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The 1987 Extractive Metallurgy Lecture

The Metallurgical Society

The Mathematical Modeling Revolution in Extractive Metallurgy

JULIAN SZEKELY

A brief review is presented of the current state of extractive metallurgy, and it is shown that it is still
a significant part of the national economy. Then a definition is given of mathematical models, and the
general philosophy of modeling is discussed, together with the cost of models, hardware, and software
options. Several illustrative examples are given, drawn from aluminum electrolysis, flash smelting,
tundish operations, and plasma systems. The paper is concluded with the future modeling tasks facing
us; these include the more widespread applications of models to represent both existing and new
processing operations. It is stressed that models can play a major role in developing a holistic approach
to metals and materials processing, where the primary extraction and refining operations are combined
with the final processing steps.

The Extractive Metallurgy Lecture was authorized in 1959 to provide an I. INTRODUCTION


outstanding man in the field of nonferrous metallurgy as a lecturer at the
annual AIME meeting. T O be chosen as the 1987 Extractive Metallurgy Lecturer
is a great honor, which is amplified by the many distin-
JULIAN SZEKELY is Professor of Materials Engineering at the guished colleagues and friends of mine who have been so
Massachusetts Institute of Technology, a position he has held since 1975. recognized in the past. These include mentors like the late
A native of Hungary, he received the B.Sc., Ph.D., and D.Sc. degrees Denys Richardson E~1and colleagues including John Elliott, t2J
from Imperial College, London, England. His main research interests are Herb Kellogg, E31Nick Themelis, t4J Noel Jarrett, f51 and Milt
in the mathematical modeling of metals and materials processing Wadsworth. [6]
operations, with emphasis on new technologies, and he has written
numerous books and over three hundred journal articles on this subject. Noel Jarrett's lecture, given last year, may serve as an ex-
His most recent and forthcoming books include The Mathematical and cellent model, because it has dealt with both the economic
Physical Modeling of Primary Metals Processing Operations, with J. W. and societal, as well as the technological, aspects of extrac-
Evans and J. K. Brimacombe (Wiley, 1988); Ladle Metallurgy: Theory tive metallurgy, that of aluminum. Noel has interpreted the
and Practice, with G. Carlsson and L. Helle (Springer, 1988); and
Mathematical Modelling Strategies in Materials Processing, with W. term "extractive metallurgy" broadly to include recycling,
Wahnsiedler (Wiley, to appear in 1989). His work has been recognized and has indeed shown that recycling from scrap, rather than
by many national and international awards, including the Mathewson the recovery of metal values from their ores, ought to be the
Gold Medal (1973), the Extractive Metallurgy Science Award (1973), main emphasis of our activities-- at least in many instances.
and the Howe Memorial Lectureship (1979) of the AIME. He received
the Sir George Beilby Gold Medal of the British Institution of Chemical
The purpose of this lecture is to discuss the very major
Engineers in 1974. In 1982 he was elected to the United States National advances that have been made in the mathematical model-
Academy of Engineering. ing of processing operations, and to explore the accom-

METALLURGICALTRANSACTIONS B VOLUME 19B, AUGUST 1988--525


plishments and the potential for the application of these product quality; and the aggressive development of new
techniques for both existing and novel technologies in markets for the company's products, coupled with a diver-
the extractive metallurgy field. It is unrealistic to consider sification into contiguous areas where use can be made of
the technological issues in isolation, and for this reason existing competence.
we shall begin by painting a broad-brush picture of the For any aluminum company, such a strategy may involve
extractive metallurgy field worldwide and in the United effort to capture a larger part of the automobile market to
States. This will be followed by a brief discussion of mathe- include some engines and body components, as well as the
matical models in a generic sense, with a review of the con- implementation of new processing technologies such as
temporary tools that have become available to the modeler. spray forming, ET,SJrheocasting [9,j~ and compocasting, [H'121
Then we shall present a selection of successful modeling the development of new alloys, and metal matrix com-
examples and will then conclude with a brief review of some posites for aircraft applications, as well as a more aggres-
potentially exciting modeling applications. sive stance toward recycling. The marked fluctuations in
aluminum price may lead one to question the wisdom of
abandoning reduction cell research altogether. In terms of
II. T H E STATUS OF new materials markets, ceramics (alumina, silicon carbide,
EXTRACTIVE M E T A L L U R G Y titanium diboride, etc.), and semiconductors closely related
For the purpose of argument, let us define extractive met- to aluminum, such as silicon and gallium products, may be
allurgy as the extraction of metals from their ores, their logical choices.
refining and transformation into saleable semi-finished In the steel area, many Japanese companies have mounted
solid shapes, such as ingots, billets, sheet, plates, bars or a major effort at diversification into superalloys, titanium
slabs. Scrap recycling and the recovery of valuables from products, high-tech ceramics, semiconductors, and the like,
solid wastes (e.g., flue dust, electric furnace, dust, etc.) is drawing heavily on their existing processing expertise. In
explicitly part of these considerations. copper research, Mitsui Mining has taken a similar tack of
In recent years it has become quite fashionable to "bury" diversifying into the more high-technology applications of
extractive metallurgy; in the United States, the major losses copper products and their derivatives. There are rather fewer
and attendant restructuring by many of the major metals similar efforts in the United States.
companies, the corresponding loss of jobs, and the virtual The statistical information to be provided in the following
disappearance of R & D functions in many organizations may provide a sense of proportion regarding these matters.
represent a very gloomy picture indeed. The situation has Tables I, II, and III contain data on the worldwide and
not really been any better for chemical/extractive metallurgy United States production of some key metallic materials,
in the United States academic field, with major cutbacks in both in terms of tonnage and value.
research support and the markedly diminishing activities in In comparison, Table IV shows corresponding figures for
many university departments. Indeed, at present there are electronic materials. The appropriate figures for "high-tech
very few funding constituencies for extractive metallurgy ceramics," which do include some of the packaging, would
research. This is in marked contrast to new (exotic) ma- be comparable.
terials development and characterization, which has been We should note, furthermore, that the comparison be-
very w e l l - - a t times lavishly--supported by both Federal tween the metals and the "high-tech" materials is not totally
agencies and by corporations. on the same basis. The metals are clearly of the semi-
Conventional wisdom has it that both industrial and aca- finished products, while values of both the semiconductor
demic operations should drastically curtail activities in the materials and the ceramic components may be significantly
extractive metallurgy field, and concentrate instead on the inflated over and above the purely material values, since
more "high value added" materials, exemplified by mono- they do include a significant component due to fabrication.
dispersed ceramic powders, semiconductors, and more re- Figure 1 shows the gross output by various selected in-
cently, superconductors.
While no one can argue with a general trend that seeks to
emphasize new materials and new technologies, a plea
should be entered for a rational balance between the pursuit
of entirely new materials concepts and the more traditional Table I. Annual Production (1986)
and Value of Some Base Metals ~t3'~4~
fields, either as a research or as an academic discipline.
This balance should be struck on both intellectual and U.S. Production World Production
pragmatic, economic grounds. Intellectually, established Metal Value Value
fields tend to be rather more rigorous, having undergone Carbon steel 82 M tons 781 M tons
the usual weeding-out processes; this rigor and method- $16 to 25 billion $152 to 238 billion
ology could be helpful, both in research and education. In Aluminum 3.5 M tons 17 M tons
the economic sphere, as will be shown subsequently, tradi- $3.7 to 5.7 billion $18 to 27 billion
tional metals processing still has a very significant impact,
Copper 1.35 M tons 9.1 M tons
both in terms of contribution to the GNP and as a source $0.6 to 1.78 billion $11 to 12 billion
of employment.
Common sense would suggest that a reasonable strategy Lead 0.39 M tons 3.8 M tons
$0.14 to 0.22 billion $1.4 to 2.1 billion
for the survival, indeed the prosperity, of metals companies
would have to include a judicious mix of significantly im- Zinc 0.24 M tons 7.5 M tons
$0.15 to 0.22 billion $4.6 to 4.9 billion
proving existing operations, from the standpoint of cost and

5 2 6 - - V O L U M E 19B, AUGUST 1988 METALLURGICAL TRANSACTIONS B


I l l I I /t i I
Table II. Annual Production and Values (1986)
of Some Special Metals (Ni, Co, Ti, Si) [13'14! Motor Vehicles t~
/
U.S. Production World Production 300 9 /
Metal Value Value
Nickel 1.1 K tons 799 K tons
>-
/ l,
$3.9 to 7.0 million $2.9 to 5.1 billion n- 250 9
Cobalt -- 35 K tons
$0.60 to 0.79 billion
cO
23 o~ A/
,, ,= I
" I

II Primary
I Metal .

Titanium 17.5 K tons 87 K tons z_ 200 :' /'\ i


$0.14 billion $0.7 billion 9 ~I 11

Silicon 0.36 K tons 3.0 M tons


>-
n'~
r
oo /a,lo I Vo.oe 9 o-
$0.45 billion $3.7 billion I--
O3
',-
.,,-
13_ O
,,o 'XL/
I--
Table III. Annual Production and Values 0 o /n/'/ O /industrial
100 3 "A" ~A/ /Chemicals
(1986) of Some Precious M e t a l s [13'14]
/ / ~.o-
U.S. Production World Production 0 Crude Petroleum .I O " ' ' "
and Gas "-~ -_~,-c~/' ...... 9
Metal Value Value . . . . . .
501--
Gold 123 tons 1.7 K tons I II,l - , r - ~ r ~,- Mining and
$1.2 to 1.6 billion $17 to 22.5 billion I ~I:15::~--- ,~ .~ .z~ c,.~ j :::~ -~ ' Quarrying
Silver 1.2 K tons 13.9 K tons I~ z ~ . ~ Electr on.ic Components
0 I', I I I I I . .. I I
$0.18 to 0.21 billion $2.0 to 2.4 billion
Platinum
Palladium
Iridium 17 tons 278 tons YEAR
Osmium $55 to 268 million $0.89 to 4.3 billion
Fig. 1 - - T h e evolution of the gross output of various industries. Adapted
Rhodium
from J. W. Evans and J. Szekely: J. of Metals, Dec. 1985, p. 40.
Rutherium

Table IV. Electronic Materials


be some important lessons here for the metals community as
A. World-Wide Ceramics Sales (1986)t~Sj a whole.
1986 1991 1995 Clearly, there are many key ingredients to a successful
$5.4 billion $12 billion $24 billion metals processing operation; these include management,
marketing, and technology. In the area of technology, we
B. Semiconductor Industry Shipments (1986) t~61 have a new key tool, mathematical modeling, which has al-
1986 1989 ready produced impressive results and promises a great deal
U.S. $8.5 billion $12.66 billion more. In the remainder of this article I shall be concerned
World-wide $23.36 billion $39.06 billion with a discussion of mathematical modeling, the techniques,
hardware, software, successes, and future possibilities.

dustries in the United States. The very important point that


Ill. MATHEMATICAL MODELS: HARDWARE,
must emerge from these data is the following:
S O F T W A R E , AND M E T H O D O L O G Y
While metals production has been declining in recent
years, both in terms of absolute quantities and as a relative What is a mathematical model? A mathematical model is
proportion of the economy as a whole, primary metals pro- a set of equations, algebraic or differential, which may be
duction and processing is still a major component of the used to represent and predict certain phenomena. The term
national economy and is likely to remain so for the fore- model as opposed to law implies that the relationships em-
seeable future. The recently experienced currency value re- ployed may not be quite exact and that the predictions de-
alignments are likely to strengthen this argument. rived from them may only be approximate.
One final point ought to be raised here. The late 1980's Mathematical modeling has been used for a long time,
and early 1990's may be regarded as the era of the niche. but in recent years major breakthroughs have been possible
Organizations have become successful by being original, because of dramatic developments both in computing hard-
and by carving out new markets and territories for them- ware and software, which allows for the far more effective
selves. Following, rather than creating, new trends could manipulation of the modeling equations.
become very hazardous, rather than a "safe" procedure. The Major successes from everyday life include the very ac-
well-documented success of many mini-mills in steel, par- curate prediction of election results from data based on an
ticularly Nucor, Chaparral, and North Star S t e e l - - extremely small number of votes taken from representative
contrasted with the quite hard times facing the integrated precincts. In contrast, weather forecasting sounds a sobering
p r o d u c e r s - - m a y serve as excellent illustrations. There may note that many key problems still remain.

METALLURGICAL TRANSACTIONS B VOLUME 19B, AUGUST 1988--527


A. The Classification of Mathematical Models t''j or minimize the production cost; in process control* we
Within the more restrictive framework of extractive met- *Process control represents a special problem, in that the calculations
allurgy, we may consider several types of mathematical have to be carried out very rapidly so that a meaningful response is possible
models, namely: in real time. For this reason, control algorithms often require a drastic
simplification of a mechanistic model.
(1) Fundamental, or mechanistic, models;
(2) Empirical, or black box models; need a quantitative relationship for the control algorithm.
(3) Population balance models; and The planning and interpretation of experimental mea-
(4) Input-output, systems models. surements is perhaps one of the most important and often
most misunderstood role of mathematical models. Very of-
Fundamental or mechanistic models, which will be the ten, the measurements are made first and then some form of
focal point of the discussion here, are based on basic physi- modeling is undertaken as an afterthought. It is important to
cal or chemical laws such as thermodynamic equilibria, realize that unless the measurements are properly inter-
chemical kinetics, heat flow, fluid flow, mass transfer, de- preted, and this interpretation leads to appropriate conclu-
formation processing, and the like. These models tend to sions, the whole effort may turn out to be useless. For this
have a broad general validity and with some ingenuity the reason, it is almost always desirable to do some calcula-
scope of application can often be expanded. tions (i.e., modeling) first, and then use this as a basis both
Empirical or "black box" models are based on obser- for planning the measurements and interpreting the data
vations on a particular system, and not on fundamentals. being obtained.
At times there is no alternative to their use, but great care It is important to stress that calculations and measure-
must be taken if these relationships are to be extrapolated ments are not alternatives, but most often must be pursued
or generalized. in a complementary fashion as illustrated in Figure 3, indi-
Population balance models deal with distributed parame- cating that mathematical modeling, physical modeling, and
ters, such as particle size distribution in a grinding circuit, actual (plant-scale) measurements may all be ingredients of
the coalescence of inclusions in steel processing, or the a successful program. Indeed, in many instances several
vapor phase synthesis of fine ceramic particles. These tend iterations may be required between mathematical modeling
to be a special class of mechanistic models because they are and physical measurements before the desired level of un-
based on fundamental concepts. derstanding finally emerges.
Input-output or systems models satisfy overall conser-
vation relationships and find a variety of uses, including C. How Are Mathematical Models Built?
cost analysis, scheduling, de-bottlenecking, and the like. At
Figure 4 shows a schematic flow chart of mathematical
times such models may be effectively combined with a
model development. It is seen that the first (and usually the
mechanistic modeling approach.
most difficult) step is the identification of the problem;
processing problems are hardly ever presented to the in-
B. The Role of Mathematical Models [18l
vestigator in a neatly defined form. Most often one has to
Figure 2 illustrates the role of mathematical models in "dig deep," form a mental picture of the key parameters
materials processing. It is seen that models, through their affecting the system, and then express this physico-chemical
representation of processes or operations in a quantitative, picture in mathematical form.
mathematical form, may play a key role in process control Once the problem is formulated, the next step is scaling,
and process optimization, as well as in the planning and scoping, and order-of-magnitude analysis. This technique,
interpretation of measurements. Furthermore, mathematical which has frequently been used by applied mathematicians,
models may provide a clear link to artificial intelligence-- is a very powerful one, providing useful insight into the
perhaps better termed knowledge-based engineering. behavior of the system. Through order-of-magnitude analy-
Briefly commenting on these, both process optimization
and process control require a quantitative representation of
the process. In optimization we seek to maximize the profit
MATHEMATICAL MODELING

t '~1 ; Artii
~ - f i m i z a ~ ~ ,ntelli~;ina~
e

t
Crucial for Planning and
Interpreting Experimental Plant and
Studies in the Lab or in the Plant Physical Modeling Pilot Plant Data
Fig. 3 - - T h e balance between mathematical modeling, physical modeling,
Fig. 2 - - T h e role of mathematical models in materials processing. and plant-scale experimentation.

528--VOLUME 19B, AUGUST 1988 METALLURGICAL TRANSACTIONS B


testing the theoretical predictions and also for providing
~oblem~"'~ property values (viscosity, thermal and electrical conduc-
tivity, reaction rate constant, and the like), should these not
be available from prior work.
The following key step is the synthesis, that is the devel-
opment of a quantitative understanding of the system, upon
which the subsequent implementation may be based. This
implementation may involve a decision whether to proceed
with a development project, the major modification of an
existing operation, the installation of a new control system,
and the like.
Scoping, Scaling The key point that one must re-emphasize regarding this
Asymptotic Solutions flow chart is that once a problem has been identified, any
investigation should start with (simplified) calculations
first, and then use this as a framework for planning experi-
mental and computational programs to be pursued in an
Numerical ~).,~_ -1~( Experiments interactive manner.
Solutions .,
D. The Building Blocks of Mathematical Models
How are mathematical models put together? In the
Synthesis early days of modeling, most of the models were "custom-
crafted," often starting from first principles and the con-
sideration of elementary control volumes. The present-day
modeler is in a much stronger position, because he or she
can rely on:
(a) many precedents and analogous situations;
(b) readily available and inexpensive hardware; and
(c) a wide range of software packages.
Fig. 4--The general methodologyof mathematicalmodel development. At present, the effective path in the development of
mathematical models relies on two key components:
ses, we can define the time scale of the problem, that is the (i) The actual building blocks of models, which are the
time required to approach thermal or chemical equilibrium; basic physical (including mechanical) and chemical laws;
and the velocity scale, that is the typical values of the fluid some of these are summarized in Table V.
velocity and the like. Furthermore, this preliminary scoping (ii) Drawing on the analogy to previous work, through the
analysis is extremely useful in defining the range of pa- consideration of some basic physical situations. Some stan-
rameters that must be covered in the subsequent com- dard, relatively well-studied physical situations are sum-
putational work. marized in Figure 5, while some less well understood, but
As seen in the figure, the next two parallel steps are still very important systems are shown in Figure 6.
machine computation and experimental work. Machine Commenting on these briefly, the fairly well-studied sys-
computation is often necessary because purely analytical tems include stirring of liquid metals with a vertically in-
results or order-of-magnitude estimates will not provide jected gas stream, with applications in ladle metallurgy, the
adequate detail. Experimental work will be needed, both for BOF, combined blowing, gas phase deoxidation of molten

Table V. The Building Blocks of Mathematical M o d e l s tl3a41

Component Application Remarks


Navier-Stokes equations fluid flow complex vector-tensor manipulation
Fourier's Law heat conduction relatively simple, more complex if phase
change is involved
Fick's Law diffusion simple for one component, very complex for
multi-component systems
Convective transport heat and mass transfer combines fluid flow, heat and/or mass transfer
Maxwell's equations electrodynamics MHD very complex problems, i.e.,
plasmas, induction furnaces, etc.
Thermodynamics equilibria phase diagrams often routine calculations
Kinetics rate predictions needs experimental input
Constitutive relationships deformation processing very complex, needs realistic input

METALLURGICALTRANSACTIONSB VOLUME19B,AUGUST1988--529
E. Hardware
In recent years there have been major developments re-
garding computing hardware. As shown in Figure 7, the cost
of doing a given calculation has dramatically decreased, so
that we can now routinely tackle complex three-dimensional
transient heat and fluid flow problems. This figure also
shows that in terms of instructions/second 9 dollar one tends
to get rather better value from the smaller machines than
from the mainframes.
Table VI shows a listing of the principal hardware possi-
bilities, together with brief notes about costs and principal
applications. This is a very rapidly changing field, so this
table will have to be updated periodically.
The following general remarks may be applicable here.
Fig. 5 - Some well-studied basic physical situations in extractive-process
metallurgy. (a) Vertical gas injection into melts. (b) Horizontal gas injec-
The distinction between the "high end" of personal computers
tion into melts. (c) Gas jet impinging onto a melt. (d) Induction melting, (e.g., 386-based machines or the Mackintosh II) and the low
stirring. (e) Submerged resistance, arc melting, smelting. (f) Gas flow end of engineering workstations is becoming quite blurred.
through packed beds. At the present cost level, it is hardly appropriate to use
personal computers for serious engineering calculations. The
bulk of this work is now being done on engineering worksta-
tions, of which the MicroVAX II and III, the Sun III and IV,

-o
C
300
O
o
O0
I=--
(1)
o..
t./)
C
.9
Fig. 6 - - Some less well-understood basic physical situations in extractive- o
process metallurgy. (a) Atomization of a liquid metal stream with a gas jet. I=.
200 - [] Mainframe -
(b) Mechanical stirring of liquid metals. (c) Mold filling. (d) Emulsifi- 09
cation at a slag-metal interface. (e) Surface waves with liquid metals. c Micro

E
copper, and the like (a). Horizontally injected gas streams E~
into liquid metals (mattes) include the AOD process copper O
converting and the Noranda Process (b). Gas jets impinging
on liquids include basic oxygen steelmaking (c), while in- C
duction stirring and melting is extensively used in both the
steel and the aluminum industries (d). Submerged resistance
._o 100
and arc furnaces are extensively used in the extractive metal-
lurgy of ferroaUoys and in scrap melting (arcs) (e). Finally,
packed beds are used in blast furnace operations, while
fluidized beds are used in the roasting of copper sulfides and
in the flash drying of alumina (f).
Among the less well-understood systems, the atomization ~
o
of liquid metal streams with gas jets is a key step in powder
metallurgy (a). Mechanical stirring (quite well understood
in the contexts of chemical engineering practice) is being 0
used in aluminum and lead processing (b). Mold filling (c) 982 1987
is common to most nonferrous operations. The emulsifica-
tion of slag-metal systems is a key desired step in ladle met-
allurgy and highly undesirable in seeking to avoid copper Thousands of Dollars
losses in converting (d). Finally, surface waves are impor- Fig. 7 - - T h e approximate cost of performing one million instructions per
tant (and not well understood) in the context of aluminum second. - - mainframe-- microcomputers. Source: Business Week, Nov. 30,
smelting and steel tundish operations (e). 1987, p. 122.

530--VOLUME 19B, AUGUST 1988 METALLURGICAL TRANSACTIONS B


Table VI. Principal Hardware Possibilities and Applications Table VII. Partial List of Available Software

Price Range Name Application Notes


I. Workstation class: $20 to 100 K ANSYS structural, thermal, finite element
MicroVAX II electrical, magnetic
DEC 8250, 8350 ABAQUS structural, thermal, finite element
Sun 3, 4 nonlinear analyses
ti. Minicomputers: $30 to 200 K NASTRAN structural finite element
MicroVAX III
DEC 8500, 86800 FIDAP fluid dynamics finite element
MASSCOMP 5000 PHOENICS fluid dynamics, heat finite volume
Intel iPSC Sugarcube transfer, chemical
III. Mini-supercomputers: $300 to 800 K reaction
DEC VAX 8700, 8800 FLOW 3-D fluid dynamics finite difference
Convex FLUENT fluid dynamics, finite difference
Intel iPSC/2-VX/d3 heat transfer
IV. Mainframe class: $500 to $2,000 K NEKTON fluid dynamics, finite element
IBM 3808, 3090 heat transfer (spectral)
Cyber 875 NISA fluid dynamics, finite difference
FPS Array Processors
heat transfer
Intel iPSC/2-VX/d4
IMSL math/statistical library
V. Supercomputers: several millions
Cray -1 and X-MP of dollars LINPACK math library
Cyber 200 MINPACK minimization/optimization
Fujitsu VP400 library
Intel iPSC/2-VX/d5 EISPACK eigenvalue library
VI. Massively parallel processors: several millions ASPEN flowsheet simulation sequential
Intel iPCS/2-VX/d6 of dollars modular
FLOWTRAN flowsheet simulation
and the Apollo DN 3000 series are good, but certainly not SOLGASMIX chemical equilibrium
all-inclusive examples. ECES aqueous chemistry
Mainframe machines are, of course, being used quite F*A*C*T phase diagrams,
extensively for computing by major organizations, but the chemical equilibrium
purchase of new standard mainframes for doing engineering/ ROMULUS solids modeling
modeling work is becoming a rather less attractive proposi- PATRAN solids modeling, finite
tion in many cases. Of course, these machines are still domi- element pre- and post-
nant in accounting, banking, inventory-control applications processing
and the like, although networked workstations may repre- SLAM II event simulation
sent a useful alternative in certain cases.
The new and emerging superstars regarding hardware are MAGNUM magnetics finite element
the vector array and parallel processing machines, offering
tremendous computational speed for suitably posed prob-
lems. The vector processing mainframes (e.g., those made G. What do Mathematical Models Cost?
by Cray Research, Floating Point Systems, or IBM) are very
expensive. However, there is a new class of machines with The cost of mathematical models may range from a low
the potential of offering vector array or parallel processing of about $20,000 to $30,000 for a simple exercise, to many
capability at a quite modest cost. The principal impediment millions of dollars for a really complex model. A mean
at this point is the adaptation of the existing programs to value in the range of about $120,000 might provide a first
these new machines, and the lack of a suitable preprocessing estimate of a reasonably complex model that might take
capability to do this task automatically. about one man-year to develop. The principal cost item is
the time of the programmer and the systems analysts (in the
E Software region of 80 pct or more of the total cost); thus the cost of
the hardware and the software tends to be a relatively minor
One of the key developments in recent times is the ready part. This is a fact often not appreciated by technical man-
availability of software to perform numerous computational agement, who too often indulge in false economies by not
tasks that would be part of a modeling operation. As shown investing in appropriate hardware and software, thus making
in Table VII, software packages are available to do thermo- the analysts' work unduly protracted. In deciding whether to
dynamic equilibrium calculations, solve heat flow and fluid undertake a modeling exercise, the cost of the model will,
flow problems, solve heat conduction and thermal stress of course, have to be weighed against the benefits that may
problems, and even tackle problems with free boundaries. be derived; by the same token, one must determine the
The intelligent use of these available software packages, proportion of the effort that has to be devoted to the comple-
with suitable modification, has to be part of most rational mentary physical modeling, pilot plant work, and plant-
modeling strategies. scale experimentation.

METALLURGICAL TRANSACTIONS B VOLUME 19B, AUGUST 1988--531


H. What Constitutes an Optimal Modeling Strategy? Anode Rods

In tackling a practical problem, a decision has to be made


regarding the extent to which one is to use mathematical
modeling, physical modeling, pilot plant and plant-scale
work. In the majority of cases, as was illustrated in Figure 3,
i Molten Electrolyte
A,~ o,u,
Covers

we may need a combination of these approaches. We should Frozen Ledge


Carbon
note that pilot-plant scale work and plant-scale experimenta- . . . . . . . . Block
tion both tend to be very expensive, so if possible one should Molten Aluminum Carbon

emphasize mathematical and physical modeling work. g L[ning

IV. SOME ILLUSTRATIVE EXAMPLES Thermal insulation

Steel Shell ~
During the past decade we have seen a very marked evo-
lution in modeling efforts. Far from being a scientific curi- Fig. 8 - - S c h e m a t i c sketch of a Hall cell.
osity, successful modeling examples now fill the materials
and metallurgical literature. Indeed, one is faced with an
embarrassment of riches, and any selection has to be some- It follows that the optimization of the system will require
what arbitrary. We shall confine ourselves to four specific a good detailed, quantitative understanding of the complex
examples: two from the nonferrous metallurgy field, one interrelationships between the process parameters. A great
from steel processing, and one from a new technology. deal of useful work has been done in this area by Evans []9J
and Moreau, [2~ and there must be much unpublished mate-
A. Aluminum Electrolysis rial in the archives of aluminum companies. Here we shall
cite the very recent, excellent work of Wahnsiedler, t2'l with
As was discussed earlier, over five million tons of alumi-
Figure 9 showing a computed bath-metal interface, and
num are being produced annually, and all the primary pro-
Figure 10 depicting the computed velocity fields. As noted
cessing involves the use of a process whose principles were
earlier, these calculations require the solution of a set of
established over a hundred years ago: the electrolytic de- simultaneous three-dimensional electromagnetic force field
composition of alumina, dissolved in a molten salt, using a
and fluid-flow field equations. Finally, Figure 11 shows the
graphite anode and a graphite cathode, and collecting the
transient response of the interface height to an interruption
aluminum product in the molten state. During the past hun- in the anode current.
dred years, major advances have been made by vastly in- Work of this type has been very helpful in both the opti-
creasing the scale of the operation, the electric efficiency, mization of existing cell operations and in the development
and also the cell productivity. Mathematical modeling has of new cell technologies.
played an important role in these accomplishments.
Figure 8 shows a schematic sketch of a typical section of B. Modeling of the Flash Smelting Process
a Hall cell. It is seen that carbon anodes are being immersed
into a molten bath that consists of alumina dissolved in The classical technology for smelting sulfide copper ores
cryolite. The electrolytic decomposition of the alumina yields involved the use of large, unwieldy reverberatory furnaces
the desired aluminum product. The key issues in Hall cell with an extremely low surface area per unit volume and
design and operation are to increase the cell productivity and attendant very slow processing rate in terms of tons/unit
electric efficiency, and to reduce the specific power con- reactor volume-time. One potentially attractive technology,
sumption. One very important objective is to reduce the pioneered by the Outokompu Company of Finland, is the
anode-cathode distance and hence the cell voltage. Two flash smelting process sketched in Figure 12, where fine
major impediments must be overcome in order to accom- copper sulfide particles (together with a flux) are injected
plish this. into a furnace with oxygen-enriched air, forming a dust-laden
One of these is that, unlike the idealized sketch shown in turbulent jet.
Figure 8, the bath-metal interface is not flat and tends to be The inherent attractiveness of this system is due to the fact
unsteady. It follows that short-circuiting may occur if the that full advantage is being taken of the very high surface-
anode and the cathode are brought too close together without to-volume ratio of the fine ore particles; thus, a fast specific
effectively controlling the surface deformation and the sur- processing rate may be achieved. At the same time, for the
face waves. proper design and scale-up of these units it is essential to
The other point is that any Hall cell must be operated so have information on the temperature and concentration pro-
that a solidified shell of the bath is formed on the side walls; files and of the local reaction rates.
this "freeze" plays an important role in protecting the walls. The accurate modeling of this system is quite a complex
In order to maintain this "freeze," the resistive (Joule) heat- task, because it involves a reacting, two-phase gas-solid
ing due to the passage of the current between the electrodes mixture with several components. Convective and radiative
has to be matched with the heat loss through the walls. heat exchange is another complicating factor.
From the standpoint of transport fundamentals, Hall cell Useful modeling efforts in this field have been done by
operations represent a very complex, three-dimensional, un- Themelis and co-workers [22!and by Sohn and his group. [23l
steady state heat flow, fluid flow, and mass transfer problem Here we shall cite the work of Hahn and Sohn, which is
in a multi-phase (bath, metal, and gas bubbles) system. The the most comprehensive to date. Figure 13 shows an outline
situation is further complicated by the presence of strong of the concentration isopleths, while Figure 14 demonstrates
electromagnetic forces and very complex geometries. excellent agreement between the theoretical predictions and

532--VOLUME 19B, AUGUST 1988 METALLURGICAL TRANSACTIONS B


PICTURE OPTION?->

/~./--~'- ___ .-~


_ ~ l~ -I
.._.--

/ . . ~ -o'~ ~ _~-~-~J

. _..~- ./--'~ I
:__-/f-~-~--~7;~/--~ ~ ::---~
:__=~- ........ " .......... /" - - - - ~ - - r L - - _ ~ : / - ~ ; 7~.......

.~.~=--=-_-_-_-_-_-_-_-~<_-.-.~7<..... .:7<... : -..~ ..... : : .......

~=_ " , , ~ ~>-..~c---~---_ __-~:_ ~>~-~.--~ ~, .:- --~ - -:,~ ~ _ .----*

- _ ~ ----...-:~.~_.- ---. --,,:...-~::. "--.. _.-- .---


. . . . . . . . .

.t ~ f ~-~ .I ~

.f...---:

/
-------_________ i: /
//j-//

P155F TEST ANODE ADJ

Fig. 9 - - T h e computed bath-metal interface in a Hall cell, after Wahnsiedler. tLgt Reproduced by permission.

the experimental measurements. Work of this type is in- was discovered that tundishes can play a very important
valuable in scale-up, and is an excellent illustration of role in promoting the flotation of inclusion particles, and
how mathematical modeling can aid in the development of also in affecting the surface quality of the continuously
new technology. cast products.
In recent years, a great deal of work has been done in
C. Tundish Design Calculations mathematically modeling the three-dimensional fluid-flow
field and associated temperature field, tracer dispersion, and
The third example is taken from steel processing, and may inclusion behavior in tundishes, t24-27j Such mathematical
serve to illustrate how modeling can help to improve ex- modeling has usefully complemented physical modeling t28J
isting technologies, and also lead to the development of and a very limited number of plant-scale investigations.
new concepts. Most tundishes employed today use dams, weirs, and baf-
Figure 15 shows a schematic sketch of a tundish serving fles to regulate the flow. But there is still a surprising num-
as a buffer vessel between the ladle and a continuous casting ber of very poor tundish designs in current operation, much
machine. Such tundishes are also used in aluminum, copper, to the detriment of product quality. Mathematical modeling
and other metals processing operations, albeit on a different can play a key role in determining the optimal tundish de-
scale. A common feature of most conventional tundishes sign and the optimal location of the weirs and baffles.
employed in steel technology is that they are essentially a Figure 16 shows the computed velocity fields in a central
horizontal trough, say a few meters long, about a meter wide vertical slice of a typical steel tundish, the key parameters
and a meter deep. Steel is being poured in from a ladle at one of which are listed in Table VIII. Here, (a) depicts the flow
end or at the center, while one or more steel streams are pattern in the absence of flow-control devices, and a strong
being discharged into the mold of a continuous casting ma- recirculating flow field occupying a significant part of the
chine through exit nozzles located at the bottom. tundish is clearly seen. (b) shows the effect of a dam and a
The originally envisioned function of tundishes was to act weir in controlling the flow, and the improvement is readily
as a buffer between the ladle and the continuous casting apparent. Finally, (c) illustrates the effect of placing a strong
machine, evening out the flow changes brought about by magnetic field on the tundish, which is seen to effectively
variations in the metal head in the ladle. Subsequently it streamline the flow.

METALLURGICAL TRANSACTIONS B VOLUME 19B, AUGUST 1988 - - 533


PICTURE OPTION?->

GA-19457,12

- ,... ... \ / ,- /
i

> > -
/

_ ~ ~ "-. ,,,.
1

, \

\ x. I ;

METAL FLOW PATTERN


D155G3 T:8.5 SEC

(a)
Fig. 1 0 - - T h e computed velocity field in the metal pad of a Hall cell, after Wahnsiedler. u91 Reproduced by permission.

This behavior is perhaps more readily discerned using the The sketch in (b) represents a transferred arc plasma,
concept of tracer dispersion or the "C" curves given in where the arc is struck both between the electrodes, and also
Figure 17. These represent the concentration of a tracer between the central electrode and a metal surface or bath
which has been added to the inlet stream in a stepwise upon which the plasma impinges. Plasmas offer very inter-
manner at the outlet, as a function of the dimensionless esting opportunities in extractive metallurgy, through pro-
residence time; the latter is defined as the ratio: tundish viding an electrically derived heat source of very high
volume/volumetric flow rate of the metal. temperature and intensity. Initially, there were many ideas
It is seen that in the absence of flow control devices there regarding the use of plasmas that ranged from iron oxide
is very marked short-circuiting and by-passing, as evi- reduction and the smelting of sulfide ores, and the recovery
denced by a sharp tracer peak at 0 ~ 1. This is somewhat of zinc from electric furnace wastes, to the melting of ti-
ameliorated by the use of inserts or baffles, but plug flow tanium scrap, stainless steel scrap, and the like.
would be approached only through the use of an externally The consensus that is emerging, and which has been well
imposed magnetic field. articulated in a recent NMAB report, t3~ is that the ideal use
of plasmas in an extractive metallurgy context will be for the
melting of refractory metals of high specific value (e.g.,
D. Plasma Systems titanium, stainless steel scrap, etc.) where emphasis is on
Figure 18 shows a sketch of two types of plasma torches product cleanliness; where there is an absolute need for a
used in materials processing applications.[291 Here, (a) repre- high-temperature (say above 1800 to 2000 K) heat source;
sents a nontransferred arc, where an arc is being struck and where a very high thermal efficiency is not mandatory.
between two electrodes and the resultant Joule heating and The use of plasmas for the more conventional smelting
electromagnetic forces produce a stream of hot gas with applications (e.g., iron oxide reduction, lead smelting, etc.)
temperatures up to 15 kK, which is then used to heat and seems to be rather less promising; however, there may
melt metallic substances. Such torches are also used for be some niche-type applications, especially in connection
spraying and for the synthesis of fine ceramic particles. with recycling.

534--VOLUME 19B, AUGUST 1988 METALLURGICAL TRANSACTIONS B


PICT.UR.E.OP.T.ION?->

GA-19457.13
/,f
,. i ,,

", ~ t /
\ 1

\ / Ii

1. 1 X \ \
I " / / r "- "" \

/ /

,...~ "---.,-- ---..,, ~ ---,~ ---" ----.,, ~ ~ .--- ~ " ,,._. ~ .,,__- -.,~--- ___...,,-__ ,,.___
,/
#

BATH FLOWPATTERN
DI55G3 T:8.5 SEC

(b)
Fig. 10 Cont.--The computed velocity field in the metal pad of a Hall cell, afierWahnsiedler, t~9~Reproduced by permission.

In recent years there have been major advances in the been successful in that the theoretical predictions were
modeling of plasma systems, including both transferred and found to be in good agreement with experimental mea-
nontransferred arcs. 131-351 These modeling exercises have surements. As an example, Figure 19 shows a comparison
between the theoretically predicted and the experimentally
0.136 I I I I I I I
measured temperature fields in a nontransferred a r c . [34]
Figure 20 shows a comparison between measurements and
0.132
predictions in a transferred arc. [35] The agreement in both
cases appears to be quite good, indicating significant
progress in this field.
O. 1 2 8
Our ability to model these plasma systems provides
an excellent base upon which to build new materials-
"~ 0 . 1 2 4
processing technology.
"~ 0 . 1 2 0
m

V. DISCUSSION
0.116
In this paper, we have sought to make the point that
0.112 I I I J I ~ I
mathematical modeling is being established as an extremely
0 5 10 15 20 25 30 35 40 valuable and cost-effective tool for both process opti-
Time since interruption, sec mization and new process development. The deployment of
this technique is very timely because of the ready availa-
Interrupted Anode Interface Peak Height bility and marked decrease in the cost of both hardware
Fig. l l - - T h e computed transient response of the bath-metal interface in and software.
a Hall cell after a current interruption, after Wahnsiedler.t'gJ Reproduced by During the past few years, major successes have been
permission. reported with modeling, not only in the mechanistic model-

METALLURGICAL TRANSACTIONS B VOLUME 19B, AUGUST 1988--535


Primary air 10 14 Contours of SO 2 Concentration (%)
1.o i r,,_t is 16
wifh porficles
I Secondaryair

~
o

o!
0.8

0.6

0.4
0.0

10

.
5

.
0.5 14

. .
1.0

Contours of O 2 Concentration

1.2

--"
,

1.5

1.0g
,

2.0 2.5

(%)

1.1

1.08
3.0

1.2 1.07
0.2
27 ;
0.0
0.0 10 5 0.5 1.0 1.5 2.0 2.5 3.0
Contours of Tg (K)
1.0
0.8 1600-~.~ 1750 1600

0.4 l l t \ ( s ' , . - - 1750

0.2 ~ ~ 0 0 !700
300-450 "It,..4 13oo 17so 16so-17oo
0.0 ~" : ~ , " " ~ ~ ~ ~
0.0 1000 0.5 1.0 1.5 2.0 2.5 3.0

AXIAL DISTANCE (m)


u(x,r) Fig. 13--The predicted contours of the SO2, 02 concentration and of the
I temperatures for a flash smelter, after Sohn.t23JReproduced by permission.

B. The application of modeling techniques in new process


r development.
X
A. Implementation of Existing Processes
During the past decade a very impressive number of models
has been developed, representing a broad range of basic
Rf physical situations. As noted earlier, these include induction
furnaces, submerged resistance furnaces, gas bubble-stirred
systems, submerged jets, packed beds, fluidized beds, par-
ticles entrained in gas jets, and laminar and turbulent flow-
through vessels, troughs, and the like.
Fig. 1 2 - - A schematic sketch of the flash smelting process, after Sohn. (23] There are many situations where these existing models
Reproduced by permission. could be readily adapted in a most cost-effective manner
from one system to another. Thus the knowledge of tur-
ing area--the topic of this discussion--but also with bulent flow phenomena in ladles holding molten steel, a
systems modeling and the representation of distributed pa- well-explored field, could be easily used in improving
rameter systems. Indeed, in a recent plenary lecture, Herbst~36j analogous processing operations in aluminum, lead, zinc,
has shown that the modeling and optimization of com- and copper processing. The knowledge gained in the in-
minution circuits has provided some 15 to 25 pet increase in duction melting of one kind of metal could be readily
capacity, without any additional capital investment in the applied to the treatment of many others. By the same
majority of cases. token, the very extensive experience gained in blast fur-
What Are the Tasks Ahead? nace technology could and should be readily adapted to
counter current moving bed-type operations in nonferrous
The tasks ahead fall in two categories: metals processing.
A. The implementation of modeling schemes for the opti- An excellent recent example that may be cited is the
mization of existing processing operations. CREM Process invented by Charles V i v ~ s , [37] that is the

536--VOLUME 19B, AUGUST 1988 METALLURGICALTRANSACTIONS B


3O
o~'._,. ~ T~ SO2 ~- & x .'<
k .xx .-,: R
~
' OC: 20 ~ [] =- I I "' - "
Or 10 9 U 9 2
O (Me xOy )

0 I
-- I I
02 I
Velocity Vectors at .15Y, No Field, case (o)
Vma x = 2.4 m/s
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
(a)
~o ~ T O = 463 K (a)
I \ S02

2 : . . . . ", ~ _ - ,, t
25

O2(Mex O y'l

(3 02
v I I I I -- I I I I

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 .0


(b)
~' 2000
"-" m 9 0.8 m/e
1750
:~ 1500 ~ -- "
(b)
1250
463 K
Ee lOOO ~ 298K
I-- 750
m 500
(.9 250 I I I I I I I

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0


Axial Distance from Top (m)
(c)
Velocity Vectors at .15Y, Bo = 3KGaus, case (c)
Fig. 1 4 - - A comparison of the predictions with measurements for various
temperatures, after Sohn. t23~Reproduced by permission. Vma x = 1.9 mls
(r
electromagnetic stirring of continuously cast aluminum
Fig. 16--The computed velocity field in the central vertical field of the
slabs and billets. While electromagnetic stirring has been tundish: (a) in the absence of flow control arrangements, (b) with a dam
used in the steel industry for some time, elegant calculations and a weir insert, and (c) when a 3-kilogauss magnetic field is imposed on
coupled with physical modeling have led to the application the system in the horizontal direction, perpendicular to the main direction
of these concepts in a rather new form, in the production of of the flow.
cast aluminum products of very high surface quality.
It is perhaps paradoxical, but mathematical modeling has
INLET STREAM been used to a much greater extent in the traditional metals
processing fields than in the "high-tech" operations. Thus
heat and fluid flow in steel tundishes is well understood, but
the largely analogous problems, concerning flow in titanium-

Table VIII. Principal Input Parameters


for the Tundish Calculations

Working fluid steel


Tundish length 6.79 m
Tundish width 0.65 m
Melt height 0.75 m
Inlet stream velocity 7.67 m/s
Inlet nozzle diameter 54 mm
Outlet nozzle diameter 54 mm
Fig. 1 5 - - A schematic sketch of a tundish.
Ratio of inclusion particles to fluid density 0.5

METALLURGICALTRANSACTIONS B VOLUME 19B, AUGUST 1988--537


O.IO BES28
---NO FLOW CONTROL -''"I .... i .... I .... I .... i . . . .

o FLOW CONTROL 12500


0.08 (1,o) Z = l m m - -

!
9 DAM WITH SLOT ~ b ~ (2,x) Z= 13mm
x TWO WEIRS ONE DAM
i0000 ~ ' ~ x ~ (3,r2) Z=25mm --
- "".~'N~"~ (4,+) Z=37mm
0.06
Cex
I~ ' uINCLINED WALLS
7500 i "~ (5'*)
Z=49mm-
0.04 dC.% .I '~jwithmagnetic 5000
; o,
" ~ i eose (b).
2500
0.02
// '\
'-... 0 2.5 5 7.5 10 12.5 15

0
0 2.00 4.00 6.00 8.00 I0.00 RADIAL DISTANCE ( r a m )
Fig. 1 9 - - A comparison between the experimentally measured and the
TIME (min.) theoretically predicted temperature profiles in a nontransferred arc system.
Fig. 1 7 - - T h e tracer dispersion, or "C" curves, for the tundish system for
various flow control arrangements.
B. The Use of Models in New Process Development

melting hearths or superalloy-pouring systems supplying It is axiomatic that as the United States metals producers
atomizing nozzles, have hardly received any attention. are in the commodity business, paying United States wages,
The main barrier to the implementation of these concepts they will not be able to survive unless they are the tech-
tends to be the nonavailability of suitably trained personnel nology leaders, or at least among the technology leaders, in
(even the most user-friendly computational package requires the world. This mandates the need for a much more rapid
experienced users in this field!). Another key problem is the rate of developing new products and new processes than has
lack of appreciation of these techniques by senior manage- been the case in the past.
ment, many of whom had their professional engineering There is a critical need to promote recycling (the alumi-
careers in the pre-computer age. One should stress here that num companies have been quite successful here), the
there are many outstanding opportunities here, with a very recovery of valuable by-products from waste streams and
impressive potential for return on investment. perhaps most important of all, the development of new mar-
kets and new product lines. Mathematical models can have
a major effect during the whole sequence of the develop-
ment process. Initially, models can help in assessing the
potential feasibility of a concept, then will provide guidance
regarding the measurements that have to be taken and their
GH --- ~ i Arc jet
interpretation, and finally in the scale-up process.

Nozzle
a) Plasm,, arc Jet (torch), non-lransfe~ed mode

Fig. 18--Typical examples of plasma torches: (a) nontransferred arc, Fig. 2 0 - - A comparison between the experimentally measured and the
(b) transferred arc. theoretically predicted temperature profiles in a transferred arc system.

538--VOLUME 19B, AUGUST 1988 METALLURGICAL TRANSACTIONS B


An excellent example of successful modeling of new interest was in metals extraction and refining, that is the
technologies has been the development of Allegheny manufacture of the semi-finished products, slabs, billets,
Ludlum Steel's continuous strip casting process, where in- rods, or bars. This barrier is not only artificial and unneces-
telligent calculations have paved the way toward a radically sary, but also positively harmful. The major challenges fac-
new technology, t38j ing us need a holistic approach to these problems, fully
Metallurgy and the materials field are unique in engineer- integrating the "primary," "secondary," and the finishing
ing, because ultimately we have to be concerned with the operations, in order to arrive at the optimal strategy. Mathe-
structure and the properties of the final solid product. It is matical models can play a key role in bringing about such
this structure and property relationship that drives both the an approach.
extraction and the refining processes, because of the key
role played by specifications for purity, internal structure,
and composition (as well as the end processing sequence) ACKNOWLEDGMENTS
for the final product. The author wishes to thank his numerous students, past
The interdependence of these processing operations is and present, who played a key role in doing some of the
clearly illustrated in Figure 21. It is seen that the nature of work that has been cited, and who are now leading major
the raw material, i.e., virgin ore, recycled scrap, or material new initiatives in the modeling fields. Thanks are also due
recovered from waste materials and the actual refining will to the various Federal agencies that have generously sup-
have a marked effect on the composition, structure, and ported this work over the years; particularly noteworthy in
properties of the finished products. the field has been the support of NASA (NAS3-24620,
As an example, using present-day technology, many of NAS3-24642, NAG3-594, NAS3-25074, NAG3-808) for
the impurities, such as copper, lead, and zinc contained in our electromagnetically driven flow work, and the DOE
"normal" steel scrap, will rule out the production of high- (DE-FG02-85ER-13331) for our plasma program. Dr. W.
grade sheet products. Starting with virgin ore and limiting Wahnsiedler and Professor H. Y. Sohn kindly supplied the
the use of "bought" scrap, with the proper technology, will original material used in Figures 8 through 11 and 12
enable one to produce very high quality end products. In- through 14, respectively. Morris Cohen, John E Elliott, and
deed, as demonstrated by Emi, 1391using sophisticated ladle Noel Jarrett kindly commented on the draft of the manu-
metallurgy techniques it is possible to produce steel that script, but the responsibility for the opinions expressed here
contains less than 50 ppm of all other impurities. Such steels is solely the author's.
would have extremely good "superplastic" formability.
At the same time, we should note that certain secondary
processing techniques, such as rapid solidification and spray REFERENCES
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/
I D I = D e c i s i o n Points
Fig. 21 - - T h e metals and materials processing sequence, also showing key decision points.

METALLURGICALTRANSACTIONS B VOLUME 19B, AUGUST 1988--539


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540--VOLUME 19B, AUGUST 1988 METALLURGICAL TRANSACTIONS B

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