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JOHNSON MATTHEY
TECHNOLOGY REVIEW

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exploring science and technology in industrial applications

Volume 59, Issue 3, July 2015

Published by Johnson Matthey

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JOHNSON MATTHEY
TECHNOLOGY REVIEW www.technology.matthey.com

Johnson Matthey’s international journal of research exploring science and technology in

industrial applications

Contents Volume 59, Issue 3, July 2015

174 Selected Electrical Resistivity Values for the Platinum Group of Metals Part I:
Palladium and Platinum
By John W. Arblaster
182 12th Greenhouse Gas Control Technologies Conference
A conference review by Christopher Starkie
188 Platinum Group Metal and Washcoat Chemistry Effects on Coated Gasoline
Particulate Filter Design
By Chris Morgan
193 “Additive Manufacturing Technologies: 3D Printing, Rapid Prototyping, and Direct
Digital Manufacturing”, 2nd Edition
A book review by Jonathan Edgar and Saxon Tint
199 Temperature Dependent Heat Transfer Performance of Multi-walled Carbon Nanotube-
based Aqueous Nanofluids at Very Low Particle Loadings
By Meher Wan, Raja Ram Yadav, Giridhar Mishra, Devraj Singh and Bipin Joshi
207 The Effects of Hot Isostatic Pressing of Platinum Alloy Castings on Mechanical
Properties and Microstructures
By Teresa Fryé, Joseph Tunick Strauss, Jörg Fischer-Bühner and Ulrich E. Klotz
218 “Exploring Materials through Patent Information”
A book review by Julia O’Farrelly
221 “Urea-SCR Technology for deNOx After Treatment of Diesel Exhausts”
An essay book review by Martyn V. Twigg
233 Sintering and Additive Manufacturing: The New Paradigm for the Jewellery Manufacturer
By Frank Cooper
243 Introduction to the Additive Manufacturing Powder Metallurgy Supply Chain
By Jason Dawes, Robert Bowerman and Ross Trepleton
257 Atomic-Scale Modelling and its Application to Catalytic Materials Science
By Misbah Sarwar, Crispin Cooper, Ludovic Briquet, Aniekan Ukpong, Christopher Perry and
Glenn Jones
284 In the Lab: Combining Catalyst and Reagent Design for Electrophilic Alkynylation
Featuring Professor Jérôme Waser

287 Johnson Matthey Highlights

http://dx.doi.org/10.1595/205651315X688091
JOHNSON MATTHEY
TECHNOLOGY REVIEW
Selected Electrical Resistivity Values for the
Platinum Group of Metals Part I: Palladium and
Platinum
Improved values obtained for liquid phases of palladium and platinum
John W. Arblaster
Wombourne, West Midlands, UK
Email: jwarblaster@yahoo.co.uk
Electrical resistivity values for both the solid and liquid
phases of the platinum group metals (pgms) palladium
and platinum are evaluated. In particular improved
values are obtained for the liquid phases of these
metals. Previous reviews on electrical resistivity which
included evaluations for the pgms included those of
Meaden (1), Bass (2), Savitskii et al. (3) and Binkele
and Brunen (4) as well as individual reviews by Matula
(5) on palladium and White (6) on platinum.
1. Introduction
Electrical resistivity (ρ) is defined in terms of the
International System of Units (SI units) as:
ρ=RA/l (i)
where
R is the electrical resistance of a uniform specimen of
material in ohms (Ω)
A is the cross-sectional area of the specimen in square
metres (m2)
l is the length of the specimen in metres (m)
The units of ρ are therefore Ω m although practically
the most useful units are μΩ cm.
174
Johnson Matthey Technol. Rev., 2015, 59, (3), 174–181
www.technology.matthey.com
The measured electrical resistivity (ρ) usually consists
of a temperature dependent intrinsic resistivity, ρi,
which is due to the pure metal and is caused by the
scattering of the charge carriers (electrons or holes)
by phonons (quantised vibrations of the lattice) and by
their collisions with each other, and a residual resistivity
(ρ0) due to impurities which also scatter the carriers and
increase the resistivity. The quantity ρ0 is considered to
be a summation of the effects of different impurities and
is also considered to be temperature independent. The
two contributions to the total resistivity are combined
according to Matthiessen’s Rule: ρ = ρ0 + ρi and because
ρ0 may vary from sample to sample then attempts are
made to evaluate values of ρi which should be universal
for a specific metal.
1.1 Correction for Thermal Expansion Effects
In order to obtain a reference value to which all other
measurements are adjusted the electrical resistivity is
evaluated at 273.15 K (0ºC).
In the low temperature region below about 30 K the
resistivity can be represented by ρ = ρ0 + A T2 + B T5
where the temperature dependent terms represent
the intrinsic resistivity, whilst up to room temperature
the experimental values are generally given in such
a form that interpolation can be achieved by using
simple polynomials rather than using the complicated
Bloch-Grüneisen formula (7–9). In the definition
of resistivity as ρ = R A / l then A and l are usually
measured at room temperature and therefore at different
© 2015 Johnson Matthey
http://dx.doi.org/10.1595/205651315X688091
temperatures both A and l have to be corrected for
thermal expansion effects. It is found below room
temperature that for the level of accuracy given for ρ,
thermal expansion corrections are generally negligible
but at higher temperature the measurements have to
be corrected, especially if they are based entirely on
the room temperature values for A and l which are
usually measured at 293.15 K, the accepted reference
temperature for length change measurements:
ρ (corrected) = ρ (uncorrected) [(AT / A293.15) × (l293.15 / lT)] (ii)
= ρ (uncorrected) [1 + (lT – l293.15) / l293.15] (iii)
where Equation (iii) can be considered to be a close
approximation of Equation (ii). However since 273.15 K
is the actual reference temperature then corrected
values of ρ(T) should be further corrected for thermal
expansion from 293.15 K to 273.15 K. Since this
correction is usually negligible at the level of accuracy
given then it is not applied.
In the case of rapid pulse heating to high temperatures,
because of inertia l generally is unaltered and it is A
that changes. If D is the diameter of the wire then:
ρ (T) = ρ (measured) (DT2 / D293.152) = ρ (measured) (VT / V293.15)
(iv)
where VT is the volume of the sample at temperature
T and V293.15 is the volume at 293.15 K. These are
essentially DT2 and D293.152 respectively since l is
assumed to be unaltered.
2. Palladium
Palladium has a face-centred cubic structure and
the melting point is a secondary fixed point on the
International Temperature Scale of 1990 (ITS-90) at
1828.0 ± 0.1 K (10).
2.1 Solid
Electrical resistivity values for solid palladium at
273.15 K are given in Table I. The selected value is an
average of the last three determinations. The ρ0 correction
to the measurement of Laubitz and Matsumura (14)
was suggested by Matula (5) who also appears to have
selected this value as the reference value.
From 71 data sets for solid palladium Matula (5)
selected only the measurements of Schriempf (17)
(1.6 K–10.6 K), White and Woods (13) (10 K–295 K) and
Laubitz and Matsumura (14) (90 K–1300 K). However
it is considered that the values of White and Woods
175
Johnson Matthey Technol. Rev., 2015, 59, (3)
have been superseded by the later high precision
measurements of Williams and Weaver (15) (0 K–300 K)
and Khellar and Vuillemin (16) (17 K–300 K), with the
latter given only in the form of an equation which was
evaluated at 17 K and then at 10 K intervals from 20 K
to 270 K. The measurements of Williams and Weaver
were interpolated above 100 K so as to also obtain a
full evaluation at 10 K intervals from 20 K to 270 K.
The measurements of Schriempf and of Williams and
Weaver agree satisfactorily and were averaged to 10 K
with the measurements of Williams and Weaver being
extended to 16 K. The measurements of the latter
and of Khellar and Vuillemin do not agree below 35 K.
However the equation of Khellar and Vuillemin showed
peculiar behaviour below this temperature with derived
values being 6% higher than those of Williams and
Weaver at 17 K but 31% lower at 20 K. Therefore the
latter measurements were given preference up to 35 K.
At this temperature and above values from the two sets
of measurements were averaged. Overall agreement
is to within 0.5% between 60 K and 180 K and to within
0.1% above 180 K. The selected values of Matula
below 273.15 K are based on a combination of the
measurements of White and Woods and of Laubitz and
Matsumura and on average the intrinsic values show a
bias of 0.02 μΩ cm above the more recently selected
values. Other measurements in the low temperature
region were discussed by Matula.
In the high temperature region Matula (5) selected
only the measurements of Laubitz and Matsumura (14)
(90 K–1300 K). After correction for ρ0 = 0.020 μΩ cm
the values were calculated at 50 K intervals from 350 to
1300 K. In the present evaluation these measurements
were combined with the more recent measurements of
Khellaf et al. (18) (295 K–1700 K) which were given in
the form of an equation which was also evaluated at
50 K intervals but over the range 350 K to 1750 K. After
correction of both sets of measurements for thermal
expansion using the values selected by the present
author (19) they were fitted to Equation (v) which
has an overall accuracy as a standard deviation of
± 0.13 μΩ cm. The two sets of measurements show
a maximum disagreement of 1.0% at 1300 K. The
equation was extrapolated to the melting point and
selected values are given in Table II.
Measurements of Milošević and Babić (20)
(250 K–1800 K) were independently corrected for
thermal expansion. Their equation differs from the
selected equation sinusoidally by trending from initially
0.3% high to 1.7% high at 400 K to 0.9% low at 1400 K
© 2015 Johnson Matthey
http://dx.doi.org/10.1595/205651315X688091 Johnson Matthey Technol. Rev., 2015, 59, (3)

Table I Electrical Resistivity of Palladium at 273.15 K

ρi,
Authors Ref. Temperature of data
μΩ cm
Powell et al. 11 9.79 At 273.15 K. Corrected for ρ0 0.144 μΩ m
Powell et al. 12 9.75 Interpolated 200 – 400 K. Corrected for ρ0 0.143 μΩ m
White and Woods 13 9.70 At 273.15 K. Average of three samples
Laubitz and Matsumura 14 9.760 Interpolated 250–300 K. Corrected for ρ0 0.020 μΩ m
Williams and Weaver 15 9.751 At 273.15 K. Corrected for ρ0 0.007 μΩ m
Khellar and Vuillemin 16 9.765 Calculated. Fit 17–300 K
Selected 9.76 ± 0.01 At 273.15 K

Table II Intrinsic Electrical Resistivity of Palladium

Temperature, ρi, Temperature, ρi, Temperature, ρi,
K μΩ cm K μΩ cm K μΩ cm
Solid
5 0.0008 140 4.36 400 14.47
10 0.0038 150 4.79 500 17.92
15 0.011 160 5.21 600 21.14
20 0.028 170 5.63 700 24.15
25 0.061 180 6.04 800 26.96
30 0.113 190 6.45 900 29.59
35 0.189 200 6.86 1000 32.03
40 0.294 210 7.26 1100 34.30
45 0.420 220 7.66 1200 36.42
50 0.566 230 8.06 1300 38.39
60 0.908 240 8.46 1400 40.23
70 1.29 250 8.85 1500 41.95
80 1.71 260 9.25 1600 43.55
90 2.14 270 9.64 1700 45.05
100 2.59 273.15 9.76 1800 46.46
110 3.04 280 10.02 1828 46.84
120 3.48 290 10.41
130 3.92 300 10.79
Liquid
1828 81.4 2200 82.2 2700 83.3
1850 81.5 2300 82.4 2800 83.5
1900 81.6 2400 82.6 2900 83.7
2000 81.8 2500 82.8
2100 82.0 2600 83.1

176 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X688091 Johnson Matthey Technol. Rev., 2015, 59, (3)

to 0.4% high at 1800 K. Figure 1 shows the deviations
of the selected values of Matula (which are considered
as incorporating the measurements of Laubitz and
Matsumura) and the experimental values of Khellaf
et al. and Milošević and Babić from the fitted curve.
Measurements of Binkele and Brunen (4) (273–1423 K)
which were also independently corrected for thermal
expansion, showed systematic biases of 1.3% high for
runs 1 and 2 and 1.7% high for run 3.
Löffler (23) (295 K–1100 K) were corrected from
RT/R295 to RT/R273.15 and were also corrected for thermal
expansion. On this basis the differences reached
a maximum of 4.1% high at 450 K but then showed
some scatter varying between 1.0% low at 800 K and
1.6% high at 1100 K. Figure 2 shows the deviations of
these three sets of measurements from the fitted curve
where the resistivity ratios of García and Löffler were
converted to electrical resistivity values for comparison
purposes.

2 2.2 Liquid
Ref. (5) Electrical resistivity values for palladium at the melting
1.5
Ref. (18)
point are given in Table III. In the liquid state neither
Ref. (20)
1 Dupree et al. (24) (1832 K–1924 K) nor Güntherodt
Deviation, %

et al. (25) (1864 K–2019 K) obtained evidence for

0.5
any variation of resistivity with temperature. Although
0 Seydel and Fischer (26) (1825 K–3000 K) did obtain
200 400 600 800 1000 1200 1400 1600 1800
evidence of such a variation, the values of Pottlacher
–0.5 Temperature, K
(22) (1828 K–2900 K) were selected and fitted to
–1
7
–1.5
6 Ref. (21)
Fig. 1. Solid palladium – percentage deviations from Ref. (23)
selected curve 5
Ref. (22)
Deviation, %

4
3
Also in the high temperature region there are a
number of other measurements which were published 2

after the review of Matula. After correction for thermal 1

expansion (19) the electrical resistivity measurements 0
of Miiller and Cezairliyan (21) (1400 K–1800 K) trend 300 500 700 900 1100 1300 1500 1700 1900
Temperature, K
from 4.0% to 6.9% high whilst the measurement of
Pottlacher (22) at the melting point is 5.9% high. Fig. 2. Solid palladium – percentage deviations from
selected curve
Resistivity ratio measurements of García and

Table III Differences Between the Solid and Liquid Electrical Resistivity of Palladium at the Melting Point
ρS, ρL,
Authors Reference ρL /ρS Notes
μΩ cm μΩ cm
Dupree et al. 24 (48.8) 83.0 1.700 (a)
Güntherodt et al. 25 47.3 78.8 1.666
Seydel and Fischer 26 50.2 79.1 1.576
Khellaf et al. 18 (45.2) 77.3 1.710 (b)
Pottlacher 22 49.6 81.4 1.641
Present assessment – 46.84 81.4 1.738
Notes to Table III
(a) Solid value based on (ρL – ρS)/ ρS = 0.70 ± 0.05
(b) Solid value based on ρL /ρS = 1.71

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Equation (vi) with selected values for the electrical
resistivity of the liquid and are also given in Table II.
3. Platinum
Platinum has a face-centred cubic structure and the
melting point is a secondary fixed point on ITS-90 at
2041.3 ± 0.4 K (10).
3.1 Solid
The resistance ratio of platinum, W T = RT/R 273.15, forms
the basis of the International Temperature Scale which
White (6) extended to 1300 K and calculated values
of intrinsic resistivity using the fixed reference value of
9.82 ± 0.01 μΩ cm at 273.15 K. Above 1300 K White
combined the selected values to this temperature with
the electrical resistivity measurements of Righini and
Rosso (27) (1000 K–2000 K), Laubitz and van der
Meer (28) (300 K–1500 K), and Flynn and O’Hagan (29)
(273 K–1373 K) and the resistance ratios of Roeser (30)
(73 K–1773 K) and Kraftmakher (31) (1000 K–2000 K)
together with resistivity measurements given by Martin
et al. (32) (300 K–1200 K). White fitted all selected
values from 100 K to 2000 K to Equation (vii) which
was extrapolated to the melting point. Differences
between values derived from this equation and the
tabulated values of White as given in Table IV do not
exceed 0.01 μΩ cm. An abridged version of the values
for the solid phase as given in Table IV was originally
given in Platinum Metals Review by Corti (33).
For comparison between these measurements
and the selected values as given in Figure 3, the
resistivity ratios of Roeser (30) and Kraftmakher (31)
were converted to electrical resistivity values and all

Table IV Intrinsic Electrical Resistivity of Platinum

Temperature, ρi, Temperature, ρi, Temperature, ρi,
K μΩ cm K μΩ cm K μΩ cm

Solid

10 0.0026 150 4.89 500 18.45

15 0.0119 160 5.30 600 22.07
20 0.0367 170 5.70 700 25.59
25 0.0855 180 6.11 800 29.00
30 0.163 190 6.52 900 32.29
35 0.270 200 6.92 1000 35.47
40 0.403 210 7.32 1100 38.54
45 0.560 220 7.72 1200 41.50
50 0.734 230 8.12 1300 44.35
60 1.12 240 8.51 1400 47.09
70 1.53 250 8.91 1500 49.74
80 1.95 260 9.30 1600 52.34
90 2.38 270 9.70 1700 54.93
100 2.80 273.15 9.82 1800 57.51
110 3.23 280 10.09 1900 60.11
120 3.65 290 10.48 2000 62.76
130 4.06 300 10.87 2041.3 63.87
140 4.48 400 14.71

Liquid

2041.3 102.8 2300 105.3 2700 109.1

2050 102.9 2400 106.2 2800 110.1
2100 103.4 2500 107.2 2900 111.1
2200 104.3 2600 108.2

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1 In the case of additional electrical resistivity

Ref. (4), runs 1 and 5
Ref. (4), runs 2, 3 and 4
measurements of Birkele and Brunen (4) (273–1497 K),
0.8 combined runs 1 and 5 trend from initially 0.8% high
Ref. (28)
0.6 Ref. (29) to 0.1% high at 1200 K to 0.4% high at 1373 K whilst
combined runs 2, 3 and 4 trend to an average of 0.5%
0.4 low above 1000 K. These trends are also shown in
Figure 3.
0.2
Deviation, %

Electrical resistivity measurements of Pottlacher (22)

0 (473 K–1573 K and 1740 K–2042 K in the solid range)
300 500 700 900 1100 1300 1500
Temperature, K are initially 1% higher then trend to an average of 3%
–0.2
higher between 900 and 1573 K before trending to
–0.4 1.2% higher and then to 0.5% higher between 1740
K and the melting point. These differences are also
–0.6
shown in Figure 5.
–0.8

Fig. 3. Solid platinum – percentage deviations from selected 3.5

curve
3

2.5 Ref. (27)

measurements except those of Flynn and O’Hagan Ref. (22), run 1
2
Deviation, %

(29) were corrected for thermal expansion using values Ref. (22), run 2
1.5
selected by the present author (34). In addition the
measurements of Martin et al. (32) were corrected to 1
correspond to the selected electrical resistivity value at 0.5
273.15 K. Because of their larger deviations values of 0
Righini and Rosso (27) are compared with the selected 300 500 700 900 1100 1300 1500 1700 1900 2100
Temperature, K
values in Figure 4.
Fig. 5. Solid platinum – percentage deviations from selected
curve

0.6
3.2 Liquid
Ref. (30)
0.4 Ref. (31) Electrical resistivity values of platinum at the
Ref. (32) melting point are given in Table V. In the liquid state
0.2 electrical resistivity measurements of Pottlacher (22)
(2042 K–2900 K) were selected as Equation (viii)
Deviation, %

since in the overlap region they are closely

0
200 400 600 800 1000 1200 1400 1600 1800 2000 confirmed by measurements of Gathers et al. (36)
Temperature, K (2100 K–7300 K) obtained at a pressure of 0.3 GPa
–0.2 which trend from 0.5% low at 2100 K to 1.0% high at
2900 K. Measurements of Hixson and Winkler (37)
–0.4 (2042 K–5100 K) are initially 7% low at the melting
point and trend 1% low to 1% high between 2100 K
and 2900 K but above 3000 K, in direct comparison
–0.6
with the measurements of Gathers et al., the trend
is to an average of 2% low. Selected values for the
Fig. 4. Solid platinum – percentage deviations from selected
curve electrical resistivity of liquid platinum from the melting
point to 2900 K are also given in Table IV.

179 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X688091 Johnson Matthey Technol. Rev., 2015, 59, (3)

Table V Differences Between the Solid and Liquid Electrical Resistivity of Platinum at the Melting Point
ρS, ρL,
Authors Reference ρL /ρS
μΩ cm μΩ cm

Martynyuk and Tsapkov 35 62.1 92.6 1.491

Pottlacher 22 64.2 102.8 1.601

Present assessment – 63.87 102.8 1.610

High Temperature Intrinsic Resistivity of Solid Palladium (273.15 to 1828 K)

ρi (μΩ cm) = 4.58639 × 10–2 T – 1.39098 × 10–5 T 2 + 1.84118 × 10–9 T 3 – 1.76742 (v)

Intrinsic Resistivity of Liquid Palladium (1828 to 2900 K)

ρi (μΩ cm) = 2.058 × 10–3 T + 77.7 (vi)
Intrinsic Resistivity of Solid Platinum (100 to 2041.3 K)
ρi (μΩ cm) = 4.681197 × 10–2 T – 3.258075 × 10–5 T 2 + 8.554023 × 10–8 T 3
– 1.594242 × 10–10 T 4 + 1.837342 × 10–13 T 5 – 1.316886 × 10–16 T 6
+ 5.678222 × 10–20 T 7 – 1.340980 × 10–23 T 8 + 1.329896 × 10–27 T 9
– 1.621733 (vii)
Intrinsic Resistivity of Liquid Platinum (2041.3 to 2900 K)
ρi (μΩ cm) = 9.604 × 10–3 T + 83.2 (viii)

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25. H.-J. Güntherodt, E. Hauser, H. U. Künzi and R.
Müller, Phys. Lett. A., 1975, 54, (4), 291
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.
181
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26. U. Seydel and U. Fischer, J. Phys. F: Met. Phys.,
1978, 8, (7), 1397
27. F. Righini and A. Rosso, High Temp.-High Pressures,
1980, 12, (3), 335
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1966, 44, (12), 66
29. D. R. Flynn and M. E. O’Hagan, J. Res. Natl. Bur.
Stand., 1967, C71, (4), 255
30. W. Roeser, “Temperature: Its Measurement and
Control in Science and Industry”, ed. M. S. van Dusen,
Vol. I, Reinhold Publishing Corp, New York, USA,
1941, p. 1312
31. Ya. A. Kraftmakher, High Temp.-High Pressures,
1973, 5, (4), 433
32. J. J. Martin, P. H. Sidles and G. C. Danielson, J. Appl.
Phys., 1967, 38, (8), 3075
33. C. W. Corti, Platinum Metals Rev., 1984, 28, (4), 164
34. J. W. Arblaster, Platinum Metals Rev., 1997, 41, (1), 12
35. M. M. Martynyuk and V. I. Tsapkov, Fiz. Metal.
Metalloved., 1974, 37, (1), 49; translated into English
in Phys. Met. Metallogr., 1974, 37, (1), 40
36. G. R. Gathers, J. W. Shaner and W. M. Hodgson, High
Temp.-High Pressures, 1979, 11, (5), 529
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1993, 14, (3), 409
© 2015 Johnson Matthey
http://dx.doi.org/10.1595/205651315X687614 Johnson Matthey Technol. Rev., 2015, 59, (3), 182–187

JOHNSON MATTHEY
TECHNOLOGY REVIEW www.technology.matthey.com

12th Greenhouse Gas Control Technologies

Conference
Advances in carbon capture and storage research

Reviewed by Christopher Starkie

Johnson Matthey Technology Centre, Plenary Speakers
Sonning Common, Reading RG4 9NH, UK Julio Friedmann (US From Vision to
Government, USA) Inheritance – The
Email: christopher.starkie@matthey.com Technical Foundation for
the Next Decade of CCS
Projects

David G. Victor Global Climate Policy and

Introduction (University of California, the Future of CCS
San Diego, USA)
The International Conference on Greenhouse Gas
Control Technology is a biennial meeting now in its Juho Lipponen Gas-Fired Power
(International Energy Generation With CCS – A
twelfth incarnation and is a highlight for carbon dioxide
Agency, France) Competitive Option
sequestration researchers around the globe. The
conference was held between 4th–9th October 2014 Michael J. Monea Boundary Dam – The
at the Austin Convention Center, Texas, USA. Over (SaskPower, Canada) Future is Here
four days the conference encompassed all aspects of
the carbon capture value chain. Approximately 30% Suk Yee Lam The UK’s CCS
(Department for Energy Programme: Policy and
of the sessions focused on CO2 capture technology
and Climate Change, UK) Delivery
and 30% on CO2 storage, with the remaining sessions
covering case studies, CO2 utilisation, commercial Gary T. Rochelle (The From Lubbock TX
issues, CO2 transport, policy and social science. University of Texas at to Thompsons, TX:
The conference was attended by 1166 delegates Austin, USA) Amine Scrubbing for
comprising of an almost even distribution of students, Commercial CO2 Capture
academics, industrial representatives, research From Power Plants
institutes and government agencies. There was
Xu Shishen (Huaneng Greengen and CO2
a high level of participation with 874 contributions Clean Energy Research Capture Projects in China
presented throughout the seven parallel sessions and Institute, China)
well-planned poster sessions. Furthermore a small
selection of exhibitors complimented the technical Emma ter Mors (Leiden The Value of Social
programme providing details of commercial ventures University, Netherlands) Science Research for
CCS Deployment
and institutional programmes.
This selective review highlights interesting advances Greg Schnacke (Denbury CO2 EOR: U.S.
presented at the conference. For a more comprehensive Resources Inc, USA) Opportunities and
overview of the area the reader is directed to a number Challenges
of encompassing reviews on the topic (1–3).

182 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X687614 Johnson Matthey Technol. Rev., 2015, 59, (3)

Status of Carbon Capture and Storage

Carbon capture and storage is at a pivotal stage. +
SaskPower’s Boundary Dam power station has started H

to operate the first large scale carbon capture unit on H H H –

a commercial power plant. The next two years will see
the commissioning of two larger power generation
projects: Kemper County in 2016 and Petra Nova,
Texas in 2016. There are over twenty large scale
projects in operation or under construction across
the globe (4). These developments are built upon the
lessons of hundreds of pilot plants around the globe
and thousands of research hours. In the past ten
years the energy consumption of amine scrubbing has
been reduced from 300–350 kWh per tonne CO2 to
200–250 kWh per tonne CO2. Although promising, this
approach to capture is limited by the large energies
required to regenerate the solvent, and by long term
solvent durability. Cost reduction is the motivation
of much of the ongoing research with advances
that increase the rate of adsorption or reduce the
regeneration energy highly sought after. It was a core
theme of the conference that carbon capture and
storage has the potential to mitigate emissions from
power generation and industrial processes for which
there are no substitutes.
New Capture Technologies
Owing to differences in their adsorption mechanism,
tertiary amines are promising candidates for CO2
adsorption with the potential to offer higher amine
efficiency and lower desorption requirements compared
to simple primary and secondary amines. The main
limitation of tertiary amines in liquid scrubber systems
is the sluggish formation of carbonic acid. Cameron
Lippert (University of Kentucky, USA) took inspiration
from the enzyme carbonic anhydrase which readily
catalyses the hydration of CO2 in the majority of plants
and animals. The mechanism of carbonic anhydrase is
well understood, beginning with the deprotonation of the
ligated water coordinated to the zinc centre (Figure 1)
(5). This is followed by the nucleophilic attack of the
enzyme on CO2. Finally ligand exchange occurs with
the Zn bound HCO3– replaced by water regenerating
the starting species. Previous studies have shown
that this enzyme denatures under conditions akin to
industrial capture units (6, 7). Much prior research has
focused on mimics, however these are retarded by
the coordination of anions blocking the active site. To
circumvent this issue Lippert investigated ligands with
O O
Zn N Zn
I N
N N
N N
–
HCO3
II
IV CO2
H 2O O
O
–
C
H H
O O III O O
Zn Zn
N N N N
N N
Fig. 1. Carbonic anhydrase cycle
strongly electron donating groups thereby facilitating
bicarbonate dissociation and retarding inhibition.
The work used Zn salen (N,N’-bis(salicylidene)
ethylenediamine) hexafluorophosphate complexes
as catalysts for liquid amine systems (Figure 2). The
incorporation of such catalysts led to a significant
increase in the rates of CO2 hydration. The catalytic
cycle is thought to mimic that of the enzyme. If scalable
the addition of these catalysts could vastly improve
the CO2 adsorption kinetics leading to more efficient
adsorption systems.
Carbonic anhydrase also provided inspiration for
Richard Blom et al. (SINTEF, Norway) who built upon
the work by Murthy et al. presenting the Zn complex
[Zn{N[CH2(2-py)]3}(μ-OH)]2(NO3)2 (8). As well as
catalysing the hydration of CO2 such complexes can
directly react with CO2 to form a metastable complex.
The complex was found to absorb CO2 in the presence
of water forming a trimeric Zn species bridged by a
carbonate species (Figure 3) (9). The absorption could
be completed at 40ºC with purely thermal regeneration
possible at 80ºC; a temperature at which liquid amines
show very little desorption. Such low desorption
– –
PF6 PF6
+ N N +
N N N N
Zn
O O
Fig. 2. Carbonic anhydrase mimic

183 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X687614
N N
H
N O N O
3/2 Zn Zn (NO3)2 + CO2
N O N
N N
H
1
Fig. 3. Trimeric zinc complex, adapted from (9)
temperatures are promising, offering significant
reductions in regeneration requirements. Furthermore
this complex was found to readily remove CO2 from
air at low temperatures opening up a series of niche
applications for this technology. The behaviour of the
complex is also being investigated under different
solvents to avoid the additional heating requirements
brought about by the high heat capacity of water and to
overcome issues relating to solubility.
There were a number of talks highlighting new CO2
capture technologies for post combustion capture.
Joshuah Stolaroff (Lawrence Livermore National
Laboratory, USA) gave a talk on microencapsulated
sorbents. These double emulsion materials feature an
active liquid phase constrained within a porous polymer
shell. They are produced using a microfluidic device
in a linear process at a rate of 50 Hz (Figure 4). In
such a process mixtures of monoethanolamine (MEA)
and water are passed through the inner capillary with
a silicone polymer pumped through the middle tube
Outer fluid Middle fluid
Inner fluid
Collection tube Injection tube
Fig. 4. Microfluidic device (Reproduced with permission
from (10))
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Johnson Matthey Technol. Rev., 2015, 59, (3)
N N
N Zn N
N
O
N Zn (NO3)3(OH) + H2O
N N O N
Zn
N
N N
to yield a coaxial flow. A poly(vinyl alcohol) (PVA)
stabiliser is pumped in a counter current manner to
achieve hydrodynamic focusing with the three streams
passing through a single exit where they form spheres.
By using a silicone polymer and additives the outer PVA
and silicone shells can be cured under ultraviolet (UV)
light to yield aqueous monoethanolamine solutions
encapsulated in a porous polymer shell.
Microfluidic devices enable monodisperse spheres
to be easily produced with particle sizes controlled
by the dimensions of the device. The team began
encapsulating simple amines such as aqueous
solutions of MEA and piperazine which yielded rapid
absorption of CO2. Their recent work in this area
highlighted that the rate determining step was not mass
transit through the polymer shell with encapsulated
absorbents having a rate twelve times that of their liquid
counterparts (11). They found that the working fluid was
stable over numerous absorption-desorption cycles.
Furthermore the capsules have soft gelatinous physical
characteristics negating the issue of attrition prevalent
in solid adsorbents and catalysts. Encapsulated sodium
carbonate slurries mitigate the issue of precipitates and
offer significantly better rates of absorption. Currently
such double emulsions are made in a serial fashion
and Stolaroff and his team are working to improve the
production capacity of such systems by combining
parallel arrays of the microfluidic devices.
Amine Degradation
Liquid amine based CO2 absorption is the most
developed capture technology and the most likely
candidate for initial full scale deployment. A typical
liquid amine absorber includes a water wash at the
© 2015 Johnson Matthey
http://dx.doi.org/10.1595/205651315X687614
end of the absorption process to remove the amine
and other water soluble products from the exhaust
gases. With liquid amine columns appearing to be
the first generation of carbon capture technology
the issue of amine slip and degradation products
needs to be thoroughly investigated. There is
much discussion surrounding the potential release
of nitrosamines and nitroamines formed by the
reaction of nitrogen oxides and amines (12–14).
Various nitrosamine structures are believed to
be carcinogenic and could present a significantly
increased hazard compared to the parent amine.
Nitrosamines have been detected in laboratory
experiments, photochemical experiments, numerous
pilot plant studies and are formed by the reaction
between an amine and a suitable nitrosating agent
(15, 16). In the flue gas, nitrogen oxide can react
with nitrogen dioxide forming dinitrogen trioxide
(Equation (i)). Nitrogen dioxide can also dimerise
to form dinitrogen tetraoxide (N 2O 4) (Equation (ii)).
These species can then react with various amines
to yield nitrosamines (Equations (iii) and (iv)) or
nitroamines (Equation (v)) depending on the reacting
isomer. Furthermore nitrate can be generated in
solution by the decomposition of either N 2O3 or
N 2O 4 which can directly react with amines.
NO + NO2 N2O3
NO2 + NO2 N2O4
HO NO + HNO
NH + N2O3 HO N 2
HO HO
NO + HNO
HO NH + ONONO2 HO N 3
HO NO2 + HNO
NH + O2NH2NO2 HO N 2
HO
HO
These species and their tautomers can react with
amines to form nitrosamines or nitroamines either in
the absorber column or desorber and recirculating
wash water. There is potential for these pollutants to
volatilise and contaminate local air or water resources.
Studies suggest that NOx concentrations down to
around 25 ppm lead to the formation of nitrosamines
(17). For reference a typical flue gas from a coal fired
power station contains 50–100 ppm NOx. After flue
gas desulfurisation and deNOx this drops to 5 ppm.
Traditionally the performance of deNOx systems is
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Johnson Matthey Technol. Rev., 2015, 59, (3)
driven by changing legislation and as such systems
to reduce these emissions further are still under
development.
The extent of solvent loss, nitrosamine formation
and potential release is highly dependent on the flue
gas and exact nature of the process used. A number
of solutions were presented at the conference.
Nathan Fine (The University of Texas at Austin)
investigated the rates of thermal decomposition
of MEA and piperazine nitrosamines. For fresh
solutions of MEA they found minimal conversion to
nitrosamine. In cases where 1% of the MEA had
degraded to N-(2-hydroxyethyl)glycine a build-up of
nitroso-2-hydroxyglycine was apparent. MEA is
regenerated at 120ºC to preserve the structure of the
amine and at this temperature the nitrosamines were
not sufficiently thermally degraded. It was found that
15% of the NO2 absorbed by piperazine was converted
to nitropiperazine. Piperazine systems could be
regenerated at 150ºC leading to appreciable thermal
decomposition of the nitropiperazine.
A forward thinking presentation by Jesse Thompson
(University of Kentucky) explored the possibility of
nitrosamine destruction as an end of pipe treatment.
The benefit of nitrosamine reduction is twofold;
mitigating the release of nitrosamine and regenerating
degraded solvent. Using nitrosopyrrolidine as a probe
(i)
molecule and a circulating up-flow reactor Thompson et
(ii) al. demonstrated that a commercial palladium catalyst
cleanly regenerated pyrrolidine at typical desorption
(iii)
temperatures. Given the low fraction of nitrosamine in
the solution, selectivity between the nitrosamine and
the parent amine is crucial. Silica based Pd, Ni and Fe
(iv) catalysts were investigated but found to have limited
stability over successive cycling. This limited stability
was attributed to the highly alkaline environment slowly
(v) degrading the silica surface leading to metal leaching.
In a move to combat this, 2×2 manganese octahedral
molecular sieves (OMS-2) (Figure 5) co-impregnated
with Fe, Pd and Ni were prepared.
In such structures the guest metal ion resides
in the centre of the cage with catalytic activity
believed to be maintained by electron transfer from
the vacant states of the OMS-2 structure. The Pd
OMS-2 showed enhanced activity compared to Ni and
Fe–OMS-2 however nitrosamine destruction was limited
to 60%. Although possessing a lower activity than Pd,
iron(II) oxide (FeO) was also investigated as a catalyst
owing to its ready availability in fly ash. Fly ash containing
5.37 wt% FeO yielded fair nitrosamine destruction
© 2015 Johnson Matthey
http://dx.doi.org/10.1595/205651315X687614
4.6 Å
Fig. 5. Structure of OMS-2 (Reprinted with permission from
(18). Copyright (2012) American Chemical Society)
behaviour under hydrogenation conditions. Successive
cycling of the fly ash catalyst exhibited a decrease in
performance attributed to active phase leaching into
the amine solution. Given the conditions, flow rates and
competitor species this is a challenging hydrogenation
however this work shows that hydrogenation has
potential to limit nitrosamine formation and regenerate
the solvent. Thompson and his team demonstrated that
supported Pd, Ni and Fe catalysts show promise for the
hydrogenation of nitrosamines back into their parent
amines in the solvent native to the process (Figure 6).
H2, catalyst
N N
NO H
Fig. 6. The nitrosamine reduction concept put forward
by Thompson et al.
Conclusion
This review presents only a fragment of the
presentations and posters disclosed. The popularity
of the conference, combined with the large number of
key stakeholders present highlights the importance of
carbon capture and storage. A significant number of the
talks and posters discussed pilot plant experiences of
both capture and storage technologies. Carbon capture
and storage is at a crucial stage in development with
first generation systems becoming a commercial reality.
The large variety of novel concepts and technologies
indicate the potential for further advances in second and
third generation systems. These technologies look to
address the core issues of regeneration requirements,
material stability and the possible behaviour of
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Johnson Matthey Technol. Rev., 2015, 59, (3)
nitrosamines. The closing session presented the clear
message that as a technology carbon capture and
storage is ready, with the greatest challenge being
policy support to incentivise deployment.
References
1 M. E. Boot-Handford, J. C. Abanades, E. J. Anthony, M.
J. Blunt, S. Brandani, N. M. Dowell, J. R. Fernández,
M.-C. Ferrari, R. Gross, J. P. Hallett, R. S. Haszeldine,
P. Heptonstall, A. Lyngfelt, Z. Makuch, E. Mangano,
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3 D. M. D’Alessandro, B. Smit and J. R. Long, Angew.
Chem. Int. Ed., 2010, 49, (35), 6058
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Anders, Inorg. Chem., 2002, 41, (6), 1454
6 R. Lavecchia and M. Zugaro, FEBS Lett,. 1991, 292,
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Didriksen, B. Arstad and R. Blom, Energy Procedia,
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10 A. S. Utada, E. Lorenceau, D. R. Link, P. D. Kaplan, H. A.
Stone and D. A. Weitz, Science, 2005, 308, (5721), 537
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Duoss, J. O. Hardin IV, J. Lewicki, E. Glogowski, W.
C. Floyd, C. A. Valdez, W. L. Smith, J. H. Satcher Jr,
W. L. Bourcier, C. M. Spadaccini, J. A. Lewis and R. D.
Aines, Nature Commun, 2015, 6, 6124
12 C. J. Nielsen, H. Herrmann and C. Weller, Chem. Soc.
Rev., 2012, 41, (19), 6684
13 A. D. Shah, N. Dai, and W. A. Mitch, Environ. Sci.
Technol., 2013, 47, (6), 2799
14 E. D. Wagner, J. Osiol, W. A. Mitch and M. J. Plewa,
Environ. Sci. Technol., 2014, 48, (14), 8203
15 B. R. Strazisar, R. R. Anderson and C. M. White,
Energy Fuels, 2003, 17, (4), 1034
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Sjøvoll and A. L. Sørensen, Energy Procedia, 2011,
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© 2015 Johnson Matthey
http://dx.doi.org/10.1595/205651315X687614 Johnson Matthey Technol. Rev., 2015, 59, (3)

17 N. Dai, A. D. Shah, L. Hu, M. J. Plewa, B. McKague

and W. A. Mitch, Environ. Sci. Technol., 2012, 46,
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Chem Res., 2012, 51, (4), 1549

The Reviewer

Christopher Starkie graduated with a MSci in Chemistry from the University of Nottingham, UK. He
is currently undertaking postgraduate study at the Engineering Doctorate Centre in Efficient Fossil
Energy Technologies under the supervision of Professor Ed Lester, Professor Sean Rigby and
Professor Trevor Drage. Working in collaboration with Johnson Matthey he is investigating novel
functionalised materials for CO2 separation. His research interests include adsorbents, surface
functionalisation of porous materials and novel material synthesis.

187 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X688109
JOHNSON MATTHEY
TECHNOLOGY REVIEW
Platinum Group Metal and Washcoat Chemistry
Effects on Coated Gasoline Particulate Filter Design
Development of gasoline particulate filters to meet Euro 6c
By Chris Morgan
Johnson Matthey Emission Control Technologies,
Orchard Road, Royston, Hertfordshire, SG8 5HE, UK
Email: chris.morgan@matthey.com
Gasoline particulate filters (GPFs) are being developed
to enable compliance with future particulate number
(PN) limits for passenger cars equipped with gasoline
direct injection (GDI) engines. A PN emissions
limit of 6 × 1011 km –1 over the New European Drive
Cycle (NEDC) will apply for new GDI vehicles from
September 2017. (A three year derogation allowing a
higher PN limit of 6 × 1012 km –1 is currently in force.)
Real-world Driving Emissions (RDE) legislation is
being finalised by the European Commission, which is
expected to impose additional restrictions on particle
number emissions in typical driving conditions.
Legislation proposed for Beijing, China, (commonly
known as Beijing 6) is also expected to set a limit on
PN emissions from GDI vehicles.
This paper, based on a presentation given to the
Society of Automotive Engineers (SAE) Light Duty
Emissions Symposium in Detroit, USA, in December
2014, discusses the results from Johnson Matthey
test programmes to understand the effects of different
driving conditions on engine out PN emissions, the
benefits obtained from applying a platinum group
metal (pgm)-containing coating onto a GPF and
the impact of such a coating on soot combustion
properties.
188
Johnson Matthey Technol. Rev., 2015, 59, (3), 188–192
www.technology.matthey.com
Effect of Driving Conditions on Particle Number
Emissions
Almost all GDI vehicles can meet the current 6 × 1012
km–1 PN target over the NEDC. It has been reported
that a limit of 6 × 1011 km–1 can be achieved through
engine design measures such as the use of high
pressure fuel injectors, injection and combustion
timing and careful design of spray patterns and piston
heads to improve mixture formation and to avoid wall
wetting (1–3). However, the NEDC is characterised
as having moderate acceleration and deceleration
rates and extended cruises at constant speed, which
are generally unrepresentative of typical real-world
driving. Harder acceleration rates and more transient
driving are observed to give higher PN emissions. For
example a Euro 5 GDI vehicle equipped with a flow
through three-way catalyst (TWC) system emitted
2.8 × 1012 particles km–1 over the NEDC. PN emissions
from the same vehicle increased almost fourfold to
9.6 × 1012 km–1 when a transient drive cycle with harsh
acceleration rates was used. Similarly, experiments
on multiple GDI vehicles indicated 30–85% higher PN
emissions from testing using the more transient US
Federal Test Procedure (FTP)-75 drive cycle compared
to NEDC data. Driver to driver variability has also been
observed. Therefore, it is likely that real-world PN
emissions from GDI vehicles are significantly higher
than NEDC test data indicate.
Furthermore, ambient temperature has a significant
effect on PN emissions. NEDC testing is conducted at
a temperature of 23ºC, significantly above the average
© 2015 Johnson Matthey
http://dx.doi.org/10.1595/205651315X688109
temperature in the UK and many other European
countries. A Euro 6 GDI vehicle equipped with a flow
through TWC system was measured to emit <4 × 1011
particles km–1 over the NEDC when tested at 23ºC
(Figure 1). When the test car was cooled to 10ºC
before the start of the test, PN emissions increased
threefold to 1.1 × 1012 km–1. Cooling the car to 0ºC
before the start of the test doubled PN emissions again
to 2.3 × 1012 km–1. Therefore, even vehicles designed
to give low PN emissions during the certified test at
23ºC are likely to emit significantly more in the ambient
conditions many drivers experience daily.
Benefits of a Coated Gasoline Particulate Filter
GPFs have been shown to be very effective at
attenuating PN emissions (4, 5). Cordierite wall
flow filters are most commonly used in development
programmes and at least one series application
employing uncoated cordierite GPFs is on sale today.
Adding an uncoated filter downstream of the existing
aftertreatment system allows PN control without
requiring significant changes to engine calibration or
on-board diagnostic (OBD) strategies. However, the
addition of an extra unit adds canning cost and the
space required can be problematic on smaller vehicles.
Applying a suitable TWC coating onto the GPF allows
it to be substituted for flow through TWC volume in
the existing aftertreatment system, resulting in a more
compact architecture. Johnson Matthey and other
coaters (6–8) have demonstrated such technologies
previously.
However, expected RDE limits on nitrogen oxides
(NOx) emissions will add further demands on the
23ºC 14ºC
4.0E + 12
3.5E + 12
Cumulative particulate
PN dependent on soak temperature
3.0E + 12
NO per km
2.5E + 12
2.0E + 12
1.5E + 12
1.0E + 12
5.0E + 11
0.0E + 00
0 200
Fig. 1. Impact of vehicle soak temperature on PN emissions over the NEDC
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Johnson Matthey Technol. Rev., 2015, 59, (3)
gasoline aftertreatment system. Many European
exhaust systems have their catalyst volume and
precious metal content optimised to meet current
NEDC emissions targets. It is well known that
conversion of NOx requires more catalyst volume than
conversion of CO or hydrocarbons. NEDC-optimised
catalyst systems may not provide sufficient NOx
conversion activity under more demanding conditions
with higher space velocities. Adding effective catalyst
volume by applying a pgm-containing coating onto
the GPF can increase the conversion of gaseous
pollutants under such conditions. For example, a
Euro 5 1.0 l GDI application was tested over the NEDC
and World-Harmonised Light-Duty Test Cycle (WLTC)
with uncoated or coated GPFs fitted downstream of
the series TWC. With the uncoated filter system NOx
emissions over the NEDC were 56 mg km–1, increasing
to 82 mg km–1 over the more transient WLTC for which
the TWC was undersized. With a coated GPF NEDC
emissions were ~10% lower than with the uncoated
filter, at 50 mg km–1. Furthermore, the coated GPF
gave good control over the WLTC with emissions of
47 mg km–1. The coated GPF is particularly effective
in avoiding NOx slip during the higher speed, higher
space velocity conditions experienced in the final 600 s
of the WLTC (Figure 2).
The benefits of a coated GPF can be further enhanced
by optimising the precious metal content of the coating.
For example, Figure 3 shows NOx emissions from
testing of a TWC plus coated GPF system on a Euro 5
2.0 l GDI vehicle over the transient Artemis test cycle.
Thrifting precious metal from the close-coupled TWC
resulted in a ca. 20% increase in NOx emissions.
However, increasing the rhodium loading on the
10ºC 0ºC –7ºC –9ºC Scheduled speed, kph
160
140
120
Speed, kph
100
80
60
40
20
0
400 600 800 1000 1200
Time, s
© 2015 Johnson Matthey
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Engine out NOx Post TWC NOx Tailpipe NOx Scheduled speed
2.0 300
1.8 NOx conversion by

Accumulated NOx emissions, g

the coated GPF 250
1.6
1.4

Vehicle speed, kph

200
1.2

1.0 150

0.8
100
0.6
0.4
50
0.2
0.0 0
0 200 400 600 800 1000 1200 1400 1600 1800
Time, s
Fig. 2. Comparison of TWC plus coated or uncoated GPF over the WLTC

TWC 100 // cGPF Rh@2 TWC 80 // cGPF Rh@2

TWC 80 // cGPF Rh@5 Scheduled speed, kph
3.5 140
Increased Rh loading on filter helps
3.0 with NOx breakthrough 120
Cumulative NOx emissions, g

Scheduled speed, kph

2.5 100

2.0 80

1.5 60

1.0 40

0.5 20

0.0 0
0 500 1000 1500 2000 2500 3000
Time, s

Fig. 3. Effect of GPF Rh loading in compensating for emissions breakthroughs from pgm thrifting of the upstream TWC

downstream coated GPF from 2 g ft–3 to 5 g ft–3 more Soot Combustion

than compensated for this effect, with significantly
improved conversion at higher speeds. A concern about the use of uncoated GPFs, particularly
Therefore, as well as controlling PN emissions, when located in remote underfloor locations, is whether
coated GPFs offer advantages over uncoated GPFs they will regularly reach sufficient temperatures to
in conversion of gaseous pollutants for RDE and regenerate collected soot without the use of extreme
more transient drive cycles. Additional pgm and engine operating conditions to artificially increase the
oxygen storage capacity (OSC) on the coated filter filter temperature. It was hypothesised that the presence
help to control emissions breakthroughs during harsh of an active coating on the GPF would enhance soot
accelerations and high speed driving. combustion. To investigate this soot-loaded coated

190 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X688109
and uncoated GPFs were fitted to a Euro 5 1.4 l
GDI vehicle and tested over a cycle comprising the
NEDC with the final, higher speed, Extra-Urban Drive
Cycle (EUDC) repeated ten times. The final EUDC
deceleration from 120 kph triggers a fuel cut-off and
the resulting oxygen-rich environment can lead to soot
combustion at suitable filter temperatures. Peak filter
inlet temperatures during the NEDC were controlled
to values between 520ºC and 650ºC by varying the
dynamometer gradient from 0 to 3%. Soot combustion
was monitored through measurement of pressure drop
over the aftertreatment system and by weighing the
filter before and after each test to measure the mass
of soot removed.
In the uncoated filter only 50% of the soot was
removed at a peak temperature of 600ºC, increasing to
90% at 650ºC (Figure 4). In contrast, soot combustion
in the coated filter increased rapidly at temperatures
above 550ºC, with complete removal of the soot at ca.
570ºC. Therefore, the presence of a pgm-containing
TWC coating reduced soot combustion temperatures
by approximately 100ºC, delivering significant benefits
for vehicle strategies to control soot build up in a GPF.
Detailed analysis of the differential pressure data
showed that at 570ºC the backpressure reduced to
a stable level after the first EUDC, indicating rapid
promotion of soot combustion.
The chemistry of the TWC coating can also be
optimised to enhance soot combustion properties.
Powder reactor studies confirmed that the presence of
pgm and ceria-containing OSC materials significantly
reduce soot combustion temperatures and that the
choice of OSC material can influence peak soot
combustion temperatures by more than 50ºC.
Bare GPF Coated GPF
100
% Soot burnt after 10 fuel cuts
90
80
70
60
50
40
30
20
10
0
450 500 550 600
Filter inlet temperature, ºC
Fig. 4. Effect of a pgm-containing GPF coating on soot
combustion under vehicle deceleration fuel cut-off conditions
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Johnson Matthey Technol. Rev., 2015, 59, (3)
Conclusions
Control of PN emissions from GDI engines is of
increasing importance to meet Euro 6c and proposed
RDE and Beijing 6 emissions standards and GPFs are
effective in reducing tailpipe PN emissions. However,
emissions of particulates and gaseous pollutants
can be significantly higher in real-world conditions,
with more transient driving, higher maximum speeds
and lower ambient temperatures all shown to have a
detrimental effect. Use of a pgm-containing coated
GPF offers benefits over an uncoated GPF, including
the abilities to control emissions breakthroughs from
upstream TWC components, to enable regeneration of
collected soot at lower temperatures and at a faster
rate and to allow substitution for TWC volume for
system compactness. These benefits can be enhanced
through careful design of the washcoat chemistry and
precious metal content.
Acknowledgements
The author would like to thank the Gasoline Product
Development and Catalyst Test Laboratory teams at
the Johnson Matthey Emission Control Technologies
Centre in Royston for the development work and test
data described in this paper.
References
1 G. Fraidl, P. Hollerer, P. Kapus, M. Ogris and K.
Vidmar, ‘Particulate Number for EU6+: Challenges
and Solutions’, IQPC Advanced Emission Control
Concepts for Gasoline Engines, Stuttgart, Germany,
21st–23rd May, 2012
2 M. Winkler, ‘Particle Number Emissions of Direct
Injected Gasoline Engines’, IQPC Advanced Emission
Control Concepts for Gasoline Engines, Stuttgart,
Germany, 21st–23rd May, 2012
3 O. Berkemeier, K. Grieser, K. Hohenboeken, E.
Kervounis and K. M. Springer, ‘Strategies to Control
Particulate Emissions of Gasoline Direct Injection
Engines’, FISITA 2012 World Automotive Congress,
Beijing, China, 27th–30th November, 2012
4 T. Shimoda, Y. Ito, C. Saito, T. Nakatani, Y. Shibagaki, K.
650 700
Yuuki, H. Sakamoto, C. Vogt, T. Matsumoto, Y. Furuta,
W. Heuss, P. Kattouah and M. Makino, ‘Potential of a
Low Pressure Drop Filter Concept for Direct Injection
Gasoline Engines to Reduce Particulate Number
Emission’, SAE Technical Paper 2012-01-1241
© 2015 Johnson Matthey
http://dx.doi.org/10.1595/205651315X688109 Johnson Matthey Technol. Rev., 2015, 59, (3)

5 K. Ogyu, ‘Requirement of Exhaust Emission Control on
Direct Injection Gasoline Engines – a New Approach
on Gasoline Particulate Filters’, IQPC Advanced
Emission Control Concepts for Gasoline Engines,
Stuttgart, Germany, 21st–23rd May, 2012
6 C. Morgan, ‘Three Way Filters for Particulate Number
Control’, IQPC Advanced Emission Control Concepts
for Gasoline Engines, Stuttgart, Germany, 21st–23rd
May, 2012
7 J. M. Richter, R. Klingmann, S. Spiess and K.-F.
Wong, ‘Application of Catalyzed Gasoline Particulate
Filters to GDI Vehicles’, SAE Technical Paper
2012-01-1244
8 K. Harth, K. Wassermann, M. Arnold, S. Siemund,
A. Siani, T. Schmitz and T. Neubauer, “Catalyzed
Gasoline Particulate Filters: Integrated Solutions for
Stringent Emission Control”, 34th International Vienna
Motor Symposium, Austria, 25th–26th April, 2013

The Author
Chris Morgan is Technology Director for Johnson Matthey’s European Emission Control
Technologies business, responsible for the development and scale-up of autocatalyst coatings
for light duty gasoline and diesel applications. Chris previously managed the Gasoline Product
Development team, developing new families of three-way catalysts and leading Johnson Matthey’s
early work on coatings for gasoline particulate filters. He joined Johnson Matthey in 1997, after
completing a DPhil at the University of Oxford, UK, on high temperature ceramic superconductors.

192 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X688406
JOHNSON MATTHEY
TECHNOLOGY REVIEW
“Additive Manufacturing Technologies:
3D Printing, Rapid Prototyping, and Direct Digital
Manufacturing”, 2nd Edition
By Ian Gibson (Deakin University, Australia), David Rosen (Georgia Institute
of Technology, USA) and Brent Stucker (University of Louisville, USA),
Springer Science+Business Media, New York, USA, 2015, 498 pages,
ISBN: 978-1-4939-2112-6, £81.00, €96.29, US$119.00
Reviewed by Jonathan Edgar*
Johnson Matthey Technology Centre,
Blount’s Court, Sonning Common, Reading RG4 9NH, UK
Saxon Tint
Johnson Matthey Noble Metals,
Orchard Road, Royston, Hertfordshire SG8 5HE, UK
*Email: jonathan.edgar@matthey.com
Introduction
“Additive Manufacturing Technologies: 3D Printing,
Rapid Prototyping, and Direct Digital Manufacturing”
is authored by Ian Gibson, David Rosen and Brent
Stucker, who collectively possess 60 years’ experience
in the field of additive manufacturing (AM). This is
the second edition of the book which aims to include
current developments and innovations in a rapidly
changing field. Its primary aim is to serve as a teaching
aid for developing and established curricula, therefore
becoming an all-encompassing introductory text for
this purpose. It is also noted that researchers may find
the text useful as a guide to the ‘state-of-the-art’ and to
identify research opportunities.
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Johnson Matthey Technol. Rev., 2015, 59, (3), 193–198
www.technology.matthey.com
The book is structured to provide justification and
information for the use and development of AM
by using standardised terminology to conform to
standards (American Society for Testing and Materials
(ASTM) F42) introduced since the first edition. The
basic principles and historical developments for
AM are introduced in summary in the first three
chapters of the book and this serves as an excellent
introduction for the uninitiated. Chapters 4–11 focus
on the core technologies of AM individually and, in
most cases, in comprehensive detail which gives
those interested in the technical application and
development of the technologies a solid footing. The
remaining chapters provide guidelines and examples
for various stages of the process including machine
and/or materials selection, design considerations and
software limitations, applications and post-processing
considerations.
Principles and Processes
The first three chapters provide a basic understanding
of why someone might want to utilise AM in the context
of traditional methods as well as developments in AM
since its inception. In the initial chapters the reason
for introducing standardised terminology is justified in
contrast to the historical terms. For example, the use
© 2015 Johnson Matthey
http://dx.doi.org/10.1595/205651315X688406
of ‘rapid prototyping’ to describe the field is no longer
relevant as the technology is now used for functional
components as well.
Brief summaries of the process are also provided in
these initial chapters in increasing detail as the reader
approaches the technical chapters. This provides a
realistic view of actions required throughout the process
and gives context to references made throughout the
book. In its simplest form the process can be universally
summarised as:
• conceptualisation and computer aided design
(CAD)
• conversion to STereoLithography (STL)/additive
manufacturing file (AMF)
• transfer to AM machine and file manipulation
• machine setup
• build
• removal and cleanup
• post-processing
• application.
Additive Layer Manufacturing Technologies in
Detail
Chapters 4–11 describe seven different printing
processes in differing degrees of detail. Topics such as
‘vat photopolymerisation’ (VP) and ‘powder bed fusion’
(PBF) are covered in such comprehensive detail that
their chapters are double the length compared with
‘binder jetting’ (BJ), despite the latter being a very
well used industrial technique. Printable materials
and delivery mechanisms are also listed here and the
chapters include a ‘process benefits and drawbacks’
section, useful for the beginner. It should be noted
that some processes (extrusion, sheet lamination
and directed-energy deposition) are omitted from this
review.
Vat Photopolymerisation
VP processes make use of liquid, light-curable resins
as their primary materials. Upon irradiation, these
materials undergo photopolymerisation, becoming
solid. Ultraviolet (UV) light is projected onto the build
plate, curing a layer before recoating. Methods for
illuminating the photopolymers are presented, including
masked projection, layer-wise processing and vector
scan point-wise processing. Expressions relating
laser power, scan speed, spot size and cure depth are
derived, forming the basis of a process model which can
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Johnson Matthey Technol. Rev., 2015, 59, (3)
be applied generally. Curable materials are discussed,
including an overview of photopolymer chemistry and
their interactions with radiation. Another method, called
the ‘two-photon’ approach, describes how a dual light
source can increase part resolution – feature sizes of
0.2 μm have been achieved. Advantages of VP include
part accuracy, surface finish and process flexibility. The
main drawback is their usage of photopolymers, which
generally do not have the impact strength or durability
of good quality injection moulded thermoplastics.
Powder Bed Fusion
PBF methods deposit layers of powder which are
sequentially fused together by an energy source
resulting in solid parts residing in a powder bed. The
prominent methods are selective laser sintering (SLS)
and electron beam melting (EBM), and these two are well
compared: EBM processes benefit from the flexibility
and high energy of their heat source, which can move
nearly instantaneously and with split beams; EBM builds
typically maintain the bed at high temperature and can
create parts with a cast, low porosity, low residual
stress microstructure. However their requirement for
a vacuum chamber and conductive target material
restricts material capabilities whereas SLS machines
can process materials such as polymers and ceramics
in gaseous atmospheres. This chapter builds on the
process model from the previous chapter, applying the
concepts to the fusion process of solids and methods
for reducing internal stresses in solidified parts. PBF
is a well commercialised technology, but due to the
lapsing of major patents there are some open-source
machines available which have led inventors to create
non-engineering applications of the technology too.
Materials Jetting
The first generation of materials jetting (MJ) machines
was commercialised in the 1980s. They relied on heated
waxy thermoplastics deposited by inkjet printheads,
lending themselves to modelling and investment
casting manufacture; however the more recent focus
has been on deposition of acrylate photopolymers,
wherein droplets of liquid monomer are formed and then
exposed to UV light to initiate polymerisation. Machines
with build spaces as big as 1000 × 800 × 800 mm are
available, as well as multi-material capability which
can print 1000+ materials by varying the composition
of several photopolymers. Research groups around
© 2015 Johnson Matthey
http://dx.doi.org/10.1595/205651315X688406
the world are working on other material groups such
as non-photopolymers, ceramic suspensions and
low melting point metals (including aluminium). The
challenge of forming molten droplets, then controlling
deposition and solidification characteristics has kept
these material systems in the research arena. A section
on the fluid mechanics of droplet formation and jetting
is included in a process model for the MJ process (a
section which is also relevant to Chapter 8).
Binder Jetting
BJ methods were primarily developed at Massachusetts
Institute of Technology (MIT), USA, during the early
1990s and feature a powder bed similar to that of the
PBF process (Chapter 5). However, instead of using
an energy source to fuse the material together, an
inkjet head deposits a binder onto each layer to form
part cross-sections. The binder forms agglomerates
with the powder particles and provides bonding
with the layer below. The chapter describes some
commercial materials available, and notes that many
of them require post-processing to increase strength,
for example by infiltration with another material.
Materials include polymers (for example, poly(methyl
methacrylate) (PMMA)), ceramics, foundry sands and
metals such as 420 stainless steel or Inconel alloy 625
infiltrated with bronze. This technology can be scaled
up quite easily, as demonstrated by machines with
an incredible 4 × 2 × 1 m build volume. Although the
subject of ink drop formation is covered in the previous
chapter, a discussion surrounding ink interaction with
the powder bed is missing here. Disappointingly for a
process described as one of the most readily scalable,
the chapter is one of the shortest – although some
aspects, such as powder handling, are discussed in
other chapters.
Guidelines for Process Selection and Ancillary
Process Tasks
The remainder of the book provides outlines and
information on software applications and physical
processes necessary for gaining maximum advantage
from AM.
Process Selection
There are software applications where the performance
attributes of each AM technology option are weighted
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Johnson Matthey Technol. Rev., 2015, 59, (3)
and ranked based on the relevance of the input
parameters (for example geometric considerations
and mechanical properties). A particular example,
RM Select, is provided (installation file and manual
are available (1, 2)). This information is particularly
pertinent to those interested in production applications
of AM.
Post-processing
AM is often viewed as a complete process and therefore,
to the uninitiated, it can be a surprise to learn of the
requirement for post-processing. The book introduces
the various types of support structures required to
achieve and maintain all levels of geometric complexity
and the subsequent post-processing methods and
design considerations to aid their removal. Depending
on the application of the part, surface finishing may
also be required. In this case it may be necessary to
design extra material in the areas to be post-processed
to ensure the desired dimensions are maintained.
Powder bed methods possess ‘natural’ supports
where the built object is encased in excess material.
They are named as such as they are an intrinsic part of
the process. The main disadvantage of natural supports
is that the part must be designed so that the excess
material can be removed, for example for powder bed
methods parts that are designed to be hollow must
have an escape hole for loose powder. In this case the
excess material is recycled as much as possible with
some sieving usually required.
‘Synthetic’ supports are required for methods that
do not have ‘natural’ supports or for methods that
have stresses as an intrinsic part of the process, for
example powder bed fusion parts need to be tethered
to the substrate to prevent warping from stresses
created by the presence of significant temperature
gradients. It is noted that these stresses can be
reduced, and therefore the requirement for synthetic
supports is decreased, by raising the temperature of
the build environment. For MJ and materials extrusion
methods the support structures can be constructed
from the build material or a secondary material. In the
case of secondary materials a second ‘printhead’ or
a purge cycle is required to prevent contamination. If
the ‘synthetic’ supports are constructed of the build
material then they must be designed such that they can
be easily removed in post-processing, it is common
for printer software to include automatic support
generation. Alternatively, the ‘synthetic’ supports can
© 2015 Johnson Matthey
http://dx.doi.org/10.1595/205651315X688406
be constructed of a secondary material with differential
solubility (with respect to the build material) and can
simply be dissolved away post-process.
Post-processing is an integral procedure of AM and
understanding the many factors to streamline and
safeguard the integrity of the printed part is paramount.
Software Issues and Considerations
The file standard for AM technologies is the STL file
format. The origin of this file extension hails to the
first stereolithography machines commercialised by
3D Systems Inc, USA. This format is expressed as
a list, either in binary or American Standard Code for
Information Interchange (ASCII) (text), of the vertices
of triangular facets used to approximate the surface of
the digital part. This approximation is most relevant,
with respect to deviation from the true geometry, when
there are a significant number of curves in the part. The
orientation of the facets is defined by the unit normally
expressed in vector coordinates.
Due to the nature of the process, i.e. layer-by-layer,
there is also the requirement to ‘slice’ the file prior to
initiating the printing process. The generation of the
support structures may be done before or during the
slicing operation.
One problem with STL, unlike other CAD formats, is
that there are no units associated with the file itself.
Therefore the scale/dimensions must be checked to
ensure the correct dimensions are applied. This can be
particularly important for international communications,
for example USA to EU or vice versa. Furthermore, it
should be noted that not all graphics software packages
can create STL files with adequate accuracy. One
common issue when converting to STL is the creation
of parts with holes (i.e. incomplete surfaces), which
are not compatible with AM machines. More modern
dedicated AM software packages are emerging,
making this issue less prevalent.
Colour and materials properties are another factor to
include into the definition of a part to print. For coloured
parts this can be done by colouring of individual facets
with solid colour (colour STL) or an image (virtual
reality modelling language (VRML)). The advantage
of applying an image is that the applied colour is not
limited by the resolution of the facet. As the STL file
format is surface data only there is the assumption
that the underlying material is homogeneous. For
AM technologies capable of multi-material printing
the file typically has to be defined as distinct objects
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Johnson Matthey Technol. Rev., 2015, 59, (3)
with materials properties defined for each. As yet,
there is not an agreed upon standard file format for
multi-material objects.
Design Considerations
Particular focus is made on the use of designed
cellular structures and void filling. These structures
can be symmetrical or conformal (with variable cell
size to appropriately fill the void space). The primary
advantage of using cellular structures is the reduction
of the required build material without compromising
overall strength. Cellular structures are a particular
strength of AM processes given the fact that the
entire structure can be designed, and with the help
of software applications, optimised to achieve the
most efficient strength-to-weight properties. The
output cannot always be reproduced but a near
approximation can be achieved with little compromise
in performance. Examples of topology optimisation
software given are Abaqus from Dassault Systèmes
and OptiStruct from Altair.
Applications
This section offers a flavour of the multitude of possible
applications of AM technologies. ‘Rapid tooling’ refers
to the use of AM to create production tools. Typically
these are reusable moulds, impressions or patterns
from which the tools can be created. This method may
be applied, in particular, if the material required for part
production is not currently available in an AM technology
or the mould can be improved upon by utilising the
design freedoms of AM, for example conformal cooling
channels for injection moulds. Medical and aerospace/
automotive applications have received significant
attention from the implementation of AM technologies.
Medical procedures can be streamlined by developing
surgical guides and tools. Prostheses and implants are
of particular interest for the application of AM as they
can be customised on a case-by-case basis. Significant
research efforts are currently being employed to print
with living cells and biomaterials for direct transplant.
Another method is to print a biocompatible scaffold for
post-process treatment with living cells to encourage
natural material growth, for example Osteopore
produces ‘bioresorbable’ implants to encourage natural
bone growth over trephination holes from neurosurgery.
Aerospace applications of AM have been quite
diverse with examples of engine system and
© 2015 Johnson Matthey
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non-structural components. The primary benefit for the “Additive Manufacturing

aerospace industry is improved fuel efficiency by better Technologies: 3D Printing,
performance and lighter weight components. Rapid Prototyping, and
Direct Digital Manufacturing”

Business Opportunities and Future Directions

The book is rounded out by highlighting the fact that

AM offers genuinely new avenues for production and
product development and thus adjusted business
models and practices could be required to accommodate
the rapidly changing landscape of manufacturing.

Conclusion

Readers desiring a comprehensive introduction to the

many technologies of AM should be satisfied. Although
it is aimed primarily at students and educators, the
authors do very well to appeal to those in research and
manufacturing positions too. Excellent explanations
of basic concepts through to the state-of-the-art make
this a great starting point for in-depth research, whilst
the process selection tools and business opportunities
chapters will be very useful for manufacturers looking
to explore this technology.
References
1 D. Rosen, ‘RM Selection, Software User Manual’,
Version 1, Georgia Institute of Technology, Atlanta,
USA, 12th August, 2005
2 The Georgia Institute of Technology: The Systems
Realization Laboratory: http://www.srl.gatech.edu/
Members/drosen (Accessed on 28th May 2015)

The Reviewers
Jonathan Edgar received a BSc and PhD in nanotechnology from the University of Technology,
Sydney, Australia. Currently he is working for Johnson Matthey on a core science and materials
development project using additive manufacturing technologies.

Saxon Tint has an MEng in Materials Science and Engineering from Imperial College London, UK.
He joined Johnson Matthey Noble Metals in 2011 as a Materials Scientist and has worked on a
range of projects including alloy development for spark plug tips, powder metallurgy and AM.

197 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X688406 Johnson Matthey Technol. Rev., 2015, 59, (3)

As a
FTSE100 company
that develops advanced
materials and specialises in
precious metals, Johnson Matthey
has a strong interest in precious metal
and speciality metal powders. If you have
an interest in precious metal powders
or speciality metal powders for
additive layer manufacturing, 3D
printing or other applications
we’d be keen to hear from
you. Please contact Alexandra French,
Sales and Marketing Director, Noble Metals on:
a l e x a n d r a . f r e n c h @ m a t t h e y. c o m o r
+44 (0) 1763 253856 / +44 (0) 7968 568532

For more information about Johnson Matthey’s expertise as

well as its investment in research and development, please visit
the corporate website: http://www.matthey.com/

198 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X688163 Johnson Matthey Technol. Rev., 2015, 59, (3), 199–206
JOHNSON MATTHEY
TECHNOLOGY REVIEW
Temperature Dependent Heat Transfer Performance
of Multi-walled Carbon Nanotube-based Aqueous
Nanofluids at Very Low Particle Loadings
Investigating the mechanism of thermal conductivity enhancement
By Meher Wan
Department of Metallurgical and Materials
Engineering, Indian Institute of Technology,
Kharagpur-721302, India
Raja Ram Yadav
Department of Physics, University of Allahabad,
Allahabad-211002, India
Giridhar Mishra and Devraj Singh*
Department of Applied Physics, Amity School of
Engineering and Technology,
An affiliated institute of Guru Gobind Singh
Indraprastha University,
Bijwasan, New Delhi-110061, India
*Email: dsingh13@amity.edu
Bipin Joshi
Department of Science and Technology, Technology
Bhavan, New Mehrauli Road, New Delhi-110016, India
Aqueous suspensions of multi-walled carbon
nanotubes (MWCNTs + deionised water) have been
synthesised. Carbon nanotubes (CNTs) were derived
by chemical vapour deposition (CVD). Transmission
electron microscopy (TEM) measurements show the
formation of MWCNTs. Three samples of CNT-based
aqueous nanofluids having MWCNT concentrations of
0.01 vol%, 0.03 vol% and 0.05 vol% were prepared with
the help of ultrasonic irradiation. A very small amount of
199 © 2015 Johnson Matthey
www.technology.matthey.com
sodium dodecyl sulfate (SDS) was used as a surfactant
to minimise the agglomeration of the MWCNTs. An
effective enhancement in thermal conductivity was
observed at different temperatures. The obtained
results are explained with percolation theory.
1. Introduction
Heat transfer management is becoming increasingly
critical in the infrastructure, industry, transportation,
defence and aerospace sectors. Several cooling
methods have been investigated recently to meet
the heat transfer requirements of 21st century high-
technology, high density heat producing industrial
equipment. Water, ethylene glycol and mineral oil
have been used as conventional coolants for different
industries. Conventional heat transfer systems used in
a wide range of applications, including petrochemicals,
refining, power generation and microelectronic devices,
are rather large and involve a significant amount of heat
transfer fluids in comparison to biomedical engineering
based applications (1). Managing high density heat
generation in microelectronic industries is a good
example (2, 3).
Modern, small scale cooling applications require very
effective coolants. Existing heat management systems
can be improved by enhancing the performance of heat
transfer fluids through the use of nanofluids, resulting in
lower heat exchange surface area, lower capital costs
and higher energy efficiencies (4). Several techniques
have been investigated to enhance the thermal exchange
performance of the fluids. Out of many tried methods,
http://dx.doi.org/10.1595/205651315X688163 Johnson Matthey Technol. Rev., 2015, 59, (3)
one is to add a very small percentage of nanoparticles
having high thermal conductivity into heat transfer
fluids to improve their overall thermal conductivity
(5–8). Such additives may include novel metals, metal
oxides and carbon nanostructures. Nanoparticles
may possess either spherical, cylindrical, fibril or
sheet-like structures. Cylindrical carbon nanostructures
(4, 9, 10) or CNTs have very high thermal conductivity
of the order of 3000 W m–1 K–1 (11). MWCNTs have
very exotic physical properties and are relatively easy
to synthesise. They have been shown to be promising
additives in conventional heat transfer fluids for diverse
heat transfer applications (9, 12). Several researchers
have tested different combinations and permutations
of CNTs, the effects of their aspect ratios (diameter
and length) and base fluids on thermal conductivity
in CNT-based nanofluids (13). For a more uniform
dispersion of CNTs, the effects of different quantities
of surfactant materials on thermal conductivity have
also been studied (14). However the addition of a large
weight percentage of filler in a fluid affects its viscous
properties. Higher viscosity does not support better
heat conduction due to the need for higher pumping
power as well as changes in other fluidic properties.
The present work is focused on the preparation
of nanofluids by dispersing MWCNTs in deionised
water and measuring the temperature dependent
thermal conductivity of the nanofluids at very small
particle loadings. The experimental observations
regarding thermal conductivity enhancements can
be explained with the help of appropriate theoretical
models. It has now been established that when CNTs
are suspended in conventional heat transfer fluids,
anomalous enhancements in thermal conductivity are
observed (15, 16). The motivation behind the present
study is to find the mechanism of thermal conductivity
enhancement at very small concentrations of MWCNTs
in suspension and the effects of MWCNT aqueous
nanofluids on thermal performance at a range of
temperatures. It is assumed that the viscous properties
of the base fluid do not change with the inclusion of
very low CNT loadings.
2. Materials and Methods
Deionised water and MWCNTs were used to produce
nanofluids. The MWCNTs were synthesised by CVD using
nickel salen [N,N’-ethylene-bis(salicylideneiminato)]-
nickel(II); Ni(C16H14N2O2) as a catalyst. The details
of the CNT growth are described elsewhere (17). Ni
200 © 2015 Johnson Matthey
salen was found to produce CNTs via a tip-growth
mechanism. Small Ni particles were observed at the
tips of the CNTs which were otherwise free of Ni. Since
Ni is used as a catalyst in relatively small amounts and
is embedded inside the CNT tips, its contribution to the
thermal conductivity enhancement can be ignored. The
MWCNTs have an average outside diameter of 30 nm,
and a length of several micrometers, as observed by
electron microscopy (field emission scanning electron
microscopy (FE-SEM) and TEM) (Figures 1(a) and
1(b)).
Nanofluids were prepared using a two step method.
First the required amounts of MWCNTs and deionised
water needed for the sample preparation were
determined. Then a very small amount of surfactant
(SDS) was dissolved in the liquid matrix, followed
by appropriate amounts of MWCNTs for synthesis of
different concentrations of nanofluids. SDS was used
to minimise the agglomeration of nanotubes in the
base fluid. The samples having MWCNTs were stirred
using a magnetic stirrer and were ultrasonicated for
20 minutes with 100 W intensity at 20 kHz ultrasonic
frequency (Sonics VC 505). As the probe sonicates
within a limited conic volume, to facilitate uniform
dispersion, sonication was followed by 10 minutes
magnetic stirring. According to the density data
provided by Jana et al. (18), 0.026 g, 0.078 g and
0.130 g of CNTs were dispersed in 100 ml of deionised
water to prepare nanofluids with 0.01 vol%, 0.03 vol% and
0.05 vol% CNTs. 100 ml suspensions of each
composition were prepared.
Thermal conductivity of the synthesised nanofluids
was measured with a Hot Disk TPS 500 Thermal
Constant Analyser which works on the temperature
coefficient of resistance principle. The transient
plane source (TPS) method is an updated version
of the transient hot wire (THW) technique (19). The
uncertainty in the measurements in this method
is ±4%. TPS overcomes many of the drawbacks of
THW due to its sensor structure and shape. TPS
has a computer controlled temperature controller for
accurate temperature settings and precise results
at typical temperatures. The TPS based instrument
can be used to measure thermal constants such as
conductivity and diffusivity via a Ni sensor, using
the temperature coefficient of resistance. Inside the
instrument, the TPS element behaves both like a
temperature sensor and a heat source. TPS uses
the Fourier law of heat conduction as its fundamental
principle for measurements.
http://dx.doi.org/10.1595/205651315X688163 Johnson Matthey Technol. Rev., 2015, 59, (3)

(a) (b)

200 nm 0.2 µm

Fig. 1. (a) FE-SEM images of the as-grown MWCNTs; (b) TEM of the MWCNTs

3. Results and Discussion be claimed that the percolation threshold exists below
0.03 vol%, leading to the conclusion that the CNTs do
Thermal conductivity measurements were taken for all not have continuous chains from one end to the other
the nanofluid samples at temperatures from 10ºC to below a certain particle loading, as predicted by Sastry
80ºC. The experimental data for thermal conductivity et al. (20).
of the nanofluid samples are presented in Figure 2. Although a number of models based on different
For comparison, the temperature dependent thermal mechanisms are available currently in the literature,
conductivity data of the base fluid (water) are also given. no theoretical model is able to explain the anomalous
It can be seen that there is no significant increase in the thermal conductivity enhancement observed
thermal conductivity with the suspension of 0.01 vol% experimentally due to controlled and uncontrolled
MWCNTs. On the other hand, there is a significant parameters in the experimental setup (21). Some
anomalous increase in the thermal conductivity of models, for example the Sastry model, are in reasonable
water with suspension of 0.03 vol% CNTs. Thus, it can agreement with the experimental data under different
assumptions and conditions. A critical analysis of the
theoretical models has been carried out by Lamas
et al. (21) who concluded that the available models
1.5 show a negative effect of temperature on thermal
DI-water + SDS conductivity enhancement in these systems. However,
1.4
Thermal conductivity, W m–1K–1

0.01 vol%
1.3 this is contradictory to the available experimental
0.03 vol%
1.2 0.05 vol% results. The agreement of theory and experiment was
1.1 achieved by adjusting parameters such as the CNT
1.0 geometry (22) and the value of interfacial conductance
0.9 (23). These theoretical models had various degrees
0.8 of empiricism and provided a limited physical insight
0.7 into the experimental observations. In past studies,
0.6 experimental data have showed that the dispersion
0.5 technique and interaction between the CNTs and
0 10 20 30 40 50 60 70 80 90 the base liquid also play a strong role, causing the
Temperature, ºC enhancement to vary by as much as 7%–40% for
Fig. 2. Thermal conductivity of nanofluids containing CNTs at
water-MWCNT nanofluid (24).
different temperatures For the present study, very low concentrations were
chosen for two reasons. Firstly, to maintain the fluidic

201 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X688163 Johnson Matthey Technol. Rev., 2015, 59, (3)

or viscous properties of the base fluid; and secondly to Li ,P L sin φi cos θ i

investigate the existence of a percolation threshold to
explain anomalous thermal conductivity enhancements
as predicted by Sastry and his coworkers. A number of
physical mechanisms have been proposed to explain
the thermal conductivity enhancement of a nanofluid.
An early concept was interfacial layering: the formation
of a solid-like, liquid molecular layer close to the CNT
interface, which has much higher thermal conductivity
than the bulk liquid itself (25). Alternatively, due to the
high aspect ratio of CNTs, interaction between them is
thought to be highly probable resulting in the formation
of a network. The phenomenon is often termed
percolation. The formation of a highly conductive
heat flow path in the liquid by the percolation network
can potentially explain the enhancement due to
concentration of CNTs in relatively low temperature
zones where Brownian motion is not dominant. A
critical volume fraction of MWCNT loading, called
the percolation threshold, was thought to exist above
which the electrical conductivity of the MWCNT
nanofluid would abruptly increase multifold. However,
initial experiments did not show any such sudden rise
in the effective thermal conductivity of the nanofluid.
Thus it was concluded that there is no percolation
threshold in thermal transport in those experiments
(25, 26), a view that was contradicted recently
(20). Sastry et al. considered percolation without
specifically approaching it from a threshold perspective
(20). Their approach relies on the basic premise of
three-dimensional MWCNT chain formation in the liquid
(percolation) and consideration of a thermal resistance
network with higher resistance contact points of CNTs
and very low resistance CNT channels. Random CNT
where RCNTi ,P = ; RFi ,P = i ,P and
KCNT A CS K liq A liq
1
RC =
GdN2
Finally effective thermal conductivity can be written as
Lcell
keff = ; where Lcell is the length of the cell and
Rnet A Cell
Acell is the effective area of the cell in which the
percolation exists. The thermal conductivity
enhancement will not be observed below a certain
particle loading, where the formation of chains of CNTs
does not occur. The enhancement in thermal
conductivity for 0.01 vol% at higher temperatures is
due to Brownian motion, which dominates the
percolation chain mechanism at high temperatures.
The percolation mechanism can be applied for
mechanically stable suspensions only. At high
temperatures, suspensions become less stable due to
Brownian motion.
Figure 3 shows the variation of thermal conductivity
enhancement ratio (Keff/Kliq) with temperature at different
MWCNT loadings. Thermal conductivity ratio is considered
as a much more suitable parameter to understand the
enhancement in thermal conductivity, irrespective of
thermal conductivity of the base fluid or liquid in which
MWCNTs are dispersed to form nanofluids.
The present experimental study was carried
out in the temperature range 10ºC to 80ºC. The
thermal conductivity was observed to increase with
temperature, contradictory to predictions made by
1.55
Thermal conductivity enhancement, Keff/Kliq

orientation and CNT-CNT contacts are introduced 1.50 0.01 vol%

by probability density function. They considered a 1.45 0.03 vol%
cubical volume of nanofluid formed by dispersion 1.40 0.05 vol%
1.35 Theoretical curve (Prasher et al.)
of CNTs. The fundamental basis of the model is an
1.30
interaction between the CNTs touching each other
1.25
to form percolating chains in the suspension. In this
1.20
mechanism, resistive points are formed at the contact 1.15
centres of the CNTs. Thus, a series of resistive contact 1.10
points offer resistance in the thermally conductive 1.05
medium of a CNT chain. The net resistance has been 1.00
calculated by Sastry et al. (20) as given in Equation (i): 0.95
0 10 20 30 40 50 60 70 80 90
  RCNTi ,P + 2RC  
N   × RFi ,p  Temperature, ºC
M
Rnet = ∑   (i)
i =1
  RCNTi ,P + 2RC   Fig. 3. K/Kf of nanofluids containing CNTs at different
  + RFi ,p  temperatures
  M  

202 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X688163 Johnson Matthey Technol. Rev., 2015, 59, (3)
available theoretical models (21). The temperature
effect on thermal conductivity of nanofluids can be
explained with the help of Brownian motion. The thermal
conductivity of the CNT-water nanofluids was therefore
calculated to examine the Brownian motion effect.
Prasher et al. (27) developed a model for water based
spherical nanoparticle nanofluids. Based on Prasher’s
approach, the present experimental observations were
modelled for CNT containing water-based nanofluids
at high temperatures. Since the CNTs have very small
diameters when suspended in the liquid, Brownian
movement of the CNTs is quite possible. The root-
mean-square velocity (vN) of Brownian particles can be
defined (18) as (Equation (ii)):
3kBT 1 18kBT (ii)
=vN = (a) conduction contribution of the CNTs
mN dN πρN dN
where kB is the Boltzmann constant, T the temperature,
mN the particle mass, ρN the density, and dN the average
diameter of the CNTs.
Now we consider the effect of the convection of the
liquid near the CNTs due to their Brownian movement.
The Reynolds number (Re) based on νN given by
Equation (ii) can be written as Equation (iii):
1 18kBT (iii)
Re =
ν πρN dN
where n is the kinematic viscosity of the liquid.
The Re for 30 nm CNTs in water, Re = 0.0132, is very
small and therefore for convection the flow falls in
Stokes regime. If a particle is embedded in a semi-
infinite medium of thermal conductivity K m, then the
Nusselt number (Nu) based on the radius of the CNTs
can be shown to be 1; i.e., h = (Km/a). In Stokes regime
‘h’ is given (28) as h = (Kf/a)[1+ (1/4)Re + Pr] where Pr
is the Prandtl number, ‘a’ is the radius of the particle
and ‘h’ is the heat transfer coefficient. Note these
relations are derived analytically from first principles.
This means that the effective K of the fluid due to
the convection caused by the movement of a single
sphere is:
Km = Kf[1+ (1/4)Re ×Pr] (iv)
Note that this is based on a single isolated CNT. In a
real system there will be interaction in the convection
currents from different CNTs. The value of Km is
substituted from Equation (iv) in Equation (v):
203 © 2015 Johnson Matthey
K  (1 + 2α ) + 2φ (1 − α )  (v)
=
K m  (1 + 2α ) − φ (1 − α ) 
which is based on the traditional Maxwell-Garnett
(MG) model where f is the particle volume fraction,
α = 2Rb K m / dN , and Rb is the interfacial resistance.
The effective K of the nanofluid can be written as
Equation (vi):
K R × Pr  (1 + 2α ) + 2φ (1 − α )  (vi)
= (1 + e ) 
Kf 4  (1 + 2α ) − φ (1 − α ) 
Equation (vi), together with the definition of Re given
in Equation (iii) has all the necessary ingredients for
predicting K, because it includes:
(b) Rb between the nanotubes and the water
(c) convection contribution (effective for smaller dN).
So far no empiricism has been included in the model.
Taking the clue from correlations for particle-to-fluid
heat transfer a general correlation for h of the form:
h = (Kf/a) [1+ A RemPr0.333φ] is proposed for the Brownian
motion induced convection from multiple nanotubes,
where A and m are constants. Convective heat transfer
relations are regime dependent, and so depending on
Re, these relations can change. Therefore it is most
likely A should be independent of the fluid type whereas
m depends on the fluid type. This modification leads to
Equation (vii):
K  (1 + 2α ) + 2φ (1 − α ) 
= (1 + ARem Pr0.333φ )   (vii)
Kf  (1 + 2α ) − φ (1 − α ) 
If Equation (vii) is valid, A and m should be the same for
different experimental data for a particular fluid.
Figure 3 shows the semi-empirical model for K of
various water based nanofluids (different f), taking Rb
= 2.5 × 10–8 Km2 W–1, m = 2.4 and A = 40,000 (as
in similar materials) for the best fit. Here in the model
a thermal boundary layer δT = 3 δF/Pr is arbitrarily
defined, where Pr is the Prandtl number and δF is
the diameter of the base fluid molecule. Here Pr =
10 has been taken. Nusselt number (Nu) is given as
Nu ~ Re2Pr2; α = 2Rb K m / dN = 0.967 has been
computed; Km = thermal conductivity of water. Re has
been computed as 0.0132.
It is important to note that in the present case
an increase in the viscosity at higher temperature
increases Brownian motion. Figure 3 reveals
http://dx.doi.org/10.1595/205651315X688163 Johnson Matthey Technol. Rev., 2015, 59, (3)
significant enhancement in the thermal conductivity of
water containing a suspension of 0.05 vol% of CNTs
at different temperatures, in good agreement with
the theoretically modelled curve based on order of
magnitude calculations.
The temperature variation of the enhancement of the
thermal conductivity (K/Kf) on experimental observation
is also in good agreement with the theoretical curve
within the measurement accuracy of the apparatus.
Thus, it may be concluded that convection induced due
to Brownian movement of the CNTs is the main cause
for the observed enhancement in K of the nanofluid at
higher temperatures in the present investigation. The
interfacial resistance Rb has also been incorporated
as interfacial resistance greatly depends on bonding
between the solid and the liquid (27).
The shelf life of the nanofluids was also investigated.
In Figure 4 the temporal stability of nanofluid containing
0.03 vol% CNTs is shown at room temperature. The
nanofluid is stable for a long time.
0.80
Thermal conductivity, W m–1K–1
0.75
0.70
CNT nanofluid (0.03 vol%)
0.65
0.60
0 5 10 15 20 25 30
Time, days
Fig. 4. Thermal conductivity of nanofluid containing 0.03
vol% CNTs at different times
4. Conclusions
It can be concluded that the observed thermal
conductivity enhancement in prepared nanofluids is
due to the suspension of CNTs in deionised water.
Sudden enhancement is observed at a concentration of
0.03 vol% CNTs in water at lower temperatures, which
is attributed to formation of CNT chains with very high
conductivity in the medium. The abrupt enhancement
of thermal conductivity at 0.03 vol% can be explained
with the help of percolation phenomena. From
204 © 2015 Johnson Matthey
observations, it can be claimed that the percolation
threshold is between 0.01 and 0.03 vol% CNT loadings
in base fluid. Thermal conductivity enhancement
increases with temperature and concentration of
CNTs in the base fluid. The temperature dependence
of the thermal conductivity enhancement is explained
well with Brownian motion theory as chains of CNTs
will not form at higher temperatures due to instability
imposed by the temperature increase. These MWCNT
+ deionised water nanofluids are very stable with time.
They therefore show potential to be used as coolants in
different fields of industry.
Acknowledgements
Meher Wan is thankful to the Council of Scientific and
Industrial Research (CSIR) of the Government of India
for a senior research fellowship to carry out the work.
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The Authors
Dr Meher Wan obtained his DPhil from the Physics Department, University of Allahabad, India. He is
currently working as research fellow in the Department of Metallurgical and Materials Engineering,
Indian Institute of Technology-Kharagpur, India. His research interests are thermal conductivity,
phonon transport in nanostructured composite materials and non-destructive techniques for
characterisation of materials including ultrasonics. He has published several important studies on
heat transfer phenomena of nanofluids in internationally reputed journals.

Professor Dr Raja Ram Yadav is presently Professor of Physics at the Department of Physics,
University of Allahabad. His research interests are in the non-destructive ultrasonic and thermal
characterisation of nanomaterials, lyotropic liquid crystalline materials, intermetallics and
semiconductors; the development of nanomaterials for biomedical applications; and theoretical
calculations of nonlinear elastic and ultrasonic properties of crystalline materials. He was awarded
the prestigious Indian National Science Academy (INSA) Teachers’ Award for the year 2012.

Dr Giridhar Mishra is Assistant Professor at the Department of Applied Physics, Amity School of
Engineering and Technology, New Delhi, India. He obtained his DPhil in Physics from the University
of Allahabad. He has worked as a Research Fellow in a project sponsored by the Department of
Science and Technology, New Delhi, in the field of materials science. His current research interests
are focused on the study of ultrasonic and thermal properties of nanofluids, nanomaterials and
other materials. He is a life member of the Indian Association of Physics Teachers (IAPT).

Dr Devraj Singh is Assistant Professor and Head of the Department of Applied Physics at Amity
School of Engineering and Technology. His research interests are in the ultrasonic non-destructive
characterisation of condensed materials. Presently, he is working on ultrasonic studies of rare
earth materials for engineering applications.

205 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X688163 Johnson Matthey Technol. Rev., 2015, 59, (3)

Dr Bipin Joshi is a Scientist at the Department of Science and Technology, Government of India,
New Delhi. His research area is optical characterisation of nanostructured fabric semiconductors.
He is a life member of various scientific societies.

206 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X688451
JOHNSON MATTHEY
TECHNOLOGY REVIEW
The Effects of Hot Isostatic Pressing of Platinum
Alloy Castings on Mechanical Properties and
Microstructures
Post processing of parts for jewellery and other applications
Teresa Fryé*
TechForm Advanced Casting Technology, 5558-D SE
International Way, Portland, Oregon 97222, USA
*Email: tfrye@techformcasting.com
Joseph Tunick Strauss
HJE Company, 820 Quaker Rd, Queensbury,
New York 12804, USA
Jörg Fischer-Bühner
Indutherm Erwärmungsanlagen GmbH, 75045
Walzbachtal-Wössingen, Germany; and Legor Group
SpA, Via del Lavoro, 1 36050 Bressanvido (VI), Italy
Ulrich E. Klotz
fem Research Institute for Precious Metals & Metals
Chemistry, Katharinenstraße 17, 73525 Schwäbisch
Gmünd, Germany
The effects of hot isostatic pressing (HIP) on castings
produced in a variety of platinum alloys was investigated.
A number of benefits were observed, including
a reduction in porosity and improvements to the
microstructure and mechanical properties. Differences
in the response to HIP of individual alloys is evaluated
as well as some inherent limitations of the HIP process.
207
Johnson Matthey Technol. Rev., 2015, 59, (3), 207–217
www.technology.matthey.com
Introduction
In earlier research a better understanding of the
solidification characteristics for a number of platinum-
based alloys was established (1). The findings
demonstrated a strong tendency toward the formation
of shrinkage and gas porosity upon solidification, and
HIP, a high-pressure thermal treatment developed as
a densification process, was proven to be an effective
method to minimise or eliminate this porosity.
While the previous results made it clear that porosity
had been significantly reduced following the HIP
process, the authors had not yet explored the full
range of HIP’s effects in terms of post-processed
microstructure and mechanical properties. The
goal of this new phase of research is to further our
understanding by characterising the post-HIP effects on
platinum based castings with respect to grain size and
shape, chemical distribution and mechanical strength.
Overview of Hot Isostatic Pressing
Companies that build HIP equipment or perform the HIP
process describe an isostatic press as something that
forms and densifies powdered and cast materials using
liquid or gas under extremely high pressure. Unlike
mechanical force which compresses a workpiece from
one or two sides, the isostatic pressure is applied
© 2015 Johnson Matthey
http://dx.doi.org/10.1595/205651315X688451
uniformly on all sides of an object, eliminating internal
porosity without changing net shape. Typical product
improvements cited by the HIP industry are the
elimination of internal voids, improvements in product
consistency, and improvements in the soundness and
mechanical properties of materials. The fundamental
material change underlying these improvements is the
attainment of a higher density material in comparison
with its pre-HIP condition.
The isostatic nature of pressure in the HIP process as
described above is key to maintaining the dimensional
integrity of a casting during HIP; the pressure being
equal on all sides lends to a uniform compression of the
material with product dimensions typically remaining
intact. Although, as seen in Figure 1, local deformations
in the form of ‘dimpling’ can occur when the sizes of
internal pores are extremely large and diffusion bonding
collapses exterior surfaces inward. This difficult to feed
thick-to-thin geometry for the channel band represents
an extreme example of subsurface shrinkage porosity
(a)
(b)
2 cm
Fig. 1. HIP dimples in a 95Pt5Ru channel band
Inert
gas
Compressor
Pressurised
Vacuum pump gas
Pressure
line
Vacuum line
Fig. 2. Schematic of a typical HIP unit
208
Johnson Matthey Technol. Rev., 2015, 59, (3)
and is a powerful representation of the pore collapsing
that can occur with HIP.
To better demonstrate how the HIP process works,
Figure 2 shows the schematic for a typical HIP unit.
The unit contains a high temperature furnace enclosed
in a pressure vessel. Parts are typically placed within
the chamber in vertical layers with the use of graphite,
steel or ceramic shelving to maximise load capacity.
During operation the HIP chamber is first placed under
vacuum, followed by flooding with an inert gas, usually
argon, which is used to apply the isostatic pressure. The
temperature and pressure is then ramped up and left
to dwell for a specified period of time depending upon
the material’s properties. Parts become densified when
the material’s yield strength is surpassed, creating a
plastic flow that forces internal voids to collapse under
differential pressure. The internal surfaces of the voids
diffusion bond together, increasing density and thereby
improving the material properties. HIP unit sizes span
from small laboratory size up to large-scale industrial.
The unit shown in Figure 3 is an example of a medium
scale unit.
Not all metals will HIP effectively and the extent to
which an alloy will respond to HIP is a function of its
creep resistance. Creep is a solid material’s tendency
to move slowly and deform permanently under stress.
In metals, creep increases with temperature and
starts at approximately 30% to 50% of an alloy’s melt
temperature (2).The rate of creep is a function of
temperature, the material’s properties, and the amount
of pressure that is applied. In order to achieve optimum
material properties, the parameters used in a HIP cycle
Power
Cooling pump controller
Cover
Cooling
jacket
Ceramic
Pressure piece
vessel
Viscous
coating
(optional)
Heater Thermocouple
Electric
line
Temperature
Exhaust controller
valve
© 2015 Johnson Matthey
http://dx.doi.org/10.1595/205651315X688451 Johnson Matthey Technol. Rev., 2015, 59, (3)

shape, chemical distribution, and mechanical strength.

The following sections report the methods used, results
and conclusions.

Test Geometry

A tapered test specimen was chosen to assess

microscopic porosity levels, density and hardness before
and after HIP. As shown in Figure 4, the test specimen
was designed to promote directional solidification with a
single heavy sprue attached to the thickest end.

(a)
23.586
Fig. 3. HIP unit, courtesy Avure Technologies, USA
1.686 4.941
must be precisely dialled in according to the needs of
the alloy. Typical parameters including both metals and
ceramics will generally fall into the ranges shown in
Table I. (b)

Table I HIP Parameter Rangesa

Parameter Typical lower Typical upper
limit limit 1.917 5.682
Temperature 500ºC 1400ºC
Pressure 7000 PSI 45,000 PSI
Fig. 4. Tapered test specimen (units in mm)
Dwell Time 2 hours 4 hours
Cooling Rate 1ºC per minute 100ºC per minute
Casting Parameters
a
Courtesy Avure Technologies
The casting parameters and conditions for these trials
Comparative Study of the Effects of HIP on are shown in Table II. Standard pour temperatures,
Platinum Alloy Microstructure and Mechanical flask temperatures and firing curves were used. The
Properties flasks were cast using a centrifugal casting machine
with induction heating and each tree contained two test
The goal of this research was to characterise post- geometries for each alloy. One casting was retained for
HIP effects on castings with respect to grain size and as-cast sampling and the second casting was HIPed.

Table II Casting Parameters

Alloy Pour temp., ºC Flask temp., ºC Casting condition
95Pt5Ru 1870 850 1 As-cast; 1 HIPed
90Pt10Ir 1870 850 1 As-cast; 1 HIPed
90Pt10Rh 1960 850 1 As-cast; 1 HIPed
95Pt5Co 1850 850 1 As-cast; 1 HIPed
Notes to Table II
(a) All patterns 3D printed for dimensional precision
(b) All trees were identically assembled with two samples per tree
(c) All flasks air cooled identically
(d) All alloys were HIPed in the same load

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http://dx.doi.org/10.1595/205651315X688451
Effects of HIP on Microstructure
Given the high levels of porosity seen in 95Pt5Ru
and the relatively low levels seen in 95Pt5Co, these
two alloys were chosen for the present report on
microstructural changes brought about by the HIP
process. Figure 5 demonstrates significant porosity
levels in the as-cast state of 95Pt5Ru. The pores in
this alloy are interdendritic microshrinkage pores; such
pores form during the spontaneous solidification of
the alloy that occurs so rapidly that continued feeding
is not possible. The HIP process has successfully
closed these microshrinkage pores, such that the
microstructure is completely dense after HIPing.
Another important finding is that grain size is not
negatively affected by the HIP process (Figure 6). A
simple heat treatment to the same thermal parameters
50 m
Fig. 5. 95Pt5Ru as-cast showing numerous interdentric microshrinkage pores present in the as-cast condition and uneven grain
size distribution with coarse columnar grains at the surface
50 m
Fig. 6. 95Pt5Ru HIP which has dense and pore-free microstructure and even grain size distribution. HIP pressure appears to
retard grain growth
210
Johnson Matthey Technol. Rev., 2015, 59, (3)
as the HIP processing (without the use of pressure)
is neither capable of fully closing the pores from the
as-cast condition, nor maintaining grain size (Figure 7).
While the amount and the size of pores are clearly
reduced, grains are growing substantially during heat
treatment. Thus, any beneficial effect of porosity
reduction is compromised by grain growth. Based on
this result, it would appear that the pressure used in
the HIP process has the added benefit of retarding
grain growth. Figure 8 demonstrates the comparative
grain sizes of 95Pt5Ru in the as-cast, HIPed and
heat-treated conditions.
The casting sample of 95Pt5Co shows no visible
macroscopic or microscopic porosity in the as-cast
condition (Figure 9). However, compared to 95Pt5Ru
the grains are extremely large. Their size and shape
indicates a relatively slow solidification process
© 2015 Johnson Matthey
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50 m
Fig. 7. 95Pt5Ru heat treatment using same thermal curve as HIP, showing reduction of microshrinkage porosity and heavy grain
coarsening during thermal processing

(a) (b) (c)

50 m 50 m 50 m

Fig. 8. Comparative microstructures of 95Pt5Ru: (a) as-cast; (b) heat treated; (c) HIPed

50 m

Fig. 9. 95Pt5Co as-cast showing very large columnar grains growing from the surface during solidification and no macroscopic
or microscopic porosity in as-cast condition

where a few grains were nucleated at the surface
of the part, which then grew into the centre. As a
consequence, there was sufficient time for feeding
and the microstructure is free of pores. Therefore,
during HIPing few changes of the microstructure
occurred in the 95Pt5Co (Figure 10). This is not to
say that HIP does not provide any benefit to 95Pt5Co
castings. The previous research on larger samples
demonstrated a tendency of this alloy to form large
gas pores and centreline shrinkage porosity that
were either eliminated or reduced in size by the HIP
process.

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50 m

Fig. 10. 95Pt5Co HIP showing no significant change of microstructure during HIPing

Alloy Density Certain defect types either do not respond to HIP or

Density of the test samples was measured using
the Archimedes’ Principle (3) to determine levels
of densification achieved through the HIP process.
Although the density of the as-cast samples was already
very high, HIP increased the levels to near 100%. This
result is impressive and effectively puts castings on a
par with wrought material. As can be seen in Table III,
HIP most effectively increased density in 95Pt5Ru and
90Pt10 Rh and was slightly less effective for 90Pt10Ir,
which we can see already starts out with higher as-cast
density. This result correlates well with the generally
lower levels of visible porosity seen in 90Pt10Ir cross-
sections from the 2011 study (1). Although 95Pt5Co
was not tested for density, one would expect similar
findings as in the case of 90Pt10Ir due to the lower
levels of porosity in the as-cast state.
have a lower densification response. A key limitation of
the process is that only porosity that is fully subsurface
will collapse; if pores are open to the surface of the
casting in any way, they will not respond to HIP.
This effect can be seen in the shrinkage porosity
(Figure 11(a)). Another limitation of HIP is seen in
gas pores. Pores created by gas are less responsive
to HIP than shrinkage pores due to the pressure they
contain. Rather than being eliminated, the pores are
typically reduced in size by HIP as can be seen in the
cross-section (Figure 11(b)).
Alloy Homogeneity and its Effects on
Segregation
Another aspect of the present study was determining
whether there had been any change in segregation

Table III Alloy Density Results

Alloy Condition Density, g cm–3 Relative density

95Pt5Ru As-cast 20.32 98.4%

95Pt5Ru HIPed 20.62 99.9%

90Pt10Ir As-cast 21.39 99.5%

90Pt10Ir HIPed 21.48 99.9%

90Pt10Rh As-cast 19.58 98.2%

90Pt10Rh HIPed 19.89 99.7%

212 © 2015 Johnson Matthey

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(a)
200 m
Fig. 11. (a) Surface connected shrinkage porosity in 95Pt5Ru; (b) sectioned Pt90Ir10 gas pore after HIP
of the alloying elements during high temperature
heat treatment or HIP. By contrasting EDX mapping
of 95Pt5Ru in the as-cast, heat treated, and HIPed
conditions, we found that Ru segregated to the primary
dendrites during solidification in a similar manner for
all three conditions. Thus, neither heat treatment nor
HIP changed the segregation of Ru. As can be seen
in the comparative images in Figure 12, after HIP the
dendrites have coarsened, but the microstructure is not
negatively affected because the dendrites have arms
that can coarsen without changing the overall size of
the dendrite (Figure 12(c)).
Tensile Testing
A literature search for mechanical properties data
on cast platinum alloys showed that there are few
publications in this area, with the exception of
microhardness values that are frequently cited by
jewellery industry sources. A publication from 1978 by
Ainsley and Rushforth (4) was likely one of the earliest
to look at tensile properties from actual castings versus
the more commonly cited mill product values. These
authors published values on nearly a dozen different
(a) (b)
90 m
Fig. 12. (a) Pt95Ru5 as-cast; (b) Pt95Ru5 heat treated; (c) Pt95Ru5 HIPed
213
Johnson Matthey Technol. Rev., 2015, 59, (3)
(b)
1000 m
platinum casting alloys including two that are also
covered in the present testing. It is notable that the
values they published for the same alloys tested here
were appreciably lower in the as-cast state. Although it is
not known why this was the case, a plausible explanation
might be the difficulty of obtaining high quality cast test
bars with the technologies available in 1978.
This relative scarcity of hard data is not so surprising
given that sophisticated platinum casting is a relatively
new development. It was not until the mid-1990s that
induction machines capable of handling platinum’s high
temperature requirements became mainstream. Prior
to that, small-scale oxyhydrogen torch melting was the
only method available and inconsistent quality coupled
with low pour weight capacity prevented investment
casting from becoming a mainstream industrial process
for platinum. All of that has of course changed and
platinum based alloys are now routinely investment
cast with induction melting methods on a global basis.
While as-cast tensile properties of platinum alloys
are of keen interest in their own right, an additional
motivation to perform this testing was as a means to
compare the strength characteristics of as-cast versus
HIPed platinum alloys. In theory, the higher density
(c)
90 m 90 m
© 2015 Johnson Matthey
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of HIPed product would show increased values for

a number of tensile properties. Table IV outlines the
testing plan that was followed to produce the data, 4.000
followed by Figure 13 depicting the test bar geometry
used for the tensile tests. Tensile testing was carried
out in accordance with international standards (5). 19.000
The results in Table V report values for yield strength
(YS), ultimate tensile strength (UTS), elongation (ε)
and reduction of area (ROA). Yield strength describes
stress levels above which plastic deformation occurs 59.720
and will generally increase with decreasing grain size.
Following yielding, the material work hardens by the
generation of dislocations. As a consequence, the
required stress for further deformation increases until
19.000
the ultimate tensile strength is reached. In metals,
the UTS values will generally correlate with Vickers
hardness values.
3.000
At strains above UTS, which marks the maximum of
the stress-strain curve (Figure 14), the cross-section is
locally reduced through necking of the sample. Further Fig. 13. Test bar geometry: simple design, heavy molten
deformation is localised in the necking region and as a feed to gauge area with double end gates, directional
solidification from interior of bar towards outer heavy
consequence the required stress for further deformation
sections optimizes gauge area (units in mm)
is continually decreasing until failure occurs. The total
elongation (ε) indicates how much plastic deformation
the material can withstand. Pores in the material will While UTS or hardness are clearly important
significantly reduce the elongation because they act properties to measure, they are not necessarily the
as stress concentration sites. The effect of pores is most critical properties to predict failure in a broad
even more pronounced on the reduction of area, which number of applications. When it comes to fatigue life,
indicates how much necking occurs until the sample elongation and reduction of area are generally viewed
finally fails. as being more important. Specifically, in cases where

Table IV Casting Specifications for Tensile Bars

Alloy Pour temp., ºC Flask temp., ºC Number of test bars Casting condition

95Pt5Ru 1870 850 12 6 As-cast; 6 HIPed

90Pt10Ir 1870 850 8 4 As-cast; 4 HIPed

90Pt10Rh 1960 850 8 4 As-cast; 4 HIPed

95Pt5Co 1850 850 8 4 As-cast; 4 HIPed

Notes to Table IV
(a) Total bars: 36; minimum tests required: 18
(b) Test bar locations in ‘upper’ and ‘lower’ centrifuge orientation
(c) All waxes turned on lathe for dimensional precision
(d) All bars identically wax assembled with double end gates
(e) All bars cooled identically
(f) All bars HIPed to the same parameters

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Table V Tensile Properties

Alloy Condition Yield strength, Ultimate Elongation, % Reduction of Change in
composition MPa tensile area,% reduction of
strength, MPa area,%

95Pt5Ru As-cast 225 412 30 55 –

95Pt5Ru HIPed 236 420 39 87 +32

90Pt10Ir As-cast 219 353 33 90 –

90Pt10Ir HIPed 226 358 36 87 –3

90Pt10Rh As-cast 140 330 37 64 –

90Pt10Rh HIPed 144 333 43 89 +25

95Pt5Co As-cast 220 452 36 76 –

95Pt5Co HIPed 189 449 38 82 +6

(a) 500
UTS
400
Strength, MPa

300

200
YS
100 ROA

0
0 10 20  30 40
Strain, %
(b) 500

400
Strength, MPa

300

200

100

0
0 10 20 30 40
Strain, %

Fig. 14. UTS scatter of 95Pt5Ru: (a) as-cast; (b) HIPed

subsequent cold working of the material is involved,
an increased ability to bend before cracking is of
paramount importance.
The HIP treatment affects the mechanical properties
of the four alloys in a different way. For all alloys the
effect on YS and UTS is rather low. For 90Pt10Ir and
95Pt5Co there is little effect on elongation and ROA.
However, for 95Pt5Ru and 90Pt10Rh a significant
increase in elongation and ROA is found through
HIPing. These results correlate well with the porosity
levels of the different alloys, and are a clear indication
that reduction of porosity increases ductility in the
alloys.
Another interesting observation came from an
analysis of UTS scatter in the sample population. The
graphs in Figure 14 demonstrate the difference in
spread between the as-cast and HIPed groups. The
HIPed bars exhibit a very tight distribution, whereas the

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as-cast bars are more scattered. This result correlates 95Pt5Ru, all alloys report values that are so close in the
well with observations of lower porosity levels together before and after HIP conditions that any difference is
with a more homogeneous grain size and structure in seen as essentially inconsequential. Even the 95Pt5Ru
the HIPed samples. that shows a 12-point spread is not considered enough
As stated above, reduction of area values posted to be characterised as an appreciably harder material
the most impressive gains in the HIPed product. by performance. Thus we can conclude that hardness
This property is of particular interest in the jewellery is not significantly impacted by HIP on the platinum-
industry given the substantial amount of bending and based alloys we tested.
forming that is inherent in stone setting, engraving,
sizing and myriad bench operations. Reduction of area Conclusions
indicates a material’s ductility and is crucial to successful
performance in many of these operations. Figures 15(a) The most significant impact of HIP on platinum-based
and 15(b) demonstrate a profound visual difference in alloys is a reduction in porosity. Reduced levels of
ductility between the test bar fractures in the as-cast porosity have several associated benefits, including
and HIPed 95Pt5Ru. a marked increase in ductility in the majority of the
alloys tested without sacrificing strength. Of the tensile
properties tested, the most impressive response was
(a) found in the values for ROA, a key indicator of an
alloy’s ductility.
Another meaningful result demonstrated here was
HIP’s effect on grain structure and size. Although
further testing is needed to fully characterise this
aspect, our initial research confirms a more uniform
grain size and structure in the HIPed samples without
(b)
any increases in grain size, at least for the alloy
95Pt5Ru.
Findings also confirm that the response to HIP is
strongly impacted by the alloy’s composition. 95Pt5Ru
benefits the most due to its higher levels of porosity
present in the as-cast condition, and 95Pt5Co having
Fig. 15. (a) 95Pt5Ru as-cast 55% ROA; (b) 95Pt5Ru HIPed lower porosity benefits the least.
87% ROA Further work is recommended to more closely
assess the impact of qualitative changes in the HIPed
product on manufacturing operations. Empirical
Hardness Testing evidence strongly suggests greater ease in post-
cast operations due to the elimination of sub-surface
Table VI reports Vickers hardness values (6) for three micro-porosity and a generally more consistent
of the tested alloys. With the possible exception of metallurgical condition, including uniformity of grains.
In addition, the increased ductility of HIPed platinum
Table VI Vickers Microhardness Results alloys should, in theory, result in a lower number of
failures during metal bending and forming operations.
Vickers Hardness HV1a
Heat
Alloy As-cast HIPed Acknowledgements
treated
90Pt10Ir 113 111 123
The authors would like to acknowledge the original
90Pt10Rh 89 89 n/a publishers, Santa Fe Symposium on Jewelry
Manufacturing Technology 2014, ed. Eddie Bell
95Pt10Ru 113 125 128
(Albuquerque: Met-Chem Research, 2014) for
95Pt5Co 126 122 n/a permission to re-publish this work.
a
Error: ± 3 HV1

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3. “Standard Test Method for Density, Oil Content, and

This research was supported in part by the German
Federal Ministry for Economic Affairs and Energy (BMWi)
under the IGF program (Project No. AiF-IGF 16413N).
References
1. T. Fryé and J. Fischer-Bühner, ‘Platinum Alloys in the
21st Century: A Comparative Study’, in "The Santa
Fe Symposium on Jewelry Manufacturing Technology
2011", ed. E. Bell, Proceedings of the 25th Symposium
in Albuquerque, New Mexico, 15th–18th May, 2011,
Met-Chem Research Inc, Albuquerque, New Mexico,
USA, 2011, pp. 201–230
2. “Elements of Metallurgy and Engineering Alloys”, ed.
F. C. Campbell, ASM International, Ohio, USA, 2008,
p. 265
Interconnected Porosity of Sintered Metal Structural
Parts and Oil-Impregnated Bearings”, (Withdrawn
2009), ASTM Standard B328-96(2003)e1, ASTM
International, West Conshohocken, Pennsylvania,
USA, 2003
4. G. Ainsley, A. A. Bourne and R. W. E. Rushforth,
Platinum Metals Rev.,1978, 22, (3), 78
5. “Metallic Materials – Tensile Testing – Part 1: Method
of Test at Room Temperature”, DIN EN ISO 6892-1:
2009-12, Deutsches Institut für Normung e.V., Berlin,
Germany, 2009
6. “Metallic Materials – Vickers Hardness Test – Part
1: Test Method”, DIN EN ISO 6507-1:2006-03,
Deutsches Institut für Normung e.V., Berlin, Germany,
2006

The Authors
Ms Teresa Fryé has over 25 years’ experience working in the investment casting industry. She
started her career at Precision Castparts Corp, USA, one of the world’s largest investment casters,
serving the international customer base for high-temperature aerospace castings. In 1994 she co-
founded TechForm Advanced Casting Technology, a company that specialises in shell casting of
platinum group metals. She holds a BA in International Affairs and graduate studies in Psychology
from Lewis & Clark College in Portland, Oregon, USA.

Joe Strauss has a PhD in Materials Engineering from Rensselaer Polytechnic Institute, USA. He
has over 30 years of experience in developing atomisation and powder metallurgy technologies
for non-traditional materials including precious metals for jewellery, dental, electronic and medical
applications. His work includes design and fabrication of atomisation systems, research and
development in powder metallurgy and engineering troubleshooting for manufacturing processes.

Dr-Ing Jörg Fischer-Bühner holds a PhD in Physical Metallurgy and Materials Technology from the
technical university RWTH Aachen, Germany. He is currently active in Research & Development
for Legor Group SpA (Bressanvido, Italy) as well as INDUTHERM Erwärmungsanlagen GmbH
(Walzbachtal, Germany). His work has included manufacturing support, failure analysis, training
and consultancy to manufacturing companies, and his research has focused on alloy properties
and manufacturing technologies, especially precious metal alloys for jewellery, dental and electrical
engineering applications.

Ulrich E. Klotz graduated from the University of Stuttgart, Germany, as a Diploma Engineer in
Physical Metallurgy and has a PhD in Materials Science from ETH Zürich, Switzerland. He is Head
of the Department of Physical Metallurgy at the fem.

217 © 2015 Johnson Matthey

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JOHNSON MATTHEY
TECHNOLOGY REVIEW
“Exploring Materials through Patent Information”
By David Segal (Abingdon, Oxfordshire, UK), Royal Society of Chemistry,
Cambridge, UK, 2015, 244 pages, ISBN:978-1-78262-112-6, £24.99, €31.24,
US$40.00
Reviewed by Julia O’Farrelly
Johnson Matthey Technology Centre, Blounts Court,
Sonning Common, Reading RG4 9NH, UK
Email: julia.ofarrelly@matthey.com
The majority of books and reviews on any area of
technology development tend to focus on information
published in the journal literature; reviews of the
patent literature are more often confined to the prior
art sections of patent documents. However, patents
remain one of the best sources of detailed technical
information, particularly where the invention may have
commercial significance, and it is good to see this
reviewed in a book.
The author, David Segal, is a graduate of Trinity
College Cambridge, UK. In his long career he has
worked widely in the fields of chemicals and materials
and has published a number of patents and papers.
Introduction: Exploring the World of Materials
through Patent Information
In Chapter 1 Segal provides a general introduction to the
topic of materials for the non-specialist. He makes the
point that materials underpin many of the technological
advances that we know in everyday life; for example,
the use of lanthanide elements as phosphors to
generate colour in display screens, or the application of
neodymium iron boron (NdFeB) magnets in computer
218
Johnson Matthey Technol. Rev., 2015, 59, (3), 218–220
www.technology.matthey.com
hard drives and magnetic resonance imaging (MRI)
scanners. The success of additive layer manufacturing
(ALM), also known as additive manufacturing (AM) or
‘three-dimensional (3D) printing’ technology, depends
on the availability of plastics that can be converted into
molten droplets and of ceramic and metal powders that
can be formulated for use in a range of different ALM
techniques.
Chapter 1 also provides a basic introduction to
patents, covering ‘what is a patent?’ and patent
structure (front page data, background to the invention,
summary of the invention, embodiments, drawings
and claims). Sections are included on patent filing,
patent infringement and patent searching. The book
stresses the importance of seeking specialist advice
from qualified practitioners. As with much of the
book, however, too many topics are included, making
coverage superficial.
Chapters 2–13 review a wide range of emerging
technologies in the context of patent information: light
emitting diodes, quantum dots, organic light emitting
diodes (OLEDs), liquid crystals and liquid crystal
displays, ALM or ‘3D printing’, healthcare, block
copolymers, aerogels, ionic liquids, flame retardants,
graphene, hydrogels and super-hydrophobic materials.
I have chosen three of these chapters to review below.
Additive Layer Manufacturing
Chapter 6 is titled ‘3D Printing’. Segal describes the
evolution of this process starting from Swanson and
© 2015 Johnson Matthey
http://dx.doi.org/10.1595/205651315X688424 Johnson Matthey Technol. Rev., 2015, 59, (3)

Kremer’s photopolymerisation by computer controlled Organic Light Emitting Diodes

laser beams. In fused deposition modelling, 3D
parts are built up layer-by-layer from a thermoplastic
material using a digital representation of the part. In
selective layer sintering a layer of metal, ceramic or
polymer powder is deposited under computer control
and sintered by scanning a laser across the surface. In
each case the process is repeated to ultimately form a
3D part. The use of the term ‘3D printing’ was coined
later by Sachs et al. and used, for example, in their
1993 patent (1).
The chapter goes on to give a number of examples of
patents on applications of ALM (Figure 1). Aerospace
components are discussed, as are dental prostheses
and biomedical implants. Among the aerospace
examples, Segal describes a high temperature AM
process to make titanium near-net-shape metal leading
edge protective strips for aerofoils (2). A key feature
is heat transfer away from the support mandrel. In the
dental field he describes the use of selective laser
powder processing to build up a jaw structure from
titanium (3). Although Segal reproduces technical
details of the laser required to melt the metal particles,
he does not discuss the significance of such a process,
which in this case is the ability to fabricate complex
shapes without lengthy pre- or post-processing and
the ability to customise parts to individual patient
requirements in the same production run.
Some examples are also given of components needed
for ALM machines such as shutter mechanisms and
wiper blades.
Chapter 4 discusses the development of OLEDs.
It starts with a review of the early development
of electroluminescence, for example the work by
Gurnee and Fernandez which showed that a doped
host material with a conjugated structure, such as
anthracene, gave off green light when placed between
two electrodes (4). Pioneering work by Friend et al. on
conjugated polymers such as poly(p-phenylvinylene)
(PPV) formed the basis of polymer light emitting
diodes (PLEDs) (5). Later it was discovered that
organic phosphorescent materials, which can emit
light in the triplet state, are potentially more efficient
than fluorescent materials which can emit only in
the singlet state. The example is given of the green
phosphorescent emitter tris(2-phenylpyridine)iridium,
Ir(ppy)3. Of course the phosphorescent emitter layer is
only one of a complex series of material layers and the
development of complex circuitry is an essential part of
the realisation of a working OLED device.
Graphene
Chapter 12 discusses graphene, a material which has
received much interest since its discovery in 2004.
The development of methods for making it, including
wet chemical processes, vapour phase processes,
the use of ionic liquids and electrochemical methods,
have been key; details of these processes are best
found in the patent literature. The chapter goes on to

500
450
400
Number filed

350
300
250
200
150
100
50
0
1992
1993
1994
1995
1996
1997
1998
1999
2000
2001
2002
2003
2004
2005
2006
2007
2008
2009
2010
1991

Year
Fig. 1. Filing rates in additive layer manufacturing (Copyright Coller IP)

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discuss potential methods for large scale production have helped to round out a promising but somewhat
of graphene, essential for successful exploitation; disappointing volume.
chemical vapour deposition is one such method.
Incorporation of graphene flakes into the polymer “Exploring Materials through
matrix of a fibre reinforced composite can increase its Patent Information”
compressive strength, potentially useful in racquets
and other sports equipment. In lithium-ion batteries,
multilayer graphene films have been evaluated for use
as an anode and graphene platelets have been used to
reinforce the matrix of a cathode material.

Conclusion

Overall, the book does effectively make the point that

patents contain a wealth of technical information and
should be considered alongside journals and other
sources when researching a topic. It successfully gives
a broad overview of the historical development of each
topic, with references in the form of patent numbers
which serve as a starting point for further reading.
The focus is very much geared to demonstrating the
technical detail that can be found, with examples
of material compositions and experimental data as
claimed in individual patents.
However, this reviewer believes that it tries to
cover too much material in too small a volume and
as a result does not really do any individual topic full
justice. Too many patents are referenced and too much
non-essential experimental detail from the patents is
included. At the same time, the significance of each
invention is often not clear without going back to the
original patent source and this detracts from the overall
readability.
Segal’s book does not touch on how patents have
altered the course of development of a technology by
impacting different companies’ freedom to exploit it;
nor does it make any reference to how the existence
of patents has affected the commercial development of
a technology. In my opinion, such a discussion would
References
1 E. M. Sachs, J. S. Haggerty, M. J. Cima and P. A.
Williams, Massachusetts Institute of Technology,
‘Three-dimensional Printing Techniques’, US Patent
5,204,055; 1993
2 M. W. Peretti and T. Trapp, General Electric
Company, ‘Methods for Making Near Net Shape
Airfoil Leading Edge Protection’, US Patent Appl.
2011/0,143,042
3 J.-P. Kruth, I. Naert and B. Vandenbroucke,
‘Procedure for Design and Production of Implant-
based Frameworks for Complex Dental Prostheses’,
US Patent Appl. 2008/0,206,710
4 E. F. Gurnee and R. T. Fernandez, The Dow Chemical
Company, ‘Organic Electroluminescent Phosphors’,
US Patent 3,172,862; 1965
5 R. H. Friend, J. H. Burroughes and D. D. Bradley,
Cambridge Research and Innovation Ltd, Cambridge
Capital Management Ltd and Lynxvale Ltd,
‘Electroluminescent Devices’, US Patent 5,247,
190; 1993

The Reviewer
Julia O’Farrelly is a Principal Information Analyst in the Technology Forecasting and Information
group at Johnson Matthey Technology Centre, Sonning Common, UK. She is interested in
emerging technologies and their development and commercialisation and the use of patents as a
tool in understanding technology landscapes.

220 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X688280 Johnson Matthey Technol. Rev., 2015, 59, (3), 221–232

JOHNSON MATTHEY
TECHNOLOGY REVIEW www.technology.matthey.com

“Urea-SCR Technology for deNOx After Treatment

of Diesel Exhausts”
Edited by Isabella Nova and Enrico Tronconi (Politecnico di Milano, Italy),
Fundamental and Applied Catalysis, Springer Science+Business Media, New York,
USA, 2014, 716 pages, ISBN: 978-1-4899-8071-7, £171.00, €239.99, US$249.00

An essay book review by Martyn V. Twigg
TST Ltd, Caxton, Cambridge CB23 3PQ, UK
*Correspondence may be sent via Johnson Matthey
Technology Review: tech.review@matthey.com
The introduction and development of catalytic control
for exhaust gas emissions from vehicles has been one
of the major technical achievements over the last four
decades. A huge number of cars were manufactured
during this time that provided society with a high
degree of personal mobility and without the continuous
development of emissions control technologies the
atmospheric pollution derived from them would have
been overwhelming. Three-way catalysts (TWC) were
introduced on traditional gasoline powered cars in the
early 1980s to control the emissions of hydrocarbons
(HC), carbon monoxide (CO) and nitrogen oxides
(NOx) and have since been developed so that today
tailpipe emissions of these pollutants can be reduced
by more than 99.5% and tailpipe emission levels can be
less than in the surrounding ambient air. During more
recent years, and especially in Europe, the proportion
of diesel powered cars has increased rapidly so
now about half of new European cars have a diesel
engine. Control of their tailpipe emissions has been
particularly challenging because of their low exhaust
gas temperature and the presence of excess oxygen.
Under these conditions TWCs cannot be used and
alternative technologies were developed for the control
of HCs and CO by oxidation catalysts. An undesirable
characteristic of older diesel engines was the black
soot they produced. This was considerably reduced
by fuelling and combustion engineering improvements
and was effectively eliminated by the use of diesel
particulate filters (DPFs) which were introduced a
decade ago. The remaining difficult challenge has
been the control of NOx emissions from both light and
heavy duty diesel vehicles. Two technologies have
been recently introduced to do this, though only one,
ammonia selective catalytic reduction (SCR), appears
to be able to provide the necessary performance
for future demands under a wide range of driving
conditions. The present book is about diesel engine
NOx emissions control by ammonia (derived from
urea) SCR, and before detailing the book’s contents
some background information is given which provides
a suitable context. Because of higher exhaust gas
temperatures control of emissions from heavy duty
diesel vehicles is less demanding than with light duty
ones, so the emphasis here is on diesel cars.
1. Background
1.1 Exhaust Gas Temperature
The control of tailpipe emissions from vehicles powered
by traditional stoichiometric gasoline engines with

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TWC is now highly advanced and can achieve almost
complete removal of the three gaseous pollutants
CO, HCs and NOx under normal driving conditions. In
practice reductions of more than 99.5% are possible,
and a contributing factor for such a good performance
is the relatively high temperature of the exhaust
gas. In contrast the control of diesel engine exhaust
gas emissions under lean conditions has been more
problematic for two main reasons. The first problem
results from the efficiency of diesel engines that under
part load conditions can result in particularly low
exhaust gas temperatures. For example, the exhaust
gas temperature of a small European car with a gasoline
engine may typically be in the region of 350ºC to 475ºC
in the urban part of the European test cycle, whereas
the same car with a diesel engine may be around
150ºC as shown in Figure 1, and designing catalysts to
operate efficiently at such low temperatures has been
a major challenge, particularly when fuel sulfur levels
were higher than they are today!
Heavy duty diesel engines in trucks generally operate
under higher engine percentage loads and over
appropriate duty cycles they can have much higher
exhaust gas temperatures than their passenger car
counterparts, typically up to around 400ºC. So here
there is considerably more scope for catalytic emissions
control.
Once diesel fuel sulfur levels were reduced from the
very high levels of two decades ago in Europe control
of CO and HC emissions from all diesel engines by
oxidation catalysts became feasible although special
catalysts had to be developed for the low operating
temperature cars.
1.2 Particulate Control with Filters
This was followed by control of particulate matter
(PM or soot) by the introduction of filter technologies
that enabled engine measures to further reduce
engine-out NOx levels without being overly concerned
about increased PM that was handled by the filter
system. Traditionally the main approach for controlling
NOx from small diesel engines has been via engine
measures, including the use of exhaust gas recycle
(EGR) and improving injection fuelling to produce ever
finer sprays via multiple smaller injector nozzles and via
increasing fuel pressures. EGR works by decreasing
the amount of oxygen in the combustion charge that
reduces the fuel burn rate and the peak temperatures
as well as somewhat increasing heat capacity of the
combusting charge.
There is a trade-off between NOx and PM. Reducing
engine-out NOx normally results in an increase in PM.
This is because a higher combustion temperature
reduces PM by increased burning of residual

800

700 1.6 l Gasoline 1.8 l Diesel

Inlet temperature, ºC/speed, kph

600

500

400

300

200

100

0
0 200 400 600 800 1000 1200
Time, s
Fig. 1. Exhaust gas temperatures during the European test cycle for the same family size car equipped with a similar
displacement gasoline and diesel engine. Throughout the test cycle the exhaust gas temperature is much lower with the diesel
engine than that with the gasoline engine

222 © 2015 Johnson Matthey

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carbonaceous PM but thermodynamically high 2M(NO3)2 → 2MO + 4NO + 3O2 (iii)

temperatures favour formation of endothermic NOx
(see Figure 2). This trade-off was broken by fitment of
DPF that recently enabled achievement of car diesel
engines with engine-out NOx levels significantly below
0.1 g km–1 in the combined European test cycle.
1.3 NOx Control Technologies
Notwithstanding the improvements just mentioned,
more recently NOx control has become increasingly
important, driven by ever more stringent NOx emissions
legislation. This legislation requires additional catalytic
aftertreatment to meet the NOx standards for diesel
vehicles, especially cars, and two approaches have
become established.
In the first of these catalytic approaches, NOx trapping,
under normal driving lean conditions NO is oxidised
to NO2 as in Equation (i). This undergoes further
oxidation as it is stored as a metal nitrate, Equation (ii),
followed at intervals by a reductive regeneration that
converts the stored NOx to nitrogen. In this process
NOx is liberated usually as NO, Equation (iii), that is
reduced over a rhodium component in much the same
way as a TWC functions on a traditional gasoline car,
Equation (iv).
NO + ½O2 à NO2 (i)
MCO3 + NO2 à MNO3 + CO2 (ii)
2NO + 2CO → N2 + 2CO2 (iv)
This technology works well on smaller diesel cars,
although it has temperature limitations reflecting
the thermodynamic stability of the metal nitrates
concerned.
The second NOx control technology, and the
subject of the present book, is ammonia SCR that
involves reaction of NOx with ammonia to form
nitrogen and water. Ammonia SCR technology was
introduced on power plant applications in Japan in
the early 1970s, and some twenty years later it was
adopted for use in heavy duty diesel vehicles that
have exhaust gas temperatures appropriately high
to use the traditional vanadium-based catalysts.
Ammonia was derived from urea solution that was
injected into the exhaust gas where it hydrolyses
forming ammonia and carbon dioxide (see
Equation (v)).
However, the temperatures on light duty diesel
vehicles are too low for efficient operation of the older
SCR vanadium-based catalyst formulations and so
after much effort base metal zeolite catalysts were
introduced that can operate effectively at remarkably
low temperatures and already increasingly large
numbers of cars on European roads are equipped
with this SCR technology.

5000
Nitric oxide concentration, ppm

4000

3000

2000

1000

1000 1250 1500 1750 2000 2250 2500

Temperature, K
Fig. 2. Concentrations of NO at high temperatures in equilibrium with nitrogen (0.8 bar) and various amounts of oxygen;
the highest curve corresponds to 0.2 bar, and subsequent lower curves 0.15, 0.05 and 0.02 bar respectively. Derived from
measurements made by W. Nernst (1); modern theoretical values are somewhat higher

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More than thirty years ago a very important
discovery was made about the effect of the ratio of
NO2 to NO on the rate of the ammonia SCR reaction
over vanadium-based catalysts. The reaction is much
faster when both are present. The reactions involved
when urea ((NH2)2CO) is the source of ammonia are:
urea hydrolysis to give ammonia, shown overall in
Equation (v); a rapid reaction when just NO is present,
Equation (vi); a particularly slow reaction when NO 2
is present alone, Equation (vii); and an amazingly
fast reaction when the ratio of NO2 to NO is 1:1, that
is known as the fast SCR reaction, Equation (viii).
Depending on the actual SCR catalyst used it can
therefore be important that an appropriate upstream
oxidation catalyst provides the SCR catalyst with
a suitable mixture of NO and NO2, although some
modern copper zeolite catalysts are less sensitive to
the NO/NO2 ratio than other catalysts.
Urea hydrolysis (NH2)2CO + H2O à 2NH3 + CO2 (v)
Standard reaction 4NH3 + 4NO + O2 à 4N2 + 6H2O (vi)
Slow reaction 4NH3 + 4NO2 à 4N2 + 6H2O + O2 (vii)
Fast SCR reaction 4NH3 + 2NO + 2NO2 à 4N2 + 6H2O (viii)
There have been extensive studies on the
mechanism of ammonia SCR reactions, and by
analogy with known reactions of discrete compounds
it may be suggested that rapid decomposition of
ammonium nitrite (Equation (ix)) is important in the
SCR surface catalysed process forming nitrogen.
At higher temperatures one route to undesirable
nitrous oxide (N 2O) emissions might be from
decomposition of ammonium nitrate-like surface
species, Equation (x). The former reaction has been
used to prepare chemically pure nitrogen (free of
atmospheric argon) and the latter to manufacture
N 2O.
NH4NO2 à N2 + 2H2O (ix)
NH4NO3 à N2O + 2H2O (x)
However, the surface SCR reactions are complex
and recently nitrate species have been shown
to have important roles in the fast SCR reaction.
Chapters in this book go a long way to help the
reader to unravel some of the mechanistic details.
224 © 2015 Johnson Matthey
2. Topics Covered
This book has 22 chapters by eminent contributors and
is appropriately edited by Professors Isabella Nova and
Enrico Tronconi from the Politecnico di Milano, Italy,
whose Laboratory of Catalysis and Catalytic Processes
(LCCP) has a worldwide reputation for research on the
control of NOx emissions especially by ammonia SCR
reactions. This very well produced book includes some
colour illustrations and it is divided into eight parts that
are detailed in the following sections.
2.1 Part 1. Selective Catalytic Reduction
Technology
The first part of the book has two chapters with the first
entitled ‘Review of Selective Catalytic Reduction (SCR)
and Related Technologies for Mobile Applications’
by Timothy Johnson (Corning, USA). It provides an
overview of relevant legislation and progress in engine
developments to reduce engine-out NOx levels, before
detailing mobile SCR systems using urea in solution
as the source of ammonia. This chapter relies heavily
on illustrations reproduced from a variety of original
publications that appear not to have been redrawn
so there is, unfortunately, a lack of style consistency.
Notwithstanding this the chapter collects together
much valuable and practical information.
The second chapter called ‘SCR Technology for
Off-highway (Large Diesel Engine) Applications’
is by Daniel Chatterjee and Klaus Rusch (MTU
Friedrichshafen GmbH, Germany) and is concerned
with large diesel engines used in marine applications,
mining trucks and trains as well as in electrical power
generation units. These engines usually operate under
high load conditions so have high temperature exhaust
gas, enabling good SCR performance with conventional
vanadium-based catalysts, but their fuel invariably
contains high sulfur levels and this can cause a variety
of problems. For example, newer zeolite-based SCR
catalysts are poisoned and do not work well, and at
these quite high operating temperatures some sulfur
dioxide (SO2) can be oxidised to sulfur trioxide (SO3),
Equation (xi). If any ammonia slip is present this can
form particulate ammonium sulfate and/or ammonium
bisulfate according to Equations (xii) and (xiii), as well
as sulfuric acid mist that can itself cause difficulties,
Equation (xiv).
SO2 + ½O2 à SO3 (xi)
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2NH3 + SO3 + H2O à (NH4)2SO4 (xii)
NH3 + SO3 + H2O à NH4HSO4 (xiii)
SO3 + H2O à H2SO4 (xiv)
This well-illustrated chapter goes on to discuss
combined SCR systems such as SCR/filter
combinations, and large scale SCR units, as well the
automated control strategies that are usually involved.
2.2 Part 2. Catalysts
The second part of the book has four chapters that
focus on SCR catalysts, and the first of these by Jonas
Jansson (Volvo, Sweden) discusses vanadium-based
catalysts used in heavy duty mobile SCR applications
and highlights the legislative requirements before
considering catalyst properties. Because the vanadium-
based catalyst operates in the temperature range of
optimum activity (say 300ºC–500ºC) they have been
widely used. Typical catalyst compositions are given
as 1%–3% V2O5 plus about 10% tungsten trioxide
(WO3) impregnated onto a high surface area titania
(normally anatase) that is coated onto flow-through
substrates. Related extruded catalyst compositions
have also been widely used. Practical aspects such as
selecting appropriate catalyst size (dimensioning), the
effects of space velocity and ageing effects (thermal
and poisoning) are considered, and it is clear vanadium
catalysts have had and will continue to have a major
role in this area. However, with reduced sulfur fuel
levels the newer, higher activity zeolite-based catalysts
discussed in the following chapter will probably become
increasingly important.
Appropriately the next chapter, by Todd J. Toop, John
A. Pihl and William P. Partridge (Oak Ridge National
Laboratory, USA), is about iron-zeolite SCR catalysts.
These were amongst the first metal zeolite catalysts
used in SCR applications, and because they can have
good high-temperature performance coupled with
reasonable stability, they were introduced into gas
turbine applications at an early stage. In contrast copper
zeolite catalysts usually have better low-temperature
activity that falls off at higher temperatures as ammonia
is oxidised to NOx. Making sweeping generalisations
about the relative performance of SCR catalysts can be
problematic because several factors are involved such
as: the type of zeolite involved, its silica to alumina
ratio, the metal loading and importantly the preparation
method. However, in general copper-based catalysts
225 © 2015 Johnson Matthey
absorb more ammonia than do iron ones and under
dynamic transient conditions this can provide a
significant performance advantage.
Because of their superior low-temperature
performance copper zeolite catalysts have been
adopted for use in car applications and these are
discussed in the third chapter in this section by Hai-Ying
Chen (Johnson Matthey, USA). The emphasis is on
the impact of the nature and physical properties of the
zeolite type on catalytic performance, and in particular
the size of the zeolite pores classified as small, medium
or large. Small pore zeolites such as chabazites and
other small pore molecular sieve materials such as
the silicon substituted aluminium phosphate SAPO-34
have outstanding hydrothermal stability, excellent SCR
activity and importantly they form very low amounts
of the undesirable byproduct N2O. The introduction
of these copper molecular sieve SCR catalysts into
the series production of diesel cars in Europe was an
outstanding technical achievement that will provide a
high degree of NOx emissions control into the future.
Indeed one might expect that new materials will be
discovered that provide the necessary acidity and
environment around the copper atoms to provide good
SCR activity and durability. However, these features
are not unique in providing excellent ammonia SCR
performance. Some simple metal oxide catalysts have
been shown to perform well and these are the subject
of the last chapter in the part on SCR catalysts.
The last chapter in this part on catalysts is the result
of a collaboration by Gongshin Qi (General Motors,
USA) and Lifeng Wang and Ralf T. Yang (University
of Michigan, USA) that deals with low-temperature
SCR involving both zeolite and metal oxide ammonia
SCR catalysts as well as touching on developments
with hydrogen SCR. They highlight the importance of
the method of making iron-ZSM5 catalysts. Aqueous
impregnation with iron(III) salts does not lead to full
metal incorporation into the pores because, it is
suggested, the heavily hydrated metal cations are
too large for easy penetration, whereas impregnation
with iron(II) species makes highly active catalysts.
The interpretation of the origin of this effect may be
more complex because reduction of catalysts derived
from iron(III) salts gives improved activity. Again the
importance of small pore acidic molecular sieves is
noted, as is the wide range of activities that can be
obtained with different copper zeolite catalysts and
their dual role in providing acid sites for formation of
ammonium cations and metal-based oxidation of NO
http://dx.doi.org/10.1595/205651315X688280 Johnson Matthey Technol. Rev., 2015, 59, (3)
to NO2, leading to highly reactive ammonium nitrite-
like species that decompose to nitrogen and water.
Manganese oxides can have excellent low-temperature
ammonia SCR activity, and clearly their oxidation
capability is important. A wide variety of promoted
oxides have been investigated, but it appears their
adoption has been restricted by a lack of tolerance
to water and in particular sulfur poisoning. Moreover,
increasing activity by using higher manganese loadings
appears to result in the formation of more N2O. It is
noted perhaps the most successful development in
this area was made by Shell who in the early 1990s
developed a relatively low-temperature ammonia SCR
process using a vanadium on titania catalyst promoted
by transition metal species.
Hydrogen can be a reductant in NOx SCR reactions
and over platinum group metal (pgm) catalysts.
The reactions that can take place are shown in
Equations (xv)–(xvii).
2NO + 4H2 + O2 à N2 + 4H2O (xv)
½O2 + H2 à H2O (xvi)
2NO + 3H2 + O2 à N2O + 3H2O (xvii)
High conversions of NO in the presence of oxygen at
low temperatures are possible, although as might be
expected, at higher temperatures the direct reaction
of hydrogen with oxygen, Equation (xvi), increasingly
takes place, and NO conversion decreases because
less hydrogen is available for the SCR reaction. As a
result an operational temperature window is formed in
which NO conversion is optimised. A serious detraction
from these hydrogen SCR pgm catalyst systems is the
high proportion of N2O that can be formed. A better
catalyst in this respect appears to be a palladium
promoted vanadium on titania/alumina that retains
good low-temperature SCR performance and has
reduced N2O formation although this is probably still
too high for practical applications.
2.3 Part 3. Mechanistic Aspects
This part of the book is concerned with the mechanistic
aspects of SCR reactions and has three chapters, the
first of which is by Wolfgang Grunert (Ruhr University
Bochum, Germany) on the nature of SCR active sites.
The range of available characterisation techniques are
first outlined before the surface science techniques
that have been used are highlighted. Vanadium-based
catalysts are considered first, and there is general
226 © 2015 Johnson Matthey
agreement that binary V—O—V moieties including
a Brønsted site are the most active structures and
a well-accepted mechanism is available for this
site. Isolated VO2+ species exchanged into zeolite
structures are also active, apparently via a different
mechanism. Tungsten promoted vanadium appears
to be effective by encouraging formation of isolated
V—O—V species. The active sites in iron and copper
exchanged zeolites are then considered; here a huge
amount of research has been done over several
decades trying to identify the intimate mechanistic
details and the nature of the active SCR sites. Much
of the earlier work involved exchanged ZSM-5,
and then more recently beta-zeolite and small pore
molecular sieves were studied. As previously noted
a key feature is the low temperature performance
of the copper catalysts and the higher temperature
durability of the iron catalysts. The metal centres may
be associated with NO oxidation. An added advantage
of the iron catalysts, like the earlier vanadium ones,
is tolerance towards sulfur that is in marked contrast
to the poison sensitive copper catalysts. Although
there has been considerable speculation about the
roles of monomeric, dimeric and oligomeric metal
active centres their general relative importance is
unclear. Brønsted acidic zeolite sites have been
thought to be a means of concentrating ammonium
ions close to the metal centres, but the importance of
this is questioned by more recent work on non-zeolite
conventional oxide catalysts some of which can have
good performance.
The next chapter by Masaoki Iwasaki (Toyota, Japan),
is about mechanistic aspects of the ammonia/NO
reaction in excess oxygen, Equation (vi), that is the
traditional standard or rapid ammonia SCR reaction.
Results are given for reactions involving copper and iron
exchanged ZSM-5, a tungsten-promoted vanadium on
titania catalyst as well as the acid form of ZSM-5. The
expected reaction order of copper was greater than
iron and vanadium catalysts. Kinetic parameters such
as apparent activation energies and apparent reaction
orders were reported for the separate oxidation of
ammonia and NO as well as the ammonia-NO-oxygen
reaction. Generalising for the ammonia NO SCR
reaction the order in NO is positive and close to one,
the order in oxygen is fractional and that for ammonia is
negative, reflecting its strong adsorption that can result
in reaction inhibition. There is a strong correlation
between SCR activity and NO oxidation activity. A
considerable amount of carefully determined transient
http://dx.doi.org/10.1595/205651315X688280 Johnson Matthey Technol. Rev., 2015, 59, (3)
response data is reported and several catalytic cycles
are presented. The mechanistic conclusions are similar
to those previously noted.
There then follows an important chapter on the role of
NO2 in ammonia SCR reactions by the editors Isabella
Nova and Enrico Tronconi (Politecnico di Milano, Italy).
The most obvious role of NO2 is in combination with
NO in the fast SCR reaction. Ammonia and NO2 are
strongly adsorbed and interact on the catalyst surface.
The reaction of NO2 with surface oxide ions affords
nitrate and nitrite ions, according to Equation (xviii),
with the latter being further oxidised by NO2 to nitrate
and NO via Equation (xix) so the overall stoichiometry
is as shown in Equation (xx). These reactions are in
equilibrium and depend on concentration, temperature
and catalyst oxidation state.
2NO2 + O2– ⇌ NO3– + NO2– (xviii)
NO2– + NO2 ⇌ NO + NO3– (xix)
3NO2 + O2– ⇌ 2NO3– + NO (xx)
The intimate mechanism of the SCR process is based
on nitrogen redox chemistry. In the standard slow SCR
reaction oxygen is the oxidant taking NO to nitrite, and
in the fast SCR reaction the more powerful oxidiser NO2
is available and so the mixed reaction involving NO
Table I S
 ummary of the Individual Steps Involved in the Fast SCR Reaction over Vanadium-based and
Zeolite Metal Promoted Catalysts
Involving NO2 only
2NO2 ⇌ N2O4
N2O4 + O2– ⇌ NO2– + NO3–
NO2 + NO2– ⇌ NO + NO3–
In the presence of NH3
2NH3 + H2O ⇌ 2NH4+ + O2–
NH4+ + NO2– ⇌ [NH4NO2] → N2 + 2H2O
NH4+ + NO3– ⇌ NH4NO3
NH4NO3 → N2O + 2H2O
In the presence of NO
NO + NO3– ⇌ NO2 + NO2–
Fast SCR
2NH3 + NO + NO2 → 2N2 + 3H2O
227 © 2015 Johnson Matthey
and NO2 is much faster. The overall fast SCR reaction
may be considered to go via the disproportionation
of NO2 to nitrite, the nitrate oxidation of NO to nitrite
and the formation of surface ammonium nitrite that
spontaneously decomposes to water and nitrogen.
All the steps involved in the fast SCR reaction are
summarised in Table I. The required oxidant provided
by NO2 in the fast SCR reaction can also be supplied
by addition of ammonium nitrate in what is called
enhanced SCR.
2.4 Part 4. Reaction Kinetics
There are three chapters in the part of the book on
the reaction kinetics of ammonia SCR reactions,
and fittingly the first is by Isabella Nova and Enrico
Tronconi. This is on SCR reactions over vanadium(V)
oxide (V2O5)/WO3 supported on titania catalyst, and
they explain how measured unsteady state kinetic
parameters for all of the reactions concerned can be
incorporated into a computer model for the control of
heavy duty diesel NOx control systems. At an intimate
mechanism level surface sites are indicated that include
a surface redox site at which oxygen is adsorbed, a
reaction site at which NO is adsorbed and an acidic
site to bond to ammonia. Reduced vanadium centres
are reoxidised by nitrate. It is concluded the fast SCR
reaction proceeds via dimerisation of NO2 followed
NO2 dimerisation
Disproportionation
Nitrite oxidation by NO2
NH3 adsorption
Nitrite reduction by NH3
Formation/dissociation of NH4NO3
Formation of N2O
Reduction of nitrate by NO
Overall reaction
http://dx.doi.org/10.1595/205651315X688280 Johnson Matthey Technol. Rev., 2015, 59, (3)
by its disproportionation to surface nitrite and nitrate.
Ammonium nitrite decomposes to nitrogen while nitrate
is reduced by NO to reform NO2.
The next chapter by Michael P. Harold (University
of Houston, USA) and Parnit Metkar (DuPont, USA)
provides a very good overview of the published
mechanistic work on ammonia SCR of NOx. They
consider not only kinetics and mechanisms but also
the role of transport effects, especially in reactions
over iron exchanged zeolites and layered catalysts
comprising separate copper and iron zeolite layers. A
number of particularly important points are highlighted.
Diffusion limitations can become significant for the fast
SCR reaction at temperatures just above 200ºC, first
diffusion within the catalyst pores; and increasing the
amount of ammonia rather than increasing the rate of the
standard SCR reaction with NO does not enhance the
reaction rate but rather slows it due to strong ammonia
adsorption causing site blocking. The reaction orders
are one in NO, half in oxygen and –0.3 in ammonia and
the corresponding activation energy of around 10 kcal
mol–1 could reflect a relatively low barrier for the rate
limiting step since this was estimated under conditions
where diffusion effects were thought to be absent.
Curiously on iron zeolite NO oxidation is inhibited by
water, but the standard SCR reaction is not. However,
the results of isotopic labelling experiments are
consistent with the decomposition of ammonium nitrite
being involved, Equation (ix), and a potentially important
route to ammonium nitrite is from NO reduction of the
nitrate. It is clear the mechanistic situation for the fast
SCR reaction can be significantly complex, and the
chapter concludes with an examination of two layer
copper zeolite/iron zeolite catalyst arrangement, and
aspects of reactor modelling.
The last chapter in this part, by Louise Olsson
(Charmers University, Sweden), complements
the previous one because it concerns the kinetic
modelling of ammonia SCR reactions over copper
zeolite catalysts. An often unappreciated fact, that is
highlighted, is under operating conditions the zeolite will
adsorb a large amount of water in addition to ammonia
with an enthalpy of adsorption of around 100 kJ mol–1
in the absence of competing adsorbates.
2.5 Part 5. Modelling and Control
The first chapter in this part, about reactor models for
flow-through and wall-flow converters, is by Dimitrios
Karamitros and Grigorios Koltsakis (Aristotle University
Thessaloniki, Greece). The arrangement of the different
228 © 2015 Johnson Matthey
aftertreatment components are discussed because of
the consequences it has on their rate of heating after
the engine starts. A number of other interesting aspects
are discussed including the complex behaviour of SCR
catalysts incorporated into a particulate filter. In the
absence of soot in the filter the pressure driven flow of
gas through the filter walls containing catalyst provides
better performance than the same amount of catalyst
on a flow-through substrate because of the absence
of diffusion resistances. However, the presence of a
substantial layer of soot can modify the situation: there
is the potential reaction of NO2 with soot that reduces
the NO2/NO ratio which, with some SCR catalysts,
can reduce its performance. To compensate for this
effect more catalyst will be required. This might not
be physically possible and if it were possible more
catalyst would increase backpressure across the filter.
It is therefore important SCR catalyst incorporated into
filters lack NO2/NO ratio sensitivity.
The other chapter in this part includes discussion
about the understanding and measurements needed for
SCR control systems by Ming-Feng Hsieh (Cummins,
USA) and Junmin Wang (Ohio State University, USA).
SCR control systems have to take into account varying
engine NOx emissions during real world driving and
adopt the urea solution injections accordingly. Forward
control strategies have been used which make major
assumptions about catalyst ageing and degradation
of ammonia capacity, but alone they are not adequate
and some degree of feedback control using sensors is
necessary. However, the present NOx sensors suffer
interference from ammonia, and this has to be taken
into consideration via sophisticated algorithms. In fact
NOx sensors also have a sensitivity to the NO2/NO
ratio resulting from the extra oxygen present in NO2.
Ammonia sensors are being experimented with to
overcome some of the practical difficulties, but there
remain significant challenges so SCR control system
development is an area of much activity.
2.6 Part 6. Ammonia Supply
The three chapters in this part are about the production
of a spray of urea solution in the exhaust gas flow, its
conversion into ammonia gas, storage of ammonia in
SCR catalysts and the modelling of these processes. The
first chapter by Ryan Floyd (Tenneco, USA) and Levin
Michael and Zafar Shaikh (Ford, USA) is about system
architecture and includes the design of injectors and
mixing devices. The computer-based design of these
systems has resulted in reliable production of gaseous
http://dx.doi.org/10.1595/205651315X688280 Johnson Matthey Technol. Rev., 2015, 59, (3)

ammonia with minimal deposition of troublesome CO(NH2)2 à NH3 + HNCO (xxi)

solids. The second chapter is about ammonia storage
and release by Daniel Peitz, Andreas Bernhard (Paul
Scherrer Institute, Switzerland) and Oliver Kröcher
(EPFL, Switzerland) that focuses attention on the
chemical reactions involved in converting urea to
ammonia, Equations (xxi) and (xxii), before going on
to discuss alternative ammonia sources. While some
of these alternatives have some attraction, the use and
distribution of urea solution is now so well established
it seems unlikely it will be displaced. The third and
final chapter in this part is about gas flow modelling by
Gianluca Montenegro and Angelo Onorati (Politecnico
di Milano). Computational fluid dynamics (CFD) have
been used for many years to optimise distributed
flow through monolithic honeycomb catalysts and the
exhaust system as a whole, and these techniques have
been successfully applied to systems involving SCR
NOx reduction (Figure 3). A high degree of mixing
ammonia with the exhaust gas is essential for high
overall performance.
HNCO + H2O à NH3 + CO2 (xxii)
2.7 Part 7. Integrated Systems
For performance, space constraints and cost
considerations it is desirable to integrate emissions
control functionality as much as possible, and the three
chapters in this part of the book are about this topic.
The first chapter details an experimental and modelling
study of dual-layer ammonia slip catalysts (ASCs)
by Isabella Nova, Massimo Colombo and Enrico
Tronconi (Politecnico di Milano) and Volker Schmeiβer,
Brigitte Bandl-Konrad and Lisa Zimmermann (Daimler,
Germany). The amount of ammonia fed to a SCR
catalyst must be sufficient to reduce the varying amounts
of NOx produced by the engine while maintaining the
quantity of ammonia stored in the catalyst to ensure
optimum NOx reduction performance. As highlighted
elsewhere in this review, the control systems designed
to maintain this situation under dynamic transient

Electronic control unit (EDC 17) Tank

or dosing control unit (DCU 17)
incl. SCR functions

Supply module SM 5.1 (PC)

or SM 5.2 (LD)
Actuators Sensors (Defined welding interface to the
Heater control unit tank. Heater, lifetime filter, level
(HPU-PC) and temperature sensor on module
(only with EDC 17) for tank integration. Pump module
Engine CAN consisting of supply and emptying
pump as replacement part)
Glow control unit (GCU)
with integrated heater
control Coolant Differential Particle NOx
(only with EDC 17) pressure sensor sensor sensor

Dosing module
DM 3.4
Lambda
sensor 2 temp. sensors

Exhaust Mixer SCR-on-filter

Oxi-cat

Fig. 3. Schematic diagram of a car exhaust gas emissions control system comprising an oxidation catalyst, wall-flow particulate
filter, and flow-through SCR catalyst. Key components include a urea solution tank (heated in cold weather), dosing spray
module and static mixer, temperature and NOx sensors. (Source: Robert Bosch GmbH)

229 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X688280 Johnson Matthey Technol. Rev., 2015, 59, (3)
conditions can be effective but occasionally in some
circumstances excess ammonia may slip from the
SCR catalyst, and oxidation catalysts have been
developed to control the amount of escaping ammonia
by converting it to nitrogen. They need to have high
selectivity towards the production of nitrogen, and they
can have SCR activity should any NOx be present. The
situations examined were the traditional arrangement
of a separate special oxidation catalyst after a SCR
catalyst, a layer of oxidation catalyst above which was
a layer of SCR catalyst as well as a physical mixture of
the two catalysts. An iron zeolite catalyst was used and
when this was present as an upper layer on the oxidation
catalyst there was enhanced selectivity to nitrogen and
a small amount of additional NOx reduction.
The second chapter in this part is about combining
NOx-trapping catalysts with downstream SCR catalysts
on diesel cars and is by Fabien Can, Xavier Courtois
and Daniel Duprez (University of Pointiers, France).
When a NOx-trap is regenerated by periodic enrichment
of the exhaust gas ammonia can be formed, and the
reactions involved in this process are detailed before
giving the fascinating history of the use of this ammonia
with a SCR catalyst. The ability of the SCR catalyst to
store significant amounts of ammonia enables it to
reduce NOx that is not retained in the NOx-trap during
normal lean operation. Although optimised systems
have been used on series production cars it seems
likely further advances will be made in the future in this
important area because it has the practical advantage
of not requiring to store and inject urea solution into the
exhaust system.
The final chapter in this part is by Thorsten Boger
(Corning, Germany) about the integration of SCR
catalysts into DPFs. The DPF materials in series
production are cordierite, various forms of aluminium
titanate, and silicon carbide. To reduce component
count, cost and possibly improve performance there
has been a move to incorporate catalytic functionality
into particulate filters especially those in light duty
diesel vehicles. This was first done with oxidation
catalyst that removes CO and HCs during normal
driving and periodically provides high temperature to
initiate filter regeneration. This is done by oxidising
partial combustion products from late injection of
fuel into the engine. Recently SCR catalyst has been
incorporated into filters, and a large amount of catalyst
is required so that exceptionally high porosity filters
are needed. Having sufficient strength and filtration
efficiency with the necessary high porosity material
230 © 2015 Johnson Matthey
has been a major challenge that has been overcome
and such filters are now in series production on some
European diesel cars.
2.8 Part 8. Case Histories
There are two chapters in the last part of the book about
practical applications of urea SCR systems to series
of production vehicles. The first, entitled ‘Development
of the 2010 Ford Diesel Truck Catalyst System’ by
Christine Lambert and Giovanni Cavataio (Ford,
USA), is a well written contribution with well sized clear
illustrations. It provides a nice overview of the SCR
work done in Ford since the early 1990s. By 1995 they
had demonstrated a SCR NOx-control system on a
light duty diesel vehicle, and development continued
culminating in the USA with the introduction of the 2010
truck system. The evolution of copper zeolite catalysts
is detailed and practical aspects such as the importance
of durability of the upstream oxidation catalyst to
maintain high NOx conversion through the then
necessary appropriate NO2 to NO ratio. Also covered
is the influence of packaging constraints, backpressure
problems, and the temperature requirements for the
NOx conversions required. It was clear a rapid heating
cold start strategy was needed to enhance the exhaust
gas temperature so the emissions control system
would work efficiently at a sufficiently early stage.
The 2011 model year system comprised two oxidation
catalysts, urea solution injection, two SCR catalysts,
and a silicon carbide particulate filter. The optimisation
work included substituting a proportion of the platinum
for palladium in the oxidation catalyst as a cost save,
although this resulted in poor (if any with an aged
catalyst) NO oxidation to NO2. This was acceptable
because a NO2 insensitive copper/zeolite catalyst had
been selected. Platinum/palladium formulations also
had the advantages of reducing potential volatilisation
of traces of platinum via its oxide that could influence
SCR catalyst selectivity, reduced low level emissions
of N2O and not oxidising traces of SO2 to the more
potent catalyst poison SO3. Both the oxidation catalyst
and the SCR catalyst had to have high thermal stability
because they experience high temperatures during
active filter regeneration. The palladium-containing
oxidation catalyst had durability, but early copper/zeolite
SCR catalysts and even those based on beta zeolite
did not have sufficient thermal stability. The availability
of SCR catalysts based on small pore zeolites in 2007
provided the required higher thermal stability. The
ammonia storage capacity of SCR catalyst with a
http://dx.doi.org/10.1595/205651315X688280 Johnson Matthey Technol. Rev., 2015, 59, (3)
suitable urea solution dosing strategy can significantly
enhance low temperature NOx conversion, although
this has to be balanced with the possibility of ammonia
slip during high temperature filter regeneration. On the
vehicle this requirement was obtained by the control
system. Exotherm problems on the SCR catalyst
during filter regeneration caused by HC adsorption and
carbon formation were all but eliminated with the small
pore zeolite SCR catalyst. This chapter illustrates the
huge amount of fundamental and development work
that goes into the introduction of a successful vehicle
emissions control system incorporating urea-based
SCR that, of course, continues to be improved upon.
The final chapter in this part, and the last in the
book, is by Michel Weibel, Volker Schmeiβer and
Frank Hofmann (Daimler, Germany) and is a short
contribution about computer models for simulation and
development of exhaust gas systems incorporating
urea-based SCR NOx control. Factors such as
maintaining the level of ammonia stored in the catalyst
are particularly important with copper-based catalysts
that operate best with a significant amount of stored
ammonia. The urea solution dosing strategy has to
satisfy this requirement under most engine operating
conditions without there being excess ammonia that
would be wasteful and potentially be an emission
problem. Independently determined kinetics for each
of the catalytic reactions and catalysts involved are
parameterised for ease of use in computer modules,
and in some instances compiled in data maps. The
resulting simulation models are important during
the development and optimisation of the individual
components and in identifying practical ways of
obtaining optimum overall operating performance.
This is complex and made more so by a need to take
into account the engine operation that determines
engine-out NOx emissions.
3. Conclusions
Ammonia SCR has become the technology of choice
for control of NOx emissions from all but the smallest
diesel vehicles, and its importance is reflected in the
231 © 2015 Johnson Matthey
huge number of publications cited in this multi-author
book. A wide variety of materials are catalytically
active in ammonia SCR reactions, and several high
performance catalysts have become established
commercially. These have the attributes of high
activity, the necessary good selectivity with minimal
undesirable formation of N 2O as well as very good
longevity associated with high thermal durability.
The book provides an important up-to-date survey
of the state of SCR science and technology that over
recent years has undergone tremendous advances.
Exceptionally high conversions of NOx to nitrogen
with amazingly high selectivity are now possible at
temperatures so low they were thought impossible
a decade ago. These improvements resulted from
development work targeting low-temperature NOx
control of emissions from diesel engine powered
cars. Development work continues in this area
and further exciting developments are likely in the
not too distant future that could take the form of
substituting urea as a source of ammonia for some
other reductant derived from on board sources such
as water or diesel fuel.
The lack of consistent illustration style, equation
numbering that could have been unified during
copyediting are easily criticised, as could the all too
brief index that does not for instance have important
terms such as chabazite and SAPO. However, these
failings do not detract from this book being a mine of
information that will be of value to researchers working
in the SCR area as well as a reference for students
in chemistry, catalysis and chemical engineering. The
editors are to be congratulated for bringing together
so many eminent contributors and completing such
a major endeavour. This book should therefore be
made available in academic and industrial research
libraries alike.
Reference
1 W. Nernst, Z. Anorg. Chem., 1906, 49, (1), 213
http://dx.doi.org/10.1595/205651315X688280 Johnson Matthey Technol. Rev., 2015, 59, (3)

The Reviewer
Following Fellowships at the Universities of Toronto and Cambridge Martyn Twigg joined a
polymer group at ICI’s Corporate Laboratory in the North West of England, and after involvement
in projects at Agricultural Division at Billingham moved there in 1977. Martyn worked on catalysts
and catalytic processes including synthesis gas production via naphtha and natural gas steam
reforming, methanol and ammonia synthesis, and proprietary catalysts and processes for herbicide
manufacture and environmental protection applications. He studied catalyst activation and built a
much used off-site catalyst reduction unit. After managing an international polymerisation project he
was head-hunted to work at Johnson Matthey as Technology Director in the autocatalyst area that
he successfully led until being appointed Chief Scientist. This provided an opportunity for research
diversity that included carbon nanotube manufacture and catalysts for medical applications. He was
associated with four Queen’s Awards, and was awarded the Royal Society of Chemistry Applied
Catalysis Prize. He has more than 200 papers, co-authored books on transition metal mediated
organic syntheses and catalytic carbonylation. He produced the “Catalyst Handbook”, co-edits the
Fundamental and Applied Catalysis series with Michael Spencer, and has 150 published patent
families on catalysts and catalytic processes. Martyn has on-going collaborations with universities
and holds honorary academic positions, and runs an active consultancy and catalyst development
business.

Erratum

Computer Simulation of Automotive Emission

Control Systems
It has come to our attention that there was a mistake in the published article: M. Ahmadinejad, J. E. Etheridge,
T. C. Watling, Å. Johansson and G. John, Johnson Matthey Technol. Rev., 2015, 59, (2), 152
(Equation (xix)):
kMax A
k=
1 + A x (xix)

The equation should read:

kMax A x
k=
1+Ax (xix)

232 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X688523
JOHNSON MATTHEY
TECHNOLOGY REVIEW
Sintering and Additive Manufacturing: The New
Paradigm for the Jewellery Manufacturer
European jewellery industry poised to develop potential of direct metal laser
melting in precious metals
By Frank Cooper
Jewellery Industry Innovation Centre, School of
Jewellery, Birmingham City University,
Birmingham, UK
Email: Frank.Cooper@bcu.ac.uk
The use of various sintering technologies, allied to
suitable powder metallurgy, has long been the subject
of discussion within the global jewellery manufacturing
community. This exciting, once theoretical and
experimental technology is now undoubtedly a practical
application suitable for the jewellery industry. All parts
of the jewellery industry supply and value chains, and
especially design and manufacturing, now need to
become aware very quickly of just how unsettling and
disruptive this technology introduction has the potential
to become. This paper will offer various viewpoints that
consider not only the technology and its application to
jewellery manufacture but will also consider the new
design potentials of the technology to the jewellery
industry. It will also briefly consider how that design
potential is being taught to future generations of
jewellery designers at the Birmingham School of
Jewellery. We shall also discuss in some detail the
economics of and potential for new and different
business models that this technological paradigm
might offer the jewellery industry.
233
Johnson Matthey Technol. Rev., 2015, 59, (3), 233–242
www.technology.matthey.com
Rationale
This paper intends to explore and open up for debate by
the jewellery industry what actions and understanding
might be required in order to facilitate the transfer
and acceptance of precious metal direct metal laser
melting (DMLM) technologies and processes into a
manufacturing process specifically tailored for the
jewellery manufacturing industries and their related
value and supply chains. The goal of the Jewellery
Industry Innovation Centre (JIIC) and its parent
institution, the Birmingham School of Jewellery, UK, is to
encourage its students to develop, design and produce
computer aided design (CAD) examples of jewellery
products to challenge, prove, and democratise the
processes and materials required for the application of
precious metal DMLM technology into the production
facilities of small and medium-sized enterprises
(SMEs) within the jewellery manufacturing sector.
The paper also assesses and attempts to quantify the
current perceived industry needs for an adaptable,
low-volume and innovative new technology that will
facilitate rapid responses by SMEs to the consumer’s
demands for more custom-made, individually designed
and personalised jewellery products. Typical jewellery
manufacturing processes like lost-wax investment
casting or stamping do not have either the necessary
quick response times or, more importantly, the design
and production flexibility required to address these
© 2015 Johnson Matthey
http://dx.doi.org/10.1595/205651315X688523
issues. This paper is intended to help increase industry
awareness, knowledge, and especially it is hoped to
speed up jewellery industry uptake of the new design
and production capabilities offered by the DMLM
processes for working with precious metals.
The Economic Argument
This section will focus primarily on the European
jewellery market sector and its financial models.
The European Union (EU) has traditionally been an
important supplier of high-quality jewellery to the world’s
markets, and is also considered to be the second or
third largest market for jewellery consumption, after
the USA (China and India vie for the other places
depending on the statistical analysis method used).
Sales of jewellery in most EU countries are thought
to have risen steadily in the decade from 2005 to the
present; however, this volume market is predominantly
supplied with jewellery items manufactured outside the
EU. Socio-economic factors mean that it is very difficult
for the European jewellery manufacturing industry
to be competitive on price alone. Recent global, and
particularly EU, economic and financial crises have
further impacted the EU jewellery manufacturing
industry and recent massive price rises in all precious
metals have somewhat weakened jewellery sales.
Consumers seem to have reduced their expenditure on
jewellery and sought personalised pieces with greater
associated personal value (1).
High-quality jewellery manufacturing has long
been an important sector within the EU economy.
Detailed information on employment statistics for the
EU jewellery industry is difficult to source and define
accurately but there are thought to be some 30,000
smaller companies, with less than 250 employees each,
and around 200 larger companies with an estimated
total of 180,000 employees. These are companies
that specialise either in a style of jewellery design or
in a stage of production (2). The World Gold Council
has estimated that in 2014 the global demand for gold
jewellery was US $100 billion (3).
Within the EU and other developed economies,
consumers have been educated by the fast-moving,
digital, online revolution to expect a continuous and
regularly updated choice of new and innovative
products. This has impacted consumer buying patterns,
resulting in a surfeit of choice and an ever increasing
competition for their disposable incomes. It could safely
be predicted that the future high-value jewellery market
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Johnson Matthey Technol. Rev., 2015, 59, (3)
could well be increasingly driven by a growing demand
for custom-made, personalised, individually designed
and innovative designs of high-quality and high-value
jewellery as high precious metal prices have resulted
in many consumers now considering the design and
innovation within a jewellery item as equal to if not
more important than its base intrinsic value (4).
Increased affluence in the newly emerging economies,
coupled with a rising number of marriages, working
women, increased shopping opportunities and an
online interest in fashion, are thought to be the main
driving forces behind the latest growth in precious metal
jewellery sales in these areas. However, consumers
are also more careful with their spending. There is a
growing fatigue towards ‘fast turnover fashions’ and
many consumers now have increasing opportunity
to favour good and uniquely personalised ‘statement’
designs and regard these as more important than the
intrinsic value of a jewellery piece.
Global economic uncertainty makes it difficult to
predict future jewellery industry trends, but the market
is predicted in some quarters to begin to expand. In
the near future the EU jewellery market is expected
to grow, especially in the Eastern EU and accession
countries due in part to their newly emerging middle
classes. It is the contention of the present article that
the EU market in particular will increasingly demand
higher quality products, coupled with original designs
and statement jewellery with added perceived value,
personalisation, or new production technologies (5–8).
A key question is therefore: “Is there a viable
economic argument for considering adoption of
DMLM technology?”. The present author believes
that the jewellery manufacturing sector in the EU
has the potential to grow significantly further if new
high-technology approaches such as DMLM are
adopted and exploited effectively. While all materials
used in the production of precious metal jewellery are
intrinsically expensive, DMLM offers a technology shift
that is able to potentially reduce material usage while
offering new market opportunities.
Technology and Design
DMLM was developed during the 1990s in Germany
(9). Beginning with CAD data, several layers of metallic
powder are successively deposited one on top of the
other. Each layer of powder is heated using a focused
laser beam corresponding to a selected cross-section of
the part to be produced. The powder bed is then dropped
© 2015 Johnson Matthey
http://dx.doi.org/10.1595/205651315X688523
incrementally and another layer of powder is applied
and smoothed by a blade prior to application of the next
pass of the laser beam, simultaneously fusing each new
layer of powder to the layer below it. The method differs
from the related technique of direct metal laser sintering
(DMLS) in that the layer of metallic powder is fully molten
throughout. The method does not require any binders or
fluxing agents. Each run of the laser beam partly overlaps
the preceding run, and a protective gas atmosphere is
maintained above the interaction zone of the laser beam
and the metallic powder. Once finished the powder bed
is removed from the machine and excess powder is
then removed and can be fully recycled, although some
sieving may be required. Figure 1 shows a schematic of
the process (10).
A key opportunity is presented to the EU jewellery
manufacturing sector through the harnessing of the
emergent and rapidly maturing DMLM technologies
and processes, which will facilitate the manufacture of
uniquely designed, high-value-added, often custom-
made, personalised, jewellery products that will be
inherently resistant to being copied (11).
The initial concept and design phases define the
innovative nature of a jewellery product during the
early stages of its development. The process of
design enables the definition and development of
concepts and ideas and individual personalisation or
customisation of an item, facilitating commercially
viable new product development. The transfer of these
Laser
Burning point
(partially
sintered
granules)
Blade for
spreading
powder
Powder delivery system
Fig. 1. Schematic of the DMLM process (10) (Reproduced with the permission of the Verein Deutscher Ingenieure eV,
Germany)
235
Johnson Matthey Technol. Rev., 2015, 59, (3)
concepts and ideas into jewellery products is achieved
through a variety of technical processes including
CAD (12), prototyping and light engineering based
processes and technical feasibility is traditionally a
vital consideration at each stage of the design process.
As previously discussed, consumer demand for
increasingly novel products has resulted in the need
for extreme flexibility in the design and production of
jewellery, the ability to respond rapidly to ever changing
demands, and the implementation of a streamlined
product development process by manufacturers of
personalised and custom-made products, not just
jewellery. The UK jewellery industry has a significant
global reputation for producing well-designed, well-made,
high quality jewellery products, manufactured in
controlled and regulated environments that meet the
high expectations of their end consumers. A radically
new manufacturing approach could be considered as
being useful to help re-energise the precious metal
jewellery manufacturing base and to help facilitate new
opportunities to boost production, increase profitability
and regain market share. DMLM, which is nowadays
routinely considered to be part of the rapid or additive
manufacturing (AM) stable of technologies, has now
become an accepted production solution within a
range of industrial manufacturing sectors including
aerospace, automotive, dental and medical, where AM
is used to manufacture parts in a range of ceramic,
polymeric and base metallic materials.
Tilted mirror
with focus
Object
Powder
Platform and
retractable table
Build space
© 2015 Johnson Matthey
http://dx.doi.org/10.1595/205651315X688523
Early research undertaken in Sweden in 2005 (13)
and much more recently in the UK (14) and Europe
has demonstrated that DMLM technologies could be
extended to the manufacture of products in precious
metals, including 18 carat golds in various colours,
silver alloys and even platinum group metals. This
discovery led to some early global interest in the use of
DMLM for precious metal parts manufacture. However,
the principal experience of precious metal DMLM to
date has been largely limited to the cosmetic dental
industry, which has adopted some digital production
solutions in precious metals (15). Additionally, this use
of the technology in dentistry was restricted to a small
number of specialist gold alloys used for restorative
dental crowns in non-jewellery specific alloys. Many
potential alternative uses for precious metal DMLM
have also been identified including electronics, fuel cell,
medical, catalytic and satellite applications and in the
manufacture of low-volume, high-value components in
the prestige automotive, biomedical and marine sectors
(16). There has also been much discussion concerning
the potential for precious metal DMLM and its intrinsic
design benefits within the jewellery and high-value
goods sectors, but the research, capital investment,
and metallurgical knowledge base required to set up
a precious metals DMLM sector have until now been
considered largely prohibitive (17).
Currently there are a small number of different DMLM
technologies at various stages of development and use
in and around the European jewellery sector. In 2011
the JIIC introduced and continues to deliver a teaching
module specifically about DMLM technologies and
their adaptation for jewellery design and manufacture
to the cohort of the Design for Industry (DFI) students
Fig. 2. Examples of students’ work from the Birmingham School of Jewellery DFI DMLM module. From left to right: Natalia
Antunovity, Suyang Li, Tesni Odonnell, Tomas Binkevic
236
Johnson Matthey Technol. Rev., 2015, 59, (3)
at the Birmingham School of Jewellery. Figure 2
shows just a few examples of their work. Each of them
explores and takes advantage various aspects of the
geometric design freedoms that the DMLM process
offers. These items were produced for the students in
a number of different metals by a UK based supplier
of a DMLM technology and were built on a Concept
Laser Mlab LaserCUSING ® by ES Technology Ltd.
The JIIC is also currently actively involved with a UK
government funded DMLM of precious metals research
scheme called the Precious project, whose mission
statement reads:
“To demonstrate the viability of precious metal
additive manufacturing within the UK Jewellery
industry from design and manufacturing through
to finishing, polishing and retail” (18).
This is a two-year project aimed at elevating the current
state of the art of DMLM AM within the UK precious
metal jewellery industry.
After a piece of jewellery has been designed and
before it can be manufactured using DMLM a small
number of core activities need to take place:
• Pre-Processing (Preparing pieces for
manufacture). This essentially refers to all front
end software-related activities including the design
process
• Processing (Manufacturing jewellery items using
DMLM). This refers to the actual manufacturing
process using DMLM technologies
• Post-Processing (Manual and automated
finishing and polishing processes). This refers to
the post-DMLM manufacture processing stages up
to the point where an article is ready for sale.
© 2015 Johnson Matthey
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Each of these steps is interdependent on the others
and they must take place in a logical sequence. When
combined together effectively this can result in the
production of novel and unique quality jewellery items.
Understanding these various activity interrelationships
has a profound effect on the eventual quality of any
DMLM printed jewellery. If a jewellery designer
understands, even on a fairly superficial level, what is
involved in each of these core activities then they will
be able to better design jewellery that not only takes
advantage of the geometric freedoms that DMLM
offers but also can be suitably post-processed to an
acceptable quality of finish.
Case Study: The Ojo Project
To illustrate this a pendant piece from the Precious
project, called ‘the Ojo’, will be used to show the various
stages of designing and manufacturing jewellery for the
DMLM process. The Ojo is intended to be an iterative
design series of 100 pendants where each pendant
produced is significantly different from the pendant
before and the pendant after. This is achieved by the
use of a CAD design algorithm that continually morphs
the basic pendant design. This pendant was conceived
and designed by Lionel T. Dean of Future Factories who
is a member of the Precious consortium of companies.
The CAD file is created, saved as a stereolithography
(STL) file and is shown in Figure 3. The next step is
to use a suitable software to generate and place the
support structures (Figure 4) that are a necessary
part of the DMLM process which requires the jewellery
design to be ‘sliced’ in the software. The parts are built
up of multiples of these slices printed by the DMLM
Fig. 3. CAD images of the Ojo
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Johnson Matthey Technol. Rev., 2015, 59, (3)
Fig. 4. An example of the CAD created support structures on
an Ojo
technology one on top of the other. Parts being built
using DMLM require a support structure (19), this is a
scaffold-like construction, and supports all overhanging
parts enabling undercuts, voids and holes to be
produced. A jewellery designer will not need to be
able to create these supports, as they are added by
the DMLM machine setter and the machine’s software
package, but they will need an appreciation of the use
and application of supports as they leave a witness
mark or scarring when they have been removed, which
will require extra cleaning up and finishing (similar to
that required when removing a casting sprue). In theory
it is possible to build any shape, however if supported
areas are visible but inaccessible, then the result will
be perceivably poor surface quality. A small change to
a design can eliminate the need for a lot of support
structures.
Support structures are required in most, if not all, laser-
powered, metal-based DMLM processes, and there
are a number of divergent reasons for their presence.
To build complex geometries with overhanging and
undercut surfaces, support structures are required
to assist in controlling any potential defects in or on
the part being built. These defects may be caused by
the typical thermal stresses of the DMLM process,
occasionally by overheating, or most commonly by
being dragged over and disturbed by the re-coater
blade applying the next layer of powder. Supports are
most principally required because the powder bed
surrounding the very small melt pool created by the
laser is not sufficient to support the liquid metal phase
in place. Other functions of supports are the bonding
of the part to the build plate and providing a thermally
conductive connection between the part and the build
© 2015 Johnson Matthey
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plate to rapidly and effectively dissipate heat from the
melt zone.
The next step is to fill the machine with powder, load
up the STL file and set it into motion. A re-coater blade,
or brush, pushes fine, powdered, gold build material
from a carefully measured powder supply hopper to
create a uniform layer over the build platform. The laser
scanning system literally draws the two-dimensional
(2D) cross-section of the CAD file slice on the surface
of the build material, melting it into a solid deposit layer
or slice (Figure 5). After the first layer is produced, the
piston beneath the build platform is lowered fractionally
and another powder layer is pushed into place using
the blade. The laser beam melts the second layer
and at the same time fuses or bonds it to the layer
below. This process is repeated layer by layer until the
part is completed. It is this layer adding process that
leads to this technology being described as ‘additive
manufacturing’ in many quarters.
Fig. 5. A laser beam scanning over the surface of the
powder and melting the gold
Fig. 6. The Ojo emerges from the powder bed
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Johnson Matthey Technol. Rev., 2015, 59, (3)
Once the build process has been completed the
build plate piston is slowly raised, the surplus unused
powder is carefully swept away and the ‘additively
manufactured’ jewellery item is exposed (Figure 6).
The part is then removed from the build platform and
the support structures are also removed (Figure 7).
The witness marks or scarring left by the supports also
have to be removed in much the same way as a casting
sprue has to be removed and cleaned up. Because
the support structures are much smaller than a typical
sprue, a small, fine, burr on a pendant or Dremmel drill
will often suffice.
Once the supports have been removed the parts
are then ready for finishing and polishing (Figure 8).
Mechanical, or mass finishing, techniques are often
found to be the best for this stage because the DMLM
of jewellery will probably prove to be most commercially
effective when used to produce geometrically complex
designs. These designs by their very nature will
Fig. 7. Support removal from the Ojo
Fig. 8. Three variants of the Ojo before finishing
© 2015 Johnson Matthey
http://dx.doi.org/10.1595/205651315X688523
present many unique and product specific challenges
when ready to be polished and finished. Mass finishing
technologies are based on the correct application of
media flow pressure and speed to the jewellery item to
be polished. Generally, the higher the pressure exerted
by the media on the jewellery, and the faster the media
flows across the jewellery parts, the faster the desired
finishing results can be achieved. But this flow has to
be either uniform or directed, depending where the
polishing is required.
Centrifugal disc finishing is an industrial mass finishing
process adapted for the surface treatment of jewellery.
The process is carried out in a cylindrical container
which is open at the top, while the bottom consists of a
turntable-like disc separated from the container wall by
a microscopically small gap. During operation, the work
pieces and the grinding or polishing media in which they
are immersed rotate at a high speed, creating a toroidal
abrasive flow; the relative difference in speed of the
components and media produces the polishing effect.
The contact between the jewellery pieces and the
medium generates a very intense finishing effect which
is up to 20 times more efficient than can be achieved
with conventional systems like vibratory finishers.
A process refined by Precious consortium partner
Finishing Techniques Ltd is the ‘stream finishing’
process (sometimes referred to as immersion
polishing). This is a fairly new concept to jewellery
polishing and features short processing times because
the medium is compressed against the wall of a large
spinning bowl (centrifugal disc finishing) and the parts
are held and rotated in this flow by use of a rotating
(a) (b)
Fig. 9. Stream finishing of an 18 carat gold Ojo: (a) the part held in a rotating fixture; (b) immersed in the polishing medium; (c)
removed from the medium
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Johnson Matthey Technol. Rev., 2015, 59, (3)
fixture similar to an electric drill chuck on an extended
shaft (Figure 9). Because the rotating head is fixed
but with an adjustable angle of attack when immersed
into the bowl, it can be easily automated and has
shown excellent reliability and repeatability. The use
of small, light media can produce an excellent finish,
the finishing energy coming from the relative speed of
both the jewellery part and the medium. A final polish
by hand completes the process (Figure 10).
Comparison with Casting
The most widely used technology in jewellery
manufacturing worldwide continues to be the lost-wax
investment casting process, accounting for an estimated
80% of all jewellery production. Current investment
casting processes have been highly developed over
time principally to facilitate traditional historical demands
for high-volume, batch- and mass-produced jewellery
products. In contrast, there is an emerging need for a
low-volume, rapid response to consumer demands for
custom-made, individually designed products, in simple
terms producing in volumes of one. DMLM could meet
this need. Additionally, yet more pragmatically, it also
offers the potential for creating items that appear solid
yet, if sectioned through, would prove to be entirely
hollow or contain a simple honeycomb or scaffolding
structure added for strength, a process sometimes
described as ‘volume without mass’. Such forms
and designs are not currently achievable using the
traditional jewellery manufacturing processes. Caution
must be applied, of course, in selecting appropriate
(c)
© 2015 Johnson Matthey
http://dx.doi.org/10.1595/205651315X688523
(b)
(a)
(c)
Fig. 10. 18 carat gold Ojo: (a) after 1 hour of stream polishing; (b) after approximately 3 hours of stream polishing; (c) after final
hand/mop polishing; (d) the finished Ojo (Ojo is Spanish for eye!)
items for this type of manufacture. For instance making
a typical wedding band hollow would result in an item
that feels valueless and cheap; whereas a bulky,
heavy, watch bezel could be produced using a weight
reducing hollow profile and the resultant watch would
still feel right, with weight being added by the watch
movement and wrist band (Figure 11). The potential
(a)
(b)
Fig. 11. Volume without mass (right and wrong): (a) watch
bezel; (b) CAD image of a hollow wedding band
240
Johnson Matthey Technol. Rev., 2015, 59, (3)
(d)
savings in the intrinsic cost of expensive raw materials
is undoubtedly now approaching the point at which
this novel manufacturing process can become more
commercially viable and attractive to the jewellery
manufacturer and the consumer.
Furthermore, it is entirely possible and correct to
consider at this point that the widespread business
model used in jewellery manufacturing throughout
the UK, especially in relation to lost-wax investment
casting – namely the use of sub-contract bureau
service providers – is equally applicable to smaller
jewellery designers and manufacturers accessing the
DMLM technological advance.
In conventional jewellery manufacturing there is a
measurable correlation between part complexity and its
manufactured cost. Using DMLM means that not only
is complexity independent of tooling costs, but also that
virtually any geometry conceived by the designer is
theoretically possible to produce. Conventional design
methods are based on the ‘design for manufacture’
principle, in which manufacturing constraints are
included at the earliest stages of the design process.
This often results in modular designs with standardised
components, meaning designers inevitably modify their
design intent to enable the item to be manufactured
using a specific manufacturing process. Using DMLM
would allow the removal of many of these constraints,
although (as in any other manufacturing process)
DMLM has its own limitations. It will be necessary to
develop specific ‘design rules’ expertise to manage and
optimise these new and exciting possibilities. Current
research at the JIIC in conjunction with the School of
© 2015 Johnson Matthey
http://dx.doi.org/10.1595/205651315X688523
(a)
Fig. 12. (a) An 18 carat gold galleon ‘printed’ on (b) a Cooksongold Precious M 080 machine
Jewellery and its students is based around discovering
these rules, which will minimise the limitations imposed
by machine modifications and CAD design adjustments,
to attain the objective of being able to produce the
widest possible range of geometries.
The Jewellery Industry Innovation Centre has
recently purchased a Cooksongold Precious M 080
direct metal ‘3D printing’ DMLM machine for teaching
and research purposes, and Figure 12 shows an
example of one of the Centre’s early explorations of
the machine’s capabilities. The ship is a little over
1.5 centimetres high.
The Future
Manufacturers are generally limited in their methods
of fabrication by the cost of tooling, which must
be amortised over the number of parts produced
during the life cycle of a tooling product. In existing
conventional jewellery manufacturing there is a
direct link between the complexity of the part and
its manufactured cost; this can be significantly
reduced with use of the DMLM processes. In gaining
knowledge and understanding of the potential design
and manufacturing advantages of DMLM, jewellery
manufacturers should be provided with the economic
impetus to consider adopting DMLM processes,
as appropriate to their company’s needs. Many
high-value products are made in small volumes or
require individual, personalised adaptations for each
customer or application. The ability to provide such
241
Johnson Matthey Technol. Rev., 2015, 59, (3)
(b)
modifications, as well as the availability of tool-less
fabrication, will influence what is designed, how it is
designed, and the quantity of products offered.
Innovative design could be considered vital for
the survival of the high-value-added industries,
including jewellery manufacturing, though it
should be remembered that the manufacture of
well-designed unique products remains an intensive,
expensive, and consumer-centred process. The
commercial pressures to reduce costs to remain
competitive, while retaining design quality, challenge
jewellery manufacturers to find ever more innovative
manufacturing techniques as well as consider
alternative routes to their markets and consumers.
The jewellery industry and other design-led creative
industries are ideally suited for developing the new
interfaces between the customer and designers,
and they will also need to consider new production
technology approaches that maintain and exploit this
competitive edge. Jewellery is therefore in a unique
position to capitalise and further develop the potential
of DMLM, while using generic fabrication criteria
which are relevant to many other high-value-added
industries where custom-made products command
correspondingly higher consumer prices.
References
1. M. Krijger, ‘CBI Trade Statistics for Jewellery’, Global
Intelligence Alliance/Centre for the Promotion of
Imports from developing countries (CBI), Ministry of
Foreign Affairs, The Hague, The Netherlands, 2014
© 2015 Johnson Matthey
http://dx.doi.org/10.1595/205651315X688523 Johnson Matthey Technol. Rev., 2015, 59, (3)

2. ‘Growth, Dedicated Call 10/00’, Topic IV 31, The
European Virtual Institute For Jewellery Technology,
EC Funded Project, Reference G7RT-CT-2001-05065,
Milan, Italy, 2002
3. L. Street, K. Gopaul, M. Kumar, C. Lu and A. Hewitt,
‘Gold Demand Trends: First Quarter 2015’, World
Gold Council, London, UK, 2015
4. M. Krijger, ‘CBI Trends: Jewellery’, Global Intelligence
Alliance/Centre for the Promotion of Imports from
Developing Countries (CBI), Ministry of Foreign
Affairs, The Hague, The Netherlands, 2015
5. D. G. Penfold, ‘New Product Development in the West
Midlands Region of the UK Jewelry Manufacturing
Industry – Evaluating the Impact of Design Support’, in
“The Santa Fe Symposium on Jewelry Manufacturing
Technology 2007”, ed. E. Bell, Met-Chem Research,
Albuquerque, New Mexico, USA, 2007, pp. 445–456
Agreements’), December 2009 (Withdrawn December
2014), Verein Deutscher Ingenieure eV, Düsseldorf,
Germany, 2009
11. A. M. Carey, ‘The Changing Demands on the Creative
Process as a Consequence of New Technologies’, in
“The Santa Fe Symposium on Jewelry Manufacturing
Technology 2010”, ed. E. Bell, Met-Chem Research,
Albuquerque, New Mexico, USA, 2010, pp. 101–118
12. S. Adler and T. Fryé, ‘The Revolution of CAD/CAM
in the Casting of Fine Jewelry’, in “The Santa Fe
Symposium on Jewelry Manufacturing Technology
2005”, ed. E. Bell Met-Chem Research, Albuquerque,
New Mexico, USA, 2005, pp. 1–24
13. N. Towe, ‘Laser Sintering Process for Making Hollow
Jewellery’, Jewellery Technology Forum Proceedings,
June, 2006, Vicenza, Italy, Legor Group, Italy, 2006

6. ‘Jewellery & Watches’, Key Note Market Report, Key
Note Ltd, Richmond on Thames, UK, 2014
7. D. G. Penfold, Design J., 2007, 10, (1), 3
8. M. Karydes, ‘Bold gold jewelry is back in style’,
Fortune, 9th May, 2015
9. W. Meiners, K. Wissenbach and A. Gasser, Fraunhofer
Ges Forschung, Germany, ‘Shaped Body Especially
Prototype or Replacement Part Production’, German
Patent 19,649,865; 1998
10. ‘VDI-Richtlinie:VDI3404GenerativeFertigungsverfahren
– Rapid-Technologien (Rapid Prototyping) – Grundlagen,
Begriffe, Qualitätskenngrößen, Liefervereinbarungen’,
(Engl. Transl. ‘VDI Guideline: VDI 3404 Additive
fabrication – Rapid Technologies (Rapid Prototyping)
– Fundamentals, Terms, Quality Parameters, Supply
14. M. Khan and P. Dickens, Gold Bull., 2010, 43, (2), 114
15. A. L. Hancox and J. A. McDaniel, Int. J. Powder
Metall., 2009, 45, (5), 43
16. L. S. Bertol, W. K. Júnior, F. P. da Silva and C. Aumund-
Kopp, Mater. Design, 2010, 31, (8), 3982
17. A. Simchi, Mater. Sci. Eng.: A, 2006, 428, (1–2), 148
18. Precious, Innovate UK, The Technology Strategy Board,
Swindon, UK: http://www.precious-project.co.uk/
(Accessed on 29th June 2015)
19. F. Cooper, ‘DMLM Supports: are they the Jewellery
Industry’s New Sprue, Riser and Gate Feed?’, in
“The Santa Fe Symposium on Jewelry Manufacturing
Technology 2014”, ed. E. Bell, Met-Chem Research,
Albuquerque, New Mexico, USA, 2014, pp. 89–109

The Author
Frank Cooper is a lifelong jewellery industry professional and is now a Senior Lecturer in Jewellery
Manufacturing Technologies, and Technical Manager of the Jewellery Industry Innovation Centre,
at the Birmingham School of Jewellery, UK. He sits on the Goldsmiths’ Craft and Design Council
and is a globally recognised expert in the application of various additive manufacturing, prototyping,
CAD and ‘3D printing’ technologies used in the jewellery industry. He is an active participant in a
number of jewellery industry-related research initiatives and has published and presented many
technical papers and articles in the UK and Europe, as well as at the Santa Fe Symposium in the
USA.

242 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X688686 Johnson Matthey Technol. Rev., 2015, 59, (3), 243–256
JOHNSON MATTHEY
TECHNOLOGY REVIEW
Introduction to the Additive Manufacturing Powder
Metallurgy Supply Chain
Exploring the production and supply of metal powders for AM processes
By Jason Dawes*, Robert Bowerman and
Ross Trepleton
Component Technologies, Manufacturing Technology
Centre, Pilot Way, Ansty Business Park, Coventry,
CV7 9JU, UK
*Email: jason.dawes@the-mtc.org
The supply chain for metal powders used in additive
manufacturing (AM) is currently experiencing
exponential growth and with this growth come
new powder suppliers, new powder manufacturing
methods and increased competition. The high
number of potential supply chain options provides
AM service providers with a significant challenge
when making decisions on powder procurement.
This paper provides an overview of the metal powder
supply chain for the AM market and aims to give AM
service providers the information necessary to make
informed decisions when procuring metal powders.
The procurement options are categorised into three
main groups, namely: procuring powders from AM
equipment suppliers, procuring powders from third
party suppliers and procuring powders directly from
powder atomisers. Each of the procurement options
has its own unique advantages and disadvantages.
The relative importance of these will depend on what
the AM equipment is being used for, for example
research, rapid prototyping or productionisation.
The future of the metal AM powder market is also
discussed.
243 © 2015 Johnson Matthey
www.technology.matthey.com
1. Introduction
A component fabricated using powder bed may consist
of many thousands of finely spread powder layers. The
uniformity of these layers can affect the properties of the
final component. The way in which a powder ‘spreads’
during AM depends on the properties of the powder
used. As will be discussed in this paper, even when
chemically equivalent, the properties of metal powders
vary widely depending on both the atomisation method
used and the manufacturing process conditions. To
obtain a greater degree of control over AM processes
service providers must be able to control the quality of
the raw powder feedstock.
The overall AM market has seen exponential growth
over the last five years and during this time the sale
of powder bed metal AM equipment, services and
products has also followed an exponential trend (1)
due to increased adoption from the aerospace, oil
and gas, marine, automobile and medical sectors. As
the benefits of using AM to manufacture functional
metallic components start to outweigh the blockers,
more component manufacturers are looking towards
metal powder bed technologies to allow them to realise
their next generation of innovatively and functionally
designed products.
Research has shown that metal powder costs will be
the biggest continuous expense through the life of an
AM machine (1). The quality and consistency of the AM
components depends, in part, on the characteristics
of the starting powder feedstock. Hence, controlling
and understanding the quality of the powder both in
http://dx.doi.org/10.1595/205651315X688686 Johnson Matthey Technol. Rev., 2015, 59, (3)

its as-supplied and reused condition is essential in
order to achieve the desired mechanical properties of
the laser melted components. Given the significance
of the metal powder feedstock it is important that AM
users make informed decisions when procuring the
raw metal powder. The current state of the AM metal
powder supply chain is that there are multiple possible
methods for the manufacture of metal powders and
many times as many potential suppliers. Furthermore
not all metal powders are equal in terms of their
fundamental properties even when manufactured via
the same technique (when procured from different
vendors). This presents quite a challenge to beginners
in AM technology when deciding on a powder supplier.
However, some AM equipment suppliers, such as EOS,
sell ‘validated powder’. ‘Validated powder’ is a powder
which has been identified as suitable for use in AM.
Whilst validated powder can de-risk procuring powders
for AM it does limit users to a single source supplier
and inhibits the development of in-house expertise.
Given the complexity of the AM metal powder supply
chain this review article aims to resolve some of the
confusion involved and address some of the frequently
asked questions by users. Additionally, the article will
highlight key issues that the market needs to address,
and make potential users aware of some of the key
factors to consider when selecting the most appropriate
powder supplier.
2. Overview of the Powder Bed AM Market
Over the last 20 year period the AM market has grown
rapidly from an industry worth <US$100 million in 1993
to around US$3000 million in 2013, see Figure 1.
Current predictions forecast that this rapid growth
will continue and that there will be a five-fold market
value increase by 2021 (1). This growth trend in AM
technology is also reflected in global raw materials
(powder) sales. Powder sales in the AM sector over the
past decade are shown in Figure 2. After a decline in
sales in 2009, due to market reaction at the beginning
of the fiscal crisis, both the AM sector value and AM
material sales have seen rapid growth since 2010.
Specific to metal powder AM, the sale of powder for
metal processes is also shown in Figure 2. It can be
seen that metal sales have followed the market trend
since 2010, with sales more than doubling in a three
year period. However, the value of the metal powder
AM market is a relatively small proportion of the whole
market. This highlights the opportunity for growth for
powder suppliers offering products into the metals AM
market.
Based on data from 2013 there are 855 powder
manufacturers worldwide (425 located in North
America, 205 in Europe and 225 in the Asia-Pacific
region) capable of producing an estimated 1.12
million metric tonnes, to a value of approximately
US$6.9 billion (2). The top six powder manufacturers
have a combined market share of 44% and generally
serve the press and sinter market. The remaining
market share is made up of small businesses, likely
producing powder for a specific purpose or application.
When the metal powder market is evaluated, only
US$32.6 million was sold for AM usage (0.0047%).
This shows that despite the enormous anticipation of
the impact of AM, traditional powder processes such
528.80
600
417.00

All AM Materials
500 Metallic AM materials only
327.10

3500
Value, US$million

Services 400
265.90
Market value, US$million

3000 Products
238.00
220.90

217.80
189.50

2500 300
151.00
128.90

2000 200
93.40
81.20
71.00

32.60

1500
24.90
18.00
13.50
12.00

100
1000
0
500
2001
2002
2003
2004
2005
2006
2007
2008
2009
2010

2012
2013
2011

0
Year
1993
1994
1995
1996
1997
1998
1999
2000
2001
2002
2003
2004
2005
2006
2007
2008
2009
2010

2012
2013
2011

Year Fig. 2. History of materials sales for AM systems worldwide:

(–) all AM materials, (–) metallic AM materials only (metallic
Fig. 1. AM market growth 1991–2013 (1) powder sale data not available prior to 2009) (1)

244 © 2015 Johnson Matthey

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as press and sinter and metal injection moulding
(MIM) still dominate the marketplace. However, as AM
processes become more established as component
manufacturing routes, rather than rapid prototyping
technologies, the potential for growth in the metal AM
powder supply is considerable.
3. Selection of AM Powder
3.1 The Importance of Powder
The AM process uses powder as its raw material
feedstock, as such the consistency of the powders
used to build AM components will have a critical
influence on the final component properties. During the
build sequence of an AM component, the raw powder
feedstock is stored in a hopper, the design of the hopper
and the method by which powder is introduced into
the build chamber depends entirely on the equipment
manufacturer. A discrete amount of powder from the
hopper is spread (either using a rake or roller system)
across the build chamber to form a thin (no more than
one to two particle diameters) continuous layer of
powder. After spreading it is critical that the layer is
homogenous over the entire area of the build chamber,
any degree of inhomogeneity may result in porosity (in
the absence of powder) or incomplete through-thickness
melting (too much powder pooled up in one area). The
spread layer is selectively fused using either a laser
source or an electron beam based on an input sliced
three-dimensional (3D) computer aided design (CAD)
model. Following selective sintering another layer of
powder is spread over the first. This iterative process
of powder spreading followed by selective melting is
continued until the build is complete. The total number
of powder layers spread will of course depend on the
size of component being built but the number could be
in the region of 7000 layers. Furthermore it is common
to build multiple components during one build event.
The layer spreading, hopper dosing and bulk packing
performance of the AM powder will depend entirely
on the properties of the powder being used. Further
complicating the use of AM powder is that the volume
of the actual component built can be significantly less
than the total volume of powder that has been spread.
As a consequence there is a large amount of unused
powder left over in the build chamber, given the high
cost of metal powders it is essential that the unused
powder is effectively recovered and reused in future
builds. However, the effect of continued recycling of
245 © 2015 Johnson Matthey
the unused powder on the actual powder properties
and hence subsequent component properties has not
been the subject of intensive scientific study. In the few
scientific journals published in the field of metal powder
recycling in AM, it has been observed that recycling
powders in powder bed AM processes results in an
increase in powder particle size distribution (PSD) (2,
3). The thermal effects that result from the process,
such as chamber temperature and the radiation energy
in selective laser melting (SLM) of metal powders,
may cause physical as well as chemical changes to
the recycled powder. Furthermore contamination,
either through impurities, foreign bodies or interstitial
elements may be introduced to the powder as a result
of handling during pre-processing or post-processing
stages.
The first step in understanding powder requirements
for AM processes is to assess the types of metallic
powder that are available. The following sections
provide an overview of the methods of metal powder
production routes.
3.2 Routes of Powder Production
The production of AM metal powder generally consists
of three major stages as outlined in the flow diagram
shown in Figure 3. Briefly, the first stage involves the
mining and extracting of ore to form a pure or alloyed
metal product (ingot, billet and wire) appropriate
for powder production; the second stage is powder
production and the final stage is classification and
validation.
The supply chain of taking ore and extracting a metal
is well established and supplies a vast range of pure
metals and specific alloys to global markets. Once an
ingot of the metal or alloy has been formed a number
of additional processing steps may be required to
make the feedstock suitable for the chosen atomisation
process. For example, plasma atomisation requires the
feedstock material to be either in wire form or powder
form, thus adding additional rolling and drawing work or
a first step powder production route.
Once the first processing form has been obtained
there are a number of methods available to produce
metal powders including, but not limited to: solid-state
reduction, electrolysis, various chemical processes,
atomisation and milling. Historically, for reasons that
will be discussed, atomisation has been identified as
the best way to form metal powders for AM due to the
geometrical properties of the powder it yields.
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Stage 1
Ore

Hydrogenation and
Extraction
dehydrogenation

Forming

Forming
Ingot
(billet, wire)

Stage 2

Plasma, PREP, REP Water atomisation

or EIGA atomisation
Gas or centrifugal
Atomisation atomisation Atomisation

Drying

Powder

Post
processing

Stage 3
Validation

Fig. 3. From ore to validated AM powder – powder production steps flow chart

None of the powder production routes actually
produce a 100% powder yield in the required size
fractions. Some post processing is therefore necessary.
As a minimum, the as-produced metal powder must be
classified into a well-defined particle size distribution
suitable for the required process: typically 15–45 µm for
SLM and 45–106 µm for electron beam melting (EBM).
3.2.1 Water Atomisation
All atomisation processes begin with melting the
feedstock alloy. The melting process has a number of
variations, but generally when atomising using water,
the feedstock is first melted in a furnace before being
transferred to a tundish (a crucible that regulates the
flow rate of the melt into the atomiser). The liquid alloy
enters the atomisation chamber from above; here
it is free to fall through the chamber. Water jets are
symmetrically positioned around the stream of liquid
metal, atomising and solidifying the particles. The final
powder exits at the bottom of the chamber, where it is
collected. Additional processing steps are then required
to dry the powder. Metal powder produced in this
way is typically highly irregular in morphology which
reduces both packing properties and flow properties.
Water atomisation is the main method of producing iron
and steel powders and typically feeds into the press-
and-sintered industries rather than the specialised AM
industry.
3.2.2 Gas Atomisation
The gas atomisation process mimics water atomisation,
with the differentiator being the use of gas instead
of water during processing. Air can be used as the
atomising media, but it’s more likely that an inert gas
(nitrogen or argon) will be used to reduce the risk of
oxidation and contamination of the metal. The process
of melting the metal ingots can be the same as described
for water atomisation, however for powders produced

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for high end applications such as aerospace, the need just before entering the atomisation chamber, as shown
to control interstitial elements has led to increased in Figure 5. This application is used when processing
use of vacuum induction melting (VIM) furnaces. A reactive alloys, such as Ti-6Al-4V, minimising the risk of
VIM furnace is typically installed directly above the contamination from exposure of the molten titanium to
atomisation chamber such that the molten stream of the crucible and the atmosphere (5).
liquid metal enters the atomisation chamber directly
from the furnace rather than through a tundish, similar
to the set-up shown in Figure 4. The stream of liquid
metal is atomised by high pressure jets of gas. Due to
the lower heat capacity of the gas (compared to water)
the metal droplets have an increased solidification time
which results in comparatively more spherical powder
particles (i.e. droplet spheroidisation time is shorter
than the solidification time). Whilst it is not possible
to have complete control over the particle size of as-
atomised powder, the distribution can be influenced by
varying the ratio of the gas to melt flow rate. Research
in the field of gas atomisation has shown that even finer Fig. 5. Schematic of the EIGA process for production of AM
powders (Courtesy of LPW Technology, UK)
particle size distributions can be achieved through the
use of hot gas atomisation (4).
Although interstitial elements can be well controlled
in gas atomised powders, there are still potential
3.2.3 Plasma Atomisation
contamination risks. Contamination most pertinent to Plasma atomisation is a method of producing highly
non-static critical components, such as aero-engine spherical particles. The feedstock used in the process
parts, include refractory materials which can originate can either be in wire form such as the method used by
from the ceramic crucibles and atomising nozzles AP&C Advanced Powders and Coatings Inc, Canada,
used. One solution to this is to use electrode induction or in powder form such as the method used by Tekna
melting gas atomisation (EIGA). EIGA is a variation of Plasma Systems Inc, Canada. The spool of wire or
gas atomisation where the metal is fed into the atomiser powder feedstock is fed into the atomisation chamber,
in the form of a rod that is melted by an induction coil where it is simultaneously melted and atomised by co-
axial plasma torches and gas jets, such as that shown
in Figure 6.
Plasma rotating electrode process (PREP) is a
Melt
variation of plasma atomisation whereby a bar of
rotating feedstock is used instead of a wire feed. As the
Gas source rotating bar enters the atomisation chamber plasma
and pump
torches melt the end of the bar, ejecting material from
its surface. The melt solidifies before hitting the walls of
the chamber.

Fine powder 3.2.4 Hydride-Dehydride Process

The hydride-dehydride (HDH) method (6) of powder
Nozzle production differs from the atomisation processes
described above due to the fact that it does not involve
Collection melting of the metal feedstock. Instead, it involves
chamber
crushing, milling and screening to resize larger lumps
of metal feedstock into finer powder particles. The
Fig. 4. Schematic of the gas atomisation process for HDH process relies on the brittle nature of certain
production of AM powders (Courtesy of LPW Technology, metals, such as titanium, when exposed to hydrogen.
UK)
In the case of titanium, titanium hydrides are formed

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Titanium
Plasma spool
torches
Vacuum
pump
Collection
chamber
Fig. 6. Schematic of the plasma atomisation process for
production of AM powders (Courtesy of LPW Technology,
UK)
in a hydride unit by introducing hydrogen and heat.
The brittle lumps can then be crushed and screened
into the required particle size distribution (PSD). The
powder is then returned to the hydride unit to remove
the excess hydrogen from the metal powder particles.
Powder particles produced using HDH are typically
highly irregular. HDH powders are typically used either
in their as-made condition or used as the powder
feedstock for plasma atomisation.
3.2.5 TiROTM Process
The TiROTM process (7, 8) is a relatively new
method for the production of pure titanium powder
developed by CSIRO, Australia. The TiRO TM
process is a two stage continuous production
method in which titanium tetrachloride (TiCl 4) is
first thermally reduced to an MgCl 2/Ti composite
under the presence of magnesium in a fluidised bed
reactor. The MgCl 2/Ti composite is then separated
using vacuum distillation to produce high purity Ti
powder. The as-processed Ti powder is unsuitable
for AM processes due to the particle size range
primarily being 150–600 µm. As such it is necessary
that the powder is modified using a high shear
milling process in a controlled environment to resize
the powder to a range suitable for AM.
248 © 2015 Johnson Matthey
3.2.6 Summary of Powder Production Routes
Each of these processes yields powder with varying
characteristics, a summary of which can be seen
in Table I. A series of micrographs highlighting the
various particle morphologies obtained from each
manufacturing route is shown in Figure 7.
3.3 Powder Key Process Variables
The quality of a component built in an SLM process
is assessed based on part density, dimensional
accuracy, surface finish, build rate and mechanical
properties. In order to achieve predictable and
consistent component qualities it is desirable that
the characteristics of the powder bed and the
parameters of the machine are maintained at a
constant level since the powder bed and machine
parameters are closely correlated. In order to
maintain a constant powder bed during each
SLM build process it is important to understand
and control characteristics such as powder bed
temperature and density. These characteristics are
governed by the KPVs of the starting powder. Due to
the complex nature of powders, characterising their
performance is not a trivial task. A list of variables
(and analysis techniques) that may be considered
to have an impact on performance is provided in
Table II.
3.3.1 Particle Morphology
Particle morphology will have a significant impact on
the bulk packing and flow properties of a powder batch.
Spherical or regular, equiaxed particles are likely to
arrange and pack more efficiently than irregular particles
(9). Research into the effect of particle morphology on
the AM process has shown that morphology can have a
significant influence on the powder bed packing density
and consequently on the final component density
(10–12), where the more irregular the particle
morphology the lower the final density. As a
consequence of this highly spherical particles tend to
be favoured in the AM process. This limits the use of
potentially cheaper powder production routes such as
water atomisation and HDH. Furthermore as can be
observed in Figure 7(b) gas atomised powders are
only nominally spherical. In the case of the titanium
alloy Ti-6Al-4V, this has led to widespread adoption of
plasma atomised powder. Plasma atomised powder is
typically highly spherical, but is currently produced by a
single source – AP&C, Canada.
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Table I Summary of Powder Characteristics by Manufacturing Process

Manufacturing
Particle size, µm Advantages Disadvantages Common uses
Process
Water 0–500 High throughput Post processing Non-reactive
atomisation Range of particle required to remove
sizes water
Only requires Irregular particle
feedstock in ingot morphology
form Satellites present
Wide PSD
Low yield of powder
between 20–150 μm
Gas atomisation 0–500 Wide range of alloys Satellites present Ni, Co, Fe, Ti (EIGA),
(inc. EIGA) available Wide PSD Al
Suitable for reactive Low yield of powder
alloys between 20–150 μm
Only requires
feedstock in ingot
form
High throughput
Range of particle
sizes
Use of EIGA allows
for reactive powders
to be processed
Spherical particles
Plasma 0–200 Extremely spherical Requires feedstock to Ti (Ti64 most
atomisation particles either be in wire form or common)
powder form
High cost
Plasma rotating 0–100 High purity powders Low productivity Ti
electrode process Highly spherical High cost Exotics
powder
Centrifugal 0–600 Wide range of particle Difficult to make Solder pastes, Zinc of
atomisation sizes with very narrow extremely fine powder alkaline batteries, Ti
PSD unless very high speed and steel shot
can be achieved
Hydride– 45–500 Low cost option Irregular particle Ti6/4
dehydride morphology Limited to metals
process High interstitial content which form a brittle
(H, O) hydride

3.3.2 Particle Size Distribution
Characterisation of PSD in a batch of powder ensures
that the optimum range of particles, by size, are used
in each process. In general, EBM uses a nominal
PSD between 45–106 µm, whilst SLM uses a finer
PSD between 15–45 µm. PSD will have an obvious
impact on both the minimum layer thickness and
the resolution of the finest detail in the component.
An inappropriate combination of PSD and layer
thickness can potentially lead to in situ segregation
due to the mechanical re-coater pushing coarser
particles away from the bed (13), segregation in this
sense could lead to variation in build quality in the
vertical direction. It is generally well reported that
using powders with a wide PSD and a high fine
content produce components with a higher fractional
density (13, 14). However, the use of fine materials
increases the risk of health and safety issues. This is
particularly true when processing reactive materials
such as titanium where finer particulates are likely to
be more flammable and explosive.
3.3.3 Bulk Packing and Flow Properties
Powder flowability is one of the most important
technological requirements for powders used in AM.
The density homogeneity of the final part depends on
the layer-by-layer melting being performed on thin and
uniform layers that are accurately deposited by the
feeding device. Cohesive powders which exhibit poor

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(a) (b)

(c) (d)

Fig. 7. Example SEM micrographs of typical particle morphologies obtained using: (a) HDH process; (b) gas atomisation; (c)
plasma atomisation; and (d) plasma rotating electrode process. In all micrographs the powder shown is Ti-6Al-4V and images
were taken using a Hitachi TM3000 SEM

Table II Powder KPVs and Techniques that Could be Used for their Measurement

Particulate properties Bulk properties

Powder property Assessment technique Powder property Assessment technique

Particle shape (morphology) SEM Apparent density Hall flow

Optical microscopy Freeman FT4
Tap density Tapped density tester
Particle size and particle size Sieve Flowability Hall flow
distribution Laser diffraction Dynamic flow testing (e.g.
Optical microscopy revolution, Freeman FT4)
Shear cell
Angle of repose
Cohesiveness Freeman FT4

Particle Porosity Particle polishing and optical Surface Area BET surface area analysis
microscope
Chemical composition ICP-OES
XRD
Inert gas fusion
Combustion infrared
detection

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flow properties are likely to be more problematic in terms
of obtaining homogenous density layers throughout
the build than powders which are comparatively more
free flowing. Powder flow is difficult to relate to any
one given parameter of a powder but there are some
general rules which can typically be applied (15, 16):
(a) Spherical particles are generally more free flowing
than irregular or angular particles
(b) Particle size has a significant influence on flow
– larger particles are generally more free flowing
than smaller particles
(c) Moisture content in powders can reduce flow due
to capillary forces acting between particles
(d) Flow properties often show a dependency on the
packing density at the time of measurement –
powders with a higher packing density are less free
flowing than powders with a lower packing density
(e) Short range attractive forces such as van der Waals
forces and electrostatic forces can adversely affect
powder flow and may cause particle agglomeration
(short range forces have a bigger impact on finer
particles).
3.3.4 Chemical Composition
The laser sintering behaviour of a metal powder will
not only depend on the physical properties, it will of
course also depend on the chemical properties.
Powder chemical composition for AM should ideally
be optimised for the machine or application. Validating
chemical composition helps to ensure that the
manufactured component has homogenous material
properties.
As well as the bulk alloying chemistry, it is important to
understand the effect of interstitial elements, such as O
and N, since component properties will depend on the
amount of interstitial elements present. For example,
it is well known that the tensile strength and ductility
properties of Ti-6Al-4V are influenced by O content
whereby an increase in O results in an increase in tensile
strength and a subsequent decrease in elongation (17).
Research has also shown that interstitial elements
can influence the melting kinetics of the powder by
interfering with the surface tension of the melt pool
resulting in Marangoni flow (18). Marangoni flow can
have a negative influence on the porosity of the final
component (11, 19).
3.4 Powder Recycling
It has been mentioned previously that for a powder bed
AM process to be economically viable it is necessary
251 © 2015 Johnson Matthey
to recycle the large amount of unused powder. The
effect of continuous powder reuse on the KPVs is
an area that has up until recently received relatively
little scientific attention. A handful of researchers have
investigated the effect of continuous reuse of powders
(2, 3) for example, however further study is required
to fully understand the impact of recycling on process
performance.
4. Procurement Options
Once a suitable atomisation route has been selected,
the AM user then faces more decisions around
powder supply. The market opportunity for metal AM
powder supply has not gone unnoticed, and three
main options for powder supply have emerged. Firstly,
users can choose to procure powder directly from the
AM machine provider. Secondly, users could choose
to procure powder from third party companies, who
offer AM machine ‘validated’ powders. Finally powder
can be sourced direct from an atomisation company.
Indeed several powder manufacturers are now offering
AM specific powders as part of their product portfolio
(the largest of these, and the alloys they provide are
listed in Table III). A summary of the advantages and
disadvantages of each procurement option is presented
in Table IV.
At present the majority of powder sales are through
AM machine manufacturers or third party suppliers.
The powder provided by these suppliers has been
optimised for each additive process, also known as
being ‘validated’.
By validating a powder, the supplier is ensuring that the
powder given to the customer is of suitable quality so
that, when being processed, it will behave as intended,
leading to a successfully built part that will adhere to the
chemical composition and the mechanical properties of
the given metal or alloy. Simply put, the machine will
successfully build with that material, thus de-risking
powder supply for the end user.
Machine suppliers can validate powder as they will
develop processing parameters on their machines for
each specific material. Once the machine repeatedly
builds reliable, mechanically suitable parts then the
parameters will be stored and sent out with batches
of that material to users. The powder being used
will be characterised using some of the techniques
discussed in Section 3.3 and all subsequent batches
will undertake the same testing to ensure that they
adhere to the same specification. This ensures that the
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Table III Supplier List of Powders Specified for AMa

Manufacturing
Supplier type Material Building process
processes

Manufacturer

Centrifugal
Third party

Co-Based
Cu-Based
Company

Fe-Based
Al-Based

Ni-Based

Precious
Ti-Based
Location

Plasma
metals

Water
EBM

SLM

Gas
Advanced Canada P P P P P
Powders and
Coatings –
AP&C
Carpenter US P P P P P P P
Technology
Corp
GKN US P P P P
Hoeganaes
Corp
H.C. Starck EU P P P P P P P P
GmbH
Höganäs EU P P P P P P P P
Sweden AB
Sandvik EU P P P P P P P P
Materials
Technology
TLS Technik EU P P P P P P P
GmbH & Co.
Spezialpulver
KG
LPW UK P P P P P P P P P P P P
Technology Ltd
a
Information obtained from the supplier websites (Accessed April 2015)

end user is receiving consistent powder across batches it contributes an almost insignificant proportion of the
that has been validated for their specific process. Third income generated by powder producers (i.e. 0.0047%
party suppliers offer a similar service, refining powder of the income generated from metal powders was due
size and morphology to ensure they work in process. to sales into the AM market). Since the AM powder
From this it can be seen that machine manufacturers market is not currently a major source of income for
and third party suppliers undertake a lot of work to powder producers it is likely that powders will not be
ensure the powder they provide is suitable for their AM produced to the strict requirements of AM. A further
process. There are a number of obvious advantages risk with this procurement method is losing the support
from procuring powder through these routes. However, of the AM machine manufacturer. This can be slightly
this increased level of material supply security does de-risked by purchasing material from one of the small
also draw some limitations. number of powder manufacturers who are starting
Alternatively, it is possible to procure powder directly validate their own powder for AM processes.
from the powder manufacturer. There are a range of The major advantage of procuring powder from this
benefits from purchasing powder directly from the route is the increased choice of materials and cheaper
manufacturer; however, there are some underlying procurement costs. To ensure that the specification of
risks that a customer must also be aware of. The most the powder is met, a customer may need to undertake
pertinent of these risks was alluded to in Section 2. The their own characterisation analysis. Further to this a
current state of the metallic AM powder market is that manufacturer may only supply the powder in a wider

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Table IV A
 dvantages and Disadvantages of Procuring Powder from Machine Manufacturers, Third Party
Suppliers and Direct from Powder Manufacturers

Supplier type Advantages Disadvantages

Machine manufacturers
Validated third party suppliers
Direct from powder manufacturers
Standard machine parameters are
provided and are ready to use
Powder that has been ‘tried and tested’
Support from the supplier should a build
have issues
Ease of sourcing
Already established procurement routes
Able to select powder from the entire
powder metallurgy industry
A wide range of batch sizes are offered
Powder that has been ‘tried and tested’
Ease of sourcing
Wide range of material choices
Potentially lower cost of powder (highly
dependent of material/process)
Choice of manufacturing process,
allowing a degree of control over powder
characteristics
Can use local manufacturers
An increased level of material traceability
Potentially higher cost of materials
Material options are limited
Experimenting with powder of a
different specification is limited
Lack of traceability of material source
and manufacturing process
Lack of traceability of material source
and manufacturing process
Lack of support from the machine
manufacturer should a build fail
Potentially higher cost of materials
Lack of support from the machine
manufacturer should a build fail
No guarantee that the material will
produce a successful build
Minimum batch orders may apply,
due to minimum powder yields from a
manufacturing process
Will powders be produced to the
exacting standards required for AM?
Lack of powder specification with each
order

PSD than the customer wants, therefore additional
sieving may be required. Both of these add complexity
to the powder supply.
5. Customer Considerations
When deciding where to purchase powder from, a
customer has a number of considerations to make.
Most importantly:
• Can they supply me with the material I require?
• Is the price of the powder competitive?
• Can they provide the batch size I require?
• Is there traceability of the material source? Do I
require traceability?
• Do I require knowledge over the powder
specification? Do I require control over the powder
specification?
Additionally, the customer should always consider
the use of the machine and powder. For instance: is
the machine being used in production or research?
What is the use of the end component? A machine
used purely for production purposes will be required
to make parts of the highest quality, therefore powder
from the AM machine supplier or third party supplier
is likely to be the best procurement route. The added
benefit of this is that the machine manufacturer will
support the customer if there are any build issues.
However, if complete control and traceability of the
powder used for the build is required, then there
may be a lack of transparency from the AM machine
supplier as to the complete history of their powder.
Research-based machines have a different range
of considerations to make. If the primary use of the
machine is to prototype or develop the technology,

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then the customer will likely want the additional
control over the powder that they are using. The
customer will also likely want to attempt building
with new materials or experiment with machine
parameters. Therefore sourcing material directly
from the powder manufacturer may be best suited
here.
There is no right answer for the procurement route
that customer takes. However, careful consideration
needs to be given to the application and desired
end results of the AM system.
6. Future of Powder Supply Chain
There are a number of theories of how this growing
material market will develop over the next five to ten
years. Here, some ideas are explored.
(a) Increased production and industrialisation of
AM drive the price of powder down: all market
predictions show the continued growth of metal AM
over the coming years. Naturally, as the technology
becomes widely used, the supply chain of
materials will also grow. Factors such as increasing
competition and larger production runs should see
the cost of powder per kilogram be driven down. As
the powder metallurgy supply chain infrastructure is
already well established, the increase in suppliers
of specific AM powders is likely to happen rapidly.
This theory also applies to processes that are
currently expensive to run, for example plasma
atomisation. If, as the market develops, this is seen
as the best atomisation route then the amount of
powder produced by it will significantly increase.
Feedstock for the process will become cheaper
and it is likely that the range of materials available
will increase.
(b) Game changing powder production techniques
emerge: throughout this article only atomisation
as a way of producing powders for AM has been
discussed. However, in the near future, there is the
likelihood that an altogether new manufacturing
method will eclipse atomisation, providing suitable
powder for a fraction of the production cost.
Companies such as Metalysis, UK, are developing
new ways in which powder can be made at a
significantly reduced price.
(c) Introduction of third party suppliers increases
competition: the emergence of third party suppliers
could see the price of powder driven down further.
Purely through competition, suppliers will be able
254 © 2015 Johnson Matthey
to procure large batches of powder and pass the
savings onto the end user.
(d) Will machine and powder supply lock down or open
up? This will be an extremely important moment
for metal AM. Other industries, namely polymer-
based AM, have seen companies use bar-coded
systems on their machines, such that a system will
not physically build unless a bar code of a material
that they supply is scanned. If this is the case with
metal AM machines then it could cause a severe
tightening on the research capabilities of these
machines. However, this is only likely to happen on
the highest value, production use systems. Again,
as seen with polymer-based machines, competitors
with machines of more open architecture are likely
to enter the market. It is highly likely that a lot of
machines of this nature will emerge as patents from
the major machine manufacturers start to expire.
7. Conclusions
The three main options available for the procurement
of AM powders include AM equipment providers, third
party suppliers and directly from powder atomisers.
There is some degree of security in purchasing powder
directly from AM equipment suppliers. This is because
the powder batch they supply will be at least nominally
the same grade as the powder batch used to develop
melt theme parameters. However, the AM equipment
supplier has ownership over the powder source thus
limiting the powder supply chain competiveness. This
results in powder costs which remain the highest of all
procurement options.
Procuring powder directly from the atomisers may
be a cheaper alternative. However, despite the recent
exponential growth, the AM market is currently a
relatively small source of revenue for most powder
atomisers. Furthermore, because of the specific
particle size fractions used in AM, powder atomisers
may not produce powder specifically for AM. Instead
atomisers may obtain the required size fractions from
an atomised powder batch intended for use in other
industries such as powder hot isostatic pressing (PHIP)
or press and sinter. The originally intended process
for these powder batches may not require the same
high quality as powders used in AM and as such their
performance in an AM process may not be adequate or
as expected.
This risk of going direct to atomisers can be limited
by using a third party powder supplier. In this case
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the third party supplier takes on the associated risks
of procuring powder batches in much higher quantities
than would be needed by any one AM service provider.
This then allows the AM service provider to procure only
the amount they need. The higher powder quantities
procured by a third party supplier potentially provides
them with the necessary influence to demand higher
quality powder batches that are atomised specifically
with AM as the intended end use. The level of pre-
sale powder qualification is also much more detailed
from third party suppliers than from the atomisers
themselves. Even with this option the procurement
costs can be higher than going directly to the atomisers
and less support will be made available from equipment
suppliers should the procured powder be considered a
potential factor for build failures.
What increases the complexity, and indeed
uncertainty, of procuring powders for AM is the lack of
AM specific powder specifications. It is commonplace
to make decisions to accept or reject powder batches
based on specifications used for press and sinter
applications. These specifications would at best include
chemical composition, sizing by sieve analysis and
flow assessment by Hall flow. Such specifications can
be inadequate to use as a benchmark for AM powder
quality. As discussed throughout this article predicting
powder performance is highly complex and can be
difficult to characterise using simple techniques. Future
work needs to be aimed at systematically identifying
the properties of metal powders that have the biggest
influence on the powder performance in terms of
hopper discharge and powder spreading and also how
the powder responds to the AM melting process. Work
in this field will allow the development of specifications
which adequately define and control the key process
variables of powders used in AM.
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255 © 2015 Johnson Matthey
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the 20th Annual International Solid Freeform Fabrication
Symposium, The University of Texas at Austin, USA,
3rd–5th August, 2009, pp. 342–353
15. P. C. Angelo and R. Subramanian, “Powder Metallurgy:
Science, Technology and Applications”, PHI Learning
Pvt Ltd, New Delhi, India, 2008, pp. 76–80
16. R. M. German, “Powder Metallurgy Science”, Metal
Powder Industries Federation, Princeton, New Jersey,
USA, 1994, pp. 9–58
17. J.-M. Oh, B.-G. Lee, S.-W. Cho, S.-W. Lee, G.-S. Choi
and J.-W. Lim, Metal. Mater. Int., 2011, 17, (5), 733
18. M. Rombouts, J. P. Kruth, L. Froyen and P. Mercelis,
CIRP Annals, 2006, 55, (1), 187
19. D. Boisselier and S. Sankaré, Phys. Procedia, 2012, 39,
455
http://dx.doi.org/10.1595/205651315X688686 Johnson Matthey Technol. Rev., 2015, 59, (3)

The Authors
Jason Dawes is a Senior Research Engineer at the Manufacturing Technology Centre (MTC)
where he leads the Particulate Engineering research group. His role is in the technical
management of highly innovative research projects involving powder based manufacturing
technologies such as additive manufacturing, laser cladding and hot isostatic pressing. He was
awarded EngD from University of Birmingham, UK, in 2014 in the field of Chemical Engineering.

Robert Bowerman is a Research Engineer at MTC where he leads projects within the field of
additive manufacturing. He has experience in the following technologies: electron beam melting
(EBM), selective laser melting (SLM), stereolithography (SLA), digital light processing (DLP) and
fused deposition melting (FDM). His projects focus on innovative research and development
work primarily on the Manufacturing Capability Readiness Levels (MCRLs) 4 to 6. Work carried
out covers all areas of additive manufacturing, including development and productionisation of
technology and designing for AM. He is presently working towards Chartered Engineer status.

Ross Trepleton is the Component Technologies Group Technology Manager at the MTC. He is
responsible for the coordination and management of the MTC Research Programme, in the area
of Component Technology to meet the needs of clients and stakeholders. The aim of this area
of research is to develop new technologies that enable improved component manufacturing. He
was awarded a PhD from University of Birmingham in the field of Metallurgy and Materials.

256 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X687975 Johnson Matthey Technol. Rev., 2015, 59, (3), 257–283
JOHNSON MATTHEY
TECHNOLOGY REVIEW
Atomic-Scale Modelling and its Application to
Catalytic Materials Science
Developing an interdisciplinary approach to modelling
By Misbah Sarwar, Crispin Cooper and
Ludovic Briquet
Johnson Matthey Technology Centre, Blounts Court,
Sonning Common, Reading, RG4 9NH, UK
Aniekan Ukpong, Christopher Perry and Glenn
Jones*
Johnson Matthey Research Centre, CSIR, Meiring
Naude Road, Brummeria, Pretoria, 0184, South Africa
*Email: gjones@matthey.com
Computational methods are a burgeoning science
within industry. In particular, recent advances have
seen first-principles atomic-scale modelling leave the
realm of the academic theory lab and enter mainstream
industrial research. Herein we present an overview,
focusing on catalytic applications in fuel cells, emission
control and process catalysis and looking at some
real industrial examples being undertaken within the
Johnson Matthey Technology Centre. We proceed to
discuss some underpinning research projects and give
a perspective on where developments will come in the
short to mid-term.
1. Introduction
The use of atomic-scale modelling, whether force-field
methods or electronic structure theory calculations
(for example density functional theory (DFT) (1, 2))
in chemical and material research within industry is
257 © 2015 Johnson Matthey
www.technology.matthey.com
becoming increasingly commonplace. This is a field
that entails linking fundamental chemical properties,
for instance electronic and geometric structure, to
activity, ultimately providing the basis from which
enhanced materials can be predicted (3). A particularly
attractive feature of computational approaches is the
flexibility and applicability to all divisions of Johnson
Matthey’s business. For instance within New Business
Development methods to simulate optical properties
of materials (for smart glass applications) are being
applied; within platinum group metals (pgm) refining
we are exploring metal extraction and applying
engineering process modelling; and within glass and
colour technologies we are using thermodynamic tools
to help us understand the formation and properties
of glass compositions. Of particular importance to
Johnson Matthey is catalyst technology (Chemical
Catalysis, Emission Control, Process Technologies and
Chiral Catalysis Technologies) where we are working
towards a multiscale modelling capability that links the
macroscopic engineering world to the atomic-scale
chemistry and physical properties of materials.
A key philosophy within the research group and what
makes the field so important for industrially relevant
applications, is the importance of linking theory with
experiment whether through measurement and
validation of the computational methods or by actively
seeking collaboration with experimentalists who can
synthesise, characterise and test interesting materials.
This overview article will firstly discuss some of the
background to the methods employed, then move on
to discuss some recent projects that have been carried
http://dx.doi.org/10.1595/205651315X687975 Johnson Matthey Technol. Rev., 2015, 59, (3)

out with a particular focus on catalytic applications. state-of-the-art approaches, with the implicit limitations
The aim is to give a feel for the types of application thereof, can be applied to a specific catalytic reaction
we have been tackling, and the underpinning research or application of interest (12–15). Critical in this
we are conducting, before moving on to conclude by approach is the development of a suitable atomic-scale
highlighting areas where continued research effort will model, from which we can extract information about the
be required in the future. electronic properties or certain chemical quantities, for
Computational catalysis is a field that has been example reaction energies and activation barriers. The
flourishing over the past two decades. This is a result idea is to understand the reaction sufficiently, such that
of two primary drivers: the development of efficient we can develop predictive models that can influence the
generic codes or algorithms and the improvement in materials development process. This can be achieved at
available computer power on which to run these codes a number of levels starting from potential energies and
(Figure 1) (4, 5). Computational catalysis as a sub- electronic properties (occupancies, d-band centres and
discipline has arguably emerged from surface science highest occupied molecular orbital/lowest unoccupied
(6, 7). This is unsurprising given that most of molecular orbital (HOMO/LUMO) gaps), before moving
heterogeneous catalytic chemistry occurs at the surface on to thermodynamic models and ultimately full kinetic
of materials. However, it is also inextricably linked to models (Figure 2) (16). One key concept is the
solid-state materials chemistry, for example the bulk identification of a key property or trend that can then be
properties of complex oxides determine the surface used as a descriptor to ‘screen’ through other potential
facets that are present and the complex reaction candidates (3, 12). This approach has met with some
atmospheres present during catalysis lead to various success, and has led to a number of initiatives working
oxidation states of the material, which all play a crucial on generating databases and computational tools to
role in the activity and stability of a given catalyst (8–11). accelerate or aid the discovery of novel materials using
A key interest of computational catalysis to the ab initio approaches (17–22). Close collaboration with
industrial arena is that of material prediction. Here experimentalists then completes the material discovery

Modelling
methods across the length scales
20 integral in Johnson Matthey’s development

19
JMTC –
Pretoria; Computational
18 Catalysis and Materials
log10 (computing power/FLOPPS)

Science
17 JMTC
Computational Chemistry
16 Group
Nobel Prize
15 Walter Kohn and John Pople
DFT and computational chemistry Multi-
scale modelling; large scale DFT
14 Perdew calculations; holistic simulation of systems
Wang
13 DFT for chemists Application of
DFT to reactions; predictive modelling
12 of catalysts and other materials
Development
11 of DFT for chemisorption
problems
10
1990

1992

1994

1996

1998

2000

2002

2004

2006

2008

2010

2012

2014

2016

2018

2020

Year

Fig. 1. Log plot showing the most powerful supercomputer, as measured in floating point operations per second (FLOPPS) (5)
vs. year. In grey are key developments in algorithms and then in blue, on the development of atomic-scale modelling within
Johnson Matthey, as an example of an industrial user

258 © 2015 Johnson Matthey

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(a) NiAl_1 NiAl_2 (b)

NiAl_3 NiAl_4

(c) 1.5
Ni:Sb 5

1.0 Ni:Sn 2
Ni:C
–1
0.5 Ni:Ga
Ni:Zn
O binding, eV

–4
Ni
0.0 –7
Ni:Al
–10
–0.5 Ni:Mo
Ni:Cr
–13
Ni:Zr
–1.0 Ni:Ti
–16

–1.5 –19
–1.0 –0.5 0.0 0.5 1.0 1.5 2.0
C binding, eV

Fig. 2. The process of developing a surface model, studying the adsorption of intermediates and transition states, culminating
in the kinetic model that is used to screen for new catalyst candidates. (Republished with permission of Maney Publishing, from
(16); permission conveyed through Copyright Clearance Center Inc)

process, allowing iterative refinements of models and
ultimately the synthesis of candidate materials.
Beyond the immediate task of predicting materials
for current needs, the second important focus of
computational catalysis is to look to the future: asking
questions such as how to go beyond the current state
of the art to describe systems more accurately or how
to place the atomic scale picture in the context of the
complete catalytic solution. Often this involves trying
out new methods and establishing collaborations with
academic researchers.
In order to illustrate some of the above we now proceed
to discuss some laboratory projects from the areas of
homogeneous catalysis, heterogeneous catalysis and
electrocatalysis that are, or have been, conducted
within the Johnson Matthey Technology Centre in more
detail. After which we shall proceed to discuss some
of the future directions of our research and show how
by working at the cusp of the industrial and academic
interface of fundamental research we are working
towards the future development of Johnson Matthey
technology.
2. Homogeneous Catalysis
Homogeneous catalysts operate in the same phase
as the reactants, usually but not exclusively dissolved
in a solvent. A wide variety of homogeneous catalysts
exist: these include Lewis and Brønsted acids, metal
ions, metal complexes, organometallic complexes
and biocatalysts. However, more recently, the term
homogeneous catalyst is often applied to organometallic
or coordination complexes.
Owing to the fact that upon completion of a reaction,
the catalyst must be recovered from the products (often
a costly process) and that in general heterogeneous
catalysts are more stable, homogeneous catalysts
enjoy only limited application in industry. There are

259 © 2015 Johnson Matthey

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however, a number of important industrial reactions
catalysed by homogeneous catalysts, including
hydroformylation, methathesis, carbonylation and
polymerisation using Ziegler-Natta catalysts. Perhaps
it is in the pharmaceuticals and fine chemicals
industries where homogeneous catalysts enjoy their
greatest success. Coupling reactions such as the
Suzuki-Miyaura reaction, Sonogashira coupling, the
Heck reaction, Stille cross-coupling and the Buchwald-
Hartwig reaction have long been employed to bring
about various organic transformations.
Computational studies with DFT methods on the
transmetallation step of the various cross-coupling
reactions first appeared just over a decade ago (23–28)
and provided useful insight into the energetics and
mechanism of the reaction. Within a couple of years,
In collaboration with experimentalists from Johnson
Matthey Catalysis and Chiral Technologies, a
modelling study was undertaken to explore some
anomalies pertaining to the direct arylation of oxazole
and 4-bromotoluene. Oxazole, 1, with three reactive
C–H sites, usually displays the reactivity order:
C5>C2>C4. However, in certain instances, the reaction
at the C5 site appears to be disfavoured, leading to a
predominance of C2 product. Table I shows how the
product distribution is affected by altering the amount
of added phosphine ligand.
1
O
5 2
4 N 3

DFT results for the full catalytic cycles were reported Oxazole, 1
(29–34). DFT theoretical studies have also recently
been used to investigate cross-coupling reactions
involving metals other than palladium; examples include:
rhodium-catalysed coupling via C–H bond activation Table I P
 roduct Distribution for the Reaction
(35, 36), nickel-catalysed cross-coupling reactions of Oxazole with 4-Bromotoluene Using
(37–42), delineating the mechanism of iron-catalysed the Pre-Catalyst Palladium Acetate
cross-coupling reaction (43–47), dialkylzinc-mediated (Pd(OAc)2)
cross-coupling (48), copper-catalysed C–N cyclisation Catalyst Ligand % % % Di % Di
Mono Mono 2,5 4,5
(49) and enantioselective nucleophilic borylation (50). 5 2

2.1 Palladium-Catalysed C–H Bond Activation Pd(OAc)2 – 66 0 28 3

of Heterocycles
Over the past decade, Pd-catalysed direct C–H arylation
has emerged as an important alternative to traditional
cross-coupling reactions for the synthesis of a wide
range of arylated heterocycles (51–56). Compared
to traditional Suzuki-type cross-coupling methods,
direct arylation has the advantage that it does not
require the preparation of stoichiometric quantities of
organometallic reagents (typically alkyl or aryl boronic
acids), thereby eliminating steps in the synthesis and
reducing the amount of toxic metallic waste.
The most widely accepted mechanism for these
reactions is the concerted metallation-deprotonation
(CMD) pathway, involving simultaneous Pd–C bond
formation and aromatic C–H bond cleavage to yield
a diaryl Pd(II) species (57–59). A second mechanism,
involving a cyclometallated complex, has also recently
been proposed to account for the much lower than
expected reactivity observed when certain tri-tert-
butylphosphine-containing Pd catalysts are reacted
with heteroarenes in isolation to the catalytic cycle
(60, 61).
Pd(OAc)2 1 × PtBu3 31 4 59 1
t
Pd(OAc)2 2 × P Bu3 6 35 50 0
In the absence of added phosphine ligand,
dimethylacetamide (DMA) solvent is believed to
coordinate to Pd. Figure 3 shows the reaction coordinate
diagram for the C–H activation step (believed to be
rate-limiting) of oxazole at positions C5, C4 and C2,
by the well-established CMD mechanism. The results
correlate well with the experimental observation that for
Pd(OAc)2 in the absence of added phosphine, mono‑5-
product is formed in preference to both mono‑2- and
mono-4-substituted product.
Figure 4 shows the reaction coordinate for oxazole
arylation, via the CMD mechanism, in the presence
of Pt Bu3 ligand. Formation of the initial intermediate
appears to be disfavoured for this mechanism, for both
coordination through N3, as well as through the C 4=C5
pi bond. The barrier heights for all three intermediates
are also fairly large. Our calculations thus suggest
that C–H activation at any of the reactive sites via the

260 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X687975 Johnson Matthey Technol. Rev., 2015, 59, (3)

30.00

25.00 O
O H N

O Pd Ar
20.00 DMA

O H ON
15.00 O Pd Ar
DMA N
ΔG, Kcal mol–1

OH O
10.00
O Pd Ar
N DMA
5.00 N O H
O O
O 14.0 O Pd Ar O
O Pd Ar N+
0.00 DMA – H
DMA O
O O Pd Ar
O Pd Ar DMA
–5.00 N
O
DMA
+ N+ O
O Pd Ar H
O –
–10.00 O O
DMA
N O Pd Ar
O DMA

–15.00 N
O Pd Ar
O
DMA
Fig. 3. Free energy diagram for direct arylation of oxazole with [(DMA)Pd(Ar)(OAc)] via the CMD mechanism

O
30.00 O H N

O Pd Ar
PtBu3
25.00 O H ON
N
O Pd Ar O
OH
20.00 PtBu3
O Pd Ar
PtBu3
N O
N N+
15.00 O O H H
O –
O O
11.0 O Pd Ar O Pd Ar
O Pd Ar
ΔG, Kcal mol–1

10.00 PtBu3 PtBu3 PtBu3

N N+ O
O – H
O
5.00 O Pd Ar
O Pd Ar
O t PtBu3
P Bu3
0.00 O

O N
–5.00 O Pd Ar O Pd Ar
PtBu3 O t
P Bu3
+
–10.00 O
N

–15.00
Fig. 4. Free energy diagram for direct arylation of oxazole with [(PtBu3)Pd(Ar)(OAc)] via the CMD mechanism

261 © 2015 Johnson Matthey

 http://dx.doi.org/10.1595/205651315X687975 Johnson Matthey Technol. Rev., 2015, 59, (3)

CMD mechanism in the presence of Pt Bu3 ligand is
unfavourable.
Hartwig et al. (60, 61) have shown that direct
arylation of pyridine N-oxide with (Pt Bu3)Pd(Ar)
(OAc) involves cooperative catalysis between two
distinct Pd centres. Figure 5 shows the modelling
results for oxazole C–H activation via this recently
proposed ‘cooperative’ mechanism and is in
agreement with our experimental findings. The
initial complex that forms has oxazole coordinated
to Pd either through N 3 or through the C 4 =C 5
pi bond. In this case, however, formation of the
latter is unfavourable by around 2 kcal mol –1. C 5
activation still has a marginally lower barrier height,
but initial intermediate formation is unfavourable.
The energy barrier for C 2 –H activation is still quite
large (around 21 kcal mol –1), but not as large as
for the DMA ligand. These findings suggest that
C 5 –H activation is not significantly favoured over
C 2 –H activation as is observed in the absence of a
phosphine ligand.
This work has shown how modelling can be
instrumental in explaining experimental observations.
A better understanding of the factors that control the
reactivity and regioselectivity of various heteroaromatic
substrates is important in designing reaction conditions
that will favour activating a specific C–H bond in
a particular substrate. Additionally, it would allow
Catalysis and Chiral Technologies to better market
their range of Pd-catalysed cross-coupling catalysts
towards specific applications. Future work includes
investigating the regioselectivities of the di-substituted
products, as well as the effect that the amount of PtBu3
has on the product distribution.
3. Heterogeneous Catalysis
Heterogeneous catalytic materials come in several
forms. Generically one could say that these are
either unsupported (for example zeolites or PdO) or
supported (for example nickel/alumina). The majority
of our research has focused on the latter type, where
either pure, doped or alloy nanoparticles are deposited
on a support that may be either inert, acid/base or
redox active. Historically, extended infinite surfaces
have been used as models corresponding to the limit

30.00
O
O H N
25.00 O Pd
t P
Bu
t N
Bu
20.00 O H O O
N OH
O Pd O Pd
t P t
Bu P
15.00 Bu t t
Bu Bu O
N+
– H
O
N
10.00 O Pd
ΔG, Kcal mol–1

N
O O H P
O t
O Bu
12.8 t
O Pd Bu
O Pd
5.00 t P t P
Bu t Bu
Bu t
Bu
N+ O
N – H
O O
0.00
O Pd
O O Pd Bu P
t
O P t
O Pd t Bu
Bu t
–5.00 Bu
t
Bu P
t
O
Bu
–10.00 + N

O O Pd
t
O P
N Bu t
–15.00 Bu

Fig. 5. Free energy diagram for direct arylation of oxazole with [(PtBu3)Pd(Ar)(OAc)] via the cooperative mechanism

262 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X687975 Johnson Matthey Technol. Rev., 2015, 59, (3)

of large nanoparticles (>3 nm – this number is slightly on specific reactions, which may be a combination
arbitrary due to the computational effort required to of electronic and geometric influences (Figures 6
explicitly define this value). There is a plethora of real and 7), and also the influence of the so-called ‘metal
examples where materials design has been influenced support interaction’ in which electronic, geometric
by the result of calculations on such systems (62, and ‘spill-over effects’ play a role (64). In fact, these
63) and indeed this is often the first approach taken influences can be reaction specific and sometimes
with our in-house modelling. However, the complexity even condition specific. It still remains a challenge to
of a catalyst is such that detailed questions remain, theoretically address these questions fully and this
surrounding for example the influence of particle size leads to much vital underpinning research.

(a) 0.8 (b)

CN: 6
CN: 7
0.6 CN: 8 or 9
CN: 12
Fraction of atoms

0.4 Terraces

0.2
Steps

Corners
0
0 1 2 3 4 5 6
d{[100]–[–100]}, nm
Fig. 6. (a) Graph showing the fraction of atoms of a given type (terrace, step or corner group by coordination number (CN)) as a
function of particle size. The plot has been generated for Pt particles using a Wulff construction from surface energies; for clarity
only CN 6, 7, 8, 9 and 12 are shown. (b) From top to bottom: three representative surface models are shown: {111} for a terrace
(CN: 9), {211} for a step (CN: 8), {532} for a corner atom (CN: 6)

(a) (b)
Total DOS Total DOS Total DOS Total DOS Total DOS

0.8 10
Single atom
0.4
Bulk
0.0 8
–10 –5 0 5 10 201
0.8 6 cluster
0.4 165
0.0 6 135
–10 –5 0 5 10
DOS

0.8 13 cluster 79
0.4 4 55
0.0–10 –5 0 5 10
43
0.8 79 cluster
0.4 2 19
0.0 13
–10 –5 0 5 10
0.8 Bulk 0 1
0.4 –10 –8 –6 –4 –2 0 2 4
0.0 E–Ef, eV
–10 –5 0 5 10

Fig. 7. Density of states for: (a) small gold clusters as a function of size (increasing from top to bottom); (b) Pt clusters as a
function of size (decreasing from top bottom). When viewed in conjunction with Figure 3, it can clearly be seen that overlaid on
the geometric effect of coordination is an electronic effect, partly as a result of low coordination, but also as a result of localised
electronic states intermediate between atomic and bulk-like

263 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X687975 Johnson Matthey Technol. Rev., 2015, 59, (3)
3.1 Methane Activation
The activation of methane is central to many
technologies, from hydrocarbon combustion and
methane oxidation in catalytic emission control to the
synthesis of hydrogen and syngas as a feedstock for
Fischer-Tropsch and ammonia syntheses (65).
In the area of steam reforming catalysis, models
have been developed to go beyond understanding
the intrinsic activity of steam reforming catalysts
and begin to consider the influence of poisons and
unwanted side reactions. For instance, building
on published models (66), extensions have been
made to account for: (a) site blocking and (b) the
electronic deactivation caused by the presence of
sulfur (67). Using the modified model the influence
of sulfur can be explicitly simulated (68), enabling
strategies to be developed to mitigate its influence.
Figure 8 shows an example of a sulfur overlayer,
along with a calculated thermodynamic isostere
for sulfur coverage on Ni {111}, as a function of
temperature and partial pressure of hydrogen
sulfide (H 2S). This figure allows direct comparison
to published experimental work (69), against which
calculated enthalpies (ΔH) and entropies (ΔS)
can be validated. This exercise showed excellent
agreement (ΔH (800 K): –145 (Exp. –155.2) kJ mol –1,
ΔS (800 K) = +38 (Exp. +35.9) J K–1 mol –1), indicating
that these more complex reactivity studies result in
good trends. Figure 9 (70) illustrates the influence
(a)
Fig. 8. (a) Optimised structure of 0.25 ml S on a Ni surface; (b) isostere of S calculated from first-principles. Good agreement for
saturation coverage (just below 0.25 ml) and entropies is found with the work of McCarty and Wise (69)
264 © 2015 Johnson Matthey
of sulfur adsorption on the steam reforming reaction
over a Ni{211} and the resulting activity trends for a
series of alternative alloys.
During the steam reforming reaction the dissociation
of methane on a nickel catalyst can lead to the
formation of polymeric carbon on the catalyst surface
(Figure 10). The carbon filaments so formed are very
problematic, ultimately leading to deactivation of the
catalyst and shutting down of the reactor. Using DFT
modelling, the origin of the deactivation has previously
been investigated along with possible mitigation
strategies (71–73). Two fundamental approaches
have been studied in-house: the first is to examine
the role of dopants and alloys on the initial formation
and nucleation of the problematic carbon, the second
to look at burn-off of any formed carbon using oxygen
based species and how this can be promoted.
The work has shown that in general if one inhibits
the formation of carbon there is a negative effect on
the activity of the catalyst; there is the unfortunate
problem that the very surface sites responsible for
catalytic activity are also the primary nucleation sites
for carbon formation. This leads one to consider the
promotion of burn-off as the pragmatic route to deal
with it (Figure 10). Through modification of the support
or surface composition of the catalyst it is hoped that
promotion of this mechanistic route can be achieved
and this is the subject of ongoing research.
Ordinarily, the presence of excess carbon is unwanted.
However, there are also reactions where the presence
(b)
–10
–12
–14
–16
–18
–20
–22
1.0 1.2 1.4 1.6 1.8 2.0
1000 k/T
 http://dx.doi.org/10.1595/205651315X687975 Johnson Matthey Technol. Rev., 2015, 59, (3)

(a) (b)

0 0
TOF Rh3Ru
1500 Rh3Ni
θH
–1 θC –1
θS Rh
θCH2

log (TOF/s–1)

Price, $ kmol–1
–2 θO –2 1000
θOH
log (θ)

θ*
–3 –3 Pt3Ru Ru3Rh
500 Ni3Rh
0 50% drop in activity
–4 –4 Pd3Ru
Pd3Co
Ru3Ru Ru3Pd Ru3Ni
–1
Co3Pd Ni3Ru
–9 –8 –7 –6 –5 0 Ni3Ni
–5 –5
–9 –8 –7 –6 –5 –4 –3 –2
log (PH S/Pstan.) 0 0.2 0.4 0.6
2 Activity

Fig. 9. (a) Calculated turn over frequency and coverage of surface species for methane steam reforming in the presence of S
over a Ni {211} surface. Kinetic models like this can be used as the basis for theoretical screening studies; (b) Pareto optimal,
intrinsic metal cost (2009), vs. activity for methanol steam reforming (MSR) catalyst, oxidised catalysts have been filtered out
following the method outlined in (70)

(a) (b) (c)

Fig. 10. Illustration of: (a) nucleation of C at step edge (or defect); (b) growth of graphitic-like carbon; (c) reaction of graphitic
carbon with surface OH (burn-off mechanism)

of carbon growth has been found to promote catalytic
activity (74). This has inspired a fundamental research
project looking at how defective graphene sheets can
potentially act as catalysts for converting propane to
propene (75). Furthermore, carbon is also used as
a support in applications such as fuel cells. These
observations highlight that it is not straightforward
to classify whether a given element is a poison; as
exemplified by the case of carbon in catalysis, it can be
both a friend and a foe.
Partial oxidation of methane over yttrium stabilised
zirconia (YSZ) has been experimentally shown to be
catalytically active for the partial oxidation of methane
(76, 77). First-principles electronic structure calculations
have been applied to explore the possible mechanism
of methane C–H bond activation over the oxygenated
YSZ [111] surface (Figure 11) (78). Previous theoretical
studies (79) and experimental evidence (80) suggest
that YSZ will favourably adsorb molecular oxygen over
intrinsic vacancy sites and partially reduce it creating
stabilised superoxide-like species. DFT calculations
of molecular oxygen adsorbed over a vacancy site on
the YSZ [111] surface showed that the O2 species was
partially reduced. Charge distribution analysis showing
it to be in an approximately –0.5 oxidation state, with
the O–O bond lengthened slightly and large regions
of unpaired electron density on each oxygen atom,
all demonstrating transfer of electron density from the
surface in to the oxygen π* anti-bonding orbital. The
adsorption was found to be energetically favourable,
the DFT model giving an adsorption energy of –0.47eV.
The oxygenated surface model described above was
used to study the methane activation process. The pure
zirconia (ZrO2) and unoxygenated YSZ surfaces were

265 © 2015 Johnson Matthey

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Alloying Pt with another transition metal is one possible

H way of overcoming some of these issues and this is an
H H H area that has been subject to intensive research in the
H
H last few years (84–89).
H The ORR at the cathode consists of several reaction
~0.5– –
H
O O O O pathways, the detailed understanding of which is still
2– –
O O
Zr4+ the subject of ongoing research (90). Generally, the
Zr4+
reaction can follow two pathways: the four electron
Delocalised route to water (Equation (i)) and the two electron route
YSZ surface YSZ surface to H2O2 (Equation (ii)):

Fig. 11. Schematic diagram of the proposed methane
activation mechanism over oxygenated YSZ surface.
The excess charge balance on the product is delocalised
throughout the ZrO2 system (78)
found to be relatively inert towards methane. However,
on the oxygenated surface, methane was found to
transfer a hydrogen to a surface lattice oxygen ion in
a site neighbouring an adsorbed O2 species to yield a
surface OH group and a triangular planar CH3 molecular
species in the gas phase. Analysis of the charge density
distribution confirms that the CH3 entity is a charge
neutral methyl radical and that the H3C–H bond has
undergone homolytic cleavage. The overall process
is predicted to be energetically favourable (–0.23
eV). Transition state calculations using a constrained
algorithm in combination with the nudged elastic band
method (81), revealed a relatively low activation barrier
of approximately 0.4 eV, suggesting that the reaction
should occur readily. Analysis of the changing geometry
and electronic structure allowed the prediction of the
simplified mechanism given in Figure 11, with the
adsorbed oxygen acting as an electron acceptor. It is
likely that similar mechanisms may operate over other
related metal oxide materials. Further information and
analysis of this work is available (78).
4. Electrocatalysis
O2 + 4H+ + 4e–à 2H2O (i)
O2 + 2H+ + 2e–à H2O2 (ii)
On Pt and Pt alloy surfaces it is generally agreed that
the ORR follows the four electron pathway to water.
This reaction can be broken down into the following
elementary steps (Equations (iii)–(v)):
½O2à O* (iii)
O* + H+ + e-à OH* (iv)
OH* + H+ + e-àH2O + * (v)
(where * denotes a surface atom or empty surface site).
In order for a surface to be an effective catalyst it
should follow Sabatier’s principle (91, 92). This states
that a good working catalyst should have the ability
to break bonds and generate intermediates. However,
it should also have a low enough interaction energy
with these intermediates not to stabilise them on
the surface, so that they can react further and free
up adsorption sites. It has been suggested however
that the reason for the slow ORR may be due to
the O intermediate binding too strongly to the Pt
surface, therefore accumulating on the surface and
blocking active sites. The surface d-band centre and
oxygen binding energies have been widely used as
descriptors for the ORR. Both these show a volcano
type relationship with catalytic activity (85).

Proton exchange membrane (PEM) fuel cells offer

a promising clean energy source for a range of both
stationary and automotive applications. However, there
are a number of issues which must be overcome in
order for these to be commercialised. These include
the high cost of the platinum electrodes, slow kinetics
of the oxygen reduction reaction (ORR) and stability
of the electrodes under operating conditions (82, 83).
4.1 Transition Metal Alloy Nanocatalysts
High throughput screening of materials using
computational approaches such as DFT has become a
powerful and valuable tool in catalyst design. The search
for the optimal material, based on predicted activity and
stability, among a great number of alloy combinations
is both a materials and a combinatorial problem. A high
throughput approach was developed and adopted for

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investigating the impact of varying the ratios of metals in

the alloy surface layer to determine which compositions
are most stable and electrochemically active. In this
work, through collaboration with project partners
Accelrys and CMR Fuel Cells, a combined theoretical
and experimental approach was taken to investigate
trends in the stability of Pt-M-Pt and M-Pt-Pt core-shell
type catalysts (M = Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Os,
Ir, Au, Ta, Hf, Cr, Nb, V, Y, Sc, Ti and Zr).
The surfaces were modelled using a 2×2 unit cell of
the face-centred cubic (fcc) crystal of Pt (lattice constant Fig. 12. Schematic depicting the under/overlayer structure of
bulk Pt system: a = 4.010 Å). The Pt-M-Pt configuration core-shell type catalysts: (a) Pt-M-Pt structure; (b) M-Pt-Pt
was modelled by substitution of the second atomic layer structure
of Pt with M atoms, whereas the M-Pt-Pt configuration
consisted of the Pt atoms in the first atomic layer being between the Pt-M-Pt and M-Pt-Pt structures with and
substituted with M atoms (Figure 12). without O/OH adsorbed. If the segregation energy is
The stability of the electrode under fuel cell operating negative the Pt skin structure is favoured, if it is positive
conditions is a significant challenge to understand, as a surface of M atoms is favoured (Equation (vi)):
the highly corrosive environment can promote surface
segregation of the alloying component, which can Eseg = E (Pt-M-Pt) – E (M-Pt-Pt) (vi)
then be leached away removing any benefit obtained
from alloying (93–95). The adsorption of O and OH and in the presence of adsorbate (O or OH) (Equation (vii)):
on the surfaces of Pt-M-Pt and M-Pt-Pt alloys was
Eseg = E (Pt-M-Pt)(O/OH) – E (M-Pt-Pt)(O/OH) (vii)
investigated, sampling all possible adsorption sites to
identify the most stable. The stability of the surface was Figure 13 shows the segregation energies for the
assessed by calculating the segregation energy, Eseg, structures with and without O and OH adsorbed.
firstly in vacuum (Equation (vi)) and then with the O The value of the segregation energy indicates how
or OH atom adsorbed (Equation (vii)). The segregation strongly a particular configuration is favoured. A more
energy is defined as the difference in total energy negative segregation energy indicates that a Pt skin is
PtMn
PtCo
PtCu

PtOs

PtRh
PtRu

PtNb
PtAg
PtAu

PtPd

PtBe
PtFe

PtCr

PtTa
PtHf
PtNi

PtAl

PtSi

PtTi
PtV
PtIr

2.00

1.00

0.00

–1.00
Eseg, eV

–2.00 Clean
–3.00 Oads
OHads
–4.00

–5.00

–6.00

–7.00
Alloy
Fig. 13. Calculated segregation energies for clean {111} surfaces of various Pt alloys in vacuum and with ¼ ml of O or
OH adsorbed

267 © 2015 Johnson Matthey

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strongly favoured. In vacuum it can be seen that the
Pt-M-Pt structure is favoured in all cases except Au
and Ag (purple bars). However when O is adsorbed
the segregation energy is weakened in comparison to
the clean surface (blue bars). For the ORR reaction,
the materials that retain a Pt skin are most promising.
For Pt-Ni-Pt, Pt-Pd-Pt, Pt-Be-Pt and Pt-Y-Pt surface
segregation of M is predicted in the presence of
adsorbed O. For the remaining alloys a Pt skin is
predicted though this is not favoured as strongly as for
the clean surface. A reversal in segregation energies
is observed for Pt-Ag-Pt and Pt-Au-Pt, which are more
stable with a Pt skin in the presence of O.
Adsorption of OH on the surface destabilises the
system resulting in a weaker segregation energy
compared to the clean surface. This destabilisation
is less pronounced than previously seen for O at the
surface, with more negative segregation energies
obtained for OH. This indicates that the tendency to
retain a Pt skin in the presence of OH is stronger than
in the presence of O.
The most promising ORR catalysts are ones in which
a Pt skin is retained, acting as a protective barrier
to prevent the leaching of M from the subsurface.
Analysis of the segregation energies in the presence
of both O and OH indicate that in terms of stability
all compositions except Pt-Be-Pt, Pt-Ag-Pt, Pt-Au-Pt,
Pt-Ni-Pt and Pt-Pd-Pt are promising, as a Pt skin is
retained in the presence of O and OH when adsorption
takes place.
Figure 14 shows the adsorption energy of ¼ ml of
oxygen on the surface of each Pt-M-Pt alloy. Alloys
to the left of Pt have a lower d-band centre and are
–3.4 –2.9 –2.4 –1.9 –1.4
–2
–2.2 PtAl PtTi
–2.4 PtNb
–2.6 PtV PtTa
E Oads, eV
–2.8
PtCr
–3
PtMn
–3.2
–3.4
–3.6
–3.8
–4
Ed–Ef, eV
Fig. 14. Correlation of d-band centre and O adsorption energy for Pt-M-Pt alloys
268 © 2015 Johnson Matthey
predicted to bind O more weakly than Pt. It is these
alloys which bind O slightly more weakly than Pt that
are predicted to have enhanced ORR activity. However
alloys such as Pt-Ti-Pt and Pt-Al-Pt are predicted to
have poor ORR activity as they bind O too weakly.
Using this approach over 2000 alloy combinations
were screened and several potential candidates
identified to put forward for further experimental testing.
This theoretical pre-screening approach allowed
the list of combinations for testing to be significantly
narrowed down, saving valuable experimental time
and resource.
4.2 Carbide Core Nanocatalysts
An alternative strategy to using a transition metal
alloy as a core particle is to explore the possibility of
using transition metal nanoparticles (96). The use of
carbides as non-transition metal cores supporting
thin films of Pt has been investigated. Through the
study of various carbides and their interaction with Pt
overlayers the project has been able to elucidate (a)
the geometric and electronic influences on the stability
of Pt on these carbides; and (b) how the presence
of the different carbide cores influences predicted
catalytic activity (Figure 15). Working closely with the
synthetic chemists at Johnson Matthey Technology
Centre, Sonning Common, the research has created
inspiration and directions for research which are being
followed in-house.
It is understood that synthesising a material where Pt
wets a carbide surface or other non-metal cores may
be challenging from a thermodynamic perspective.
PtSc
PtHf/PtZr
PtCo
PtCu
PtRu
PtOs PtFe PtRh PtAg
Pt
PtIr PtAu
PtPd
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(a)
1.5
Eseg, eV atom–1
0.5
Ir Pd Ga Sn
–0.5
–1.5
–2.5
Fig. 15. (a) Stability of Pt forming an outer shell with several tie-layer candidates. Overlaid is the oxygen adsorption energy
relative to pure Pt; (b) schematic illustrating the carbide core material with the tie-layer/Pt overlayers
Therefore the work, in its second phase, investigated
strategies to promote the stability of Pt, for instance
through the use of so-called tie-layers. Figure 15
illustrates the stability of a test set of tie-layer/Pt
combinations, showing the propensity for the Pt to
remain as a skin or to be sandwiched between the tie-
layer and carbide support.
5. Emission Control Catalysis
The use of catalysts in emission control is wide
and varied. Along with the supported nanoparticle
catalysts discussed to this point, another significant
class of catalyst is the zeolite. Zeolites are crystalline,
microporous materials in which the atoms are
arranged to form a network of molecular sized pores
and channels. This unique porous structure combined
with their huge internal surface area gives rise to a
vast number of applications. By tailoring the pores and
channels, molecules can be excluded on the basis
of size and shape and catalytic processes can be
driven to yield only preferred reaction products. Within
Johnson Matthey’s business areas alone, zeolites are
key components of selective catalytic reduction (SCR)
catalysts, as additives for fluidised catalytic cracking
(FCC) catalysts, and as catalysts in the petrochemicals
refining process.
Zeolites have been extensively studied over the last
decade using a wide range of modelling techniques. The
structure of the framework, effects of doping, location
of ions and adsorbates within the pores, diffusion of
reactants and products within the structure and the
reaction pathways leading to the catalytic breakdown
of molecules can be readily computed. Atomistic
modelling has been used to aid the characterisation of
269 © 2015 Johnson Matthey
(b)
Eseg (100)
Eseg (111)
Eseg (001)
ΔEads (100)
ΔEads (111)
Eads (001)
zeolites used for SCR of nitrogen oxides (NOx) species
for emission control – in particular to help elucidate the
location of ions within the pores and to understand
how these interact with other species located within
the voids, such as water, nitrogen oxide (NO) and
ammonia (NH3).
Small pore zeolites such as CHA have recently
gained a lot of interest due to their very good low-
temperature activity and enhanced stability compared
to medium and large pore zeolites such as MFI and beta
(97–103). An understanding of the nature and location of
transition metal ions such as Cu and Fe within the pores
and how these interact with key NH3-SCR adsorbates
such as NO and H2O is crucial in understanding the
mechanism of NOx reduction in these zeolites and this
in turn can help in devising strategies to improve the
performance of these catalysts. A combined simulation
and experimental approach was used to investigate
Cu location in CHA using techniques such as energy
minimisation based on interatomic potentials and
quantum mechanics/molecular mechanics (QM/MM)
methods to identify stable cation exchange sites
within the pores and study the influence of adsorbate
interactions (Figure 16). These results were compared
to high resolution X-ray diffraction (HR-XRD) and
infrared (IR) measurements of probe molecules to
elucidate the ion location and how this is modified by
interaction with adsorbates.
Diffusion of reactants and products to and from the
active sites within the zeolite pores is a key part of the
catalytic cycle and can have a significant impact on a
catalyst’s performance. Therefore an understanding of
this process is crucial to optimising the use of zeolites
as catalysts. An ongoing project is using modelling to
understand diffusion of various molecules within these
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(a) (b)
2.869 2.177
2.148
2.020 2.035
2.010
2.562
Fig. 16. Two low energy sites for Cu+ identified using: (a)
interatomic potentials; and (b) QM/MM methods
materials, including NO, NH3, H2O, propane, xylene
and CO2. The atoms in a zeolite can be arranged in a
variety of ways to form rings, channels and pores with
different sizes and dimensionalities, leading to a large
number of possible framework structures. Molecular
dynamics (MD) simulations are being used to try and
understand the influence of ring size, pore volume,
dimensionality and chemical composition on diffusion
through the framework and to predict which structures
and compositions would allow optimal diffusion.
The self-diffusion coefficients calculated using MD
simulations can also be measured using experimental
techniques such as pulse field gradient-nuclear
magnetic resonance (PFG-NMR) and quasi-elastic
neutron scattering (QENS) techniques and a project
is underway in collaboration with University of
Cambridge, UK, and the UK Catalysis Hub at Harwell,
UK, to measure diffusion of selected molecules in
selected frameworks to compare with MD simulations.
Some initial MD simulation results investigating xylene
diffusion in USY are presented in Figure 17 for ortho-,
meta- and para-xylene. Figure 17 shows diffusion
coefficients at temperatures between 300 K and 700 K
for each isomer. The diffusion coefficients increase with
temperature and indicate that diffusion of the para
isomer is faster than meta or ortho isomers. Initial PFG-
NMR measurements at University of Cambridge at
318 K gave a diffusion coefficient of 4.6 × 10–10 m2 s–1
which is in good agreement with MD simulated values
of 5.92 × 10–10 m2 s–1 at 323 K.
6. Underpinning Research
In addition to the more applied research reported
above, a key philosophy is to look at underpinning
270 © 2015 Johnson Matthey
research for the methods used to enable continuous
improvement in modelling capability. This research is
often carried out in collaboration with academic groups.
We now proceed to discuss some of the academic
collaboration Johnson Matthey has been involved in
and how the underpinning knowledge is being used to
improve understanding of catalytic materials.
6.1 Redox Active Oxides and Metal Support
Interactions
Certain oxides provide a challenge to standard
computational methods. Working with academics at
Cardiff University, UK, and also via a Royal Society
Industrial Fellowship at University College London
(UCL), UK, we have been running academic projects
looking at pragmatic ways to model ceria and other
redox active metal oxides for catalytic activities. A
pertinent question in this work was whether trends in
metal screening studies need to go beyond standard
DFT methods (Figure 18). The inclusion of the so
called Hubbard U parameter has been found not
only to be vital for obtaining the ‘correct’ electronic
structure (105), but also to have a significant influence
on obtained formation energies and, importantly for
catalysis, shows that reaction energetics can be highly
sensitive to the choice of U (Figure 19) (105–107).
Once a reasonable model for the support phase of
the catalyst is obtained, the interaction between the
nanoparticle and the support must be considered.
A crucial question here is: how big are your
nanoparticulate catalysts? The answer clearly has a
bearing on how to consider modelling the system. For
instance Figure 6 shows three separate regimes for
catalysts of different sizes: smaller than 2 nm, between
2 nm and 3 nm and beyond 3 nm where the facets of
3.5
3
Ds, m2 s–1, ×10–9
2.5
2
ortho
1.5 meta
1 para
0.5
0
0 100 200 300 400 500 600 700 800
Temperature, K
Fig. 17. Diffusion coefficient (Ds) as a function of
temperature (T) for ortho, meta and para xylene in zeolite
structure USY
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(a) (b) (c)

5 5 50
0 0 0
2 5 5.5
4 4 40

Density of states
Density of states

Density of states
3 3 30

2 2 20

1 1 10

0 0 0
–10 –8 –6 –4 –2 0 2 4 –10 –8 –6 –4 –2 0 2 4 –6 –4 –2 0 2 4 6
Energy, eV Energy, eV Energy, eV
Fig. 18. Density of states calculated using standard DFT (red) and with the Hubbard U correction (blue): (a) lanthanum oxide
(La2O3), wide band gap oxides are reproduced quite well; (b) palladium (II) oxide (PdO), standard DFT predicts PdO to be
a metal, the Hubbard U correction is required to obtain the correct band gap (as seen in Figure 13, this also improves the
calculated energetics); (c) CeO2, whilst the overall band gap (2p–5d) is reproduced well with standard approaches, the width
and location of the Ce-4f is highly sensitive to the choice of Hubbard U parameter, it is this state that is responsible for the facile
redox properties of CeO2 (104)

(a) (b)
CeO2 + CO CO/CeO2 CeO2–d + CO2
2 0

1
–1
Adsorption energy, eV

0
Energy, eV

–1 –2
0.0 eV
ΔE (Pd4O4) 2.5 eV
–2 ΔE (band gap) 4.5 eV
ΔE (vacancy) –3 5.5 eV
6.5 eV
7.5 eV
–3 8.5 eV

0 1 2 3 4 5 6 –4
U, eV
Fig. 19. (a) dependence of various properties of PdO as a function of Hubbard U parameter, compared to benchmark results.
Vacancy formation energy compared to Heyd-Scuseria-Ernzerhof (HSE) calculations of Delley (106). Band gap compared
to (107) and Pd4O4 compared to in-house coupled cluster calculations. The region where the difference in properties and
energetics approach zero identifies the required value of U; (b) CeO2 reaction profile adapted from (105), here the acute
dependence of reaction profile on the choice of U parameter is illustrated, which necessitates a deeper study of choosing U for
catalyst problems (105)

the nanoparticle are sufficiently large to begin to think (a) <2 nm: a regime that is modulated by both electronic
in bulk terms (it should be noted the 3 nm bound is a and geometric effects and significantly different
slightly arbitrary choice of bound for this regime). From reactivity from the bulk terminated surfaces would
Figure 7, bulk-like electronic structure can be observed be expected
even before the facets grow significantly large. This has (b) 2–3 nm: a regime where the intrinsic electronic
now been confirmed by massively parallel calculations nature of the metal is ‘bulk-like’, but influence of
of nanoparticles (108–110). This suggests the following transport or limited numbers of a given facet could
general regimes: be influencing the observed catalysis (for example

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the availability of hydrogen in the methanation
reaction)
(c) >3 nm: the geometry and electronic influences are
sufficiently bulk-like to use extended surfaces as
‘good’ models.
In general the size of a nanoparticle has a profound
influence on the observed chemistry and subsequent
catalytic behaviour. This has been well documented for
Au, however limited attention has been given to other
metals (111, 112). In Figure 20, this point is illustrated
for the activation of methane over silver. Not only does
the small size increase the activity of the particle relative
to the extended system, it produces a catalyst that is in
a different chemical state, thereby opening up chemical
routes that would not otherwise have been present.
For small clusters and nanoparticles, the combination
of small size and the presence of surface oxide species
opens up even more combinations of chemistry. For
the case of a small nanoparticle which can be modelled
explicitly, the presence of the support introduces an
interfacial region that is critical for the chemistry and
for the case of reducible oxides it also changes the
availability of oxygen for reaction.
6.2 Metal Support Interactions
The chemical interactions between a metal particle
and its metal oxide support are of critical importance
for the chemical industry and have been the focus
of numerous computational modelling investigations
(113–118). The typical size of these metal particles
is of the order of the nanometre. At such scales the
interaction of the particle with its chemical surrounding
is of great importance as it impacts its stability (with
public health and economic impacts) and may impact
its catalytic activity as well. As a consequence, a PhD
project in collaboration with UCL was initiated with the
aim of using DFT computational modelling methods to
investigate how transition metals such as Pd, Pt and Ni
interact with an α-alumina support.
The initial investigation studied how single metal
atoms adsorb on the (0001) and (1102) α-alumina
surfaces. On both surfaces, the binding strength
follows the trend Pt>Ni>Pd (119). When bonding to the
surface, all transition metals promote a charge transfer,
moving electron density from a neighbouring surface
oxygen to a surface aluminium atom (Figure 21).
In order to take into account alumina’s strong affinity
for water, a thermodynamic model of a different surface
environment was developed. By including the chemical
potential of water in the gas phase it was possible
to compute the Gibbs free energy of several water
coverages of α-alumina surfaces and to predict the state
of the surface at a given pressure and temperature.
Figure 22 presents the evolution of the Gibbs free

(a) (b)
3 3

NO* NO*
2.5 CH3* 2 CH3*
CH3O* CH3O*
2O* 2O*
2 2H* 2H*
1
1.5

1 0
eV

eV

0.5
–1
0
–2
–0.5

–1 –3
Reaction coordinate (gas → surface) Reactioncoordinate
Reaction coordinate(gas
(gas→
→surface)
surface)

Fig. 20. Free energy diagrams for surface species present on: (a) a Ag {111} facet and (b) 13 atom cluster: solid = 423 K,
dashed = 623 K, dot-dashed = 823 K. It can be seen for the Ag {111} surface only O is present at low temperature and at higher
temperatures the surface is clean. However for the small cluster at 423 K, O, H, NO and CH3O are present, while at 623 K
O and NO are present and at 823 K, O is still on the surface. The presence of O has significant influence on the calculated
activation barriers. Eact[Ag {211}] = 2.15 eV, Eact[Ag13] = 1.57 eV, Eact[Ag13O6] = 0.74 eV; implying that O covered Ag13 is as
active as Ni for the dissociation of methane (8)

272 © 2015 Johnson Matthey

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Fig. 21. Top view of an adsorbed Pd single atom on (0001)
α-Al2O3 Figure adapted from (119)
energy of the clean, low (5 OH nm–2) and high hydrated
(10 OH nm–2) states of the (0001) surface. At 3.2 kPa,
the (0001) surface gradually changes from a heavy
hydration state to a fully clean surface at around 900
K. On the (1102) surface, the transition between the high
OH coverage and the clean surface is much more sudden
without an intermediate moderate hydration state (120).
Surface hydration has a strong impact on the
interaction of the transition metal with its support as
the surface aluminium sites are now fully occupied by
OH groups and are not available to receive electron
density moved from surface oxygen atoms. Instead,
upon adsorption, all three investigated transition metal
atoms trigger the rupture of a surface OH group,
followed by the migration of the hydrogen atom to the
metal atom. This mechanism is called ‘spill-over’ and
3.0
2.5
Surface energy, J m–2
2.0
1.5
1.0
0.5
0.0
200 400 600 800 1000 1200 1400 1600
Temperature, K
Fig. 22. Gibbs surface free energy at 3.2 kPa water partial
pressure for the clean (blue), 5 OH nm–2 (green), and 10 OH
nm–2 (red) hydration coverage of (0001)) α-Al2O3 (Adapted
with permission from (120). Copyright (2003) American
Chemical Society)
273 © 2015 Johnson Matthey
enables a significant stabilisation of Pt and Ni atoms on
the alumina surface (120).
In order to gain some insight into the catalytic activity
of supported metal nanoparticles, the interactions
of a carbon monoxide probe with a supported Ni6
nanocluster has been studied. CO was chosen for its
relative simplicity and its wide use in catalytic processes
such as steam reforming, where supported Ni catalysts
are also of relevance. The (0001) α-alumina surface
has a strong influence on the CO interaction with
the Ni6 cluster. The favoured adsorption site on the
supported Ni6 cluster is on a hollow site on the side of
the particle. On that site, CO is also able to interact with
a surface aluminium atom (Figure 23) (121). The CO
bond is elongated (1.28 Å vs. 1.13 Å in the gas phase
and 1.20 Å on a (111) Ni hexagonal close-packed (hcp)
site) and its stretching frequency is lowered (1397 cm–1
vs. 1899 cm–1 on a (111) Ni hcp site). This dramatic
activation of the CO molecule illustrates how, even
though considered as inert, the catalyst support may
play an active role in the reaction cycle.
For small nanoparticles, it is important to provide an
explicit computational model to describe mechanistic
aspects of sub-nanometre particles supported on
oxides. Work in collaboration with David Willock,
Cardiff University, has been bringing together studies
on redox active supports and small metal nanoparticles
in a bid to understand the metal support interaction and
its influence on reactivity (122). For the probe reaction
of CO oxidation, new mechanistic pathways have
been opened up due to the metal/oxide interface that
radically changes the rate-determining step (Figure 24)
(123). The theme of metal support interaction has also
seen some experimental contribution and recent work
with Tsang’s group in Oxford has been published on the
Fig. 23. Side view of CO on the Ni6 (0001)) α-Al2O3 system
(Adapted with permission from (121). Copyright (2010)
American Chemical Society)
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(a) (b)
O..CO (ts)
100
catalyst
50 + CO (g)
E Grey: [O] = Au-O
0
Black: [O] = Fe-O
–50 C, D

–100 B

–150
A
–200
CO (ads)
–250
–300
CO2 (ads)
–350

Fig. 24. (a) Au_10 nanoparticle adsorbed on iron (III) oxide (Fe2O3) (0001) surface, (blue: Fe, red: surface oxygen, yellow: Au,
grey: carbon, green: CO oxygen); (b) reaction profile for the adsorption and reaction of CO with different surface O in the vicinity
of the Au cluster. It can be seen there are a several distinct adsorption site Fe2O3, Au and interfacial, that lead to very different
adsorption energies, furthermore the different reacting surface oxygens also lead to different activation barriers. (Adapted from
Scott Hoh PhD thesis (123))

role of hydrogen spill-over influence on the reducibility
of ceria supported pgm catalysts (64).
Obtaining an explicit description of large metal
nanoparticles interacting with an oxide support is still
a computational challenge beyond current computing
capacity. However, a simple thermodynamic screening
model has been developed with the potential to predict
the general behaviour of certain transition metal/oxide
support combinations, in the limit of large nanoparticles.
Taking inspiration from the field of electrochemistry
where a chemical reaction is considered in terms
of the half-reaction, we can consider the following
approximations:
(a) metal supported oxides can be split into two
components (metal and oxide)
(b) redox catalysts can be considered analogous to
electrochemical half reactions
(c) one half reaction occurs on the metal, the other on
the oxide.
Taking the example of simultaneous CO oxidation
and NO reduction it can be assumed that NO reduction
occurs on the metallic component while CO oxidation
occurs on the oxide component. Calculating the free
energy profile for a simplified reaction pathway allows
firstly existing databases of metal components to be
used, secondly new databases to be developed for
the oxide component and finally metal/oxide pairings
to be identified using calculations that are currently
tractable on available resources. Figure 25 illustrates
the approach being used in the example of CO and
NO. Early results in this area are promising and new
methods are currently being explored to screen for
novel catalyst candidates.
Whilst models can be developed either explicitly
or indirectly for the metal/support interaction for the
two outer-bounds of the nanoparticle regimes under
investigation, there is still a significant computational
challenge in simulating the intermediate regime. The
following section describes work towards developing
a capability that will allow the 2–3 nm regime to be
tackled explicitly, starting with an electronic structure
theory of the metal nanoparticle itself.
6.3 Large-scale Calculations of Metal
Nanoparticles
One of the significant barriers to developing complex
models of real catalysts is the limitation on system size
that can be tackled explicitly. Significant progress can
be made with a judicious choice of model and some
prior understanding of the system in question. If one is
simply interested in geometric structure then arguably,
embedded atom or other parameterised potential
approaches can be utilised (124, 125). However
in catalysis, especially when trying to understand
chemical activity, there is often interest in linking
the electronic structure to reactivity. This requires
methods for conducting large scale electronic structure
theory calculations, for instance computer codes with
favourable scaling over many computer cores (for
example GPAW, Order-N Electronic Total Energy
Package (ONETEP) (126, 127)) or semi-empirical
approaches (128).

274 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X687975 Johnson Matthey Technol. Rev., 2015, 59, (3)

4 Au
Ag
Ceria surface Cu
2 Pd
Pt
Ni
Rh
0 Co
Ru
ΔG (450 K), eV
Fe
Re
–2 Mo
W

–4
Metal surface

–6

–8
) * M * * * M *
(g M
O
M
O
M
O 5N
2
NO NO *+ + +
O + 0.
)+ )+ M
N N2 5N
2 5 N2 )+
(g (g + 0.
5
0. 0. (g
CO ) )+
CO (g )+ x*+ (g CO
2

CO (g O
2
CO CO CO

Fig. 25. Reaction profile for the NO reduction, CO oxidation, occurring on a series of metals left hand side and Ce surface, right
hand side. The highlighted dashed line illustrates the interpolation between reactants and products. To a first approximation this
interpolation minimises the free energy pathway and shows the region where an optimal catalyst can be found

One part of this research is looking at exploiting and the propensity for the oxidation state of the
the linear scaling capabilities of ONETEP through surface to change during reaction. A significant
collaboration with Chris-Kriton Skylaris, Southampton challenge to utilising the DFTB approach is to find
University, UK. Enhanced functionality of ONETEP has truly transferable parameters to describe all of the
been exploited to help in the simulation of metals (129) necessary interaction present in the simulation
and work is now underway benchmarking speed and (130). Figure 26 illustrates geometrical structures
scaling for the adsorption of molecules such as O2, CO, obtained from ONETEP, GPAW and DFTB for
OH and atomic O. The difference in adsorption energies nanoparticles that are tractable with current
between constrained but pre-optimised nanoparticles computational resources, the future will see this
and ligands and between fully geometry-optimised capability extended.
systems of nanoparticles and ligands has been studied There are several fundamental experimental projects
by looking at various sizes of cuboctahedral Pt clusters to augment the theoretical work on nanoparticles.
(Pt13, Pt55, Pt147) and comparing to more conventional The first of these involves the Nellist group from
slab models. The results show significant deviations Oxford Materials, UK, who have derived experimental
in binding strength between the fully relaxed and methods using quantitative annular dark-field scanning
constrained systems. transmission electron microscopy (ADF-STEM)
Another project with the University of Limpopo, (131). Pt nanoparticle atomic coordinates have
South Africa, is developing parameters to describe been determined for particles up to Pt943 atoms. The
Pd nanoparticles and their interaction with oxide systems were geometry optimised using a damped
supports via the semi-empirical, density-functional MD and interatomic force-field approach, before being
tight binding (DFTB) approach, which potentially electronically minimised in ONETEP and studied
allows thousands of atoms to be simulated using quantum mechanically. Atomic oxygen adsorption
limited computational resources. A model system calculations were then performed on the most exposed
to understand the usefulness of this approach facet, which exhibits fcc-{111} surface symmetry and
has been methane oxidation using Pd supported the least coordinated sites were found to be the most
on titania (TiO 2). This system has a number of strongly binding, agreeing with terrace measurements
complexities, including the metal/ceramic interface from experimental literature.

275 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X687975 Johnson Matthey Technol. Rev., 2015, 59, (3)

methods are being developed to create well defined

(a) (b) nanoparticle samples for use in ambient pressure
X-ray photoelectron spectroscopy (XPS) synchrotron
beamlines (132). The ultimate aim is to bridge the
ubiquitous temperature, pressure and materials gaps
between surface science and real catalysts. The
ambient pressure XPS allows the oxidation of different
sized nanoparticles to be observed as a function of
(c) (d) reactive atmosphere, which in turn can be correlated
back to theoretical predictions. This project is ongoing
and in the future will make use of the forthcoming
versatile soft X-ray (VERSOX) beamline at Diamond
Light Source, Harwell, UK, to develop even further new
understanding of catalysis materials.

6.4 Moving Beyond the Atomic Scale

Fig. 26. Representations of geometrically relaxed
nanoparticles, calculated using the different approaches
discussed in the text. (a) Pt309 nanoparticle electrostatic
potential and (b) Pt309 electron density, both calculated
using ONETEP; (c) Pd321 nanoparticle calculated using
the DFTB + approach; (d) 79 atom Pd/Pt core-shell with a
monolayer of O adsorbed calculated using GPAW
The second experimental project is looking at
methane oxidation, in order to provide data about
nanoparticle surface composition under a reactive gas-
phase atmosphere that in turn can be used to validate
theoretical predictions. The project is being run with
Professor Georg Held, University of Reading, UK, and
The emerging field of modelling across length scales
is ideally suited to modelling catalysis since catalyst
solutions rely not only on the intrinsic chemical
properties of an active material, but also on the transport
properties of the material at different scales. Figure 27
(133) illustrates the case of an automotive monolith,
highlighting the levels that need to be modelled to
develop a holistic description of the catalytic solution.
A complete description of a technical solution includes
describing, for example, the atomic or electronic level
of matter, the porous structure of the catalyst layer
(at two distinct levels: small nanopores and large
macropores) and the reactor itself. Furthermore it also

Picosecond Seconds, minutes

Minutes, hours
Femtosecond
Days
Microscale
(macropores)
Nanoscale
1000 (mesopores)

900
macroscale
800
Inlet ck (z), T (z) ~1 mm
700 gas
0 z l
~10 cm
600

500 ~100 nm
400
0.0 0.5 1.0 1.5
~10 µm

Fig. 27. Schematic illustrating some of the regimes encountered when modelling a catalyst solution, in this case a monolith
reactor for emission control. Starting at the left hand side we have the intrinsic kinetics resulting from the atomic scale
interactions, moving across to the meso and macroporous structure where diffusion of the reactant gases is necessary to find
the active catalytic sites, finally on the right hand side the macroscale model of the reactor channel in the monolith. (Adapted
from (133))

276 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X687975 Johnson Matthey Technol. Rev., 2015, 59, (3)

requires the study of different time scales ranging from
femtoseconds (the timescale on which the chemistry
happens) to years (corresponding to the expected
lifetime of the catalyst). A combination of physics,
chemistry and engineering are required to generate
statistical methods and engineering models, which
along with chemical insight into mechanisms will
provide a more complete picture of the catalytic system.
This project started through a Royal Society
Industrial Fellowship held at UCL, Johnson Matthey
Technology Centre and the Institute of Chemical
Technology, Prague. Its aim is to look at applying the
Prague group’s meso-scale methods to simulation of
transport and reaction in porous catalysts (133–142).
This project has been developing over the last few
years and has an experimental component, which
is essentially for benchmarking and validating the
theoretical methods. Through the careful preparation
of active catalyst it has been possible to construct
layered catalysts consisting of a uniform active layer
overlaid by an inert layer with well-defined morphology
(thickness, porosity, particle size) that serves as a
diffusion layer (Figure 28) (143, 144).
Through this approach it has been possible, firstly, to
validate the computational models by simulating the
transport and activity of the precise geometry prepared
in the lab; and secondly, to develop a novel approach
to determining the diffusivity of gases through porous
media. This second aspect is important because
it provides insight into the structural properties of
the catalyst layer and how they influence its overall
performance, as well as providing a simple relationship
for determining diffusivity that can be utilised in simpler
models of an entire catalytic reactor (144). With the
development of ab initio oxidation models a fully holistic
ab initio description of the catalytic system is becoming
closer.
7. Research Outlook
This brief review has described some of the projects
run within the atomic-scale groups at Johnson Matthey.
Looking to the future, the following areas appear as
natural progressions. Broadly speaking there are three
aspects:
Firstly, theoretical development and understanding.
Continued work on model systems aims to enhance the
description of nanoparticles and oxides and ultimately
bring them together. The description is not just about the
structure of the material, it is perhaps more importantly
about using thermodynamic models to understand the
state of a catalyst under reaction conditions. If one has
a good model of the catalyst under reaction conditions,
the reaction can be decomposed to its elementary
steps and the key bond making and breaking that
controls the activity and reactivity of a given material
can be understood.
Secondly, further development of the correlation
between a theoretical understanding of catalyst
structure, activity and stability with experimental
characterisation. There has undoubtedly been huge
progress in this respect over the last two decades.
However, specific challenges remain. For instance
the combination of synthesising ideal shapes and

0.5 0.08
r CO, kmol s–1

0.4 0.06
y CO, %
inert

0.3 0.04

0.2 0.02
0.1 0.00
active

0.0

20 µm

Fig. 28. (a) Scanning electron micrograph depicting the inert alumina layer, active Pt/alumina layer and substrate material; (b)
simulated concentration profile of CO in reconstructed porous media; (c) rate of CO consumption as a function of position in the
porous media. Note the activity is purely located in the active region of the catalyst. (Adapted from (144))

277 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X687975 Johnson Matthey Technol. Rev., 2015, 59, (3)
structured nanoparticles for catalyst testing, with
advanced characterisation techniques (for example the
upcoming VERSOX beamline at Diamond) along with
the detailed models from ab initio theory, provides an
exciting prospect for developing a deep fundamental
understanding of catalyst materials.
Thirdly, the possibility of going beyond catalyst
materials problems to include thermodynamic
modelling (using the MTData code (145)) and
process modelling using tools like gPROMS (146).
Furthermore, traditional materials physics problems
can also be studied, for instance smart materials
where the challenge lies in describing both the
thermodynamic and electronic properties adequately
to make material predictions. Another burgeoning
area is in battery materials technology where
simulation and modelling will play a significant role.
8. Conclusions
To conclude, if the last twenty years have seen growth
in the capability of computational chemistry and
widespread acceptance of the field as a sub-discipline
of science, the next two decades hold the prospect
of even greater progress. Utilisation of petascale
computing, the accessibility of high performance
computing and open source code development
means that even larger and more complex systems
are accessible and can be tackled by more
people. Multiscale models that capture not only the
fundamental physics and chemistry of the electronic
and molecular level process, but also the macroscopic
properties of the device in question will also become
routine. Automation of simulations coupled with high
throughput synthesis will revolutionise the way in which
we discover new materials. Atomic-scale modelling
and its subsequent expansion to other scales is
helping Johnson Matthey be part of this computational
revolution that will continue to provide increasing
opportunities and will be at the heart of developing
catalytic and materials science into the 21st century.
9. Acknowledgements
The work presented herein is a result of a number
of internal and external collaborations. It is hard to
acknowledge everyone who has been involved in the
projects over the last seven years or so, however along
with our experimental colleagues within Johnson
Matthey, the Engineering and Physical Sciences
Research Council (EPSRC) should be acknowledged
278 © 2015 Johnson Matthey
for funding of Collaborative Awards in Science and
Engineering (CASE) and doctoral training centre
students. Misbah Sarwar acknowledges J. L. Gavartin
(Accelrys) and the Technology Strategy Board (TSB)
for support in the iCatDesign project (DTI Project No:
/5/MAT/6/I/H0379C). Glenn Jones acknowledges the
EU for supporting the IMPRESS project (Contract
NMP3-CT-2004-500635, co-funded by the European
Commission in the sixth Framework Programme and
European Space Agency) and the Royal Society for
supporting his industrial fellowship at UCL (IF090100).
Ludovic Briquet acknowledges the EU for supporting
his Framework 6 Program Marie-Curie Early Stage
Training studentship. Crispin Cooper gratefully
acknowledges support from the EPSRC Collaborative
Training Account: UCL (GR/T11364/01). Glenn Jones
and Crispin Cooper also acknowledge the UK’s super
computing facility for time on HECToR, which has
now been superseded by ARCHER, through the UK’s
HPC Materials Chemistry Consortium (EPRSC: EP/
L000202).
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The Authors

Misbah Sarwar is currently a Principal Scientist at Johnson Matthey Technology Centre (JMTC),
Sonning Common, UK. She has an MSci in Chemistry from University College London (UCL), UK,
and a PhD from UCL and the Royal Institution (RI). Misbah joined Johnson Matthey in 2007 to work
on the Technology Strategy Board (TSB) funded project iCatDesign. In April 2014 Misbah joined
the Emission Control Technology research group at JMTC.

Crispin Cooper is a computational chemist working in the JMTC Emission Control research group.
He has a BSc (hons) in Chemistry for Drug Discovery from the University of Bath, UK, and an
EngD in Molecular Modelling and Materials Simulation from UCL. He has recently joined Johnson
Matthey following an industrial postdoctoral project modelling complex metal oxide catalyst
materials.

Ludovic Briquet is a Senior Scientist at JMTC, Sonning Common. He gained his PhD in Chemistry
at UCL, UK, in 2010 and specialised in molecular modelling applied to various systems. His main
interests however lie in surface science and catalysis.

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Aniekan Ukpong is a Senior Scientist at JMTC, Pretoria, where he has been working since 2013. He
completed his PhD in Physics at the University of Cape Town, South Africa, in 2008. His research
focuses on the fundamental study of materials from theory to applications.

Christopher Perry originally trained as a bio-inorganic chemist. He became interested in modelling

whilst lecturing at the University of the Witwatersrand, South Africa. Prior to that, he completed
two postdoctoral research projects: one in nuclear magnetic resonance (NMR) spectroscopy at
Manchester University, UK, and a second in organic synthesis at the University of the Witwatersrand.
He has been working at Johnson Matthey since 2013 and is a Senior Scientist at JMTC, Pretoria.

Glenn Jones has extensive experience in the fields of surface science, catalysis and computational
materials chemistry. He gained his PhD from the University of Cambridge, UK, before moving to the
Technical University of Denmark as a post-doctoral student. He joined JMTC, Sonning Common,
UK, in 2008 and was awarded a Royal Society Industrial Fellowship in 2010 which he held jointly
between JMTC and UCL. He moved to Pretoria, South Africa, in 2013 to initiate JMTC’s new
modelling laboratory in South Africa, where he is currently Research Manager.

283 © 2015 Johnson Matthey

http://dx.doi.org/10.1595/205651315X688587 Johnson Matthey Technol. Rev., 2015, 59, (3), 284–286

JOHNSON MATTHEY
TECHNOLOGY REVIEW www.technology.matthey.com

In the Lab

Combining Catalyst and Reagent Design for

Electrophilic Alkynylation
Johnson Matthey Technology Review features new laboratory research

Jérôme Waser is an Associate Professor in the

Institute of Chemical Sciences and Engineering at the About the Researcher
Ecole Polytechnique Fédérale de Lausanne (EPFL),
Switzerland. His research focuses on the development
of new reactions based on catalysis and synthons with
non-conventional reactivity.

About the Research

Alkynes are essential building blocks in synthetic and

medicinal chemistry, materials science and chemical
biology. Due to their linear geometry and electronic
properties, they are important structural elements in
supramolecular assemblies and organic materials. The
unique reactivity of the triple bond also makes them
ideal precursors of other functional groups, not only
in a classical chemistry setting, but also for biological
applications. The development of new methods to
make alkynes is consequently an important field of
research in fundamental organic chemistry.
The transfer of terminal alkynes is one of the most
successful approaches for introducing triple bonds into
organic molecules. This field has been largely dominated
by the use of acetylide anions or their equivalents as
nucleophiles, due to their ease of formation. Processes
such as the Sonogashira coupling and the addition
of alkynes to carbonyls are highly reliable and are
widely used in synthetic chemistry. Nevertheless,
the drawback of this approach is that alkynes can
be introduced only to the electrophilic positions of
molecules. If good electrophilic alkyne synthons were
available, alkyne chemistry would become even more
versatile for applications in chemistry and in biology.
• Name: Jérôme Waser
• Position: Associate Professor
• Department: Institute of Chemical Sciences and
Engineering
• University: EPFL
• Street: EPFL SB ISIC LCSO, BCH 4306, Av. Forel 2
• City: Lausanne
• Post Code: 1015
• Country: Switzerland
• Email Address: jerome.waser@epfl.ch
Waser’s group have designed new methods for
the introduction of alkynes into organic molecules
using transition-metal catalysis and electrophilic
alkynylation reagents. The direct alkynylation of
electron-rich heterocycles was developed first
(Scheme I). The group harnessed the unique properties
of ethynylbenziodoxolone (EBX) reagents for the
gold-catalysed alkynylation of indoles, pyrroles,
thiophenes and furans. The cyclic hypervalent iodine

284 © 2015 Johnson Matthey

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C–H Alkynylation: most electron-rich position Domino cyclisation-alkynylation: unreactive position

R1
R R1
R R R
N N S O
H O
R2 MeO N
R
AuCl catalyst SiiPr3
O I SiiPr3 O I
Room temperature, F 3C AuIII or PtII catalyst
O open flasks F3 C Room temperature,
TIPS-EBX TIPS-F6-EBX
open flasks

SiiPr3
SiiPr3
R R R R1
R1 i
N S O Pr3Si
H SiiPr3N SiiPr3 SiiPr3 N
R O R
R2
C2-pyrroles and C3-indoles C2-thiophenes C2-furans C3-furans C5 and C6-indoles
48–93% 48–83% 45–90% 53–97% 31–84%
21 examples 21 examples 12 examples 12 examples 24 examples

Scheme I. Gold and platinum-catalysed C–H alkynylation vs. domino cyclisation functionalisation for accessing alkynylated
heterocycles

reagent 1-[(triisopropylsilyl)ethynyl]-1,2-benziodoxol- To access triple bonds on other positions of aromatic

3(1H)-one (TIPS-EBX) (Figure 1) was initially
discovered by Zhdankin and although it displays an
enhanced stability in the presence of transition metals,
it still acts as a strong electrophilic alkyne source. The
alkynylation of heterocycles with TIPS-EBX is a user-
friendly method, which proceeds in open flasks at
room temperature and can tolerate a broad range of
functional groups.
The developed C–H alkynylation is highly selective
for the most electron-rich position of heterocycles.
Fig. 1. X-ray structure of TIPS-EBX
rings, the group decided to use a new strategy
based on a domino cyclisation-alkynylation process
(Scheme I). This approach was first applied to the
synthesis of 3-alkynylated furans starting from allene
ketones. The key for success was electronic tuning of
the hypervalent reagent, with TIPS-F6-EBX being most
successful. The synthesis of indoles alkynylated on
the benzene ring is even more challenging, due to the
much higher reactivity of the pyrrole ring. In this case,
no successful C–H functionalisation method has yet
been reported. Using the platinum-catalysed domino
cyclisation-alkynylation of homopropargylic alkynyl
pyrrole ethers, 5- or 6-alkynylated indoles could be
synthesised in good yield and selectivity. Overall, the
domino strategy is therefore highly complementary to
C–H alkynylation.
To introduce alkynes onto C–sp3 centres, Waser’s
group focused on the metal-catalysed multi-
functionalisation of olefins. The intramolecular oxy-
and amino-alkynylation of olefins using TIPS-EBX and
a palladium(II) catalyst to give lactones and lactams
at room temperature in open flasks was developed
first (Scheme II). To access tetrahydrofurans and
pyrrolidines, the combination of a Pd(0) catalyst and
alkynyl bromides was more successful. In this case,
the reaction was run at 65ºC under inert gas. Currently,
the transformation cannot be made intermolecularly.

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22 examples O R O Me SiiPr3 10 examples

R3 43–87%
55–92% R3
O I SiiPr3
R1
O
O
Boc TIPS-EBX
20 examples N R Br R R 3
O SiiPr3 10 examples
51–86% R3 69–83%
Pd0 catalyst PdII catalyst R2
R1 65ºC, N2 Room temperature,
F3C XH 2 O
air
28 examples 4 O R2 R3 R X 20 examples
R R1 R 3
NTs SiiPr3
51–98% R N Y 50–89%
R3 R2

Scheme II. Palladium-catalysed olefin oxy- and amino-alkynylation

Nevertheless the group recently reported a first step
in this direction by the use of an in situ tethering
strategy for palladium-catalysed synthesis of vicinal
aminoalcohols bearing an alkyne group starting directly
from allyl amines. The use of trifluoroacetaldehyde in
its commercially available hemiacetal form as a tether
played an important role in this reaction.
In conclusion, the metal-catalysed electrophilic
alkynylation approach has allowed heterocyclic and
aliphatic alkynes to be synthesised with high efficiency.
The obtained products are expected to be highly useful
as building blocks in synthetic and medicinal chemistry,
as well as in materials science.
Y. Li and J. Waser, Angew. Chem. Int. Ed., 2015, 54,
(18), 5438
Y. Li, J. P. Brand and J. Waser, Angew. Chem. Int. Ed.,
2013, 52, (26), 6743
J. P. Brand and J. Waser, Chem. Soc. Rev., 2012, 41, (11),
4165
S. Nicolai, C. Piemontesi and J. Waser, Angew. Chem. Int.
Ed., 2011, 50, (20), 4680
S. Nicolai and J. Waser, Org. Lett., 2011, 13, (23), 6324
J. P. Brand and J. Waser, Angew. Chem. Int. Ed., 2010,
49, (40), 7304

S. Nicolai, S. Erard, D. Fernández González and J. Waser,

Selected Publications Org. Lett., 2010, 12, (2), 384

U. Orcel and J. Waser, Angew. Chem. Int. Ed., 2015, 54, J. P. Brand, J. Charpentier and J. Waser, Angew. Chem.
(17), 5250 Int. Ed., 2009, 48, (49), 9346

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http://dx.doi.org/10.1595/205651315X688596
JOHNSON MATTHEY
TECHNOLOGY REVIEW
Johnson Matthey Highlights
A selection of recent publications by Johnson Matthey R&D staff and
collaborators
EMISSION CONTROL TECHNOLOGIES
Increased NO2 Concentration in the Diesel Engine
Exhaust for Improved Ag/Al2O3 Catalyst NH3-SCR
Activity
W. Wang, J. M. Herreros, A. Tsolakis and A. P. E. York,
Chem. Eng. J., 2015, 270, 582
Fast-SCR was investigated for NOx reduction in internal
combustion engines. H2 addition was found to increase
NO2 formation over a Ag/Al2O3 catalyst. This led to
an improved NH3-SCR activity at low temperature. It
is concluded that NO2 formation before the Ag/Al2O3
catalyst either in the engine or a Pt/Al2O3 based DOC
will improve SCR performance. This NO2 promotion
effect was less at higher temperatures.
Thermochemical Recovery Technology for Improved
Modern Engine Fuel Economy – Part 1: Analysis of a
Prototype Exhaust Gas Fuel Reformer
D. Fennell, J. Herreros, A. Tsolakis, K. Cockle, J. Pignon
and P. Millington, RSC Adv., 2015, 5, (44), 35252
Reformed exhaust gas recirculation (REGR) provides
H2 to the combustion process to recover heat from
exhaust and improve fuel conversion efficiency. A full
scale prototype reformer for gasoline direct injection
engines is presented and its performance is assessed.
The performance is better at higher temperatures with
a decline in performance at lower exhaust temperature.
The reformate quality is also dependent on process
temperature and reactant composition.
FINE CHEMICALS
Palladium-Catalyzed ɑ-Arylation Reactions in Total
Synthesis
S. T. Sivanandan, A. Shaji, I. Ibnusaud, C. C. C.
Johansson Seechurn and T. J. Colacot, Eur. J. Org.
Chem., 2015, (1), 38
New methods for synthesising natural products and
active pharmaceutical ingredients have been explored
using palladium-catalysed ɑ-arylation of carbonyl
compounds. The advantages of this particular method
are an increase in the overall yield, an improved
synthesis scope and a reduction in the number of steps.
287
Johnson Matthey Technol. Rev., 2015, 59, (3), 287–289
www.technology.matthey.com
The significance of palladium-catalysed ɑ-arylation
methods are discussed and a number of case studies
have been included.
The Effects of 1-pentyne Hydrogenation on the Atomic
Structures of Size-selected AuN and PdN (N = 923 and
2057) Nanoclusters
K.-J. Hu, S. R. Plant, P. R. Ellis, C. M. Brown, P. T.
Bishop and R. E. Palmer, Phys. Chem. Chem. Phys.,
2014, 16, (48), 26631
The variation in atomic structures of size-selected Au
and Pd nanoclusters (containing 923 and 2057 atoms)
supported on amorphous carbon films before and after
being exposed to the vapour-phase hydrogenation
of 1-pentyne was studied. The populations of the
nanoclusters were studied at atomic resolution before
and after the reaction using an aberration-corrected
high-angle annular dark field (HAADF) scanning
transmission electron microscopy (STEM). The
atomic structures of the observed nanoclusters were
determined by comparing the multi-slice HAADF-STEM
and experimental images for a full range of cluster
orientations. The results show that Au nanoclusters
consisting of 923 ± 20 and 2057 ± 45 atoms are robust
and exhibit high structural stability. A big proportion of
Pd923 ± 26 nanoclusters, on the other hand, appear to be
amorphous before the treatment and after the reaction
were found to exhibit high symmetry structures which
suggests the reduction of oxidised Pd nanoclusters in
reaction conditions.
FINE CHEMICALS: CATALYSIS AND CHIRAL
TECHNOLOGIES
Stereoselective Synthesis of the Halaven C14-C26
Fragment from D-Quinic Acid: Crystallization-Induced
Diastereoselective Transformation of an α-Methyl Nitrile
F. Belanger, C. E. Chase, A. Endo, F. G. Fang, J. Li,
S. R. Mathieu, A. Z. Wilcoxen and H. Zhang, Angew.
Chem. Int. Ed., 2015, 54, (17), 5108
A series of substrate controlled stereoselective reactions
with crystalline intermediates was carried out via an
α-methyl nitrile to produce a C14–C26 fragment of
halichondrin B/Halaven. The synthesis does not require
© 2015 Johnson Matthey
http://dx.doi.org/10.1595/205651315X688596
chromatography and relies entirely on crystallisation
for quality control. D-quinic acid is the starting material,
providing all four chiral centres, and is readily available.
Raw material cost and waste are both reduced by the
present synthesis.
A Halogen- and Hydrogen-Bonding [2]Catenane for
Anion Recognition and Sensing
J. M. Mercurio, A. Caballero, J. Cookson and P. D. Beer,
RSC Adv., 2015, 5, (12), 9298
Halogen bonding has been little explored outside the
areas of solid state crystal engineering. A novel halogen
bonding rotaxane structure was prepared for use in
anion recognition and exhibits good anion recognition
and sensing properties. An ion templated Grubbs’ II-
catalysed RCM clipping mechanical bond forming
was used to synthesise the structure which contains
both halogen- and hydrogen-bonding macrocyclic
components. 1H NMR spectroscopy and fluorescence
titration experiments were carried out and showed that
the new structure can strongly associate with acetate
and dihydrogen phosphate.
NEW BUSINESSES: FUEL CELLS
Platinum-carbide Interactions: Core-shells for Catalytic
Use
J. L. R. Yates, G. H. Spikes and G. Jones, Phys. Chem.
Chem. Phys., 2015, 17, (6), 4250
Five carbides (TiC, NbC, TaC, WC and SiC) were
investigated using density functional theory with the aim
of determining their suitability as core-shell components
in fuel cell applications. The fcc forms of the carbides
were compared with hexagonal close-packed (hcp)
WC and zinc blende SiC and the latter was found to
support Pt overlayers on surfaces, therefore, showing
potential for full Pt encapsulation. The transition metal
surface resonances (TMSRs) play a vital role during the
adsorption of Pt on fcc (111) carbide surfaces and fcc
(100) was found to be adverse towards Pt adsorption.
Reduced oxygen adsorption energies was displayed by
several Pt-WC surfaces during the oxygen adsorption
study; the authors conclude that ORR activity should be
promoted or maintained with respect to nanoparticulate
Pt catalysts.
PROCESS TECHNOLOGIES
Dual Doping Effects (Site Blockage and Electronic
Promotion) Imposed by Adatoms on Pd Nanocrystals
for Catalytic Hydrogen Production
S. Jones, S. M. Fairclough, M. Gordon-Brown, W.
Zheng, A. Kolpin, B. Pang, W. C. H. Kuo, J. M. Smith
and S. C. E. Tsang, Chem. Commun., 2015, 51, (1), 46
Additives based on polymer or metal adatoms can
modify the electronic structure of metal nanoparticles
but greater understanding of atomic level effects
288
Johnson Matthey Technol. Rev., 2015, 59, (3)
[010] [110] [1010]
[001] [0110]
[001]
[100] [111] [0001]
[010] [110] [1010]
[001] [001] [0110]
Reproduced by permission of the PCCP Owner Societies
from J. L. R. Yates, G. H. Spikes and G. Jones, Phys.
Chem. Chem. Phys., 2015, 17, (6), 4250
is needed to rationally design better catalysts by
surface tailoring. Electronic and geometric effects of
various metals on unsupported Pd nanocrystals were
investigated using the decomposition of HCOOH
to H2 and CO2 as a probe reaction. Bi was found to
occupy high index sites causing a decrease in HCOOH
dehydration, Te occupies terrace sites which reduces
the dehydrogenation rate while Ag induced strong
electronic effects and increased the activity of the Pd
surface sites. Ag and Bi were concluded to be the
most effective additives for a surface reaction, while Te
should be added at corner sites to promote the desired
reaction route.
Surfactant Mediated CO2 Adsorption: The Role of the
Coimpregnation Species
C. M. Starkie, A. Amieiro-Fonseca, S. P. Rigby, T. C.
Drage and E. H. Lester, Energy Procedia, 2014, 63,
2323
Carbon capture and storage requires novel, second
generation adsorbent systems to potentially reduce
costs associated with this technology. Solid supported
amines have been investigated. These consist of basic
amines either tethered or impregnated on silica or
alumina and co-impregnated with surfactant additives.
The mechanisms of adsorption of these systems were
studied and they were shown to have 55% improved
working capacity relative to single component systems.
Triethanolamine and sodium dodecylsulfate produced
the best adsorbent properties.
The Synergistic Effect in the Fe-Co Bimetallic Catalyst
System for the Growth of Carbon Nanotube Forests
D. Hardeman, S. Esconjauregui, R. Cartwright, S.
Bhardwaj, L. D’Arsié, D. Oakes, J. Clark, C. Cepek, C.
Ducati and J. Robertson, J. Appl. Phys., 2015, 117, (4),
044308
© 2015 Johnson Matthey
http://dx.doi.org/10.1595/205651315X688596
The growth of multi-walled carbon nanotube forests using
an active bimetallic Fe-Co catalyst was investigated.
When this bimetallic catalyst system was compared
to pure Fe or Co a synergistic effect is observed.
The height of the forests was considerably increased
and an improvement of the homogeneity in the
as-grown nanotubes was found. The catalyst system
was characterised using energy dispersive spectroscopy
and in situ X-ray photoelectron spectroscopy. The
authors conclude that the growth rate of the nanotubes
is greatly improved in the presence of Fe and Co.
TEM Characterization of Simultaneous Triple Ion
Implanted ODS Fe12Cr
V. de Castro, M. Briceno, S. Lozano-Perez, P. Trocellier,
S. G. Roberts and R. Pareja, J. Nucl. Mater., 2014, 455,
(1–3), 157
The performance of oxide dispersion strengthened
(ODS) ferritic/martensitic steels under irradiation is
studied. This is essential in the design of advanced fusion
reactors. Transmission electron microscopy was used
to characterise a simultaneous triple ion implanted ODS
Fe12Cr steel with the aim of investigating the impact of
irradiation on the grain and dislocation structures, oxide
nanoparticles and other secondary phases present in
289
Johnson Matthey Technol. Rev., 2015, 59, (3)
steel. The ODS steel was irradiated simultaneously with
Fe8+, He+ and H+ at room temperature to a damage
of 4.4 dpa at the Joint Accelerators for Nanosciences
and NUclear Simulation (JANNUS) Saclay facility. The
authors concluded that ODS nanoparticles are very
stable under these irradiation conditions.
An Experimental Investigation of Biodiesel Steam
Reforming
S. Martin, G. Kraaij, T. Ascher, D. Wails and A. Wörner,
Intl. J. Hydrogen Energy, 2015, 40, (1), 95
The optimum operating conditions of a proprietary
precious metal based catalyst for biodiesel steam
reforming was investigated with the aim of preventing
catalyst deactivation. Different operating conditions
include varying the temperature from 600ºC to 800ºC,
applying different pressure from 1 bar to 5 bar and
altering the molar steam-to-carbon ratio from 3 to 5.
Coke formation and sintering have been determined
as the main deactivation mechanisms. The authors
conclude that coking can be reduced by using low feed
flow rates (31 g h–1 cm–2) and a relatively high catalyst
inlet temperature (>750ºC).
© 2015 Johnson Matthey
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