special feature
Finding a future
for manganese
by cutting costs
The yo-yo prices of commodities have affected the powder
metals market as much as others. PM producers are looking
hard at materials they may once have discounted in order to
gain commercial advantage. Joe Capus reports…
C
oncerns over the sky-rocketing
prices of conventional alloy
elements such as nickel, cop-
per and molybdenum used in
traditional high-performance PM steels,
rightly took up a fair amount of discussion
at the summer’s MPIF PowderMet2006
annual conference in San Diego. In a
previous issue of Metal Powder Report,
(July/August 2006) some of the approaches
studied by North American companies
were reviewed. In this article, the subject
will be taken up again in reviewing presen-
tations from European researchers.
Professor Francisco Castro and colleagues
from CEIT and TECNUN, San Sebastian,
Spain, along with co-authors from PM parts
manufacturers AMES of Spain, and Schunk
in Germany, began by noting that a lot of
studies had been made in the past on the
use of manganese as an inexpensive alloy-
ing addition, but these efforts had not led to
significant industrial applications.
Manganese additions have been tried
in various forms: as a pre-alloyed powder
element, as an elemental blended addition
(e g in the form of electrolytic manganese
powder) and in various grades of ground-
up ferro-manganese and master-alloy pow-
ders. While manganese is a highly-effec-
tive and economical hardening agent in
wrought low-alloy steels, in the powder
metallurgy arena it suffers from several
adverse factors that have limited its use.
Thus in pre-alloyed form, manganese low-
ers the compressibility of ferrous-based
powders, while in sintering of admixed
combinations, the high vapour pressure can
result in significant loss of manganese even
during the heating up phase. Furthermore,
20 MPR January 2007
oxides that may form
during atomisation and
in subsequent process-
ing are much harder to
reduce than those of tra-
ditional alloy elements,
even at high temperatures
and low dew points. Such
oxides are particularly
deleterious to mechani-
cal properties of sintered
steels. Also, master alloys
with hard particles (man-
ganese is a carbide-form-
ing element) can cause
accelerated wear of com-
paction tools. Finally, the
hoped-for homogenisa-
tion of manganese in a
ferrous matrix by solid-
state diffusion has proved
Figure 1. Microstructures of Fe-Mn-C compacts after sintering 1
difficult, even at elevated hour at 1120°C. Constant carbon contents of 0.37 per cent; manga-
sintering temperatures. nese master alloy additions of 2 per cent (a and b), 3 per cent (c
Castro et al. set out and d), 4 per cent (e and f ). (After Castro et al.)
to design a new manga-
nese-rich master alloy that would produce atomised powder and the minus 20 micron
a liquid phase at the conventional sintering fraction was used in the experimental work
temperature of 1120ºC and so enhance to blend with various iron–based powders
diffusion of manganese. Based on ther- and graphite to make sintered manganese
modynamic calculations and metallurgical steels. The blend compositions were chosen
considerations they came up with an Fe- to provide manganese levels between 0.75
Mn-C composition containing 35 per cent and 1.5 per cent and combined carbon
manganese and 4.4 per cent carbon. This ranging from 0.37 to 0.67 per cent. Samples
composition was also calculated to have a compacted to 7.25 - 7.35 g/cm³ were sin-
manganese vapour pressure about 10 times tered at 1120ºC or 1160ºC with an atmos-
lower than that of pure manganese or low- phere of 90 per cent nitrogen, 9 per cent
carbon ferro-manganese, at temperatures hydrogen and 1 per cent methane.
above 1000ºC, thus diminishing the poten- Metallographic studies showed that
tial loss of manganese during sintering. The vaporisation of manganese during heating
desired master alloy was prepared as a gas- Turn to Page 22
0026-0657/07 ©2007 Elsevier Ltd. All rights reserved.
 Figure 2. Tensile test curves for PM manganese steels sintered at
1120°C or 1160°C, and containing different amounts of manganese mas-
ter alloy and graphite. HT = heat treated. (After Castro et al.)

to the sintering temperature contributed significantly to alloying of

the iron matrix through diffusion-induced grain-boundary migration.
Liquid phase formation at the sintering temperature also contributed,
but the liquid phase was short lived due to solution of iron in the liquid
phase and the transfer of manganese and carbon to the matrix (Figure
1). Because of the low diffusion rate of manganese in the solid state,
sintering at the higher temperature showed little improvement over that
found at 1120ºC. Nevertheless, the resulting sintered manganese steels
showed attractive tensile properties, attributed to the highly-alloyed
(hence stronger) regions adjacent to the pores and the sintering necks.
Castro et al showed a series of tensile testing curves for manganese
steels based on plain iron, as well as on pre-alloyed steel powders
containing chromium and molybdenum (Figure 2). Heat treatment
of a sintered 1.5 per cent manganese, 0.37 per cent carbon steel by
quenching and tempering increased the yield strength by a factor of
three. The manganese steels based on pre-alloyed powders were shown
to be capable of sinter-hardening, producing sintered hardness values
up to 28 HRC.
The authors concluded that sintered manganese steels prepared
with the master alloy they had designed provide attractive dimensional
and mechanical properties comparable with those of more highly-
alloyed and expensive materials. They verified the suitability of the new
compositions by successfully producing some proto-type components
under industrial conditions (Figure 3).
From another part of Europe, IPS Steel Powder AB of Sweden has
been pursuing for several years now the development of its own high-
manganese/high-chromium master alloy powder using atomisation
with kerosene as a way to avoid oxidation during manufacture. The
objective has been to provide an economical alternative for producing
high-performance PM steels and avoiding the expensive conventional
alloy elements already referred to.
In previous studies presented at the 2005 Montreal and Prague PM
conferences (Metal Powder Report, January 2006, pp. 36-42), Professor
Paul Beiss of RWTH Aachen University, Germany, showed the results of
adding the IPS master alloy powder to either plain iron or a pre-alloyed
steel powder containing 0.85 per cent molybdenum. Carbon contents
ranged from 0.6 to 0.9 per cent. The master alloy contains 10 per cent
chromium, 10 per cent manganese, 1 per cent nickel and 0.9 per cent
carbon, and was added at either 9 per cent or 12.5 per cent levels in
those studies.
Sintered steels prepared with the pre-alloyed base powder showed
yield strengths above 500 MPa after sintering at 1280ºC. Strength was

22 MPR January 2007 metal-powder.net

improved by about 10 per cent by tempering
at 300 - 600ºC. Lower strengths were obtained
for steel samples based on plain iron, so that
approach was not pursued any further as
similar properties could be obtained with
less-expensive conventional materials.
In his San Diego presentation, Professor
Beiss showed the results of further sintering
tests on steels containing the same Cr/Mn
master alloy. From studies of continuous-
cooling transformation diagrams it was esti-
mated that the molybdenum content of the
base powder could be reduced from 0.85
per cent to 0.50 per cent for a potential cost
reduction, if the carbon content was raised
slightly. The new set of test samples were
based on a pre-alloyed 0.50 per cent molyb-
denum steel powder, ATOMET 4001. This
was mixed with 10 per cent of the IPS master
alloy, which had been pre-screened to minus
36 microns to assist in achieving better alloy
homogenisation during sintering. Graphite
was also added to provide total carbon levels
of 0.8, 0.9, and 1 per cent (0.75, 0.81, and
0.91 per cent after sintering). Tensile test
pieces according to ISO 2740 were com-
pacted and sintered in an industrial walking
beam furnace as in the previous tests, for
about 30 minutes at 1280ºC in 70 per cent
nitrogen/30 per cent hydrogen, followed by
slow cooling, resulting in as-sintered densi-
ties of 7.07-7.11 g/cm³. To provide a base for
comparison, a parallel set of test pieces were
made without the master alloy addition, but
with the same carbon levels. Yield strength
in the as-sintered condition was improved
35 per cent by the master alloy addition,
rising to 650 N/mm², or over 50 per cent
above the base steel after tempering at 400 -
500ºC (Figure 4). The optimum carbon level
appeared to be 0.81 per cent, as the tensile
Figure 6: Microstructures of sintered steels made from ATOMET 4001 + 10 per cent IPS master alloy. Combined carbon: 0.75 per cent (left) and
0.91per cent (right). (After Beiss)
metal-powder.net
strength dropped by about 10 per cent at the
higher carbon level of 0.91 per cent. With
0.81 per cent carbon (Figure 5), the tensile
strength exceeded 800 N/mm² for all tem-
pering conditions. With these strength levels,
Professor Beiss claimed that “many high-per-
formance applications in gear boxes could
be served without the traditional 4 per cent
diffusion-bonded nickel”. Microstructures
of the master-alloy-containing steels with
0.75 per cent and 0.91per cent show that
the high sintering temperature of 1280ºC
was insufficient to provide a completely
homogeneous distribution of alloy elements
(Figure 6).
The matrix molybdenum alloy steel trans-
formed to a mix of upper and lower bainite,
depending on the carbon level. The former
master alloy particles were surrounded by a
martensitic zone with a non-etching core of
retained austenite. The results showed that
the molybdenum content in the base pow-
der could be lowered to 0.5 per cent from
0.85 per cent and still obtain satisfactory
mechanical properties.
Figure 4. Yield strength of steels made from
ATOMET 4001 + 10 per cent IPS master alloy
(hatched) compared with the base powder.
Test conditions: S = as-sintered; 2 = temper-
ed 200°C; 3 = tempered 300°C; 4 = tempered
400°C; 5 = tempered 500°C. (After Beiss).
Figure 3. Sintered proto-type component pro-
duced under industrial conditions using man-
ganese master alloy. (After Castro et al.)
It was concluded from these studies that the
results were sufficiently promising to pursue
further economies in alloying cost by inves-
tigating lower master alloy content levels in
conjunction with elemental copper additions.
It would seem that while high prices for
traditional alloying elements persist, the PM
industry will continue in the search for lower-
cost alternative solutions for high-strength
applications. This is an important issue for
the high-performance sector of the PM indus-
try as many competing wrought materials
employ lower-cost alloying elements such as
chromium and manganese.
Figure 5. Ultimate tensile strength of steels
made from ATOMET 4001 + 10 per cent IPS
master alloy (hatched) compared with the base
powder. Test conditions: S = as-sintered; 2 =
tempered 200°C; 3 = tempered 300°C; 4 = tem-
pered 400°C; 5 = tempered 500°C. (After Beiss).
January 2007 MPR 23