, 109,
81, 84, 88, 89, 91, 92, 94, 96, 97, 99,
110, 113, 114, 115, 116, 117
102, 103, 106, 112, 114, 116, 117, 118
IFM, 5
microhardness, vii, 20, 23, 38, 41
industrial application, 20, 21
microscope, 23
industry, 2
microscopy, vii, 20, 23
inert, 23
microscopy optical, differential calorimetry,
inherent flaw model, vii, 1, 4, 5, 6, 13
vii, 20
initial state, 24
microstructure, 22, 32
integration, 58
mirror, 22
126 Index
modeling, 42 pressure, 3, 4, 17
models, 49, 102, 103 principles, 3
modulus, viii, ix, 39, 45, 47, 53, 54, 59, 60, probe, 102
77, 80, 92, 93, 101, 107, 109, 111, 113, propagation, viii, ix, 8, 47, 54, 60, 76, 92,
114 101, 109, 113
momentum, 59, 63, 75, 92, 111, 117 pseudo-alloy-atom (PAA), viii, 49, 61, 64,
monocrystalline, vii, 20, 21, 22, 23, 24, 39, 70, 72, 81
41, 44, 45 purity, 22
N R
needles, 30, 31, 32 radiation, 23

Newton, 7, 10 radius, 67, 118
Ni, vii, 20, 21, 22, 39, 40, 41, 42, 44, 45 Raman spectroscopy, 102
nickel, 45 range, 21, 23
nitrogen, 23 real-space sum, viii, ix, 47, 101, 103
reference system, 103
relaxation, 39, 40
O relaxation process, 39
relief, 22, 23, 31, 32
optical microscopy, vii, 20, 23 researchers, 71, 89
resistance, 3, 20, 21
P response, 71, 73, 76, 89, 90, 92
reversible martensitic transformation
PAA, viii, 49, 61, 64, 70, 72, 81 (RMT), vii, 19, 20, 21, 22, 23, 24, 29, 31,
parameter, 3, 7, 17 32, 35, 36, 37, 38, 39, 40, 41, 44
percentile, 113 rhombohedral, 21
periodicity, 71, 89 Robotics, 44
phase transformation, 21, 23, 32, 45 room temperature, 22, 75, 92
phase transitions, 102
philosophy, 3
S
phonon dispersion curves (PDC), viii, ix,
48, 60, 63, 70, 71, 81, 88, 89, 96, 102, safety, 2
103, 113, 117 sample, 32
phonons, 49, 82, 96, 102, 103 scaling, 67, 118
physical and mechanical properties, 21 scanning calorimetry, 22, 23
physical properties, 102 scatter, 7
plastic, 3, 4, 40, 45 scattering, 48, 49, 71, 82, 89, 97, 102, 103
plastic deformation, 40, 45 scope, 3
plasticity, 21 shape, 20, 43, 44, 45
Poisson ratio, 114 shape memory alloys, 43
polarization, 67, 118 shear, 53, 107
polarized light, 23
Shear modulus ( C  ), deviation from, viii,
polycrystalline, 20
ix, 47, 101
Index 127
showing, 63, 86, 99, 117 thermal treatment, 24, 25, 26, 28, 29, 30, 31,
SME, 20, 21, 32, 39, 40 33, 34, 35
solid phase, 103 thermodynamic properties, 49, 76, 77, 92,
solid solutions, 60, 68, 113 102, 103
solution, 48, 68 titanium, 4, 43, 45
specific heat, 102 tolerance, 17
stability, viii, 20, 27, 40, 41 toughness, 8, 9
stabilization, 41 transformation, vii, 19, 20, 21, 22, 23, 24,
stabilize, 24 29, 31, 32, 35, 36, 37, 38, 39, 40, 41, 42,
stable crack, 17 44, 45
standard deviation, 38, 39 transformations, 21, 42, 43, 45
standard error, 8, 10 traveling waves, 102
Standard error, 11, 12, 13, 14 treatment, vii, 8, 20, 21, 22, 23, 24, 25, 26,
steel, 3, 17 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38,
steel pipe, 3 39, 40, 41, 72
strain, 2, 39 twinning, 32
strength, vii, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,
12, 13, 14, 16, 17
stress, 2, 3, 4, 8, 21, 22, 31, 32, 39, 40, 45, V
76, 92
stress intensity factor, 3, 4 valence, 48, 50, 73, 74, 90, 91, 104
structural characteristics, 22 validation, vii
structural defect, 21 validity, 8
structural defects, 21 valuation, vii, 1, 4, 8
structure, 2, 3, 4, 21, 22, 23, 24, 31, 38, 39, values, 4, 7, 10, 38
40, 41, 44, 45, 67, 71, 72, 75, 82, 89, 92, variation(s), 21, 36, 39
97, 103, 118 vector, 49, 82, 97, 104
symmetry, 63, 71, 89, 117 velocity, viii, ix, 48, 54, 60, 77, 92, 102,
109, 113
vessels, 3, 17
T
techniques, 102 W
temperature, vii, 20, 21, 22, 23, 24, 26, 28,
29, 32, 39, 40, 41, 77, 80, 92, 95, 102 wave number, 50, 73, 90, 104
tensile, 1, 2, 4, 5, 6, 10, 17 wave vector, 49, 77, 81, 93, 96, 103
tensile strength, 2, 5, 10
tension, 4, 9, 10, 11, 12, 13, 14 X
test data, vii, 1, 2, 6, 10, 14, 15, 16
testing, 49, 103 X-ray analysis, 24, 30, 31
thermal analysis, 22 X-ray diffraction (XRD), vii, 20, 22, 23, 32,
thermal cycling treatments underload 40, 75, 92
(TCL), vii, 19, 22, 23, 24, 26, 27, 28, 29, X-ray diffraction, optical, vii, 20
30, 31, 32, 36, 37, 38, 39, 40, 44
thermal expansion, 102
128 Index
Y Z
Young modulus, viii, ix, 47, 54, 60, 101, Zn, 20, 42
109, 113

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MATERIALS SCIENCE AND TECHNOLOGIES

METAL MATRIX COMPOSITES

FOCUS ON ALLOYS AND LATTICE

Additional books in this series can be found on Nova‟s website

Additional E-books in this series can be found on Nova‟s website

METAL MATRIX COMPOSITES

FOCUS ON ALLOYS AND LATTICE

Nova Science Publishers, Inc.

NOTICE TO THE READER

Independent verification should be sought for any data, advice or recommendations

Library of Congress Cataloging-in-Publication Data

Published by Nova Science Publishers, Inc. †New York

This book presents current research in the study of metal matrix

GENERATION AND VALIDATION OF FAILURE

S. Rajakumar and T. Christopher

Modifications are made in the inherent flaw model of Waddoups,

Aerospace industry recognized two types of failure criteria: yielding and

2. MODIFIED INHERENT FLAW MODEL

KQ  NC (c  a ci ) (3a)

Figure 1. The characteristic length (aci) in a center-crack wide tensile panel.

Thus, a ci can be considered equivalent to the half crack length of an

The unknown characteristic length a ci  is to be obtained from the test

where the finite width correction factor [15] is,

Knowing the characteristic length a ci  , equation (4) gives the fracture

) with the correction factor (Y).

Equation (10) represents a failure assessment diagram useful for fracture

3. RESULTS AND DISCUSSION

where N is the number of test specimens.

The relative error (%) is computed as

Alloy Specification Temp., Material Un- Specimen N* Fracture

(MPa) (M Pa√m)  aci

) in equation (7), the characteristic length (aci) is obtained. Values of aci ,  NC

Table 2(a). Comparison of analytical and test results of center crack

Specimen Dimensions (mm) Un-notched Fracture strength, Relative Error

Table 2(b). Comparison of analytical and test results of center crack

Specimen Dimensions Un-notched Fracture strength, NC Relative Error

Table 3. Comparison of analytical and test results of center crack tension

Specimen Dimensions (mm) Un-notched Fracturestrength, Relative

Table 4. Comparison of analytical and test results of center crack tension

Specimen Dimensions (mm) Un-notched Fracture strength, Relative

Table 5. Comparison of analytical and test results of center crack tension

Specimen Dimensions (mm) Un-notched Fracture strength, Relative

203.2 25.4 1028.7 724.0 699.5 3.4

Table 6. Comparison of analytical and test results of center crack tension

Specimen Dimensions (mm) Un-notched Fracture Relative

Figure 6. Comparison of fracture strength of different high strength Alloys.

Trans. ASME Journal of Pressure Vessels Technology, Vol. 126, pp.

EFFECT OF APPLIED LOAD ON THE

E. C. Pereira, L. A. Matlakhova, A. N. Matlakhov,

monocrystalline Cu-13.5wt.%Al-4.0wt.%Ni alloy. The TCL was

Keywords: Monocrystalline Cu-13.5Al-4Ni alloy; reversible martensitic

superior plasticity and formability as well as resistance to the accumulation of

The alloy phasic structure was determined at RT by X-ray diffraction

Figure 1. Schematic diagram indicating the thermal cycling treatment of the

The RMT critical temperatures as well as its intervals of temperature and

3.1. X-Ray Diffraction after 300 TCL Finishing with a Half

Figure 2 shows the X-ray patterns of 300 cycles thermal treatment

with higher intensities are the coherent (111)1|(0015)R and (222)1|(027)R,

3.2. X-Ray Diffraction after 300 TCL Finishing with a Half