1 57 PMR Jan14 PDF

Published by Johnson Matthey Plc
Vol 58 Issue 1
January 2014
www.platinummetalsreview.com
E-ISSN 1471-0676
A quarterly journal of research on the
science and technology of the platinum
group metals and developments in their
application in industry
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1 2014 Johnson Matthey
E-ISSN 1471-0676 Platinum Metals Rev., 2014, 58, (1), 1
Editorial Team: Sara Coles (Assistant Editor); Ming Chung (Editorial Assistant);
Scott Turnbull (Scientic Information Assistant)
Platinum Metals Review, Johnson Matthey Plc, Orchard Road, Royston, Hertfordshire SG8 5HE, UK
Email: jmpmr@matthey.com
Platinum Metals Review
A quarterly journal of research on the platinum group metals
and developments in their application in industry
JANUARY 2014 VOL. 58 NO. 1

Contents
Platinum Metals Review is Changing in 2014 2
An editorial by Sara Coles
Focused Ion Beam and Nanomechanical Tests for High Resolution 3
Surface Characterisation: New Resources for Platinum Group Metals Testing
By Marco Sebastiani, Marco Renzelli, Paolo Battaini and Edoardo Bemporad
High Temperature Thermomechanical Properties of 20
Titanium-Rhodium-based Alloys Containing Scandium
By Yurii V. Kudriavtsev and Elena L. Semenova
EuropaCat XI 31
A conference review by Silvia Alcove Clave, Francesco Dolci,
Peter R. Ellis and Cristina Estruch Bosch
The Discoverers of the Isotopes of the Platinum Group of Elements: 38
Update 2014
By John W. Arblaster
PGMs in the Lab: Platinum Group Metals in Polyoxometalates 40
Featuring Ulrich Kortz
Publications in Brief 43
Abstracts 46
Patents 50
Final Analysis: Effects of Platinum Group Metals Doping 54
on Stainless Steels
By Andrew Fones and Gareth D. Hatton
http://dx.doi.org/10.1595/147106714X677955 Platinum Metals Rev., 2014, 58, (1), 2
Platinum Metals Review, Johnson Mattheys journal
of research on the science and technology of the
platinum group metals (pgms) and developments
in their application in industry, has a long and
proud history having been published by Johnson
Matthey since 1957 continuous publication for 58
years.
From mid-2014,regular readers will see changes, not
least of which will be to the name of the journal:
Platinum Metals Review will become the Johnson
Matthey Technology Review.
This change refects our intention to cover a
much wider range of technologies than at present.
Today, Johnson Matthey is more than just a precious
metals company, with interests which extend to
base metal catalysis, products for pharmaceutical
and medical applications and battery materials,
among others. These technologies will also begin
to feature in future issues of the journal alongside
pgms, which remain indispensable for so many
applications and processes.
The format of a peer-reviewed scientifc journal,
which has worked well for us in the past, will
remain as it is important to maintain a high quality
publication that our readers will want to read and
cite.
We welcome and encourage submissions from all
who are working in felds of interest to the journal,
which is provided as a service to the community
who work with pgm and now, non-pgm science and
technology in a range of relevant felds.The journal
will still be free to access and free to publish; all of
the costs are absorbed by Johnson Matthey as part
of its service to the community.
On behalf of Johnson Matthey I would like to
thank all of Platinum Metals Reviews readers,
authors, reviewers, Editorial Board members and
other stakeholders for your input over the years
and I hope that you will be interested in continuing
your contribution to the success of the journal in
future.
Please look out for further announcements,
including the wider range of topics which we will
begin to cover, via our website,Twitter, email and in
the next issue of the journal. We hope you are as
excited as we are about this opportunity to greatly
expand the range of subjects that will fnd a home,
and an interested audience, in the Johnson Matthey
Technology Review.
SARA COLES, Assistant Editor
Contact Information
Johnson Matthey Plc
Orchard Road
Royston
Hertfordshire
SG8 5HE
UK
Email: sara.coles@matthey.com
Editorial
Platinum Metals Review is Changing
in 2014
Platinum Metals Rev., 2014, 58, (1), 319
Focused Ion Beam and Nanomechanical
Tests for High Resolution Surface
Characterisation: New Resources for
Platinum Group Metals Testing
Use of two high resolution techniques allows process optimisation and prediction of
in-service behaviour
http://dx.doi.org/10.1595/147106714X675768 http://www.platinummetalsreview.com/
By Marco Sebastiani and Marco Renzelli
University of Rome Roma Tre Engineering Department,
Via della Vasca Navale 79, 00146 Rome, Italy
Paolo Battaini
8853 SpA Via Pitagora 11, I-20016 Pero, Milano, Italy
Edoardo Bemporad*
University of Rome Roma Tre Engineering Department,
Via della Vasca Navale 79, 00146 Rome, Italy
*Email: edoardo.bemporad@uniroma3.it
Recently, the increasing importance and scope of
nanotechnology has extended the need for high
resolution characterisation tools beyond their traditional
domains. As a consequence, advanced high-resolution
tools at the nanoscale are now increasingly used in
research and development (R&D) activities,offering the
chance for a better understanding of submicron feature
size dependence. This paper gives an overview of the
synergic application of two high resolution techniques
on the platinum group metals (pgms): focused ion beam
(FIB) coupled with electron beam imaging, milling and
deposition techniques; and nanoindentation testing.
After a brief description of both techniques (architecture,
probe-sample interaction basics and operation
modes), the effectiveness of this combined approach is
demonstrated for microstructural and nanomechanical
investigations on very small samples. The advantages
are low cost, fast and site-specifc sample preparation
for transition electron microscopy (TEM) analysis; study
of the mechanical hardening effect on microstructure
and hardness profle at the micron scale; failure analysis;
and understanding of plasticity and elasticity behaviour.
Two specifc case studies related to a platinum-copper
alloy for jewellery use and a platinum-rhodium alloy for
sensor manufacturing are presented and discussed.
1. Introduction
The structural characterisation of engineered surfaces
is of increasing importance due to the growing
application of surface modifcation processes and
coating techniques, which are usually applied to
improve either mechanical or functional surface
performance. Some examples include surface
hardness, load bearing capacity, impact bearing
capacity,wear resistance,specifc surface area (related
to surface free energy and chemical reactivity),
http://dx.doi.org/10.1595/147106714X675768 Platinum Metals Rev., 2014, 58, (1)
electrical resistivity, thermal conductivity and smart
optical properties (1).
The development of nanostructured materials and
the increasing use of nanosystems and nanostructures
make the use of advanced procedures for nanoscale
mechanical characterisation necessary to understand
chemical and physical phenomena at this scale (2).
The in-service macroscale mechanical behaviour
of micro- and nanocrystalline metals (for example,
their fracture and plastic deformation behaviour) is
strictly related to the complex interactions between
the different micro- and nanostructural features
(for example dislocation sources, grain boundaries
and nanoscale porosity). These latter aspects are
particularly critical in the advanced metallurgy of
pgms alloys, where the actual role of phase transitions,
the microstructural evolution of interfaces during
processing and the correlation with their mechanical
properties are not yet completely understood.
The in-service performance of such materials
is dependent on the evolution of nano- and
microstructural features during processing, including
development of nanodispersed phases, grain growth,
evolution and composition of grain boundaries,
dislocation density and distribution. Therefore an
understanding of the correlation between the micro-
or nanostructure and the mechanical properties
of a material is critical for the development of
new and improved materials. High resolution
microscopy analysis together with nanomechanical
characterisation are powerful tools that can allow
such understanding.
The present paper gives an overview of the
synergic use of two high resolution techniques,
which are expected to be established as enabling
technologies for improving the current understanding
of the correlations between process, microstructure,
properties and performance for precious metal alloys.
These are:
y FIB coupled with electron beam for imaging,
milling and deposition (referred to as dualbeam
(35))
y Nanoindentation (612) for hardness measurement
with a very low load.
1.1 Advantages of the Techniques
A key advantage of these two techniques (FIB/SEM and
nanoindentation) for high-technology manufacturing
is that both are very site-specifc and virtually artefact
free in measuring as well as in imaging or shaping
samples in order to expose the region of interest.
Moreover, some analysis on cross-sections and even
TEM lamellae extraction are virtually nondestructive,
as the sample size required is just a few cubic microns.
In this paper,two examples are outlined to show how
the combined use of nanomechanical testing and high
resolution microscopy can help gain understanding of
the processing mechanisms and in-service behaviour
of components. In particular:
y Cross-section cut-and-view for rapid
microstructural investigation (grain size and
inclusions) on very small samples without any
sample preparation or preprocessing (dualbeam)
y Low cost,fast and site-specifc sample preparation
for TEM analysis (dualbeam)
y Deformation mechanisms at the nanoscale
(dualbeam and nanoindentation)
y Mechanical hardening effect on microstructure
and hardness profle at the micron scale
(dualbeam and nanoindentation)
y Separate measurement of elastic modulus,
apparent hardness, true hardness, plasticity and
hardening behaviour (nanoindentation).
The article will focus on two case studies,explaining
the importance of the combined use of dualbeam and
nanomechanical testing for the correct evaluation
of mechanical and functional performances of
nanostructured systems in the pgms:
y Order hardening of platinum-5 wt% copper
alloys: microstructural and nanomechanical
characterisation for this alloy used in jewellery;
y Infuence of process history on microstructure
and mechanical properties of platinum-rhodium
alloys, used in thermocouples.
In both cases, it will be demonstrated that
nanoindentation testing can give valuable information
on the microstructural changes due to phase transition
and intragrain microstructure. In addition, the
combined use of FIB/scanning electron microscope
(SEM) and TEM techniques could help to understand
how and why microstructural changes due to heat
and/or mechanical treatments affect the mechanical
behaviour of samples.
1.2 Brief Introduction to Focused Ion Beam
(FIB) Techniques
FIB technology was frst introduced in the 1980s in the
semiconductor industry. FIB instruments derive their
design from the SEM. However while SEM instruments
use electrons that are accelerated and focused on a
surface, FIB uses ions (usually gallium). The image
is derived from secondary electrons resulting from
the particle irradiation. The use of ions means that it
is not only possible to image the surface but also to
mill it,using sputtering phenomena to remove material.
From an engineering point of view,the two instruments,
albeit similar in concept, are different in construction:
the high mass of the ions requires electrostatic lenses,
instead of electromagnetic lenses as used in SEM (35).
The new generation of FIB equipment is equipped
with both an ion beam column and an electron
beam column (SEM), providing imaging of the ion
beam milling process. In this case the instrument is
called a dualbeam microscope (Figure 1(a)). It can
be seen from Figure 1(a) that the instrument can
use the electron and ion columns at the same time;
considering that the resolution of the FIB is 5 nm, it is
possible to mill the surface in real time with nanometre
resolution, working it with ions and observing it with
electrons, as in Figure 1(b). In dualbeam with in situ
SEM three dimensional tomography can be obtained
by the slice-and-view process (35). An additional
feature of FIB is the capability to deposit thin flms (for
example, made from Pt or carbon) by ion- or electron-
assisted chemical vapour deposition (CVD), as shown
in Figure 1(b).
FIB milling can be performed on hard, soft and
biological materials with minimal artefacts (35).
Some Ga atom implantation and amorphous layers
will typically be observed but these artefacts can be
limited to a thickness of a few nanometres by careful
selection of the milling parameters (mainly current
and voltage). FIB systems use a focused beam of Ga
+

ions at low beam currents (of the order of pA) for
imaging and at high beam currents (of the order of
nA) for site-specifc milling.
FIB techniques can be also used for TEM lamella
preparation: a fnished electron transparent portion
of the sample (usually 5 m 20 m) is obtained by
FIB milling (performed at 30 kV by using a decreasing
sequence of ion milling currents, from 9 nA down to
0.28 nA for the fnal polishing) and then carried by a
micromanipulator on a sample holder to be inserted
into the TEM microscope: this procedure at present
represents the best site-specifc and artefact-free TEM
sample preparation methodology. Figure 2 illustrates
how a dualbeam can be used to prepare site specifc thin
sections for high resolution TEM imaging and analysis.
1.3 Brief Introduction to Nanoindentation
Testing
Nanoindentation testing (6) has been widely adopted
in the last two decades for the surface mechanical
characterisation of bulk materials and coatings.
The method involves the controlled penetration
of a diamond indenter of known shape into the
material. Usually, a three-sided pyramidal indenter
(Berkovich) is used in conventional nanoindentation.
By measuring the load and displacement during the
loading and unloading parts of the test, hardness (i.e.
resistance to plastic deformation) and elastic modulus
can be calculated (6, 7). In this way, a very accurate
characterisation of the elastic and plastic properties
at a materials surface can be achieved, with a depth
resolution and a lateral spatial resolution of the order of
a few nanometres.
SEM
F
I
B
52
~4.1mm
(a)
10 m
(b)
Fig. 1. (a) Schematic of dualbeam FIB/SEM equipment; (b) an example of a cross-section by FIB. A thin layer of
Pt is deposited before ion milling
During a basic indentation test an ideally rigid
indenter of known geometry is pressed against the
sample surface up to a controlled maximum load,
following a controlled loading (or displacement)
rate. When the indenter is driven into the material,
both elastic and plastic deformation processes occur,
producing a hardness impression that conforms to the
shape of the indenter to a certain contact depth, h
c

(Figure 3(a)).
The hardness H is easily obtained as a function of
load (or penetration depth) by the following equation:
H
P
A
c
= (i)
where P is the maximum load and A
c
is the indenter
projected contact area, which is given as a polynomial
function of the contact depth,h
c
,for a Berkovich indenter:
A a h a h a h a h
c c c c c
= + + + +
0
2
1 2
1 4
3
1 8 / /
...

(ii)
The contact depth is defned as follows (see also
Figure 3(a)):
h h
P
S
c
=

(iii)
The coeffcient can range between 0.72 and 1;
a value of 0.75 is usually adopted for the Berkovich
indenter.
The contact area expressed in Equation (ii) is
evaluated by calibration on a certifed fused silica
reference sample, performed before and after each
series of tests. As the indenter is removed from the
surface,a purely elastic recovery phenomenon occurs,
thus giving a measurable unloading elastic contact
10 m
(a)
20 m
(b)
5 m
(c)
Fig. 2. Sequence for TEM lamella preparation by FIB techniques for a Pt-Cu alloy: (a) FIB milling of a thick
lamella and cutting section (~300 nm, milled at 0.92 nA); (b) lift-out of the lamella by the micromanipulator;
(c) welding of the lamella on the TEM sample holder and fnal thinning to electron transparency (~80 nm, at a
current of 0.28 nA)
Load (P)
A
c
=f(h
c
)
h
t
Y h
c
(a)
500
450
400
350
300
250
200
150
100
50
0
Displacement into surface, nm
0 1000 2000
Unloading
curve
Loading
curve
L
o
a
d

o
n

s
a
m
p
l
e
,

m
N
(b)
Fig. 3. (a) Contact geometry usually adopted in modelling sharp indentation testing. The equivalent cone angle
is equal to 70.3 for the Berkovich and Vickers indenters; (b) an example of a load-displacement curve for an
amorphous fused silica reference sample
stiffness, which can be analytically correlated to both
the materials and the indenters elastic properties by
the use of the Sneddon solution for the contact on an
axisymmetric elastic body on a fat surface (6):
E
S
A
r
=
2

(iv)
S = dP/dh is the elastic contact stiffness which is
evaluated, after ftting the upper portion (usually 50%)
of the unloading curve to a power-law relation (Oliver-
Pharr method (6)),as the slope of the unloading curve
at maximum load P
max
.
E
r
is the reduced modulus (which takes into account
both the elastic deformation of sample and indenter),
given by:
1
1 1
2 2
E
s
s
E
i
i
E
*
=
( )
+
( )

(v)
where E
i
and
i
are, respectively, the Youngs modulus
and the Poisson ratio of the indenter. is a numerical
correcting factor equal to 1.034 for a Berkovich
indenter, which is introduced to correct for the lack
of symmetry of the indenter with respect to the ideal
conical shape. As recently reviewed by Oliver and
Pharr (6), values in the range of 1.0226 1.085 can
be found in the literature; in the present work the value
of 1.000 is adopted, as suggested by the ISO 14577-1-2
standard.
Equations (i)(v) give a short synthesis of the Oliver-
Pharr method (see also Figure 4),which is conventionally
adopted for the analysis of hardness and elastic modulus
from a generic nanoindentation test.
An interesting modifcation of the conventional
nanoindentation is the so called continuous stiffness
measurement (CSM) method. In the CSM method
(7), the contact stiffness S is dynamically measured
during indentation and continuous hardness/depth
and modulus/depth curves are obtained using
Equations (i)(v).
Apart from the most conventional analysis,
nanoindentation testing has been used for the
evaluation of several other surface mechanical
properties, such as yield strength and strain hardening
behaviour of metals (7, 8), damping and internal
friction in polymers (i.e. storage and loss modulus),
activation energy and stress exponent for creep (8),
fracture toughness of bulk ceramics and coatings
(9), adhesion of thin flms and work of adhesion (11),
scale effects in mechanical behaviour of small scale
specimens (11) and residual stress (12, 13).
In the case of metals, signifcant dependence of
the measured hardness on the applied load is usually
observed, even if a self-similar indenter is used for
testing (for example, a pyramidal indenter). This
experimental evidence, which is usually referred to
as indentation size effect (ISE), is not only due to the
effects of surface preparation (i.e. surface hardening)
and/or indenter tip blunting (i.e. not perfectly sharp
indenters), but also to a real material scale-dependent
plasticity, that has been related to subsurface
modifcations of the dislocation density across the
plastically deformed volume which is created during
indentation.
The most diffused model to understand ISE was
proposed by Nix and Gao (10). The model is based
on a simple concept, that geometrically necessary
dislocations (GNDs) must be created in the plastically
deformed volume (beneath the indenter) to
accommodate the deformed material from the surface.
The GNDs exist in addition to the other statistically
stored dislocations (SSDs), which are usually present
in any polycrystalline metal. The additional amount
of GNDs gives rise to an additional hardening effect,
which is higher as the size of indentation decreases,
thus explaining the observation of increasing hardness
with decreasing applied load.
Starting from this idea and assuming a conical
rigid indenter, Nix and Gao came out with a simple
equation describing the variation of hardness as a
function of the penetration depth during indentation:
H H
h
h
= +
0
1
*
(vi)
where H
0
is the macroscale hardness and h* is a
characteristic length scale,which depends both on the
materials properties and the indenter geometry.
2. Case Study 1: Microstructural and
Nanomechanical Characterisation of
Pt-5%Cu Order Hardened Alloys
Pt-5 wt% Cu alloys are used in jewellery mainly
because the addition of Cu signifcantly improves
the mechanical properties compared to pure Pt,
particularly its resistance to plastic deformation (i.e.
yield strength and hardness); it is also known that
heat treatment of Pt-5 wt% Cu alloys can result in
a further increase of indentation hardness (often
F
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measured by Vickers microhardness testing) (14).
This phenomenon is related to the fact that the Pt-Cu
binary system forms an ordered structure (described
by the CuPt7 model) from the disordered face-
centred cubic (fcc) solid solution, in the composition
range 1225 at% Cu (14).
It has also been previously reported that the
order-disorder transition can be strongly enhanced
by inducing a certain quantity of microstructural
defects in the structure, for example, by quenching or
by plastic deformation (14).
A recent paper (15) reports a study of the order-
disorder transition in Pt-5 wt% Cu alloys using TEM-
selected area electron diffraction (SAED) probing,
showing that initially quenched specimens were
characterised by relatively larger ordered domains
after heat treatment and by a lower increase of
Vickers hardness in comparison with cold plastically
deformed samples. Nevertheless, a deeper analysis of
the infuence of the mechanical hardening process
on the microstructural and structural characteristics
of order-disorder transition is still required, in order to
discover the optimal cold working process in terms
of induced plastic strain and induced modifcation
of hardness and of hardening coeffcient, which can
guarantee the maximum increase of hardness after
heat treatment. Furthermore, there is still a strong
necessity for the development of more reliable
and accurate procedures for the technological
assessment of phase transitions after heat treatment.
In this section, an innovative procedure for the
mechanical and microstructural characterisation
of Pt-Cu order hardened alloys is presented,
essentially based on the combined use of micro- and
nanoindentation testing and ISE modelling, dualbeam
and TEM techniques. It is shown that the correct
modelling of micro- and nanoindentation hardness
results coupled with high resolution dualbeam and
TEM observations can give deeper information on
the actual infuence of the preliminary cold working
process on the order hardening transition.
2.1 Experimental Details
One as cast Pt-5 wt% Cu ingot was subjected to
homogenisation at 1000C for 15 h and then plastically
deformed by uniaxial compression (milled) with a
thickness reduction of 75%. From the milled plate
two samples were cut. One of these two samples
was heat treated at 290C for 3 h and fnally cooled
in air. The hardness of both samples was studied by
nanoindentation testing by means of a Berkovich
diamond indenter, using an Agilent G200 Nano
Indenter, in a CSM mode under a constant strain
rate of 0.05 s
1
and a maximum penetration depth
of 2000 nm (other test and ftting parameters were
chosen according to ISO 14577-1-2 standards) (18).
Cross-section SEM-feld emission guns (SEM-FEG)
microstructural observation and TEM-SAED analyses
were performed after FIB sample preparation in a
dualbeam (FEI Helios Nanolab 600).
Cross-sections were obtained by FIB milling after a
preliminary in situ Pt deposition to protect the surface
layers during ion milling; the sectioning process
consisted of a preliminary high ion current milling
(9 nA) followed by cleaning the section (0.9 nA) until
the desired section was obtained. Microstructural
observation was performed using both the ion probe
(maximum microstructural contrast) and the electron
probe (maximum morphological contrast),secondary
electrons were detected in both cases. The dualbeam
technique was also used to extract electron transparent
foils for TEM (Philips CM 120, LaB6 analytical). TEM
analyses consisted of bright feld high magnifcation
observation followed by SAED, performed both at the
surface of the TEM foil and at its centre.
2.2 Results and Discussion
The results of the nanoindentation testing are
reported in Figure 5 and summarised in Table I.
The nanohardness profles presented in Figure 5
clearly confrm that the hardness is signifcantly
increased after heat treatment. Furthermore, in this
case, the presence of a surface hardened layer is
observed for penetration depths lower than 500 nm.
Nanoindentation testing allows a more detailed
analysis of this effect to be performed: it is very
important to note that the hardness profles for both
samples have a very similar shape, i.e. a very similar
skin effect is observed in both cases.
This observation suggests that the microstructure
derived from the cold working process (which likely
involves the formation of a surface hardened layer) is
completely maintained after heat treatment, because
the same hardness gradient is observed in both
cases. This also means that neither recrystallisation
nor changes of grain size occurred during the heat
treatment at 290C, suggesting that the order-disorder
phase transition is realised at a subgrain level with no
signifcant modifcation of dislocation density.
Another relevant observation comes from SEM-
FEG imaging of the nanoindentation marks. Figure 6
shows the rounded shape of the indent lateral profle.
Fig. 5. (a) Nanoindentation hardness depth for both Pt-Cu samples under investigation; (b) analysis of hardness
data through the Nix-Gao ISE model. Hardness is confrmed to be higher for the heat treated sample
From Figure 6(b) it can be clearly seen that for
the heat treated sample there was a higher amount
of piling up at the edge of indentation. This suggests
that the heat treatment may have infuenced not only
hardness, but also the hardening coeffcient of the
sample. As reported earlier (8), a different hardening
coeffcient usually involves a different amount of
piling-up during indentation.
H
0
= 3.72 GPa
h
*
= 0.077 m
{
Cold worked and heat treated at 290C
Only cold worked
H
0
= 2.76 GPa
h
*
= 0.186 m
{
1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8
1/h, m
1
(
H
/
H
0
)
2
H
2
h
*
H
0
h
= 1 +
( )
(b)
6.5
6
5.5
5
4.5
4
3.5
3
2.5
2
1.5
1
0.5
0
0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200
N
a
n
o
h
a
r
d
n
e
s
s
,

G
P
a
Only cold worked
(a)
This observation is confrmed by an analysis of
the hardness data using the Nix-Gao ISE model
(10), where a signifcantly different value of the h
*

parameter is found (see Table I and Figure 5(b)),
thus suggesting that the two samples may have a
different hardening coeffcient. This leads to a very
important conclusion: the hardening behaviour (not
only hardness) of the heat treated sample is modifed,
which can have a signifcant effect on workability
and on service performance of materials heat treated
in such a way.
The results of the indentation modulus profle are
reported in Figure 7, where elastic modulus is shown
to be constant with penetration depth and does not
depend on sample microstructure (as expected).
The elastic modulus seems to be ~5% higher for the
heat treated sample, however this is not considered
statistically signifcant. This difference is likely due to
the observed pile-up during indentation. As widely
reported in the literature, piling up always involves an
over-estimation of the measured elastic modulus, due
to incorrect evaluation of the real contact area by the
Oliver-Pharr method (7). The observed difference in
the elastic modulus is therefore likely not to be a real
effect, thus suggesting that modulus does not change
signifcantly after the heat treatment (as expected).
In both Figures 8 and 9, the left column refers
to the cold worked sample, while the right column
refers to the cold worked and heat treated sample.
Dualbeam characterisation analysis clearly shows
that the microstructure and microscale morphology
of both samples are very similar. In both cases,
a strongly oriented (biaxial) grain structure is
observed, which is likely to be a consequence of the
cold forming process. These results confrm that the
microstructure of the sample is not modifed by the
Table I
Summary of Results for the Micro- and Nanomechanical Characterisation of Platinum-5 wt%
Copper Samples
Hardness
a,
GPa Modulus
a
, GPa
Nix-Gao parameters (Equation
(vi)) (H
0
; h
*
), GPa; m
Cold worked sample 3.08 0.11 205.1 4.7 2.76; 0.186
Cold worked and heat
treated sample
3.88 0.21 215.2 7.1 3.72; 0.077
a
Average in the penetration depth range of 300900 nm
5 m
(a)
5 m
(b)
Fig. 6. Dualbeam (SEM column) micrographs on Berkovich nanoindentation marks for: (a) cold worked sample;
(b) cold worked and heat treated sample. A higher amount of piling up is observed in case of the heat treated
sample, thus suggesting that order hardening also involves a modifcation of the hardening coeffcient
heat treatment and that the order-disorder transition
is likely to happen at a subgrain level. A similar
result can be achieved by a careful analysis of the
nanoindentation hardness profle.
The results of TEM-SAED analysis on dualbeam
prepared thin foils are reported in Figure 9. Figures
9(a) and 9(e) show detail of the grain structure at
the sample surfaces. It is clear that the grain structure
has been maintained almost identically after heat
treatment and that the dislocation density is similar
in both cases, confrming the results obtained
by nanoindentation and dualbeam cross-section
observation. In addition, a very thin surface hardened
layer (characterised by a fner grain size) is clearly
shown in Figures 9(b) and 9(f). Figures 9(c)(g)
show details of the intragrain morphology, which are
signifcantly different for the two samples. In the case
of the heat treated sample the ordered domains are
clearly visible confrming that the phase transition
happens at a subgrain level.
In addition, a complete change of dislocation
distribution is evident in the ordered domain,
suggesting that dislocations (or generally speaking,
all defects coming from plastic deformation) can be
considered the main nucleation sites for the phase
transition. This explains why the order-disorder
transition is usually observed only for seriously
plastically deformed samples and not for quenched
or as-cast samples.
3. Case Study 2: Infuence of Process
History on Microstructure and Mechanical
Properties of Platinum-Rhodium Alloys
Alloys of Pt and Rh (19, 20) are widely used in
many industrial sectors, due to their high strength
compared to pure Pt, good workability and very
good corrosion resistance even at high temperature.
Examples from industry include thermocouples
for high-temperature measurement, clean and inert
heating elements in experimental high-temperature
furnaces, components in the manufacture of glasses,
catalyst gauzes and laboratory equipment (2124).
The use of Pt-Rh alloys has been increasing due to
the fact that Rh dissolves in all proportions in Pt, thus
forming a substitutional solid solution which usually
involves an increase of hardness with no signifcant
loss of workability.
However, there are still controversial results in
the literature on the actual phase evolution of
Pt-Rh systems at temperature below 1033 K. Some
authors have proposed the presence of a miscibility
gap below 1033 K (19), which was not confrmed
Fig. 7. Elastic modulus as measured by nanoindentation testing for both samples
240
220
200
180
160
140
120
100
0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200
E
l
a
s
t
i
c

m
o
d
u
l
u
s
,

G
P
a
Only cold worked
(a)
20 m 10 m
(c)
1 m
(b)
1 m
(d)
1
6
0
.
8

n
m

(
c
s
)
Fig. 8. Dualbeam (FIB and SEM column) analysis of samples: (a) and (b) the cold worked sample; (c) and
(d) the cold worked and heat treated sample. It is worth noting that the microstructure obtained after cold
working is maintained after heat treatment, including the surface hardened layer
by other similar studies, thus suggesting that
further investigations should take place to achieve
a better and deeper understanding of the actual
microstructural and phase evolution of Pt-Rh systems
after heat treatment and cooling to room temperature
(20).
Another issue of interest is represented by the
observed tendency to oxidation of Rh after heat
treatment of Pt-Rh systems, which usually involves a
decrease in the indentation hardness of the samples;
in the case of industrially produced components
(for example, wires) the mechanisms of oxidation
behaviour as a function of process parameters have
not been completely investigated. These examples
suggest that innovative characterisation procedures
are strongly needed, with the main objective of fnding
out the existing correlations between the observed
microstructures and the technological performance
(for example, hardness) of the components. This data
can then be used to optimise the process parameters.
In this work, the usefulness of the above
described procedure for the microstructural and
nanomechanical characterisation is demonstrated for
Pt-10 wt% Rh wires.Two different industrially produced
samples (which were expected to be identical) were
investigated by high resolution microscopy techniques
(dualbeam-TEM) and nanoindentation testing. A
correlation between the observed differences in terms
of indentation hardness and the actual microstructure
is fnally presented.
(d)
(h)
(e)
200 nm
(f)
200 nm
(g)
20 nm
(b)
200 nm
(a)
200 nm
(c)
20 nm
Fig. 9. TEM-SAED analysis on dualbeam prepared thin foils: (a), (b), (c) and (d) cold worked samples; (e),
(f), (g) and (h) cold worked and heat treated samples. High dislocation density is observed in both cases.
Order hardening is observed at a subgrain level; (d) and (h) SAED patterns clearly show the change of crystal
structure after heat treatment
3.1 Experimental Details
Two sets of Pt-10 wt% Rh wires from two different
producers, referred to as Sample 1 and Sample 2, were
investigated. The samples were nominally produced
by the same process, consisting of various stages of
drawing and annealing from the initial ingot down
to the fnal section of about 350 m.Vickers hardness
(applied load 100 gf) was preliminarily performed
on both samples and a signifcant difference was
observed (as briefy reported in Figures 11(a) and
11(b)). In particular the Vickers hardness was about
15% higher for Sample 2.
Starting from this preliminary result, characterisation
activities consisted of dualbeam-TEM microstructural
observations and nanoindentation testing. The ion
beam was used at a current of 48 pA in the dualbeam
microscope to produce physical etching of the
microstructure: in this way, the cross-section grain
structure of the wires could be investigated by using
the ion source and detecting secondary electrons.
A TEM lamella was realised at the external edge of
each sample: one grain boundary was included at the
centre of each lamella, as reported in Figure 10. In
this way, all microstructural features infuencing the
mechanical properties of the wires were able to be
investigated (for example, subgrain microstructure,
grain boundary oxidation, presence of precipitates at
grain boundary or in the matrix and oxygen diffusion
from the sample edge).
Nanoindentation testing was used to evaluate
the subgrain hardness profle: one line of Berkovich
indentation (maximum penetration depth 1 m, CSM
mode, 0.05 s
1
constant strain rate) was realised across
the section of each wire. The measured hardness
profle was then compared to the observed grain
structure.
3.2 Results and Discussion
Conventional metallographic observations are shown
in Figure 11. Dualbeam observation with ion source
5 m
(a)
5 m
(b)
100 mm
(b)
100 mm
(a)
Fig. 10. TEM lamella for: (a) Sample 1; and (b) Sample 2. A grain boundary is clearly visible in both cases
Fig. 11. (a) Cross-section of Pt-10 wt% Rh wire Sample 1: Vickers hardness HV0
0.1
= 92 4 (optical
microscope after polishing, 50, applied force: 0.1 N); (b) cross-section of Pt-10 wt% Rh wire Sample 2:
Vickers hardness HV0
0.1
= 105 4 (optical microscope after polishing, 50, applied force: 0.1 N)
of the cross-sections of both wires are reported in
Figure 12. In Figure 11(b) a coarser grain size is
clearly observed for Sample 2. It is important to note
that twins and low-angle grain boundaries can also be
revealed by using the FIB source for surface etching,
thus explaining why a larger number of grains are
revealed by this method compared to the conventional
chemical etching and optical microscopy. The
difference in observed grains was resolved with the
FIB, which showed that the large grains of Sample 2
are composed of smaller subgrains.
Nanohardness section profles (Figure 13)
confrmed a higher hardness for Sample 2.
Nevertheless, the observed differences are reduced
in comparison with data from microhardness testing
(performed at 100 gf): this suggests that some artefacts
are present during microhardness testing, likely due to
bending (or buckling) of the wires during indentation.
For nanoindentation testing, the results reported in
Figure 13 correspond to a penetration depth of
300 nm (applied load of about 1 gf), to avoid any
artefact due to buckling or bending of the wire. It is
also worth noting that some variation of nanohardness
is observed from one grain to another.
A grain boundary is clearly visible for both samples.
In the case of Sample 2 the TEM lamella was likely
created at a twin boundary, as clearly identifable
in Figure 14. Looking at Figures 14(b) and 14(d),
100 mm
200 mm
(a) (b)
Fig. 12. Example of dualbeam analysis for: (a) Sample 1; and (b) Sample 2. Grain structure is clearly visible
by using the ion source. The nanoindentation section profle is also clear in both cases. The TEM lamella was
obtained at the sample edge corresponding to a grain boundary for each sample
0 50 100 150 200 250 300 350
Radial position over the wire section, mm
N
a
n
o
h
a
r
d
n
e
s
s
,

G
P
a
2.5
2
1.5
1
0.5
0
Pt-10 wt% Rh Sample 2
Pt-10 wt% Rh Sample 1
Fig. 13. Nanohardness
cross-section profles for
both Pt-Rh wires under
investigation (error bars
have been removed for
clarity)
signifcant microstructural differences can be
identifed between the two samples. In particular,
Sample 1 is characterised by the presence of
precipitates in the matrix (average diameter ~15 nm).
In Sample 2, a different intragranular microstructure
can be observed, mainly characterised by very fne
precipitates dispersed in the matrix. The observed
difference in micro- and nanoindentation hardness
may therefore be due to differences of the intragrain
phase distribution,which are likely strongly infuenced
by cooling rates during processing.
It is also worth noting that no differences in terms of
crystal structure (SAED) and composition (EDS) were
detected between the two samples, thus meaning that
observed differences are essentially due to different
(or not completely controlled) cooling rates during
some of the processing steps.
To verify this latter hypothesis, both samples were
subjected to a heat treatment at temperature of 450C
for 1 h, followed by cooling in air. Results of the TEM
analysis are reported in Figure 15, where a similar
microstructure is observed in both cases. In this case,
precipitates in the matrix of average diameter ~15 nm
are also observed for Sample 2, thus confrming that
the much fner subgrain microstructure that had been
observed in the as-received Sample 2 was likely due to
higher cooling rates during processing.
This example clearly explains how critical it is to
properly control all parameters during the processing
of these components. The use of high-resolution
microscopy was in this case absolutely necessary
to examine the actual correlations between the
measured technological performance (for example,
indentation hardness), the actual microstructural
features of samples and the main process parameters.
4. Conclusions
This paper presents the application of high resolution,
multitechnique and multiscale procedures to the
nanomechanical characterisation of materials.
It was observed that a comprehensive
characterisation of complex alloys can be achieved
(a) (c)
100 nm
100 nm
(b) (d)
20 nm
20 nm
Fig. 14. TEM-SAED analysis on Sample 1: (a) TEM, 120 kV, 140.000; (b) (TEM, 120 kV, 660.000) (TEM-
SAED, 120 kV, Z = [100]); and Sample 2: (c) TEM, 120 kV, 230.000; (d) (TEM, 120 kV, 660.000) (TEM-
SAED, 120 kV, Z = [114])
by the combination and synergic use of micro- and
nanohardness testing and dualbeam-TEM techniques.
Two case studies were reported relating to the
nanomechanical and microstructural characterisation
of an order hardened Pt-Cu alloy and a Pt-Rh wire
alloy. In particular, the analysed case studies showed
that nanoindentation testing can give valuable
information on the level of microstructural changes
as a consequence of phase transition and intragrain
microstructure.The use of dualbeam-TEM combination
technique may fnally help to understand how and
why microstructural changes due to heat treatment
affect the mechanical properties of materials.
In the frst case it was shown how the order-
disorder transition in Pt-Cu alloys can be evaluated
by indentation testing and that the analysis of
hardness depth profles can be extremely useful in
suggesting the mechanisms of phase transition, which
were later proved using high resolution microscopy,
demonstrating that the order-disorder transition
happens at a subgrain level only in previously cold
worked alloy.
In the second case the use of FIB showed that
the results from optical imaging of the grains were
misleading, as were those from the microhardness test,
because they did not give correct information of the
real grain structure and the actual nanomechanical
properties of the Pt-Rh wires. High resolution TEM
imaging pointed to a likely mechanism (differences
in nanoprecipitates) explaining the differences in
hardness of the grains.With this work the existence of
a miscibility gap and the absence of oxidation have
been clearly shown, clarifying a point of contention
between researchers in the feld.
Such results clearly show how nanomechanical
testing in combination with high resolution
microscopy can be usefully applied to the
characterisation of nanostructured systems for
functional (or non-mechanical) application and how
they can be a powerful tool for process optimisation
and/or prediction of in-service behaviour.
Acknowledgments
This paper is dedicated to the memory of our wonderful
friend and colleague, Dr Paolo Battaini, who recently
passed away. The authors acknowledge the assistance
of Daniele De Felicis during dualbeam characterisation
activities, carried out at the Interdepartmental
Laboratory of Electron Microscopy(LIME), University
ROMA TRE, Rome, Italy, http://www.lime.uniroma3.it.
References
1 P. H. Mayrhofer, C. Mitterer, L. Hultman and H. Clemens,
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2 S. Zhang, D. Sun, Y. Fu and H. Du, Surf. Coat. Technol.,
2003, 167, (23), 113
3 M.W. Phaneuf, Micron, 1999, 30, (3), 277
4 Introduction to Focused Ion Beams Instrumentation,
Theory, Techniques and Practice, 2nd Edn, eds. L. A.
Giannuzzi and F. A. Stevie, Springer Science+Business
Media, New York, USA, 2005
5 L. A. Giannuzzi and F. A. Stevie, Micron, 1999, 30, (3), 197
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(1), 3
8 A. Bolshakov and G. M. Pharr, J. Mater. Res., 1998,
13, (4), 1049
9 S. J. Bull, J. Phys. D: Appl. Phys., 2005, 38, (24), R393
100 nm
50 nm
(a) (b)
Fig. 15. (a) Sample 1 after heat treatment at 450C for 1 h (TEM, 120 kV, 230.000); (b) Sample 2 after heat
treatment at 450C for 1 h (TEM, 120 kV, 380.000) (Z = [100])
10 W. D. Nix and H. Gao, J. Mech. Phys. Solids, 1998, 46,
(3), 411
11 M. D. Uchic, D. M. Dimiduk, J. N. Florando and
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Appl. Phys. Lett., 2007, 91, (11), 111915
13 A. M. Korsunsky, M. Sebastiani and E. Bemporad, Mater.
Lett., 2009, 63, (22), 1961
14 C. Mshumi and C. Lang, Platinum Metals Rev., 2007, 51,
(2), 78
15 M. Carelse and C. I. Lang, Scripta Mater., 2006, 54,
(7), 1311
16 ASTM Standard E384, Standard Test Method for Knoop
and Vickers Hardness of Materials, ASTM International,
West Conshohocken, PA, 2011
17 D. Tabor, The Hardness of Metals, Oxford University
Press, New York, USA, 1951
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indentation test for hardness and materials parameters
Part 1: Test method and Part 2: Verifcation and
calibration of testing machines
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A, 1998, 29, (6), 1545
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The Authors
Marco Sebastiani,
PhD, is an Assistant
Professor of Materials
Science at the
University of Rome
Roma Tre. His
research is focused on
surface engineering,
micron-scale residual
stress analysis and
nanomechanical
testing of thin flms
and nanostructured
materials. He is the
author of more than
40 papers in peer
reviewed international
journals.
Marco Renzelli
received his Msc in
Physics in 2010 at La
Sapienza University
of Rome. In January
2012 he started his
PhD in Engineering
at the University of
Rome Roma Tre.
His interests lie in
advanced materials
production and
characterisation,
surface engineering,
PVD technologies,
focused ion beam
microscopy and
nanomechanical
characterisation.
Paolo Battaini held
a degree in nuclear
engineering, had been
a consulting engineer
with 8853 SpA,
and was a Professor
of Precious Metal
Working Technologies
at Milano Bicocca
University, Italy, from
2003 to 2011. He has
been a recipient of the
Santa Fe Symposium
Research and
Ambassador Award.
He died on 27th
September 2013.
Edoardo Bemporad
is a nuclear engineer
and holds a PhD in
Materials Engineering.
He is a full Professor
of Materials Science
and Technology at the
University of Rome
Roma Tre. He is the
author of more than
300 papers published
in international and
national journals,
and his interests lie
in structured and
nanostructured
coatings, especially
for wear resistance,
corrosion resistance
and high temperature
oxidation.
High Temperature Thermomechanical
Properties of Titanium-Rhodium-based
Alloys Containing Scandium
Unusual shape memory effects observed in scandium-substituted alloy system
By Yurii V. Kudriavtsev*
G. V. Kurdyumov Institute of Metals Physics of the National
Academy of Sciences of Ukraine (NASU) Vernadskiy Str. 36,
03142, Kiev, Ukraine
*Email: kudra@kiev.ua
Elena L. Semenova**
I. N. Frantsevich Institute for Problems of Materials Science
of NASU Krzhyzhanovsky Str. 3, 03680, Kiev, Ukraine
**Email: selena@ipms.kiev.ua
At high temperatures, the equiatomic binary
compounds formed by Groups 4 and 8 transition metals
are known to undergo martensitic transformation,
which may be accompanied by a shape memory effect.
Among these compounds, titanium-rhodium (TiRh) is
of special interest not only because it undergoes two
martensitic transformations at high temperature,for one
of which the shape memory effect has been observed,
but also because it demonstrates unusual shape
recovery behaviour at temperatures higher than 400C.
The present work focuses upon the thermomechanical
and mechanical properties of 50 at% rhodium-
scandium-titanium ternary alloys where Ti is substituted
by Sc. These alloys were investigated for the frst time
using electrical resistance, dilatometry and three-point
bending techniques in the temperature range 20C to
850C. It was found that the sample with 0.1 at% Sc
exhibited full shape restoration in the ranges of both
martensitic transformations at ~340C and ~750C.
Two-way shape recovery was also observed. A small
temperature hysteresis,desirable for alloys used in actuator
applications, is present in TiRh and Rh-Sc-Ti alloys. Both
TiRh and Sc-containing alloys exhibit continuity of the
deformation process on cooling and shape restoration
on heating in a wide range of temperatures.This feature
of both TiRh and Rh-Sc-Ti alloys implies the possibility
of their application in different heat-regulating elements
at temperature ranges from room temperature to 850C.
Introduction
An important feld for the application of commercial
alloys with shape memory effect is heat regulation.The
alloys considered in this paper are being investigated
for use in this application at high temperatures.
Thermomechanical regulators have a number of
advantages over electromechanical and electronic
regulators, which are prone to failure under certain
conditions. Regulators made from shape memory
alloy, such as locking devices for control rods in
nuclear power stations, could provide more robust
safety systems as they do not require any external
power source for their activation, for example.
One of the challenges in high-temperature materials
science is to discover alloys that exhibit a high-
temperature shape memory effect and to investigate
the conditions, including temperature range, under
which these properties are observed. The Rh-Ti
system is considered promising taking into account
information on the alloys based on equiatomic phase
(15) and data on the thermoelastic properties of the
equiatomic TiRh alloy at high temperatures (6).
There is limited literature data on the character and
temperatures of transformation in near-equiatomic
Rh-Ti binary alloys. Such data are to a certain extent
conficting, and concern mainly the crystal structure
of the phases formed (15). An X-ray study of TiRh
in the temperature range from room temperature to
1000 showed that a high-temperature phase with a
caesium chloride (CsCl) type cubic crystal structure
transformed to a phase with tetragonal structure at
84520 when cooled from 1000,then transformed
to a monoclinic phase at 835 (3). Both transitions
were considered as second order transitions. It was
noted that no domain of coexistence of cubic and
tetragonal phases was observed, while the tetragonal
character of the phase structure increased on cooling
gradually from 845C to 83. At temperatures lower
than 83 further distortion of the crystal lattice
toward monoclinic symmetry took place.
Observed temperature intervals of three
modifcations of TiRh (3) confrmed previously
published data (2) that the TiRh phase crystal structure
at 700 is tetragonal and of the AuCu type, while at
room temperature the phase is monoclinic with lattice
parameters different from those previously given (3).In
alloys with compositions deviating from stoichiometry
towards 10 at% Rh content, according to the Rh-Ti
phase diagram, a phase with orthorhombic crystal
structure was observed at room temperature (2) within
the homogeneity range of the equiatomic phase (4, 5).
Two transformations in TiRh were revealed by
an electrical resistance method with temperatures
that differ from those previously obtained (3, 6)
(Figure 1(a)). Both transformations occurred almost
without hysteresis. The fact that they are clearly
separated by temperature (6) puts in doubt the
interpretation of the transformation as a second order
transformation (3).
The shape memory effect accompanies the
formation of a phase with a monoclinic crystal
structure in TiRh at temperatures close to those
obtained by the electrical resistance method, M
s
2
~340C. Anomalous behaviour of the sample when
heated to 400C has been observed (6).
The aim of the present paper is to study the infuence
of the third component, Sc, on the properties of TiRh-
based alloys and particularly the thermomechanical
behaviour of these alloys in the temperature range
from ambient to 850C. Sc was chosen to substitute
Ti because it is similar to Ti by chemical properties
and also forms an equiatomic compound with Rh.
However the crystal structure of ScRh, which is of the
CsCl type (the same as the TiRh parent phase),is stable
from subsolidus temperature to room temperature (7).
This makes it easy to follow changes that occur in
the Rh-Sc-Ti ternary alloys with increasing scandium
content.
Information on the effect of scandium on the
martensitic transformation (MT) in TiRh is almost
unknown. It was noted earlier that substitution of
Ti by Sc would lead to a decrease of the martensitic
transformation temperature (8).The phase relations in
the ScRh-TiRh system have been studied elsewhere (9).
Experimental
The starting metals used for alloying were iodised
Ti, Rh powder (99.97 wt%), distilled Sc to prepare
the alloys with 0.1 at% and 1 at% Sc, and Sc metallic
powder (chemical analysis: 1.3 wt% O and less than
0.15 wt% of metal admixture) to prepare the remaining
alloys. Before melting the alloys, the rhodium powder
was sintered in vacuum at 1200C and melted in an arc
furnace in order to avoid sputtering during alloying.
The alloys with 0.1 at% and 1 at% Sc were melted
directly from the components and those with 2.2 at%,
3.5 at%, 16.7 at% and 21 at% Sc were melted from the
ligature (the Sc-Rh binary alloys) with additions of
titanium in an arc furnace with a non-consumable
tungsten electrode on a water-cooled copper hearth
under an atmosphere of purifed argon gas.The ingots
were melted four times to ensure a complete melt.The
weight losses on melting were small (below 0.5 wt%)
so nominal compositions are reported.
Samples of the six alloys were prepared along the
ScRh-TiRh section.The as-cast alloys were investigated
by electrical resistance and dilatometry tests. The
electrical resistance was measured by the four-probe
method with continuous heating of the sample at
a rate of 20C min
1
. The change in sample length
(l
20C
= 14.7 mm) on heating and cooling in the dilatometry
test was measured by an induction micrometer Micron-02
200 100 100 200 300 400 500 600 700 800 900
Temperature, C
1.3
1.2
1.1
0.9

(a)
r
/
r
0
1.3
1.2
1.1
0.8
0.7
0.6
200 100 100 200 300 400 500 600 700 800 900

(b)
1.3
1.2
1.1
p/p
0
0.8
0.7
200 100

100 200 300 400 500 600 700 800 900
(c)
A
f
2
M
f
2
A
s
2
M
s
2
M
f
1
A
s
1 M
s
1
A
f
1
M
f
2
A
s
2
M
s
2
A
f
2
M
f
1
A
s
1
M
s
1
A
f
1
M
f
2
A
s
2
M
s
2
A
f
2
M
f
1
A
s
1
M
s
1
A
f
1
r
/
r
0
Temperature, C
Temperature, C
r
/
r
0
Fig. 1. Dependence of electrical resistance on temperature in ScRh-TiRh alloys: (a) TiRh; (b) Rh-0.1 at% Sc-Ti;
and (c) Rh-1 at% Sc-Ti
supplied by All-Union company Stankoimport,
Moscow, Russia, with accuracy 0.1 micron. The
temperature of each sample was measured with a
chromel-alumel thermocouple welded to the sample
that was placed in a quartz holder.Thermomechanical
properties of the alloys were examined using the three
point bending technique by thermocycling through the
transformation range during cooling under load and
heating after unloading (10).Thermomechanical curves
were taken several times for each sample at different
loads.The sample sizes were 0.4 0.4 10 mm (alloys with
0.1 at% and 1 at% Sc) and 0.4 1.5 8 mm (alloys with
2.2 at% and 3.5 at% Sc). The loads varied between
50 g and 375 g. The sample of the alloy with 0.1 at%
Sc underwent more detailed investigation in the
temperature range which covered both transformations
according to data on electrical resistance.The sizes of
the sample and the load applied in this experiment
are presented and discussed together with the results.
The alloys were characterised by X-ray diffraction
(XRD) and microstructure analyses and the results are
presented elsewhere (9).
Results and Discussion
Electrical Resistance
The TiRh resistance curve shows two transformations
in the solid (Figure 1(a)). The transformation at
~750C (
M
s
1
), of small intensity and without hysteresis,
is indicated by a point of infection on the curve of
resistance. The transformation at ~340C (
M
s
2
), of
greater intensity, occured with a small hysteresis: the
change in electrical resistance reached ~10%.
Investigation of MT in the ScRhTiRh ternary alloys
by the electrical resistance method was carried out on
the samples with 0.1 at%, 1 at%, 2.2 at%, 3.5 at%, 16.7 at%
and 21 at% Sc (Figures 1(b), 1(c) and 2(a)2(d)).
The resistance curves for the frst four alloys exhibit
two transformations as was observed in the TiRh alloy.
The heating and cooling curves of the alloys with
0.1 at% and 1 at% Sc almost superimpose in a wide
temperature range (Figures 1(b) and 1(c)).The effect
that corresponds to the second transformation is more
pronounced in these alloys,although unlike that in TiRh
the transformation became almost without hysteresis.
Given that the temperature of both transformations
slowly decreased with increasing content of scandium
in the alloys, the resistance curves were observed to
behave similarly to TiRh.
In contrast to the curves of TiRh and the alloys with
0.1 at% and 1 at% Sc, a larger change in resistance with
decreasing temperature was observed in the curves
for the alloys with 2.2 at% and 3.5 at% Sc (Figure 2).
The frst martensitic transformation (
M
s
1
) for these
alloys was clearer and more intense (Figures 2(a)
and 2(b)). Its temperature varied little with increasing
scandium content. At the initial transformation
stage (740C705C) a sharp change in electrical
resistance took place which is a characteristic of the
transformation and gives reason to believe that in the
process of structural transformation an intermediate
phase with a crystal structure similar to the R-phase in
TiNi might form frst (premartensitic transformation)
(11).The second MT was identifed by a change in the
slope of the resistance curve.The critical temperatures
of the martensitic points in the forward and reverse
transformations coincide.
With increasing scandium content in the alloys to
16.7 at% Sc only one transformation was observed
in the resistance curve at approximately 400C,
a temperature signifcantly lower than the frst
transformation in alloys with lower scandium content
(Figure 2(c)).The shape of the alloy curve on cooling
repeated that for alloys with 2.2 at% and 3.5 at% Sc
(Figures 2(a) and 2(b)).Tests on the alloy with 16.7at%
Sc at temperatures below room temperature (down
to 196C) showed the absence of any effect. This
confrms the assumption that with increasing content
of scandium in the alloys the second transformation
disappeared instead of lowering its temperature.
According to X-ray analysis this alloy has a tetragonal
crystal structure of AuCu type at room temperature
(9).Thus, it may be concluded that the effect observed
on the resistance curve of the alloy with 16.7 at% Sc
corresponds to the structural transformation CsCl
AuCu. Given the above as well as data on the electrical
resistance of TiRh and the alloys with lower scandium
content, even without direct studies of the structure by
high-temperature X-ray analysis, it seems clear that the
product of the frst MT in all alloys of the ScRh-TiRh
system is a phase with a tetragonal crystal structure of
the AuCu type.
Only a little variation in the slope of the resistance
curve of the alloy with 21 at% Sc was observed at
about 200C, indicating that the intensity of the
transformation decreases with increasing content of
scandium in the alloys (Figure 2(d)).This alloy is two-
phased at room temperature: CsCl + AuCu (9).
Thus, according to electrical resistance studies,
substitution of Sc for Ti in TiRh resulted in inhibition of
the second MT,the product of which would be a phase
with monoclinic crystal structure, and in lowering the
characteristic points of the frst transformation, which
disappeared with increasing content of scandium in
the alloys.
The electrical resistance data concerning the two
stage transformations in the solid Rh-Sc-Ti ternary
alloys and similar data on TiRh point to the existence of
a two phase region in these alloys and are at variance
with earlier conclusions (3) on the attribution of the
transformation in TiRh to second order transformation.
Fig. 2. Dependence of electrical resistance on temperature in ScRh-TiRh alloys: (a) 2.2 at% Sc; (b) 3.5 at% Sc;
(c) 16.7 at% Sc; and (d) 21 at% Sc
(a)
1.1
(b)
1.1
1
(c)
1.1
20 100 200 300 400 500 600 700 800 900 1000
Temperature, C
1.1
1
1
1
(d)
20 100 200 300 400 500 600 700 800 900 1000
Temperature, C
20 100 200 300 400 500 600 700 800 900 1000
Temperature, C
20 100 200 300 400 500 600 700 800 900 1000
Temperature, C
M
s
2
M
s
1
M
s
2
M
s
1
M
s
1
M
s
1
r
/
r
0
r
/
r
0
r
/
r
0
r
/
r
0
X-ray analysis of the ScRh-TiRh alloys with 0.1 at%16.7at%
Sc showed regions of coexistence of phases of TiNi and
AuCu types as well as those of AuCu and CsCl types
(9). The electrical resistance data on TiRh-TiCo alloys
in which rhodium atoms were replaced with cobalt
atoms also demonstrated two stages of transformation
that were distinctly separated (6). In addition, some
effects related to both transformations have been
observed on the thermal analysis curve of TiRh (9).All
these data strongly suggest that the transformations in
TiRh and alloys based on it are frst order.
Thermomechanical Tests
Thermomechanical tests were carried out for the
alloys with 0.1 at%, 1 at%, 2.2 at% and 3.5 at% Sc
(Figures 35). There was a continuous bend for the
sample with 0.1 at% Sc cooled under a load of 50 g
from ~900C50C, and this was more intense in the
range 750C650C. On heating (after unloading) the
sample recovered its shape completely. In the range
400C200C the degree of deformation on cooling
increased almost linearly. At a load of 100 g a bend
occurred in the same temperature range (Figure 3(a),
dashed lines) and the deformation of the sample
proved to be twice as large in comparison with that at
a load of 50 g; however the sample recovered fully on
subsequent heating.Some residual plastic deformation
that occurred after loading and unloading of the
sample at ~850C indicated the inconsistency of the
applied load with the elastic parameters of the sample
at this temperature. Note the basic similarity of the
thermomechanical curves of the alloy at different
loads (Figure 3(a)).
The frst transformation in the alloy containing 1 at%
Sc occurred in the same temperature range,750C650C
(Figure 3(b)). In the temperature range from 650C to
room temperature the thermomechanical curve was
almost linear. After unloading at 20C and subsequent
100 200 300 400 500 600 700 800 900
Temperature, C
0.6
0.4
0.2
0
H
e
i
g
h
t
,

m
m
P
1
P
2
+P
2
+P
1
M
s
1
A
f
1
(a)
100 200 300 400 500 600 700 800 900
Temperature, C
0.6
0.4
0.2
0
H
e
i
g
h
t
,

m
m
P
M
s
1
A
f
1
(b)
+P
Fig. 3. Dependence of bending on temperature in ScRhTiRh alloys: (a) 0.1 at% Sc; and (b) 1 at% Sc
Fig. 5. Dependence of bending on temperature in TiRh alloy
Fig. 4. Dependence of bending on temperature in ScRhTiRh alloys: (a) 2.2 at% Sc; and (b) 3.5 at% Sc
100 200 300 400 500 600 700 800 900
Temperature, C
0.2
0
H
e
i
g
h
t
,

m
m
+P
(b)
P
M
s
1
+P
2
(b)
A
f
1
100 200 300 400 500 600 700 800 900
Temperature, C
0.2
0
H
e
i
g
h
t
,

m
m
M
s
1
+P
P
(a)
100 200 300 400 500
Temperature, C
+0.2
0
0.2
H
e
i
g
h
t
,

m
m
B
+P
P
M
s
2
heating to 850C, the samples shape restored fully.
Cooling under load to the temperature of liquid
nitrogen (196C) showed that the M
f
temperature
of the alloy was about 20C. Below this temperature
cooling did not lead to additional defection of the
sample. The thermomechanical curves of both alloys
were without hysteresis except in the MT temperature
range for the transition CsCl AuCu, where a small
hysteresis occurred (Figures 3(a) and 3(b)).
The thermomechanical curves of the alloys with 2.2at%
and 3.5 at% Sc are similar to those of the alloys with
0.1at% and 1 at% Sc (Figures 4(a) and 4(b)).The curves
in Figures 35 show the results of the thermomechanical
experiments. They show the presence or absence of the
shape memory effect and the unusual feature of the
expansion of shape recovery at temperatures between
20C700C. Such a feature has not been observed in
other alloys exhibiting a shape memory effect.
The unusual performance of TiRh alloy observed
during a study of its thermomechanical properties has
already been mentioned (6). No further experiments
had been carried out to study the samples behaviour
when heated above the temperature of 400C and
it was only noticed that on reducing the elastic
constants of the alloy with temperature, the bend of
the sample would remain constant or increase with
increasing temperature. Instead, during experiments
further straightening of the sample was observed.
In order to study this anomalous behaviour, further
tests were carried out during the present study on a
sample of the ternary alloy with 0.1 at% Sc composition,
chosen for being closest to TiRh. The similarity of the
resistance curves of the two alloys (Figures 1(a) and
1(b)) together with the proximity of their compositions
is believed to justify treating the test results obtained
for the 0.1 at% Sc alloy as being comparable to those
expected for the TiRh binary alloy. Figure 6 presents
thermomechanical test curves of the 50 at% Rh0.1at%
Sc-Ti alloy in different temperature ranges. The full
bending curve taken in the range 20C900C for the
sample with parameters 0.5 1.3 8 mm repeated the
curves that were obtained in previous experiments
(Figures 3(a) and 6(a)): under constant load (P
1
= 250 g)
in the temperature range 750C20C continuous bend
on cooling and subsequent full shape restoration on
heating of the sample were observed. More intense
bending took place in the temperature range of the
frst MT compared to that in the range of the second
MT. While approaching the
M
s
1
point on the cooling
curve, a distinct bend was observed. This might be
caused by the appearance of deformation martensite
overtaking the tetragonal thermal martensite at the
temperature
M
s
1
(Figure 6(a),A).
The fact that the contribution of the second MT
to the overall bending is smaller than the frst might
be due to insuffcient loading. With decreasing
temperature, the coeffcients of elastic deformation
of all metals and alloys increase. Therefore for more
accurate detection of bending in the temperature
range of the second MT a bigger load of 600 g was
used for the same sample. A partial bending curve
for the interval of the second transformation is shown
in Figure 6(b). A partial bending curve for the frst
transformation for another sample with parameters
0.9 1.4 8 mm and a load of 250 g is shown in
Figure 6(c). Applying a load greater than 250 g was
not possible, due to expected plastic deformation at
850C when the alloy is in a high temperature phase
with a cubic crystal structure.
These partial curves demonstrate full shape
restoration and almost no hysteresis between
the forward and reverse transformations. Alloys
exhibiting transformation with a very small
temperature hysteresis are known to be very useful
for actuator applications (12). Another quality of
thermomechanical behaviour of the alloy with 0.1 at%
Sc was observed earlier for the TiRh binary alloy in
the range of the second MT, which at the time was
not explained (6). Upon heating of the sample free
of load gradual spontaneous bending took place,
followed by outward bending on subsequent cooling
throughout the temperature range corresponding to
the second transformation without a load (Figure 5,
B). A bend on cooling and heating curves of the
unloaded sample of the ternary alloy with 0.1 at%
Sc was also observed in the temperature range of
both transformations. (Figures 6(a), B, and 6(b)).
In the case of the frst transformation the effect was
quite pronounced. This is thought to be evidence of
a two-way shape memory effect in these alloys. This
performance can be amplifed by mechanical work
hardening of the samples at 20C. During abrading
of the 0.9 mm sample to the 0.5 mm sample it
spontaneously began to bend at room temperature.
One possible explanation for the simple shape of the
bending and recovery shape curves in the 20C750C
temperature range, while the resistance curves
demonstrate two separate effects at 750C650C
and 350C250C corresponding to two martensitic
transformations, is that the electrical resistance
measurement technique registers the occurrence
of only thermal martensite whereas bending of the
sample may be caused by the formation of both
thermal and deformation martensites. The latter
may appear above the M
s
point as a result of bending
load, as was observed in the case of alloys based on
TiNi (13).
Thus despite the high temperature (~750C) the
frst martensitic transformation in Rh-0.1Sc-Ti alloy is
accompanied by a shape memory effect when heated
at a rate of about 20C min
1
. It has recently been
reported that the ZrIr equiatomic compound with
a temperature of martensitic transformation about
740C reveals a partial shape recovery, ~75%, only on a
rapid heating of the sample (~100C sec
1
) (14).
Dilatometry
The results of dilatometric analysis of alloy with 0.1at%
Sc agree with those of the electrical resistance and
thermomechanical tests. There are two infections in
Fig. 6. Thermomechanical curve of the 50Rh-0.1ScTi alloy: (a) full bending curve; (b) partial bending curve in
the region of the second MT; (c) partial bending curve in the region of the frst MT; A area of deformation
martensite prior to the frst transformation; and B a two-way shape memory effect
M
s
1
M
s
1
M
s
2
0.5
0.4
0.3
0.2
0.1
0
(a)
P
1
A
B
(b)
P
2
+P
2
+P
1
100 200 300 400 500 600 700 800 900
Temperature, C
(c)
+P
1
P
1
0.1
0
H
e
i
g
h
t
,

m
m
H
e
i
g
h
t
,

m
m
M
s
1
M
s
1
M
s
2
the dilatometric curve,corresponding to the beginning
of the frst (A) and second (B) MTs (Figure 7). A
sharp change in the length of the sample in a narrow
temperature range related to the frst MT was observed
as an abnormal effect on the electrical resistance
curve at the same temperature for the alloys containing
more scandium (Figures 2(a) and 2(b)).
Ductility
It was noticed that the Rh-Sc-Ti alloys are only slightly
oxidised at 20C950C and are quite ductile at 900C.
A sample of the alloy with 0.1 at% Sc having a section
of 0.5 1.3 mm was bent at an angle of 90, then was
straightened and bent again in the opposite direction
by 90 at 900C. It remained undestroyed and without
any sign of cracks. In order to elucidate the degree of
plasticity of the alloy, hot rolling of a 0.4 6 2 mm
sample cut from ingot was performed. The sample
was packed in an envelope made of stainless steel.
Initial package thickness was 2.3 mm. As a result of
15 cycles of rolling and heating to 950C the thickness
of the package decreased to 0.8 mm. The obtained
sample was 0.18 mm thick and 17 mm long. From the
experiment it follows that at 950C this alloy is ductile
whereas at 20C it is not. Therefore, parts of heat
sensitive items can be manufactured by hot rolling
and extrusion. Not all alloys with a shape memory
effect can be used for high-temperature materials; from
observations on the mechanical properties of 50 at%
Rh-0.1 at% Sc-Ti alloy, it can be assumed that material
based on it would not meet diffculties in processing.
Conclusion
The transformation characteristics and recovery
behaviour of ScRh-TiRh alloys have been studied.
The results show that ScRh-TiRh alloys containing
100 200 300 400 500 600 700 800 900
Temperature, C
A
B
0.15
0.10
0.05
0
S
a
m
p
l
e

l
e
n
g
t
h
,

m
m
Fig. 7. Dilatometric curve of the 50Rh-0.1Sc-Ti alloy: A, B effects related to transformation in the alloy (see
text for explanation)
03.5at% Sc undergo two high-temperature martensitic
transformations:
M
s
1
750C and
M
s
2
340C; while
alloys with 16.7 at% and 21 at% Sc reveal only one
MT. Both transformations are responsible for the
shape memory effect in these alloys. The temperature
of martensitic transformations in ScRh-TiRh alloys
depends on the scandium content and decreases on
substitution of scandium for titanium. The martensitic
transformation temperatures of ScRh-TiRh alloys
demonstrate low hysteresis.Transformations occurring
in TiRh and ScRh-TiRh alloys are frst order.TiRh binary
and 50 at% Rh-Sc-Ti ternary alloys can display 100%
shape memory effect in two temperature ranges up to
850C; TiRh and ScRh-TiRh alloys also exhibit a two-
way shape memory effect.
All characteristics of ScRh-TiRh alloys observed in
the study make them good candidate materials for
high-temperature shape memory alloys. Both TiRh and
50 at% Rh-Sc-Ti alloys display the unusual features of
continuity of the deformation process on cooling and
continuity of shape recovery process when heated in
a temperature range from 20C to 750C, which might
be due to two stages of transformation. The large
range of shape memory effect observed in this work
suggests that these alloys may be useful in different
temperature-regulating elements that are designed to
work in a wide temperature range.
This article presents the results of a preliminary
investigation of the unusual properties of Rh-Sc-Ti alloys,
in particular with respect to their thermomechanical
behaviour. Further experimental work is required in
order to confrm the effects observed. It is hoped that
the article will be of interest to other scientists and will
stimulate cooperation.
References
1 A. Raman and K. Schubert, Z. Metallkd., 1964, 55,
(11), 704
2 P. Rogl, Atomic Energy Rev., 1983, Special Issue 9, 201
3 S. S. Yi, B. H. Chen and H. F. Franzen, J. Less Common
Met., 1988, 143, (12), 243
4 T. D. Shtepa, Interaction of Titanium with Platinum
Group Metals. It was placed in collected articles
(compendium) titled Physical chemistry of condense
phases, superhard materials and their interface,
Naukova Dumka, Kiev, 1975, pp. 175191
5 J. Balun and G. Inden, Intermetallics, 2006, 14, (3), 260
6 E. L. Semenova, V. M. Petyukh and Yu. V. Kudryavtsev, J.
Alloys Compd., 1995, 230, (2), 115
7 H. Okamoto, J. Phase Equilib., 2000, 21, (4), 413
8 E. L. Semenova and Yu. V. Kudriavtsev, The Effect of
Scandium on Martensitic Transformation in TiNi and
TiRh in the Programme and Abstracts of the 13th
International Conference on Solid Compounds of
Transition Elements (SCTE 2000), Stresa, Italy, 4th7th
April, 2000, P-C42
9 O. L. Semenova, Yu. V. Kudriavtsev, V. M. Petyuch and
O. S. Fomichov, Powder Metall. Metal Ceramics, in press
10 V. V. Martynov and L. G. Khandros, Phys. Met. Metallog.,
1975, 39, (5), 1037
11 V. G. Pushin, V. V. Kondrat'ev and V. N. Khachin, Izv.
Vyssh. Fiz., 1985, 28, (5), 5
12 K. Otsuka and X. Ren, Mater. Sci. Eng. A, 1999,
273275, (12), 89
13 V. N. Khachin, Izv. Vyssh. Fiz., 1985, 28, (5), 88
14 Yu.V. Kudryavtsev and O. L. Semenova, Powder Metall.
Metal Ceramics, 2011, 50, (78), 471
The Authors
Yurii Kudriavtsev is a scientifc researcher at
the Kurdyumov Institute of Metals Physics of
NASU. His interests are in the feld of physics
metals and martensitic transformation. He
is involved in the investigation of shape
memory effect at high temperatures of
platinum-based alloys.
Elena Semenova is a senior researcher at the
I. N. Frantsevich Institute for Problems of
Materials Science of NASU . She has been
working there since graduating from Kiev
State University. Her key feld of research has
been focused on the interaction in binary
and multicomponent systems formed by
transition metals (including platinum group
metals) and the equiatomic phases of which
undergo martensitic transformation. Physical
and chemical properties of the alloys have
been investigated for characterisation.
EuropaCat XI
Highlights of catalysis by pgms and base metals from the biennial congress
Reviewed by Silvia Alcove Clave, Francesco
Dolci, Peter R. Ellis* and Cristina Estruch Bosch
Johnson Matthey Technology Centre, Blounts Court,
Sonning Common, Reading RG4 9NH, UK
*Email: ellispr@matthey.com
1. Introduction
The 11th EuropaCat meeting was hosted in Lyon,
France,on the 20th anniversary of the frst meeting held
in 1993 in Montpelier bringing it back to its origin in
France. The event was a large gathering of delegates
in many disciplines of catalysis from across Europe
and further afeld.The schedule was busy, with plenary
lectures and keynote talks from invited speakers, oral
and poster presentations and a full programme of
discussion sessions where the presentations were brief
and discussion amongst the delegates was promoted.
Of particular note was the high quality of the six
plenary lectures. These are discussed in more detail
below, followed by selected highlights on the themes
of emissions control, biomass conversion, process
chemistry and catalyst synthesis.
Further information on the EuropaCat XI conference,
including details of the scientifc programme and
biographies of the invited speakers, can be found on
the conference website (1).
2. Plenary Lectures
Each session began with a plenary lecture given by a
notable professor in the feld of catalysis.
The frst presenter was Bert Weckhuysen (Utrecht
University, The Netherlands) who provided an overview
of in situ characterisation to understand issues such
as catalyst coking and catalyst poisoning in fuid
catalytic cracking and methanol-to-olefn processes.
Combinations of techniques such as ultraviolet-
visible (UV-Vis) microscopy, fuorescence, hard micro-
X-ray diffraction, time-of-fight-secondary ion mass
spectrometry (ToF-SIMS) and X-ray absorption near
edge structure (XANES) spectroscopy using different
energies managed to evidence three-dimensional
(3D) dis-homogeneities in the elemental distribution
of samples (zeolites in particular) and correlate them
with the specifc reactivity of different regions on the
catalyst surface.
Ferdi Schth (Max-Planck-Institut f. Kohlenforschung,
Germany) was invited to present different preparation
routes for controlled nanoparticle systems. He
proposed the introduction of a size-controlled gold
nanoparticle in a zirconium dioxide (ZrO
2
) system
starting from a colloidal suspension with the aim of
preventing the sintering of catalytically active particles
.
This has been extended to the formation of alloys
(platinum, ruthenium) coated onto carbon shells for
fuel cell catalysts and CoPt for biomass conversion.
A second interesting idea was the use of ball milling
to promote catalytic reactions. For example, carbon
monoxide could be oxidised over cobalt(II,III) oxide
(Co
3
O
4
) in a ball mill, but the reaction stopped when
the mill was switched off. The milling was thought
to generate transient sites on the Co
3
O
4
which were
highly active.
Marc Fontecave (Collge de France, France) gave
a talk on recently developed Co and nickel-based
catalysts for the (photo)catalytic production and
oxidation of hydrogen. The insertion of Co into
iron(III) oxide/tungsten oxide (Fe
2
O
3
/WO
3
) catalysts
for the (photo)anode was suggested. Co
3
O
4
has been
shown to have good storage properties but has no
effect on H
2
production. Fe-Ni compounds and some
Co complexes are currently used for the production
of H
2
. More recently, Ni complexes have been grafted
onto carbon nanotubes (CNTs) and deposited on
an electrode. They have also been modifed to be
resistant to CO; however, it has been suggested that a
diimine-dioxime Co complex binding system may be
more robust under acidic conditions. At the moment,
other metals such as Ru and iridium are under
investigation in the photosynthesis feld.
During the Michel Boudart Award lecture, Jens
Norskov (Stanford University, USA) gave an interesting
overview on the possibilities offered by computational
modelling applied to catalysis. The speaker showed
how linking catalytic activity to the electronic
structure and chemical composition of a material
is feasible if the problem is approached correctly.
The main message of the presentation lay in the
importance of fnding the appropriate descriptors for
catalytic activity and selectivity. Once this information
is available, the design and optimisation of a process
becomes possible, and catalyst and process selections
can be carried out on a more rational and effective
basis. Examples such as ammonia synthesis were
provided and illustrated these concepts well.
Enrique Iglesia (University of California, USA) gave
the Franois Gault lecture in which he discussed the
challenges presented by the conversion of molecules
without a CC bond, such as methane, methanol
and dimethyl ether. Overcoming thermodynamics,
the use of inexpensive oxidants, protecting species
with weaker CH bonds, inhibition of carbon and
CO
2
formation are some of the issues faced when
working with these reactions. The speaker presented
several examples during his talk. When considering
CH
4
pyrolysis the C
2
C
10
yield is limited by both
thermodynamics and polynuclear aromatic chain
growth.The C
11+
formation can be controlled by using
catalytic materials, such as Mo/H-ZSM5, that can stop
chain growth.The thermodynamics and kinetics for this
reaction can be improved by removing the hydrogen.
Indirect paths can be used to reduce the conversion
of CH
4
to the undesired CO
2
or C. The process will
include chemically protected intermediates which are
less reactive than methane. For example, synthesis gas
is a thermodynamically protected form of activated
methane. This is quite reactive and can be converted
to a broad range of hydrocarbons.
The fnal plenary lecture, given by Dmitry Murzin
(bo Akademi University, Finland) was a fascinating
insight into the synthesis of pharmaceutical materials
from naturally-occurring biomolecules. On the face
of it, this may seem like an unpromising avenue,
but as both classes of molecule contain high levels
of functionality, signifcant progress can be made
by appropriate selection of the starting material
and effcient use of catalytic functional group
transformations.A good example of material selection
was the lignan 7-hydroxymatairesinol (Figure 1(a)).
The knots found in wood are particularly rich in
such lignans and since they cannot be processed
into paper due to their hardness they are essentially
a low value waste material. 7-hydroxymatairesinol
can be converted into a number of useful products,
including 7-oxomatairesinol (Figure 1(b)) which
is has potential anticarcinogenic and antioxidative
properties. This conversion was achieved using an
Au-catalysed selective oxidation reaction. In these
reactions,achieving excellent selectivity to the desired
product is critical to applications in pharmaceutical
materials.
3. Emission Control Technologies
The catalytic conversion of environmentally hazardous
pollutants in automobile exhausts was a thoroughly
debated topic in the conference and a wide range of
research studies were presented, including theoretical
modelling of materials or processes, optimisation
of the current state of the art and new ideas and
concepts. Those presentations presenting original
ideas and newly achieved insight can have a more
general appeal and have been selectively covered in
this report.
3.1 Selective Catalytic Reduction
Many advances have been achieved in selective
catalytic reduction (SCR) technology over the years.
Fe- and copper-zeolite and vanadium-based catalyst
technology is still the most studied for the NH
3
-SCR
reaction. A keynote speaker in this area was Isabella
Nova (LCCP Politecnico di Milano, Italy), who
proposed a detailed and universal SCR mechanism
over the standard commercial catalysts (Figure 2)
(2). Several speakers provided information on the
reaction mechanism and metal active sites in Cu-
zeolites. Florian Gltl (Universit de Lyon, France)
suggested a new type of active site for Cu in chabazite
structures (SSZ-13) by modelling the adsorption of
CO to a Cu(I) site. Janos Szanyi (Pacifc Northwest
National Laboratory, USA) also focused his studies on
Cu-SSZ13 and proposed that the formation of Cu-nitrosyl
adsorbed onto SSZ-13 could be the key intermediate
for the NH
3
-SCR reaction. Regarding V-based catalysts,
a ceria loaded Sb-V/TiO
2
catalyst was mentioned by
Heon Phil Ha (KIST, South Korea). The addition of
CeO
2
to the Sb-V/TiO
2
catalyst resulted in superior
catalytic activity over a wide range of temperatures,
higher thermal stability and improved sulfur dioxide
tolerance.
The addition of H
2
to the gas feed containing nitric oxide
and NH
3
has also been considered over silver/alumina
catalysts. Stefanie Tamm (Haldor Topsoe) provided a
global kinetic model for this reaction. Another type of
SCR system uses hydrocarbons (HC) instead of NH
3

as a reductant, although at the moment these systems
cannot offer the performance of NH
3
-SCR systems.
Asima Sultana (Advanced Industrial Science and
Technology (AIST),Japan) showed that by adding NH
3

into a HC SCR over Ag/Al
2
O
3
catalyst nitrogen oxides
conversion could be improved.
3.2 NOx Storage-Reduction Technology
NOx can be removed from a lean gas stream by
chemical adsorption onto a catalyst and subsequently
reduced to N
2
. Several materials were proposed for
NOx storage during the conference. The commercial
Pt-Ba/Al
2
O
3
catalyst was mentioned by two speakers.
Laura Righini (Politecnico di Milano) proposed a
mechanism for the reduction by NH
3
of NOx stored
on this catalyst, suggesting that the release of stored
OMe
OH
O
O
HO
MeO
(b)
O
OMe
OH
O
HO
MeO
(a)
O
HO
Fig. 1. The structure of: (a) 7-hydroxymatairesinol; and (b) 7-oxo-matairesinol
Fig. 2. A
proposed
mechanistic
model for
standard and
fast NH
3
-SCR
reaction (2, 3)
NH
4
+
NO
NH
4
+
NH
4
NO
3
NH
3
+ HNO
3
N
2
O + 2H
2
O
NO
3
2NO
2
NO
2
NO
2
NH
4
+
O
2
NO
NH
4
NO
2
N
2
+ 2H
2
O
NOx is the rate determining step for the reduction of
nitrates. Beat Pereda-Ayo (University of the Basque
Country, Spain) provided evidence that the addition
of Ce improves the NOx storage capabilities of
Pt-Ba/Al
2
O
3
.The optimum Ce loading was found to be
5%. Manganese and Co-based lanthanum perovskite
doped with Pd were also presented as optimum
catalysts with high NOx storage capacity and good
S-uptake/release properties. Merve Do ga and
Emrah zensoy (Bilkent University, Turkey) proposed
lanthanum manganite (LaMnO
3
) perovskite as the
best example, with a higher surface area compared to
a Co-based equivalent.
3.3 Soot Oxidation
Marzia Casanova (University of Udine, Italy)
introduced Fe/V catalysts supported on ceria-zirconia
(Ce
0.75
Zr
0.25
O
2
) for simultaneous activity for both
SCR and soot oxidation. Obtaining a good activity for
both processes remains challenging and further work
seems to be needed before this concept can acquire
commercial viability. Michela Klots (Centre National
de la Recherche Scientifque (CNRS), Saint-Gobain,
France) and Emil Obeid (Institut de Recherches sur
la Catalyse et LEnvironnement de Lyon (IRCELYON),
France) showed how the design of a soot oxidation
catalyst can be improved by exploiting knowledge of
oxygen and electronic diffusion processes commonly
used in designing solid state fuel cells.
By using a theoretical modelling approach,
Andrzej Kotarba (Jagiellonian University, Poland)
explored the key parameters of the soot oxidation
process for a platinum group metal (pgm)-free soot
oxidation catalyst. The interaction between the soot
grains and the oxide catalyst, topology of the soot
molecular framework and infuence of potassium
doping on the work function were investigated. For
K-Fe-O systems a strong correlation was observed
between the catalytic activity and the work function.
The infuence of potassium on the nanostructure of
iron oxide, leading to tunnelled and layered forms,
together with surface decoration by CeO
2
helped to
lower the work function, resulting in a substantial
increase in catalytic activity. It was proposed that
enhanced electron availability is benefcial for the
generation of surface reactive oxygen species that
initialise the combustion process.
3.4 Methane Oxidation
Zbigniew Sojka (Jagiellonian University) presented
a model for rationalising the activity of deposited
oxo-clusters for methane oxidation. The crucial
parameters of the proposed model are the CH bond
activation energy, the highest occupied molecular
orbital-lowest unoccupied molecular orbital (HOMO-
LUMO) gap of the surface transition metal oxo-
clusters and the properties of the Lewis basic support
(gauged by the optical basicity, ), accommodating
the detached proton. By optimising different
parameters at the same time the authors managed
to show how catalytic activity can be improved. A
very interesting concept for obtaining an active and
ageing-resistant CH
4
oxidation catalyst was presented
by Paolo Fornasiero (University of Trieste, Italy). Core-
shell structures of Pd encapsulated in CeO
2
appear
to stabilise the active phase of the catalyst, not only
preventing agglomeration of palladium(II) oxide
(PdO) particles during the catalytic reaction, but also
preventing PdO from being transformed to Pd at its
usual transition temperature. The authors speculated
also on the role played by hydroxyl groups on the
loss of catalytic performance and how regeneration
strategies impact the recovery of catalytic activity.
4. Biomass Processing
In recent years interest in the conversion of biomass
into biofuels and biochemicals has increased due
to growing demand for energy and more stringent
environmental requirements.This interest was refected
throughout the conference. In the area of biofuels, the
conversion of glycerol to form hydrogen by aqueous
phase reforming (APR) was discussed by Pedro Arias
(University of Basque Country). His group compared
the activity of Pt/-Al
2
O
3
, Ni/-Al
2
O
3
and PtNi/-Al
2
O
3

catalysts prepared by two different methods: sol-gel
and impregnation. The catalyst prepared by the sol-gel
method initially showed a higher H
2
production but
subsequent deactivation reduced the levels to the
same as those of the impregnated catalysts. For these
catalysts the -Al
2
O
3
was converted into boehmite
(-AlOOH) during APR, resulting in Ni sintering. The
stability of the catalyst is a well-known problem in APR
and the use of other supports such as carbon may be
a solution. Another example of hydrogen production
was delivered by Dimitri Bulushev (University of
Limerick, Ireland). He explained that the production
of hydrogen from biomass-derived formic acid at low
temperatures (60C) could be improved by doping the
Pd/C catalyst with K ions.
Several talks focused on the production
of biochemicals. The production of 1,2- and
1,3-propanediol from glycerol using a Pt/WO
3
/Al
2
O
3

catalyst was examined by Sara Garcia Fernandez
(University of Basque Country). The catalyst was
prepared by sequential impregnation of Al
2
O
3
. The
Lewis/Bronsted acidity could be tuned by the amount
of WO
3
. An increase of Lewis sites decreased the
selectivity towards 1,2-propanediol. The effect of Pt
was also studied, showing an increase in activity with
increasing metal content.
The hydrodeoxygenation of biomass derived ketones
was presented by several groups. Ivan Kozhevnikov
(University of Liverpool, UK) showed high conversion
of methyl isobutyl ketone (MIBK) to 2-methylpentane
over Pt/H-ZSM-5 at 200C. At lower temperatures the use
of Pt loaded on acidic heteropoly salt Cs
2.5
H
0.5
PW
12
O
40

catalyst for the hydrogenation of MIBK and diisobutyl
ketone to the corresponding alkanes gave yields of
97%99%. This catalyst was stable for over 16 h and
little coke formation was observed. A bifunctional
metal-acid catalysed pathway was identifed for these
catalysts. The effect of Pd and Pt particle sizes on the
hydrodeoxygenation of 5-nonanone to form n-nonane
and 5-nonanol was investigated by Irina Simakova
(Boreskov Institute of Catalysis, Russia). The catalysts
studied were Pd/ZrO
2
and Pt/ZrO
2
. An increase in
selectivity to n-nonane was observed with decreasing
particle size.
5. Process Chemistry
5.1 Syngas Processing
Freek Kapteijn (Delft University of Technology, The
Netherlands) took an engineering approach to the
Fischer-Tropsch (FT) reaction, describing the effects
of diffusion and H
2
:CO ratio. CO diffuses more slowly
than hydrogen and so the real H
2
:CO ratio in catalyst
pores could be much higher than that supplied to the
reaction. He also reported a Co/ZSM-5 catalyst which
maximised the yield of the petroleum fraction made
and decreased C
21+
to almost zero. The CH
4
selectivity,
however, increased from 6% to 15% when compared
with a similar Co/SiO
2
catalyst, although the Co/ZSM-5
catalyst was more active.Ye Wang (Xiamen University,
China) used Ru/zeolite catalysts for the same reaction.
Ru nanoparticles gave lower selectivity to CH
4
and C
24

than Co and using a wide pore zeolite support gave
less secondary cracking to low C
n
products due to a
reduced residence time. A Co/TiO
2
-SiC catalyst was
described by Y. Liu (University of Strasbourg, France).
This performed well, with C
5+
selectivity at 90% and
50% conversion at a gas hourly space velocity (GHSV)
of 2850 h
1
.
Processing syngas to higher olefns was also
discussed by James Spivey (Louisiana State University,
USA). He used a CuCo catalyst and found through
modelling that a bimetallic active site gave the best
performance. Ard Koeken (Utrecht University) used an
Fe catalyst for the same reaction; typically for Fe-based
FT, iron carbide was thought to be the active site.
The formation of iron carbide was measured using
a tapered element oscillating microbalance. The
formation of carbon phases was also observed when
the catalyst was exposed to 20 bar syngas at 350C,
although this could be supressed by increasing the
H
2
/CO ratio from 1 to 2.
Conversion of syngas to alcohols using Pd and Rh
catalysts was presented by Shuichi Naito (Kanagawa
University, Japan). A Pd/CeO
2
catalyst gave methanol
and HCs, whilst Rh/CeO
2
gave mostly hydrocarbons.
Increasing Rh particle size increased hydrocarbon
selectivity. Addition of lithium to either system
decreased hydrocarbon formation and increased
selectivity to oxygenates.
5.2 Selective Hydrogenation
Selective hydrogenation was a major theme at the
conference. One of the main feedstocks investigated
was alkynes which can be selectively hydrogenated
to alkenes. One talk of particular interest by Daniel
Lamey (Ecole Polytechnique Fdrale de Lausanne
(EPFL), Switzerland) described the use of supported
Pd nanoparticles in the hydrogenation of acetylene
to ethane in the presence of excess ethane. The
nanoparticles were made by reduction of Pd salts in the
presence of polymer stabilisers.Catalyst testing showed
that the larger particles (10 nm) were the most active,
whilst the smallest particles (2 nm) were the most
selective to ethane and gave the lowest amounts of the
by-product green oil.The best catalyst described was a
4 nm nanoparticle stabilised with polyvinylpyrrolidone
(PVP) and using a polyethyleneimine polymer to block
unselective sites on the catalyst.
Gianvito Vil (Eidgenssische Technische
Hochschule (ETH) Zrich,Switzerland) reported silver-
based catalysts for propyne hydrogenation, supported
on titania or silica. Catalytic measurements suggested
that splitting H
2
was the rate limiting step on these
catalysts as the hydrogen concentration increased,
the rate increased. However density functional theory
(DFT) calculations suggested a lower energy route
which reacted molecular hydrogen directly with the
alkyne (Equation (i)).
(i)
The selective hydrogenation of dimethyl oxalate to
ethylene glycol was reported using Cu/SiO
2
catalysts
by Y. Yuan (Xiamen University, China).The catalyst was
reduced at 350C prior to reaction, leading to Cu(0)
and Cu(I) active sites. Decoration of the catalyst with
low levels of Au increased the conversion and the
selectivity to ethylene glycol. Meanwhile P. Chen (Ruhr
University, Germany) investigated CNTs doped with
oxygen or nitrogen as supports for the hydrogenation
of olefns. Addition of Pt or Pd gave an active catalyst;
X-ray photoelectron spectroscopy (XPS) showed that
the N- or O-dopant had an electronic impact on the
precious metal.
5.3 Oxidation Catalysis
Again, a wide range of substrates, processing methods
and catalysts were described for selective oxidation.
Selective oxidation attracted much more attention
than total oxidation, despite the relevance of the latter
to pollution control. As is often the case in oxidation,
a wide range of materials were reported, including
pgms, Au, base metals and combinations of two or
more of the above. Au catalysts were inevitably well
represented. This was especially true of Au/TiO
2

which has taken the role of a benchmark oxidation
catalyst, amongst the academic community if not the
industrial one. Bimetallic catalysts containing Au were
also popular choices, especially PdAu and CuAu on a
range of supports.
One notable feature of the oxidation work presented
was the range of substrates being investigated.
Whilst the oxidation of CO and of benzyl alcohol
could be considered as standard gas-phase and
liquid-phase reactions, respectively, more complex
substrates were also investigated. For example,
Stefania Albonetti (Universit di Bologna, Italy) and
Florentina Neatu (University of Bucharest, Romania)
both reported the oxidation of hydroxymethylfurfural
to furandicarboxylic acid. Hydroxymethylfurfural
is of interest as it can be readily synthesised from
cellulose (Figure 3). Albonetti used Au and CuAu
catalysts whilst Neatu used CuMn and FeMn,
illustrating the range of materials which are active
oxidation catalysts.
6. Catalyst Synthesis
A number of talks were focussed on materials synthesis
rather than understanding of reactions. The main
catalyst preparation technologies impregnation,
deposition and so on were well-represented. The
synthesis of catalysts using pre-formed nanoparticles
is growing in popularity, as parameters such as particle
size and shape and the addition of second metals can
be controlled.
One talk which stood out was by Gonzalo Prieto
(Utrecht University). He described a Cu/SBA-15
material which was prepared by impregnation
and calcined in two ways. When calcined under
N
2
, the CuO particles were well dispersed through
the support, whilst calcination using a 2% NO/N
2

atmosphere led to only some of the supports channels
containing the particles. The catalyst calcined under
nitrogen resisted sintering as the particles were
further apart (Figure 4). The work has been reported
in full elsewhere (4).
Sintering control was also discussed by Ferdi
Schth in his plenary lecture. He reported a multistep
synthesis of Au nanoparticles captured in zirconia
shells (Figure 5). The shells were porous enough to
oxidation
Hydroxymethylfurfural
HO O
Furandicarboxylic acid
HO
2
C CO
2
H
Fig. 3. The oxidation of
hydroxymethylfurfural to
furandicarboxylic acid
H
2
C CH
2
hydrogenation
HC CH
Fig. 4. A Cu/SBA-15 material was calcined in two ways:
(a) NO/N
2
calcined which sintered easily; and (b) N
2

calcined which resisted sintering
(a)
(b)
allow reagents and product to diffuse in and out, but
the particles were trapped and therefore could not
sinter. A similar approach was described by Paolo
Fornasiero, as discussed in Section 3.4.
7. Summary
Overall this EuropaCat conference was very well
attended and managed in a very effcient way, despite
the volume of participants. The different parallel
sessions and discussion symposia (up to seven
parallel sessions in the same time slot) covered almost
all possible topics, established and new, relevant
for the catalysis community. As a general feeling
heterogeneous catalysis received more attention
than homogeneous catalysis, but both were covered.
The next EuropaCat conference (EuropaCat XII)
will take place in Kazan, Russia, in 2015, reaching
the geographical boundaries between Europe
and Asia and hopefully again bringing together a
comprehensive and stimulating programme.
References
1 XIth European Congress on Catalysis:
www europacatlyon2013.fr (Accessed on 6th December
2013)
2 A. Grossale, I. Nova, E. Tronconi, D. Chatterjee and
M. Weibel, J. Catal., 2008, 256, (2), 312
3 I. Nova, C. Ciardelli, E. Tronconi, D. Chatterjee and
M. Weibel, AIChE J., 2009, 55, (6), 1514
4 G. Prieto, J. Zecevic, H. Friedrich, K. P. de Jong and
P. E. de Jongh, Nature Materials, 2013, 12, (1), 34
Au nanoparticle
SiO
2
coated
ZrO
2
Shell Au in ZrO
2
Shell
Si Source Zr Source HF etching
Fig. 5. The multistep synthesis of Au nanoparticles captured in ZrO
2
shells
The Reviewers
Silvia Alcove obtained her
BSc from Rovira i Virgily
University, Spain. She
joined the Emission Control
Technologies department
at Johnson Matthey
Technology Centre, Sonning
Common, UK, in 2009. ,
She is currently undertaking
an Engineering Doctorate
(EngD) in collaboration with
Nottingham University. Her
research project mainly
consists of improving the
NH
3
-SCR catalysis technology
for high NOx reduction and
better mercury oxidation in
power plant industries.
Francesco Dolci obtained
a BSc and a PhD from the
University of Turin, Italy. He
then moved to The Institute
of Nanotechnology in
Karlsruhe, Germany, and to
the Joint Research Centre of
the European Commission
in Petten, The Netherlands
for working on solid state
hydrogen storage materials.
In August 2012 he joined the
Emission Control Research
department in Johnson
Matthey, working mainly
on three-way catalysis
development.
Peter R. Ellis gained his
BSc and PhD from Durham
University, UK. Following
post-doctoral placements in
Reading University, UK, and
Queens University Belfast,
UK, he joined Johnson
Matthey in 2001. His current
research interests are
heterogeneous catalysts for a
range of processes including
Fischer-Tropsch, direct
hydrogen peroxide synthesis
and selective oxidation
and also the utilisation of
pre-formed nanoparticles in
heterogeneous catalysis.
Cristina Estruch Bosch studied
Chemistry followed by a
Masters in Catalysis at the
Rovira i Virgili University . She
carried out her masters nal
project during an internship
at Johnson Matthey
Technology Centre, studying
liquid phase methane
oxidation. After that, she
became a Johnson Matthey
employee and continued
to work in heterogeneous
catalysis. She then started
a PhD in collaboration with
Ghent University, Belgium,
within a European project in
which Johnson Matthey is a
project partner. She is now
working on new projects
involving biomass conversion
and hydrogenation whilst
writing up her thesis.
The Discoverers of the Isotopes of the
Platinum Group of Elements: Update 2014
A resolution of the discovery circumstances of
195
Os plus new isotopes found for Ru
Further to a previous update (1),a new investigation of
the discovery circumstances of
195
Os by Juan Flegen
(2) has shown that Bar and Rey almost certainly
discovered this isotope in 1957 (3, 4). A previous
suggestion that they had only observed the isotope
81
Rb was due to a misunderstanding which was only
resolved by a critical assessment of the papers of Rey
and Bar by Birch et al. (5). In addition Reed et al.
(6) have identifed an isomer of
195
Os by determining
the half-life on the bare nucleus, Os
76+
. They obtained
32
+154
16
m for the half-life which NUBASE 2012
(7) normalised to a value of 2 1.7 h. The details
surrounding the discoveries of
195
Os isotopes are
summarised in Table I. In addition the new isotopes
85
Ru and
86
Ru have been discovered at the RIKEN Nishina
Center in Japan (8) with the discovery circumstances
summarised in Table II.Table III shows the total number
of isotopes to date for each platinum group element.
JOHN W. ARBLASTER
Wombourne, West Midlands, UK
Email: jwarblaster@yahoo.co.uk
Table I
The Discoverers of the
195
Os Isotopes
Mass number Half-life Decay modes Year of discovery Discoverers References
195 6.5 min
? 1957 Bar and Rey 3, 4

195m 2 h
?, IT? 2012 Reed et al. 6

Table II
New Isotopes of Ruthenium
Mass number Half-life Decay modes Year of discovery Discoverers References
85 ps EC +
+
? 2013 Suzuki et al. 8
86 ps EC +
+
? 2013 Suzuki et al. 8
ps: Particle stable (resistant to proton and neutron decay)
EC: Orbital electron capture in which the nucleus captures an extranuclear (orbital) electron which reacts with a proton to
form a neutron and a neutrino, so that the mass number of the daughter nucleus remains the same but the atomic number
decreases by one
+
: Beta or proton decay for nuclear decient nuclides is the emission of a positron (and a neutrino) as a proton in the
nucleus decays to a neutron. As with EC the mass number of the daughter nuclide remains the same but the atomic number
decreases by one. However this decay mode cannot occur unless the decay energy exceeds 1.022 MeV (twice the electron
mass in energy units)
Table III
Total Number of Isotopes and Mass Ranges Known for Each Platinum Group Element to 2014
Element Number of known isotopes Known mass number ranges
Ru 40 85124
Rh 38 89126
Pd 38 91128
Os 43 161203
Ir 42 164205
Pt 44 166209
References
1 J. W. Arblaster, Platinum Metals Rev., 2012, 56, (4), 271
2 J. Flegen private communication to J. W. Arblaster,
June 2013
3 G. Bar and P. Rey, Z. Naturforsch., 1957, 129, (6), 520
4 P. Rey and G. Bar, Publs. Com. Nucl. Energia Atmica
(Buenos Aires) Ser. Quim., 1957, 1, (10), 115
5 M. Birch, J. Flegenheimer, Z. Schaedig, B. Singh and M.
Thoennessen, Preprint arXiv: 1312.3985v1 [nucl-ex],
14th December, 2013
6 M. W. Reed, P. M. Walker, I. J. Cullen, Yu. A. Litvinov,
S. Shubina, G. D. Dracoulis, K. Blaum, F. Bosch, C.
Brandau, J. J. Carroll, D. M. Cullen, A. Y. Deo, B.
Detwiler, C. Dimopoulou, G. X. Dong, F. Farinon, H.
Geissel, E. Haettner, M. Heil, R. S. Kempley, R. Knbel,
C. Kozhuharov, J. Kurcewicz, N. Kuzminchuk, S. Litvinov,
Z. Liu, R. Mao, C. Nociforo, F. Nolden, W. R. Pla, Zs.
Podolyak, A. Prochazka, C. Scheidenberger, M. Steck,
Th. Sthlker, B. Sun, T. P. D. Swan, G. Trees, H. Weick,
N. Winckler, M. Winkler, P. J. Woods, F. R. Xu and T.
Yamaguchi, Phys. Rev. C, 2012, 86, (5), 054321
7 G. Audi, F. G. Kondev, M. Wang, B. Pfeiffer, X. Sun, J.
Blachot and M. MacCormick, Chinese Phys. C, 2012, 36,
(12), 1157
8 H. Suzuki, T. Kubo, N. Fukuda, N. Inabe, D. Kameda, H.
Takeda, K. Yoshida, K. Kusaka, Y. Yanagisawa, M. Ohtake,
H. Sato, Y. Shimizu, H. Baba, M. Kurokawa, T. Ohnishi,
K. Tanaka, O. B. Tarasov, D. Bazin, D. J. Morrissey, B. M.
Sherrill, K. Ieki, D. Murai, N. Iwasa, A. Chiba, Y. Ohkoda,
E. Ideguchi, S. Go, R. Yokoyama, T. Fujii, D. Nishimura,
H. Nishibata, S. Momota, M. Lewitowicz, G. DeFrance,
I. Celikovic and K. Steiger, Preprint arXiv:1310.5945v1
[nucl-ex], 22nd October, 2013
The Author
John W. Arblaster is
interested in the history of
science and the evaluation
of the thermodynamic and
crystallographic properties of
the elements. Now retired,
he previously worked as
a metallurgical chemist in
a number of commercial
laboratories and was involved in
the analysis of a wide range of
ferrous and non-ferrous alloys.
PGMs IN THE LAB
Platinum Group Metals in Polyoxometalates
Here another researcher whose work has benefited
from the support of Johnson Matthey and Alfa
Aesar, A Johnson Matthey Company, is profiled.
Ulrich Kortz is a Professor of Chemistry at Jacobs
University in Bremen, Germany, and he is interested
in the synthesis and characterisation of noble metal-
containing polyoxometalates.
About the Research
Polyoxometalates (POMs) are a large class of discrete,
soluble metal-oxo anions of early transition metals
in high oxidation states, such as tungsten(VI) or
molybdenum(VI). Due to a unique combination of
properties, such as thermal and oxidative stability,
tunability of acidity and redox activity, solubility
in various media, and ability to undergo multistep
multi-electron transfers without structural changes,
POMs keep attracting more and more attention in
different areas of fundamental and industrial science,
in particular in homogeneous and heterogeneous
catalysis.
Kortzs group are world leaders in the synthesis and
characterisation of noble metal-containing polyanions.
They prepared the frst example of a Pt(IV)-containing
polyoxovanadate, [H
2
Pt
IV
V
9
O
28
]
5
by a facile synthetic

procedure, using the Pt(IV) precursor H
2
Pt(OH)
6
. The
polyanion [H
2
Pt
IV
V
9
O
28
]
5
was characterised in the
solid state by X-ray diffraction (XRD) and in solution
by
195
Pt and
51
V NMR spectroscopy.
Their research also includes the frst example
of a Pd(II)-containing heteropolyoxometalate,
[Cs
2
Na(H
2
O)
10
Pd
3
(-Sb
III
W
9
O
33
)
2
]
9
which consists
of two (-SbW
9
O
33
) moieties linked by three square
planar-coordinate Pd
2+
ions resulting in a sandwich
type structure (Figure 1(a)). The central belt is
completed by two Cs
+
and a Na
+
ion which occupy the
vacancies between the adjacent Pd centres, resulting
in a polyanion with idealised C
2v
symmetry (Figure
1(b)).
Kortzs group have pioneered the class
of polyoxopalladates with the discovery of
[Pd
II
13
As
V
8
O
34
(OH)
6
]
8
, which has the shape and
dimensions of a molecular nanocube (Figure 2).
Meanwhile the same group has isolated several other
polypalladate derivatives of various shapes, sizes
and compositions. Kortzs group has also pioneered
the class of polyoxoaurates with the discovery
of [Au
III
4
As
V
4
O
20
]
8
. The Se(IV) derivative of this
polyanion has also been reported very recently.
Polyoxo-noble-metalates can be used in a wide
range of applications such as catalysis, analysis,
medicine, biochemistry and materials science.
Johnson Matthey and Alfa Aesar support new platinum group metals research
About the Researcher
* Name: Ulrich Kortz
* Position: Professor of Chemistry
* Department: School of Engineering and
Science
* University: Jacobs University
* Street: Campus Ring 1
* City: Bremen
* Post or Zip Code: 28759
* Country: Germany
* Email Address: u.kortz@jacobs-university.de
* Website: http://www.jacobs-university.de/
ses/ukortz
Professor Ulrich Kortz
Selected Publications
Y. Xiang, N. V. Izarova, F. Schinle, O. Hampe, B. Keita and U.
Kortz, Chem. Commun., 2012, 48, (79), 9849
M. Barsukova-Stuckart, N. V. Izarova, R. A. Barrett, Z. Wang,
J. van Tol, H. W. Kroto, N. S. Dalal, P. Jimnez-Lozano, J.
J. Carb, J. M. Poblet, M. S. von Gernler, T. Drewello, P.
de Oliveira, B. Keita and U. Kortz, Inorg. Chem., 2012,
51, (24), 13214
N. V. Izarova, M. T. Pope and U. Kortz, Angew. Chem. Int.
Ed., 2012, 51, (38), 9492
N. V. Izarova, A. Banerjee and U. Kortz, Inorg. Chem., 2011,
50, (20), 10379
N. V. Izarova, N. Vankova, T. Heine, R. N. Biboum, B. Keita, L.
Nadjo and U. Kortz, Angew. Chem. Int. Ed., 2010, 49,
(10), 1886
N. V. Izarova, N. Vankova, A. Banerjee, G. B. Jameson, T.
Heine, F. Schinle, O. Hampe, U. Kortz, Angew. Chem. Int.
Ed., 2010, 49, 7807
E. V. Chubarova and U. Kortz, Exxonmobil Chemical Company,
Novel Heteropolyanions with Late Transition Metal
Addenda Atoms and Process for their Preparation, US
Patent Appl. 2009/0,216,052
U. Lee, H.-C. Joo, K.-M. Park, S. S. Mal, U. Kortz, B. Keita and
L. Nadjo, Angew. Chem. Int. Ed., 2008, 47, (4), 793
E. V. Chubarova, M. H. Dickman, B. Keita, L. Nadjo, F.
Miserque, M. Mifsud, I. W. C. E. Arends and U. Kortz,
Angew. Chem. Int. Ed., 2008, 47, (49), 9542
L.-H. Bi, M. Reicke, U. Kortz, B. Keita, L. Nadjo and R. J. Clark,
Inorg. Chem., 2004, 43, (13), 3915
Cs3
Na1
Pd2
Cs3
Pd1
Pd2
(a) (b)
Fig. 1. (a) Combined polyhedral/ball-and-stick representation of [Cs
2
Na(H
2
O)
10
Pd
3
(-Sb
III
W
9
O
33
)
2
]
9
.
The WO
6
octahedra are shown in red and the balls represent palladium (blue), antimony (green), caesium
(yellow), sodium (purple) and water molecules (red); (b) ball-and-stick representation of the central belt of
[Cs
2
Na(H
2
O)
10
Pd
3
(-Sb
III
W
9
O
33
)
2
]
9
(Reprinted with permission from L.-H. Bi, M. Reicke, U. Kortz, B. Keita,
L. Nadjo and R. J. Clark, Inorg. Chem., 2004, 43, (13), 3915. Copyright 2004 American Chemical Society)
Fig. 2. Ball-and-stick representation of
[Pd
II
13
As
V
8
O
34
(OH)
6
]
8
. The colour code of the balls is
as follows: Pd (green), As (blue), O (red). Hydrogens
not shown (Copyright 2013 Professor Ulrich Kortz)
BOOKS
A Theoretical Study of Pd-Catalyzed C-C Cross-
Coupling Reactions
By M. G. Melchor (Autonomous
University of Barcelona, Spain),
Springer Theses, Springer International
Publishing Switzerland, 2013, 136
pages, ISBN: 978-3-319-01490-6,
90.00, US$129.00
The Springer Theses series
recognises outstanding PhD
research. This thesis describes how
theoretical calculations are used
to determine, elucidate and propose mechanisms
for Pd-catalysed C--C cross-coupling reactions. Due
to its versatility, broad scope and selectivity under
mild conditions, the Pd-cross-coupling reaction can
be applied in felds as diverse as the agrochemical
and pharmaceutical industries. The thesis also
covers reaction intermediates and transition states
involved in the Negishi, the copper-free Sonogashira
and the asymmetric version of Suzuki-Miyaura
coupling.A detailed picture of the associated reaction
mechanisms is included.
Calorimetry and Thermal Methods in Catalysis
Edited by A. Auroux (Institut de
Recherches sur la Catalyse et
IEnvironnement de Lyon, France),
Series: Materials Science, Vol. 154,
Springer-Verlag, Berlin, Heidelberg,
Germany, 2013, 561 pages, ISBN: 978-
3-642-11953-8, 117.00, 139.09,
US$179.00
This book discusses calorimetry
and thermal analysis methods,
alone or linked to other techniques and applied to the
characterisation of catalysts, supports and adsorbents,
and to the study of catalytic reactions in various
domains: air and wastewater treatment, clean and
renewable energies, refning of hydrocarbons, green
chemistry, hydrogen production and storage. This book
aims to fll the gap between the basic thermodynamic
and kinetics concepts and the use of experimental
techniques such as thermal analysis and calorimetry
to answer practical questions.The book is suitable as a
reference for researchers and engineers,and useful as a
tutorial for graduate students.
Computational Catalysis
Edited by A. Asthagiri (Ohio State
University, USA) and M. J. Janik
(Pennsylvania State University, USA),
RSC Catalysis Series No. 14, The Royal
Society of Chemistry, Cambridge, UK,
276 pages, ISBN: 978-1-84973-451-6,
139.99
The ultimate goal of computational
catalysis is the design of a novel
catalyst entirely from the computer.
This book gives a comprehensive review of the
methods and approaches being adopted to push
the boundaries of computational catalysis. There are
applied examples to support each method and the
editors share over two decades experience in this feld.
This book is an essential reference to postgraduates
and professionals working in the feld.
Green Diesel Engines: Biodiesel Usage in
Diesel Engines
By B. Kegl, M. Kegl and S. Pehan
(University of Maribor, Slovenia),
Series: Lecture Notes in Energy, Vol.
12, Springer-Verlag, London, UK, 2013,
263 pages, ISBN: 978-1-4471-5324-5,
90.00, 106.99, US$129.00
Diesel engines are explored in
relation to current research and
developments, with a focus on
ecology, economy and engine performance. The
most frequently used alternative fuels in diesel
engines, the properties of various types of biodiesel
and the concurrent improvement of diesel engine
characteristics are examined in this book. Green
Diesel Enginesprovides a solid foundation in current
research.
Hydrometallurgy: Fundamentals and
Applications
By M. L. Free (University of Utah, USA),
John Wiley & Sons, Inc, Hoboken, New
Jersey, USA, 2013, 444 pages, ISBN:
978-1-118-23077-0, 90.50, 108.60,
US$135.00
This book provides a condensed
collection of information that can
be used to improve the effciency
and effectiveness with which metals
Publications in Brief
are extracted, recovered, manufactured and utilised
in aqueous media in technically viable and reliable,
environmentally responsible and economically
feasible ways. The book is suitable for students and
researchers.
MWW-Type Titanosilicate: Synthesis, Structural
Modication and Catalytic Applications to
Green Oxidations
By P. Wu, H. Xu, L. Xu, Y. Liu and M. He
(East China Normal University, China),
Series: SpringerBriefs in Molecular
Science, Springer, Heidelberg, Germany,
125 pages, ISBN: 978-3-642-39114-9,
44.99, 53.49, US$49.99
A comprehensive review of a new
generation of selective oxidation
titanosilicate catalysts with the
MWW topology is provided in this book which gives
an overview of the synthesis, structure modifcation
and catalytic properties of Ti-MWW. Ti-MWW can
be prepared by direct hydrothermal synthesis with
crystallisation-supporting agents, using dual structure
directing agents and a dry gel conversion technique.
It can also be post-synthesised through unique
reversible structure transformation and liquid phase
isomorphous substitution. A summary of the structural
conversion of Ti-MWW into materials for processing
large molecules is provided.
New Trends in Emission Control in the
European Union
By J. Merkisz, J. Pielecha (Poznan
University of Technology, Poland)
and S. Radzimirski (Motor Transport
Institute, Poland), Series: Springer Tracts
on Transportation and Trafc, Vol.
4, Springer International Publishing,
Switzerland, 2014, 170 pages, ISBN:
978-3-319-02704-3, 90.00, 106.99,
US$139.00
Recent changes in the European
legislation for exhaust emissions from vehicles are
discussed in this book. The structure and range of
applicability of new regulations such as Euro 5 and
Euro 6 for light-duty vehicles and Euro VI for heavy-
duty vehicles are analysed. This comprehensive book
also covers:
The latest procedures for performing exhaust
emissions tests under both bench and operating
conditions
Reports on portable emission measurement
systems and their application for assessing
gaseous and particulate matter emissions under
actual operating conditions and in all transport
modes
Selected fndings from exhaust emissions
research on engines for various vehicles such as
light-duty, heavy-duty and non-road vehicles.
Transition Metal-Catalyzed Couplings in
Process Chemistry: Case Studies from the
Pharmaceutical Industry
Edited by J. Magano and J. R. Dunetz
(Pzer Inc, USA), Wiley-VCH Verlag
GmbH & Co KGaA, Weinheim,
Germany, 2013, 401 pages, ISBN: 978-
3-527-33279-3, 115.00, 138.00,
US$190.00
The focus of this book is on case
studies of large scale industrial
applications, presenting the
information and facts that are otherwise hard to fnd
in the current literature. There are contributions by
authors from Pfzer, Merck, DSM, Novartis, Amgen and
Astra Zeneca and they use case studies to showcase
project evolution from inception to early and late
development, including commercial routes where
applicable. At least one transition metal-catalysed
cross-coupling step is included with each case study.
Metal removal from the reaction mixtures is also
discussed.There is a small section which covers novel
technologies for cross-coupling with high future
potential for applications on a large scale such as metal
removal on a large scale, microwave, fow chemistry
and green chemistry. This book is aimed at chemists
working in the pharmaceutical,agrochemical and fne
chemical industries and also for synthetic chemists
working in academia.
JOURNALS
Special Issue: Fuels and Chemicals from
Synthesis Gas: State of the Art
Catal. Today, 2013, 214, 1152
This special issue is dedicated to
a selection of papers presented at
the Syngas Convention Fuels and
Chemicals from Synthesis Gas: State
of the Art which was organised
by the national DST-NRF Centre of


Excellence in Catalysis (c*change) at the University of
Cape Town, South Africa, and run under the auspices
of the Catalysis Society of South Africa (CATSA).
This convention focused on the generation and
uses of synthesis gas for the production of fuels and
chemicals. The technologies used for the conversion
of synthesis gas into liquid fuels and chemicals
are well established but these processes need to be
improved to meet the requirements on current and
future generations of these technologies. The papers
presented at the Syngas Convention were aimed at all
areas of synthesis gas conversion.
ChemElectroChem
Editor: G. Heydenrych; Wiley-VCH;
e-ISSN: 2196-0216
ChemElectroChem is a sister
journal to Angewandte Chemie,
ChemPhysChem and nine more
journals of the ChemPubSoc Europe
journal family. Electrochemistry
in terms of basic and applied
chemistry is one of the fastest-
growing felds in chemistry today. Moreover, it has
developed a strong interdisciplinary favour due
to the emergence of bioelectrochemistry and the
development of alternative energy sources. A sample
of articles includes: Composition-Dependent Oxygen
Reduction Activity and Stability of Pt-Cu Thin Films,
Promotion Effects of Sn on the Electrocatalytic
Reduction of Nitrate at Rh Nanoparticles and
Topologically Sensitive Surface Segregations of Au-Pd
Alloys in Electrocatalytic Hydrogen Evolution.
CATALYSIS APPLIED AND PHYSICAL
ASPECTS
Mild Synthesis of Mesoporous Silica Supported
Ruthenium Nanoparticles as Heterogeneous
Catalysts in Oxidative Wittig Coupling Reactions
A. L. Carrillo, L. C. Schmidt, M. L. Marn and J. C. Scaiano,
Catal. Sci. Technol., 2014, Advance Article
A new effcient approach for in situ synthesis of anchored
ruthenium nanoparticles (RuNPs) in three different kinds
of mesoporous silica materials (MCM-41, SBA-15 and
HMS) has been developed. The solids were synthesised
under very mild conditions from RuCL
3
H
2
O salt reduced
in 1 h at room temperature in the mesoporous silicas
grafted with aminopropyltriethoxysilane (APTES).The Ru
nanoparticles were well dispersed with an average size
of 3 nm.These materials have a molar ratio of Si:Ru = 40.
Porous MOFs Supported Palladium Catalysts for
Phenol Hydrogenation: A Comparative Study on
MIL-101 and MIL-53
D. Zhang, Y. Guan, E. J. M. Hensen, L. Chen and Y. Wang,
Catal. Commun., 2013, 41, 4751
Two metal organic frameworks, chromium
benzenedicarboxylates MIL-101 and MIL-53 were
synthesised and used as supports for Pd catalysts.
MIL-101 is highly hydrophilic and benefcial as
support for fne Pd nanoparticles, of average size
2.3 nm. Microporous MIL-53 is relatively hydrophobic
and larger Pd particles of 4.3 nm formed on the
external surface. The phenol adsorption behaviours
on the MILs were studied with different initial phenol
concentrations (0.05 M, 0.1 M, 0.15 M, 0.2 M and
0.25 M) at 20C to compare surface hydrophobicity.
Pd/MIL-101 showed better phenol selective hydrogenation
activity to cyclohexanone (>98%) under mild reaction
conditions. The results show that MIL-101 is superior to
the MIL-53 as a support when aqueous PdCl
2
is used as
a precursor.
CATALYSIS INDUSTRIAL PROCESS
Characterization and Performance of the
Bifunctional Platinum-Loaded Calcium-
Hydroxyapatite in the One-Step Synthesis of Methyl
Isobutyl Ketone
N. Takarroumt, M. Kacimi, F. Bozon-Verduraz, L. F. Liotta and
M. Ziyad, J. Mol. Catal. A: Chem., 2013, 377, 4250
Ca-hydroxyapatite catalysts loaded with different
amounts of Pt(Pt(x)/CaHAp) were synthesised and
characterised by N
2
-adsorption, XRD, TEM, FT-IR,
UV-VIS-NIR spectroscopy and TPR. The loaded
Pt exchanged and dispersed on the apatite
surface, forming particles of average size 2 nm.
The specifc surface area of CaHAp decreased as
Pt loading increased. The catalysts were tested for
dehydrogenation of butan-2-ol into MEK. The important
activity at low temperatures was attributed to Pt and Pt
2+

species associated with the basic Ca
2+
-O
2
groups of the
apatite. Optimal performance for acetone conversion
to MIBK was achieved with sample loaded with
0.5 wt% Pt. At 150C and stationary state a MIBK yield
of 23% was obtained with a selectivity of 74%. All the
Pt(x)/CaHAp catalysts showed acceptable stability
over time on stream with no production of heavy
compounds.
CATALYSIS REACTIONS
Poly (Styrene-co-Divinylbenzene) Amine
Functionalized Polymer Supported
Ruthenium Nanoparticles Catalyst Active in
Hydrogenation of Xylose
D. K. Mishra, A. A. Dabbawala and J. Hwang, Catal.
Commun., 2013, 41, 5255
The title catalyst has been evaluated for the frst
time in hydrogenation of xylose to xylitol. The
Ru/PSN catalyst was characterised by XRD, TEM
and CO chemisorption. Experiments were carried
out using the catalyst with different Ru loading of
1.03.0%, at different temperatures of 100400C
under different H
2
pressures of 3055 bar and with
varying stirring speeds from 4001200 rpm. The
catalyst could be reused up to four times.
An Effective Strategy for Immobilizing a
Homogeneous Palladium Complex onto Silica:
Efcient and Reusable Catalyst for Suzuki-
Miyaura Reactions
C. Sarmah, D. Sahu and P. Das, Catal. Commun., 2013, 41,
7578
A strategy to immobilise a homogeneous Pd complex
onto silica gel by introducing 4-pyridinecarbaldehyde
into the coordination sphere of Pd has been
investigated. The material was characterised by FTIR,
Abstracts
BET measurements, XRD, SEM-EDX and ICP-AES.
The supported material is an efficient catalyst for
the Suzuki-Miyaura reactions of aryl halides with
low Pd loading, 0.04 mol%, in an environmentally
friendly reaction. The reaction proceeded smoothly
and 96% 4-methoxybiphenyl was isolated after 6 h
reaction time.
Ruthenium-Catalyzed ortho-C-H
Halogenations of Benzamides
L. Wang and L. Ackermann, Chem. Commun., 2014, 50,
(9), 10831085
The first Ru-catalysed ortho-selective CH
halogenations on arenes through CH activation
are reported. A catalytic system of Ru
3
(CO)
12
and
AgO
2
C(1-Ad) allowed site-selective brominations
and iodinations on amides with ample scope and
excellent functional group tolerance. Preliminary
mechanistic studies provided evidence for a
reversible CH metallation event.
EMISSIONS CONTROL
Self-Regeneration of Three-Way Catalyst
Rhodium Supported on La-Containing ZrO
2
in
an Oxidative Atmosphere
H. Kawabata, Y. Koda, H. Sumida, M. Shigetsu, A. Takami
and K. Inumaru, Catal. Sci. Technol., 2013, Accepted
Manuscript
Rh supported on lanthanoid (La, Ce, Pr or Nd)-
containing ZrO
2
was investigated as a TWC, following
an ageing treatment by oxidation at 1273 K to
simulate 80,000 km in real vehicles. The properties
of Rh were assessed by TEM, CO chemisorption and
TPR using CO. The aged catalyst exhibited superior
activity for the steam reforming reaction. The
hydrogen produced reduced the previously oxidised
Rh in Rh/Zr-La-O, regenerating the catalyst. The
results highlight the potential of the present strategy
for developing active TWC with high tolerance to
oxidative conditions. The Rh particles supported on
Zr-La-O maintained their low oxidation state during
the reaction.
FUEL CELLS
The Electrooxidation Mechanism of Formic
Acid on Platinum and on Lead ad-Atoms
Modified Platinum Studied with the Kinetic
Isotope Effect
M. Betowska-Brzezinska, T. uczak, J. Stelmach and R.
Holze, J. Power Sources, 2014, 251, 3037
Poisoning of the electrode surface by CO-like species
was prevented by suppression of dissociative
chemisorption of FA due to a fast competitive
underpotential deposition of lead ad-atoms on
the Pt surface from an acidic solution containing
Pb
2+
cations. HCOOH was oxidised 8.5 times faster
on a Pt/Pb electrode than DCOOD. CH and OH
bonds were shown to be simultaneously cleaved in
the rate determining step. CH bond cleavage was
found to be accomplished by COH and not OH
bond split during FA decomposition.
PHOTOCONVERSION
A Simple Synthetic Route to Obtain Pure
Trans-Ruthenium(II) Complexes for Dye-
Sensitized Solar Cell Applications
C. Barolo, J. H. Yum, E. Artuso, N. Barbero, D. Di Censo,
M. G. Lobello, S. Fantacci, F. De Angelis, M. Grtzel, M.
K. Nazeeruddin and G. Viscardi, ChemSusChem., 2013, 6,
(11), 21702180
A synthetic route to obtain a functionalised
quaterpyridine ligand and its trans-dithiocyanato Ru
complex based on a microwave-assisted procedure
is presented. This Ru and quaterpyridine ligand
complex is used as a sensitiser in dye-sensitised solar
cells yielding a short circuit photocurrent density of
>19 mA cm
2
with broad incident photon to current

OH
OH
OH
SiO
2
SiO
2
SiO
2
APTES @APTES @APTES-Pd
EtO
EtO
EtO
O
O
O
Si
Si
N
2
NH
2
Toluene
Reux,
Reux
[Pd]
Ethanol,
NH
2
O
O
O
O
O
O
Si
Si
CH
CH N
N N
Pd
P
(CIO
4
)
2
N
N
C. Sarmah, D. Sahu and P. Das, Catal. Commun., 2013, 41, 7578
+
=
=

conversion effciency spectra ranging from 400900
nm, exceeding 80% at 700 nm.
CHEMISTRY
Growth of Concave Polyhedral Pd
Nanocrystals with 32 Facets through in situ
Facet-Selective Etching
Z-c. Zhang, F. Nosheen, J-c. Zhang, Y. Yang, P-p. Wang,
J. Zhuang and X. Wang, ChemSusChem, 2013, 6, (10),
18931897
Concave Pd polyhedra have been successfully
prepared by selectively etching the {100} facets
in situ by I
ions. Due to the presence of a high density

of atomic steps and surface relaxation, the concave
Pd polyhedra exhibit an enhanced electrocatalytic
activity towards ethanol oxidation.
ELECTRONICS
Efcient Electronic Communication of Two
Ruthenium Centers through a Rigid Ditopic
N-Heterocyclic Carbene Linker
M. Nussbaum, O. Schuster and M. Albrecht, Chem. Eur. J.,
2013, 19, (51), 1751717527
A ditopic benzobis(carbene) ligand precursor
containing a chelating pyridyl moiety was prepared
and used to obtain bimetallic Ru complexes by
transmetalation. The two metal centres were found
to be electronically decoupled when the Ru is in a
pseudotetrahedral geometry imparted by a cymene
spectator ligand. Ligand exchange of the Cl
/cymene
ligands for two bipyridine or four MeCN ligands induced
a change of the coordination geometry to octahedral.
As a consequence, the Ru centres, separated through
space by more than 10 , became electronically
coupled, evidenced by two different metal-centred
oxidation processes. These results demonstrate the
effciency of carbenes and, in particular, of the bbi
ligand scaffold for mediating electron transfer and for
the fabrication of molecular redox switches.
ELECTROCHEMISTRY
Activation of Nickel for Hydrogen Evolution by
Spontaneous Deposition of Iridium
M. Duca, E. Guerrini, A. Colombo and S. Trasatti,
Electrocatalysis, 2013, 4, (4), 338345
Activation of Ni electrodes was performed by
deposition of Ir from HCI solutions of IrCl
2
. Effciency
of deposition was dependent on precursor and
aqueous solution ageing. Cyclic voltammetry
showed hydrogen de/adsorption peaks with
magnitude proportional to the amount of Ir
deposited. Tafel plots showed slope decrease from
120 mV, typical of bare Ni, down to 40 mV typical of
pure Ir.
MEDICAL
Cyclic RGD-Linked Polymeric Micelles for
Targeted Delivery of Platinum Anticancer Drugs
to Glioblastoma through the Blood-Brain Tumor
Barrier
Y. Miura, T. Takenaka, K. Toh, S. Wu, H. Nishihara, M. R. Kano,
Y. Ino, T. Nomoto, Y. Matsumoto, H. Koyama, H. Cabral, N.
Nishiyama and K. Kataoka, ACS Nano, 2013, 7, (10), 8583
8592
A highly effcient drug delivery to intractable human
glioblastoma (U87MG) tumours has been achieved by
using a Pt anticancer drug incorporating polymeric
micelle with cyclic Arg-Gly-Asp (cRGD) ligand
molecules. A rapid accumulation and high permeability
from vessels into the tumour parenchyma was revealed.
The selective and accelerated accumulation of cRGD/m
into tumours occurred via an active internalisation
pathway (possibly transcytosis), thereby producing
signifcant antitumour effects in an orthotopic mouse
model of U87MG human glioblastoma.
NANOTECHNOLOGY
Pure Platinum Nanostructures Grown by
Electron Beam Induced Deposition
C. Elbadawi, M. Toth and C. J. Lobo, ACS Appl. Mater.
Interfaces., 2013, 5, (19), 93729376
A method for localised, mask free deposition of high-
purity Pt employs room-temperature, direct-write EBID
using the precursor Pt(PF
3
)
4
, and a low temperature
(400C) postgrowth annealing in H
2
O.This annealing
removes phosphorus contaminants. The resulting Pt is
indistinguishable from pure Pt flms by WDS.
PHYSICAL METHODS
Osmium Isotope Evidence for a Large Late
Triassic Impact Event
H. Sato, T. Onoue, T. Nozaki and K. Suzuki, Nature Commun.,
2013, 4, 2455
A report on the Os isotope fngerprint of an

extraterrestrial impact from Upper Triassic chert
successions in Japan is presented. Os isotope data
exhibit a marked negative excursion from an initial Os
isotope ratio (
187
Os:
188
Os
i
) of ~0.477 to unradiogenic
values of ~0.126 in a PGE-enriched claystone layer.
The timing of the Os isotope excursion coincides
with both elevated Os concentrations and low Re:Os
ratios. The magnitude of this negative Os isotope
excursion is comparable to those found at Cretaceous-
Paleogene boundary sites. The geochemical lines
of evidence demonstrate that a large impactor of
3.37.8 km in diameter, produced a global decrease
in seawater
187
Os:
188
Os ratios in the late Triassic.
CATALYSIS APPLIED AND PHYSICAL
ASPECTS
Producing a Ruthenium Catalyst
Kyoto University, Japanese Appl. 2013-115,378
A method for producing a Ru catalyst is claimed.
Ru supported by a metal oxide is pretreated with
an aldehyde compound, a phosphorus compound
and a lower alcohol compound. This Ru catalyst
can be used for producing an alkyl group- or
alkenyl group-substituted compound. Treating this
tris(acetylacetonato) Ru catalyst supported on
cerium oxide with formaldehyde, triphenylphosphine
and methoxyethanol gave a catalyst useful for adding
styrene on -tetralone.
Manufacture of Supported Ruthenium Oxide
Sumitomo Chemical Co, Ltd, Japanese Appl. 2013-169,517
A supported Ru oxide is manufactured by contact
treatment of a support with a solution containing a
Ru compound, drying in a gas stream while stirring,
and fring in an oxidising gas atmosphere. Preferably,
the support contains TiO
2
, Al
2
O
3
and/or SiO
2
. The
supported Ru oxide is used in preparation of Cl
2
by
oxidation of HCl.
Magnetic Nanoparticle Supported Osmium
Oxide Catalyst
National Institute of Advanced Industrial Science &
Technology, Japanese Appl. 2013-181,025
Magnetic nanoparticle (Fe
3
O
4
) supported Os oxide
catalysts for dihydroxylation of an olefn are prepared.
During dihydroxylation the title catalysts exhibit little
leaching of Os. As an example, a Fe
3
O
4
nanoparticle
supported compound was synthesised by reaction
of Fe
3
O
4
, K
2
OsO
4
and a precursor. The compound
is used as a catalyst for dihydroxylation of trans--
methylstyrene.
CATALYSIS INDUSTRIAL PROCESS
Electrically Insulating Material using Platinum
Catalyst
OAO KZSK, Russian Patent, 2,490,739; 2013
Insulating material is claimed based on addition
curing a silicone rubber containing both vinyl and
hydride-containing silicones and fllers, crosslinked
under the infuence of a Pt catalyst. The
silicone rubber contains 40--70 wt% of a cyano-
organophosphorus compound and/or 10--150 wt%
of a modifed aluminium hydroxide with
respect to the amount of polyorganosiloxane.
CATALYSIS REACTIONS
Producing Ethanol Using Rhodium Catalysts
Celanese International Corporation, US Appl. 2013/8,536,383
A process for producing ethanol involves hydrogenating
acetic acid in the presence of a hydrogenation catalyst
containing Rh and Sn. The molar ratio of Rh to Sn is
from 20:80 to 80:20. The Rh and Sn are present in
0.1 wt% to 25 wt% based on total weight of the catalyst;
the metal loading of rhodium is from 0.5 wt% to
2 wt%.The catalyst may further contain an active metal
selected from Co, Zn, Cr, Cu, Pt, Pd, Ni, Fe, W, Mo,V and
combinations thereof.The hydrogenation is performed
in the vapour phase at a temperature from 250--375C;
with a pressure of 10 kPa to 3000 kPa, and a hydrogen
to acetic acid mole ratio greater than 4:1.The support
is selected from silica, silica/alumina, pyrogenic silica,
high purity silica, carbon, alumina, and mixtures
thereof. This support is present in 25 wt% to 99 wt%,
based on total weight of the catalyst. The acetic acid
conversion is greater than 30%.
EMISSIONS CONTROL
Palladium and Gold Catalysts
WGCH Technology Ltd, US Appl. 2013/0,217,566
An emission control catalyst for treating an engine
exhaust includes an oxide carrier, and Pd particles
and Au particles supported on the oxide carrier. The
catalyst has a Pd to Au weight ratio in a range of about
0.5:1 to about 1:0.5. The emission control catalyst
further comprises a substrate having a honeycomb
structure with gas fow channels, wherein the oxide
carrier and the Pd and Au particles are coated on the
walls of the gas fow channels. A second oxide carrier
may have Pt and Pd particles. An example is given
of a supported catalyst containing 1% Pd and 2% Au
prepared by adding 1% Pd, 2% Au colloid solution to
a fask while stirring; adding MI-386 alumina powder
to the fask, and then stirring the mixture for 18 h. The
Patents

mixture is then fltered and dried at 130C for 3 h, and
then ground to a fne powder.The powder is calcined
in air at 500C for 2 h using a heating ramp rate of
8C min
--1
.
FUEL CELLS
Gas Diffusion Electrode Applying Platinum
Nanowires
The University of Birmingham, World Appl. 2013/128,163
A gas diffusion electrode comprising a gas diffusion
layer with a surface to which Pt nanowires have
been applied and the surface is at least partially
weakly hydrophobic or hydrophilic is claimed. The
Pt nanowires are applied substantially or on regions
of the surface. The surface area may be 50--100%
weakly hydrophobic or hydrophilic. The gas diffusion
layer has a water contact angle less than 130. The Pt
nanowires cover 75--99% of the total surface.These are
uniformly distributed. The Pt nanowires are of length
50--500 nm, with a diameter 1--10 nm. The nanowires
form a catalyst layer of thickness 50 nm--1 m.The gas
diffusion layer is selected from carbon cloth or carbon
paper.
Polymer Electrolyte Fuel Cells
Toshiba Corp, Japanese Appl. 2013-178,963
The title fuel cells have a MEA with a Ru-containing
anode catalyst layer and a Pt-containing cathode
catalyst layer. Either (i) a means for application of
voltage above its open circuit voltage is provided or
(ii) the anode catalyst layer, the electrolyte layer or
their interface contains a catalyst to oxidise Ru(III)
to Ru(IV) or Ru(III) adsorbent. The PEFC is operated
with application of voltage higher than its open circuit
voltage under open circuit conditions and the output
can be recovered by reactivating the cathode catalyst.
CHEMISTRY
Manufacture of Aqueous Ruthenium Nitrate
Solutions
Tanaka Noble Metal Industrial Co Ltd, Japanese Appl. 2013-
180,936
Aqueous Ru nitrate solution of <1000 ppm Cl is
prepared by neutralisation of a starting aqueous Ru
nitrate solution with alkali hydroxide (e.g.KOH,to pH 8--13),
rinsing the formed Ru hydroxide with dilute nitric
acid 1 time(s) to remove the hydroxide-derived alkali
metals, then dissolving the rinsed Ru hydroxide in
nitric acid.
ELECTRICAL AND ELECTRONICS
Structure Comprising Ruthenium Metal
Micron Technologies Inc, US Appl. 2013/0,221,420
A semiconductor device includes a smooth Ru metal
layer which may form a capacitor bottom plate or a
transistor gate such as a control gate. The smooth Ru
may be on an oxide such as a gate oxide.The thickness
of the Ru layer may be 150--800 and there may
optionally be a capping material of thickness 100--500 .
Ruthenium Seed Layer in a Magnetic Recording
Medium
Hitachi Global Storage Technologies, US Appl.
2013/0,235,490
An apparatus is claimed with a perpendicular magnetic
recording medium including a substrate, a soft
underlayer above the substrate, a seed layer structure
which contains Ru and a magnetic recording layer
above the Ru seed layer. The seed layer structure is 10
nm or less in thickness.This structure has composition
of NiW (2--10 at%) Ru (3--9 at%). The concentration of
Ru is 3--9 at%.
ELECTROCHEMISTRY
Mesostructured Thin-Films as Electrocatalysts
V. Stamenkovic and N. Markovic, US Appl. 2013/0,209,898
The manufacturing of thin flm catalysts comprises of
(i) providing a substrate; (ii) providing a source of Pt
group metal and alloying metal; (iii) using physical
vapour deposition to deposit both metals; and (iv)
annealing the thin flm at a temperature of 300--400C,
forming a morphology of (111) hexagonal faceted
surface grain structure in the thin flm having a
catalytic activity approaching Pt
3
Ni(111).The Pt group
metal is selected from Pt, Pd and Rh. The transition
metal is selected from Fe, Co, Ni,V and Ti.The thin flm
electrocatalyst thickness is about 5--20 nm.
MEDICAL
Platinum Based Antitumour Agent
Yamaguchi University, Japanese Appl. 2013-155,159
A polymeric antitumour agent characterised
by containing an ionic complex of a Pt-based

antitumour agent and a styrene-maleic acid based
copolymer is disclosed. The agent containing
the ionic complex is accumulated in a tumour
site due to enhanced permeability and retention
effect. In an example, cisplatin and styrene-maeic
acid copolymer were reacted, and the obtained
ionic complex was freeze-dried to give stable
nanoparticles, which inhibited proliferation of HeLa
cells with an IC
50
value of 104.1 m.
NANOTECHNOLOGY
Imaging Mass Analysis Using Platinum
Nanoparticles
Nissan Chemical Industries Ltd, World Appl. 2013/122,225
A method for imaging mass analysis is characterised
by preparing a sample by physical vapour deposition
of Pt nanoparticles.This provides an improved method
for imaging mass analysis using a matrix to assist in
ionising a sample with high ionisation effciency,
reduction in visible information and migration,
absence of interference peaks originating from the
matrix and high spatial resolution.
PHOTOCONVERSION
Iridium Complexes Contained in Luminescent
Materials
Mitsubishi Chemical Corp, World Appl. 2013/105,615
The title complexes show good organic solvent solubility,
and can be stored without precipitation. The title organic
electroluminescent devices, preferably having emitter layers
containing charge-transporting N-containing aromatic
heterocyclic compounds as hosts and the complexes as
dopants,have a low operating voltage and long service life.The
title complexes are represented by 1 (A = 5- or 6-membered
aromatic hydrocarbon ring or aromatic heterocycle including
carbon atoms C
1
and C
2
; B = 5- or 6-membered aromatic
heterocycle including carbon atom C
3
and nitrogen atom
N
1
; L = organic ligand; p,q= 1--4; n = 1--3; R
1
, R
2
= substituent;
>1 of R
1
and R
2
= (Ar
1
Z)
m
X
m1
; X = C
6--20
(hetero)arylene;
Ar
1
= C
3--20
(hetero)aryl; Z = [C(R
)
2
; R
= H, F, Cl, Br,
C
1--20
alkyl, etc.; m = 1--3; m1 = 0--3; m2 = 1--20).
Platinum Phosphine Diphenyl Ether Derivative
Complexes
Ube Industries, Ltd, Japanese Appl. 2013-155,131
The title complexes are represented by [L
1
L
2
Pt(o-C
6
(R
14
)
4
-X-
o-C
6
(R
58
)
4
]where X = O,S,NR
9
,silylene; R
9
= H,halo,(cyclo)
alkyl, alkenyl, aryl, aralkyl, alkoxyl, arylalkoxyl; R
1
--R
8
= H,
halo, (cyclo)alkyl, alkenyl, aryl, aralkyl, alkoxyl, aryloxyl,
dialkylamino, alkylsily; L
1
, L
2
= electronically neutral
monodentate phosphine ligand; L
1
L
2
may form a bidentate
phosphine ligand. The title complexes can be used in
electroluminescent devices that emit light from blue to green.
REFINING & RECOVERY
Separating Platinum Suldes
OAO Krastsvetmet, Russian Patent, 2,490,349; 2013
The invention involves pulping a concentrate of Pt
and Re sulfdes in an aqueous ammonia solution.
The pulp is treated with hydrogen peroxide solution
at a temperature of 25--45C. This reaction mixture
is acidifed with sulfuric acid until a pH 0.2--2.0 is
achieved.This is heated and aged.The precipitate of Pt
compounds is separated from the solution by fltering.
The effect is to enable separation of Pt at the step for
extracting Re from a sulfde concentrate.
SURFACE COATINGS
Films with Absorbent Palladium Coating
Morgan Adhesives Company, European Appl. 2,626,379;
2013
A multilayer flm has a polymeric flm layer and
an absorbent layer containing a Pd complex. The
absorbent layer also contains at least one of a
cyclodextrin, a hydrophobin protein, or a derivative
thereof and is effective to absorb an odour, a volatile
organic compound or both. The absorbent layer
comprises between 0.1--0.75 wt% Pd complex, 2--7 wt% of
cyclodextrin and 0.1--0.5 wt% of hydrophobin protein.
The polymeric flm layer comprises at least one of
polyethylene, polypropylene, polyvinyl chloride and
polyethylene terephthalate. The absorbent layer has a
(R
1
)
a
A
C
1
C
2
C
3
(R
2
)
b
B
n
N
1
lr L
3-n
World Appl. 2013/105,615
1

surface area between 280--320 cm
2
and when placed
in a chamber having a volume of 400 cm
3
with 2 ml of
an n-butanol saturated atmosphere injected into the
chamber it absorbs greater than 80% of the n-butanol
in 1 h.
Sulfonation of Plastic and Composite Materials
M. Wotjtaszek et al., US Appl. 2013/0,209,689
A method of preparing a plastic article to accept
plating is claimed. A portion of the plastic article is
rendered plateable by sulfonation by: (i) exposing
the plastic article to an atmosphere containing a
sulfonating agent to sulfonate at least a portion of
the plastic article; (ii) contacting the sulfonated
plastic article with a conditioner; (iii) contacting the
plastic article with a Pd metal activator so that the
noble metal is adsorbed on at least a portion of the
surface of the plastic article; and (iv) contacting the
plastic article with an accelerator to react with the
adsorbed Pd to increase the catalytic activity of the
adsorbed noble metal towards plating. The plastic
may be selected from poly(ether-ether-ketone) resins,
polyamide, polyethylene, polypropylene, etc., or a
combination.The sulfonating agent comprises fuming
sulfuric acid or vapour phase sulfur trioxide.Timing of
contact between the sulfonating agent and the plastic
article is between 1 sec and 60 min.
Obtaining Platinum Group Metal Coatings
FGUP Radievyl Institut im. V. G. Khlopina, Russian Appl.
2,489,516; 2013
An invention to help obtain pore-free microcrystalline
coatings with high adhesion to substrate materials
is claimed. Coatings are obtained from Ir or Rh by a
thermal decomposition process at a temperature
between 250--450C and pressure 0.01--0.05 mm Hg.
The precursors are Ir tetratrifuorophosphine hydride
of formula Hlr(PF
3
)
4
or Rh tetratrifuorophosphine
hydride of formula HRh(PF
3
)
4
.
FINAL ANALYSIS
Effects of Platinum Group Metals Doping
on Stainless Steels
The positive effects of palladium and ruthenium on
the corrosion properties of titanium alloys are well
known and led to the development of new grades
to extend the operating window for titanium alloys
(1). The same mechanism, cathodic modifcation,
should also function in any alloy that is protected by
a corrosion resistant oxide flm. This is the case for
stainless steels, which typically rely on a chromium
oxide flm to protect the alloy.
Passivation Behaviour
Cathodic modifcation refers to the increase in
cathodic activity caused by the presence of platinum
group metal (pgm) at the surface of the metal. This
causes an increase in the cathodic current at any
given potential, which will increase the open circuit
potential (OCP) to higher voltages. Classical Tafel
behaviour would show that the increased OCP would
also lead to a higher anodic current (increasing
corrosion) (2, 3). However, passivating alloys do not
follow Tafel behaviour at all potentials, due to the
formation of a passive region (where the passive flm
dominates the behaviour). The increase in cathodic
potential can push the OCP into this passive region,
preventing corrosion. If the increase in OCP is not high
enough to reach the passive region, some dissolution
will occur. However, during this dissolution the pgm
will not dissolve into solution and more pgm will be
revealed as the other metals do dissolve. This leads
to an enrichment of the surface in pgm, which will
increase the cathodic modifcation, pushing the
OCP further towards the passive region and often
passivating the alloy (4).
Stainless steels are more complicated than titanium
alloys, due to both design (more elements are added
to provide specifc functions) and the use of recycled
scrap steel in their production.The location of the pgm
within the microstructure, which has a controlling
effect on the benefts gained,is much harder to predict
in stainless steels. Further, the OCP of a stainless steel
in an oxidising solution is close to the transpassive
region. Adding pgms will increase the OCP further,
potentially out of the passive region and into the
transpassive region, which allows attack to occur.
Corrosion in Doped Steels
Corrosion in pgm doped stainless steels is therefore
dependent on the alloy composition and the
environment that the steel is exposed to. Corrosion in
stainless steels occurs at breaches in the oxide flm.
These are discrete and the initial breaches cause
metastable pits to form, which will only stabilise if the
diffusion distance out of the pit is suffciently long to
present a barrier to loss of the solution within the pit.
Pitting is a therefore a localised phenomenon and
as such the location of the pgm relative to the pit is
important to the corrosion resistance. One technique
for investigating this is electron probe micro analysis
(EPMA), which produces high resolution elemental
maps of the surface. EPMA on polished sections
through pits in ruthenium-doped 304 stainless steel
showed that the ruthenium was enriched by the pit
edge compared to the bulk (Figures 1(a) and 1(b)),
as predicted by the theory outlined above.This implies
that some regions within the pit will become cathodic
with respect to the bulk, potentially allowing cathodic
processes to operate within the pit. The results of
this are likely to be system specifc and could be
investigated by artifcial pit studies.
Platinum Group Metal Doping and Chloride Ions
Pits are more common in chloride containing
solutions, though the exact mechanism by which
chloride causes flm breakdown is not agreed
(57). Chloride containing environments have also
presented a situation where the choice of doping
pgm is important. Electrochemical studies coupled
with examination of the surfaces following the
electrochemical testing on samples of 304 doped with
either palladium, ruthenium or undoped, in solutions
containing 0.05 M sulfuric acid and 0.1 M sodium
chloride clearly showed the possible outcomes
(Figures 2(a)(c)).
Undoped 304 rapidly initiated pits at the exposed
surface (Figure 2(a)). As expected these pits initiated
under lacy covers of oxide flm which provide the
increased diffusion distance required to maintain the
aggressive solution within the pit.
Palladium doped 304 showed a much lower current
than the undoped steel during potentiodynamic
testing (Figure 2(b)). However, after the experiment
was completed, it was discovered that the surface of
the alloy had disintegrated into powder. It is believed
that this powder had acted as an insulating layer on
the surface, reducing the current passed. Analysis of
the powder showed a much higher palladium content
than the doping level, which can be explained by
remembering that the other elements are dissolving
into the solution.
Ruthenium doped 304 showed virtually no sign
of attack (Figure 2(c)) and the measured current
density was orders of magnitude lower than had
200 m
Level
1592
1393
1194
995
796
597
398
199
0
326
200 m
Ru
Ru Level
508
444
381
317
254
190
127
63
0
108 Average Average
Fig. 1. (a) Secondary electron image of a section through a pit in ruthenium-doped 304 stainless steel showing
the topography of the surface; (b) ruthenium concentration map of the section through the pit showing the
increased level of ruthenium at the pit edge
100 m 100 m 100 m
(a) (b) (c)
Fig. 2. Corrosion damage on: (a) undoped 304 stainless steel; (b) palladium doped 304; and (c) ruthenium
doped 304 following electrochemical testing
been measured on the undoped steel. This shows
that the steel was well protected by the addition of
ruthenium.
For a further practical example of how pgm
doping can protect a steel, the effect of ruthenium on
sensitisation in 304 stainless steel can be considered.
Sensitisation is a degradation mechanism operating
in stainless steels that are heated to between
500C and 800C. At these temperatures, chromium
diffuses to the grain boundaries to form chromium
carbides, resulting in the formation of chromium
depleted regions by the grain boundary. These
allow intergranular attack to develop in corrosive
media. In ruthenium doped steels, the formation of
carbides was observed, however the alloy resisted
corrosive attack beyond a slight etching of the grain
boundaries.
This observation can be explained by considering
the local electrochemical potentials and the effect of
ruthenium on these. Initially, the reduced chromium
content at the grain boundary prevents the formation
of the protective oxide flm and the boundary will be
anodic with respect to the rest of the steel, which
will galvanically drive the corrosion of the grain
boundary. However, during corrosion, ruthenium will
become enriched at the grain boundary, increasing
the OCP. As corrosion continues, the enrichment
continues, further increasing the OCP of the grain
boundary. Once this OCP rises suffciently for the
grain boundary to be cathodic with respect to the rest
of the steel, the corrosion at the grain boundary will
cease. EPMA mapping of a corroded grain boundary
in such a steel clearly showed both the formation
of chromium carbides at the grain boundary and
increased ruthenium content along that same grain
boundary (Figures 3 and 4).
Conclusions
While not as consistently benefcial as additions of
palladium have been seen to be in titanium grade7,
C Elemental Percents
140
135
130
125
120
115
110
90 95 100 105 110 115
X, mm
3
2.8
2.6
2.4
2.2
2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
Y
,

m
m
Fig. 3. Carbon
EPMA map
showing
concentration
increases at a
grain boundary
in a sensitised
304 doped steel
sample
additions of the correct pgm to stainless steels can
increase the corrosion resistance of the steel. To
successfully protect steels in this manner,the corrosive
environment and the pgm additions must be carefully
considered. The location of the pgm within the steel
can greatly affect its local protectivity.
ANDREW FONES* and GARETH D. HATTON
Johnson Matthey Technology Centre, Blounts Court,
Sonning Common, Reading RG4 9NH, UK
*Email: fonesar@matthey.com
References
1 R. W. Schutz, Corrosion, 2003, 59, (12), 1043
2 Platinum Metals Rev., 1958, 2, (4), 117
3 J. H. Potgieter and H. C. Brookes, Corrosion, 1995, 51,
(4), 312
4 M. A. Streicher, Platinum Metals Rev., 1977, 21, (2), 51
5 E.-S. M. Sherif, J. H. Potgieter, J. D. Comins, L. Cornish, P.
A. Olubambi and C. N. Machio, Corros. Sci., 2009, 51,
(6), 1364
6 V. S. Agarwala and G. J. Biefer, Corrosion, 1972, 28,
(2), 64
7 T. Itagaki, H. Kutsumi, H. Haruyama, M. Igarashi and
F. Abe, Corrosion, 2005, 61, (4), 307
The Authors
Andrew Fones is a Research Scientist at
the Johnson Matthey Technology Centre,
Sonning Common, UK, working in the
Platinum Group Metals Applications
group. He is a corrosion scientist with a
materials background, interested in the
effects of platinum group metals doping
on alloys.
Gareth Hatton received his BSc in
Archaeological Sciences at the University
of Bradford in 2000. Subsequently he
undertook a DPhil at the University of
Oxford working on the analysis and
replication of ancient vitreous materials.
He joined the electron microscopy group
at Johnson Matthey in 2005 where he
specialises in the application of EPMA.
Ru Elemental Percents
140
135
130
125
120
115
110
90 95 100 105 110 115
X, mm
Y
,

m
m
1.45
1.4
1.35
1.3
1.25
1.2
1.15
1.1
1.05
1
0.95
0.9
0.85
0.8
0.75
0.7
0.65
0.6
Fig. 4. Ruthenium
EPMA map showing
concentration increases
at a grain boundary in
a sensitised 304 doped
steel sample
This page is intentionally blank.
EDITORIAL TEAM
Sara Coles
Assistant Editor
Ming Chung
Editorial Assistant
Scott Turnbull
Scientic Information Assistant
Email: jmpmr@matthey.com
Platinum Metals Review is Johnson Mattheys quarterly journal of research on the science and technology
of the platinum group metals and developments in their application in industry
www.platinummetalsreview.com
Johnson Matthey Plc
Orchard Road
Royston
SG8 5HE
UK
%
: +44 (0)1763 256 325
@: jmpmr@matthey.com
Editorial Team
Sara Coles Assistant Editor
Ming Chung Editorial Assistant
Scott Turnbull Scientic Information Assistant

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