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Combining old and new to squeeze every part per billion (ppb) of profit from Steel
Scrap

A “Moore Power Law” describing the empirically observed increase in computer performance
incorporating wind-fall from applied numerical methods (performance X 2, every 18 months)
could well be going on unobserved in the field of phase diagrams so fundamental to the study
of materials and in particular to metallurgy; it’s metal alloy products their chemical reactants,
slags, ceramic and refractory materials used in their manufacturing processes. Methods for
calculating phase diagrammes, commonly known by it’s abbreviation, Calphad, named after
the group established 30 years ago to study such methodologies have now reached relative
maturity. Until now adequately rapid experimental techniques and methodology to fine-tune
these powerful calculation routines appeared to have remained out of reach despite research
which started roughly at the same time as Calphad. This is set to change due to new
combinatorial methods reported recently by R.W.Cahn in Nature (1) and others. From this
excellent assessment and list of references, two key authors, Zhao (7-8), and Xiang (2)
together with their publications in Advanced Engineering Review and Annual Materials
Review (2) respectively were chosen to do a “combinatorial” web search. This produced the
additional reference list (3 to 10). Reassuringly Xiang, Zhao and Cahn, appear on the
reference list together with the up-dated reference to Zhao’s latest work (7). The search added
a further 5 titles to those drawn up by Cahn a year earlier (1). If rapid research on numbers of
publication is any guide, the eight web search listed of papers were all published in 2001
compared with Cahn’s list of 9 significant papers over the last decade( 3 of which were
published in 2001). As surmised by this experienced and highly respected metallurgist and
materials scientist (1), it would appear that this field. is flourishing indeed.

Many excellent examples of the use to which Phase Diagramme Calculation may be put are
given in the literature on alloy design and improvement; from iron based alloys, high and low
alloy steels, stainless steels, through high speed steels & metal cemented carbides, nickel
based superalloys and titanium alloys, to magnetic alloys, solder alloys, intermetallic
compounds and semi-conductor materials (11). From this impressive list, Ishida (11,12)
reports on work published no later than 1997(13,14) namely, the continued interest in one
classical but hopefully disappearing occurrence, that of surface cracking during hot rolling.
Traditionally and more generally, surface cracking is often classed in the loss of ductility or
hot shortness, category of metallurgical defects, of interest to all high temperature
deformation processes and many materials. Surface cracking in many steel grades
incorporating recycled scrap is attributed to residual copper(Cu) and trace elements, in
particular tin(Sn) introduced mainly through ever increasing use of scrap but in some cases
from poorly screened raw materials. For example it has been known to find traces of lead(Pb)
from galena, PbS, contained in fluorspar, CaF2, used to fluidify slag, the complex glassy like
chemical reacting agent, used in steelmaking). Ishida in Japan, like EU steelmakers consider
conservation of energy and natural resources to be of great importance and perhaps, as never
before, of great concern. Continuing effort therefore still appears necessary to ensure efficient
ways of recycling scrap iron in steelmaking within an overall “whole life cycle framework”,
particularly relevant to many, environmentally stressful, metallurgical products and activities.

Residual metallic elements, in recycled scrap iron(Fe) that are less readily oxidised than Fe,
gradually increase to worrying levels if these elements are undesirable for alloying. R. J.
Fruehan et al. at Carnegie-Mellon Univ. in Pittsburgh have studied ways to remove copper
from scrap (15,16). As yet, there has been no major break through in achieving any effective
and economically viable removal process. The difficulty is such that in the EU one method

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consisted of redesigning electrical transformer steel cores for cars in more friable powder
material which crush(crash) during scrap compaction thus allowing magnetic separation of the
Fe car scrap from the Cu wire windings. While bids may be open for innovative processes to
separate Cu and Sn from Fe scrap, steelmakers will still be confronted with the determination
of tolerance levels of Cu and Sn among others in order to avoid surface cracking and hot
shortness(20). Accurate and complete phase diagrammes constitute a basic proven approach
to such problems. Cu, which is less readily oxidised than Fe, is enriched in the surface
oxidised layers during billet heating before hot deformation. Ishida et al (11,12) measured the
liquid phase composition at the interface between the surface oxide layer and the Fe
containing Cu and Sn, matrix specimens heated at 1200°C in air. In these conditions the
specimens containing liquid phase are in equilibrium with austenite. The results are
superimposed on the calculated phase diagram for the Fe-Cu-Sn system (Fig.1) from (11,13)
The series of diverging lines traced from the solid matrix (alpha or gamma crystal structures)
and the bulk liquid phase are called tie lines. They indicate the chemical composition of the
liquid in equilibrium (liquidus composition) with the solid phase composition (solidus
composition) at any one temperature(isothermal), in this instance 1200°C. All specimen alloy
compositions were found to lie on the calculated liquid (L)/ (L + austenite) front (phase
boundary) From this it is deduced that surface cracking is strongly related to the
austenite/liquid phase boundary in the Fe-Cu based system. When the concentration of Cu in
the surface layer exceeds the solubility of Cu in Fe of the steel matrix, liquid Cu forms which
penetrates, grain boundaries during hot rolling, leading to surface cracking. From Fig.1, it
may also be seen that increasing amounts of Sn increases the (L+austenite) two-phase region
and hence the amount of liquid available to penetrate grain boundaries. This results in
decreased resistance to the tearing, tensile stress during deformation and an increased
tendency towards surface cracking or worse. In Fig.2 the calculated effect of alloying
elements on the solubility of Cu is well illustrated (14). Nickel(Ni) and cobalt(Co) increase
Cu solubility, while aluminium (Al) decreases it up to 2.5 wt-% then increases it again(in
ferrite). All other alloying elements such as silicon(Si), vanadium(V), manganese(Mn),
chromium(Cr) and particularly Sn decrease the solubility of Cu. The effect of Sn is pretty
drastic

The above example has a long history. Traditionally metallurgists and practitioners will have
relied upon experience, statistics and quite lengthy and costly metallurgical testing (not to
mention “some” scrap generation). J.W. Menter (FRS) gives an excellent account in his
Hatfield Memorial lecture 1970. Surface cracking is a relatively “mild” condition.
Metallurgists who have experienced hot shortness, live, are unlikely to forget the experience
(cf. photo, fig. 3) from Mentor (17) who, to avoid such continuing spectacles of mild steel hot
shortness, reports the following formula:
Cu + 8Sn <0.4 (units in wt %)
obtained from empirical observations. Menter (17) quotes Melford (18) who found that
surface hot shortness was related to a local enrichment of the oxide/steel interface in elements
less susceptible to oxidation, notably copper, tin, nickel, arsenic and antimony (photo, fig.4.)
Local concentration at this interface were shown by electron probe microanalysis to be 7% Cu
& 1%Sn for 0.2% Cu and 0.06% (600ppm) Sn respectively in the bulk of the billet. Melford
combined quantitative probe analysis with quantitative studies of synthetic alloys of Fe-Cu-X,
where X=Sn, Sb, As, or Ni. This helped Melford to construct phase diagrammes illustrating
the effects of these elements on the solubility of Cu in austenite (Fig. 5) (note that fig 5 is a
representation at 1200°C like Fig.1 above). From this he deduced the enrichment factors
which, if exceeded in the subscale region, would lead to the creation of a Cu rich phase which
was liquid at the hot working temperature causing a loss of mechanical strength and

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consequent surface break up under the tensile stress of rolling. Figs.1 & 5 were determined for
the Fe-Cu-Sn system at the same temperature 1200°C. Both authors conclude the presence of
liquid low melting Cu-Sn rich alloy. In spite of the different epochs the approach is very
similar. Although Menter measured alloy enrichment of 7%Cu & 1%Sn, Ishida et al
calculated and carried out calibration measurements situating enriched liquid, liquidus
compositions, at Cu-Sn couples around Cu ~90%wt-Sn~0.05% to Cu~70%-
Sn~20/25%wt.This is a full order of magnitude difference and thus requires clarification.
Responses may perhaps be found in the non-equilibrium effects between the calculated
solidus and liquidus two-phase (L+ austenite) region. Menter’s measurements, lie near the
solidus where the amounts of liquid are necessarily reduced and where liquid viscosity is
high.

Menter further describes immediately applicable remedial action and future action, which he
foresaw as inevitable, due to the constraints imposed by the Fe scrap cycle in Steelmaking. He
also pointed out that in the absence of exceeding phase diagram solubility limits some
elements may still contribute to loss of bulk ductility by grain boundary segregation. The new
combinatorial approach used by Zhao whereby huge numbers of sample are analysed; by
scanning electron microprobe providing data for special composition variation and by
mechanical nanoprobe diamond tipped hardness testing providing data for hardness and
elasticity is expected to make light work in completing such metallurgical history finally both
quite recent compared to the history of the profession (19). The benefits to design and
diagnosis from as complete, precise and as rapid as possible, phase diagram determinations, is
fundamental to modern scientific steel and alloy manufacturing. Already familiar problems
encountered by metallurgists and materials scientist may be more satisfactorily addressed and
explained with the improved facility to extend simple systems to multi-component ones by
calculation rather than by measurement. It is certainly to be expected that the trend towards
rapid combinatorial methods of measurement of phase diagrammes and simultaneous
measurement of phase properties will progress as anticipated, lending even more support to
the rapid and powerful calculation methods and why not to the founding of a metallurgy-
materials, minerals-resources, mining and processing, performance power law M4P3L!

REFERENCES:

1.Cahn, R.W: Rapid Alloy Assessment, Nature, Vol 410 p.643, 5 April 2001

2. Combinatorial materials synthesis and screening: An integrated materials chip approach to

discovery and optimization of functional materials, Xiang, XD
ANNUAL REVIEW OF MATERIALS SCIENCE
29: (1) 149 1999
WEB LIST OF REFERENCES (3-10) key Xiang, XD. Annual Review… ref 2:
3. Russek, SE. Bailey, WE. Alers, et al.
Magnetic combinatorial thin-film libraries
IEEE T MAGN 37: (4) 2156-2158 Part 1 JUL 2001

4. Yoo, YK. Ohnishi, T. Wang, et al.

Continuous mapping of structure-property relations in Fe1-xNix metallic alloys
fabricated by combinatorial synthesis
INTERMETALLICS 9: (7) 541-545 JUL 2001

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5. Evans, JRG. Edirisinghe, MJ. Coveney, et al.

Combinatorial searches of inorganic materials using the ink jet printer: science,
philosophy and technology
J EUR CERAM SOC 21: (13) 2291-2299 NOV 2001

6. Ohnishi, T. Komiyama, D. Koida, et al.

Parallel integration and characterization of nanoscaled epitaxial lattices by concurrent
molecular layer epitaxy and diffractometry
APPL PHYS LETT 79: (4) 536-538 JUL 23 2001

7. Zhao, JC
A combinatorial approach for efficient mapping of phase diagrams and properties
J MATER RES 16: (6) 1565-1578 JUN 2001

8. Zhao, JC
A combinatorial approach for structural materials
ADV ENG MATER 3: (3) 143-147 MAR 2001

9. Cahn, RW
Materials science - Rapid alloy assessment
NATURE 410: (6829) 643-644 APR 5 2001

10. Cassell, AM. Verma, S. Delzeit, et al.

Combinatorial optimization of heterogeneous catalysts used in the growth of carbon
nanotubes
LANGMUIR 17: (2) 260-264 JAN 23 2001

11. Computational Materials Design Ed. Saito, Pub. Springer

12. Ishida, K. Phase Equilibria and Microstructure of Iron-base alloys in Computational

Materials Design Ed. Saito, Pub. Springer

13. Akamatsu, S. Semuna, T. Akisue, O: Effects of Cu and Other Tramp Elements on

Steel Properties, ISIJ, 1997, p126.

14. Ohtani, H. Suda, H, Ishida K: ISIJ Intl. 37, 207, 1997.

15. "Metal Decontamination and Recycle Using Liquid Metal Melt-Slag Technology": E. L.
Joyce, B. Lally, B. Ozturk and R. J. Fruehan, International Journal of Environmentally
Conscious Design and Manufacturing], Vol. 2, No. 3, pp. 1-9, 1993.
16. "A New Low Temperature Process for Copper Removal from Scrap": A. Cramb and R. J.
Fruehan, Trans ISS, Iron and Steelmaker, November 1991, p. 61.
17.Menter, J.W: The Heterogeneity of Steel, Hatfield Lectures Vol. II, Ed. P. Beeley,
Pub. Maney; original source: JISI, April. 1971, 294.

18. Melford, D.A: (a) JISI, 1962, 200, 290; (b) JISI, 1966, 204, 495.

19. West, DRF. and Harris JE. Metals & the Royal Society, IOM Communications 1999.

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20.Alexander, J. Blazy, M. Burgmann, W. Joyeux, J.-C.

An approach to trace element control in aeronautic grade high strength low alloy steels such
as 35NCD16 and 4340
1972, Unpublished.

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