Proceedings of 2007 Japan-China-Australia

Cooperative Symposium on

Materials Science and Nanotechnology

November 14-17, Toyama, Japan

Edited by
K. Nishimura and K. Matsuda
Proceedings of 2007 Japan-China-Australia Cooperative Symposium on Materials
Science and Nanotechnology

November 14-17, 2007

Toyama, Japan

Edited by

K. Nishimura
University of Toyama

K. Matsuda
University of Toyama

This is an International Symposium to promote collaboration and academic exchange

between the University of Toyama and Shanghai University, Shandong University,
Dalian University of Technology, the University of New South Wales, the Norwegian
University of Science and Technology, Institute of Scientific Instruments Academy of
Sciences of the Czech Republic, Assiut University, the University of Virginia.
This symposium has the subtitle, Japan-China-Australia Cooperative Symposium on
Materials Science and Nanotechnology, since this was subsequently planned after the
Sino-Nippon Cooperative Symposium on Materials Science and Nanotechnology in
Shanghai University on November 2006.

ISBN978-4-9903248-1-0 C3040 00000E

Published by IKENO Laboratory,
Graduate School of Science and Engineering for Research, University of Toyama

All Rights Reserved @2007

No part of the material protected by this copy notice may be reproduced or utilized in
any form or by any means without written permission from the copyright owner.
Organizing committee:

Chairpersons
Katsunori MORI (U. Toyama) Jincang ZHANG (Shanghai U.)

Committee Members
Susumu IKENO (U. Toyama)
Jingping QU (Dalian UT)
Guoqun ZHAO (ShanDong U.)
Wayne D. HUTCHISON (UNSW)
Qingyi PAN (Shanghai U.)
Shixun CAO (Shanghai U.)
Chuanbing CAI (Shanghai U.)
Yong ZOU (ShanDong U.)
Hiroshi ANADA (U. Toyama)
Kiyoshi TERAYAMA (U. Toyama)
Noritatsu TSUBAKI (U. Toyama)
Zheng TANG (U. Toyama)
Yosikazu ISIKAWA (U. Toyama)
Kenji MATSUDA (U. Toyama)

Sponsored by:
UNIVERSITY OF TOYAMA

Supported by:
PACIFIC STEEL MFG. CO, LTD., TOYAMA WORKS.
SMK CORPORATION
SHIN NIKKEI CO, LTD.
ORIGIN CORPORATION
SANKYO TATEYAMA ALUMINIUM INC.
TOYAMA ALLOY CO, LTD.
HITACHI HIGH-TECHNOLOGIES CO.
TOMIKI MEDICAL INSTRUMENTS CO., LTD.
ST PRODUCTS INC.
TAKAHASHI INDUSTRIAL AND ECONOMIC RESEARCH FOUNDATION

Scientific Secretariat
Katsuhiko NISHIMURA
Graduate School of Science and Engineering for Research, University of Toyama
Gofuku 3190, Toyama 930-8555, Japan
E-mail: nishi@eng.u-toyama.ac.jp
Tel: +81-76-445-6844; Fax: +81-76-445-6703
 Opening Address

Welcome to the Cooperative Symposium on Materials Science and Nanotechnology in

Toyama. On behalf of the University of Toyama, I would like to thank all the
participants for joining the first international symposium organized in our university to
promote collaboration and academic exchange between your university.
Two years ago, three national universities in Toyama Prefecture were integrated into
the University of Toyama which now houses 8 faculties, 6 graduate schools, the
University Laboratory, Hospital, and Library. There are approximately 9,300 students
including 330 international students. In our Philosophy and Goals, we have made a
declaration that this university will uphold a global standard of education and research
as a university open to the regional community and to the world. Towards this line,
we really welcome international exchange programs and collaborations. Therefore,
it is indeed gratifying to meet representative persons who play a key role to enhance
cooperative relationship with the University of Toyama. Taking this opportunity I wish
to convey my thanks for your dedicated contributions for us.
This university is in Toyama Prefecture, which locates on the west coast, in the center
of Japan. A variety of industries have gathered together to form one of the best
industrial areas on the Japan Sea side. There are several leading companies in
aluminum, steel and other metal products. We have appreciated financial supports for
this symposium from those companies.
Lastly, I hope all the participants enjoy a rewarding meeting through this symposium.

November 15, 2007/10/17

Tokuso Saito
President, University of Toyama
 Symposium Program JCACS2007
November 14
16:00 Registration
16:30 Tour in Faulty of Engineering, University of Toyama
19:00 Welcome Party
November 15
8:40 open reception desk
9:00 A commemorative photo at the entrance of the Hall
9:10 Opening Address
9:20 Plenary Talk
9:40 Keynote Talk
10:25 coffee break
10:45 Keynote Talk
11:20 Keynote Talk [1]
12:00 Lunch
13:30 Keynote Talk [9]
14:00 Invited Talk [11]
14:20 coffee break
14:40 Invited Talk [13]
15:00 Oral Talk [19]
15:20 Oral Talk [23]
15:40 Oral Talk [27]
Kuroda Lecture Hall
Chairman: Prof. Y. Isikawa (U. Toyama)
Prof. T. Saito (President)
Prof. K. Mori (Dean)
Chairman: Prof. Q. Pan (Shanghai U.)
Prof. Z. Ren (Shanghai University)
Solidification and crystallization of materials under applied
magnetic field
Chairman: Prof. L. Frank (ASCR)
Prof. G. Zhao (Shandong University)
Brief Introduction to Shandong University - Study on grain
refinement mechanism in producing bulk ultra-fine grained
materials using severe plastic deformation process -
Prof. W. Hutchison (University of New South Wales)
Wide Ranging Studies of Magnetism in RNiAl 4 Compounds
Chairman: Prof. K. Matsuda (U. Toyama)
Prof. L. Frank (Academy of Sciences of the Czech Republic)
Methodology for experimentation, diagnostics and
nanotechnologies
Prof. I. Mullerova (Academy of Sciences of the Czech Republic)
Applications of the scanning low energy electron microscopy in
materials science
Chairman: Prof. S. Cao (Shanghai U.)
Prof. J. Zhang (Shanghai University)
Low-temperature Abnormal Transport and Spin Correlation
Effect in Manganites
Dr. T. Kawabata (University of Toyama)
HRTEM observation of the precipitates at early stage of aging in
Mg-16.9%Gd-Zr alloy
Mr. J. Nakamura (University of Toyama)
The effect silver-addition on crystal structure of rod-shaped
precipitates in Al-Mg-Si-Ag alloy
Ms. Q. Yu (Shanghai University)
Secondary M-I transition with unusual temperature dependency
in multi-spin Co-doping La2/3Ca1/3Mn0.9Co0.1O3 manganite
November 16 Prefecture Hall F7
Chairman: Prof. W. Hutchison (UNSW)
9:30 Keynote Talk [31] Dr. C. D. Marioara (Norwegian University of Science and
Technology , SINTEF)
Recent Advances on Precipitation in AlMgSi(Cu) Alloys
10:00 Keynote Talk [37] Dr. J. P. Hadorn (University of Virgina)
Analysis of massive transformation for amorphous Al 90 Sm 10
binary alloy during crystallization
10:30 Keynote Talk Prof. A. Gaber (Assiut University)
Effect of heat treatment on the precipitation in Al-1at%Mg-
xat%Si (x= 0.6, 1.0 and 1.6) alloys
11:00 coffee break
Chairman: Prof. Gaber (Assiut U.)
11:20 Keynote Talk [45] Prof. K. Matsuda (University of Toyama)
Effect of Mg Content on the Precipitation in Al-Mg-Ge Alloys
11:50 Invited Talk [49] Prof. Y. Zou (Shandong University)
Effect of the Nanocrystalline Phase on the Properties of the
Electroless Ni-P Deposit

12:10 Luncheon Seminar Hitachi High-Technologies Corporation

Chairman: Prof. Y. Zou (Shandong U.)

13:20 Invited Talk Prof. A. Moharram (Assiut University)
Photo-induced absorption change in thermally evaporated
Arsenic Selenides films
13:40 Invited Talk [53] Prof. S. Cao (Shanghai University)
Domain wall pinning effects in the dilute Cu-doped perovskite
LaMn1-xCuxO3 manganites
14:00 Invited Talk [57] Prof. K. Xu (Shanghai University)
The progress of MTG-YBCO bulk in Shanghai University
14:20 coffee break
Chairman: Dr. C. Maroara (SINTEF)
14:40 Oral Talk [63] Ms. A. Furihata (University of Toyama)
HRTEM observation of precipitates in excess Mg type Al-Mg-Si-
Ag alloy
15:00 Oral Talk [67] Ms. S. Wang (University of Toyama)
The effect of Mg 2 Si content on tne hardness of Al-Mg-Si alloys
with different aging temperatures
15:20 Oral Talk *[71] Mr. K. Doi (University of Toyama)
Magnetic properties and magnetocaloric effect in Ho 1-x Er x Co 2
compounds
15:35 Oral Talk *[75] Mr. R. Yamagata (University of Toyama)
Magnetic and transport properties of R 3 Al
15:50 coffee break
 Chairman: Prof. A. H. Moharram (Assiut U.)
16:10 Oral Talk [69] Mr. J. Tsukiyama (University of Toyama)
Relationship between tensile deformation and crystallographic
orientation of grains in Al-Mg-Si-Cu alloys
16:30 Oral Talk [71] Mr. L.W. Li (University of Toyama)
Structure and superconductivity for Li 2 (Pd 1-x Ni x ) 3 B boride
system
16:50 Oral Talk [74] Mr. S. Zhang (University of Toyama)
Magnetization and specific heat of new cubic PrCu 4 Au
17:10 Invited Talk [78] Prof. C. B. Cai (Shanghai University)
Crossover behaviors of magnetization transport in
superconducting RBaCuO multilayers and quasi-multilayers

17:30 Conclusion Remarks Prof. K. Mori

18:00 Fellowship Banquet Restaurant Castle F8

Chairman: Dr. T. Kawabata
Opening speech Prof. H. Anada (U. Toyama)
Toast Prof. L. Frank (ASCR)
20:00 Closing speech Prof. K. Terayama (U. Toyama)

November 17
8:00 Technical Tour Prof. Nishimura and Prof. Matsuda
 Wide Ranging Studies of Magnetism.., 1

JCACS
2007

Wide Ranging Studies of Magnetism in RNiAl4 Compounds

W.D. Hutchison1* and K. Nishimura2
1
School of PEMS, The University of New South Wales, ADFA, Canberra ACT 2600, Australia
2
Graduate School of Science and Engineering for Research, University of Toyama, Toyama 930-8555, Japan

Abstract

A review of studies on the intermetallic series RNiAl4 (R = rare earth) is presented. This compound exhibits intriguing magnetic properties,
including metamagnetism and multiple magnetic phase transitions in both temperature and magnetic manifolds. The choice of R as a
Kramers or non-Kramers ion is critical to the observed magnetic behaviour. Many techniques have been applied to various RNiAl4
compounds, including heat capacity, magnetisation, resistivity, low temperature nuclear orientation, Mssbauer spectroscopy and powder
neutron diffraction. Results to date are presented and discussed, together with current and proposed measurements.
Keywords: rare earth intermetallics, magnetisation, antiferromagnets, neutron diffraction

A range of techniques have been used in the study of

the RNiAl4 series, including bulk techniques such as heat
1. Introduction capacity, magnetisation, susceptibility and resistivity, as
well as the microscopic techniques of neutron scattering,
The rare earth intermetallic series RNiAl4 (R = rare earth) low temperature nuclear orientation and Mssbauer
forms with the orthorhombic (space group #63, Cmcm) spectroscopy. Here we review some of these studies,
YNiAl4-type structure in which the R and Ni atoms each explore the emerging trends, and discuss some current
occupy single crystallographic sites. The Ni sites are non- work aimed at further improving the understanding of the
magnetic but the system exhibits some intriguing systematics of the RNiAl4 series..
magnetic properties due entirely to rare earth magnetism.
For the compounds with R = Pr, Tb and Gd it is known
that there are at least two magnetic phase transitions as a
2. Experimental details
function of decreasing temperature, including an
intermediate incommensurate magnetically ordered phase
The RNiAl4 compounds used in this work was
(e.g. [1-3] and references therein). In addition, the low
variously made at Toyama or UNSW@ADFA. The
temperature magnetisation of TbNiAl4 exhibits at least
material for powder measurements, and as starting
two transitions as a function of applied magnetic field [4].
material for crystals, were synthesised by repeated argon
The choice of rare earth is crucial in determining the
arc melting of stoichiometric amounts of high purity
magnetic anisotropy. For example, the Kramers ion Nd
elements. The resulting ingots were annealed, generally
in NdNiAl4 orders along the b-axis [1,5], perpendicular to
for several days at up to 1100 C wrapped in tantalum foil
that of neighbouring non-Kramers PrNiAl4 which orders
under vacuum. The resulting material was checked for
along the a-axis [1,6]. Non-Kramers TbNiAl4 also shows
impurity phases by powder x-ray diffraction (XRD) and
a-axis ordering. Furthermore NdNiAl4 and ErNiAl4,
followed by further annealing if required. Where single
involving Kramers ions, do not appear to show any
crystals were used these were grown at Toyama by the
obvious signs of a second magnetic phase transition, at
Czochralski pulling method using an induction furnace
least down to 2 K.
with an argon atmosphere. Samples were spark-cut to

* Corresponding author. Tel.: +91 2 6268 8804; fax: + 91 2 6268 8786.

E-mail address: w.hutchison@adfa.edu.au
2 W. Hutchison et al.

appropriate sizes and the crystallographic orientation was

determined by Laue X-ray back reflection.
Bulk measurements were done at Toyama.
Magnetisation and susceptibility using a SQUID
magnetometer in applied magnetic fields up to 7 T and in
the temperature range from 2 to 300 K. The specific heat
was measured in zero magnetic field using the relaxation
method on a Quantum design PPMS system or using an
adiabatic method with a mechanical heat switch employed
to cool the sample and NbTi superconducting electrical
leads. Resistivity measurements used a conventional 4-
point probe configuration.
Powder specimens for neutron diffraction were Fig. 1. Specific heat measurement for powder ErNiAl4 in zero
prepared by grinding a number of ingots (ErNiAl4) or magnetic field. A single phase transition is apparent at approximately
5.8 K [9].
remanent single crystal pieces (TbNiAl4). Neutron
powder diffraction data were collected using the MRPD at 0.02
(a)
the HIFAR reactor, Lucas Heights, Australia. Use of a
closed cycle refrigerator allowed these measurements for 0.019
temperatures down to a nominal base temperature of 5 K.
Data were analysed using Rietica [7] and FullProf [8], the
latter allowing for refinement of magnetic structures. 0.018
Low temperature nuclear orientation (LTNO) is a M (B/f.u.)
useful addition to the more standard techniques in that the
0.017
use of radioactive labelling allows the tracking of the
moment directions for individual rare earth species. Our
LTNO was mostly done at UNSW@ADFA using a 0.016
dilution refrigerator, with neutron activations to produce
142
Pr, 147Nd and 160Tb carried out at the HIFAR reactor.
0.015
The 155Gd Mssbauer spectroscopy measurements,
applied to GdNiAl4, employed a 155Eu:SmPd3 source
(b)
25
cooled to 4.2K and were done at the University of
Paderborn. While the TmNiAl4 work was done at
20
UNSW@ADFA using a room temperature 169Er:ErAl3
source to probe the hyperfine levels of 169Tm in the
(-cm)

specimen. 15

10
3. Results - bulk measurements
5
RNiAl4 with R = Nd, Pr or Tb, and mixed systems such
as Pr1-xNdxNiAl4 have been studied in single crystal form.
While those with R = Gd, Er and Tm have been studied (c)
25
only as polycrystalline powder. The bulk measurement
techniques, specific heat, magnetisation, susceptibility
and resistivity were routinely applied to all these systems. 20
C (J/mol-K)

Specific heat measurements, particularly in zero magnetic

field, are very useful for both powder and crystals, 15
delivering the most accurate estimates of transition
temperatures in all cases (see table 1). The Kramers ion 10
systems NdNiAl4 [1,5] and ErNiAl4 [9] (see fig. 1) have
only one magnetic phase transition visible in zero applied 5
magnetic field. Non-Kramers systems involving Pr [1]
0
0 10 20 30 40 50
T (K)
Fig 2. (a) Magnetisation (with Bapp = 0.1 T), (b) electrical resistivity
(zero field), and (c) specific heat (zero field), data for polycrystalline
GdNiAl4 [2].

and Tb [10,3], as well as Gd [2], show two phase
transitions in zero applied magnetic field. As an example
of a system with two such transitions, data for GdNiAl4 is
shown in fig. 2. Note that it is not clear that Kramers ion
case TmNiAl4, has two transitions. However, the low
Nel temperature in this case taxes the experimental
resolution. The same can be said for the ErNiAl4 data of
fig. 1 (see the later discussion under neutron diffraction).
60
Inverse susceptibility (mol/emu)
40
20
0 Low temperature nuclear orientation (LTNO) employs
0 50 100 150 200
Temperature (K)
Fig 3. Inverse susceptibility data for TbNiAl4 in an applied magnetic
field of 1 T [3].
For the polycrystalline specimens the techniques of
magnetisation, susceptibility and resistivity have provided
evidence of the various phase transitions that is generally
less definitive than, but complimentary to specific heat.
However, the former also provide clear evidence for the
antiferromagnetic nature of the low temperature phases.
(Again the reader is referred to the Gd NiAl4 data of fig. 2
as an example). Magnetisation and susceptibility provide
more useful information when applied to single crystals.
PrNiAl4 [6] and TbNiAl4 [10] (see fig 3) are observed to
order as aaxis antiferromagnets at low temperature. In
contrast, with the Kramers Nd3+, NdNiAl4 is b-axis
aligned [5]. Magnetisation of RNiAl4 single crystals
measured as a function of magnetic field applied along
the AF axis at low temperature reveal interesting
behaviour. All three compounds for which single crystals
have been studied show a metamagnetic transition
occurring at ~3 to 5 T to a state which has net
magnetisation but not full amount that would reflect the
full (near free ion) moment, as data for TbNiAl4 in fig. 4
illustrates. Mizushima et. al. showed that TbNiAl4
undergoes at least one, possibly two, further transitions to
a final high moment state beyond about 9 T [4]. These
authors suggested that the intermediate low magnetisation
state involved a spin flop. The LTNO work outlined in
the next section rules out this suggestion. Instead, it can
be noted from fig. 4 that the first transition in TbNiAl4 has
a large associated hysteresis indicative that the
intermediate state may involve domain formation.
Wide Ranging Studies of Magnetism.., 3
4
35 K
3 25 K
15 K
M (B/ion)
2 7 K up
2 K up
1 7 K down
2 K down
a axis
0
b axis 0 1 2 3 4 5 6 7
c axis Magnetic Field(T)
Fig 4. Magnetisation verses applied field for TbNiAl4 at various
temperatures in the region of the phase transitions and below. Note that
the lower temperature (2 K and 7 K) data shows discernible hysteresis
and the up and down sweep data are plotted separately in these cases [3].
4. Results - LTNO
250 300 radioactive tracers. If these tracers are created in situ via
neutron activation then the unique radiation emissions of
the activated isotopes allow discrimination between the
magnetic behaviour of various bulk ions in ternary, and
higher complexity, compounds. This capability was
illustrated neatly using the ferromagnet Pr0.5Nd0.5Ni [11].
Where concurrent LTNO measurement via 142Pr and
147
Nd respectively showed that the Pr3+ and Nd3+ ions in
this compound maintained separate orthogonal easy axes.
With similar motivation LTNO has been applied to
various R1R2NiAl4 and R1R2R3NiAl4 compounds (Rx = Pr,
Nd or Tb) [12]. In the context of this paper it is the
LTNO of the end point compounds (RNiAl4 again with R
= Pr, Nd or Tb) that is of most interest. The gamma ray
anisotropy from 160Tb in TbNiAl4 is seen in fig. 5 to be
essentially invariant as a function of magnetic field
applied along the a-axis up to 7 T. The same result was
observed for 142Pr in PrNiAl4 and implies a constant
magnitude and direction of the rare earth moment
throughout in both cases. The equivalent experiment
using 147Nd in NdNiAl4, with applied field along the b-
axis, can be seen in fig. 6. Here the result is much the
same as for the other two systems except for a small
temporary reduction in anisotropy at ~4.5 T, right at the
first phase transition. A general observation from all the
LTNO work is that Nd ions are less magnetically hard
than Pr or Tb in these compounds. Finally we note that
the saturation gamma ray anisotropy, particularly for
160
Tb, in these compounds will be attenuated due to
neutron damage unless the specimen is annealed post
activation [13]. Taking this into account, the LTNO data
shows that the rare earth ions are in a high moment state
at all values of applied magnetic field. For example, the
Tb3+ moment in TbNiAl4 is estimated to be 8.4 B from
LTNO [13]. A value is consistent with the high field
magnetisation [4]. With the exception of the glitch for
Nd at ~4.5 T, the rare earth moments also remain are
4 W. Hutchison et al.

aligned along their respective easy axes throughout these those of TbNiAl4 [3]. The fact that S-state Gd3+ in
experiments. GdNiAl4, for which the CF interaction is negligible, has
magnetic behaviour quite similar to its neighbour Tb3+ in
TbNiAl4, implies that the R-R exchange interaction is far
more important in determining the magnetic structure
than the CF for RNiAl4. This notion is explored further in
section 7.

Fig 5. -ray anisotropy of 1272 keV emission from 160Tb in TbNiAl4

at 8 mK, observed at the a, b and c axes with external magnetic field
applied along the a-axis up to 7 T.

Fig 6. -ray anisotropy of 531 keV emission from 147Nd in NdNiAl4

at 8 mK, observed at the a, b and c axes with external magnetic field
applied along the b-axis up to 7 T.
155
Fig 7. Representative Gd Mssbauer spectra for GdNiAl4 with
zero applied field [2].
5. Results Mssbauer

Gd3+ is an S-state ion, which means that the Mssbauer

isotope 155Gd is useful in that it can probe just the rank 2
crystal field (CF) parameters and, furthermore any
magnetic behaviour in GdNiAl4 is not likely to be CF
driven. This compound was studied with these reasons
and Mssbauer effect spectroscopy in mind. GdNiAl4
Mssbauer data was collected from room temperature
down to 4.2 K. Representative spectra can be seen in fig.
7, where the well defined quadrupolar doublet for T > TN
is broadened by magnetic interactions below TN.
Analysis of the fits to these spectra gave the a temperature
dependence of the 155Gd magnetic hyperfine field, as
shown in fig. 8, whose character is remarkably similar to
that of the temperature dependence of the Tb moment of Fig 8. Temperature dependence of the magnetic hyperfine field, Beff,
fig. 10. Indeed, the character of the bulk measurements acting at the 155Gd nuclei in GdNiAl4 [2].
for GdNiAl4 (fig. 2 and [2]) also have similar features to
 Wide Ranging Studies of Magnetism.., 5

Another outcome of the Gd Mssbauer analysis was the

assignment of the magnetisation direction in GdNiAl4 as
either b or c-axis. By comparison with other RNiAl4
systems, which all show the c-axis as least favoured, leads
to a conclusion that the b-axis is the magnetic direction in
this case. The Gd data also provided useful rank 2 CF
parameters. These can be combined with other data, such
as the inelastic neutron scattering results for ErNiAl4 or
TmNiAl4 Mssbauer, in the quest for a full set of CF
parameters. Both of these measurements are in progress.

6. Results - neutron scattering

Neutron powder diffraction (ND) on PrNiAl4 clearly

established that the lowest temperature (and low magnetic
field) phase is a commensurate linear antiferromagnet [6].
The moments lie along the a-axis in the PrNiAl4 case,
with propagation vector (0 1 0). Our ND study of another
Kramers ion system in TbNiAl4 showed the same for the
low temperature structure [3]. Additionally, with benefit
of an intermediate phase extending over a much larger
temperature range in this second case, the intermediate Fig 10. Staggered Tb ion moment in the low temperature region [3].
AFM = antiferromagnetic, P = paramagnetic, IC = incommensurate.
structure was determined. This intermediate magnetic This result from TbNiAl4 has a similar form to the temperature
phase in TbNiAl4 is incommensurate with propagation dependence of the Gd moment measured via Mssbauer in Fig 9.
vector (0.171 1 0.038). Fig. 9 is taken from the ND data
for TbNiAl4 and tracks the strong (010) magnetic peak as As mentioned above the compounds involving
the temperature rises. This peak disappears abruptly at Kramers ions appear to not show an intermediate phase,
the phase transition to the intermediate phase in which at least when considering bulk measurements carried out
instead peaks of the incommensurate antiferromagnetic to date. To further explore this question, ND studies of
structure are present (e.g. peak at ~7). ND patterns ErNiAl4 have commenced [9]. Data collected close to the
collected from 14 K up to room temperature were fitted. (single) phase transition temperature 5.8 K, as determined
The extracted Tb3+ magnetic moment verses temperature by specific heat, are shown in fig 11. This data has been
is shown in fig. 10. fitted using FullProf to reveal incommensurate magnetic
14K order. A propagation vector of (0.191 1 0.015) is
6000
17.5K
assigned with the moments in an antiferromagnetic
configuration along the b-axis. This structure, similar to
20.3K
5000 the incommensurate phase of TbNiAl4, was perhaps
23K unexpected in this Kramers ion case. Energy arguments
4000
24.3K would suggest that the lowest temperature magnetic phase
should be commensurate. Therefore in this ErNiAl4 case
Intensity

3000 25.9K
the question is whether our data was collected, by
28.1K
2000
serendipity, precisely at the temperature of an until now
32K unresolved, intermediate phase or is there a lower
1000 34.6K
undetected transition? The new OPAL reactor should be
operational soon and experiments to lower temperature
37.1K
0 are scheduled. Another proposed experiment for the new
4 5 6 7 8 39.3K reactor is diffraction experiments with TbNiAl4 single
2 (degrees)
crystals as a function of applied magnetic field. The
interest is to obtain the structure of the intermediate
Fig 9. Extract from low temperature ND data for TbNiAl4. The left phase/s in the magnetic manifold.
hand peak is the dominant commensurate magnetic reflection and on the
right is the lowest angle incommensurate diffraction peak.
ErNiAl4 has also been the subject of recent inelastic
neutron scattering measurements. The CF levels have
been measured. Work is underway currently to use these
levels in conjunction with the GdNiAl4 Mssbauer data to
derive crystal field parameters that might be applicable
across most of the heavy rare earth versions of RNiAl4.
6 W. Hutchison et al.

40

30

TN (K)
20

10

0
0 1 2 3 4
|gJ -1|J

Fig 12. Experimental Nel temperatures for various RNiAl4 plotted

against the exchange coefficient, |gJ - 1|J. The straight line fit is used to
predict the bracketed values of table 1.
Fig 11. Neutron diffraction data for ErNiAl4 powder, collected in
zero applied magnetic field and at a sample temperature close to 5.8 K.
The FullProf refinement suggests incommensurate magnetic order
(starred peaks). 8. Discussion

Clearly in the RNiAl4 family of compounds there is

7. Results general trends strong magnetic anisotropy which depends on the choice
of the rare earth R and this anisotropy would appear to be
Experimentally measured ordering temperatures TN (as largely driven by the R-R exchange interaction. There is
well as TN where it occurs) for some RNiAl4 are listed in also an apparent bifurcation in characteristics based on
table 1, together with estimates of TN for some other R. Kramers verses non-Kramers ions. We are poised to
The estimates of TN were made using the slope of the line establish whether this division extends to the existence or
fitted to fig. 12, which is a plot of TN verses the exchange otherwise of intermediate magnetic phases in the
coefficient |gJ - 1|J. temperature manifold. Exploration of the intermediate
phase in the magnetic manifold will also be interesting.
R |gJ-1|J TN [K] TN [K] Ref.
Pr 0.8 8.1 6.9 [1]
Nd 1.23 9.3 - [1] Acknowledgements
Sm 1.79 (15)
The authors wish to thank the University of Toyama,
Gd 3.5 24.7 20.8 [2]
UNSW@ADFA and the Australian Institute of Nuclear
Tb 3.0 34.0 28.0 [3] Science and Engineering for funding assistance. We also
Dy 2.5 (21) gratefully acknowledge all our co-authors (of papers
Ho 2.0 (16.5) referenced here-in) who have contributed to this work. In
Er 1.5 5.8 - [9] particular, we thank D.J. Goossens, G.A. Stewart, Y.
* [14] Isikawa, D.H. Chaplin and K. Mori for important
Tm 1.0 5
contributions and/or discussions.
Table 1. Nel temperatures for selected RNiAl4 compounds. Those
entries with a reference are experimental values. The bracketed values
are estimates based on fig. 12. References

[1] K. Nishimura, T. Yasukawa, K. Mori, Y. Isikawa, W.D. Hutchison

and D.H. Chaplin, Jpn. J. Appl. Phys., 42 (2003) 5565.
[2] G.A. Stewart, W.D. Hutchison, A.V.J. Edge, K. Rupprecht, G.
Wortmann, K. Nishimura and Y. Isikawa, J. Mag. Mag. Mat., 292
(2005) 72-78.
[3] W.D. Hutchison, D.J. Goossens, K. Nishimura, K. Mori, Y. Isikawa
and A.J. Studer, J. Mag. Mag. Mat., 301 (2006) 352-358.
[4] T. Mizushima, Y. Isikawa, A. Mitsuda, K. Kobayasi, F Ishikawa, G.
Goto, S. Kawano, J. Mag. Mag. Mat. 272-276 (2004) e475-e476.
[5] T. Mizushima, Y. Isikawa, T. Yasuda, T. Kuwai and J. Sakurai, J.
Phys. Soc. Jpn, 68 (1999) 637.
 Wide Ranging Studies of Magnetism..,
[6] T. Mizushima, Y. Isikawa, J. Sakurai, M. Ohashi and Y. Yamaguchi,
J. Phys. Soc. Jpn, 66 (1997) 3970.
[7] B.A. Hunter and C.J. Howard, Rietica (available from
www.ccp14.ac.uk).
[8] J. Rodriguez-Carvajal, Physica B, 192 (1993) 55.
[9] W. D. Hutchison, D. J. Goossens, B. Saensunon, G. A. Stewart, M.
Avdeev & K. Nishimura, Proceedings 31st Annual Condensed
Matter & Materials Meeting, Wagga Wagga (2007) p42-44.
[10] H. Sakai, University of Toyama internal report (1998), in Japanese.
7
[11] K. Nishimura, W.D. Hutchison, D.H. Chaplin, S.J. Harker, K. Mori
and S. Ohya, Hyperfine Interact., 133 (2001) 121.
[12] K. Nishimura, W.D. Hutchison, D.H. Chaplin, T. Yasukawa, K.
Mori, Y. Isikawa, S. Ohya and S. Muto, J. Mag. Mag. Mat., 226
(2001) 1126.
[13] W.D. Hutchison, D.H. Chaplin and K. Nishimura, Hyperfine
Interact., submitted (2007).
[14] K. Nishimura, Unpublished data.
 Methodology
hodology forfor
M et experimentation,
Exper diagnostics...
im entation,diagnostics...

JCACS
2007

Methodology for experimentation, diagnostics and nanotechnologies

L. Frank*, J. Lazar, P. Zemnek, Z. Staruk, jr., P. Jurk, J. Sobota, I. Mllerov
Institute of Scientific Instruments, v.v.i., Academy of Sciences of the Czech Republic, 61264 Brno, Czech Republic

Abstract

Methodology for experimental physics, for instrumentation in biomedical sciences, general measurement science, diagnostics of materials
and products of technologies, and even methodology for proper micro- and nano-technological processes, is a discipline requiring to cover
a broad scope of activities from formulation of basic theory and models of structures and processes, through invention, development and
verification of novel methods, up to their application in prospective fields of applied science and high-tech industry. Several long-term
methodological projects are briefly characterized as regards their definitions and recent results.

Keywords: optical frequency standards, interferometry, micro- and nano-manipulation with light beams, magnetic resonance spectroscopic imaging, vacuum
technologies, particle beam technologies, very low energy electron microscopy

lasers, on advanced laser metrology and production of

1. Introduction
Strong competition in the market segments of scientific
instruments and equipment for modern high technologies
motivates for industrial research and development
activities. In parallel, also importance of academic
activities in relevant branches of methodology grows.
While in the industrial R&D new projects are usually
judged upon early marketability of results, the academic
science should have the possibility of paving new ways.
Several long term methodological projects of the
Institute of Scientific Instruments (ISI) in Brno are briefly
characterized (see www.isibrno.cz). In addition to these,
ISI is dealing with theoretical and computational electron
optics, detection of electrons, electron beam lithography,
and low temperature physics and technologies.
high-purity absorption gas spectroscopic cells. In the field
of optical frequency standards, highly coherent
semiconductor laser in the extended-cavity configuration
with a line width below 100 kHz at 633 nm, and an etalon
of optical frequency in the telecommunication spectral
region at 1542 nm have been developed. Activities in the
laser metrology led to a unique differential interferometer
with quadruple passage of the laser beam and the total
resolution of 0.3 nm, and to measurement of the refractive
index of air using the Fabry-Perot interferometer.
Fig 1. Iodine-filled absorption cell for stabilization of lasers.

Optical micro- and nano-manipulation techniques

2. Research projects
Laser beams are used to manipulate objects in
nanometer and micrometer ranges of size. Compact
Optical frequency standards and interferometry
optical tweezers have been developed, fitting to optical
Program focuses on the design of primary standards of
microscopes without any modifications. More advanced
optical frequencies based on He-Ne and semiconductor
methods use interference of laser beams to confine

* Corresponding author. Tel.: +420-541-514-299; fax: +420-541-212-118.

E-mail address: director@isibrno.cz.
 L. Frank et al.,
L.Frank etal.,

thousands of sub-micrometer objects and to deliver them

over millimeter distances (so-called optical conveyor
belt). Sophisticated methods have been found for sorting
components of polydisperse suspensions or colloids
according to sizes, just by illumination with light (so-
called optical sorters), and, similarly, a light-induced self-
arrangement of a soft-matter has been performed.

Fig 4. Application example of the selective impedance cardiography.

Fig 2. Thousand polystyrene particles (radius 175 nm) are confined
in a standing wave formed by two counter-propagating non-diffracting Vacuum and particle beam technologies
beams (picture composed of ten CCD frames see the white rectangle). The group is concerned with development of
technologies and with design and construction of
Methodology of the nuclear magnetic resonance
technological equipment forming the basis for building
Research is oriented mainly to biomedical in-vivo
electron optical and other devices operated in vacuum or
magnetic resonance spectroscopic imaging (MRSI), and
ultrahigh vacuum conditions. Radio frequency magnetron
aims at development of a virtual scanner for pulse
sputtering of thin films and of sophisticated multilayer
sequence design and data analysis, and at development of
systems as well as their diagnostics is pursued, too.
pulse sequences and data processing for fast MRSI on
present and future MR systems operating at 1.5 to 7 T.
The search for solutions of the major challenges
technical and safety limitations, artifacts, coupled spin
systems, and signal-to-noise ratio is based on numerous
past achievements concerning selective excitation and
water suppression, which are in use around the world.
Recently, NMR of gases, particularly hyperpolarized
xenon, has been introduced. Fig. 5 Table-top electron beam welder (beam power up to 2 kW,
beam energy up to 60 keV, computer control of the beam and of the two
axes manipulator); production starts in Focus GmbH, Germany.

Scanning microscopy with very low energy electrons

Principle of retarding the illumination beam of the
scanning electron microscope by means of the cathode
lens has been utilized to lower the electron energy to
arbitrarily low values without sacrificing the image
Fig 3. NMR spectra from 6 selected 250 Pl voxels in the human resolution. The resolution has been obtained in units of
brain, distribution of the N-acetyl aspartate in the slice, and the
conventional MR image of water in the same slice (measured in 9.5 min nm at units of eV and plenty of novel image contrasts
at 1.5 T by a double spin-echo sequence). have been demonstrated (diffraction contrast of the
surface crystallinity, contrast of the local density of
Bioinformatics
electron states, injected charge contrast in semiconductors,
Various original non-invasive and inexpensive
high vacuum observation of insulators, etc.).
methods for detection of blood circulation control
disorders have been developed and patented. Methods
provide both research and clinical examination of the
haemodynamic system. Goals include definition of the
measurement protocols, development and implementation
of measurement devices, and analysis of the signals.
Defined excitation according to the protocol and complex
analyses of simultaneously measured signals (ECG, EEG,
blood pressure, blood flow, etc) provide improved
differentiation of subjects according to risk factors of the
sudden cardiac death, arrhythmia or hypertension. Close
cooperation exists with the St. Anne's University Hospital Fig 6. UHV scanning microscope with very slow electrons.
Brno and the Mayo Clinic, USA.
The ISI activities are supported by the Research Plan
no. AVOZ20650511.
 Applications of the scanning low energy .. 1

JCACS
2007

Applications of the scanning low energy electron microscopy in materials

science
I. Mllerov
Institute of Scientific Instruments ASCR, v.v.i., Krlovopolsk 147, 612 64 Brno, Czech Republic

Abstract

The cathode lens mode in the scanning electron microscope is employed in imaging of surfaces. Contrast mechanisms can be examined
throughout the full energy range of electrons from tens of keV down to units of eV with nearly unchanged image resolution. Multi-channel
and one channel detectors have been used for the signal collection. By the multi-channel detector even the low take-off angle electrons can
be acquired in parallel so that the grain contrast and surface topography can be very well distinguished. Imaging of crystal grains at landing
energy as low as 10 eV has been demonstrated.

Keywords: low energies, contrast formation, multi-channel detection

lateral resolution. The signal electrons are accelerated

between the specimen and detector and collimated toward
1. Introduction the optical axis, and so a high amplification as well as
high collection efficiency is obtained. Both one- and
The emission electron microscope (EEM) is one of the multi-channel detectors have been used in selected
oldest versions of electron microscope (EM). In this type applications presented in this paper.
of a directly imaging device the specimen itself is the
source of electrons, which are emitted under various types
of excitations (impact of electrons, ions or photons, 2. Experimental
heating etc.). Electrons emitted from the specimen at a
low energy ESP are accelerated to high energy E and The immersion lens, in which the specimen itself
utilized to form the image on the screen. Already in 1941 forms one of the electrodes, is called cathode lens (CL).
Recknagel demonstrated that the immersion lens, formed In our version of the CL mode (Fig. 1) the negatively
by the specimen and an electrode above it, has biased specimen forms the cathode while grounded
surprisingly small basic aberration coefficients, detector serves as the anode. In this configuration both the
proportional to the ratio ESP/E [1] and hence even one-channel single crystal YAG detector [4] and the
decreasing with the emission energy. Modern EEM are multi-channel detector, formed by a multi-channel plate
mostly of the PEEM (photoemission electron microscope) (MCP) with eight equi-areal ring shaped collectors [5],
type, excited by means of strong radiation sources like the
synchrotron. In the LEEM (low energy electron
microscope) the specimen is illuminated by a parallel
coherent wave of slow electrons, generated just in front of
the specimen by retarding high energy electrons in the
same field that accelerates the emitted electrons [2].
The scanning electron microscope (SEM) is widely
used for imaging of surfaces with the scanned electron
probe at relatively high energy. We introduced the
retarding principle (the immersion lens) to the SEM [3]
and generated a low and very low energy electron probe.
The advantage is in the possibility of following the
contrast mechanisms throughout the full energy range
(from, say, 10 keV to 10 eV or even below) with a high Fig 1. A schematic drawing of the cathode lens mode in the SEM.

Corresponding author. Tel.: +420 541514300; fax: +420 541514402.

E-mail address: ilona@isibrno.cz
2 I. Mllerov
can be used. The inner/outer diameters are 0.3/10 mm for
the YAG detector and 3/19 mm for the multi-channel
detector, respectively.
3. Results and discussion
Examples of the images taken by the multi-channel
MCP detector and by the one-channel YAG detector are
shown in Figs. 2 and 3, respectively.
Fig. 2. Ni grains [6] taken by the innermost (a) and outermost (b)
collector of the multi-channel MCP detector; ESP = 5 keV, E = 10 keV.
The width of the field of view is 150 m, the VEGA TS 5130MM SEM
was adapted to the CL mode.
Fig. 3. Surface of the polycrystalline Cu sheet etched in nitric acid;
Tesla BS 340 SEM adapted to the CL mode, E = 10 keV, ESP = 5 keV
(left) and 10 eV (right). The width of the field of view is 70 m.
Owing to acceleration in the CL field, high
amplification is obtained even for very low energy
electrons. In addition, collimation to the axis enables one
to detect also electrons emitted nearly tangentially to the
surface. While the inner detector ring (Fig. 2a) shows a
clear grain contrast mediated by the elastically reflected
electrons, the outer ring collector acquired image (Fig. 2b)
exhibits a strong topography contrast formed by the low
take-off angle electrons.
Fig. 3 shows the Cu polycrystalline sheet with surface
oxides and contaminants removed by wet chemical
etching. While at 5 keV the image is strongly dominated
by the edge effect appearing on steps made by etching
along grain boundaries, and also on other etch pits, at very
low energies (10 eV) these over-brightened features are
not visible. Instead, the fine surface relief combined with
the grain contrast appears as the most pronounced one,
with some residual islands of contamination still present.
The use of the CL in the SEM can be very useful in
the materials science as the imaging mode revealing the
development of contrasts throughout the full energy range.
Even some extremely attractive LEEM applications [2]
can be performed [7].
The work is supported by the Czech Science
Foundation under grant no. 102/05/2327, and by the
Venture Business Laboratory of the Toyama University,
Japan.
References
[1] A. Recknagel, Z. Phys. 117 (1941) 689-708.
[2] E. Bauer, Rep. Progr. Phys. 57 (1994) 895-938.
[3] I. Mllerov, L.Frank, Adv. Imaging Electron Phys. 128 (2003) 309-
443.
[4] R. Autrata, Scanning Microsc. 3 (1989) 739-763.
[5] I. Mllerov et al., Materials Transactions 48 (2007) 940-943.
[6] Specimen provided by Dr. Burk from IPM Brno, Czech Republic.
[7] L. Frank et al., Scanning 21 (1999) 1-13.
 Low-temperature Abnormal Transport.. 1

JCACS
2007

Low-temperature Abnormal Transport and Spin Correlation Effect in

Manganites
J.C. Zhang * a, Y. Xua, M. Q. Chen, L. M. Yu, S. X. Cao and Y. G. Zhaob
TPF FPTP P P P P T PT

a
P Department of Physics, Shanghai University, Shanghai 200444, China
P

b
P Department of Physics, Tsinghua University, Beijing 100084, China
P

Abstract

An abnormal low-temperature transport was studied systemically by the electric and magnetic measurement for
perovskite manganites. A Kondo-like behaviour was observed at low-temperature and it can be fitted in the
framework of Kondo scattering, electron-electron (e-e) and electron-phonon (e-p) interaction models. The results
show that the abnormal behavior depends strongly on thedegree of the spin-disorder of the system and can be
tuned by external applied magnetic field. It proves also that the existence of spin disorder caused form intrinsic
magnetic inhomogeneity. The existence of e-e interaction should be a general characteristic and reflect the strong
correlated interaction between electrons in the mixed-valent manganites. The magnetic results provide interesting
information about the strong coupling of charge-orbital and/or spin-orbital degrees of freedom. This proves a
possible existence of quantum orbital transfer resulted from the change of orbital ordering (OO) modes and
accompanied with spin reorientation and carrier delocalization. The carrier delocalization is closely related to the
coupling of charge-orbital and can be proved from the low temperature resistivity minimum behaviour. These all
show the importance of the strong interaction between spin, charge and orbital in the strong correlated system.
Keywords: Resistivity minimum, electron-electron interaction, weak spin disorder, step-like transport jump, strong correlated manganites

serves as a fundamental model for understanding

1. Introduction
In the past two decades, enormous effort have been
exerted to understand systems with strongly correlated
electrons, for example, the high-Tc superconductors in
cuprate and the colossal magnetoresistance (CMR) in
correlated electron physics. As a consequence, the
interplay between electronic and magnetic degrees of
freedom has intensely studied in manganites for these
years. For the existence of the possible quantum phase
transition [8] and the intrinsic disorder [9] caused by the
B B chemical substitution of the A site in the general chemical
formula ABO3, to make clear the underlying mechanism
B B

mix-valent manganites, because both of them have wide of the CMR manganites, more and more attentions focus
range of technological applications and the strong on the electronic and magnetic properties of manganites at
correlated characteristics [1,2]. However, despite the low temperatures. At low temperatures, the contribution
efforts have made, the nature of the strongly correlation from the electron-lattice interaction is weakening and the
physics is still not clear. Especially, in the manganites, the Coulomb correlation effect is obviously. In this way, the
strongly coupling between the charge, spin, orbit and the low-temperature transport properties of the manganites
lattice freedom lead to rich phase diagrams [3-7]. may reflect the intrinsic mechanism of the systems.
Meanwhile, the multiple interactions in these materials Therefore, extensive studies of magnetic, structural and
would give more obstacles to the comprehension on the transport properties on the manganites at low
correlated electron system. It is well known that the temperatures have been carried out [10, 11]. Beside the
coupling between localized spin and conduction electrons distinct low-field magnetoresistance (LFMR) effect at

*
TP PT Corresponding author. Tel.: +86-21-66133262; fax: +86-21-66133262; e-mail: jczhang@shu.edu.cn.
2 J. C. Zhang et al.

low temperatures, many recent experiments have provide 3. Results and discussion
evidences for the existence of the resistivity minimum and
novel step-like magnetization jump at low temperatures in 3.1. A general characteristic of resistivity minimum for
the manganites. The present study focuses on the low- the La2/3Ca1/3MnO3bulk sample and La2/3Sr1/3MnO3
B B B B B B B B B B B B

temperature abnormal electronic transport and magnetic epitaxial film

properties of the manganites. The electronic transport
properties for the La2/3Ca1/3MnO3 (LCMO) bulk sample
and La2/3Sr1/3MnO3 (LSMO) epitaxial film at low
B B B B
temperatures indicate that the resistivity minimum of the
manganites mainly caused from the electron-electron
interaction and the weak spin disorder of the system.
Study on the (La1-xYx)2/3Ca1/3MnO3(LYCMO) and (La1-
xPrx)5/8Ca3/8MnO3(LPCMO) systems give evidences that
B B B B B B B B
the resistivity minimum at low temperatures have
correction with the spin-disorder scattering, which is
similar with the Kondo effect. The correlated research on
B B B B B B Figure 1 show the temperature dependence of
B B resistivity under the various applied fields between 0 and
8.0 T in 2-50 K for LCMO sample, normalized resistivity
was used by (T)/ (T =50K). Its inset shows the resistivity in
whole temperature range of 2-300 K at the field-free and
B B B B B B B B B B B 8.0 T, respectively, which indicates the existence of the
B CMR effect. It can be seen that distinct resistivity minima
appear below 30 K and show strong dependence on
applied fields. It is worth noting that, the resistivity upturn
below Tmin was gradually suppressed at low fields but
B B

the magnetic properties show novel single and triplex almost achieves saturation when the filed is larger than
irreversible resistivity sharp drop accompanying with the 1.0 T. Tmin, the resistivity begin upturn with the B B

magnetization-step at low temperature and propose a temperature decreasing, moves monotonously toward
newly microscopic competing mechanism for coexisting lower temperature with increasing applied field. They
clusters in the LPCMO systems. We discuss that the step- indicate that when the field is smaller than 1.0 T the low-
like transport jump originates from possible single or temperature resistivity abnormal behavior is sensitive to it
triplex quantum orbital transfer under weak magnetic but almost independent on it when the field is larger than
field, proving the coupling of charge-orbital and/or spin- 1.0 T. However, there is a discrepancy of the effect of
orbital degrees of freedom, respectively. applied magnetic field between the experimental data in
this paper and the result of refs 12 and 13. For the ref 13,
the resistivity minimum of used sampleLa0.5Pb0.5MnO3 B B B B B B

2. Experimental containing 10 at. % of Agunder applied external field

which was different from our sample. But the other work
The usedLYCMO and LPCMObulk samples were done by the same group used single crystal and ceramic
prepared by conventional solid-state reaction method. The La0.8Sr0.2MnO3 [14] also did not find the same rule, i.e.,
B B B B B B

LSMOepitaxial film was prepared by PLD method. The

B B the resistivity upturn disappears at a certain field Hcr. For B B

structure was analyzed by scanning electron microscopy the ref 12, the used sample was La0.7Ca0.3MnO3 films. B B B B B B

(SEM) and x-ray diffraction (XRD, 18kWD/max-2500 On this problem the polycrystal and the film sample may
model, Cu-K radiation). The XRD pattern shown the
B B have difference. Moreover, in the ref. 12, the B and n
spectra are well characterized without detectable extra were correlated with the depth of minima and Tmin may be B B

peaks appearing that indicate the samples are well controversial.

crystallized and good single-phase. The thickness of the For comparing, we also prepared LSMO epitaxial film
film is about 100 nm. Only the (001) and (002) diffraction employing the PLD. Figure2 show the resistivity cures
peaks were observed in the LSMO epitaxial film, which in the temperature range from 2 K to 300 K under various
indicating that the film has c-axis epitaxial growth and in applied fields. It can be seen that the film was metallic in
good single-phase.The electric transport, magnetic and
Reduced resistivity / (50K)

specific heat measurements were carried out using PPMS a 1

La2/3Ca1/3MnO3

0.99
cm

(Quantum Design) in the temperature range of 1.8-400 K 0.0 T

and the magnetic field of 0-9 T with a precision of 10-5. P P
0.1 8.0 T
0.96
The magnetic field is perpendicular to the measurement 0 100 200 300
T (K)
current and parallel to the c axis of the film. The
R(0.0T)
temperature and magnetic field dependence of resistivity 0.93 R(0.3T)
R(0.5T)
(-T and -H curves) were measured using the standard R(1.0T)
R(2.0T)
four-probe technique in a temperature range of 2 to 300 K. 0.90 R(4.0T)

All the -T curves were measured under field cooling. For 0 10 20 30 40

R(8.0T)
50
the -H and M-H curves, before each run, sample was Temperature ( K )
heated above its Tc and cooled to the measuring B B Fig.1 R-T curves under various applied fields in a lowtemperature
temperature under zero field, in order to ensure a prefect region of 2-50 K for La2/3Ca1/3MnO3bulk sample. Reduced resistivities B B B B B B

demagnetization of the sample. The experimental results were used.

are well repeatable.

1.0000
(H,T)/(H,10K)
12
0.9998
Resistivity (arb.unit)
0.9996
6 2
0
0 100
Fig.2 R-T curves under various applied fields for La2/3Sr1/3MnO3 film.
Inset show the low-temperature region on an enlarge scale
the whole temperature range even under the self-field. But
when the low-temperature resistivity (T<10 K) were
plotted on an enlarged scale as show in the inset of Fig.2,
the exciting results appeared, i.e., the resistivity minimum
appear in various fields. Moreover, the upturn below the
Tmin almost does not affect by the external applied
B B
magnetic fields up to 8 T, which is different with the bulk
sample. According to analyse in the ref.15, the low-
temperature resistivity of the LSMO epitaxial film were
fitted using the equation (T ) = 0 + e ln T + pT 5 . Best
fitting was obtained as shown inset, in which the symbols
are experimental data and the line is the fitting results.
The good fitting results confirm the e-e interaction is the
main reason induced the resistivity minimum appearance
in the epitaxial film. The e-e interaction is insensitive to
the applied magnetic field also give an explanation to the
problem that why the Tmin of the film almost did not
change with the applied magnetic field. However, the
quality single crystal is necessary to reveal the nature
physical mechanism of the novel transport properties.
3.2. The abnormal transport properties of the A-site
doped manganites at low temperatures
In order to understand the correlation between the low-
temperature abnormal electronic transport properties and
the magnetic disorder of the manganites system, A-site
doped samples LYCMO and LPCMO were investigated.
For the LYCMO system, we prepared samples with x=0.0,
0.1, 0.2 and 0.4. Here, Y has smaller ionic radius, 0.94
than La, 1.15 and there are evident effects on CMR
properties due to Janh-Teller effect and spin-glass
behavior caused by phase separation. This is a typical
example of spin-disorder system and is suitable for
studying the physical mechanism and their relative
change 21with the increasing of the Y content. As shown
P P
in the Fig. 3, there are resistivity minma for all the
LYCMOsamples in the temperature range 2.0 to 40 k.
Low-temperature Abnormal Transport.. 3
To show the change of the resistivity minimum for
different samples normalized resistivity were used
La2/3Sr1/3MnO3 by (T ) / (T = 2.5K) .It can be seen that with the Y content
increase, the depth of the resistivity curve is increasing.
Meanwhile, the spin-glass phase in the system also
increases with the Y content increasing. It is said that the
Y content can be a measure for spin disorder degree as
4 6 8 10
showing above. Combining the change of electrical
Temperature (K) resistivity, this proved that the spin scattering intensity is
0T increasing as x increases. According to the ref.16, it can
1T be seen that the spin-glass phase partly contribute to the
8T low-temperature abnormal electronic transport properties
200 300 for spin-disorder scattering. This induces a kind of
Temperature (K) possible explanations for the physical mechanism of
Konko-like transport in perovskite manganite.
B B B B B B
1.1
x=0.0
x=0.1
x=0.2
x=0.25
x=0.4
/2.5 1.0
0.9
0 10 20 30 40
Temperature (K)
Fig.3 The normalized resistivity /(2.5 K) in low temperature
region for (La,Y)2/3Ca1/3MnO3with x= 0.0, 0.1, 0.2, 0.25, 0.4 under zero
B B B B B B
field.
For LPCMOsystem, it is well known that the charge
B B
order (CO) state will appear with the Pr doped. Figure 4
shows / 2.4 -T results under 0, 0.3, 1.0, 1.8, 2.2, 3.0
and 6.0 T for x=0.35, respectively. Above 2.2 T, the
curves are independent of field and superpose each other
over a range from 2.4 K to 30 K. Inset of Fig. 4 shows M-
T data measured on heating after the sample was either
ZFC or FC. The low-temperature ZFC and FC M-T curves
separate from each other at 1.8 T while superposes at 2.2
T. This clearly suggests it is a coexistence of
ferromagnetic (FM) and charge ordered antiferromagnetic
(COAFM) phases below 2.0 T, and a FM state after
destroying of CO above 2.0 T. For COAFM and FM
B B
coexisting systems, Varelogiannis [17] obtained four
different quasiparticle branches E (k ) . k and k are
related with electronic dispersion of the nearest and next
neighbors hopping. Due to the interplay among spin,
charge and orbital in the COAFM phase, CO and AFM
will interfere to produce quasiparticle poles
with Wk +Mk and Wk Mk . W k Mk
can cause E+(k) and E (k ) 
branches to become zero and the COAFM state to be
melted. E+(k)= k2 +(Wk Mk)2 +k Fk BH and k < 0 for hole-
doped LPCMO, under sufficient applied field, the k , FM
4 J. C. Zhang et al.

1.01 0.005
6.0T
a 3 3.0T
0.0035
0.275 0.3
3
0.35

M( /f.u.)
0.0030 0.004

( cm)
1.8 T(ZFC) 2.2T
1.00 2
1.8 T(FC)

2 1.8T 0.0025 0.003
1.0T 1
0.0020
1 0.3T 0.002
0.99 0T 0.0015
4 4 0
4
/(2.4 )

0 50 100 150 200 250 300 2 2

M( /f.u.)
2
0.98 Temperature (K) 0 0 0

-2 -2 -2
3
M( /f.u.)

0.97 -4 -4 -4
-6 -4 -2 0 2 4 6 -6 -4 -2 0 2 4 6 -6 -4 -2 0 2 4 6

2
4 4
10 10 10
5

( cm)
2.2 T(ZFC) 0.4 0.5
0.96 1 2.2 T(FC) 2 2 3 0.625
10 10 10
1
10
0
10
0 10
0 50 100 150 200 250 300
0.95 -2 10
-1

5 10 15 20 25 30 10 10
-2

M( /f.u.)
-3
4 4 104
Temperature(K)
2 2 2

0 0 0
Fig.4 The normalized resistivity /(2.5 K) in low temperature -2 -2 -2
region at different fields. Insets are the M-T results (ZFC and FC) for 1.8 -4
-6 -4 -2 0 2 4 6
-4
-8 -6 -4 -2 0 2 4 6 8
-4
-8 -6 -4 -2 0 2 4 6 8
T and 2.2 T. field(T) field(T) field(T)

order parameter Fk and Zeeman contribution B H all Fig.5-H and M-H results at T=2.0 K for La5/8-xPrxCa3/8MnO3 (0.275 B B B B B B B B

have a negative sign and cooperatively compete with x0.625)

COAFM phase to make easily melting of the COAFM
phase. Meanwhile, the kinetic energy of the carriers polaron and favored the carrier localization in the vicinity
overcomes the binding energy of orbital and the Coulomb of the orbital. The triplex resistivity drops depend on the
energy, causing sudden liberation of carriers from the varying of orbital structure with increasing field and
COAFM state. As a result, this can induce delocalization results in the change of carrier localization state. These
of carriers and a sharp drop in resistivity to bear analogy are consistent with the coexistence of localized and
with the spin reorientation due to destruction of orbital itinerant carriers at low temperature as assumed by Jaime
ordering by magnetic field. et al[19]. A number of experiments have indicated the
coexistence of localized and free carriers near TC[20-22]. B B

3.3. Step-like transport jump and possible quantum However, the result at low temperature is absent until now.
orbital transfer Low field induces the alignment of spins and the
strong field changes the topology of COAFM and FM
We also investigate the magnetic properties of the domains[23].This is consistent with the change of the
LPCMO system for x=0.275, 0.3, 0.35, 0.4, 0.5, 0.625. resistivity under the applied magnetic field. Thewidth of
Figure5 gives -H and M-H curves at T=2 K. It can be the step-like transition at the M-H curves shows an abrupt
seen that for 0.3x0.4, an initial FM phase grows with characteristic and implies a spin reorientation behavior.
increasing field and a magnetization step appears, which Compared with conventional AFM transition, Hc is very B B

shows the transition of COAFM to FM phase. While, low even for x=0.625 (Hc<8.0 T), which indicates that the B B

there occur triplex-steps after initially lineal increase for x COAFM-FM transition is susceptible despite a very large
0.5. Surprisingly, the -H curves have nearly the CO gap ( ~0.5 eV, [24,25] several hundreds of teslas P P

similar change with M-H curves, and there are  all about ). It is interesting to note that once in the FM state,
single-drop for 0.3x0.4 and triplex-drops for x0.5. the system can not be transformed back to the AFM state
It was noted that the first drop corresponding to the first as H0, i. e, the COAFM-FM transition is irreversible.
step for x0.5 is not shown here due to huge value of And the -H curves for x 0.3 behave the similar
resistivity. The abrupt drop should be intrinsic because history-dependent phenomenon. This memory effect
the largest reduce infor x0.5 is over four orders of indicates field-induced change in the orbital occupancy of
magnitude and it is unlikely that such a strong effect eg electron[26,27], which will directly affect the carriers
B B

would result from the grain boundaries in the present and spins due to the interaction of charge-orbital and spin-
samples where grain sizes exceed 10m. Moreover, the orbital, respectively.
field associated with the sharp resistivity drop is nearly The temperature dependence of step-like
identical to the critical field HC associated with B B
magnetization jump was also investigated for sample
magnetization step, even for the triplex steps. These Pr2/3Ca1/3MnO3. We plot the M-H curves at T=2.4 K, 5 K
B B B B B B

suggest that localized carriers probably dominate the and 10 K respectively, as shown in Fig. 6. When T = 2.4
abrupt drop of resistivity. The coexistence of COAFM K, via a threshold field, denoted as HCA-F, the branch B PB P

and FM phase is formed thermodynamically as field exhibits abrupt steps (g = H / Hmax 0.02) separated by
varies[18], which amplified the tendency for orbital almost flat plateaus, implying a field-induced first order
 Low-temperature Abnormal Transport.. 5

system will be easier to transform into a FM phase under

4 applied field, resulting in the step fields shifting to lower
value. Therefore, we can conclude that thermal
4
perturbation plays an important role in such step
3 2.4 K
5K
transitions.
2 10 K
MB/f.u.

0
In summary, the electronic transport properties at
2 low temperatures for the La2/3Ca1/3MnO3 bulk sampleand B B B B B B

-2

La2/3Sr1/3MnO3 epitaxial film indicate that the resistivity

B B B B B B

-4
-90000 -60000 -30000 0 30000 60000 90000
2.4 K minimum of the manganites mainly caused from the
1
5K electron-electron interaction and the weak spin disorder of
10 K the system. Study on the transport properties of (La1- B

xYx)2/3Ca1/3MnO3 and La5/8-xPrxCa3/8MnO3 systems give

B B B B B B B B B B B B B B B B B

0
0 20000 40000 60000 80000
evidences that the novel transport properties at low
H(Oe) temperatures strongly dependent on the degree of the
spin-disorder of the system. The correlated research on
Fig.6 Magnetization of versus magnetic fieldfor Pr2/3Ca1/3MnO3 at B B B B B B
the magnetic properties show novel single and triplex
different temperatures. Inset shows the complete field-scans registered irreversible resistivity sharp drop accompanying with the
on this sample. magnetization-step at low temperature and propose a
newly microscopic competing mechanism for coexisting
phase, which results in the formation of step [28,29]. clusters in the La5/8-xPrxCa3/8MnO3 systems. We discuss B B B B B B B B

After the second jump, the magnetization reaches
saturation value 3.72 B/f.u., consistent with the fully Mn
B B
spin polarization. As the field is decreased, one observes a
rather flat curve down to about 1.2 T, followed by an
abrupt drop of magnetization yielding a remanent
magnetization value of about 0.33 B/f.u.. This suggests
that the step-like transport jump originates from possible
single or triplex quantum orbital transfer under weak
magnetic field, proving the coupling of charge-orbital
and/or spin-orbital degrees of freedom, respectively.
B B

that the phase-separated property is eliminated by initial References

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 HRTEM observation of the precipitates.. 1

JCACS
2007

HRTEM observation of the precipitates at early stage of aging    

in Mg-16.9%Gd-Zr alloy
T.Kawabata1), K Matsuda1), S. Kamado2), Y. Kojima2) and S. Ikeno1)
P P P P P P P P P P

1.Graduate School of Science and Engineering for Research,University of Toyama, Toyama 930-8555, Japan

2. Nagaoka University of Technology,1603-1, Kamitomioka, Nagaokashi, Niigata, 940-2188, Japan

Abstract

High resolution transmission electron microscopyHRTEMobservation was performed to clarify morphology of precipitates at early
stage of aging in Mg-Gd-Zr alloy. In the specimen aged at 423K, monolayer was observed on {1100}Mg planes. With increasing aging B B

time, the monolayer and phase grew along the <1120>Mg directions. Arrangement of bright dots corresponding to {020} except for the
B B B B

monolayer and phase was observed before peak aging stage. phases formed at the same aging stage.
Keywords: high resolution transmission electron microscope, Mg alloy, precipitates, aging

clarify the morphologies of the precipitates in the binary

1. Introduction Mg-Gd (-Zr) alloy.

Magnesium-rare earth (Mg-RE) alloys are well known

for age hardenable alloy [1-12]. Addition of Gd in
magnesium exhibits higher strength compared to
commercial Mg-RE alloy i.e. Mg-Y-RE (WE alloy).
Precipitation sequence of Mg-Gd system alloys are
investigated by using transmission electron microscope.
Vostry et al. [1] reported that the Mg-Gd alloy had three
P P
stage precipitation sequences as follows: Super saturated
solid solution (S.S.S.S) (D019) (cbco) B B
(fcc). Recently Gao et al. [2] reported the microstructure
evolution in Mg-15.0%Gd-0.5%Zr alloy aged at 523 K.
They proposed a four stage precipitation sequences as
follows: S.S.S.S (D019) (cbco) 1 (fcc)
B B
(fcc). In our recent study [3-4], morphology of
precipitates in the ternary Mg-Gd-Y(-Zr) alloys were
clarified by using the high resolution transmission
electron microscopy (HRTEM). In the early stage of
aging, monolayers formed by periodical arrangements of
Gd and Y atoms on the {1100}Mg plane, and phases
B B
2. Experimental
The Chemical composition of the experimental alloy
was Mg-16.9%Gd-0.51%Zr (mass%, hereinafter called
G17K alloy). An alloy ingot was homogenized at 773 K
for 6 hours and then hot rolled at 773 K under argon
atmosphere. After hot rolling, specimens were
encapsulated in pyrex glass tubes under argon atmosphere.
Then the specimens were solution treated at 773 K for 1 h,
quenched by breaking the glass tube in chilled water at
273 K, aged in a silicone oil bath at 423 K. TEM
B B specimens were thinned by the twin-jet electro-polishing
technique using a mixture of 1/5 nitric acid and 4/5
methanol as the electrolyte at about 243 K. HRTEM
observations were performed on the EM-002B TEM
(Topcon Co., Ltd., Japan) operated at 120 or 200 kV.

were observed. Furthermore, in the peak aged specimen,
the phase was found dominating with co-existence of
some phases. In the ternary Mg-Gd-Y(-Zr) alloys,
however, it was difficult to study the effect of an
additional element on the morphologies of precipitates
3. Results and discussion
Fig.1 (a) shows HRTEM image aged at 423 K for 64 h. The
bright and dark dots of a 0.32 nm spacing are arrayed in a row
along the {1100}Mg planes with length of about 2 nm. This
B B

because of the addition of two elements, Gd and Y. In contrast is similar to monolayer consisting of Mg atoms and rare
this study, HRTEM observation has been performed to earth atoms on {1100} planes reported in Mg-Y-RE alloy [5]
and Mg-Gd-Y-Zr alloys [3-4]. Fig.1 (b) shows the SAED
2 T. Kawabata et al.
pattern in this aging stage. The weak spots are apparent in the
SAED pattern at 1/2 distance of 1100 or 2110 magnesium spots.
B B
Fig.1 HRTEM image (a) and the SAED pattern (b)
of G17K alloy aged at 423K for 64h .
Fig.2 (a) shows a SAED pattern of the specimen aged at 423
K for 256 h. The small five spots are visible between 1100
magnesium spots. These small spots correspond to the spots of
phase with base centered orthorhombic structure (a=0.64nm,
b=2.22nm, c=0.521nm) [8-10]. Only one spot at 1/2 distance of
{1100}Mg or {2110}Mg in these five spots of Fig.2 (a)
B B B B
correspond to the spot of phase. The spots at the 1/2 distance
of 1100Mg and 2110Mg reflections are to be caused by
B B B B
superimposing of the diffractions from and phases in these
positions. It is not distinguish from and phases in the dark
field image obtained from this SAED pattern. Thus, HRTEM
observations were performed in the specimen aged at the same
time.
In the specimen aged at 423K for 256h, the length of
monolayer is about 3.2 nm and longer than that of Fig.1 (a). In
Fig.2 (b), combination of three magnesium matrix layers
between two monolayers appears here in a couple. The overall
size of the feature along the [1100]Mg direction is about 2.2 nm,
B B
what fits to the lattice parameter b of the phase as reported for
the Mg-RE alloy [8-10]. Thus, the group of atoms in Fig. 2(d) is
(001). The arrangement of dark dots with spacing of 0.64 nm
B B
connected this contrast of phase are observed. This
arrangement correspond to a part of phase with D019 type
B B
ordered structure (a=0.64nm, a=0.521nm) [3]. From above
HRTEM observations, the monolayer, and phase co-exist
at this aging stage.
Fig.2 TEM images of G17K alloy aged at 423K for 256 h :
(a) SAED pattern (b) HRTEM image of phase and
a part of phase.
Fig.3 (a) shows a SAED pattern of Fig.3 (a). The five spots
corresponding to the spots of the phase are visible clearer,
compared to that of Fig.2(a). Arrangement of bright and dark
dots in these five layers corresponds to atomic positions in the
(020) plane and (010) plane are observed in Fig.3 (b). In the
B B B B
dashed circles, the arrangement of dark dots corresponding to a
part of phase are visible. In the peak aged specimen, the
monolayer, and phase still co-exist, the phase forms
predominantly compared to another precipitates.
From above TEM and HRTEM observations, it is revealed
that the monolayer lying on {1100}Mg grows to <1120>Mg
B B B B
0000
 HRTEM observation of the precipitates..
directions and act as precursor of phase and phase.
phase grow to <1120>Mg directions preferentially. The mono
B B
layer on {1100}Mg is ordering and thickening during aging and
B B
lead to the formation of phase. This precipitation behavior is
similar to that of the Mg-Gd-Y-Zr alloy aged at 423K reported
by the previous our reports [4].
Conclusions
The HRTEM observation was performed to clarify the
morphology of precipitation in early stage of aging in
Mg16.9mass%Gd-0.51mass%Zr alloy. In the early stage of
aging at 423 K, the monolayers were appeared on the {1100}Mg B
B planes. Before peak aging, the contrast corresponded to a part
of the phase with D019 type ordered structure and phases
B B
with base centered orthorhombic structure were appeared at the
same aging stage. The monolayers, and phase were co-
existed at the peak aging stage. It is revealed that the
monolayers act as precursor for both the and phases, the
further aging, the phases grew along the <1100>Mg directions.
B B
Fig.3 TEM images of G17K alloy aged at 423K for 1024 h :
(a)SAED pattern and (b) HRTEM image of large area.
3
References
[1] P. Vostry, B. SMOLA, I. STULIKOVA, F.VON BUCH and
B.L. MORDIKE, phy. stat. sol. (a) 175 (1999), 491.
[2] X. Gao, S. M. He, X. Q. Zeng, L. M. Peng, W. J. Ding, J.F.
Nie, Materials Science and Engineering A, 431 (2006) 162-
167.
[3] T. Kawabata, K. Matsuda, S. Kamado, Y. Kojima and S.
Ikeno, J. Japan Institute of Metals, 10 (2006), 828-834.
[4] T. Kawabata, Y. Fukuda, K. Matsuda, Y. Kojima and S.
Ikeno, Materials Transactions, (2006), .954-959.
[5] C. Antion, P. Donnadieu, F. Perrard, A. Deschamps, C.
Tassin and A. Pisch, Acta Materialia 51 (2003) 5335-5348.
[6] S. M. He, X. Q. Zheng, L. M. Peng, X. Gao, J. F. Nie and W.
J. Ding, Journal of Alloys and Compounds, 421 (2006) 309-
313.
[7] T. Honma et al, Material Science and Engineering A, 395
(2005) 301-306.
[8] Nie J. F. and Muddle B. C. Scripta Mater, 40 (1999) 1089-
1094.
[9] J. F. Nie and B. C. Muddle, Acta mater, 48 (2000) 1691-
1703.
[10] Lorimer G, Azari-Khosroshaki R, Ahmed M: Proc. Int.
conf. on Solid-Solid Phase Transformations, (The Jpn. Inst.
Metals, 1999) pp.185-192.
[11] P. J. Apps, H. Karimzadeh, J. F. King, G. W. Lorimer,
Scripta materialia, 48 (2003) 1023-1028.
[12] T. Sato, Isao Takahashi, Hiroyasu Tezuka and Akihiko
Kamio: J. Inst. of Light metals, (1992) 804-809.
 The effect of Silver-addition on crystal.. 1

JCACS
2007

The effect of Silver-addition on crystal structure of rod-shaped

precipitates in Al-Mg-Si alloy
J.Nakamura1, K.Matsuda2, * , Y.Nakamura3, T.Sato3, and S.Ikeno2
P P P P F F P P P P P P

1Graduate School of Science and Engineering for Education, University of Toyama, Toyama, 930-8555, Japan
.2Graduate School of Science and Engineering for Research, University of Toyama, Toyama, 930-8555, Japan.
3Graduate School of Science and Engineering, Tokyo Institute of Technology, Tokyo, 152-8552, Japan

Abstract

The purpose of this study is to identify the crystal structure of a metastable phase in Ag added Al-Mg-Si alloy to compare with the
formation of -phases in Al-Mg-Si alloys without Ag, using high resolution transmission electron microscope (HRTEM) images, selected
area electron diffraction (SAED) patterns and energy dispersive X-ray spectroscopy (EDS). The results of these SAED patterns and
HRTEM images have been simulated and then compared with actual precipitate images. SAED patterns and HRTEM images obtained
from the metastable phase in the Ag added Al-Mg-Si alloy appeared similar to those of the -phase in Al-Mg-Si alloy without Ag, but the
lattice spacings changed because of the effect of Ag.

Keywords: precipitation, high-resolution TEM, Ag added, -phase, Al-Mg-Si alloy, crystal structure

1. Introduction 2. Experimental

There are some reports about modification of The Al-1.0mass%Mg2Si-0.5mass%Ag and Al -1.0
B B

homogeneous elongation during tensile testing and the mass% Mg2Si alloys were used for observation. Samples
B B

increase of the age-hardening rate in Ag added Al-Mg-Si
alloys [1-3]. However, the crystal structure and the
chemical composition of the metastable phase in the alloy
have not yet been yet clearly determined [4]. In this
present work, the -phase in the Al-1.0 mass% Mg2Si-
0.5 mass% Ag (Ag-addition alloy ) and Al-1.0 mass%
Mg2Si (base alloy) alloy is observed by using HRTEM
B B
and electron diffraction to clarify the effect of Ag on the
crystal structure of the -phase. Furthermore, the crystal
structure of the precipitates in the Ag addition alloy and
the alloy without Ag were compared. The chemical
composition of the precipitates was analyzed by EDS.
These results were compared with simulated results.
Detailed crystal structure of the -phase in this alloy is
proposed.
of TEM were cut into 1015mm from 0.2 mm thick
sheets, polished mechanically to 0.15mm thickness,
solution heated at 848K for 1hr, quenched by chilled
water, and then aged at 523K. After aging, samples were
B B polished with two types of electrolytic solution
(perchloric acid: ethanol=1:9, and nitric acid:
methanol=1:3) used for making thin films for TEM.
HRTEM (Topcon EM-002B) with EDS was operated at
120 or 200 kV. HRTEM (JEOL 4010T) of 400 kV was
also used to obtain Energy filter and EDS data. The
computer simulation of HRTEM images was performed
using a conventional multi-slice method.

* Corresponding author. Tel.: +76-445-6841; fax:+76-445-6841.

E-mail address: matsuda@eng.u-toyama.ac.jp.
2 J. Nakamura et al.

3. Results and discussion of Ag addition alloy is shown in Fig.3 (a) and(b) the
base alloy is shown in Fig.3 (c) and (d). When the
precipitate is assumed to be hexagonal by calculating
Fig.1 shows an age-hardening curve of the Ag-addition
T

alloy aged at 523K. The highest hardness appears at

1.92ks aging time. The range of the aging time used for
the observation of -phase was 12ks. T

Fig 1. The age hardening curve of the Ag-addition alloy at 523K T

Fig.2 (a) shows a TEM bright field image of Ag added

alloy aged for 120ks. Rod-shaped precipitates in Ag-
addition alloy arranges along [100] and [010] directions
of the matrix, similar to Al-Mg-Si alloy. Therefore, black
spots in this figure are cross sections of vertically oriented
rod-shaped precipitates arranged in the [001] direction of
the matrix (It is referred to as the rod-section). Fig.2 (b) is
a typical example of the HRTEM image obtained from
the rod-section, which has an oval shape and an
observable array of hexagons within the precipitate. The
hexagon side length is 0.69 nm. Fig.2 (c) show SAED
patterns obtained from a cross section of the precipitate.
The diffraction spots show both the array of the matrix
phase and positive hexagons from the precipitate. The
lattice spacing calculated by d1, which is the distance B B

between the 000 spot and the nearest diffracted spot from
the precipitate was 0.59 nm. Also, secondary near space,
d2 was 0.34 nm. From the comparison of the -phase of
B B

both alloys, d1 and d2 became narrower with Ag addition

B B B B

than the d1 = 0.61nm and d2 = 0.35nm valuescalculated

B B B B

from

precipitates in the base alloy at plane {1120} and {1 A EA A

100}. This precipitate has the same crystal structure as the

EA

-phase in the base alloy; the lattice parameter of a- Fig 2. Transmission electron micrographs of the Ag-addition alloy aged
axis is 0.69nm. This result corresponded to the HRTEM at 523K for 120ks.(a) A bright field image, (b) a high resolution image
image. In our previous study there were three types of and (c) its SAED pattern obtained for the rod-section of the precipitate.
precipitates from orientation relationship between matrix plane intervals between 000 spot of SAED patterns and
and cross section of precipitates. The predominant the nearest diffracted spot, Fig.3(a) and (c) are along the
precipitate

was a medium type [5]. In this medium type, [1100] precipitate zone axis of precipitate, and Fig.3(b)

A E EA

<1 1 00> or <11 2 0> precipitate directions and <130>

A E EA A E EA

and (d) are along the [11 20] precipitate zone axis. The
A E EA

matrix directions were almost parallel. The rod shaped diffraction pattern obtained from the precipitate by Ag
precipitate was perpendicular to its longitudinal direction addition alloy is more spread out than the diffraction
by <130> matrix direction. Related SAED patterns taken pattern of base alloy, so we can understand that Ag
by this direction was shown in Fig.3. The SAED patterns addition alloy has the smaller d-spacing. The calculated
 The effect of Silver-addition on crystal..
plane distance from dark lines were 0.35 nm and 0.61 nm
but the calculated plane distances from bright lines were
0.34 nm and 0.59 nm.
Fig 3. Two kinds of electron diffraction patterns taken from the rod-
shaped precipitates. An incident beam direction is normal to the
longitudinal direction of the precipitates and is parallel to the <310>
matrix direction. (a) and (b) are for Ag-addition, and (c) and (d) are for
the base alloys.
Fig. 4 shows the chemical composition of the rod-
shaped precipitate from EDS. In order to ignore the
influence of the matrix, the extrapolation method was
used to obtain Mg, Si and Ag contents. The ratio of Mg:
Si: Ag is about 3:2:1. According to the base alloy, the
ratio of the -phase is Mg/Si=2, so the result shows that
Ag substitutes into the Mg position; (Mg+Ag)/Si=2. The
atomic radius of Ag is smaller than Mg, which explains
the observed d-spacing shrinkage when Ag is added.
Fig 5. The sample observation from several directions of this model, and the corresponding HRTEM images.
3
Fig 4. Chemical composition of the rod-shaped precipitates detected
by EDS
Finally, using these data, a more accurate crystal
structure of the -phase is proposed than that proposed in
previous work[6]. There are proposal for crystal structure
from HRTEM image, and simulation of those precipitate.
The power spectrum from Fig.2 (b) is very similar to the
actual SAED patterns in Fig.2 (c). Therefore, it is thought
that this array reflected the structure of -phase.
From the comparison of the array shown in HRTEM
image, and the previously reported model, it seems that
the small hexagon rotates 10 and enlarges by 5%. As the
atomic position for the model that was regarded by
putting in capitation both basal plane and half plane Ag,
Ag : Mg = 0.167 : 0.833 for the half plane and Ag : Mg =
0.5 : 0.5 in Mg for the basal plane. The observation was
4 J. Nakamura et al.

but the a-axis is smaller than that in Ag-free alloy. As a

done from different directions than that of this model, and
result of the EDS analysis, Ag was detected in the rod-
was compared with HRTEM images of the sample from
shaped precipitate.
the same direction. The result is shown in Fig.5. From the
comparison of the HRTEM images and the model, five
HRTEM images from different directions agreed with the
crystal model. Also, simulation was in good agreement References
with each of these HRTEM images.
[1] Polmear, I.: Trans. AIME, Vol. 230, pp.1331-1338, 1964.
[2] Baba, Y. and Takashima, A.: J. Japan Inst. Light Metals, Vol.19,
pp.90-98, 1969.
4. Conclusion [3] Matsuda, K., Kido, K., Kawabata, T., Uetani, U. and Ikeno, S.: J.
Japan Inst. Light Metals,
Vol. 53, No. 11, pp. 528-533, 2003.
[4] Gaber, A., Matsuda, K., Ali, A.M., Ziu, Y. and Ikeno, S.: Mat. Sci.
A rod-shaped precipitate in Ag-addition alloy was Tech., Vol. 20,
observed in <100> direction, similar to the previous work pp.1627-1631, 2004.
for Al-Mg-Si alloy. HRTEM images and the SAED [5] Kenji Matsuda, Shizuo Tada and Susumu Ikeno :J Electron Microsc.,
patterns of the rod-shaped precipitate were almost the Vol. 42,1 (1993) 1-6
[6] Matsuda, K., Ikeno, S. and Tada, S.: J. Japan Inst. Metals, Vol. 57,
same as those taken from the -phase in the Al-Mg-Si No. 10, pp. 1107-1113, 1993..
alloy. The crystal structure of -phase in Al-Mg-Si-Ag
alloy has the hexagonal system, the c-axis is not changed
 Secondary M-I transition with unusual 1

JCACS
2007

Secondary M-I transition with unusual temperature dependency in

multi-spin Co-doping La2/3Ca1/3Mn0.9Co0.1O3 manganite B B B B B B B B B B

Qianying YU, Jincang ZHANG *, Rongrong JIA, Chao JING, and Shixun CAO F F

Department of Physics, Shanghai University, Shanghai 200444, PR China

Abstract

Based on the importance of spin structure and character in CMR manganites, the multi-spin Co-ion doping for Mn-site was studied
for La2/3Ca1/3Mn1-xCoxO3 samples (x=0,0.1) with an excellent single phase structure. A secondary metal-insulator (M-I) transition is found
B B B B B B B B

in the electric transport measurement for x=0.1, which shows the peak temperature TPH for first high temperature peak (corresponding to B B

normal M-I transition) and TPL for secondary low temperature peak. With increasing the external magnetic field, the TPH shifted to high B B B B

temperature but the TPL was almost field-free. Combining with the magnetic results, we could conclude that the high temperature peak
B B

should be related to the M-I transition of undoped system, the abnormal behavior of low temperature peak may have some relationship with
the oxygen vacancy and high spin state induced by Co3+ substituting Mn4+ in the present system. P P P P

Keywords: CMR manganites, Co-doping for Mn-site, M-I transition

phenomena to us. Gayathri et al. [5] studied the P P

La0.7Ca0.3Mn1-xCoxO3 system and found a transition from

B B B B B B B B B B

1. Introduction long-range ferromagnetic order to a cluster type transition

due to Co doping, and semi-conducting behavior in the
whole temperature range for x>5%.Rivadullla et al [6] P

Since the discovery of mixed-valent manganites studied La2/3Ca1/3Mn1-xCoxO3 system with x 0.1; all the
P B B B B B B B B B B

perovskite R1-xAxMnO3, where R is the rare earth B B B B B B

samples showed metallic conducting behavior at low
elemental and A is the divalent alkaline-earth metals, temperatures. They also found the absence of long range
these materials have attracted considerable attention FM order and a signature of cluster-glass-like behavior
because of the observation of clossal magnetoresistance around 5%. In order to further understand Mn site Co
(CMR) effect and more generally due to the unusually doping effect and clarify such problems, the structure,
strong coupling between their lattices, spin and charge magnetic and transport properties are studied in Co
degree of freedom[1-2]. The transport and magnetic P P
substitution La2/3Ca1/3MnO3 system. The results are B B B B B B

properties of R1-xAxMnO3 have strong dependence on B B B B B B

discussed in the related theory and possible explanation is
doping lever. Lots of work has been done through doping given.
at Mn sites by many transition elementals, which can
modify the Mn3+-O-Mn4+ network and in turn largely P P P P

affects their physical properties as well as CMR[3,4]. The P P

2. Experimental
electronic configuration of Co is very complicated due to
the existence of several possible valence (Co3+ (t2g4 eg1 ) P P B PB P B PB P
Polycrystalline samples were prepared by solid-state
Co3+ (t2g5 eg1 ) and Co4+ (t2g4 eg1 ))and spin states(low,
P P B PB P B PB P P P B PB P B PB P reaction method from dried high-purity La2O3, CaCO3, B B B B B B

intermediate and high spin configurations),which should Co2O3 and MnO2 powders. The powders with the
B B B B B B

have a substantial effect on the magnetic and electrical stoichiometric composition of La2/3Ca1/3Mn1-xCoxO3 B B B B B B B B

properties ,then will lay out an abundance of physical (x=0,0.1) were mixed, grinding and calcined. All the
samples were prepared in identical conditions. The phase

*
TP PT Corresponding author, e-mail: jczhang@staff.shu.edu.cn HTU UTH
2 Q.al.
Q. Yu et Yu et al.

of these samples was characteristic by powder X-Ray see that the resistivity curves show two M-I transition
diffraction experiments conducted on the Rigaku D/max- namely, double-peak effect. The resistivity peak close to
2550 diffractometer (18KW, Cu-K). The transport and TC is defined as TPH, which is the temperature of M-I
B B B B

magnetic properties were measured using the physical transition caused by the PM-FM phase transition. And an
property measurement system (PPMS-9) made by additional temperature TPL corresponding to the bump at B B

Quantum Design. Temperature dependence of resistivity lower temperature grows up after it. This anomalous
was measured by standard DC four-probe method under transport behavior closely relates to the substitution of Co.
different DC magnetic fields with a range of 0-6 T and
temperature in the range of 2.5-300 K. Fig.2. shows the temperature dependence of
resistivity at various applied magnetic fields for
La2/3Ca1/3Mn0.9Co0.1O3
B B (H=0,0.5,1.0,3.0,6.0T).As the
B B B B B B B B

external field increases, the M-I transition peaks both at

3. Results and discussion
high and low temperature are suppressed, which
performances a negative magnetoresistance effect,and the
high M-I transition peak almost disappears at H=6.0T. In
0.025 X=0.0 Fig.3.(a) we show the corresponding peak resistivity
X=0.1
( PH , PL ) as a function of magnetic field. The
0.020
(ohm-cm)

resistivity PL is bigger than PH , namely, the

0.015 secondary M-I transition corresponding to the low
20 temperature plays a dominant role comparative to the
0.010
high-temperature M-I transition. Both the corresponding
resistivity of M-I transition peaks decrease as the external
0.005
field increases ,and the curve of PL almost undergoes the
0.000 same rule as the one of PH .But the corresponding peak
0 50 100 150 200 250 300 temperatures TPH and TPL have an absolutely different B B B B

T(K) behaviors .From Fig.3(b), we can see that TPH produces a B B

Fig.1. Comparation of temperature dependence of resistivity for approximately linear increasing to the external field ,but
Co doping free and Co doping sample with x=0.1 of La2/3Ca1/3Mn1- B B B B B
there is no obvious change for TPL as the external field B B

x CoxO3 systems.
B B B B B
0.028

0.024 ( a) pL
pH
0.025 H=0 T 0.020
( Ohm-cm )

H=0.5 T
H=1.0 T 0.016
0.020 H=3.0 T
H=6.0 T 0.012
(ohm-cm)

0.015
0.008

0.004 La2/3Ca1/3Mn1-xCoxO3: x=0.1

0.010
0.000
0.005
La2/3Ca1/3Mn1-xCoxO3: x=0.1
240
( b)
220
(K )

0 50 100 150 200 250 300 200 TpL

T (K) TpH

180
Fig.2. Temperature dependence of the electrical transport

160
properties of La2/3Ca1/3Mn1-xCoxO3 (x=0.1) at various applied magnetic
B B B B B B B B B B
La2/3Ca1/3Mn1-xCoxO3: x=0.1
fields (H=0,0.5,1.0,3.0,6.0T) 140

120
The temperature dependence of resistivity under 0 1 2 3 4 5 6
zero-field for La2/3Ca1/3Mn1-xCoxO3 (x=0,0.1) is shown in
B B B B B B B B B B
H ( Tesal )
Fig.1. For x=0, it shows an M-I transition ( TP 260 K )
near Curie temperature ( Tc 253 K ),which consistents Fig.3. (a) Corresponding peak resistivity ( PH , PL )as a

with previous studies and shows a high degree of function of magnetic field for La2/3Ca1/3Mn1-xCoxO3 (x=0.1).(b)Magnetic B B B B B B B B B B

reliability of the sample. Interestingly ,When Mn is partly field dependence of the two M-I transition temperatures TPH and TPL for B B B B

La2/3Ca1/3Mn1-xCoxO3 (x=0.1) respectivelylines are guided to the

substituted by Co, the system displays a more B B B B B B B B B B

eyes
complicated and interesting transport behavior .We can
 Secondary M-I transition with unusual 3

increases. A typical temperature dependence of ac and other members[9-10], we may believe that in our
P P

susceptibility and the differential coefficient for the
sample of La2/3Ca1/3Mn0.9Co0.1O3 are shown in Fig.4. The
B B B B B B
result shows that there is only one transition at high
temperature in the curve corresponding to TPH , and no
obvious change around TPL can be found at all. The
coherence of Fig.3.(b) and Fig.4. may indicate that the
samples, the oxygen vacancy caused by Co which
B B B B occupies in the crystal structure with the valence of +3
have resulted in the second peak in the low temperature
B B range .Then the external magnetic field can do no
B B influence on it .That is the main reason why the low-
temperature peak TPL doesnt change anymore under the
B B

secondary M-I transition with the dependent of external magnetic field as shown in Fig.3(b) ,and why
temperature (TPL) is independent of the magnetic field,
B B there is only one transition in the curve at high
namely, the secondary M-I transition has the temperature range corresponding to TPH in our experiment
B B

characteristic of field-free. And at the same time, the (Fig.4). So we could conclude that the abnormal transport
resistivity peak at TPH is believed to have inherent B B behavior may have a close correlation with the
different principle with that of TPL. B B complicated configuration of Co and magnetical
inhomogeneity induced by Co substitution in this system,
0.02 and the high temperature peak should be related to the M-
La2/3Ca1/3Mn1-xCoxO3
0.20 x=0.1
I transition of undoped system, the abnormal behavior of
low temperature peak may have some relationship with
Differential coefficient
TPL=123.5K 0.01 the oxygen vacancy and high spin state induced by Co3+
0.15
P P

substituting Mn4+ in the present system.

P P
M'(emu/g)

This work is supported by the National Natural

0.00
0.10 Science Foundation of China (NSFC, No.10574087,
10504019), Special Research Fundation for the Doctoral
0.05 -0.01 Discipline of University (Grant No. 20050280004), The
Shanghai Nano-technology Promotion Center and the
Science & Technology Committee of Shanghai
0.00
-0.02 Municipality (No.0652nm046).
0 50 100 150 200 250 300
T( K )
References
Fig.4. A typical temperature dependence of ac susceptibility and the [1] S. Jin et al., Science 264 (1994) 413.
differential coefficient for the sample of La2/3Ca1/3Mn0.9Co0.1O3. B B B B B B B B B B

[2] H.Y. Hwang et al., Phys. Rev. Lett. 77 (1996) 2041.

[3] J. Blasco et al., Phys. Rev. B 70 (2004) 094426.
So far, for the high-temperature peak , the
[4] X. Xiao et al., Solid State Communications 141 (2007) 348.
magnetism and transition properties can be understood in
the framework of DE model as the undoped sample. In [5] N. Gayathri et al.,Phys. Rev. B 56 (1997) 1345
our system, the substitution of Mn4+ by Co3+,which causes P P P P

[6] F. Rivadulla et al., Phys. Rev. B 62, (2002) 5678

breaks in the Mn3+O2Mn4+ chains and destroys the DE
P P P P P P

interaction after the formation of Mn3+O2-Co3+,may P P P P P P

[7] W.J. Li et al.,J. Magn. Magn. Mater. 305 (2006) 325.
lead to the decrease of Tc , the increase of resistivity .And B B

[8] H.Gencer et al., J.Alloys Compd.422 (2006) 40

these characteristics have been studied and described in
the literature for Cu, V, Cr, Ru doping systems which [9] J.R.Sun et al.,Appl. Phys. Lett.72 (1998) 3208.
have the similar double-peak effect[3,4,7,8] .But the physical P P

[10] L.Malavasi et al., Solid State Commun.123 (2002).321

mechanism on low- temperature peak has not come to a
conclusion. In our system , the valence has changed due
to the substitution of Mn4+ by Co3+, then the oxygen P P P P

vacancy has been induced on the anion basing on the law

of charge balance .According to the research of J.R.Sun
 Recent Advances on Precipitation .. 1

JCACS
2007

Recent Advances on Precipitation in AlMgSi(Cu) Alloys

C.D. Marioara * 1, S.J. Andersen1, R. Vissers2, R. Holmestad2
F FP P P P P P P

1
P SINTEF Materials and Chemistry, N-7465 Trondheim, Norway
P

2
P Department of Physics, Norwegian University of Science and Technology, N-7491 Trondheim, Norway
P

Abstract

Extensive TEM investigations, combined with quantitative electron diffraction (MSLS) and first principles quantum mechanical
calculations (VASP) have been used to solve the crystal structures of most metastable precipitate phases in the AlMgSi(Cu) system. It was
found that all these phases are structurally related through the arrangement of Si in their crystal structures. More precisely, the Si atoms are
configured in triangular planes that can be derived from {111}Si planes in one specific orientation diamond Si crystals take in the Al matrix.
The triangular Si planes are parallel to {100}Al planes for , U2 (Type B), B (Type C) phases in Cu-free alloys, and for Q-precursors, Q,
Q phases in Cu-containing alloys. Pre- and phases also belong to this category, but with the Si arrangement in their structures more
distorted and deviating from the near-hexagonal symmetry. In the U1 (Type A) phase the triangular Si planes are parallel to {310}Al planes.

Keywords: TEM, AlMgSi(Cu) alloys, crystal structure, precipitation

AlMgSi alloys to be solved. For this system the following

1. Introduction
The AlMgSi(Cu) alloys are an important group of age-
hardening materials. Properties like high strength/weight
ratio, good formability and weldability, combined with an
excellent corrosion resistance, rank them among the most
attractive materials and have made them widely used by
the industry. The significant increase in hardness during
the ageing heat treatment is caused by the formation of a
high density of metastable precipitates in the Al matrix.
Therefore, in order to improve control over alloys
mechanical properties, detailed knowledge about the
precipitate crystal structures, morphologies and the type
of precipitates that form under different heat treatments in
alloys with different compositions is essential. The quality
of modern high resolution (HREM) microscopes, the use
of recently developed quantitative electron diffraction
techniques (MSLS, [1]), the availability of computer
power and open source programs to perform first
principles calculations (VASP, [2-5]) have enabled the
crystal structures of most precipitates in the ternary
precipitation sequence has been found:
Clusters -> GP (pre-[6,7]) -> [8] -> [9], U1[10,11],
U2[10,12], B[13,14] -> , Si.
The U1, U2 and B phases are also called Type A, Type B
and Type C respectively [15].
Cu additions to the ternary AlMgSi system change the
precipitation sequence and produce new phases [16-20].
The precipitation sequence for the AlMgSiCu system
becomes [20]:
Clusters -> GP -> (), L[17,20], S (QC)[19,20], C[20] ->
Q[14] -> Q[21].
Except for the equilibrium Q phase [21], little has been
known about the crystal structures of the other Cu-
containing phases. However, in [20] it was demonstrated
that the peak-hardness L, S and C precipitates are Q-
precursors, with L and S having partly disordered crystal
structures.

* Corresponding author. Tel.: +47 98283908.

E-mail address: calin.d.marioara@sintef.no.
2 C. D. Marioara et al.
Here we present an essence of our recent findings
showing that the structures of all metastable phases in the
AlMgSi(Cu) system are related and can be viewed in a
simple, unified way based on the structure of diamond
silicon.
2. Experimental
Several pure alloys were prepared for this work, each
having a constant amount of solute (Mg+Si)=1.3at%, but
with Si/Mg ratios ranging from 5 to 0.5. Some Cu-
containing variants of alloys were produced by adding
0.13at% Cu to each selected composition. Different
metastable phases were produced with two isothermal
heat treatments at 175oC and 250oC. The microscopy
P P P P
work was performed with a Philips CM30-UT/FEG TEM
operated at 300kV (0.17nm point resolution) and with a
Jeol 2010F TEM/STEM operated at 200kV (0.20nm point
resolution). The STEM Annular Dark Field (ADF)
technique [22] was also used for the Cu-containing alloys.
This technique provides Z-contrast due to Rutherford
scattering of incoming electrons at high angles. By
choosing an inner detector angle of ~28mrad and a probe
size of 0.2nm, only the position of Cu atomic columns in
the precipitate structures became visible, because of the
high Z difference between Cu (Z=29) and Mg (Z=12), Al
(Z=13), Si (Z=14).
Nano-diffraction (NBD) patterns were recorded with a
Tietz Photometric 1024x1024 slow scan CCD camera (12
bits dynamical range) attached to the Philips microscope.
The processing of diffraction data and crystal structure
refinements were done with the computer software MSLS
[1]. With this method spot intensities are extracted from
experimental diffraction patterns and compared to the
intensities generated from an input atomic model. To
verify the stability of the precipitate structures with
coordinates refined by MSLS, formation enthalpies were
calculated using the first principles (ab initio) VASP code
[2-4] employing ultrasoft pseudopotentials [5]. In this
process an independent refinement of the crystal
structures is performed and compared with the MSLS
result.
3. Results and discussion
First indications that metastable phases in the
T
AlMgSi(Cu) system must share a common structural
fundament came from a study by Cayron et al. [19]. He
observed that all metastable precipitate unit cells could be
fit onto a 2D hexagonal grid with parameters
a=b=0.393nm or 0.407nm. A good explanation for this
observation could not be given because the only crystal
structures known at the time were of , and Q.
However, after the , U1 and U2 phases were solved [9-
12], a proper comparison of the precipitate structures
could be achieved. In fact, Cayrons results were
independently rediscovered, now from an atomic
perspective. An additional phase, B, can also be taken
into consideration. Although the structure is still
unpublished, details have been inferred from first
principles calculations, where the structural similarity
with the Cu-containing Q and Q phases was confirmed
[13,14,21].
An important finding is that the crystal structures of ,
T
U2 and B phases are related and consist of different
arrangements of Al and Mg atoms on a triangular, near-
hexagonal grid (network) of Si atomic columns as viewed
along the 0.405nm coherency direction with the Al matrix.
This is also parallel to the needle axis. The distance
between two Si columns is on average close to 0.4nm.
The precipitates unit cells may therefore be subdivided
into near-hexagonal a=b=0.4nm sub-cells (SC) with
different compositions, defined by the Si columns. See
Fig. 1.
Fig 1. Schematic drawings with the same scale showing structures of
a) , b) U2 and c) B viewed along their 0.405nm periodicity with the
Al matrix. The similarity between these phases is obvious when their
atomic structures are referred to the common near-hexagonal grid
defined by the Si columns. Atomic heights are indicated by open
(z=0nm) and solid (z=0.2025nm) circles. a) Solid lines: unit cell
(a=b=0.715nm); the similarity with U2 is shown with dashed lines. b)
Solid lines: U2 unit cell (a=0.67nm, c=0.79nm); the similarity with the
phase is shown with dashed lines. c) Solid lines: B unit cell
(a=b=1.04nm); the similarity with the U2 phase is shown with dashed
lines. All phases can be decomposed into near-hexagonal 0.4nm sub-
cells (SC) (connected with pointed lines) defined by the Si columns. The
phases are essentially different arrangements of Mg and Al atoms on this
Si grid (network).
In a recent study [20] it was demonstrated that, although
T
Cu modifies the precipitation sequence of AlMgSi alloys
(see the Introduction part), the Cu-containing phases
follow the same basic construction as in Fig.1. This is
 Recent Advances on Precipitation ..
obvious for Q and Q, where the main difference with B
is a replacement of Al with Cu in the symmetrical 1/3, 2/3
positions of the unit cell (see Fig. 1c) [13,14]. Using ADF,
HREM and NBD techniques we found that the early Cu-
containing precipitates in the T6 condition that form prior
to Q and Q are all precursors of Q with partly disordered
crystal structures [20]. Nevertheless, they could all be
viewed as different arrangements of Al, Mg and Cu atoms
on the same near-hexagonal a=b=0.4nm Si grid viewed
along the c=0.405nm periodicity with the Al matrix. The
ADF images in Fig. 2 show the existence of the common
Si grid (network) in two Cu-containing precipitates: an
ordered Q phase and a partly disordered Q-precursor.
Fig 2. a), c) ADF images of needle precipitates in the AlMgSiCu
system viewed in cross section along a <001>Al projection
(corresponding to their 0.405nm periodicity with the Al matrix). Only
the Cu-containing atomic columns are visible. a) Ordered Q phase. c)
Partly disordered Q-precursor. In b) and d) the positions of Cu-
containing columns (open circles corresponding to the white dots in the
ADF images) are related to the Si positions in the precipitates of a) and
c), respectively. It can be observed that all Cu columns fit on the
hexagonal a=b=0.4nm Si grid (solid circles). Note that only projected
positions of Cu and Si atomic columns are shown. d) Local ordering of
Cu (the mirror planes m) is shown in features 1 (Q atomic
arrangement) and 2 (C-plate atomic arrangement [20]). In b) and d) the
periodic arrangement of the Cu columns is indicated by solid lines. In b)
two Q unit cells are overlaid (dashed lines). The Si networks in the two
precipitates are rotated relative to each other.
3
The Si network present in all metastable phases of the
T
AlMgSi(Cu) system can be derived from the structure of
diamond Si seen along a <111> direction. Indeed, by
considering only one of the three double {111}Si planes,
the projected distance between the hexagonal Si atomic
columns is 0.384nm, which can be compared to 0.4nm
found in the precipitates. Consequently, all the precipitate
unit cells can be drawn as supercells in diamond Si using
as vertices atoms of a single (111)Si layer (open circles in
Fig. 3). T
Fig 3. Schematic drawing of a <111>Si projection. Open, gray and
solid circles are the three double layers. Supercells of all metastable
precipitate phases of the AlMgSi(Cu) system can be drawn by
considering only one of the three {111}Si double atomic planes (the
open circles A-plane in the above image). Compare the positions of A-
plane Si columns in the , U2 and B Si supercells with the actual Si
positions in the respective unit cells in Fig. 1.
Although less obvious, the structures of pre- and are
also based on the same Si network as the rest of phases.
Fig. 3 shows supercells of these phases on a (111)Si plane.
The main difference is that the Si network in (or pre-
) is more distorted and deviates from the near-
hexagonal arrangement. This is a consequence of pre-
and phases having more coherent crystal structures and
interfaces with the Al matrix as they form earlier in the
precipitation sequence. Supercells of both phases can be
found in the Al matrix as well, with atomic coordinates
close to those of the Al atoms [6-8]. The connection
between the arrangements of Si atomic columns (the Si
network) in and diamond Si is shown in Fig. 4. Recent
HREM investigations and first principles calculations
have indicated that part of this Si network, in the form of
Si2 pillars along the 0.405nm periodicity direction,
B B
confers structural stability to both pre- and phases
and is invariant during the transformation from pre- to
[7]. Another important observation is that the pre-
and phases are structurally connected to the other
metastable precipitates in the AlMgSi(Cu) system and in
particular to the U2 phase [12].
4 C. D. Marioara et al.
Fig 4. The Si atoms of pre- and phases may be viewed in the
same Si network as the other precipitates of the AlMgSi(Cu) system. A
higher coherency with the Al matrix seems to cause the Si network of
pre- and to deviate more from the hexagonal symmetry. a)
crystal structure viewed along the 0.405nm periodicity (needle length).
Unit cell (a=1.52nm, c=0.67nm, =105.3o, drawn with solid lines) and
P P
subunits (dashed lines) show the similarity with diamond Si. b) <111>
diamond Si projection with supercell (compare with Fig. 3). Atomic
heights are shown only for the structure. The scale of the drawings is
the same as in Fig. 1.
Interestingly, there is one specific orientation of diamond
Si in the Al matrix that can help to explain the origin and
morphology of all metastable precipitates (Fig. 5). For
the chosen system of reference this orientation is (110)Si
|| (001)Al, [1-1-1]Si || [010]Al, [1-12] Si || [100]Al. It
relates to the precipitates via two {111}Si planes, (1-1-
1)Si and (1-11)Si. The first is parallel to the (010)Al plane,
in the same way as the trigonal Si planes of the Si
network in , U2, B and Cu-containing precipitates are
parallel to a {100}Al plane, stacked with 0.405nm
periodicity along the needles. The connection between the
(1-1-1)Si planes with the Si network in these precipitates
can be achieved as following: Choose only one double
{111}Si layer (see Fig. 3). Stack this double layer with
0.405nm periodicity. Contract the two single layers from
0.235nm to 0.2025nm by removing half of the Si atoms.
What Si atoms are removed depend on the precipitate (e.g.
symmetry of the structure). The only exception from this
rule is the U1 phase that has its triangular Si planes
parallel to one of the {310}Al [11]. This phase must
instead be derived from the (1-11)Si plane of the diamond
Si in Fig. 5. A U1 supercell can be constructed with its c-
axis along the [1-11]Si direction as shown in Fig. 6. From
Fig. 6 it can also be seen that the transformation to U1
would involve the replacement of some Si atoms from the
supercell with Mg and Al and interchange of the two
central Al planes [11].
Fig 5. HREM image of a diamond Si particle nucleated in an Al
matrix. <001>Al zone axis. The orientation of the Si grid relating all the
metastable precipitates can be derived from this specific orientation of
diamond Si in the Al matrix: (110)Si || (001)Al, [1-1-1]Si || [010]Al, [1-
12] Si || [100]Al. Two {111}Si planes are of importance. For the chosen
reference system the first is (1-1-1)Si plane, parallel to (010)Al, used
by the pre-, , , U2, B and all Cu-containing phases. All these
precipitates are needles along the [010]Al direction with 0.405nm
periodicity. The other plane, (1-11)Si, parallel to (310)Al, is used by
the trigonal U1 phase. U1 is coherent with the Al matrix along one of its
a=b=0.405nm directions (that is parallel with [001]Al and needle length).
The trigonal axis c=0.674nm is parallel with [310]Al. This phase
therefore has a different orientation of the Si network.
Fig 6. The U1 phase is structurally similar to diamond Si along a
<111>Si direction, as all the other metastable phases. a) U1 unit cell. b)
Supercell in diamond Si that resembles the U1 crystal structure. The
transformation from the supercell to U1 can be performed by
substitution of some Si atoms with Mg and Al followed by an
interchange of the central Al planes.
In conclusion, it has been demonstrated that all metastable
phases in the AlMgSi(Cu) system are structurally related.
The unifying element is Si that forms a common network,
a backbone on which all the phases are being
constructed. The connection of this network to diamond
Si crystals nucleated in the Al matrix suggests that
clustering of Si may be important in the early stages of
precipitation. Atom probe experiments seem to confirm
this observation [23]. Other studies showed that Si rich
alloys nucleate a higher number density of precipitates
[24]. All these results give a deeper insight into the
 Recent Advances on Precipitation .. 5

fundamentals of metastable phase precipitation and may

consitute a basis for further alloy development.

Acknowledgements

This work was financially supported by The Norwegian

T

Research Council via two projects:

1) BIA programme: Kimdanningskontroll (Nucleation
T

Control) which is also financed by the following

Norwegian companies: Hydro Aluminium AS and
Steertec Raufoss AS.
2) Research project: Fundamental investigations of
T

solute clustering and precipitation.

C.D. Marioara also acknowledges technical support from
T

Delft University of Technology, The Netherlands. T

References

[1] J. Jansen et al., Acta Cryst. A54 (1998) 91.

[2] G. Kresse, J. Furthmller, Comput. Mater. Sci. 6 (1996) 15.
[3] G. Kresse, J. Furthmller, Phys. Rev. B 54 (1996) 11169.
[4] G. Kresse, J. Hafner, Phys. Rev. B 47 (1993) RC 558.
[5] G. Kresse, J. Hafner, J. Phys.: Condensed Matter 6 (1994) 8245.
[6] C.D. Marioara et al., Acta Mater. 49 (2001) 321.
[7] J.H. Chen et al., Science. 312 (2006) 416.
[8] S.J. Andersen et al., Acta Mater. 46 (1998) 3283.
[9] R. Vissers et al., Acta Mater. 55 (2007) 3815.
[10] A. Frseth et al., Phys. Rev. B 67 (2003) 2241061.
[11] S.J. Andersen et al., Mater. Sci. Eng. A 444 (2007) 157.
[12] S.J. Andersen et al., Mater. Sci. Eng. A 390 (2005) 127.
[13] C. Ravi, C. Wolverton, Acta Mater. 52 (2004) 4213.
[14] C. Wolverton, Acta Mater. 49 (2001) 3129.
[15] K. Matsuda et al., J. Mater. Sci. 35 (2000) 179.
[16] K. Matsuda et al., Metall. Mater. Trans. A 32 (2001) 1293.
[17] D.J. Chakrabarti, D.E. Laughlin, Progr. Mater. Sci. 49 (2004) 389.
[18] W.F. Miao, D.E. Laughlin, Metall. Mater. Trans. A 31 (2000) 361.
[19] C. Cayron et al., Phil. Mag. A 79 (1999) 2833.
[20] C.D. Marioara et al., Phil. Mag. 87 (2007) 3385.
[21] L. Arnberg, B. Aurivillius, Acta Chem. Scand. A 34 (1980) 1.
[22] P.D. Nellist, S.J. Pennycook, Ultramicroscopy 78 (1999) 111.
[23] G.A. Edwards et al., Acta Mater. 46 (1998) 3893.
[24] C.D. Marioara et al., Metall. Mater. Trans. A 36 (2005) 691.
 Analysis of massive transformation .. 1

JCACS
2007

Analysis of massive transformation for amorphous Al90Sm10 binary alloy B B B B

during crystallization
J.P.Hadorn, G.J.Shiflet
Department of Materials Science and Engineering,University of Virginia, Charlottesville, VA 22904, USA

Abstract

The devitrification of amorphous Al90Sm10 ribbon, prepared via melt-spinning, was performed by isothermal heat-treatment and
B B B B

characterized via x-ray diffraction, transmission electron microscopy, and electron dispersive spectroscopy. The crystallization of the initial
amorphous state was observed to occur via a massive transformation mechanism. The single-phase metastable product phase was found to
nucleate sparsely and to maintain a barrel-shaped morphology during growth. The metastable crystals were observed to exhibit linear
growth without chemical partitioning across the interface, which is characteristic of a massive transformation.

Keywords: massive transformation, metallic glasses, devitrification.

Although few in number, there are other binary

1. Introduction
Massive transformations are characterized by a several
criteria that must be satisfied. First of all, during growth,
there exhibits no chemical partitioning; that is, there is no
observed concentration gradient across the interface
between the parent matrix and a product precipitate [1].
Long-range diffusion does not act as a mechanism for
such a transformation, but rather short-range atomic
jumps across the interface between the two phases [2-3].
systems, in which polymorphic transformations are
reported from an initial metastable amorphous phase.
These include Ni-P, Mg-Zn, Ni-Zr, and Fe-B [8-12].
However, beyond statements, no additional evidence
suggesting that these transformations are massive is
provided. However, for Fe-B, evidence of linear growth
kinetics, which is a characteristic of massive
transformations, is reported [12].
In this work, direct techniques and measurements are
used to determine if the crystallization of amorphous
Al90Sm10 ribbon obeys the criteria necessary for a massive
B B B B

As a consequence of this criterion, massive
transformations involve only a single parent phase and
only a single product phase. Therefore, for the case of a
multi-component system, a massive transformation is
polymorphic [2-3]. Thermodynamically, this can be
satisfied if at a given composition and temperature, it is to
the left of T0 on a G-X plot.
B B
transformation. Such techniques involve the use of
transmission electron microscopy (TEM), electron
dispersive spectroscopy (EDS), and x-ray diffraction
(XRD). Data obtained from this work are analyzed and
used to examine the mechanism surrounding this
devitrification transformation.

Using the criteria/characteristics of a massive

transformation, the purpose of this work is to determine if 2. Experimental procedures
metastable amorphous binary metal of composition
Al90Sm10 undergoes a massive transformation during
B B B B An Al90Sm10 ingot was produced in an arc-melter from
B B B B

devitrification. Previous work has been done on pieces of 99.999%Al and 99.9%Sm; Ar gas was used
amorphous material of this composition [4-7]. The during this stage. X-ray diffraction on pieces of the ingot
authors of this previous work analyzed XRD patterns of indicated that the as-cast Al90Sm10 consisted of a two-
B B B B

heat-treated ribbon through each of the observed phase mixture of fcc-Al and Al11Sm3, consistent with B B B B

transformation steps en route to equilibrium. The first
transformation, which is a crystallization stage, the
authors note to be a polymorphic transformation to a
single metastable phase [4-7]. However, beyond this
statement, no experimental evidence suggesting massive
previous work [4]. Pieces of the cast ingot were placed
into a quartz crucible and then melt-spun in an He
atmosphere onto a Cu wheel rotating with a surface speed
of 42m/s.
Samples were analyzed in a LaB6 filament B B

crystallization is reported for this material. transmission electron microscope (TEM) at 200kV. The
2 J. P. Hadorn et al.

TEM specimens were prepared in a twin-jet representing the polycrystalline MS2 structure,
electropolisher. The electrolyte used consisted of a 4:1 simultaneously occur.
volume ratio of methanol : nitric acid between -
30C and -15C; the applied voltage was 10V.
EDS analysis was performed on heat-treated Al90Sm10 B B B B

ribbon samples that were air-quenched during the

crystallization transformation. Composition profiles were
obtained by performing collinear EDS scans through the
matrix and across a crystalline precipitate, a technique
simulating a line scan.
During EDS experiments, the sample thickness at each
of the scanned spots was consistent in order to ensure a
constant k-ratio. This was done by scanning parallel to the
foil hole and noting the relative intensities. The raw
datasets were quantitatively analyzed, but only relative to
each other. No k-ratio corrections were performed to
accurately determine the composition of the phases from
the output, because only relative solute (Sm) partitioning
information was required; the goal of these experiments
was to determine if composition changes across the Figure 1. XRD patterns for amorphous Al90Sm10 ribbon samples
B B B B

crystalline/amorphous matrix. isothermally heat-treated between 10min. and 40min. at 200C: pattern
In-situ experiments were also performed on the shows change from amorphous state to crystalline MS2 phase (2 in
Al90Sm10 amorphous ribbons. The specimens were placed
B B B B
degrees, CuK = 1.54)
B B

into a hot-stage TEM holder and heated to temperatures

where the crystallization of the sample could be Figures 2a-b show TEM images of MS2 precipitates
monitored and recorded using a DVD player connected to growing within the amorphous matrix, projected along the
a camera and a TV monitor. Because of the sparse [100] and [110] zone axes, respectively, along with the
nucleation of the crystalline precipitates, in-situ corresponding diffraction patterns and crystallographic
recordings were performed at a low magnification, directions. The MS2 crystals growing within the
between 3kX and 10kX. amorphous matrix maintain a symmetrical barrel-faced
Crystallite growth was examined along different low- morphology; the precipitates possess polygonal geometry,
index zone axes to study the difference in growth kinetics except with the faces bowed outwards. This suggests
along different crystallographic directions. By that during growth of MS2, there is shape preservation of
performing this analysis starting from a small precipitate, the particles and constraints imposed on it by their
it was also possible to monitor how its shape changes, if crystallographic anisotropy.
at all, as a function of size. The growth rate was
isothermally measured at 190C, 200C, 210C, and
220C. From these rates, the activation energy for
precipitate growth was quantitatively estimated using an
Arrhenius plot.
Interface displacement of the growing crystallites
relative to a reference position was measured as a
function of time and temperature. For each segment of
monitored growth, the displacement was noted after
designated time intervals relative to the appropriate
reference time.

3. Results: growth morphology systematics

When heat-treated, amorphous as-spun Al90Sm10 B B B B

ribbon crystallizes into a single phase, which previous

authors named MS2 [4]. Figure 1 shows XRD patterns of
ribbon samples isothermally heat-treated at 200C for
different times and then air-quenched. Within this time
range, a decline of the broad peaks representing the
amorphous phase, and the emergence of sharp peaks
 Analysis of massive transformation ..
Figures 2a-b. Growth of MS2 precipitate within amorphous matrix
along [100] and [110] zone axis projections, respectively; 190C heat-
treatment; low-index crystallographic directions and corresponding
diffraction pattern shown
XRD and transmission electron microscopy (TEM)
analyses reveal the Bravais lattice of the crystal structure
of MS2 and the corresponding lattice parameters. TEM
diffraction patterns are taken along different angles for
different precipitates. These patterns along with their
corresponding relative tilt angles establish the MS2 phase
as body-centered cubic. Diffraction patterns of three low
index zone axes, namely [110], [110], and [111], are
shown indexed in Figure 3 along with the angles between
them. From analysis of the XRD patterns corresponding
to this MS2 phase, the lattice parameter of the unit cell, a,
is determined to be a 13.8 via Braggs law using XRD
analysis software. The MS2 XRD diffraction pattern is
shown in Figure 4 with the peaks indexed.
Figure 3. TEM diffraction pattern for MS2 (bcc) along [100], [110],
and [111] zone axes; calculated and theoretical angles between these
zones also shown
3
Figure 4. XRD pattern of the MS2 phase with main peaks indexed (2
in degrees, CuK = 1.54)
B B
Although some expected MS2 peaks are not
significantly distinguishable in the XRD pattern of the
ribbon [4], all peaks that do appear in the pattern
correspond to an expected peak for a bcc crystal where a
13.8. Most of the peaks can also be fit to a simple
cubic crystal structure with a lattice parameter of a
9.76. However, as indicated in Figure 4, for the bcc fit,
the (642) peak, which corresponds to N = 56, is clearly
visible. If this crystal structure were simple cubic with a
9.76, then that peak would correspond to N = 28,
which is impossible for a cubic system, since N m2(8n - P P
1), where m and n are integers (22[8(1) - 1] = 28).
Therefore, MS2 is not sc, but rather bcc.
4. Results: energy dispersive spectroscopy (EDS)
measurements using TEM
Figure 5 shows an MS2 precipitate embedded within
the amorphous matrix of a partially crystallized Al90Sm10 B B B B
ribbon sample. Seven collinear spots are chosen for EDS
to produce a line composition profile across the
precipitate; the numbers label the spots of the location of
each EDS scan. The thickness of the sample at the point
of each scan is essentially the same so that the k-ratio for
each scan is also the same. Although the raw EDS output
of a single scan by itself has no quantitative merit without
chemical correction, all the scans together can be
qualitatively compared amongst each other since the k-
ratio essentially remains constant. The corresponding raw
compositional data output, shown in Table 1, shows no
observed difference in composition amongst each of the
probed spots (Table 1); the composition profile is
therefore uniform.
4 J. P. Hadorn et al.

Figure 5. TEM micrograph of Al90Sm10 ribbon isothermally heat-

B B B B

treated at 200C for 17min. showing an MS2 precipitate embedded in an

amorphous matrix; collinear black spots indicate points where EDS line
scan is taken

Table 1
Compositional EDS output for the EDS line scan corresponding to
Figure 5

5. Results: TEM in-Situ growth analysis of MS2

precipitates during crystallization

The crystallization of MS2 is recorded in-situ at 190C

and the displacement of the precipitates is measured as a
function of time along specific crystallographic directions,
namely, [100], and [110]. For this analysis, three
different precipitates within the sample, call Precipitates 1
through 3, are measured in each of these directions. In
each case, the precipitate is aligned along a low-index
zone axis that is perpendicular to these two
crystallographic directions to ensure that the growth
measured in the in-situ TEM projection is the true growth
and not a partial angular projection. Figure 6 shows
frames displaying 4min. intervals of in-situ growth of one
of the precipitates (namely, Precipitate 3), which is
oriented along [100]. In this case, Precipitate 3 is the
same one that is shown in Figure 2a. Growth of the
precipitates is measured starting at a specific reference
time where t 0.
 Analysis of massive transformation .. 5

220C. For each temperature, the length of displacement

Figures 6a-d. Chronological timeframe sequence of microstructure
images showing growth of MS2 (Precipitate 3) along <100> zone at
is equal to the measured displacement normal to the
190C in 4min. intervals interface. Representative displacement vs. time plots for
each temperature is shown in Figure 8. For each plot, a
With respect to a reference time, the displacement of linear regression line p(t) (p for position) is fit. Table 2
the MS2/amorphous interface is measured at periodic summarizes the growth rate results at these studied
time intervals. Figures 7a-b show the interface temperatures.
displacement vs. time plots of Precipitates 1-3 along the
[100] and [110] directions, respectively. For each plot, a
linear regression line x(t) (x for position) is fit, from
which the displacement rate (constant), dx/dt is
calculated. The calculated errors are based on uncertainty
involved with recording data directly from a display
screen.

Figure 8. Interface displacement vs. time plots (p vs. t) for MS2

growing within an amorphous matrix at 190C, 200C, 210C, 220C:
measurement error is 0.25m for each plot

Table 2
Summary of growth rate of isolated MS2 precipitates growing within the
amorphous matrix of Al90Sm10 ribbon at various temperatures
B B B B

In-situ growth kinetics measurements are also

Figures 7a-b. Interface displacement vs. time plots for an MS2
precipitate growing along [100] and [110] directions, respectively within
an amorphous matrix at 190C: plot of linear regression lines also shown
in each plot along with corresponding slope (dx/dt), R2 value, and error
P
P
performed for pairs of MS2 precipitates growing toward
each other, to detect, if possible, any soft impingement, i.e.
the distance between the impinging precipitates is
measured as a function of time up to hard impingement.
This is a very sensitive method to test whether any
diffusion into the matrix occurred, which would result in
constantly reduced kinetics as the interphase boundaries
approach each other. Figure 9 shows an interface spacing
vs. time plot for adjacent MS2 precipitates growing at
210C along with a fit linear regression line representing
s(t). Again, the very high R2 value verifies the strength of

P P

According to these plots, there is a strong linear the linear relationship.

relationship between the position of the interface and
time; the high R2 value verifies the strength of this
P P

linearity. Additionally, on average, the growth rate, dx/dt,

along the [100] direction is approximately the same as
that along the [110] direction.
The growth rate of MS2 precipitates is also monitored
at different temperatures, starting at a specific reference
time, t 0, and a reference position, p 0. The
temperatures monitored are 190C, 200C, 210C, and
6 J. P. Hadorn et al.
Figure 9. Interface spacing vs. time plot (s vs. t) for two MS2
precipitates growing towards each other within an amorphous matrix at
210C: linear regression line also shown along with corresponding slope,
R2 value, and error
P P
6. Discussion
During crystallization of amorphous Al90Sm10 ribbon, B B
the metastable MS2 phase forms; again, its XRD pattern
is shown in Figures 1, and 4. This unique XRD pattern
has been documented in only one other material. In 1994,
J.Q. Guo et al published a paper regarding the
crystallization of metastable phases on amorphous Al-RE
alloys. One of the compositions, Al92Ce8, shows an initial
B B B B
crystallization to a phase similar to MS2 [14]. Namely,
the metastable phase is bcc with a similarly large lattice
parameter of a = 13.871 and the XRD pattern looks
similar to that of MS2 [14].
There is strong evidence that this devitrification
reaction occurs via a massive mechanism. One
characteristic of a massive phase transformation is that it
is polymorphic. The crystallization of homogeneously
amorphous Al90Sm10 ribbon to the single metastable MS2
B B B B
phase does possess this trait.
Another crucial component of a massive
transformation is that there is no concentration gradient
near the interface between the parent matrix and the
growing product precipitates. According to Table 1, no
evidence of chemical partitioning during the
crystallization of the initially amorphous Al90Sm10 ribbon B B
is detected. Since there is no chemical partitioning, short-
range diffusion is present; otherwise, long-range diffusion
would result in a chemical gradient from the precipitate,
through the interface, and into the amorphous matrix.
For a precipitate growing massively in the parent
matrix, its growth rate, V, is constant and given by [15-
16]:
dp h Q G (Equation 1)
= v exp
dt RT RT
where h and are the height and thickness of growth
ledges, respectively, = phase boundary thickness, v =
jump attempt frequency of atoms across phase boundary
interface, Q = activation energy for the short-range
diffusion, R = universal gas constant, T = temperature,
and where G = total free energy of massive
transformation [1,14-15]. Since v is constant, the growth
rate of the product phase is therefore expected to be linear.
In Figures 7a-b and 8, linear precipitate growth is
observed at a constant temperature, from 190C to 220C.
The s vs. t plot for MS2 precipitate impingement,
shown in Figure 9, is also linear, as indicated by the high
R2 value. Additionally, for a given temperature, if the
P P
growth rate of the MS2 precipitates is v, then the rate of
impingement of two precipitates must be -2v; that is, for a
precipitate spacing of s:
ds dp (Equation 2)
= 2
dt dt
From Figure 8 and 9, at 220C, the calculated
impingement rate, ds/dt -2dp/dt, as predicted.
An unusual imaging phenomenon present during in-
B B
situ observation qualitatively verifies linear and uniform
growth. It is observed that when the growth of an MS2
crystallite is arrested by sufficiently cooling down the
temperature and then reheated so that it can once again
grow, a ring will form, outlining the crystallite interface
during the time of growth arrest; for every cooling
heating cycle performed, a ring will be left behind. Such
a phenomenon is reminiscent of growth rings of a tree; by
finding a precipitate and counting the number of rings
(including the current interface), it can be determined how
many cooling/heating cycles a precipitate endures during
growth since the time of its nucleation.
An example of a ringed isolated MS2 crystallite is
shown in Figure 10 along a [100] projection. In this case,
the heating part of the cycle is isothermal at 190C. After
two minutes at this temperature, the sample is then cooled
sufficiently quickly so that its growth is arrested. This
cycle is then repeated several more times under the same
conditions, each time producing a ring.
B B
 Analysis of massive transformation ..
Figure 10. Image of ringed MS2 precipitate along <100> zone axis
The spacing between each ring in the figure therefore
represents the interfacial displacement of the precipitate
after 2min. of heating at 190C. Since the rings are
concentric and since their adjacent spacings are uniform,
the MS2 precipitate does indeed undergo linear and
uniform growth.
The rings themselves are composed of small
crystallites and the reason for their appearance as well as
what they physically represent were investigated and will
be discussed in a future publication.
By knowing the v = dp/dt values for the growing MS2
precipitates for each of the temperatures investigated, the
activation energy of the massive growth is estimated via
construction and analysis of an Arrhenius plot, ln(v) vs.
(1/T), which should be approximately linear via the
equation:
H 1 (Equation 3)
ln (v * T ) = C * consume the matrix, nucleation is sparse; the population
R T
where C is a constant, and where H = activation energy
of precipitate growth. From Equation 3, the activation
energy is then be approximated by Equation 4:
ln (v * T ) ln (v ) (Equation 4)
H = R * R *
1 1
orientation relationship can exist between it and the
T T
Within the temperature range of 190C to 220C,
where MS2 growth is linear, the corresponding Arrhenius
plot is also linear, as expected; from it, an activation
energy of 250kJ/mol is predicted. This Arrhenius plot is
shown in Figure 11 along with the corresponding linear
regression function. Since the R2 value is fairly high (R2
P P
= 0.9757), this Arrhenius plot shows strong linearity.
7
Figure 11: Arrhenius plot for growth of MS2 precipitates in the
amorphous Al90Sm10 matrix with calculated precipitate growth activation
B B B B
energy; plot of linear regression line also shown along with
corresponding slope and R2 value P P
For both growth directions, [100] and [110], the
growth rate of MS2 is essentially the same. However, at
first glance, this is not expected since these precipitates
are not spherical, but rather barrel-shaped. For Precipitate
3, whose growth along the [100] projection is shown in
Figure 2a, the image projection appears to be a square.
For a perfect square growing concentrically, the growth
rate along its diagonals is about 1.4 times (square root of
2 times) that normal to its sides. Therefore, in this case,
the growth rate along the [110] direction is expected to be
about 1.4 times that for the [100] direction. However, the
MS2 precipitates are not perfectly faceted; the sides are
slightly bowed outward. Specifically, in Figure 2a, the
displacement of the bow is greatest along [100]. As a
result, the growth rate along [100] is faster than it would
be for a perfectly faceted precipitate, which may explain
why the measured [100] growth rate for the MS2
precipitates is about the same as the [110] growth rate.
Also, during crystallization, although MS2 precipitates
of precipitates is low. Therefore, on average, the MS2
precipitates are free to grow to a fairly large size, up to
several micrometers, before they impinge on each other.
This observation is consistent with previous publications,
which have demonstrated that massive product
precipitates are initially difficult to nucleate, but once
nucleated, can grow very rapidly if there is no preferred
crystallographic orientation relationship [17-18]. In this
case, since the parent matrix is amorphous, no preferred
crystalline MS2 product precipitates.
7. Conclusions
P P
Amorphous Al90Sm10 was observed to undergo a
B B B B
massive phase transformation during devitrification.
8 J. P. Hadorn et al.
There are several characteristics that a transformation
must have in order to be massive. First, a massive
transformation is represented by a non-equilibrium
transformation from a one-phase microstructure to
another one-phase microstructure. Secondly, during the
transformation there is no chemical partitioning between
the product precipitates and the parent matrix. Thirdly,
the growth of the interface of the product precipitates is
linear. It was concluded that this crystallization
transformation obeyed all three of these criteria.
For this massive transformation, the product phase was
a metastable crystalline phase with a body-centered cubic
crystal structure and a large lattice parameter of a 13.8.
The only other known observance of a phase with a
similar XRD pattern was a metastable phase in the
Al92Ce8 binary system, which also had a body-centered
B B B B
cubic crystal structure and a comparable lattice parameter
of a 13.9 [14].
During crystallization, the population of MS2
precipitates was sparse, which allowed them to grow
fairly large before impinging on one another. The
morphology of the precipitates was barrel-shaped; the
edges appeared to be slightly bowed out from an
otherwise faceted position. When measuring the growth
kinetics at 190C, although the precipitates maintained
their overall shape, the linear growth rate in the [100]
direction was found to be the same as that in the [110]
direction. This equivalence, although geometrically
contradicting for a perfectly faceted precipitate, may exist
due to a bowing out effect of the precipitates. Finally, in
all cases, the MS2 precipitates displayed linear growth
kinetics with an activation energy of 250 kJ/mol.
References
[1] T.B. Massalski, Metall. Trans. A 33A (2002) 2277-2283
[2] T.B. Massalski, in Phase Transformations, ASM, Metals Park, Ohio
(1970) 433
[3] H.I. Aaronson, Metall. Trans. A 33A (2002) 2285-2297.
[4] L. Battezzati et al., Mat. Sci. Eng. A A179-180 (1994) 600-604.
[5] P. Rizzi et al., Materials Science Forum 1995, 195 (1995) 111-116.
[6] P. Rizzi et al., NanoStructured Materials, 10 (1998) 767-776.
[7] J.Q. Guo et al.., The 4th international Conference on Aluminum
P P
Alloys, Atlanta, USA 2 (1993) 753-759.
[8] A. Calka et al., Scripta Metall. 11 (1977) 65-70.
[9] B.G. Bagley, D. Turnbull, Acta Metall. 18 (1970) 857-862.
[10] Y.D. Dong, G. Gregan, M.G. Scott, J. of Non-Cryst. Solids 43
(1981) 403-415.
[11] Y.D. Zhang et al., J. Appl. Phys. 61(8) (15 April 1987) 3231-3233.
[12] T. Spassov, S. Budurov, Cryst. Res. Technol. 23(10-11) (Oct.-Nov.
1989) 1225-1230.
[13] F. Casteels, JLCM 12 (1967) 210-220.
[14] J.Q. Guo et al., Materials Letters 21 (1994) 279-284
[15] J.E. Burke, D. Turnbull, Prog. Metall. Phys. 3 (1952) 220
[16] J.W Cahn, W.B. Hillig, and G.W. Sears, Acta Metall. 12 (1964)
1421
[17] T.B. Massalski, Mat. Sci. and Eng. 25 (1976) 119-125.
[18] B.C. Giessen, 4th Int. Conf. on rapidly Quenched Metals, 1 (1982)
P P
13
 Effect of Mg Content on the Precipitation 1

JCACS
2007

Effect of Mg Content on the Precipitation in Al-Mg-Ge Alloys

Kenji Matsuda1, *, Teruyoshi Munekata1,2 and Susumu Ikeno1

P P P P P P

1: Graduate School of Science and Engineering for Research,University of Toyama, Toyama 930-8555, Japan .*: matsuda@eng.u-toyama.ac.jp

2; Present address: Sumitomo Wiring Systems, Ltd., 1-14 Nishisuehiro, Yokkaichi, Mie, 510-0058, Japan.

Abstract

Rod-shaped precipitates in Al -1.1 mass% Mg2Ge (balanced) and Al -1.0 mass% Mg2Ge 0.5 mass% Mg (excess Mg) alloys aged at 523
B B B B

K were observed by high-resolution transmission electron microscope (HRTEM) to understand their crystal lattices and chemical
compositions. Rod-shaped precipitates were parallel to <100> directions of the matrix. There were 2 groups for rod-shaped precipitates in
the base alloy, namely, small cross sections about 10 nm and large ones over 20nm in diameter. Small precipitates showed a hexagonal
network of bright dots in their HRTEM images, and its crystal lattice was estimated as a hexagonal having a= 0.72 and c= 0.405 nm based
on analysis of HRTEM images and selected area electron diffraction (SAED) patterns. This lattice parameter was slight larger than that of
the -phase in Al-Mg-Si alloy.

Keywords: Al-Mg-Ge alloy, metastable -phase, precipitation, HRTEM

using a solution of 90% ethanol and 10% perchloric acid.

1. Introduction
It has been well known that the precipitation sequence of
Al-Mg-Ge alloys is similar to that of Al-Mg-Si alloys[1].
The analysis of crystal structure, however, has not been
reported in detail by the electron diffraction and/or HRTEM
observation. In our recent work, precipitates in an Al -1.1
HRTEM images, EDS and selected area diffraction (SAED)
patterns were obtained by 200 kV (Topcon EM-002B) and
400 kV (JEOL 4010T) TEMs.
3. Results and discussion
Fig. 1 shows bright field images of Al-1.0 mass% Mg2Si B B

mass% Mg2Ge (balanced) alloy has been observed by TEM,

B B
and the -phase and the A-type precipitate were confirmed.
The former one is the typical metastable phase in the Al-
Mg-Si alloy and the latter one is the major phase in the
over-aged Al-Mg-Si alloy including Si in excess. In the
present work, precipitates in the balanced Al-Mg-Ge alloy
and Al-Mg-Ge alloy with Mg in excess have been
compared by HRTEM technique.
(AMS balanced) and AMG balanced alloys aged at 523 K
for 12 ks which is nearly peak aging condition of Al-Mg-Si
alloy. Rod-shaped precipitates were shown in there and rods
are parallel to <100> directions of the matrix. Other shapes
of precipitates, for example, particle or plate could not be
observed in this aging time. Precipitates in AMG balanced
alloy are finer and denser than those in Al-Mg-Si alloy.

2. Experimental

Al -1.1 mass% Mg2Ge (Al -0.52 at% Mg -0.24 at% Ge,

B B

(AMG balanced)) alloy and Al -1.0 mass% Mg2Ge -0.5 B B

mass%Mg (Al -0.95 at% Mg -0.22 at% Ge, (AMG excess

Mg)) alloy were prepared by a conventional casting
technique in atmosphere. Ingots obtained were cut and
rolled to thin sheets. hese sheets were solution heat treated
at 873 K for 3.6 ks and quenched into chilled water about
273 K. The aging treatment was performed in a salt bath
controlled to 523 K. Thin foils for TEM observation were Fig. 1. Bright field images of alloys aged for 12 ks. (a) Al-Mg-Si and (b)
prepared by a conventional electrolytic polishing method Al-Mg-Ge alloys
2 K. Matsuda et al.

The precipitate which shows the similar feature to the
-phase in AMS balanced alloy [2,3] has been confirmed
as shown as Fig. 2. This precipitate shows higher Mg
content by EDS analysis and this is the same behavior as
the -phase in the AMS balanced alloy. Rod-shaped
precipitates were parallel to <100> directions of the matrix.
There were 2 groups for rod-shaped precipitates, namely,
small cross sections about 10 nm and large ones over 20nm
in diameter. Small precipitates showed a hexagonal network
of bright dots in their HRTEM images, and its crystal lattice
was estimated as a hexagonal having a= 0.72 and c= 0.405
nm based on analysis of HRTEM images and SAED
has been confirmed. But, no large precipitate like as Fig. 3
has been observed in the present work. As the -phase in
Al-Mg-Ge alloy consists of higher Mg and lower Si
contents than those in Al-Mg-Si alloy, namely Mg:Ge=3:1,
Ge becomes enriched rather than Mg in Al-Mg-Ge balanced
alloy by precipitation of the -phase. Thus it shows the
similar behavior to the Al-Mg-Si alloy with excess Si, and it
includes the same precipitate as the A-type precipitate. On
the other hand, the same precipitate as the A-type
precipitate has not been confirmed in the AMG excess Mg
alloy, because there is enough Mg content to form the -
phase of Mg3Ge in this alloy .
B B

patterns. This lattice parameter was slight larger than that of

the -phase in AMS balanced alloy. Its orientation
relationship with the matrix was as follows: 4. Summary

{0001} p //{001}m, < 1120 > p // < 100 > m Rod-shaped precipitates in Al -1.1 mass% Mg2Ge and Al B B

-1.0 mass% Mg2Ge -0.5 mass% Mg alloys aged at 523 K

B B

were observed by high-resolution transmission electron

microscope (HRTEM) to understand their crystal lattices
and chemical compositions. Rod-shaped precipitates were
parallel to <100> directions of the matrix and there were 2
groups for rod-shaped precipitates in the AMG balanced
alloy, namely, the -phase and the A-type precipitate. The
A-type precipitate did not confirm in AMG excess Mg alloy
because of enough Mg content in the matrix.

Fig. 2. A typical HRTEM image of the cross-section of the -phase in

AMG balanced alloy aged for 600 ks.

Precipitates having large cross section showed a

rectangular network having 0.68 and 0.35 nm in Fig. 3. This
was similar feature to the A-type precipitate in the Al-Mg-
Si alloy with excess Si [4]. A crystal lattice of this
precipitate was estimated as a hexagonal having a= 0.405 Fig. 3. An HRTEM image for a large precipitate in the AMG balanced
and c= 0.68 nm based on analysis of HRTEM images and alloy. It shows a similar arrangement of bright dots having a rectangular
SAED patterns. Mg and Ge elements were detected from network to the A-type precipitate in the Al-Mg-Si alloy with excess Si.
these precipitates by energy dispersive X-ray spectroscopy
(EDS) and the ratio of Mg to Ge (Mg/Ge) for the small
precipitate which is similar to the -phase in Al-Mg-Si
alloy, was about 3, not 2 as shown in Fig. 4(a). The Mg/Ge
for large precipitates which are similar to the A-type
precipitate in Al-Mg-Si alloy was 2 (Fig. 4(b)), and this
ratio was larger than that of the A-type precipitate in Al-
Mg-Si alloy. It has been expected that these differences of
chemical composition for precipitates caused the increment
of lattice parameters of precipitates in Al-Mg-Ge alloy. In
the AMG excess Mg alloy, the same precipitate as Fig. 2
 Effect of Mg Content on the Precipitation 3

References

[1] A. Lutts: Acta Met. Vol. 9 (1961), p.577 .

[2] K. Matsuda, S.Tada and S. Ikeno: J. Electron Micro. Vol. 42 (1993),
p.1 .
[3] K. Matsuda, S. Ikeno and S. Tada: J. Japan Inst Metals, Vol. 57 (1993),
p.1107.
[4] K. Matsuda, et al: Scripta Met. Mater. Vol. 32 (1995), p. 1175.

Fig. 4. Summary of EDS analysis for precipitates. (a) the -phase and (b)
the A-type precipitate in AMG balanced alloy.
 Effect of the Nanocrystalline Phase 1

JCACS
2007

Effect of the Nanocrystalline Phase on the Properties of the Electroless

Ni-P Deposit
Y.Zou * , Y.H. Cheng, L. Cheng, J.W. Song, W.J. Du
TPF FPT

Institute of Thermal Science and Technology, Shandong University, Jinan 250061, P.R. China

Abstract

The Ni-P deposits with different contents of nanocrystalline phase could be obtained through adjusting the process of electroless. The
addition of nanocrystalline phase increased the microhardness of deposits, and improves the thermal stability of deposits. The crystalline
temperature shift higher temperature with the increasing of amount of nanocrystalline phase. However, the experimental results of
corrosion resistance also showed that the addition of nanocrystalline phase deteriorate the corrosion resistance. The almost whole
amorphous matrix showed the best corrosion resistance.

Keywords: Ni-P, Nanocrystalline phase, amorphous, corrosion resistance

The substrates were cleaned and polished before plating.

1. Introduction
The Ni-P deposit have attracted much attention of many
researchers due to their unique properties, such as the
corrosion resistance, wear resistance, paramagnetic
characteristic, hardness and the electro catalytic activity
of hydrogen evolution [1-8]. Electroless plating is a very
convenient technique for preparing Ni-P deposit. The
composition and microstructure of the electroless deposits
are controlled by the process condition [9-10]. By
The composition of the electroless solutions were listed in
Table 1. The samples were plated in the electroless
bathing for 2 hours at specified temperature. The structure
of the deposits was determined by X-ray diffractometer
with Cu K radiation. The scanning rate and scanning
step were fixed at 4C/min and 0.02, respectively. The
microhardness measurements were carried out under a
load of 50g. The crystallization behavior of the deposits
was measured at a heating rate of 40C/min by a
differential thermal analysis (DTA). The corrosion
resistance in 5% H2SO4 solution was determined by
B B B B

adjusting the process parameters, we could obtain Ni-P measuring weight loss as a function of immersion time.
deposit with different microstructure. In other word, we
could obtain the amorphous, nanocrystalline or the 3. Results and discussion
mixture of them. However, the study about the effect of
XRD results of sample 1, 2 and 3 indicated in Fig. 1.
T

nanocrystalline phase on the properties of Ni-P deposit is
limited. In this work, we report briefly on the effect of
nanocrystalline phase on the properties of Ni-P deposit,
such as hardness, thermal stability, and corrosion
resistance.
2. Experimental
Low carbon mild steels with a size of 15153mm
were used as substrates for electroless plating NiP alloys.
Sample 1 shows the obvious amorphous pattern, and
sample 2 and 3 shows the characteristic of mixture of
amorphous and nanocrystalline phase. However, it also
noted that the crystalline peak of sample 3 is sharper than
sample 2. Therefore, sample 3 contains more amount of
nanocrystalline phase than sample 2. Here, we draw a
conclusion that the crystalline phase in sample 2 and 3
belongs to nanocrystalline phase because these peaks
have wider full width at half maximum (FWHM) than

*
TP PT Corresponding author. Tel: +86-531-88399596 Fax: +86-531-88399598
E-mail: yzou@sdu.edu.cn (Yong Zou)
HTU UTH
2 Y. Zou et al.

other crystalline Ni, and no other crystalline peaks were than amorphous matrix, and these stable nanocrystalline
observed. These results indicated that the deposits with phases inhibit movement of some Ni or P atoms in
different crystalline state could be controlled through amorphous matrix, so these disorder atoms need higher
adjusting the process of electroless. T
temperature to finish the crystalline process. Although
more works are needed to reveal the difference of there
1 2 3 crystalline products, it still indicated that the formation of
nickel sulphategl-1 P P 20 26 40 nanocrystalline phase improved obviously the thermal
NaH2PO26H2Ogl-1 B B B B B B P P 30 30 30 stability of Ni-P deposit.
lactic acidgl-1 P P 11 11 11
Glycingl-1 P P 7 7 7
citric acidgl-1 P P 6 6 6 900
PH 7 7 7
Temperature C 80 70 80
800

Microhardness (Hv)
Table 1Concentrations of the bath and the sample number for
700
the electroless process

600

500

400
1 2 3
Intensity (a.u.)

Sample No.

Fig 2. Microhardness variation for deposit of sample 1, 2 and 3.

sample 3
sample 2
sample 1
sample 3
15 20 25 30 35 40 45 50 55 60 65 70 75
2(degree)
T

sample 2
Fig 1. XRD patterns of deposit of sample 1, 2 and 3

sample 1

Figure 2 shows the variation of microhardness for

these samples with different microstructure. It showed the 200 300 400 500 600
hardness increased with the increasing of the Heating temperature C
nanocrystalline phase. For the sample 3 which contains
most nanocrystalline phase, the value of hardness is
Fig 3. DTA curves of sample 1, 2 and 3 deposit .
nearly reached to 800Hv. This value is close to the results
after being heat treated 1-2 hours of Ni-P deposit [11].
The corrosion properties of these deposits were studied
This could attribute to the strengthening role of
by immersing them in 5% H2SO4 solution. Figure 4 show B B B B

nanocrystalline phase.
the function between the weight loss and immersion time
Figure 3 shows the differential thermal analysis (DTA)
for these samples. From these experimental data, it can be
results, in which the deposits were heated up to 600C. seen that the amorphous sample (sample 1) owning the
The main exothermic peaks of sample 1 and 2 are almost minimal weight loss, meaning the amorphous sample
in similar temperature range. However, there is a shoulder have the best corrosion resistance. With the increasing of
after main peak in the sample 2 as marked by arrow, the amount of nanocrystalline phase, it shows the
which showed some characteristic of two stages decreasing trend of corrosion resistance. The possible
crystallization. For the curve of sample 3, the exothermic reason is that nanostructure should accelerate corrosion
peak shift obviously to the higher temperature. The by forming much more micro electrochemical cells
possible reason is that nanocrystalline phase is stability between the huge amount of grain boundaries and the
 Effect of the Nanocrystalline Phase
matrix while the amorphous structure should exhibit
inherently high corrosion resistance because of its
extreme structure homogeneity without preferential
corrosion paths like grain boundaries or other structural
defects [5].
15 sample 3
sample 2
Weight loss, mg/cm2
sample 1
10
5 2(degree)
0
1 2 3 4 5 6
Immersion time, days
Fig 4. Weight loss versus time immersed in 5% H2SO4 solution for
B B
different deposit.
The other interesting problem is whether there is
structural variety of these Ni-P deposits after being
corrosion. Figure 5 show the X-ray diffraction patterns of
there Ni-P samples which were immersed in 5% H2SO4
solution for two weeks. As a comparison, the results
before corrosion also were showed in this figure. From
these diffraction results, no other peaks except for
amorphous or nanocrystalline peaks were observed.
However, the relative intensities of sample 2 and 3 have a
decreasing than that of before corrosion, as showed the
dashed line in Fig.5. With increasing of the amount of
nanocrystalline phase, the relative intensity shows a rapid
decreasing trend, as seen sample 2 and 3. This could be
attributed to nanocrystalline phase eroded. The sample 1
that is almost whole amorphous phase keeps the same
shape with before corrosion. This means that structure of
amorphous Ni-P deposits is stable.
3
before corrosion
after corrosion
Intensity (a.u.)
sample 3
sample 2
sample 1
15 20 25 30 35 40 45 50 55 60 65 70 75
Fig 5 X-ray diffraction patters for different deposits before and after
corrosion.
7
B B
4. Conclusions
The Ni-P deposits with different contents of
nanocrystalline phase could be obtained through adjusting
the process of electroless. The microhardness increased
with the increasing of nanocrystalline phase. The
B B B B
increasing of nanocrystalline phase could improve the
thermal stability, the crystalline temperature shift higher
temperature. However, the experimental results of
corrosion resistance also showed that the nanocrystalline
phase deteriorate the corrosion resistance. The almost
whole amorphous matrix has the best corrosion resistance.
References
[1] A. Bai et al., Mater. Chem. Phys. 82 (2003) 93.
[2] I. Bakonyi et al., Z. Metallkd. 77 (1996) 425.
[3] M.C. Garcia-Alonso et al., Corros. Sci. 38 (1996) 515.
[4] W. Sha et al., J. Alloy Compd. 182 (1992) L1.
[5] Y. Gao et al., Mater. Sci. Eng. A 381 (2004) 98.
[6] T. Mimani et al., Surf. Coat. Technol. 79 (1996) 246.
[7] B. W. Zhang et al., Mater. Sci. Eng. A 281 (2000) 286.
[8] Y. S. Huang et al., Surf. Coat. Technol. 201 (2007) 5416.
[9] H.S. Yu et al., Surf. Coat. Technol. 148 (2001) 143.
[10] H. Ashassi-Sorkhabi et al., Appl. Surf. Sci. 185 (2002) 155.
[11] H. Ashassi-Sorkhabi at al., Surf. Coat. Technol. 176 (2004) 318.
 Domain wall pinning effects.. 1

JCACS
2007

Domain wall pinning effects in the dilute Cu-doped perovskite LaMn1-

xCuxO3 manganites
Tian Gao, Shixun Cao, Jincang Zhang, Liming Yu, Baojuan Kang, Shujuan Yuan
Department of Physics, Shanghai University, Shanghai 200444, China

Abstract

The magnetic properties of the dilute Cu-doped LaMn1-xCuxO3 have been studied in the temperature range of 2~300 K. A visible
unexpected drop is observed in the ac susceptibility and the zero field cooled dc magnetization curves for xd0.10 near 100 K, which
depends on the measuring frequency and field. Measurements on frequency dependence for the ac susceptibility, observation of magnetic
relaxation, and the existence of critical field, indicate that it can be attributed to the domain wall pinning effects. This is directly proved by
the results of ball milled nano-sized powder counterparts compared with the bulk materials.

Keywords: manganites, domain wall pinning effects, ball milling

and the domain wall pinning effects can be confirmed by

1. Introduction
The study on the magnetic properties at low
temperatures has been an interesting object for the past 10
years for the perovskite manganites,1-3 which is known to
be one of the future promising resources in detecting and
recording magnetic signals. It is well known that LaMnO3
matrix is a type of A-type antiferromagnetic (AFM)
insulators, and dilute substitution with other magnetic or
transition elements for Mn can induce strong
ferromagnetism at low temperatures.4-6 In this work, the
magnetic properties are investigated in bulk and powder
materials of LaMn1-xCuxO3 (0<xd0.40), and a visible
unexpected drop is observed in the samples with xd0.10 at
temperatures much below TC. Such an anomalous
behavior has been observed in several other works on La1-
7 8 9
xMnO3, La0.9Ca0.1MnO3 and La0.85Ca0.15Mn0.95Fe0.05O3
etc., but the mechanism is still not clear. Sankar et al.7
studied the magnetic properties of the self-doped
lanthanum manganites, and ascribed the anomaly to the
domain wall pinning effect, which varies with the degree
of self-doping or Mn4+ concentration. Sudyoadsuk et al.10
believe that the anomalous behaviour in La0.86Ca0.14Mn1-
yCryO3 is caused by the re-entrant spin glass transition and
the spin freezing temperature is at T~100 K. However,
both of them have no direct evidence for their conclusions.
Therefore, it is definitely worthwhile to clarify the
intrinsic mechanism of the anomalous behavior in
perovskite manganites. The anomalous behavior in dilute
Cu doped LaMn1-xCuxO3 system is studied systematically,
the measurement results, and is directly proved by the
magnetic data of ball milled LaMn1-xCuxO3 powders by
reducing the grain sizes compared with the bulk samples.
2. Experimental
The compounds LaMn1-xCuxO3 (0.05, 0.10, 0.20, 0.30,
0.40) were prepared by the standard solid state reaction
method, and x-ray powder diffraction confirmed that all
samples were in high purity. The temperature dependence
of the ac susceptibility was measured at different
frequencies in the temperature range of 2-300 K using the
physical property measurement system (PPMS-9T) made
by Quantum Design Inc. The dc magnetizations were
recorded under different applied magnetic fields while
warming after the sample cooled in zero or a certain
corresponding field from room temperature using the
vibrating sample magnetometer (VSM option on the
PPMS-9T). The magnetization after cooled in zero fields
was also performed versus time up to 5000 seconds at
different temperatures with the VSM option.
3. Results and discussion
The temperature dependence of the ac susceptibility
for LaMn0.95Cu0.05O3 at different frequencies is displayed
in figure 1. On lowering the temperature, the real part
(M) of the ac susceptibility rises sharply while the virtual
part (M) shows a corresponding sharp peak at TC ~157
2 S. Cao et al.

K, indicating the strong ferromagnetic ordering which is
commonly existed in the perovskite manganites at low
temperatures.11-14 And the TC is immutable with the
frequency altering. However, when the temperature
decreases to about 100 K, the real part drops abruptly and
the virtual part shows a corresponding sharper peak than
that at TC. And the peak shifts to higher temperature with
increasing frequency (plotted in the inset of Fig.1). Such
frequency-dependence behavior is different from the spin
glass regime,15,16 in which the peak should systematically
not only shifts toward higher temperature but also
decreases in height with the increases in frequency. It is
clear that the height of the peak near 100 K doesnt
decrease in figure 1. Therefore, the anomaly is not caused
by spin glass, nor cluster glass freezing. In fact, there
have been many studies on well-defined ferromagnetic
and ferrimagnetic systems showing frequency dependence
of the features in the ac susceptibility below TC. For
example, the neutron diffraction studies on the
ferrimagnetic oxide YFeMnO5 show magnetic ordering
down to 2.9 K, whereas a frequency dependence of the ac
susceptibility is observed below TC=165 K.17 Fe3O4, the
well known ferrimagnetic oxide, exhibits a frequency
dependence of a low-temperature anomaly in the ac
susceptibility, and this has been ascribed to the freezing
out of domain wall motion due to the rearrangement of
the electron states within the domain walls.18 Similarly,
studies on single crystals of FeCr2O4 suggest that domain
wall pinning effects are responsible for the similar
features.19
magnetization declines slowly down to about 100 K and
then shows an unexpected drastic decrease in ZFC
magnetization. Thermomagnetic irreversibility
(divergence of FC and ZFC magnetizations) is a common
feature observed for ferromagnetic manganites,20,21 which
was earlier thought to be a characteristic feature of spin
glasses. In fact, a large magnetic relaxation effect is
observed in the temperature region where the anomaly is
observed. The inset in figure 2 shows the time
dependence of the ZFC magnetizations of
LaMn0.95Cu0.05O3, measured at three different
temperatures as indicated in the figure: (1) 60 K, where
the corresponding ZFC dc magnetization becomes almost
constant after the anomalous decrease, (2) 85 K, where
the maximum slope change is observed, and (3) 105 K,
slightly above the anomaly. For each measurement, the
sample was cooled from room temperature down to the
required temperature in zero field, and then the
magnetization was recorded as a function of time
immediately after applying a magnetic field of 50 Oe. It
can be seen that there is no appreciable variation in the
magnetizations for cases (1) and (3), whereas the
magnetization continuously increases with time in case
(2). A large magnetic relaxation effect is usually observed
at the temperature where the domain walls is in the
process of being unpinned,22 and a high driving field is
required to overcome the pinning forces. The origin of the
relaxation processes can be attributed to the temperature
dependence of the magnetocrystalline anisotropy after
applying a magnetic field.

110
0.6 0.05 3.0
105
T (K)

0.5 100 2.5

0.04 ZFC
f

95
M'(emu/g)

0.4
M''(emu/g)

90 2.0 FC
M(emu/g)

10 100 1000 10000 0.03

0.3 f (Hz) 1.5
2.7

33 Hz 0.02 2.6 H=50 Oe

0.2
1.0
M(emu/g)

331 Hz 2.5
T=60K
1000 Hz 0.01
0.1 2.4 T=85K
T=105K
7771 Hz 0.5 2.3

0.0 0.00 10 100 1000 10000

50 100 150 200 250 300 350 0.0 time (sec)

T(K) 0 50 100 150 200 250 300

Figure 1. Temperature dependence of the ac susceptibility of
LaMn0.95Cu0.05O3 at different frequencies with hac=10 Oe. The inset
displays the frequency dependence of the peak of virtual part of the ac
susceptibility near 100 K.
The similar phenomenon is observed in the
temperature dependence of the dc magnetizations for the
present dilute doped LaMn1-xCuxO3 (x=0.05 and 0.10)
after zero field cooling (ZFC) and 50 Oe field cooling
(FC). Figure 2 shows the case for LaMn0.95Cu0.05O3.
According to the dc magnetization measurements, there is
a PM-FM transition at about 157 K. The FC and ZFC
magnetizations have the same value around and above
157 K. Below 157 K, the FC magnetization rises slowly
with the decrease of temperature down to 2 K while the
T(K)
Figure 2. Temperature dependence of the magnetization for
LaMn0.95Cu0.05O3 under applied field of 50 Oe after zero field cooling
(ZFC) and 50 Oe field cooling (FC). Inset: Time dependence of the ZFC
magnetization of LaMn0.95Cu0.05O3 recorded at three different
temperatures, as indicated by arrows in the ZFC magnetization curve,
H=50 Oe.
In order to get an insight into the anomalous behavior,
we carried out the measurement of ZFC magnetizations of
LaMn0.95Cu0.05O3 in different dc magnetic fields, as
shown in figure 3. A systematic change in the ZFC
magnetization behavior is observed with the applied field
increasing, and no anomaly can be observed when it
reaches 800 Oe. The magnetization increases
continuously with decreasing temperature when measured
 Domain wall pinning effects..
using higher magnetic fields ( 500 Oe). This directly
indicates that there exists a critical field, above which no
drop could be observed below TC in the ZFC
magnetizations. In addition, the difference among the
ZFC magnetizations, recorded at different fields,
decreases continuously with increasing temperature and
magnetic field. That is, the unexpected drop appears to be
originating from some features which can be affected by
sufficient activation energy in the form of high thermal
activation and strong magnetic field. It is true that a high
magnetic field can shift the domain walls and completely
destroy the pinned state at low temperature when the field
is higher than the pinning field.23 This can also be
approved by the demagnetized MZFC(T) measurements,
recorded at 50 Oe in warming after applying and then
degaussing a field from the ZFC sample. The anomaly
exists in lower demagnetized field (100 Oe) but not in
higher field (10000 Oe). This gives an evidence to the fact
that the decrease in magnetization is not caused by any
kind of magnetic transition which would have been
reflected in both FC and ZFC measurements and would
not have been destroyed after degaussing the sample at
low temperature.
1.0
0.8
M/Mmax
0.6 50 Oe
100 Oe
0.4 200 Oe
250 Oe
0.2 500 Oe
800 Oe
0.0
0 50 100 150 200
T(K)
Figure 3. Zero field cooled magnetization curves of LaMn0.95Cu0.05O3
measured at different dc magnetic fields.
The above phenomena indicate the anomalous
behaviour should be associated with domain wall pinning
effects. There are two aspects to answer for the frequency
and field dependence behaviors, as well as the large
magnetic relaxation effects in LaMn0.95Cu0.05O3. Magnetic
domains are formed as soon as the sample is cooled below
TC24. Firstly, when field cooled, the moments of domains
are aligned to the field direction, and considerable domain
wall displacement takes place depending on the applied
field strength. The magnetization continuously increases
with the decrease of temperature because of the
decreasing thermal energy. Furthermore, the domains can
not freely rotate below the pinning temperature so that the
magnetization at a given field is not further affected and a
higher external field is needed to overcome the pinned
state. Upon zero field cooling the domains are pinned into
random orientations. When a low field is applied there is
3
a competition between the random local magnetization
orientation of the individual domain and the applied
magnetic field, and the former dominates the competition,
therefore the magnetization will be lower than expected.
However, when it exceeds a certain value, the high
applied field can unpin the domain walls and make the
most of domains align to the field direction. The pinned
domain walls can also be activated by increasing the
temperature so that the thermal activation takes place.
Therefore, the magnetization increases slowly with
increasing temperature, and a visible jump takes place at
the temperature where the pinning effects are overcome.
Similarly, when a larger magnetic field is applied and
degaussed at low temperature, the applied magnetic field
is sufficient to overcome the barrier for the wall
displacement and, therefore, no jump in the ZFC
magnetization is observed at the right temperature. The
domain wall pinning effects are probably destroyed or the
domains move into a metastable state because of the high
energy of the strong field during the process of field
degaussing.
0.5 (b) 2.0
(a) 0h
0.4 9h 1.5
18 h
M'(emu/g)
M(emu/g)
0.3
1.0
0.2 f =331 Hz
0h
0.5
0.1 9h
18h
0.0 0.0
0 50 100 150 200 250 300 0 50 100 150 200 250 300
T(K) T(K)
Figure 4. (a) Real part of the ac susceptibility (hac=10 Oe, f=331 Hz),
(b) ZFC magnetization curves (H=50 Oe) of LaMn0.97Cu0.03O3 for
different ball milling time.
To clarify if the anomalous drop also exists in lower
doped LaMn1-xCuxO3, we prepared the lower doped
LaMn0.99Cu0.01O3 and LaMn0.97Cu0.03O3 samples
renewedly, and also found the identical anomaly in ac and
dc magnetic measurements at the same temperature.
Therefore, the anomaly commonly exists in the dilute
doped LaMn1-xCuxO3 (0<xd0.10) manganites. Then, we
ground the sample with x=0.03 into different-size
powders by ball milling method. Figure 4 shows the data
for the samples with different ball milling time. With the
increase of milling time the drop near 100 K becomes
tempered gradually, and finally disappears in both ac
susceptibility and ZFC dc magnetization curves when the
milling time reaches more than 18 hrs. Furthermore, we
also estimated the sizes of the crystalline grains of both
the bulk and the ball milled powder materials from XRD
data. We found that the grain sizes of powders are close to
that of bulks when the milling time is less than 18 hrs
while the former is slightly smaller than the latter when it
is more than 18 hrs, which is the order of several hundred
nm. The reason is that the domain walls are destroyed
after long time ball milling, so that the domain wall
pinning effects can not appear when decreasing the
4 S. Cao et al.
temperature. And the magnetization decreases with the
increase of milling time because of the smaller grain sizes
than the bulk materials. The experiment results on the
measurement of ball milled powders directly verified that
the low-temperature anomalous drop behavior of
magnetization near 100 K is not caused by AFM
transition or spin freezing/spin glass, and it is mainly due
to the domain wall pinning effects. Finally we also found
the similar behavior in dilute doped La0.7Ca0.3Mn1-xCoxO3
and Pr0.5Ca0.5Mn1-xCrxO3 manganites. So the unexpected
drop in magnetic properties, induced by domain wall
pinning effects, may commonly exists in dilute doped
perovskite manganites.
The anomalous behavior in dilute Cu doped LaMn1-
x Cu xO3 manganites is studied systematically, and the
domain wall pinning effects can be confirmed by our
measurements on (1) frequency dependence for the ac
susceptibility, (2) magnetic time relaxation effect at the
temperature where the anomaly is observed, (3) the
existence of critical field above which the anomaly
disappears, and (4) the demagnetized MZFC(T)
measurements recorded at 50 Oe in warming after
applying and then degaussing a field from the ZFC
sample. And this is directly proved by the results of ball
milled LaMn1-xCuxO3 powders by reducing the grain sizes
compared with the bulk samples.
Acknowledgement
This work is supported by the National Natural
Science Foundation of China (Grant Nos.10674092,
10574087, 10504019), the Specialized Research Fund for
the Doctoral Program of Higher Education (SRFDP, No.
20050280004), Shanghai Nano-technology Promotion
Center and the Science & Technology Committee of
Shanghai Municipality (No.0652nm046), and the
Shanghai Leading Academic Disciplines Project
(No.T0104).
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 Observations of the influence of Y-211.. 1

JCACS
2007

Observations of the influence of Y-211 inclusions on melt

textured growth process of Y-Ba-Cu-O single domain
Ke-xi Xu
Physics Department, Shanghai University, Shanghai 200444P. R. China

Abstract

Single domain Y-Ba-Cu-O(YBCO) samples composed of YBa2Cu3O7-(Y-123) matrix with Y2BaCuO5(Y-211)

B B B B B B B B B B

inclusions were fabricated by using top-seed melt textured growth (TSMTG) process. The influence of the
Y-211 inclusions on the melt textured growth mode has been studied for the precursor pellets with the ratio of
Y-123:Y-211 in 1:0.2, 1:0.3 and 1:0.4 in molar. The surface morphologies obtained from these sintering pellets
quenched from 1000 oC, 997 oC and 994 oC, respectively, have revealed that the initial peritectic recombination
P P P P P P

process near the seed crystal seems to take place earlier for the Y-123 matrix with low Y-211 inclusions than for
that with the high lever of Y-211 inclusions, and that, however, the melt textured growth rate of the single
domain seems to be faster in high Y-211 inclusion system than in the low one.

Key words: Melted Textured Growth, YBCO single domain, Y211 effects

1. Introduction Therefore, it is necessary to make an attempt to

Large cross-section of Y-Ba-Cu-O (YBCO) single
domain bulk is desirable for industrial
applications because of its capability of trapping
very high magnetic fields. However, the
explore the growth kinetics of this kind of
materials, especially for the solidification
dynamics around the seed crystal.
It has been known that in melt-textured growth
(MTG) process, YBa2Cu3O7-(Y-123) single B B B B B B

production of this type of single domain with a domain growth is promoted by peritectic
diameter larger than 50mm has technological recombination of Y2BaCuO5(Y-211) particles and
B B B B

difficulties such as a slow growth rate and a liquid phase consisting of BaCuO2 and CuO [9]. B B

relative narrow growth window, resulting in The rear earth ions Y3+ needed for the nucleation
P P

unwanted spontaneous nucleation during the
growth processing. In order to overcome those
difficulties some research groups[1-3] are now
making effort to develop new generation of Light
Rear-earth Barium-Cupper-Oxide (LReBCO)
superconductor bulk, where Re=Nd, Sm, Eu and
Gd, which is believed with high Tc and Jc, and
B B
with faster growing rate compared to YBCO .
Other groups [4-8] are interested in developing
new type of generic seed crystal for producing
large size of single domain bulks of Y-based
materials and LRe-based ones. Although many
valuable works have been made in the field
mentioned above, the growth kinetics in the
process is still not understood completely for this
kind of materials. This situation obstructs, to a
certain extent, the fabrication progress of the large
and high grade of single domain ReBCO bulks.
of the Y-123 phase is provided by the
decomposition of Y-211 particles in the liquid.
When this decomposition process is relatively
slow with respect to the peritectic recombination
process some of the Y-211 particles will be
trapped in the Y-123 matrix, resulting in residual
B B solidified liquid phase in the matrix. These
residual solidified liquid phase dramatically
reduce the superconducting properties of the bulk.
In order to consume the residual liquid phase
during the growth process, extra Y-211 inclusions
are usually added to the precursor bulk. In contrast
to the residual solidified liquid phase, the Y-211
particles trapped in the final matrix have positive
effects on the superconducting properties.
Up to now, there have been many
investigations about influence of the Y-211
particles on the superconducting properties of the
2 K. Xu
MTG-YBCO bulk, such as the Y-123/Y-211
interfaces are suspected to be good pinning center
[10-13], and the addition of Y-211 particles allows
one to reduce the loss of liquid phase and also to
enhance the mechanical properties of the domains
[14-16]. However, the investigations about the
influence of the Y-211 inclusions on the growth
process, especially on the initial stage of
crystallization around the seed crystal, have not
yet been reported.
In this paper, the initial growth process around
the seed crystal for the top-seed melt textured
process (TSMTG) has been studied by using the
YBCO pellets with 20 mol%30 mol%and 40
mol% Y-211 inclusions, respectively. All those
pellets were prepared with the same batch of
Y-123 and Y-211 precursor powders, and then
treated with the same heat treatment program. In
order to observe the influence of the Y-211
inclusions on the initial stage of the growth
process the pellets were quenched at the
temperature, from where the initial growth process
around the seed crystal is suggested to start. By
observing the surface morphology of these
quenched samples, we find that the initial
solidification behaviors around the seed crystal
seem to be different for those pellets. For the
pellet with 20 mol% or 30 mol% Y-211 inclusions,
the initial solidification process takes place earlier,
with about 2oC in advance, than the pellet with 40
P P
mol% Y-211 inclusions does. This indicates that
the peritectic combination temperature Ts of the
B B
Y-123/Y-211 system might be affected by the
amount of the Y-211 inclusions involved. If this
assumption is universally acceptable the growth
window of the TSMTG process would be
adjustable via changing the Y-211 inclusions.
Additionally, our experiment also reveals that the
melt-textured growth rate of the single domain
seems to be faster for the pellet with the 40 mol%
Y-211 than the 30 mol% Y-211. This result is
supported by the present growth model of the
TSMTG.
2. Experiments
The chemical reagents of Y2O3 (99.99%),
B B B B
CBaO3(99.9%) and CuO(99.5%) were mixed with
B B
molar ratio of 2:1:1 to synthesize Y-211
composition, which is then sintered within a box
furnace at 950 oC for 20 h. The sintered Y-211
P P
powders were then milled for 3 h using ZrO2 balls
in acetone. The size of the as-made Y-211 powder
was analyzed with special instrument, and an
average size of 6.5m in diameter was obtained.
The Y-123 composition was made in same way as
the Y-211 composition, except for the sintering
o
P C
P
1045
1010
Ts B B
930
t
Figure 1. Heat treatment temperature profile
for pellets with Y-211 inclusions of 20 mol%
30 mol% and 40 mol%, and a quenching is
applied to the system at Ts. B B
temperature at 960 oC for 20 h. These Y-123 P P
powders were then mixed with Y-211 powders in
molar ratio of Y-123: Y-211 = 1: 0.4, 1: 0.3, and1:
0.2, respectively, and with addition of 0.5 wt%
CeO2 chemical reagent to each one. The mixed
precursor powder was uniaxially pressed into a
pellet with 20mm in diameter. A Sm-123 (001)
crystal fabricated by TSMTG process was used as
seed, which was centrally placed on the top of the
pellet. In order to study the effects of the Y-211
inclusions on the initial growing process at the
vicinity of seed, three pellets with Y-211
inclusions of 40 mol%30 mol%20 mol% were
put together into a vertical tube-type furnace,
undergoing a same heat treatment. Those
precursor pellets were heated to 930 oC at a rate of
P P
100 oC / h holding for 5 h, and then heated to 1045
P P
o
C holding for 1 h, from where they were cooled
P P
to 1010 oC with a rapidly cooling rate, and then
P P
slowly cooled at a rate of 0.3 oC / h to Ts , a
P P B B
temperature from where the initial peritectic
combination process around the seed is supposed
to take place. When the samples reach to the
temperature Ts, they were quenched with a rate of
B B
250 oC/ h -300 oC/ h. The purpose of the
P P P P
quenching application is to catch original initial
growing mode at the earlier stage of the TSMTG
process, from which the influence of the Y-211
inclusions on the initial growing behavior could
be studied by observing its surface morphology.
The pictures of the surface morphologies of the
quenched samples were taken with a digital
camera via an X20 optical microscope. In fact, the
actual value of Ts for each of the samples is hardly
B B
determined precisely, and therefore some
B B
evaluations for Ts have been made in the practical
B B
heat treatment. In our experiments, the actual
value of Ts was estimated near 1000 oC according
B B P P
to our previous experiences, and therefore three
temperatures of 1000 oC, 997 oC, and 994 oC were
P P P P P P
chosen, from where the quenching was applied.
2
 Observations of the influence of Y-211..
Figure 1 gives out the illustration of the heat
treatment profile, and figure 2 shows the surface
morphologies of the pellets. In the discussions
below, the above samples were nominated as
1000-20%1000-30%1000-40%997-20%
997-30% 997-40% 994-20% 994-30%
994-40%, where the left-side of the nominative
indicates the quenching temperature and the
right-side symbolizes the Y-211 inclusions for
each sample.
3. Results and discussion
In figure 2, there are nine pictures of the surface
morphologies of the samples, which are arranged
in such a way that those with the same quenching
temperature are arranged in one row and those
with the same amount of Y-211 inclusions are
arranged in one column. By observing the
morphologies quenched from 1000 oC, it can be
P P
found that there is a dark area appearing closely
around the seed crystal for each of the three
pellets, and that the color of this dark area turns
into darker and darker with the Y-211 inclusions
decreasing from 40% to 20%. Additionally, in the
area away from the central seed there are some
nucleation signs randomly distributed in sample
1000-20% and the 1000-30%, but there is no such
indication for sample 1000-40%. Further close
observation to sample 1000-20% and the
1000-30% could also find some detailed
difference in morphology for both of them.
Although we have not yet understood the physical
origins of the dark area phenomenon around the
seed, its growing behavior affected by the amount
of Y-211 inclusions is obviously observed.
In order to reveal further the effects of Y-211
inclusions on growth mode of the single domain
the second group of precursor pellets were used,
which were also inclusive of 20%30% and 40
Y-211 inclusions. This group of pellets was
undertaken the same heat treatment as the first
group did, but quenched from 997 oC, not from
P P
1000 oC. The corresponding morphologies of the
P P
quenched are showed in the middle row of figure
2, from where we can find that the surface of the
sample 997-30%, or 997-20%, presents a
polycrystalline structure characterized by a
collection of randomly distributed Y-123 phase
grains. However, for the sample 997-40% the
surface morphology is quite different. There is no
collection of the randomly distributed Y-123 phase
grains on its surface, only with the appearance
quite similar to that of sample 1000-30%. The
difference in the morphologies between sample
997-40% and the 997-30% could be reasonably
attributed to the different amount of Y-211
3
inclusions involved in each of them.
It has been known that the formation of the
Y-123 phase in the melt textured growth process is
based on two peritectic reactions [17]; one is
so-called the peritectic decomposition process
occurring at temperature Tp, where the solid Y-123 B B
phase is decomposed into a solid Y-211 phase and
a Ba- and Cu-rich liquid phase according to the
equation: 2YBa2Cu3O6.5Y2BaCuO5 + 3BaCuO2 B B B B B B B B B B B B
+ 2CuO, and the other is called peritectic
recombination process occurring at temperature
Ts (Ts < Tp), where the solid Y-123 phase is then
B B B B B B
reformed according to the reaction: Y2BaCuO5 + B B B B
Liquid 2YBa2Cu3O6.5. The difference between B B B B B B
Tp and Ts is the measuring of the system
B B B B
undercooling. When the pellet is well-controlled
to undergo a small undercooling near Ts, a suitable B B
driving force will be produced within the pellet
matrix. Under this driving force the Y3+ ions P P
separated from the Y-211 particles will diffuse
through the liquid with a well-matched speed to
front of the Y-123/lioquid interface, where they
reacts with the local solution to form a new Y-123
phase with a textured single domain structure. In
other case, a randomly distribution of the Y-123
grains would be produced if the pellet is applied to
a large undercooling near the temperature Ts. B B
According to this growth model it could be
thought that the reason why a well-textured single
domain has not been formed for the case showed
in the middle row of figure 2 is possibly that the
peritectic recombination temperature Ts for the B B
sample 997-30% and the 997-20% is just located
near below 997 oC. When these pellets were P P
treated at high temperatures above 997 oC, the P P
chemical potential of this composite system is not
strong enough to promote the nucleation of the
Y-123 phase until the temperature was decreased
down to near Ts, from where a well-textured B B
single domain growth processing will take place
around the seed. However, this process was now
interrupted by the quenching applied near the
temperature Ts. The quenching provided an
B B
extremely large undercooling that produces a large
local thermodynamic driving force to speed up the
local nucleation of Y-123 phase, and thus an
unwanted spontaneous nucleation of Y-123 phase
would be formed within the pellet matrix. The
corresponding polycrystalline structure was just as
showed in samples 997-30% and 997-20%.
However, for sample 997-40%, it still presents a
pre-solidification morphology as the one showed
in sample 1000-30%. This result tell us that the
peritectic recombination temperature Ts for B B
sample 997-40% is still far below from 997 oC, P P
otherwise it should give out the similar growing
morphologies as the others do. By comparing
 4 K. Xu
a 1000-20% b
000-20% 1000-30%
994-40%
d 997-20% e
997-20%
g
994-20% h
94-20% 994-30%
Figure 2. Pictures of the morphologies for pellets with Y-211 inclusions of 20
mol%30 mol% and 40 mol%, and quenched at temperatures of 1000 oC
997 oC and 994 oC, respectively.
P P P P
these morphologies showed in the second row of
figure 2, we can make assumption that the higher
Y-211 inclusions system might have a lower value
of the peritectic recombination temperature Ts.
If we dont interrupt the growing process by
quenching the pellets at 997 oC the well-texture P P
growth process around the seed crystal will start
after temperature Ts. In order to understand what
B B
would happen after Ts the third group of pellets B B temperature Ts of the pellets with 20%mol and
was used to observe their growing mode. Those
pellets were applied to undergo the same heat
treatment program as the other two groups did, but
quenched at 994 oC. In the pictures on the bottom
P P
row in figure 2, the characteristics of the growth
behavior within the temperature range from 997
o
PC to 994 oC have been illustrated. From those
P P P a lower peritectic recombination temperature Ts as
figures, a single domain around the seed crystal
can be clearly observed for all of these pellets.
The surface of the single domain is characterized
by the presence of parallel lines perpendicular to
the macroscopic growth direction of the domain.
Under higher magnification it is observed that
these lines are composed of Y-123 phase layers
with parallel edges and therefore correspond to the
a- or b-axis facet lines derived from the tetragonal
symmetry in the a-b plane of the single domain
[18]. This is because the Y-123 phase has a
tetragonal crystal structure at the grain growth
temperature. These lines are indicative of the
crystallographic structure and are not
superconducting current limiting grain boundaries
[19]. The presence of continuous facet lines in this
region results from a uniform grain growth in the
1000-30% c 1000-40%
997-30% f 997-40%
994-30% i 994-40%
P P
vicinity of the seed and a homogeneous
microstructure result [9]. When the distance from
the seed increases, the continuous facet lines are
B B interrupted by a random distribution of the Y-123
grains. This randomly distributed grains region
gives the same surface morphology as the ones
showed in samples 997-20% and 997-30%, which
further confirms that the peritectic combination
B B
30% mol Y-211 inclusions is just near 997 oC. P P
As for the sample 994-40%, we can find that
the quenched pellet also presents a well-textured
single domain around the seed, and the size of the
single domain seems to be equal to that of two
others. This is because the 40% Y-211 system has
B B
suggested in the previous section, and here we
suppose it to be 995 oC, with a 2 oC decreasing in
P P P P
comparison with that of the 30%Y-211 system.
When these two different pellets were put together
and cooled down slowly from above Tp to below B B
Ts such as 994 oC, the peritectic recombination
B B P P
process would take place first within the
30%Y-211 pellet, and then the 40%Y-211 one.
The textured growth processing for both of them
will be carried out under way until the quenching
is applied at 994 oC. During this period, the time
P P
spent in the well-textured growth process is
different from each other, the 30%Y-211 system
with a longer effective growing time and the 40%
Y-211 system with a shorter one. If we suggest the
40% Y-211 system has a higher growth rate the
question about the same size in single domain for
4
 Observations of the influence of Y-211.. 5

them can be answered. This question can also be

interpreted in terms of the present growth model
a b
of TSMTG [20], in which the rate of peritectic
recombination of yttrium ions and BaCu- rich
liquid is determined mainly by the diffusing time
of yttrium ions through the liquid. When the
density of Y-211 particles is increased the
diffusion distance of the Y3+ ions will become P P
060507-1 060507-2
smaller, and so the recombination process will be
performed in a shorter time. c d
There is another experiment that supports the
above discussions. Figure 3(a-d) presents the
growth morphologies of hexagonal MTG-YBCO
pellets with Y-211 inclusion of 30 mol% and 40
mol%. The corresponding temperature profile of 060521-1 060521-2
the heat treatment for these pellets is showed in
figure 4, where To indicates the temperature where
B B
Figure 3. The growth morphologies of
the pellets were dwelling for 1.5 hours to ensure a hexagonal MTG-YBCO pellets, (a) and (c)
complete decomposition of the Y-123 phase into with Y-211 inclusions of 30 mol%, (b)
Y-211 and liquid, and T1 indicates the temperature B B and (d) with Y-211 inclusions of 40
from where a slow cooling rate is applied to mol%.
promote a well-controlled textured growth, and T2 o
C
B B

indicates the temperature from where the system

P P

ToB B

is quenched with a large cooling rate. All these

pellets were treated with the same heat treatment T1 B B

temperature profile. For the pair of pellets

T2
060507-1(30%Y-211) and 060507-2(40%Y-211),
B B

930
T1 = 1005 oC, and T2 = 976 oC, and the cooling
B B P P B B P P

rate in the growth window (T1T2) is 0.3 oC/h, B B B B P P

and for another pair of pellets

060521-1(30%Y-211) and 060521-2(40%Y-211)
the same heat treatment program was used , only
the setting value for T1 in the program was B B
t
changed from 1005 oC to 997 oC . P P P P
Figure 4. Temperature profile of the heat
According to the morphologies showed in treatment for the hexagonal MTG-YBCO
figure 3(a-b), we can find that the first pair of pellets with Y-211 inclusions of 30 mol% and
pellets present the different growing behavior 40 mol%, where appropriate setting for T1 is B B

from each other. The pellet 060521-1 gives out a quite important to the growth process.
relatively larger grown-up single domain around
the seed, and the 060521-2 does a smaller one, within the pellets would grown large in size due to
although there is still a part of non-textured region the Oswald ripening phenomenon at high
surround the textured single domain. When the temperature in the melt[21]. It has been known
setting value for T1 was moved from 1005 oC that as the average diameter of the Y-211 particles
increase to a critical size the resolving of the Y3+
B B P P

down to 997 oC, without changing any other heat P P

P P

treatment parameters, the pellets were grown up from the Y-211 particle would be suppressed and,
completely, as showed in figure 3(c-d). in turn, the textured domain growth processing
The results of figure 3(a-d) seem to illustrate would stop. The corresponding situations are
that as the pair of pellets was cooling down from showed in figure 3(a-b).
1005 oC the peritectic solidification around the When the setting value for T1 of the heat B B

treatment is moved down to 997 oC, a temperature

P P

seed first take place within the pellet with P P

30%Y-211 inclusions and then the pellet of that is approximate to the Ts of the 30%Y-211
B B

40%Y-211. Due to the effective growth time is system, the pellets avoided staying in high
different for both systems the size of the grown-up temperature for long time, and the coarsening of
single domain is also different for them. Y-211 particles could be greatly suppressed. The
Additionally, the pellets have stayed in high pellet of 30%Y-211 would first start its textured
temperature (>1000 oC) for long time as they were domain growth from near 997 oC, and after P P

temperature was cooled down about 2 oC from

P P

cooling down from 1005 oC, some Y-211 particles P P

997 oC the 40%Y-211 system then began to grow

P P

P P
6 K. Xu
the textured domain process. Although the growth
rate is different from each other for the pair of
pellets the growth time, however, is sufficient
enough for each of them to grow up into a
complete single domain. This is because the
quenching temperature T2, setting at 976 oC, is far
B B P P
from the setting value of T1. B B
4Conclusion
In this paper, the initial growth process around the
seed crystal for the top-seed melt textured process
(TSMTG) has been studied by using the YBCO
pellets with 20 mol%30 mol%and 40 mol%
Y-211 inclusions, respectively. All those pellets
were prepared with the same batch of Y-123 and
Y-211 precursor powders, and then treated with
the same heat treatment program. In order to
observe the influence of the Y-211 inclusions on
the initial stage of the growth process the pellets
were quenched at the temperature, from where the
Reference
[1] Nariki S, Sakai N, Kita M, Fujikura M, Murakami M
and Hirabayashi I 2006 Supercond. Sci. Technol. 19
S505
[2] Iida K, Babu N H, Shi Y H, Cardwell D A and
Murakami M 2006 Supercond. Sci. Technol. 19 641
[3] Matsui M, Nariki S, Sakai N, Iwafuchi K and
Murakami M 2006 Supercond. Sci. Technol. 19 S601
[4] Cardwell D A, Hari Babu N, Shi Y and Lida K 2006
Supercond. Sci. Technol. 19 S510
[5] Hari Babu N, Shi Y H, Lida K and Cardwell D A 2005
Nat. Mater. 4 476
[6] Muralidhar M, Kono T, Jirsa M, Sakai N, Murakami M
and Hirabayashi I 2006 Supercond. Sci. Technol. 19
S550
[7] Nizhelskiy N A, Poluschenko O L and Matveev V A
2007 Supercond. Sci. Technol. 20 81
[8] Shi Y, Hari Babu N, Lida K and Cardwell D A 2007
Supercond. Sci. Technol. 20 38
[9] Cloots R, Koutzarova T, Mathieu J-P and Ausloos M
2005 Supercond. Sci. Technol. 18 R9
[10] Nariki S, Sakai N, Murakami M and Hirabayashi I
2004 Supercond. Sci. Technol. 17 S30
[11] Obradors X, Puig T, Granados X and Sandiumenge F
2002 Physica C 378381 1
6
growth process around the seed crystal is
suggested to start. By observing the surface
morphology of these quenched samples, we find
that the initial solidification process around the
SmBCO seed crystal seems to be different for
those pellets. For the sample with 20 mol% or 30
mol% Y-211 inclusions, it takes place earlier, with
2oC - 3 oC in advance, than the sample with 40
P P P P
mol% Y-211 inclusions does. This indicates that
the peritectic combination temperature Ts of the
B B
Y-123/Y-211 system might be affected by the
Y-211 inclusions involved. If this assumption is
universally acceptable the growth window of the
TSMTG process would be adjustable to an
optimum temperature range by changing the
Y-211 inclusions. Additionally, our experiment
also reveals that the melt-textured growth rate of
the single domain seems to be faster for the pellet
with the 40 mol% Y-211 than the 30 mol% Y-211.
This result is supported by the present growth
model of the TSMTG.
[12] Hari Babu N, Kambara M, Reddy E S, Shi Y and
Cardwell D A 2005 Supercond. Sci. Technol. 18 S38
[13] Vandewalle N, Ausloos M, Mineur N, Cloots R,
Hong G W and Kim C J 1996 Supercond. Sci.
Technol. 9 665
[14] Kim C J and Hong G W 1999 Supercond. Sci.
Technol. 12 R27
[15] Mathieu J P, Cano I G, Koutzarova T, Rulmont A,
Vanderbemden Ph, Dew-Hughes D, Ausloos M and
Cloots R
2004 Supercond. Sci. Technol. 17 169
[16] Vandewalle N, Pirard E, Cloots R and Ausloos M
1998 PhilMag. Lett. 77 301
[17] Desgardin G, Monot I, and Raveau B 1999 Supercond.
Sci. Technol.12 R115
[18] Lo W, Dewhurst C D, Cardwell D A, Vanderbemden
P, Doyle R A and Astill D M 1996 Appl. Supercond.
4 507
[19] Cardwell D A 1998 Mater. Sci. Eng. B53 1
[20] Masato Murakami, 1992 Melt Processed
High-Temperature Superconductors World Scientific,
pp45-56
[21] Kim C J, Kuk I H, Hong G W, Song T H, Han S C
and Kim J J 1998 Mater. Lett. 34 392
 HRTEM observation of precipitates 1

JCACS
2007

HRTEM observation of precipitates

in excess Mg type Al-Mg-Si-Ag alloy
A.Furihata, J.Nakamura, K.Matsuda*, S. Ikeno
Graduate School of Science and Engineering for Research,University of Toyama, Toyama 930-8555, Japan

Abstract

It is well known that excess Mg causes increased hardness, elongation and extrusion resistance than Al-Mg2Si quasi-binary alloy. The Ag
B B

addition to Al-Mg-Si alloy also causes modification of mechanical properties, particularly its elongation. In this work, the age-hardening of
excess Mg type Al- 1.0 mass% Mg2Si- 0.4 mass% Mg 0.5 mass% Ag (ex.Mg-Ag alloy) alloy has been investigated. It showed an
B B

increase in hardness and age-hardening response. Precipitates in this alloy aged at 523 K have been observed by high resolution
transmission electron microscopy (HRTEM) and classified into five type.

Keywords: excess Mg, Ag addition, Al-Mg-Si, HRTEM

to 1.0mm thickness and then cut into 11cm pieces. After

1. Introduction
Excess Mg added alloy has the property of higher value
in maximum hardness (HVmax) and shortened the time to
achieve maximum hardness in aging treatment compared
with binary alloy[1-2]. Our laboratory has paid attention to
HRTEM images of intragranular precipitates in excess Mg
addition Al-Mg-Si alloy. For instance, there were quite a
large quantity of precipitates, which we classify as -phase,
that had interior angles of 60. On the other hand, we had
reported an increase of tensile strength and uniform
elongation with Ag addition into balanced composition Al-
Mg-Si alloy[3-5].
The purpose of this study is to figure out the influence of
addition of excess Mg and Ag on the aging treatment and
mechanical properties by using Ag addition excess Mg type
Al-Mg-Si alloy. The alloy has been aged and the resulting
intergranular precipitates have been observed by HRTEM
in order to examine the changes of precipitate type by the
mechanical polishing, the samples were solution treated at
848K in an atmospheric furnace for 3.6ks, quenched in ice
water, and then electropolished. AKASHI MVK-E was
used for hardness measurement with a load of 100g, and a
maintained time of 15s. Aging treatment was then done in a
salt bath at 523K. TEM samples were polished by using
two types of electrolyte to make foil: perchloric acid:
ethanol=1:9, and nitric acid: methanol=1:3.
Topcon EM-002B, equipped with energy dispersive X-
ray spectroscopy (EDS)of EDAX, was observed with
accelerating voltages of 120kV and 200kV, and
JEOL4010T transmission electron microscope, equipped
with Noran Instruments Voyager-4 EDS analysis
equipment and post column type energy filter by the Gatan
Company GIF200, was observed at 400kV.
3. Results and discussion
Fig. 1 shows an aging hardness curve and changes of
T

aging condition.. number of density per area for each aging treatment of
ex.Mg alloy and ex.Mg-Ag alloy. The circles represent
ex.Mg-Ag and the squares represent ex.Mg alloy;
2. Experimental furthermore, solid spots indicate hardness and outline spots
indicate number of density. Comparing hardness curves
We used Al-1.0mass%Mg2Si-0.4mass%Mg-
B B
from both alloys indicates that ex.Mg-Ag alloy is harder
0.5mass%Ag alloy (ex.Mg-Ag) for observation and Al- than ex.Mg alloy from early period to later period. Ex.Mg-
1.0mass%Mg2Si-0.4mass%Mg alloy ex.Mg as
B B
Ag alloy shows a rapid increase in the hardness curve in the
comparative material. Samples were tailored to a prescribed early period of aging time. Later, after the period of
hardness peak (into overaging), the curve gently decreases,
thickness by hot rolling and cold rolling the initial ingot.
The samples for Vickers hardness measurement were rolled
 2 A. Furihata et al.

eventually following parallel to the ex. Mg alloy hardness (a)0.48ks,(b)0.96ks, and (c)1.92ks. Fig(a) appears shows
curve the aging time of 0.48ks with inner angle sparsely
T
distributed between 87 and 61. Fig.4(b) shows the aging
1000
time of 0.96ks with the inner
120

Density of Number (m-2)

ex.Mg-Ag
Microvickers hardness /HV

800
100
ex.Mg
80 600

60
400

40

200
20
T

0 0 1 2
0
3
10 10 10 10
asQ
Aging time, t / ks
Figure 1: Age-hardening and Density of Number curves of ex.Mg-Ag and
T

ex.Mg aged at 523K

Figure 2: Bright Field images at near to maximum hardness aging time (a)
ex.Mg-Ag alloy 523K 0.48ks (b)ex.Mg alloy 523K 0.60ks

The number of density increases suddenly after the

T

hardness peak of ex.Mg alloy and then decreases. T

Compared with ex.Mg, the number of density increases

Figure 3: Five type of precipitate (a) random type (b) parallel-type (c)
rapidly from starting period of aging treatment to the peak T

phase (d) phase and (e) parallel-type of innrr angle close to 60

of number precipitate before maximum hardness, and then
decreases gently. angle distributed between 85 and 61; especially small
T

Fig. 2 shows bright field image at close to each maximum

T

inner angles have been pointed out a lot. Fig. 4(c) shows
hardness aging time. These images are observed along the the aging time of 1.92ks with the inner angle distributed
[001] direction of the base phase. Contrast of very small between 81 and 61, especially near 60.Taken altogether,
grains is observed in Fig. 2 (a); these fine grains also the inner angle of the parallelogram accumulates around
appear to precipitate sparsely. Fig. 2 (b) shows needle- 60 at aging pass over.
shape precipitates in high density, aligned in the [100] and T Fig.5 shows the result of frequency of each type of
[010] directions. Therefore, the black dot contrast, which precipitate with respect to aging time. Each inner array has
appears along with the needle-shape, are cross sections of precipitate cross sections that can be separated into the five
needle shaped precipitates. types. A feature of ex.Mg-Ag is that initial stage of aging
Cross section of precipitates were classified into five types,
T

has large number of random type; decrease the amount by

from the arrangement of bright dots, as random-type, providing heat treatment and there will be a lot of parallel-
parallel-type, parallel-type that has near to interior angle of type in period of maximum hardness. Parallel-type that has
60, phase, and phase. Fig. 3 shows HRTEM images of near to interior angle of 60 will then increase and decrease
(a) random-type from aging time, 0.48ks, (e) parallel-type the number of precipitates, and -phase trend then
that has near to interior angle 60 from aging time, 1.92ks, increases afterwards. Additionally, compared with ex.Mg
(c) phase as same aging time as (a), and (d) phase from alloy, there is still random type in the maximum hardness
12ks. in ex.Mg alloy, but it is hardly to say observable in ex.Mg-
Each parallelogram from cross section was focused.
T

Ag alloy. The term of peaking decreases the existence

Particularly, Fig.4(a)-(c) shows the arrangement of a frequency of parallel-type and parallel-type that has near to
parallelogram changing in each aging time, interior angle of 60. Furthermore, -phase will become
 HRTEM observation of precipitates 3

100% at 12ks of ex.Mg alloys but few parallel-type References

observed in same aging time of ex.Mg-Ag alloys. For this
reason, parallel- type might stablize by Ag addition. Also,
the cubic-phase reported for the ex.Mg alloy, was not
observed in ex.Mg-Ag[6]. This might be another influence
of Ag addition.
(a)
[1] Matsuda, K, Yoshida, A, Wada, T, Yoshida, A, Uetani, Y, Sato, T,
Kamio, A, Ikeno, S, J. Japan Inst. Light Metals, Vol.62, pp.718-726,
1998
[2] Suzuki,H, Kanno, M, Shiraishi, Y, .: J. Japan Inst. Light Metals,Vol.28,
pp.233-240,1978
[3] Polmear, I.: Trans. AIME, Vol. 230, pp.1331-1338, 1964.
[4] Matsuda, K., Kido, K., Kawabata, T., Uetani, U. and Ikeno, S.: J.
Japan Inst. Light Metals, Vol. 53, No. 11, pp. 528-533, 2003.
0.48ks
[5] Maeguchi, Y, Yamada, K, Sato, T, Vol.66 No.3 pp.127-130, 2002
[6] Suzuki, H, Kanno, M, Itou, G, .: J. Japan Inst. Light Metals, Vol.32,
pp.290-293,1982

(b) 0.96ks

(c) 1.92ks

Figure 4: Arrangement of a parallelogram changing in each aging time,
T

(a)0.48ks,(b)0.96ks and (c)1.92ks

100 4CPFQOV[RG
0.48ks 1.92ks 12ks RJCUG ex.Mg-Ag 120
80 2CTCNNGNQITCOV[RG 100
2CTCNNGNQITCOCTTC[ENQUGVQq
Microvickers hardness /HV

60 uRJCUG 80
60
40
40
Frequency(%)

Aging hardness of ex.Mg-Ag

20 20
at523K

0 100 101 102 103

0
104
asQ
100 4CPFQOV[RG
RJCUG ex.Mg 120
80 2CTCNNGNQITCOV[RG 100
2CTCNNGNQITCOCTTC[ENQUGVQq
60 uRJCUG 80
60
40
Aging hardness of ex.Mg 40
20 20
at523K

0 100 101 102 103

0
104
asQ
Aging time, t / ks
Figure 5: Frequency of each type of precipitate for aging time
 The effect of Mg2Si content 1

JCACS
2007

The effect of Mg2Si content on the hardness of aluminium

B B

alloys with different aging temperatures

Shumei Wang, Kenji Matsuda * , Susumu Ikeno F F

Graduate School of Science and Engeering for research, University of Toyama, 3190 Gofuku, Toyama, 830-8555, Japan

Abstract

The aging hardness of aluminium alloys was investigated to compare the effect of Mg2Si content on the aging hardenability at different aging temperatures.
B B

The dispersoids, which produced some hardening, were included in the alloy with high Mg2Si content, such that the aging hardenability was not decreased at
B B

higher aging temperature.

Keywords: aluminium alloy, hardenability, Mg2Si

B B

1. Introduction 2. Experimental

Aluminium is essential to modern civilizations The aluminium alloys, obtained in the form of
because of its light weight, strength, and workability. The homogenized sheets, are remarked as quasi-binary alloys:
6xxx series Al-Mg-Si alloys account for a large percentage Al-1.10%Mg2Si (O2), Al-1.15%Mg2Si-0.2%Cr (C2), Al- B B B B

of the total aluminium production in the world because of 1.63%Mg2Si-0.2%Cr (C3), respectively. All specimens
B B

their large increase in strength upon the artificial aging were solution heat treated at 575oC for 1h in a circulating P P

treatment. The importance of the age-hardening response of air furnace, and then cold water quenched. Artificial aging
this family of aluminium alloys leads to the investigation in treatments at three temperatures of 150oC, 200oC, and P P P P

detail of all the phenomena that defines the proper heat 250oC were performed in the corresponding oil bath for
P P

treatment sequence aimed at optimizing the balance of 150oC-, 200oC-aging and the salt bath for 250oC-aging, and
P P P P P P

mechanical properties. On the other hand, the hardening
progress is very complex and difficult to optimize, because
it is governed by many parameters [1], such as the aging
temperature and chemical composition.
The aim of the present investigation is to study the effect
of Mg2Si content on the hardness of alloys with different
B B
aging temperature.
then cold water quenched. Hardness was measured using an
Akashi MVK-EII hardness tester (load: 0.98N, holding
time: 15s). The hardness values reported here represent the
average of at least ten measurements. The test samples,
heat treated and used for hardness measurements, were ~10
10 1mm in size.
Conventional transmission electron microscopy (TEM)
was used to study the development of microstructures. The
specimens for all TEM observations were thinned in a
DBR70A thinner to the thickness of 0.2~0.15mm. The
samples used for aging were ~15mm in length and ~10mm
in width, artificially aged at 200oC in the oil bath to the P P

* Corresponding author. Tel.: +76-445-6841; fax: +76-445-6841.

E-mail address:matsuda@eng.u-toyama.ac.jp
2 S. Wang et al.

peak hardness, and then electropolished using the standard behaviour was influenced by the aging temperature in the
three-step electronic polishing method. TEM observations usual manner: aging at the higher temperature produced an
were performed using Topcon EM-002B. The accelerating earlier but somewhat lower peak hardness compared with
voltage was 200 kV. aging at the lower temperature [2]. On the other hand, both
the quench-in hardness and aging hardness increased with
the increase of the Mg2Si content. B B

3. Results and discussions Fig. 2 shows the difference between the peek hardness
and the quench-in hardness (H), which are indicated in
Fig. 1. There is little difference between the aging
hardenability of O2 and C2 alloys. The aging hardenability
110
(a)
increases by increasing the content of Mg2Si just with B B

100
higher aging temperature (200oC and 250oC). The P P P P

90 difference of alloys with high and low content of Mg2Si

Vickers hardness, H/HV

B B

80 becomes large though the aging hardenability decreases

70 with an increase of the aging temperature, which is
60 smoothed by increase of Mg2Si content. The aging B B

50
hardenability of the alloys with different Mg2Si content B B

40
o
150 C remains similar with each other when the aging temperature
is low (150oC), which agrees with the former results [3].
o
200 C
o
250 C
P P

30
~
~

As1 Q. 10 100 1000 10000 100000

80
Aging time, t/min

70
Ability of aging-harding, H /HV

110
(b)
60
100

90 50
Vickers hardness, H/HV

80

70 40
O2
C2
60 C3
30
50 140 160 180 200 220 240 260
o
o
150 C Aging temperature ( C)
40
o
200 C
o
30 250 C
~
~

As 1Q. 10 100 1000 10000 100000 Fig. 2 Difference of aging hardenability of three alloys
Aging time, t/min

The bright-field images were taken for the C2 and C3

alloys aged at 200oC to the corresponding peak hardness. P P

Fig. 3 (a) indicates the bright-field TEM image of C2 alloy

(c)
120 coarse precipitates with contrast inhomogeneously
110 distributed over a background covered with needle-shape
100 precipitations orientated along the [100]Al and [001]Al zone B B B B
Vickers hardness, H/HV

90
axes. Fig. 3 (b) and (c) indicate the EDS analyses of the
precipitates marked with and in Fig. 3 (a), which
80
H suggest that they can be referred to as -Al(Cr, Fe)Si and -
70
AlCrSi, respectively [4]. If sufficient Mg2Si is present, it B B

60
0
150 C
may be replaced at least partly by (FeCr)MgSiAl
50
o
200 C
o
composition, which will produce some hardening. This
40 250 C
kind of dispersoid is inhomogeneously but widely
~
~

As1Q. 10 100 1000 10000 100000

Aging time, t/min
distributed in the present C3 alloy, which can be seen from
Fig. 4. This is maybe one reason why the hardness of the
C3 alloy is higher than that of the C2 alloy.
Fig. 1 Vickers hardness curves of alloys (a) O2, (b) C2, (c) C3 aged at
different artificial aging temperature

Fig. 1 shows age-hardening curves of alloys aged at

different artificial aging temperatures. The age-hardening
 The effect of Mg2Si content 3

(a) [100] [100]


[010] [010]

100nm 100nm

(b) Fig. 4 Bright-field image of C3 alloy aged at 200oC.

P P

Al

4. Summary

The behavior of age-hardening and precipitation in 6000

aluminum alloys including different Mg2Si contents and Cr
B B

were compared. Both the quench-in hardness and aging

hardness increased with the increase of the Mg2Si content. B B

There is little difference between the aging hardenability

Si Cr Fe (H) of O2 and C2 alloys, but the difference between these
alloys and C3 alloy became large.
C2 and C3 alloys included dispersoids, which should be
(c) -Al(Cr, Fe)Si and -AlCrSi according to EDS analysis.
This dispersoid existed in the matrix inhomogeneously, but
Al widely distributed in the C3 alloy.

Reference

[1] C.D. Mariomark, H. Nordmark, S.J. Andersen, and R. Holmestad, J.

Mater. Sci., 41, (2006) 471.
[2] G. A. Edwardsi, K. Stilier, G. L. Dunlop and M. J. Couper, Acta
mater. 46, (1998) 3893.
Si Cr [3] K. Matsuda, K. Kido, S. Taniguchi, Y. Uetani, and S. Ikeno, J. Jpn.
Ins. Light Met., 52, (2002) 398.
[4] H. Westengen, L. Auran, and O. Reiso, Aluminium, 57, (1981) 797.

Fig. 3 Bright-field image of C2 alloy aged at 200oC (a), EDS analyses of

P P

precipitation (b) and (c).

 Magnetic properties and.. 1

JCACS
2007

Magnetic properties and magnetocaloric effect in Ho1-xErxCo2 B B B B B B

compounds
K. Doi, K.Nishimura * , L. W. Li K.Mori
F F

Graduate School of Science and Engineering for Research,University of Toyama, Toyama 930-8555, Japan

Abstract

A series of single phased Ho1-xErxCo2 compounds were prepared by an arc-melting method. The crystal structure, magnetocaloric effect
B B B B B B

have been investigated by X-ray powder diffraction, and magnetization measurements. The Curie temperature TC decreases linearly from B B

79K to 74K with increase of Er substitution content x. The magnetic entropy change (SM) as a function of temperature in external B B

magnetic fields (0.5 and 1 T) was estimated from the results of isothermal magnetization at various temperatures. The substitution effect on
magnetic properties and the potential application of magnetocaloric effec for Ho1-xErxCo2 compounds were also discussed.
B B B B B B

Keywords: magnetocaloric effect, Ho1-xErxCo2 compounds

order magnetic transition (FOMT) when R=Dy, Ho and

Er. The Curie temperatures are 135, 80 and 32 K for
1. Introduction DyCo2, HoCo2 and ErCo2, respectively [1,5,6]. Reflecting
B B B B B B

the FOMT, these compounds exhibit a large

In recent years, the intermetallic compounds RTM2 (R B B magnetocaloric effect. The magnetic properties and MCE
= rare earth or yttrium, TM = transition metal) belonging in Laves phase pseudobinary compound, such as Er1- B

to the Laves-phase family with a large magnetocaloric xGdxCo2 [7], (Ho,Tb)Co2 [8], and Er(Co1-xNix)2 [9,10]
B B B B B B B B B B B B B

effect (MCE) have attracted considerable attention due to have been systematically studied theoretically and/or
their intrinsic magnetic structures and transport properties experimentally. In this paper, the crystal structure, and
as well as potential applications to the magnetic MCE for Ho1-xErxCo2 compounds have been investigated
B B B B

refrigeration technology [1-4]. MCE is defined as the by X-ray powder diffraction, and magnetization
heating and cooling of a magnetic material when it is measurements.
subjected to a varying magnetic field. Magnetic
refrigeration utilizes the magnetocaloric effect. Magnetic
refrigeration has a number of advantages over 2. Experimental
conventional gas refrigeration, such as high energy
efficiency, and no use of environmentally harmful gases. Polycrystalline samples of Ho1-xErxCo2 (x=0, 0.05, 0.1, B B B B B B

So, it is expected to be an environmentally friendly
alternative cooling method. Magnetic refrigeration
technology has a potential application fields.
The intermetallic rare-earth compounds RCo2 have
attracted much attention due to their interesting magnetic
properties related to the magnetic instability of the cobalt
3d electrons. In these compounds, they exhibit a first
0.15) were prepared by an arc melting method using a
tungsten electrode under an argon atmosphere. Firstly, we
melted the stoichiometric amounts of Ho, Er and Co on
B B the water-cooled copper hearth. Then, the sample was
melted more than six times for homogeneity. Finally, the
samples were annealed at 1000 for 1 week in evacuated
quartz tubes. All the samples were prepared in identical

* Corresponding author. Tel.: +76-445-6844; fax:+76-445-6703.

E-mail address: nishi@eng.u-toyama.ac.jp.
2 K. Doi et al.

conditions. The crystal structures were determined by X-

3
ray powder diffraction experiment (XRD). The [10 ] 8
magnetization measurements were done using a SQUID x=0

Magnetization(emu/mol)
(Quantum Design MPMS) in the temperature range from x=0.05
60 to 90 K and DC magnetic fields with a range from 0 to 6 x=0.1
1.5 T. The results are well repeatable. x=0.15
4 79 H=0.1T
78
77

Tc(K)
3. Results and discussion 76
2 75
74
The XRD spectra were performed on all of the samples 73
0 0.05x 0.1 0.15
and the results are shown in Fig. 1. No impurity peaks 0
were found within experimental errors; all the samples are 60 70 80 90
single phased with the C15 cubic Laves phase MgCu2- B B
Temperature(K)
type structure.

Fig 2. Temperature dependence of magnetization of Ho1-xErxCo2 (x = B B B B B B

0 - 0.15). The inset shows Curie temperature TC vs, Er content x. B B

4
[10 ]
x=0.15 72K
In ten sity (-)

Magnetization(emu/mol)
74K
76K
2
x=0.1 78K
80K
82K
x=0.05 84K
1
(311)

86K
(220)

88K
(511)
(422)
(222)
(111)

(440)
(331)

x=0 0
20 30 40 50 60 70 80 0 0.5 1 1.5
2(degree) Magnetic Field(T)

Fig 1. Powder XRD patterns for Ho1-xErxCo2 (x=0-0.15) system. B B B B B B

Fig 3. Magnetization isotherms of Ho1-xErxCo2 (x=0.05). B B B B B B

The temperature dependence of magnetization (field The magnetic entropy change -SM was calculated B B

cooled) under 0.1 T magnetic field for Ho1-xErxCo2 (x=0- B B B B B B

based on the results of magnetization isotherms using the
0.15) system is shown in Fig. 2. All the samples show a integrated Maxwell relation [11]:
H M (H , T )
steep single paramagnetic-ferromagnetic (PM-FM) S M (T , H ) = dH 
transition. The Curie temperature TC, which is defined as B B
0
T H
the inflection point of M-T curve, is shown in the inset of
1 H
M (T + T , H )dH M (T , H )dH
H
Fig. 2. For all the samples we can note that TC decreases B B

(1)
almost linearly with increasing Er content x. In the past
T 0 0
research, some compounds, such as (Er,Gd)Co2 and B B

(Gd,Tb)Co2 displayed nonlinear phenomenon which was

B B
The -SM was calculated using this technique for eachB B

attribute to the different f-d exchange interaction with sample near its ordering temperature under 0.5 and 1.5 T,
changing content. In our work, the degree of nonlinear is as shown in Fig. 4. All the present samples exhibit large
much smaller than that of those compounds. It might SM values. The maximum values of SM occur almost at
B B B B

result from the smaller difference of the lattice TC. Because the Curie temperature decrease with
B B

parameters and the magnetic properties between HoCo2 B B

increasing Er content, the peak of SM shifts notably to B B

and ErCo2. B B
low temperature. The materials with such high and
Magnetization isotherms of Ho1-xErxCo2 (x=0-0.15) B B B B B B
uniform peaks are useful to design the magnetic
system were measured at selected temperatures near TC, in B B
refrigeration around liquid nitrogen temperature.
which the maximum applied field is 1.5 T. Fig. 3 shows Moreover, the half-peak width was narrow and almost
the typical curves of M-H loops for Ho1-xErxCo2 (x=0.05). B B B B B B
unchanged with increasing x, i.e. all the samples show the
In this figure, data were converted from M-T curves in first order phase transition similar with that of HoCo2 and B B

various magnetic fields. ErCo2. B B

 Magnetic properties and.. 3

From the present results of the large MCE and the tunable
temperature range, Ho1-xErxCo2 compounds appear to be a
B B B B B B

possible candidate for magnetic refrigerant materials

x=0 0-0.5T
x=0 0-1.5T around liquid nitrogen temperature.
3 x=0.05 0-0.5T
-Smag(J/molK)

x=0.05 0-1.5T This work is partially supported by the Takahashi

x=0.1 0-0.5T Industrial and Economic Research Foundation.
2 x=0.1 0-1.5T
x=0.15 0-0.5T
x=0.15 0-1.5T References
1
[1] N. K. Singh, K. G. Suresh, A. K. Nigam, S. K. Malik, A. A. Coelho,
S. Gama, J. Magn. Magn. Mater. 317 (2007) 68.
0 [2] P. J. von Ranke, D. F. Grangeia, A. Caldas, N. A. de Oliveira, J.
70 80 Appl. Phys. 93 (2003) 4055.
[3] J. H. Albillo, F. Bartolome, L. M. Garcia, Phys. Rev. B 73 (2006)
Temperature(K) 134410.
Fig 4. Temperature dependence of magnetic entropy change -SM B B
[4] F. W. Wang, X. X. Zhang, F. X. Hu, Appl. Phys. Lett. 77 (2000)
for Ho1-xErxCo2 (x = 0 - 0.15) under 0.5 and 1.5 T.
B B B B B B
1360.
[5] D. Wang, H. Liu, S. Tang, S. Yang, S. Huang, Y. Du, Phys. Lett. A
297 (2002) 247.
[6] N. H. Duc, T. D. Hien, P. E. Brommer, J. J. M. Franse, J. Magn.
Conclusions Magn. Mater. 104 (1992) 1252.
[7] X. B. Liu, Z. Altounian, J. Magn. Magn. Mater. 292 (2005) 83.
In summary, we have reported the Er substitution [8] M. Balli, D. Fruchart, D. Gignoux, J. Magn. Magn. Mater. 314
(2007) 16.
effect on magnetic properties and MCE of single phased
[9] N. A. de Oliveira, P. J. von Ranke, A. Troper, Phys. Rev. B 69
Ho1-xErxCo2 (x=0-0.15) pseudobinary compounds. We
B B B B B B

(2004) 064421.
found that TC decreases almost linearly with increasing Er B B
[10] H. Wada, Y. Tanabe, M. Shiga, H. Sugawara, H. Sato, J. Alloys
content x. From the results of M(H,T), the temperature Compd. 316 (2001) 245.
dependence -SM under 0.5 and 1.5 T magnetic fields for B B
[11] V. K. Pecharsky, K. A. Gschneidner Jr., J. Appl. Phys. 86 (1999)
565.
each sample near its ordering temperature was estimated.
 Magnetic and transport.. 1

JCACS
2007

Magnetic and transport properties of R3Al B B

K. Nishimura * , R. Yamagata1, L. W. Li1, K. Mori1, T. Fukuhara2

P PF F P P P P P P P P

1
P Graduate School of Science and Engineering for Research,University of Toyama, Toyama 930-8555, Japan
P

2
P Department of Liberal Arts and Sciences, Toyama Prefectural University, Kosugi, Toyama 939-0398, Japan
P

Abstract

Electrical resistivity, specific heat, magnetization measurements were carried out using pseudo-binary (Ce1-xNdx)3Al and (Nd0.9Gd0.1)3Al B B B B B B B B B B B B

compounds. Nd3Al was found to possess a ferromagnetic character with a transition temperature of 74 K. The observed magnetic
B B

properties suggested that impurity Kondo effect of Ce ions and magnetic order states of Nd ions coexist in (Ce1-xNdx)3Al with 0.3<x<1.0. B B B B B B

The saturation magnetic moment of (Nd0.9Gd0.1)3Al was approximately half of that of Nd3Al, which indicated that the magnetic moments of
B B B B B B B B

Nd and Gd ions coupled antiferromagnetically.

Keywords: Nd3Al, Curie temperatue, resistivity, specific heat, magnetization

B B

1. Introduction 2. Experimental

The binary intermetallic compounds of rare-earth The polycrystalline samples of (Ce1-xNdx)3Al, B B B B B B

elements (R) and aluminum, R3Al (R=La, Ce, Pr and Nd), B B (Nd0.9Gd0.1)3Al and La3Al (as a reference material) were
B B B B B B B B

crystallize in the Ni3Sn-type hexagonal structure (space prepared by arc melting the constituent elements (of at
group P6/mmc) at room temperature [1, 2]. La3Al and B B least 99.9% purity) in an argon atmosphere. The samples
Ce3Al undergo a structural transition from the hexagonal
B B of (Ce1-xNdx)3Al and La3Al were annealed in vacuum for
B B B B B B B B

to a monoclinic structure at low temperature [3, 4]. three days at 735 K, and subsequently for a week at 473 K.
Studies of electromagnetic properties have revealed that A heat treatment with (Nd0.9Gd0.1)3Al was done for a B B B B B B

La3Al is a superconductor of the critical temperature of

B B week at 735 K. X-ray diffraction data recorded at room
6.16 K [5], Ce3Al and (La1-xCex)3Al show Kondo effect B B B B B B B B temperature with CuK radiation indicated that the B B

and magnetic ordering [6-9], Pr3Al is an B B samples were mainly in the hexagonal phase with
antiferromagnetic compound [10, 11]. As far as we are impurity phases less than 5 %. The substitution of Gd for
aware, there is little information on physical properties of Nd in Nd3Al was found to be only attainable with the Gd
B B

Nd3Al. This paper reports electromagnetic properties of

B B concentration less than 20 %. Figure 1 shows obtained X-
Nd3Al and its mixing compounds of (Ce1-xNdx)3Al and
B B B B B B B B ray diffraction patterns for the selected samples.
(Nd0.9Gd0.1)3Al via resistivity, specific heat and
B B B B B B The electrical resistivity was measured using standard
magnetization measurements. four-probe dc method in the temperature range from 2 to
300 K. Magnetization measurements were carried out
from 2 to 300 K with external fields B up to 7 T using a
SQUID (MPMS). The specific heat data were obtained
with PPMS from 2 K.

* Corresponding author. Tel.: +76-445-6844; fax:+76-445-6703.

E-mail address: nishi@eng.u-toyama.ac.jp.
2 K. Nishimura et al.

Fig. 1 X-ray diffraction patterns for selected samples of R3Al system. B B

Fig. 3 Specific heat of the (Ce1-xNdx)3Al, (Nd0.9Gd0.1)3Al, and La3Al . B B B B B B B B B B B B B B

The data points are shifted vertically to make the data lines clear.

3. Results and discussion The specific heat measurements were carried out to
clarify further the magnetic phase transitions of the
The temperature dependence of the resistivity is shown
T

samples. The results of the measurements are shown in

in Fig. 2 for the present samples. There are four apparent Fig. 3, in which the specific heat of La3Al is also
features. Nd3Al was found to have a magnetic transition
B B

displayed. If we take inflection points of the specific-

temperature of 74 K. This magnetic order-temperature is
higher than that of Nd3Co (25 K) [12, 13], but lower thanB
that of Nd3In (114 K) [14]. The order temperature of
B B
Nd3Al was raised by the Gd substitution to 80 K in
B B
heat peaks as transition points, magnetic-order
B
temperatures obtained from these measurements are well
correlated with those from the resistivity measurements.
A broad peak observed with La3Al around 55 K has been B B

(Nd0.9Gd0.1)3Al. B B Magnetic transition temperatures

B B B B ascribed to the crystal structure transition [3]. The
decrease with increasing Ce concentrations most likely superconducting transition temperature was estimated to
due to the weak exchange interactions of Ce ions. The be 5.7 K from the specific-heat peak, which is a little
resistivity at low temperature increases with the Ce lower than the previously reported one, 6.16 K [5].
concentration, suggesting that the impurity Kondo effect
works among the Ce ions like in the (La1-xCex)3Al system B B B B B B
The temperature dependences of the susceptibility and
[8, 9]. The different point is, however, that the impurity reciprocal susceptibility for the present samples were
Kondo state of the Ce ions exists together with the measured with an external field of 0.1 T. The results in
magnetic order state of the Nd ions. Broad peaks around Fig. 4 indicate that the all the samples exhibited
45 K observed with x = 0.5 and 0.7 probably originate in ferromagnetic nature. The reciprocal susceptibilities of
the structural transition from hexagonal to monoclinic [8, (Ce0.7Nd0.3)3Al, Nd3Al and (Nd0.9Gd0.1)3Al appear to
B B B B B B B B B B B B B B

follow the Curie-Weiss law above 150 K. The least-

9].
square fit with a straight line to the data yields the
paramagnetic Curie temperature and the effective
magnetic moment for (Ce0.7Nd0.3)3Al, Nd3Al, and B B B B B B B B

(Nd0.9Gd0.1)3Al to be -31 K, 55 K, 7.7 K, and 2.88 B,

B B B B B B B B

3.40 B, 4.24 B, respectively. The deduced values of the

B B B B

effective magnetic moment are rather close to the

theoretical ones of 2.86 B for (Ce0.7Nd0.3)3Al, 3.62 B for B B B B B B B B B B

Nd3Al, and 4.24 B for (Nd0.9Gd0.1)3Al using the R3+ free

B B B B B B B B B B P P

ion values.

Figure 5 presents the low temperature parts of the

resistivity and susceptibility of (Ce0.7Nd0.3)3Al to B B B B B B

investigate the detailed variation versus temperature.

From the thermal hysteresis observed on the resistivity, it
Fig. 2 Electrical resistivity of (Ce1-xNdx)3Al and (Nd0.9Gd0.1)3Al.
B B B B B B B B B B B B
was found that the crystal transformation started around
Magnetic transition temperatures are indicated by arrows.
45 K and finished around 17 K. The temperature variation
 Magnetic and transport.. 3

In conclusion, it is found that Nd3Al is a ferromagnet

B B

with Curie temperature of 74 K, the impurity Kondo

effect of Ce ions and the magnetic order of Nd ions co-
exist in (Ce1-xNdx)3Al, and Gd ions antiferromagnetically
B B B B B B

interact with the Nd ions in (Nd0.9Gd0.1)3Al. The detailed

B B B B B B

transport properties of Nd3Al (thermal conductivity,

B B

thermoelectric power, Hall coefficient, etc.) will be

published elsewhere.

This work is partially supported by the Takahashi

Industrial and Economic Research Foundation.

Fig 4. Temperature dependence of susceptibility of the present

samples measured with an external filed of 0.1 T.

Fig 6. Magnetization of the present samples at 4.2 K.

Fig 5. A comparison betwenn the resistivity and susceptibility of References

(Ce0.7N0.3)3Al at low temperature.

[1] K. H. J. Buschow and J. H. N. van Vucht, Z. Metallk. 57 (1966) 162 .

of the susceptibility provided the Curie temperature of [2] G. Borzone, N. Parodi, R. Ferro, J. P. Bros, J. P. Dubs and M.
about 10 K, most likely brought about by the exchange Gambino, J. Alloys Compd. 320 (2001) 242.
interactions of Nd ions. The negative temperature [3] C. S. Garde, J. Ray and G. Chandra, J. Alloys Compd. 198 (1993)
dependence of the resistivity below 10 K is perhaps due to 165.
the impurity Kondo effect of the Ce ions, like observed in [4] A. C. Lawson, J. M. Lawrence, J. D. Thompson and A. Williams,
(La1-xCex)3Al [9].
B B B B B B
Physica B (1990) 587.
[5] K. Yasuk-ochi, Y. Kuwasawa and K. Sekizawa, Phys. Lett. A28
The ferromagnetic characters of the present samples are (1968) 12.
also clear in the magnetization versus external field [6] Y. Chen, J. M. Lawerence, J. Thompson, and J. Willis, Phys. Rev.
curves at 4.2 K in Fig. 6. The value of the magnetization B40 (1989) 10766.
of Nd3Al at 7 T yields a rough estimation of the saturation
B B
[7] J. Sakurai, Y. Murashita, Y. Aoki, T. Fujita, T. Takabatake, and H.
magnetic moment of Nd ion to be 1.9 B, which is far B B
Fujii, J. Phys. Soc. Jpn. 58 (1989) 4078.
[8] Y. Y. Chen and Y. D. Yao, B. C. Hu and C. H. Jang, J. M. Lawrence,
smaller than that of the Nd3+ free ion value of 3.27B. P P B B

H. Huang and W. H. Li, Phys. Rev. B55 (1997) 5937.

The similar phenomena (reduction of the saturation [9] A. N. Medina, M. A. Hayashi, L. P. Cardoso, S. Gama, and F. G.
moment), have been observed in the Nd3In [14], Pr3Al B B B B
Gandra, Phys. Rev. B57 (1998) 5900.
[11]. A striking feature in Fig. 6 is that the magnetization [10] K. H. Mader and W. E. Wallace, J. Lees-Common Metals 16 (1968)
of (Nd0.9Gd0.1)3Al is about half of that of Nd3Al. This
B B B B B B B B
85.
result can be explained by antiferromagnetic interactions [11] T. Sakurai, Y. Murashita, H. Fujiwara, H. Kadomatsu, I. Oguro, and
J. Sakurai, J. Magn. Magn. Mater. 115 (1992) 250.
between the Nd and Gd moments. This interpretation is
[12] I. Umehara, Q. Lu, M. Endo, Y. Adachi, K. Sato, J. Phys. Soc.
supported by the observed paramagnetic Curie Japan 67 (1998) 4213
temperature for (Nd0.9Gd0.1)3Al, which is about one B B B B B B

[13] Y. Adachi, Y. Lu, I. Umehara, K. Sato, M. Ohashi, K. Ohoyama, Y.

seventh of that for Nd3Al. Assuming the magnetization B B
Yamaguchi, J. Appl. Phys. 85 (1999) 4750.
values of 1.9 B for Nd and 8.0 B for Gd ions in B B B B
[14] R. D. Hutchens, W. E. Wallace and N. Nereson, J. Solid State
(Nd0.9Gd0.1)3Al, the antiparallel coupling gives a result of
B B B B B B
Chem., 9 (1974) 152.
3.1 B, which appears a reasonable estimation.
B B
 Relationship between tensile deformation 1

JCACS
2007

Relationship between tensile deformation and crystallographic

orientation of grains in Al-Mg-Si-Cu alloys
J.Tsukiyama1, K.Matsuda2, *, Y.Uetani3, S.Ikeno2
1 Graduate School of Science and Engineering for Education, University of Toyama, Toyama, 930-8555, Japan
2 Graduate School of Science and Engineering for Research, University of Toyama, Toyama, 930-8555, Japan.
3 Toyama Prefectural University, 5180 Kurokawa, Imizu, Toyama, 939-0398, Japan

Abstract

A popular method to improve the mechanical properties of Al-Mg-Si alloys is to add other elements. The addition of transition metals is
useful because grain size refinement can be achieved, and with the addition of Cu can increase the strength and hardness of these materials.
However, even now it has not yet been clarified why Cu is useful in improving alloys elongation. In this work, we have investigated the
tensile behavior of excess Si-type Al-Mg-Si alloys, which contain Cu. Tensile test and hardness measurements were performed. SEM was
used to investigate the fracture surfaces and individual crystallographic orientations. A crack was observed at an interface between higher
Schmid Factor (S.F.) and lower S.F. grains. It was concluded that this crack influenced fracture from fracture surface.

Keywords: Al-Mg-Si, elongation, EBSP, orientation, SEM

crystallographic orientation of grains in excess Si-type

1. Introduction
6000 series Al-Mg-Si alloys have been used as
industrial materials due to their good mechanical
properties and formability. It can improve mechanical
properties of these alloys can be improved by the addition
of transition elements. Elongation of these alloys
decreases when excess Si-type Al-Mg-Si alloys are peak
aged and have the maximum hardness. Intergranular
fracture is remarkable in these alloys. Though Cu is added
as industrial materials, the effect of Cu has not been
understood. We have reported in our previous studies [1]
that when tensile tests were carried out on Al-
1.0mass%Mg2Si alloys with Cu addition aged at 423K to
maximum hardness, priority deformation near grain
boundaries was prevented as compared to those alloys
without Cu.
In this study, hardness measurement, tensile test, and
SEM observation were performed in order to understand
the relationship between tensile deformation and
Al-Mg-Si alloys with Cu. The electron backscattered
pattern (EBSP) technique was performed in order to
analyse individual crystallographic orientations of grains
in samples, and to clarify the relationship between slip
system, S.F. and fracture.
2. Experimental
Al -1.0 mass% Mg2Si -0.4 mass% Si (Cu-free) and Al
-1.0 mass% Mg2Si -0.4 mass% Si -0.5 mass% Cu (Cu-
bearing) alloys were prepared from high purity Al, Mg, Si
and Cu ingots. 1mm thick sheets were made by hot- and
cold-rolling, followed by solution heat treatment at 848K
for 3.6ks and then quenching to room temperature with
chilled water. Quenched sheets were aged at 423K in oil
bath. The micro-vickers hardness was measured with
AKASHI MVK-E II (load: 0.98 N, holding time: 15 s).
Tensile specimens each had a cross-section of 0.8
mm5.8 mm and gauge length of 17.5mm. Fracture
morphologies and crystallographic orientations were

* Corresponding author. Tel.: +76-445-6841; fax:+76-445-6841.

E-mail address: matsuda@eng.u-toyama.ac.jp.
2 J. Tsukiyama et al.
observed using optical microscopy (OM) and SEM
(Hitachi S-3500 and OXFORD Opal).
3. Results and discussion
Fig. 1 shows the age-hardening curves at 423K for both
alloys. The hardness of the Cu-bearing alloy was higher
than that of the Cu-free alloy. Fig. 2 shows the stress-
strain curves for both alloys aged to maximum hardness.
For the Cu-bearing alloy, the 0.2%proof stress and
ultimate tensile strength (UTS) were higher than those of
the Cu-free alloy. The elongation to failure and the
uniform elongation both increased by Cu addition.
Fig 1. The age-hardening curves at 423K for both alloys
Fig 2. The stress-strain curves for both alloys aged to maximum
hardness
The fracture morphologies of these alloys were observed
using SEM. Intergranular fracture was seen in both alloys.
Part of transgranular fracture can be seen in Cu-bearing
alloy. The surface of the Cu-bearing alloy was observed
using OM. Individual grains of this alloy was investigated
using the EBSP technique. There was no special texture
for this alloy. The slip system and S.F. were investigated
from crystallographic orientations to the tensile axis of
individual grains. Fig. 3 shows OM images obtained from
the Cu-bearing alloy deformed up to 0.2%, 0.6%, 1.1%,
and UTS. After 0.2% deformation, slip bands can be seen
at the surface. Lower S.F. grains do not show slip bands,
while higher S.F. grains do. Folds at grain boundaries
were observed. After 0.6% deformation, the surface
became a slightly rough. Slip bands can be seen along the
entire surface of this alloy. After 1.1% deformation, the
surface was much rougher. A crack can be seen. The
interface between higher S.F. and lower S.F. grains is
fractured. After UTS, this alloy deformed uniformly and
the surface remained rough. Many cracks can now be seen.
The crack which observed after 1.1% deformation
extended.
Fig 3. OM images obtained from Cu-bearing alloy deformed up to 0.2%,
0.6%, 1.1%, and UTS
The relationship between fracture morphology and
surface were observed. It is concluded that the crack
influences fracture from fracture surface.
4. Conclusion
Maximum hardness, elongation and strength of the Cu-
bearing alloy were each higher than that of the Cu-free
alloy. Partial transgranular fracture can be seen in Cu-
bearing alloy. Slip bands were seen all over the surface of
the Cu-bearing alloy. The interface between higher S.F.
and lower S.F. grains was fractured. It was concluded that
tensile deformation depends on the crystallographic
orientation of grains.
References
[1] Kenji Matsuda, Yasuharu Myoutoku, Kousuke Kido, Yasuhiro
Uetani, Susumu Ikeno: J. Japan Inst. Light Metals, Vol. 53, No. 1
(2003), pp.2-7
 Structure and superconductivity . 1

JCACS
2007

Structure and superconductivity for Li2(Pd1-xNix)3B boride system B B B B B B B B

L. W. Li, K.Nishimura * , J. Ishiyama, K.Mori F F

Graduate School of Science and Engineering, University of Toyama, Toyama 930-8555, Japan

Abstract

The crystal structure and superconductivity for Li2(Pd1-xNix)3B system are systematically studied by means of x-ray diffraction method, B B B B B B B B

transport properties and magnetization measurement. The limiting solubility of Ni substitution at Pd site was less than 0.2. The lattice
parameter a and superconducting transition temperature Tc decrease gradually with the increasing of Ni content x. Low critical field Hc1 and B B B B

upper critical field Hc2 were estimated from the isothermal magnetization (M-H) measurements, and the results are shown to follow a
B B

decrease tendency with increaseing x. The present results supported that Li2(Pd1-xNix)3B system were conventional type-II superconductor. B B B B B B B B

Keywords: Li2(Pd1-xNix)3B system, superconcuctivity parameters, solid solution

B B B B B B B B

indicated which is due to broken inversion symmetry in

Li2Pt3B by B11 and Pt195 NMR measurements [8]. This
1. Introduction behavior is contrast to those in the isostructural Li2Pd3B
which is a spin-singlet, s-wave superconductor [9].In
The recent discovery of superconductivity below 7-8 order to further understanding the physical properties of
K in the ternary lithium borides Li2Pd3B has attracted B B B B this system and searching new superconductors. In this
wide attention for its rich physical properties [1, 2]. This paper, the lattice parameter, superconducting transition
compound is known to crystallize in a perovskite-like temperature Tc, together with low critical field Hc1, upper
B B B B

cubic structure (space group of P4232) consisting of B B critical field Hc2 were reported in Li2(Pd1-xNix)3B system.
B B B B B B B B B B

distorted Pd6B octahedral [3], which is structurally similar

B B

to the superconductor MgCNi3 [4]. The theoretical and B B

experimental (NMR measurement and photoemission 2. Experimental

experiment) suggestion that the superconductivity in
Li2Pd3B is due to Pd 4d-electrons and these d-electrons
B B B B Polycrystalline samples of Li2(Pd1-xNix)3B were B B B B B B B B

have strong coulomb correlation dominating the prepared by a two-step arc melting method under argon
electronic properties of this system [5,6]. Elemental atmosphere. In the first step, alloys of (Pd1-xNix)3B (x = 0- B B B B B B

substitution, as well as in other superconductors, serves as
a useful way to modify the structure and other physical
properties of Li2Pd3B system to study the underlying
B B
mechanism of superconductivity. Badica et al. [7]
reported the basic superconducting parameters for
pseudo-binary Li2(Pd1-xPtx)3B (x = 0-1) system. The B B
results suggested that the observed superconductivity is of
bulk type and the superconductivity parameters are
similar to those for conventional type-II superconductors.
Recently, spin triplet superconducting state were
1) were melted from the stoichiometric amounts of high-
purity Pd, Ni and B on the water-cooled copper hearth.
B B The total loss of this step having negligible that is less
than 0.3%. In the second step Li has been introduced with
additional 10-40% for compensate the evaluated of it. The
B B B B B B second procedure was repeated several times and chose
the best ones by measuring the weight and x-ray powder
diffraction experiment (XRD). The samples were cut to
rectangular for measurements of electrical resistivity,
which were made using a standard four-probe technique

* Corresponding author. Tel.: +76-445-6844; fax:+76-445-6703.

E-mail address: nishi@eng.u-toyama.ac.jp.
2 L. W. Li et al.

in the temperature range from 1.8 K to 280 K conducted method from the powder XRD data. It can be seen that the
by PPMS system (Quantum Design). The magnetization lattice parameter a decreases gradually with the
measurements were done using a SQUID (Quantum increasing of x.
Design MPMS) in the temperature range from 2 K to 30
K and the DC magnetic fields with a range of 0-6 T. The
results are well repeatable.
8 by R(T)
by M(T)

Tc / K
3. Results and Fiscussion

7
Ni2B
unknown

0 0.1 0.2
x=1.0 x / Ni
x=0.3
Fig. 3. Superconducting transition temperature Tc deprived from
I / CPS

B B

x=0.2 (T) and M(T) curves as a function of x for Li2(Pd1-xNix)3B (x = 0-0.2) B B B B B B B B

system.
x=0.15
x=0.1
The temperature dependence of electrical resistivity
x=0.05
(T) and magnetization M(T) (under field cooling mode)
(221)

for Li2(Pd1-xNix)3B (x = 0-0.2) system were performed B B B B B B B B

(210)
(211)
(111)

(310)
(110)

(311)

from 5 K to 9 K. The superconducting transition

(222)
(220)

(321)

(330)
(410)

(420)
(332)
(430)
(510)
(520)
(521)

(532)
(531)

x=0 temperature Tc was determined and the results are shown B B

in Fig. 3. Generally, Tc decrease systematically with the B B

20 40 60 80 100 increasing of Ni substitution content x. The decrease of Tc B B

2 / degree is possibly due to the decreases in density of the states

  N(0) and the increases of average characteristic phonon
Fig. 1. Powder XRD patterns for Li2(Pd1-xNix)3B (x = 0-1) system. B B B B B B B B

frequency. Mochiku et al. [10] found the distortion of the

Pt6B octahedra was larger than that of Pd6B octahedra for
B B B B

6.75 Li2(Pd,Pt)3B by neutron powder diffraction which is the

B B B B

main reason caused the Li2Pt3B has lower Tc than that of B B B B B B

a/

6.74 Li2Pd3B. So, for the present Ni substituted Li2(Pd1-xNix)3B

B B B B B B B B B B B B

system, the change of structure which has a close

relationship with the distortion of Pd6B octahedra is
6.73
B B

another reason caused the decreases of Tc. B B

In order to understand the effect of Ni substituted

6.72
0 0.05 0.1 0.15 0.2 effect on critical fields, isothermal magnetization curve
(M-H) were measured at different temperature for Li2(Pd1-
x / Ni B B B

  xNix)3B (x = 0-0.2) system. Upper critical field Hc2 was

B B B B B B B

Fig. 2. The inset is the lattice parameter a as a function of x for determined as the point where the M(H) curve at a fixed
Li2(Pd1-xNix)3B (x = 0 - 0.2) system.
B B B B B B B B
temperature reach the background. The results of Hc2 B B

estimated from these curves as a function of temperature

The XRD spectra were performed on all of the Li2(Pd1- B B B
are estimated. Extrapolation to T = 0 K of the linear fitting
xNix)3B
B samples and the results are shown in Fig. 1. For x
B B B B
of the experimental data for each sample is resulting in
< 0.2, there were no impurity peaks were found within the Hc2(0)linear (as shown in the inset of Fig. 4). The values of
B B P P

experimental errors, all samples have single phase could Hc2(0)linear almost linearly decrease from 6.2 to 3.2 T with
B B P P

be indexed to a cubic crystal structure with space group the increasing of x. On the other hand, by applying the
P4232; when x 0.2, there were some Ni2B and some
B B B B
Werthamer-Hefland-Hohemberg (WHH) approximation
unknown phases were found. We were failed to synthesis of Hc2(0) = 0.691(dHc2/dT)TcTc [11], and the results of
B B B B B B B B

the Li2Ni3B sample by the present method. So the limiting

B B B B
Hc2(0)WHH are also shown in Fig.4. Hc2(0)WHH show
B B P P B B P P

solubility of Ni substitution at Pd site in Li2(Pd1-xNix)3B B B B B B B B B

approximately the same x dependence tendency with that
system was in the range of 0.15-0.20. Fig. 2 gives the of Hc2(0)linear, and are decreasing from 4.6 to 2.2 T. In the
B B P P

change of lattice parameter a with x in Li2(Pd1-xNix)3B (x B B B B B B B B

following calculations, we have used Hc2(0)WHH for Hc2(0). B B P P B B

= 0-0.2) system, which are calculated by the least-square Another important parameter characterizing
 Structure and superconductivity . 3

superconductivity is the lower critical field Hc1. Values of B B Conclusions

Hc1 for certain x and temperature has been taken as the
B B

field where M(H) curve deviates at low fields from the In summary, we have been systematically studied the
linear behavior generated by the perfect diamagnetism. crystal structure and superconductivity for Li2(Pd1-xNix)3B
B B B B B B B B

The Hc1(0) was estimated and results are shown Fig. 5

B B system. The limiting solubility of Ni substitution at Pd
which was fitted with the formula Hc1 = Hc1(0) [1- B B B B site was less than 0.2. The lattice parameter a and
(T/Tc)2]. The value of Hc1(0) decreases gradually from 230
B B P P B B superconducting transition temperature Tc decrease B B

Oe to 70 Oe with the increasing of x. gradually with the increasing of Ni content x. From the
isothermal magnetization (M-H) measurements, low
critical field Hc1(0) and upper critical field Hc2(0) were
B B B B

estimated and decrease continuously with the increase of

6 linear x. The present results supported that Li2(Pd1-xNix)3B

Hc2(0) / T

B B B B B B B B

system were conventional type-II superconductor.

WHH
4 Acknowledgments

2 This work is supported by the Takahashi Industrial

and Economic Research Foundation.
0 0.05 0.1 0.15 0.2
x / Ni
References
Fig. 4. Higher critical field Hc2(0)linear and Hc2(0)WHH (from WHH
B B P P B B P P

estimation) as a function of x for Li2(Pd1-xNix)3B (x = 0 - 0.2) system.B B B B B B B B

[1] K. Togano, P. Badica, Y. Nakamori, S. Orimo, H. Takeya, K. Hirata,
. Phys. Rev. Lett. 93 (2004) 247004.
[2] P. Badica, T. Kondo, T. Kudo, Y. Nakamori, S. Orimo, K. Togano,
Appl. Phys. Lett. 85 (2004) 4433.
240 [3] U. Eibenstein and W. Jung, J. Solid State Chem. 133 (1997) 21.
[4] T. He, Q. huang, A. P. Ramirez, Y. Wang, K. A. Regan, N. Rogado,
Hc1(0) / T

M. A. Hayward, M. K. Haas, J. S. Slusky, K. Inumaru, H. W.

160
Zandbergen, N. P. Ong, R. J. Cava, Nature (London) 411 (2001) 54.
[5] M. Sardar and D. Sa, Physica C (2004) 120.
[6] T. Yokoya, T. muro, I. Hase, H. Takeya, K. Hirata, K. Togano, Phys.
Rev. B 71 (2005) 92507.

80 [7] P. Badica, T. Kondo, K. Togano, J. Phys. Soc. Jpn., 74 (2005) 1014.

[8] M. Nishiyama, Y. Inada, G. Q. Zheng, Phys. Rev. Lett. 98 (2007)
47002.
0 0.05 0.1 0.15 0.2 [9] H. Q.Yuan, D. F. Agterberg, N. Hayashi, P. Badica, D. Vandervelde,
K. Togano, M. Sigeist, M. B. Salamon, Phys. Rev. Lett. 97 (2006)
x / Ni 17006.
[10] T. Mochiku, H. Takeya, T. Wuernisha, K. Mori, T. Ishigaki, T.
Kamiyama, H. Fujii, K. Hirata, Physica C 445-448 (2006) 57.
Fig. 5. Lower critical field Hc1(0) as a function of x for Li2(Pd1-
B B B B B

[11] N. R. Werthamer, E. Helfand, P. C. Hohenmberg, Phys. Rev. 147

xNix)3B (x = 0 - 0.2) system.
B B B B B (1966) 295.
. .
 Magnetization and specific heat 85

JCACS
2007

Magnetization and specific heat of new cubic PrCu4Au

S. Zhang, Y. Isikawa
Graduate School of Science and Engineering for Research,University of Toyama, Toyama 930-8555, Japan

Abstract

The magnetic and thermodynamic properties of new cubic PrCu4Au crystals were investigated based on the magnetic susceptibility (T)
and the specific heat C(T). A clear transition observed in C(T) with a peak about 7.1 J/mol K at 2.4 K, together with antiferromagnetic
(AFM) transition behavior (TN = 2.5 K) of (T) indicates the low temperature properties are ascribed to the AFM order in the cubic crystal
electric field (CEF) of Pr3+. The strong dependence on external field of the peak in C(T) and the appearance of 141Pr nuclear specific heat
below 0.7 K show evidence for internal magnetic field, which is the origin of this anomaly. The electronic specific heat coefficient was
calculated as about 0.77 J/mol K2, suggesting a heavy-electron-like behavior. All the features imply that CEF ground state (GS) of
PrCu4Au might be a magnetic triplet 5.

Keywords: PrCu4Au, AFM, CEF, GS, specific heat, heavy-electron, cubic crystal

1. Introduction the good agreement between the behavior of transition in

The explorations of Pr-based correlated electron
systems are highly indicated because Pr3+ is the most
direct analog of U4+, which has been studied deeply and
discussed in kinds of theoretical models [1, 2]. It has been
considered that various intriguing behaviors can be
caused by the c-f interaction and the CEF configuration at
low temperatures. The 4f configuration of Pr3+ can have a
CEF GS that has non-magnetic, non-Kramers 3 doublet,
the fluctuating quadrupole moment of which could
interact with the conduction electrons to produce strongly
correlated properties, such an example is provided in
PrAg2In [3, 4], PrCu2In [5] and PrPb3 [6]. The former is
characterized by the enhanced Sommerfeld coefficient
~6.5 J/mol K2, and the unusual +lnT dependence [7] of
electrical resistivity might indicate the non-Fermi-liquid
(NFL) nature of the GS in this compound. In the present
study, we report the low-T properties on a new Pr-based
compound PrCu4Au with the MgSnCu4 type cubic
structure, which exhibits a heavy-electron-like in internal
magnetic field caused by the antiferromagnetic order state
below 2.5 K. We focus on the strong dependence on
external field of the anomaly in C(T) and the appearance
of 141Pr nuclear contribution on specific heat below 0.7 K.
In this paper, we report possible evidences indicating that
the heavy-electron-like state is formed via electric
interaction in the cubic CEF and emphasize the CEF GS
in PrCu4Au might be a magnetic triplet 5. We also note
(T) and C4f(T).
2. Experimental
The polycrystalline samples of PrCu4Au were prepared
by arc melting the constituent elements (of at least 99.9%
purity) in an argon atmosphere. The crystal structure was
confirmed to be of the cubic MgSnCu4 type from X-ray
powder diffraction, and the lattice parameter was
evaluated as = 7.219 . The electrical resistivity was
measured from 1.8 K to 290 K by a conventional four-
probe DC method. The magnetization and magnetic
susceptibility measurement were performed from 2.0 to
300 K in magnetic field up to 7.0 T in a SQUID
magnetometer. The specific heat was measured by the
thermal relaxation method down to 0.54 K.
3. Results and discussion
Figure 1 and the inset show the T-dependence of (T)
and its inverse, respectively. (T) increases monotonically
with decreasing T and exhibits a sharp peak at 2.5 K,
which is thought to be the antiferromagnetic transition
temperature TN. The paramagnetic Curie temperature P
and the effective Bohr magneton number eff deduced
from the -1(T) versus T plot from 40 to 300 K are -5.1 K
86 S. Zhang et al.

0.2 9 60
200

8 PrCu Au
4
: PrCu Au

C (J/mol K)
(mol/emu)
40 4

0.15 7 : YCu Au
4
100
6
(emu/mol)

20

-1

C (J/mol K)
5
0.1 0
0 0 25 50
0 100 200 300 4 Temperature (K)
Temperature (K)

3
0.05 PrCu Au
4 2
: C (T)
N
1 : C4f(T) YCu Au
4
0 0
1 10 100 300 0 2 4 6 8 10
Temperature (K) Temperature (K)

Fig 1. T-dependence of the (T) and -1(T) of PrCu4Au under field 1.0 Fig 3. T-dependence of specific heat of PrCu4Au () and YCu4Au ()
T. A clear transition peak was observed at 2.5 K. at low temperature.

nuclear contribution to specific heat was observed below

60
0.7 K. The 4f contribution of C(T) is evaluated as C4f =
PrCu Au C(T) CYCu4Au(T) CN(T), where the CYCu4Au(T) is the
50 4 specific heat of YCu4Au representing the contribution of
phonons. The peak in (T) at 2.5 K and a large anomaly
40
observed in C4f(T) at 2.4 K, is the anomaly caused by an
(cm)

20 antiferromagnetic phase transition. In this case, the word

30 antiferromagnetic does not mean a simple AFM structure.
Nevertheless, it is apparent that the GS of PrCu4Au is
(cm)

18

20 magnetic. The contribution CN(T) was analyzed as CN =

16
10
14
0 5
Temperature (K)
0 following equation,
0 50 100
Temperature (K)
150
Fig 2. T-dependence of electrical resistivity of PrCu4Au. The inset
shows (T) at low temperature below 20 K.
and 3.50 B, respectively, which is slightly smaller than
3.58 B for a free Pr3+ ion. The magnetization M in fields
up to 7.0 T was measured at various temperatures, and
M(H) at 2.0 K shows a saturation tendency to the value
2.0 B/Pr3+ at high fields. By a simple calculation of cubic
CEF, the value of M is calculated as 2.0, 4.0, 0 and 0
B/Pr3+ when the GS is 5 (triplet), 4 (triplet), 3
(doublet) and 1 (singlet), respectively. We can, therefore,
predict reasonably that CEF GS in PrCu4Au might be a
magnetic triplet 5.
As shown in Fig 2, (T) decreases monotonically with
decreasing T at high temperature above 10 K. However,
as expected, (T) decreases rapidly at about 2.5 K shown
in the inset of Fig 2, showing an evidence of magnetic
transition. The residual resistivity 0 and the residual
resistivity ratio RRR are evaluated as 15.6 cm (1.8 K)
and RRR (290/1.8) = 3.4, respectively.
As shown in Fig 3, C(T) exhibits a sharp peak at 2.4 K
that suggests a cooperative phase transition, and 141Pr
/T2 with = 0.33 J K/mol from C(T) at low temperatures.
From the value of , the internal field at the position of Pr
10 15
20 nucleus could be calculated as Hint = 195 T using the
200 250 300
{
H int = 3k B2 / h 2 N2 RI ( I + 1) }
141
where I and N are the Pr nuclear spin and the
gyromagnetic ratio, respectively, the other definitions are
conventional. The value of Hint is 56% of the hyperfine
field caused by a free 4f Pr ion (HHF = 350 T)[8],
suggesting that the magnetic moment of Pr3+ ion in
PrCu4Au is correspondingly reduced to 1.8 B/Pr ion (3.2
56%) which is in good agreement with the measured
value. It can be concluded, therefore, from the appearance
of the CN that the internal magnetic field exists at low
temperatures under zero field, and the CEF GS in
PrCu4Au is confirmed again to be a magnetic triplet 5.
Hext dependence of (T) and C(T) has been measured to
make a phase diagram of TN versus Hext. (T) at low
temperatures below 20 K was measured in various fields.
TN show no apparent dependence on field below 1T,
however, disappears at about 3 T. On the other hand,
C4f (T) at low temperatures below 9 K was shown in
various Hext in Fig 4. The peak position shifts to lower
temperatures, and the height decreases with increasing
fields. In the curve of C 4f (T) under 3 T, it makes a
shoulder with no peak around 2 K (solid line in Fig 4).
 Magnetization and specific heat
8 14
7 PrCu Au
4
6
C (J/mol K)
5
4
4f
3 Rln2
: 0.0 T : 2.0 T
2 : 2.5 T : 3.0 T
: 3.5 T : 4.0 T
1 2
: 4.5 T : 6.0 T
0 0
0 2 4 6 8 10
Temperature (K)
Fig 4. The low-T part of C4f(T) of PrCu4Au under external fields from
0 to 6.0 T. All the data have been corrected by subtracting CN(T) .
Thus, TN in (T) and C(T) seems to be consistent with
each other and disappears around 3 T.
Figure 5 shows the 4f contribution to the entropy S4f(T).
Initial value of S4f at 0.54 K, assuming that the gradient of
C4f(T)/T versus T is constant below 0.54 K. The entropy at
TN is considerably smaller than Rln3, and S4f(T)
approaches Rln3 around 7 K. In general, in the vicinity of
TN, magnetic fluctuation remains above TN and thus the
entropy at TN is usually less than the value calculated
from the degree of freedom of the magnetic ground state.
We propose a tentative model to explain why the entropy
is considerably smaller than the calculated value. This
compound has quadrupole moments in the GS of 5,
consequently, quadrupole fluctuations exist at low T, and
may cause a plateau of C(T) at low temperatures, as seen
in PrInCu2 and PrInAg2. On the other hand, we calculated
the C4f(T) to compare the experimental result under 6.0 T
based on the model that the degeneracy of the triplet GS
is lifted by the Zeeman effect with the equal splitting
energy of 10 K. The calculated C4f(T) is shown by the
dotted line in Fig 4.
Finally, we discuss the characteristic feature in C(T)/T
versus T (not shown here). The phonon part is, however,
negligibly small in the low-T region, and the nucleus part
would be subtracted from C/T. We analyzed the C/T in
Hext = 0 assuming that C/T = /T3 + + cT2 in narrow
temperature range below 1.8 K down to 0.54 K, where the
last term is assumed to be a magnetic contribution. From
this equation, = 0.33 J K/mol and = 0.77 J/mol K2 are
87
12 PrCu Au
4
10
S (J/mol K)
8
Rln3
6
4f
4
1/2Rln2
0 5 10 15 20
Temperature (K)
Fig 5. T-dependence of S4f(T), the 4f contribution to the entropy of
PrCu4Au.
obtained. The large might mean that the 4f electrons
behave like heavy-electron. The tendency of this large
does not change when external field is applied. We
remind of the quadrupole fluctuation model discussed
previously. The GS of PrCu4Au is 5, and have both
magnetic and quadrupole moments. PrCu4Au is, therefore,
a complex system because this compound has both
magnetic fluctuation leading an antiferromagnetic order
and quadrupole fluctuation which does not make an order.
Theoretical studies are expected to solve this fantastic
compound with two fluctuations.
Details will be published in the Journal of Physical
Society of Japan soon
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 Proceedings of JCACS 2007, Nov. 14-17, Toyama,Japan 89

JCACS
2007

Crossover behaviors of magnetization transport in superconducting

RBaCuO multilayers and quasi-multilayers
C. B. Cai, J. L. Liu, B. Gao, L. Peng, C. Z. Chen, Z. Y. Liu, S. X. Cao, J. C. Zhang
Department of Physics, Shanghai University, Shanghai 200444, China

Abstract

To study flux pinning modulation due to intentional adjustments of rare earth cations, layer sequences and island-like secondary phases, we
built up a series of artificial multilayers consisting of binary rare earth R123 as well as quasi-multilayers consisting of Y123/M (M= oxides
such as Yttria Stabilized Zirconia) on single crystalline SrTiO3 by pulsed laser deposition. The field dependence of transport critical current
density Jc was measured at various temperatures and directions of the applied magnetic field. Comparing with pure Y123 films, almost all
present multilayers and quasi-multilayers showed a crossover behaviour of flux pinning, evidenced by an existing medium field (Hcro)
below which Jc is lower than of pure Y123 films, whereas above Jc is higher. Furthermore, a strong temperature dependence of such a
crossover field was observed. The higher the temperature, the higer Hcro, implying that an artificial tailoring of flux pinning may appear in a
narrow range of fields as the mixed vortex state moves towards to the region of weak vortex glass and vortex liquid. However, the
improvement of flux pinning is hardly observed in the state of strong vortex glass.

Keywords: RBaCuO, thin films, flux pinning, crossover behavior