Summary of the proceedings of the fourteenth calphad meeting

CALPHAD Printed

Vo1.9,

pp.

No.3,

201-226,

1985

0364~5916/85

in the USA.

(cl 1985 Pergamon

SUMMARY

$3.00 t .OO Press Ltd.

OF THE PROCEEDINGS OF THE

FOURTEENTH CALPHAD MEETING lo-14 June 1985, MASSACHUSETTS INSTITUTE OF TECHNOLOGY Cambridge, Massachusets, USA Organized by:

L. Kaufman, ManLabs, Inc. and W. S. Owen, MIT, Cambridge, Mass.

Sponsored by:

CALPHAD, Inc. American Society for Metals Pergamon Press, Inc.

Rapporteur:

L. Kaufman ManLabs Inc. Cambridge, Massachusetts

1. Introduction The fourteenth CALPHAD meeting was held at M.I.T. in Cambridge, Massachusetts during lo-14 June 1985. thirteen countries.

It was attended by 110 participants from

While it Is expected that many of the papers presented will

appear as future articles In the CALPHAD journal, the following summary is provided to permit a timely interchange of information between interested parties. 2. Summary of Papers M. Sluiter and D. deFontalne used a fourth-degree polynomial expression for the enthalpy to fit known metastable coherent mlscibillty gaps in Al-Ag (1) and-Al-Zn (2,s).

Enthalpy values for Ag-Zn were taken from

201

1, KAUFMAN

202

Hultgren

(3).

coherent

miscibzlity

three

The

gaps

in the

R. Luck and B, Predel (2)

with

ahiftlng

in the

of

structures

the of

oonfirm

extrema

sizes

depends

the findings

non-periodic structure

of

Hoch and Arpshofen

This modification

equiatomic

of

atomlc

enthalpies

space

(1)

in the non-periodic

deformation,

shifts

composition. radii

The

as well

in SI-Sn

tiling.

point

ar Penrose

two atoms range

short

space

diffusion,

tiling

when the

and the configuration exhibits

plastic

ratio

mixing

model

sizes,

from the

on the

plausible

88 on the?

were used

to

(cj,g),

of glassy

introduced

complex

atomic

mixing

to calculate

system,

the

differing of

were used

Al-Ag-Zn

Measured

R. Luck discussed generation

of

enthalpy

the melt,

sets

eonsfdered

the modification

the extrema

binary

edge

order.

These

defects

tiling

involved

in the

have different c8n be

Defects

defects

permit

and deviations

elastic

from

and

ideal

concentration. L. Kaufman reported extended

to cover

Ge02’

coworkers

(14,15)

expansion

coefficients

performance

of

silica

base metallic

in fron

based

glassy

embrittlement

and B; Fe,

Ni and 33; and Fe,

by Auger electron

the observations base

covering

lanthanide

several

solid

the Redlich-Kister species

similar

method

in the

analyses

of

V. P. Itkin Iron

binary

(24). T. NishIzawa,

of

pieces

of of

exhibiting pressure

data

of data

of

the

A method for

and annealed

the

molar

free

family

of

extensive The entire in terms of

energy

of

descriptions

reviewed

for

thermodynamic

d&t& for to the

close

adopted

for

each

(22,231.

regions

8 consistant

values

of

(181, thermodynamic

has been treated Previous

phase

Ni,

arguments a large

were

can be Fe,

The results

8 chemical for

dioxides

developing

erroneous

annealing

P, C and Si;

from stoichlometry.

base

that

surface

CaF2 structure,

the partial

noted

Cr,

classical

the

and solid

that

sputtering.

e&n be cafculated.

to correct

and

synthesls

in the quenched

deviations

f2l_) so that

out

Fe,

Ar ion

construction

and large

in the Ziquld

and applied

using

thousand

sol.ution

was being

enhancing

low temperature

Alloys

uranium and plutonium

had been re-assessed. derived

after

on the basis

and C. B. Alcock

alloys

8lLoys

Cr have been studied

temperature-composition-oxy~8~ oxide

alloys

dioxides

(8-2)

by Schlicting

to SiC2 permit

metallic

C. Joud pointed

on the

solutions

database studies

coatings.

spectroscopy

reported

and actinide

oxide-oxide

for

116-19).

were discussed

T. B. Lindemer

ceramic Recent

Ge02 additions

A. R. Yavarl.and J.

with

data

current

to match those

correlated state

the

has shown that

D. Bijaoui, segregation

that

HPC2, and Tl02.

data

set

some

solidus has be&n

the Fe-Cr

and Fe-Mn

systems

NbC In austenite (30)

to

solution

compute

H. Chtanl (25)

with

and M. Hasebe

descriptions

theiron-rich

sublattice

model

Fe-C-Nb (31).

It

coupled

of Fe-C was

Phase diagram found

recent

(261,

that

Fe-Nb

solubility

data

(127-B)

on the basfs the solubillty

for

and Nb-C

of

the

regular

curve

in the

P

SUMMARY OF THE PROCEEDINGSOF THE FOURTEENTH CAlPHAD MEETING

high carbon

range deviates

activity

carbon

of

from a simple

in austenlte

hyberbola

1s reduced

203

due to the fact

remarkably

that

by the addition

the

of

niobium. L. Kaufman noted superalloy8 barriers

that while

are currently

based

the phase diagrams

these

systems

Ni-Al,

Nf-Cu,

are poorly Ni-Sl,

compute Isothermal

many coating on formation

which control

defined.

sections

J.

Lacaze,

G. Lesoult,

0. Relave,

by calculation

the component

blnary

systems

data base information

systems

and NI-Al-S1

systems

(35-37). -reported that

the edge ternary

sections

Isopleths

calculated

with

an extended

studies

(2)

region

model of the

satisfactory.

the quarternary

system were

inspired

a model thermodynamic

by earlier

description

work of Okokawa and Iwa

The model uses a picture of a lattice-like (40) and of Lln and Pelton (4l_). silica network in which a number of covalent silicon-oxygen-silicon bridges broken

by basic

expressed only order

metal-oxide

as a function

binary

of

coefficients

SlO2,

(42,43)f’or has also higher

liquid

silicates

(45) achlevlng -

systems

T. R. Bramblett calculates temperature, The output

is

phase fraction

charts

B. Jonnson,

breaking

network.

are

is

The model uses

to binary

and higher

for

each phase

with additions have developed

ternary

systems.

In an alloy (46,47).

and reaction

two dimensional

for

based model

to the PbO-Si02 and Fe-0-SI02

with experimental

and composition sections

it

structure

findings.

This method

NIO-Si02 and ZnO-SiO2 a9 we1I as the

of phase present

isothermal

J. 0. Andersson, Jansson,

the silica

Flood-Knapp

and applied

and J. E. Morral

& regular lines

(3)

to CuOo 5-Si02,

pressure

phase diagrams,

a generalized

based on’Fe-O-S102

phase fraction

the amount and type

bridge

and has been applied

good comparison

been applied order

of

of

CaO, FeO, MgO, MnO, N&20, NiO, PbO and ZnO.

B. Bjorkman presented systems

The energy

of polymerization

Interaction

mixtures

molecules.

from

(2).

and E. Wesker formulated melts

systems

Comparison

were quite of

system has

Redllch-Klster

compound phases.

observations

in the aluminum-rich

with experimental

of

to

between 700K

Ansara and J. P, Riquet

ternary

on the

sections

the Al-Cu-Mg-Si

on the basis

of

(32-34) were employed --

of

ternary

silicate

oxygen

and performance

of

calculated

M. A. J. Mlchels

or alumina

and investigation

of stolchlometrlc

of multicomponent

I.

base

investigation

with an assumption

found to agree

silica

nickel

computed and experlmented

and computatIona

been performed

binary

ln the NI-Cr-Sl

and 1500K and compared with partial an experimental

of

for

the preparation

Accordingly

and Al-Si

Cr-Si

systems

isopleth

of CU, Nl, a computer

Zn and Pb.

program which

These charts

represent

system as a function The required

input

of

are binary

triangles. diagram contalnlng

color-coded

present.

A. F. Gulllermet,

K. Frisk,

P. Gustafson,

8. Sundman and J. Agren reported

M. Hillert,

on the Thermo-Calc

bank (48-50) which includes software for Interactive (48~5ljcalculation -This software phase equillbria and automatic mapping of phase diagrams.

B. data of is

L. KAUF~N

204

to several

connected for

iron

based

C. Chatlllon data

for

activity

of

these

streams

with

Xn the

Specific

latter

or S102 reactor

oxidation

are

58)

uncertainties

number of

not

are

materials

resistance

of

has been known for

it

used

to calculated

reported

topology currently

not

fInlte

NI-Al-Pt

of

using

well

for

the

current

the

system

fourteen

base

from the

element

thermochemical lattice

data and phase

stability ten

characterization

communication This

by computer

process

(3).

of

phase

of

visual

Nevertheless,

of

the

of

the

of

(70) for each topologlcally the algebra correspond uniquely

(edges) of

blvarlant

(surfaces),

The elements phase

diagram

and retrieval.

of

the

and

to the

etc.,

equilibria

data

Interpretation exists

distinct

Incidence

is a

phase

invariant

transltion algebra

providing

Multlcomponent

diagram there

algebra

diagram.

storage

the

was presented.

to complete

algebraic

Graphical

emulated

a ncalculusl*

computer

a method

human interpretation.

monovariant of

is reactions

on nickel

ternary

diagram

have been Incorporated

diagrams.

Incidence

(vertices), equilibria

that

analyses.

The elements

diagram.

defining

(61-68) --

system

requires

unique

and the

(54) the reasons for this and recent thermochemical

(55,561

Pt-Al

the extension

presented

of phase

usually

for

data

Orser

considered

exist

while

coatings

(59,601 to cover vanadium based on pair potential, -Previous assessments as well as available diagram data. binary

species

that

aluminide

the

The calculated

systems.

L. Kaufman described

D.J.

to

resolving

was noted

base

fourteen

phaSeS.

or with Hz0 In the gas

ten years

Data bank values

clear.

being

binary

thermochenleal

is one

related

for

examples

gaseous

case

L. Kaufman and W. L. Worrell

enhanced by platinum

(7,

there

and Solution

and methods

Investigations.

where a large

Al203

superalloys

component

chemical

thermochemistry

activity.

enhancement data

compounds

to errors.

W. G. Barker, of

and in particular

for

Ni-C and Co-C where CH4/H2 and CO/CO, equilibration

carbon

pases

discovery

(2)

C In Fe-C,

can lead

bases base

considered

system

Independent

system

used to measure of

binary

between

were the Ga-Cl

data

and the SGTE data

and C. Bernard

assessment

discrepancies

thermochemical

alloys

are

sets

an efficient

systems

means

can be stored

by

this

methodology. R. E. Watson noted calculations 3d metals energies observed differences results.

that

senlrelatlvlstlc

have been done for employing

the

linear

the 5d metals augmented

were obtained for these metals low temperature atomic volumes. were compared

with

self-consistant La through

Slater

type

in both

the

Au, and for

orbltals fee

The resulting

the Kaufman-Bernstein

band theory LASTO.

and bee forms structural

and disparate

some of

the

Total at the

energy Engel-Brewer

In addition the issues arising from evaluation of the difference energy between an alloy and the elemental solids from which It forms was discussed.

In

205

SUMMARY OF THE PROCEEDINGSOF THE FOURTEENTH CALPHAD MEETING

R. F. Brebrick of

and C-H. Su discussed

Zn, In and Sn in solid

Ge.

The excess

entropy ideal e.u,

term for the

previous

14.6

R. St.

modified systems.

by Welser Pierre shell

energies,

Taking

to deal of

elements

in solid

an enthalpy

standard

binding

and an

state

as the

at 950°K is within

These findings

3

were compared with

model based on a

with expected

can lead

interface

shells

to severe

in alloys grain

The solvation

shell

and relations

concentrations

excess and ceramic

boundary

in harsh environments

in the interface excess

mechanical

solvatlon

attack

applications.

Interfacial

of

and solubility

these

into

the solute

entropy

a statistical

enrichment

distortion

of

was resolved

Ge itself.

approach

intergranular

materials for

the binding

potential

and Van Vechten.

presented

Such solute

account

for

in the distribution

embrlttlement, electronic

solute,

Cal/X g-atom

solvatlon

concentration

binding

gas at O’K, the excess

analysis

G.

of

the neutral

monoatomic of

Ge in terms of

energy

Gibbs

the chemical

and instabflities energies

between

and solvation

in

are modified

to

interfacial

shell

energies

were

discussed. Hoch

M.

discussed

MgO-SiO2 and Fe-Fe01e5 compound formation

exists

P. Gustafson, new model for available

data for

size

physical

additional

suggested the entire

J.

that

of the and

reported

of condensed

application

properties

Consequently

of

on a

phases

by considering

the

data for

this

work (72) the physical of short range order were

atomic

size

differences

and

the LI-Ba system where the relative

has been studied.

Agren and B Jansson

by Hillert

in earlier

showed the effect

70 percent

and thermochemical

system

applied

A comparison resulting

was made of

from this

the two sublattlce

study,

model

to the Mg-Sn system in order to assess the properties of They compared the results with previous calculations

phase diagram.

iso-entropic

and To temperatures*

N. Saunders treatment

and M. Hillert

properties

it’s

on physico-chemical studies.

is

B. Jonsson,

of

and J. Saar noted

These studies

difference

to analysis In the liquid

Fe, C, MO, Cu, and W.

and Influence

prompted

A. F. Guillermet

the thermodynamic

to use and illustrated

H. Ruppersberg Investigated.

(71)

gaps occur

as well,

representing

convenient

of’ the complex model

where miscibility

J-O Anderson,

which is

origin

application systems

of

employed

the glass

a previously

forming

ability

reported of binary

(22)

thermodynamic

metallic

alloys

and kinetic to deal

with

The method was illustrated by predicting the multicomponent alloy sytems. critical cooling rates in NI-Pd-P alloys in the composition range up to 30 atomic percent phosphorous. B. Bergman and J. Agren analyzed Nio in terms of

the Debye model coupled

Thermodynamic functions be a miscibility

for

gap below

the thermodynamic with a model for

the solid and liquid C and permftted

410’

properties magnetic

of MnO and transitions.

state suggest that there should calculation of the complete

t. KAUFMAN

206

phase

diagram. and L. Ostlund

A. F. Guilfermet in

the Fe-NT-W system

equilibria

derived

1273K for

between

couple

Cr-Fe-Ti,

in the Fe-NI-W-C

Fe-SI-TI data

and Fe-TI-V

available

in the

system

percent

between

silicon

addition calculate

equllibria

in the

and J.

F. Eliott

found

describe

the

in off-gases

of

Such metal

sysems.

are mixed with etremely

high

conventional of

of metal

of

formation are

Redlieh-Kister between

dimensional with

temperature

or activity

the Ca0-Fe0-A1203-Fe203-S102 of

liquidus

contours

K, E. Spear, multi-component and associate base

pressures function

binary

to describe and ternary

incorporating interaction

pressure, and J.

the variation transition with

S.

Kirkaldy of

glass

metal

carbides,

component

composition.

of

The model

figure

equilibrium. of

for component

with

a data

partial

systems

as a

potential.

a statistical

potentials

entropy

a five

within

models

activities,

and ceramic

nitrides

of

he calculation

in conjunction

constructed

lines

slices

mixing

and oxygen

the chemical

other

simple

Ideal compute

composition

vapors.

component

vertices

on phase

discussed

be used

Model

zinc

on the

to illustrate

incorporating could

of

a two dimensional

pressure

such as SOLGASMIXto

the vibrational energy

high

W. Hastie

in multicomponent

temperature,

K. Balasubramlan model

Such models

and equilibria of

systems

of

for

pressure

geometry.

six

to

calculation

straight

six

A number of

ordinate.

effects

programs

basis

were discussed

and J.

species.

as the

six

gases

by

partial

based

and the

system

and the oxide

through

as the

P, K. Lfao liquid

and general

serves

of

and system

defines

of

correspond

permits

slices

This

typical

described

the oxidation is

to

vapor-laden

of

The procedure

model

conditions

readily

rate

In

to

and combustion

metal

The model

in a pseudobinary

Each line

figure.

attempts

particles

as a function

calculated

th,e ternary.

processing These

studies

the

reported.

oxide

not

gas flow

coefficients.

composition

into

nucleation

when hot,

particles

systems.

pseudobinary

a selected

of

and are

experimental

and alumina-silicate

were

of

than 50 atomic

Initial

a chemical

mechanisms.

aerosol

less

extend

systems

and cooled.

R. A. Howald and M. W. Scanlon silicate

all

formed

temperature,

with

emPlOyiW3

studies

with

observed.

and growth

nucleation

oxidation

vapor,

were made at

in the Al-TI-Fe,

diffraction

high-temperature

gases

of

were compared

are

supersaturation

distribution

sections

alloys

proposed

various

oxygen-bearlng levels

X-ray

ternary

aerosols

hormogeneous

the size

results

oxide

observed

comparisons

1223K and 1623K by

Ni31 Si12

compound phases

phase

those

that

and 1000°C for

P. Bolsaites quantitatively

isothermal between

NISI FeSi,

ternary

experimentally

SeCtiOnS

system.

system

800’~

show that

several

isothermal

literature.

G. Inden and S. Bruns reported Fe-NI-Si

calculated

Further

data.

G. Ghosh and V. Raghavan calculated binary

the

l273K and 1673K with

from diffusion

equilibria

compared

of

mechanical

the

components

and carbonitrides

and the variation

has been applied

of

pair

to the Bl

of

SUMMARY OF THE PROCEEDINGSOF THE FOURTEENTHCALPHAD MEETING

structure

in the binary

iron-base

austenites

calculate

the influence

of different fraction

alloy

of precipitates

and their

concentration ternary

with

systems

formation

of

rare

ternary

for

complex

observed

carbides

in most carbide

metals

of

latter

systems

the iron

Ternary

carbide transiton

Their

translton

metals

in metal

metals

of

of

face

the 4th,

the 4th,

structure

the binary

is

5th,

centered

features

metals

cubic

hlgh

Au-Pb-Bl

system

between

Pb-Bi system given intermetallic

phases

isothermal

experimental

phase boundary

I.

the high

of

extreme high melting

complex

carbides

the transltlon In the systems

metals

isothermal

sections

thermodynamic

data for

by Okamoto and Massalski

points

obtained

in

solid

there

are

for

the

Ideal

(74,751 mixing

the AU-Bi

and data for between

Pb and Bi edge. with

using the Smith Differential Thermal

Technique. Wang,

equilibrium

M.

Grujicic

compositions

and W, S. Owen considered of austenite

the

has been assumed and the

AuPb2 and AuPb are restricted to the Au-Pb binary 3 sectlons were compared in the form of isopleths

The computed Analysis

these

Co, and Nl.

the Laves phase, TPb,Bi)Au2

of

in the

carbides.

by Zimmerman and Lukas (76).

atoms on the sublattice

of

and ternary

with Mn, Fe,

300K and 1200K using

reviewed

complete

with rhenium and platinum temperature

with compounds.

of

them exhibiting

the systems

F. H. Hayes and W, T. Chao computed ternary and he Au-Pb systems

those

by mostly

group

are

have been studied

among carbides of

the 3rd

There are many

intermetallic

i.e.,

many of

systems

of

The phase equilibria

and 6th group,

the iron

and 6th group

metals

and

compounds are also

stable

Importance,

5th,

characterized

of

by pronounced

and the actinldes

metals. by very

monocarbldes,

eutectic

transition

earths

The

5th and 6th groups

Such ternary

the rare

of

(3).

each category

uranium and thorium.

cases.

technoIogica1

of

and the metals

the 4th,

metals

determined

are characteristic

of high melting ternary

of

Quasi-binary

properties. rich

metals

series

the transition

of

equilibria

both within

system of

group and the platinum

systems

detail.

solution

in these

indicating

are characterized

of

metals

This description exist,

the heterogeneous

carbides,

elements

systems

frequentfy

are

melting great

transition

the actlnide

the transition

compounds In the systems

and actlnides the binary

The carblde

group with high melting known only

of

of

phases

for

and other

ranges

and volume

findings.

carbides

temperatures.

parameters

earths

of mixed phases

among the categories. well

with experimental

at elevated

to

to

on the stability

in the austenite

and ternary

the components

and N and applied

nonstolchlometry

in which the respective

and temperature

phases

Ti,Nb,C

1273 and 1473K in order

concentration

binary

behavior

the ranges

of

between

in agreement

described

reaction

represents

systems

of precipitate

precipitates,

H. Holleck

those

and ternary

at temperatures

207

the variation

in he

and titanium-niobium-carbonitride

prclpltates in Fe-Mn-Si-Mo-Ti-Nb-C-N over a range of alloy composition included typical compositions of ultra low carbon microalloyed steels.

which The

L. KAUFMAN

Kohler

temperature-dependent-subregular

austenlte

phase.

The (Ti,Nb)

Hillert-Staffansson components

sublattice

mixed

In pairs.

for

model

allowing

boron

on the preclpltate/austenlte

the primary

solid

Fe-Cr-Mn-Nl-C. iron

as all

phases

the

of

of

being

a function “best-setll

results

in each

to the deposition

For the chloride was applied

of

the

method,

to the

parameters

GaAs from both

a novel

composition

levels

source

ratios

close

to be greatest

that

the

pseudo-steady

liquid

and hybrlde vapor

the gas phase with

phase

the quartz

up to lppm under

typical

that

good

state

to the

operation

defect with

the

conditions

structure complex

of

which mlnlmlzed

equillbrlum

ones.

formed

the Sl contamination.

of

The degree the

In design

by the

are present

conditions.

analysis

processes. values

are hot-wall

at

Sl is

an

of Sl by this techniques. A model

Si doped GaAs was developed

chemical

the

method using

amphoterlc dopant in GaAs and the unintentional lncorportlon process presents an inherent limitation In these deposition the point

by the

constraint

In calculated

wall,

the

equilibrium

mass transfer

Sl species, reactor

with

and hybrlde

techniques

In

the latter

Calculations

chloride

for

selecting

mlnlmlzed

experimental

In the

C

their of

chemical

and resulted

pet.

and the

agreement

chloride

in

(DTA).

tie-lines,

in the model.

a complex

saturated

Indicated

of

consisted

system

were,in

as

of

wt.

analysis

and calculated

and

as a

Composltions

and to extend

This

Investigated.

of

of

Both the chloride

interaction

results

the parameters

carbon

have iron

couples,

thermal

the alloy

both

this

and Fe-Mn-NI-C,

1750K.

applied

phase mole

and the analysis

of

system,

(FCC) equilibria

equilibrium

and

system

by 0 to 1.2

systems

was found

source.

bounded

was developed.

phase

of measurements

liquid-gamma

the

the Ga to As vapor

operating

carbon

liquid

contain that

Anderson

of

supersaturation

which

by differential

experimental

the

the quinary

from 1811 to about

model

between

D. J. Meyer and T. J.

for

of

The results

on ultra-low

Fe-Cr-NI-C

consisted

liquid-solid

model

in a thermodynamic

experimental

conjunction

The effect

the quinary

(78) sub-systems

pentahedron

ranged from

of

systems

among the experimental

difference

model employing

solid

phase.

data

comprise

Fe-Cr-Mn-C,

(BCC) and the

the Gibbs

a mathematical

Implicitly

analysis

quaternary

the equilibrium,

to interpolate

usefulness, of

was explored

discussed.

between

corner that

investigation

were obtained

temperatures

Iron-rich

viz.:

liquid-delta

corner

the tie-lines

square

experimental

with

two phases

was also

the

by the

solution,

the

the precipitate

relationships

and ternary

The temperature

parameters

with

quaternarles

components;

the binary

for

Fe).

order

In the

The experimental

Iron-rich

(bal.

of

on phase

to the three

the

of

component. the

reported

was limited

tie-lines

between

to describe

was described

a four-component

equilibrium

agreement

Of the five

as two of

well

phase

steels.

D. M. Kundrat

study

for

the nonstolchiometry

were shown to be in good

model was used

precipitate

The equilibrium

while

mlcroalloyed

solution

(C,N)x

and used in

to search

for

It was shown that

SUMMARY OF THE PROCEEDINGSOF THE FOURTEENTH CALPHAD MEETING

the formatlon

of

amounts of water

vapor

phase Si species

or by replacing

The unintentional

doping

Si species

addition

of HCl or arsenic

operation

has the opposite emphasis

carrier

Si can also

rich

on stability

sodium and sodium chloride

side

of

solid

solutions.

of

the mageslowustlte

In the solid

at finding

pressure

four-phase

polyhedra.

the

decreasing

the

the Fe-Sn phase diagram with Fe3Sn, Fe3Sn2 and

measured

the activity

the entire

the concentration

and temperature

and E. Woermann calculated three-component

systems

of

relationships

consideration.

The phase

program SOLGASMIX, aimed

stablllty

were included

for

of Fe 3+ in

The presence

minlmlzatlon

ranges

Molar volumes

dependencies

MgO-FeO-S102 and

data.

was taken Into

by the free-energy and temperature

sodium

range.

the phase equilibria

activity-composition

from experimental

solution

of

concentration

mixtures.

system yielding

MgO-FeO-Ti02 were calculated diagram calculations,

while

the compound phases

in these

E. Jacobsson

In the MgO-Fe0-S102-T102 all

through

It was shown that

purity

between 960K and 1373K across

G. Eriksson,

the

effect.

the iron

These data were used to calculate of

small species,

by shifting

species

In addition,

gave improved

of

gas with an inert

be decreased

Fe1 3Sn In the temperature range 781 to 9Ol’C. . S. Kamoushi, J. P. Bros and M. Gaune-Escard In Na/NaCl melts

by the additon

to chlorine-rich

trichloride.

temperature

S. Bhan discussed particular

of

from hydrogen-rich

at lower

pressure

the hydrogen

levels

volatile

can be reduced

209

of the most Important

In the high pressure

calculations. N. S. Srinlvasan, their

J-E.

work on development

Iron-making

processes

between

metal

by Erlksson,

is

of Technology

slag

the production

composition plant

for

composition

data for

to a thermochemical

contains

some operating

raw materials of

at the Royal specie-and

dilute

and the

as input

the models

The slag

the hot metal.

representing conditions

in

the

Group Thermodata Europe)

Tables

It is

of elements

Technology

The databank

and composltlon

consider

the processes.

rate

model predictions

were given

and

for

and compared with

data.

J. Agren, system

rate

new Swedish

The models

the equilibrium

are connected

the various

reported

program SOLGASMIX, developed

and Materials

In Stockholm.

of

thermochemical

by SGTE (Scientific

and top gas rate.

Inred and Plasmasmelt pilot

for

three

the distribution

to determine

the models

of

zones

The equlllbrlum

Metallurgy

With the compostlons

authors. predict

compiled

Thus, of

rule

for

Staffansson

and Elred.

reactlon

considerations

The requlrements

are huge.

data

the various

and L.-I.

models

Plasmasmelt

and gas phase.

at the School

Institute solution

thermochemical

used as a subroutine

phases.

calculations databank

for

equilibrium

slag,

the various

of

S. Seetharaman

named Inred,

heat and mass balances assumed that

Tapp,

by high

S. Hassem, M. Gaune-Escard temperature

calorimetry

and J.

P. Bros.

and thermal

analysis;

examined

the Ag-Au-@

the enthalples

of

L. KAUFMAN

210

formation

of

obtained

over

using

the

liquid

the available

equilibrium

alloys

),

equilibrium

calculated

phase

and experimental

data the

(enthalples

thermodynamic

diagram

phase

of

For each

range.

bibliographic

temperatures...

the ternary

and the temperatures

a wide concentration

of mixing

the calculated

content

than that

N. J.

calculations

out on the

match with

system

to martensitic

U. Kattner Ga-Sn after

Ansara

congruently,

the

diagram

heats

of

neutral

data,

the

reOsultlng

ternary

In selected

regions

data the fee

for

the

Sn-Te the

for

binary

systems of

subsequent

the

Inclusion

and bee phases

In copper

thermodynamics

of

optimlsed

ternary

this

phases

the Gibbs

system

and for The

Ga-Sn-Te.

and decomposes

were taken

energy

of

A least

of

above

room

the associate

optlmisation

entahlples

potentials

melt

as stoichlometric.

the liquid

squares

measured

and chemical

earlier

Two GaTe and Ga2Te3,

perltectically

Ga Te was used. 2 3 calorimetrically

the liquid,

into

the previously

to describe noted

melts

sublattice.

of

was done

the liquid,

Ga and Te in solid

capacities

model of

of

metallurgical between

and

of

capacities of

slags,

capacities

In terms

basic of

of melts

sulfide

are generally is

and can be

In particular,

the ability

such

of

(79). slags

exhibited

correlations

CaO-SIOS mixtures)

It

equilibria to as

can be

underway utilizing

independently

has now

by Lln and Pelton.

general

types

for

to allow

the model

interest. describe

model

salts

the model

various

capacities

sulfide

version

Is now very

and are a measure

being correlated with the basicities misleading. An analYSi8 of sulfide Ionic melts. For simple slags (e.g. sulfide

model

sulfide

between metal and slag phases desulfurlze metals. Although

two-sublattice

In this

by modification

transitions that

developed

from the reciprocal

the anion

to slllcate

M. Blander

Calculate

combined

and Al-Zn

phases.

these

the two-sublattlce As a consequence, applied to most kinds of melts of can be used

data

forms of

which originated

species

been applied

germanium

the

In applying

Intermetallic

Ga2Te5,

extended

phases

mole

samples

M. Hlllert liquid

three

description

an associate

Te In liquid

to a higher

were offered for

importance

In the optimisation

with

specific

experimental calculations

contributions

of

third,

model with

of

and

For each

valley.

Cu-Al

how far

and Bergman to calculate

For the analytical

the

transformations.

contains

phase

the Cu-Zn,

and H. L. Lukas took

Ga-Te system temperature.

of

existing

ordering

which are

alloys,

between sections

temperatures

and A. P. Miodownlk

to assess

Preliminary

system.

corresponded

and

experimentally.

L. Chandrasekaran

mdlficatlons,

of more specific rich

composition

characterizations

further

Cu-Zn-Al

observed

Saunders,

thermodynamic without

eutectlc

activities,

A comparison

was carried

were

system,

was Investigated

KAg/KAu = l/3 , 1/l and 3/l showed good agreement for the except In the vicinity of the eutectic fractions as well, section

equilibrium, binary

consistency

was calculated.

diagrams

phase

limiting

theories

one can readily

determinable

of

211

SUMMARY OF THE PR~EEDINGS OF THE FOURTEENTH CALPHAD MEETING

thermodynamic

quantities

baslclties.

Calculations

Illustrate melts

and illustrate

the problem

provide

for with

more complex

of

sulfide

steelmaking

slags

approach

capacities

capacites

slags

the correlations

a more general

predictions

why sulfide

(e.g.

with

CaO-FeO-Si02

baslcltles.

many slags

the composition

in

enthalples

of

formation

are very

exothermic.

mixtures

and very

materials. of

An increasing

of

systematic

thermodynamic

these

are generally

the stability

mixtures

interest

of

Investigation

the enthalpy

and eighty of

binary

range. of

of mixing

for

This

to

LIF-ZrF4

LIF.

The

percent

some flourlde glass-forming

systems:

‘a sound

mixtures

would allow

study

is part

ZrF,,-MF systems

has only

ionic

lead

of

than five

of these

multleomponent

of

basic

percent

better

is developing

the subsidiary

composition

complex

of formation

on the thermodynamics

the thermodynamics

prediction

zero

with an accuracy

few data exist

These materials

knowledge

range between

obtained

mixtures)

and should

including

In the CaO-FeO-MgO-Al 0 -SlOB system. 2 3 measured the enthalpy

with

Theories

than such correlations

for

G. Hatem and M. Gaune-Escard

at 1145’K

correlate

of a

(M=alkali

been measured for

a

metal),

For

the NaF-ZrF&

system. W. Thompson, for

aqueous

C. W. Bale and A. Pelton

species

and three

program which provides a large

number of

efficient

program

temperatures,

reactions

Interactive

input

C. W. Bale,

In this

the F*A#C*T system

binary

terminal,

system

for

the

facilities the graphics

with redifined

SOLGASMIX

features

at user to deal

lie

A

functions

terminal,

diagrams

the calculated

for an

specified

with mass

largely

in the

one to carry

capabilities

and versatility

one to calculate

Pourbaix

(E-pH)

calculated

or supplied diagram.

of

by the user.

That is,

FACTPACKalso

region permits

of

of

the personal

diagrams,

mode

and data either

With FACTPACKone

one can transfer

the

FACTPACXthen enables using

graphics

the phase diagram

several

that

in text

from thermodynamic

phase diagram on the screen

to zoom in on a selected

tasks

the central

and print

acqeous

with

the PC can be used

out special

handling

are

a program called

one to communicate

Although

them in the PC and on diskettes.

the enhanced axes.

enables

line.

that

and database

enables

The diagrams

data and store

It is possible

IBM-PC that

a modem and telephone

phase diagrams,

to download

one to regenerate it

upon Erlcksson’s

In the F*A*C*T main database

necessary

including:

form a computing Pourbaix

program the novel

FACTPACKpermits

with

diagrams.

Is able

data

thermochemical

and W. T. Thompson reported

The F*A*C*T system

and ternary

stability stored

via

the calculating

computer.

by a user

these

database

and output. A. D. Pelton

FACTPACKhas been developed

mainframe

a thermodynamic

which exploit of extensive

multicomponent

and a program based equilibria.

aa a ‘dumb’

sheet

entered

to generate

constrained

combine

programs

a spread

described

diagrams

mode.

and retrace

to be

The diagrams can be dumped OntO a matrix printer superimposed over each other. Many of the F*A*C*T programs or plotted on paper with an HP multlpen plotter.

also

operate

as stand-alone

F@A*C*T main database may be of

interest

of

modules over

optimization

and the

subsequent

of

thermodynamic

calculation

POTCOMP)have been adapted calculates J.

ternary

Sangster

ternary

systems

carried

out.

interpolation

having

obtained

there

Interaction

are terms

experimental completeness

of

sub-system

there

ternary

interaction

Calculated into

are

binary

the

systems

the part

of

excess

diagrams

in the

this

of

ternary of

property

for

energy

of

taking

literature

P. Talley,

J.

database

Sangster,

computing

of

all

systems,

The system

systems. Analysis

of

will

Chemical

be able

to calculate

a given

multicomponent

calculatons Liquid-Liquid system

of

be made available

as part

(F*A*C#T),

equilibrium

liquid

composition

(equilibria

properties

developed

liquid

(bubble

and vapour

equilibria

can be calculated

the

solutions.

can also

liquid

be performed.

analyzed,

evaluated

optimized

include

vapour-liquid

equilibrium

liquid

propertles

temperature between

this

are

dependence and other

expressed of

the

as polynomials enthalpy

common approaches

is

data

is the

diagram

an organic

for

the will

and pressures

at

flash

T and P).

thermodynamic

are

search being are

on any critically

simultaneously

at a variety data,

of

enthalpies

coeffecients.

in mole fractions. that

that

or to perform

systems

of mixing

in the

system

at given

as the

temperatures and pressures, liquid-liquid equilibrium mixing, excess heat capacities, and limiting activity

taking

evaluated phase of the phase

the on-line

Data which

(VIE)

a

phase

the Facility of

bibliographic

by computer.

of

among the alkali

tempertures

as well

the

ternary

nonelectrolyte

calculations)

Over 3000 binary

and optimized

of

compositlons

A complete

these

reported

for

Users

and vapour

and

account

data has been used.

and A. D. Pelton

being

The~odyn~~cs

is

Into

available

formed

thermodynamic

C. W. Bale system

ternary

and the uncertainty

data

on-line

of

have been compared,

survey

available

ternary

expression.

diagram

the

these

calculation

evergy

diagram

70 binary

binary

in the binary

the

Gibbs

diagrams

been

Calculated

In a few of

to enable

reported

the 60

the calculation expresslon.

work.

excess

for

their

has been performed with a view to obtaining a “best” A computer assisted coupled analysis for each system. with

(program

TERNFIG

by means of

halides, diagram

together

diagram

In a few of

work.

this

phase

the

all

data

to permit

data

total

A complete

sub-systems.

and thermodynamic

It

FITBIN)

has also

estimated

and the uncertainty

part

enough experimental

completeness

phase

survey

have been compared,

diagram

in the first term

the

which perform

(program

systems

are

thermodynamic data

and experimental

account

from

total

reported

binary

and 60 reciprocal

these

Gibbs

the

the

data

a literature

enough experimental phase

diagram

of

In the

obtained

systems

for

in the first

ternary

can access

on a hard disk.

IBM-PC as has the program

completed

common ions models

stored

diagrams.

and A. D. Pelton

solution

sub-systems systems

and plotting

Phase diagrams

is

the F*A*C*T programs

and phase

to work on the phase

The programs

which

to CALPHADmembers that

coupled

which

on the PC.

5000 species

allowed. optimized

of Excess

A linear The difference parameters

are

SUMMARY OF THE PROCEEDINGSOF THE FOURTEENTH CALPHAD MEETING

not restricted

to one set

reliable

extrapolations

phase is

taken

Into

and G. Kalonji

simulating

thermodynamic

simulation

of

simple

as walls

quantities

systems

to reduce

volume,

researcher

to be unconcerned

Independent

In different

conferences.

mail

researchers

countries

for

regular field

differences

with

measurements

of

this

Is

by modularizing allows of

the

state

when

simulation system

method to to problems

emphasis of

from that

which reflect

K. Frisk

studied between

systems,

excess

stability

as defined

e.g.

In their

the phase equilibria

both as extensions

compounds.

couples

and determination

The experimental macro-probe. available data.

results

Recent energy

composition. differences

electronic

of

Na

three

of

Is strikingly Is not located Consequently,

the

thermodynamic

properties. and Cr-MO-N1 at

fields

experimentally

were presented

exhibit

in their

intermetalllc

concentration

lnflectlon

of mixing

Indicative

alloys

of known binary

of equilibrium

of liquid

of multiple

by Bhatia

in Fe-Mo-Ni

These have been studied

that many

mail.

the one Inflection

Several

than

of a class

features

have unexpected

IS

electronegativity

Gibbs free

of K-Pb liquid

950°C and 1200’C.

ternary

costly

do

which

by SGTE has used

It is evident

the presence

show additional

differences

undertaken

properties

but at the equlatomic

Na-Pb and K-Pb systems

and much less

for

systems

a connection

characteristics.

demonstrate

Na-Pb and Li-Pb;

the K4Pb composition

These mall

but offer

large

on unusual

and

which make It possible

project

relatively

The behavior of

telephones

from the use of elecronic

the partial

functions

ordering.

temperatures

with

mall,

a new way to Communicate

contacts.

the thermodynamic

where the excess

The entropy

In these

approach

this

and discussions.

profit

on the Na-Pb system

with composition short-range

contacts

reviewed

In the variations

exist

than telephone assessment

could

two metals

special

systems

offer

means of contact

more relaxed

In this

composed

behavior

can then be

of

the simulating

to ordinary today

to have regular

the ordinary

M. L. Saboungi

L1-Pb,

systems

changes of

the

by subprograms

approach

Internal

to extend

systems

In Europe a joint

electronic

different

of

in addition

mail

Many such mail

not replace any of faster than letters,

near

that

the electronic

researches.

extrema.

simulations

The application

and methods

B. Sundman reported

Points

with details system.

of

was discussed.

conferences

alloys

The purpose

This lltoolkltft

for

of extensive

The composite

complex

objects.

the composite

phase diagram generation

People

more

the gas

subprograms

to the flow

systems.

of preparing

Into

between

of

to the problem

Individual

and “Interconnectedfl

or mass.

yet more complex

the difficulty

In klnetlcs

and hence provide Non-ldiallty

a new approach

LISP.

or norestrlctlve

subsystems constructing

using

are written

restrictive Into

presented

processes

such as energy,

Interconnected

conditions regions.

account.

K. J. Meltsner

serving

of experimental

from the measured

213

phase fields

occur

and as purely by use of

by means of

diffusion

electron

and compared with other

214

L. KAUF~N

Y-Y. Chuang , Y.A. Chang and R. Schm5.dproposed a generalalized approach to calculate the magnetic contribution to the thermodynamic functions of alloys. This approach was applied specifically to the Fe-N1 binary system. The predicted magnetic specific heat of the fee phase at 75 atom X Nl Is in agreement with the experimental data withln the accuracies of the data and the predicated values. The magnetic contributions to the Gibbs energies of the fee and bee phases for Fe-N1 alloys so obtained are added to the nonmagnetic contributions. The nonmagnetic portion of the Gibbs energy of the fee phase is obtained from extensive thermochemicaldata at high temperature. The total Gibbs energies of the fee, bee and the ordered FeNi. phases are then used to calculate/predictphase equilibria of the Fe-Ni binary from the liquid range down to 500 K.

A. Schultz, Y-Y. Chuang and Y. A. Chang described a computer program, 3DMAT, which uses graphics techniques to display surfaces in space. 3DMAT Is an interactlveprogram that couples smoothly with either empirical expressions or mathematical models to display ternary and quarternary equilibrium surfaces in realistic perpective. In addition the surfaces are displayed with full hidden line removal. The Gibbs energies and equilibrium surfaces for a variety of alloy systems were presented as examples: (1) Fe-Cu-Ni, including plots Gibbs energy, activity coefficient and miscibility gap; (2) Gibbs energy surfaces for several III-V ternarles; (3) sulidus surfaces for the four ternaries of the quaternary Mo-Nb-Ti-V system, and (4) the llquldus surfaces for the Cu-Ag-Cu3P and Al-Mg-Zn systems. E. Hayer, F. Gehrlnger, K. L. Komarek, M. Gaune-Escard and J. P. Bros measured the partial and integral enthalples of formation of liquid gold-aluminum alloys between 1355 and 1587 K by direct reaction calorimetry. Experiments were performed using high purity argon as a protective gas after passing it over columns filled with a Cu-based catalyst (15O'C) and Ti-Sponge (~so'c), successively. Each series was started with pure gold or aluminum followed by successive additions of the other component. The concentration range covered with one series of measurements was about 60 to 80 mole percent. However, the results due to the different series were very close together demonstrated by a standard deviation of less than 1 percent. The minimum In the enthalpy of formation was determined to be -34.0 kj/mol; x(Au) = 0.54;T/K = 1450. The partial entalples of Au were found constant in the concentration range O
SUMMARY OF THE PROCEEDINGSOF THE FOURTEENTH CALPHAD MEETING

containing

Zr14,

H2 and CO2 a thermodynamical

1700 and 1900 K in which It conditions

is possible

where ZrI,, and CO2 are

to deposit

in large

S+ K. Lee and D. N. Lee employed Parameters was based

of

the system

only

Zr02 under

Zr-I-H-C-O

excess.

a regular

the TI-W, Pd-W, Zr-W and HF-W phase diagrams, the interaction

study

215

solution

model to calculate

the method used to evaluate

on employing

data near the center

of

the phase diagram. H. L. Lukas, palladium-rich optimlsed

prtlons

experimental

analysis. systems.

U. Kattner

of the Pd-Ga,

Pd-In and Pd-Sn systems by thermal,

phases

model in order

Such palladium

alloys

IV-VI compound phases,

considered

as a replacement

such as SnTe, temperature

Y. Chuang, J. metastable

S. Paik,

equilibria

equlllbria.

J.

for

diagrams

it

with

of

of a stable

phase

have been examined both experimentally

modeling.

With undercooled

liquldus

reactions boundaries

accurately data. a/o

a stable Cd, 275’C)

this of

with

illustrates feedback

droplets

and lnvarlant

miscibility the value

liquid

equilibrium

which occurs

in a

and metastable phase separation

and

metastable

have been reproduced monotectic

which were overlooked

of metastable

experiment

hat

of a existing

model and existing thermodynamic

gap and an invariant

have been established

the

were presented,

a metastable

The observed

temperatures

solution

that

and with thermodynamic

metastable

have been ldentlfled.

for

model for

Chang suggested

In the Pb-Cd system the stable

a sub-regular

between

phases

equilibrium

restricted

these

to several

It was found

as an extension

the extrapolation

of

the model.

and Y.A.

equilibria liquid-solid

field.

defect

For these

be regarded

the clarification

a point and applied

PbTe, and PbSe.

adequately

H. Perepezko

can often

Alternatively,

may allow

Chang derived

compound phases

data can be described

Pressure-composition

by means of a

are being

T-W. Ngai and Y.A.

experimental

were characterized

description

J-C.

semiconducting

based on

and metallographic

a complete

applications.

Lin,

X-ray

the

to obtain

In dental

non-degenerate

and G. Petzow calculated

data obtained

The Intermediate

Wagner-Schottky, gold

E. Schmld,

equilibrium

and modeling

reaction in past

(Pb-75 studies.

data and the importance

in optimizing

a phase diagram

evaluation. Z. Moser, the enthalpy calorimeter Fifty

percent

W. Gasior, of mixing

between

G. Schwltzgebel,

of liquid

691 and 938’K

and between eighty

Li-Sn

F. Sommer and B. Predel

alloys

for lithium seven

measured

with a high temperature compositions

and ninety

between one and Due to the

nine percent.

high compound forming tendencies of L2-Sn alloys the enthalpy of formation vs. concentration curve is trlangular with a maximum near -40 KJ/mole LIQSn. In addition, measurements of the emf for the cell Li3BI/LIF,LiC1/LI-Sn were made between 800 and 9OOK for lithium

near

was

L. KAUFMAN

216

concentrationsup to 50 percent in order to derive partial and integral These

Gibbs energies. measurements.

A. S. Bhansali compute

and A.K.

solid-liquid

interaction

Fe-P,

Mallik

assessing

order

for

the

using

Miedema’s

phase,

method.

of

the calorimetrfc

regular

composition

the. limitation Miodownik

solution

of

of

and estimation

The phase

Variations

this

of

stability

the binary

Incorporating

term representing missing of

to

in the were

approach.

characterized

a Sharkey

model

and temperature

a common procedure

the addition

liquid

the

with

in MO-V-W and Cd-Pb-Sn.

and A.P.

Cu-P and NI-P using model with

to agree

applied

as a function

L. Chandraskaran solution

were found

equilibria

parameters

used as a means for for

results

diagrams

a regular short

range

compound stabilities

metallic

phosphurus

has

been re-assessed using high pressure data. The entropies of fusion of many compounds in these systems appear to be substantially lower than is the case for average transiton metal compounds, and this may be a contributing factor to the good glass forming ability in these systems. The calculated diagrams are in reasonable agreement with available experimental data. Some preliminary calculations for the ternary system Fe-Cu-P were also presented. This Information can be employed to provide a better knowledge of solidus and liquidus temperatures as wel.1as solubllity limits of various phosphlde phases at different temperatures. Such data for multicomponent alloy systems would substantially aid the development of optimum sintering schedules In commercially important systems, containing phosphorus. This is Important since phosphorous is one of the few elements available to the powder metallurgist which produces liquid phases at temperaturesaround llOO°C and aids densificatlon on sinterlng. R. 0. Wllllams Investigated the effects of Fe, Al, Si, Ti, Nb, Cr, Co and Mn on the width of two phase fields in the Ni-MO system. There are three stable intermediate phase8 in the NI-MO system with compositions Ni,+Mo,Ni3Mo and NlMo (of a different structure) and Ni2Mo. The occurrence of these phases Is observed to lower the ductility and the corrosion resistance so that In alloys of commercial Interest the formation of these phases of

is undesirable.

these phases

rate reduce

of

using

formation. the problem

It

ia not

commercial A commercial

always practice

possible 80 It

alloy(Hastelloy

has been available

for

to prevent is

desired

the formation to

reduce

the

B) In which Fe Is added to

many years.

The calculated

results for Fe are in only fair agreement with the observations. The origin of this problem lies primarily with the uncertainty in the representationof the Ni-Fe and Nl-MO systems. The results can be divided Into two distinct claeses. The elements Al, Sl, Tl and Rb all greatly widen the two phase fields whereas Cr, Mn, and Co glve narrow fields much like Fe. The origin of this behavior 28 very sfmllar to the work of Meijerlng in the early 50"s in which he showed that in a ternary system formed from two or more or less

SUhitMRYOF THE PROCEEDINGS OF THE FOURTEENTH CALPHAD MEETING

and a third

ideal systems

the three

binaries.

mixing

Al,

of

fields;

additions deduced

predictions

the theory.

atoms or the value

for

liquids.

Comparisons

usefulness

of

substances

needed

because

of a lack

for

since

shell

structure second site

information

sites

model of

and Schottky

nearest

of

and twelve

arrangements the second energies

of

second cations

nearest that

and set

the site

will,

internal

transition

composition

and changes

but can be determined vertical

section.

the addition examination substrate

of

In the Zn-Al-Cu aluminum becomes

and thermal for

nucleation

the perltectlc

peritectic-eutectic and

be determined Al,

analysis

eutectic

trace

of

zinc Into

transitton

neighbor

and of

anions

program has

fraction,

equations

and calculate

some simple real mixtures. that the position of the

liquid

is not strictly

dependent

the participating

segregation

the binary

projected

peritectic

with

to be an ineffective

the path of

occurs

zinc

so close of

reaction

be experimentally

segregation

Furthermore,

to a ternary

the ternary

cannot

liquid

field.

a

L+e/Zn,

has shown the e phase causing

on

phases onto

Microstructural

the primary

in

and configurational

systems

system,

of an anion

the eutectic,L/e+Zn.

and the nature or perltectic,

vacancy these

In the amount of

from the path of

up to

positional

sites

A computer

of mixing,

in ternary

of

to have the same shell

composition,

energy

contains

nearest

Different

them.

, solve

functions.

shell

first

heighbor

This was illustrated for and A. Hellawell suggested

perltectic-eutectic the overall

sites.

are considered

energies

and the

on development

shell

cation

a given

simple

AX-BX with a NaCl

the salvation

nearest

of

Illustrate

energy

For example, neighbor

in

are not available

Each salvation the six

integrals

vapor molecules

progress

the type

the

data on many

plus

sites

shell

with

is also

halides

and free

is made between for

of

distribution,

entropy of mixing. T. A. Lograsso

cannot

nearest

energy

funcitons

for

alkali

reported of

in the first

neighbor

temperature

cross

site

and no distinction

been written

salts

sites.

energy

thermodynamic

vacancies.

the anion

the theory

phase equilibria

Pierre

of

which provides

molecules

predictions

on entropies

fused

type

neighbor

consists

that

liquid

of

G. R. Holcomb and G. R. St. a solution

heats

and free for

and free

standard

calculations

of

theory

data

indicates

atoms and for

the theory

negative

to the wide two-phase

entropies

of entropies

to a

ideal.

on either

of the theoretical

of up to seven

rise

a gap in any of

of a sum of multidimensional

study

predictions

gives

being

leads

mechanical

based

A preliminary

applicable clusters

are more nearly

a statistlcal

molecules

of mixing

there

directly

of the non-electronic

of vapor

same number of

heat

work the strongly

Ti and Nb in nickel

the other

functions

a negative

system without

In the present

Sl,

M. Blander reliable

having

gap in the ternary

mlsclbility

217

reaction, involving, distinguished.

to the that

it

L,e,Zn, In

Cu-Al-Sn system, the monovariant reaction begins as L/a+b, and with the decreasing temperature changes to perltectlc L+a/b at approximately 3 wt.% Sn,

218

L. KAUFMAN

7.75 wt. % Al.

In this case, alloys which solldfy in the eutectlc region must

follow the eutectlc valley to the perltectlc. D. F. Redmlles, J. L. Murray and J. S. Sims reviewed their efforts In developing a software package for the entry, display, analysis and retrieval of phase diagram and crystal structure data.

The package includes software

that produces publication-quality graphics and serves as an expert system for phase diagrams. design,

The discussion covered the planning and design stages of the

the formulation of specifications for both programming and database

project,

the importance of the computer architecture and operating system,

criteria for the choice of programming language and the Importance of establishing procedures and dedicating adequate staff time for database maintenance and administration. R. Berkane, J. C. Gachon and J. Hertz reported the results of direct high temperture reaction measurements of the enthalpy of formation of transition metal carbides.

In particular, new values were reported for titanium carbide

and chromium carbides. J. C. Gachon and J. Hertz reported on experimental data obtained by direct ractlon calorimetry for the following compounds listed as compound enthalpy of formation In Joules per mol, standard deviation in Joules per mole and temperature In degrees Kelvin: Fe 0 5O Tl 0 5O (-31000)(1300)(1440),

Fe Co Ni Fe co Co Ni Ni Pd Pd Pt Pt Pt

0.67 Ti 0.33 (-27600)(1000)(1514j,Co o i. TI o.5o (-44300)(500)(1490), 0.67 T1 o 33 (-34100)(600)(1432),Ni o i3 Tl o-67(-2930o)(500)(1202), (-34000)(2000)(1475), Ni'0.75 Ti o.25 (-42900)(1000)(1513), 0.50 Ti o'5o . (-29700)(1700)(1760), Co 0.33 Zr 0.67 (-33000)(2o00)(1290)~ 0.67 ITr0.33 0.50 Zr o .50(-42200)(1000)(1512),Co o 67 Zr o.33 (-41000)(1600)(1708), 0.80 Zr o.2o (-29800)(1500)(1596),Ni b 33 Zr o 67 ~-36800~~1000~~1230~, 0.50 Zr o.5o (-51500)(2000)(1405),Ni 0'78 Zr o:22 (-39500)(500)(1670), 0.83 Zr o 17 (-32400)(3000)(1479),Pd o:50 SC o.5o (-106000)(7000)(1681), 0.50 Ti o~50(-53~~~)(ll~~)(1578),Pd o.50 Zr o 5. (-62000)(5000)(1667), 0.50 Hf o~50(-79000)(7000)(1685),Pt o.53 Ti o:47 ~-75000~~7000~~16~3~, 0.50 Zr o~50G90000)(10000)(1629), Pt o.5o Hf o,50 (-113000)(6000)(1336), 0.23 ' 0.77(-33600)(1000)(1694),Pt o 5. V o.5o (-39300)(300)(1659), 0.74 v 0.26 (-30000)(4000)(1259), Fe'0.82 V 0.18 (-4200)(1200)(1525) Ch. Cunat and J. Hertz compared the results of numerical simulations and

experiments on glassy or amorphous products having different thermal histories.

Numerical simulations were performed with the help of a

relaxation model which tends to maintain Internal equilibria In liquids.

The

agreement between observations and numerical results showed that glassy or amorphous products are truly liquids In non-equilibrium states linked to their histories.

SUMMARY OF THE PROCEEDINGS OF THE FOURTEENTH CALPHAD MEETING

S. M. Hudson, A. !I’, Dinsdale, MULTXPHASE,a sophisticated Physical

Laboratory

in systems calculations

solution

phases.

alloys,

molten

using

compositions for:

steels,

of

nuclear

reactor

the large

state

operation

elements)

between matrix

low-alloy

steels.

J. Charles, consistent

of

of adjustable

parameters

model.

stoichlometric (p+q)

coefficients of

with phase,

stoichlometric

and all

compounds.

phase,

and a solid

liquid

or solid

introduced multiplied

mathematical by weighing

or entropic

equations,

experimental

permit

thermodynamic differences

between

the experimental experimentally

described

two phase each phase with a set

which is also binary

a good

systems solving

and entropies

and also of

this

set

requirements

the calculated

uncertainties.

in the phase diagram.

enthalpies

of are

is

then to entalpic

to each of

the

and the use of weighing to agree

with a good degree of

the

to the

factor

analysis

of equations

enthalpy of all

determined,

the same Importance

a reliability

The estimates

free

or free

Each equation

and experimental

known, are satisfactory,

of

p equations,

experimentally way, a value

regression

a set

T, between a liquid

entropies

to give

to assign

square

they write

at temperture

In order

with N

These unknown mathematical the excess

this

(tramp

in which there

enthalpies

in

to

of a self

of miscibility,

unknown quantities.

the solution

lmpurlties

describing

factor

experimental

relevant

parameters

assigning,

A least

data.

of

formalism

the enthalpies,

phase

the

phases

the formation

All

constraints

sigma phase

casting;

systems

program for

which have been already

in Q equations,

corresponding

not

phase.

and the

characteristics

calculation binary

unknown factors,

an equilibrium

phases,

over

calculated

residual

enthalpy

wide ranges

types

compounds in high-strength

From the phase diagram

each of which represents

factors

a computer

r < (p+q)

of

to formulate

free

in a mathematical

are the adjustable

the liquid

for

In order

the excess

compunds without

equations

of

discussed

properties

They proposed

control

during

and intermetallic

of miscibility.

they represent

system

and condensed

and the distribution phases

thermodynamic

are no wide ranges

physical

impurities

and

The program has

of

the solidification

aqueous

M. Noten and J. Hertz

set

equilibrium,

of

between gaseous,

solutions

the embrittling

involving

steels;

to segregation

iodine

models.

Examples were given

reactions

1818 stainless

phase equilibria

up to 100 species, aqueous

diversity

The user has great

on the system.

relevant

partition

and sublattice

Solid

complex

elements,

sulphides,

to deal

with

at the National

MULTIPHASEIs programmed to perform salts,

conventional encountered.

can be imposed

In multicomponent of

of

several

robust

equilibria

calcultion

involving

species

range of

the automatic

as many as 15-20

been made very that

and T. Chart described

program developed

currntly

and including gaseous

for

contianing

R. H. Davies

computer

219

values

with

the

are consistent

thermodynamic

in the range of

all

of accuracy. quantities,

temperature

The with

220

L, KAUFMAN

3.

is

A partial list given below. Agren Allen Ansara Argent Baker

J. S. I. 8. H. K. B8lfiSUbr8ln8tli8!l C.W. Bale R. Berkane C. Bernard S. Bhan D. Birnie B. Bjorkman M. Blander P. Bolsaites T. Bramblett R. Brebrick J.P. Bros. P. Bunyan B. Burton L. Chandrasekaran Y.A. Chang T.G. Chart M. Ch8Se J.B. Clark J.R. Cuthlll D. de Fontaine J.F. Elliott G. Eriksson D. Evans A.F. Gulllermet K. Frisk J.-C. Gachon M. Gaune-Escard G. Grimwall

LIST OF PARTICIPANTS

of participants at the fourteenth CALPHAD

Sweden U.S.A. France U.K. U.S.A. Canada Canad France France India U.S.A. Sweden U.S.A. U.S.A. U.S.A. U.S.A. France Australia U.S.A. U.K. U.S.A. U.K. U.S.A. U.S.A. U.S.A. U.S.A. U.S.A. Sweden U.K. Sweden Sweden France France Sweden

P. Nash U.S.A. M. Grujlclc U.S.A Sweden T. Nishizawa Japan P. Gustafson M. Notis F. Hayes U.K. U.S.A. France H. Okamoto J. Hertz U.S.A. Sweden D. Orser M. Hillert U.S.A. W.S. Owen M. Hoch U.S.A. U.S.A. Canada A. Pelton G, Holcomb U.S.A. H.W. Holleck W-Germany A. Prince U.K. M. Rand R. Howald U.S.A. U.K. W.Germany D. Redmiles G. Inden U.S.A. C8n8d8 H. Ruppersberg W.Germany V. Itkin Sweden M.L. Saboungi E. Jacobsson U.S.A. Sweden J. Sangster Canada 3. Jonsson France N. Saunders U.K. J.C. Joud W.Germany R. Schlim W.Germany U. Kattner A. Schlyper Netherlands L. Kaufman U.S.A. D. Kundrat J.F. Smith U.S.A. U.S.A. H, Lee H.S. Spacil U.S.A. U.S.A. K. Spear S.K. Lee Korea U.S.A. P.J. Spencer W.Germany Y. Lee U.S.A. B. Legendre France G.R. St. Pierre U.S.A. T. Llndemer B. Sundman Sweden U.S.A. W. Lin Canada P. Talley Canada T. Lograsso U.S.A. L.E. Tanner U.S.A. R.V. Luck Sweden W.Germany J.-E. Tapp H.L. Lukas Canada W. Germany B. Thompson A.K. Malllk India B. Uhrenius Sweden C. Maso Canada H. Wad8 U.S.A. K. Meltsner U.S.A. T. Wad8 U.S.A. M.A.J.Mlchels Netherlands J. Wallace U.S.A. A.P. Miodownlk U.K. I-J. Wang U.S.A. J. Morral U.S.A. R.E. Watson U.S.A. 2. Moser Poland R.O. Williams U.S.A. J. Murray U.S.A.

SUMMARY OF THE PROCEEDINGS OF THE FOURTEENTH CALPHAD MEETING

221

4. SUBJECTS AND SITES FOR FUTURE CALPHAD MEETINGS The times, locations and organizers for future CALPHAD meetings were selected and are listed below.

CALPHAD xv XVI XVII XVIII XIX xv XXI

Date Location London, England 7-11 Stuttgart,W. Germany Berkeley, California Stockholm, Sweden The Netherlands Phoenix, Arizona Jerusalem, Israel

July 1986

May 1987 May 1988 May

1989

May 1990 May 1991 May

1992

Organizers A.P. Miodownfk,T.G. Chart H.L. Lukas, G. Inden L. Brewer, A. Searcy M. Hillert, B. Uhrenius H. Bank, A.R. Miedema A. Narrotsky L. Kaufman and'A.S. Kertes Joint CALPHAD-IUPAC SolubilityData Project Meeting.

At the conclusion of CALPHAD XIII a number of topics were listed for Inclusionin future meetings (see CALPHAD volume 8 page 217(1984)1. A number of these topics were consideredat this meeting. In addition to the forgoing the following subjects were recommendedor future meetings: Physical Models, Lattice Stabilities,Slags, Teaching Methods, IndustrialApplications,Data Storage and Retrieval, CALPHAD descriptionsof a Model System, I.e. Fe-NI. An Overview of CALPHAD XIV The fourteenth CALPHAD was distinguishedby a very large number of papers. A total of eighty two papers in the form of lectures and poster presentationswere contributed. The subject material covered physical models; de Fontaine and Luck (page 201) Luck (page 202), Kaufman and Watson (Page 204), Hoch, Gustafson and Rupersberg (Page 205), Spear (Page 207) and Blander (Page 217); CVD and electropticalmaterials, Brebrick (Page 204), Anderson(Page208), Bernard (Page 214) and Chang (215); ceramic, amorphous, glass-formingand metastable systems, Kaufman and Llndemer (2021, Saunders and Agren (2061, Bolaaltes (2071, Chang (2l5), and Hertz (218); alloy steels and iron alloys, Nishlzawa (2021, Raghavan (206), Balasubramianand Inden 5.

(2071, Grujicic and Kundrat (2081, Bhan (209) and Chang (214); hardmetals, Balasubramlanand Holleck (207) and Berkane (217); segregationand SUrfaCe phase diagrams, Joud (202) and St. Pierre (205); slags, mattes and molten salts, Michels (2021, Bjorkman (2031, Howald (206), Erikeson (210), Blander and Hillert (211) and Holcomb (216); software and data banks, Sundman (203), Thompson and Bale (2111, Sangster and Pelton (212), Tafley and Meltsner (213), Sundman (214), Chang (2141, Lukas (2141, Redmiles and Murray (217) and Chart (21g), ExperimentalThermochemistry,Bernard (2041, Bras

L. KAWM4N

222

(209) and(214), Gaune-Escard (211), Moser (215) and Gachon (218); binary systems, Itkin (202), Kaufman (204), Jonnson (205), Chandraskaran (210), Saboungi (214) Lee (214), Miodownik (215), and Hertz (219); and ternary systems and multicomponent systems, Kaufman, Ansara and Bramblett (203), Orser (204), Gulllermet (206), Hayes (208), Gaune-Escard and Kattner (210), Frisk (214), Mallik (215), Williams (216) and Lograsso (217). Development of ThermochemicalModels for three new steel making processes Using an eXh?nSlVe data base and computer models was reported by Tapp(Page 210). Finally three Independent studies of the ternary interaction parameters in the fee phase of ternary Fe-C-Me systems (Me=TI, V, Cr, Mn, Fe, Co, Nl, and Cu) by Nlshizawa (page 202), Grujicic (208), and Kundrat (page 208) produced excellent general agreement even though the approaches and subject matter differed substanitlallythe results showed large negative ternary Interaction parameters at the beginning of the series at Ti which increase rapidly to values near zero for Mn, Fe, Co, Ni, Cu. REFERENCES

1.

R. Baur, and V. Gerold, Z. Metallkunde, 52 671 (1961).

2. J. Lasek, and J. Czech, Phys. 15, 848 (1965). 3. R. Hultgren, et al., Selected Values of Thermodyam~c Properties of Metals and Alloys, 2nd ed., American Sot. Metals, Metals Park, Ohio (1973). 4. M. Hoch and I. Arpshofen, Z. Metallkde. 75, 30 (1984). 5.

R. Luck and B. Predef, Hauptversa~lung DGM, Villach/Austria, (1982).

6. M. J. Pool, I. Arpshofen, B. Predel and E. Schultheib, Z. Metallkde. -70 656 (1979). 7. R. Mosserl and J. F. Sadoe, Structure of Non-Crystalline Materials, Proc. of the Second International Conference, Cambridge, 1982. ed. by P. H. Gaskell, J. M. Parker and E. A. Davis, 137. 8.

L. Kaufman and H. Nesor,

9.

L. Kaufman, CALPHAD 2, 27, (1979).

CALPHAD 2, 35, (1978).

10. L. Kaufman, CALPHAD 3, 279, (1979). 11. L. Kaufman, F. Hayes and D. Blrnie, CALPHAD &163,(1981),

SUMMARY OF THE PROCEEDINGS OF THE FOURTEENTH CALPHAD MEETING

12.

L. Kaufman, J. Nell, K. Taylor and F. Hayes,~ALPHAD,2,185 (1981).

13.

L. Kaufman, J. Agren, J. Nell and F. Hayes, CALPHAD, 1, 71 (1983).

14.

J. Schlichting, and S. Neumann, J, Non-CrystallineSolids 48, 185,

15.

(1982).

241 (1978).

J. Schllchting, High Temperatures-HighPressures, lo,

16. H. S. Chen, Mat. Sci. Eng. 26, 79-85.(1976) 17.

C. Janot, 3. George, D. Teirllnck, G. Marchal, C. Tete and P. Delcrois, Phil. Mag. A, 47, 301-313.(1983)

18.

J. L. Walter, F. Bacon and F. E. Luborsky, Mat. Scl. Eng, 2, 239-245.(1976)

19.

D. Bljaoul,

A. R. Yavari, J. Wasselin, J. C. Joud, Amorphous

Metals and Non-equilibriumProcessing, 171-174,

Les Editions de

Physique.(l984) 20.

Interfacial Segregation - American Society for Metals, W.C. Johnson and J. M. Blakely Editors, (1979). (1948).

21.

0. Redlich and A. T. Kister, Ind. Eng. Chem. %,345

22,

T. B. Lindemer and T. M. Besmann, J. Nucl. Mater., January 1985.

23.

T. M. Besmann and T. B. Lindemer, J. Nucl. Mater.,

24.

R. Hultgren et al. tfSelectedValues of the Thermodynamic

January 1985.

Properties of Blnary Alloysw, ASM, Metal Park, Ohlo,(1973) 25.

H. Ohtanl, M. Hasebe, and T. Nishizawa to be contributed to Metall. Trans. A.

26,

H. Ohtani, M. Hasebe, and T. Nishizawa, Trans. Iron Steel Inst. Japan, 3,

27.

857 (1984).

W. S. Gibson, J. R. Lee, and W. Hume-Rothery J. IrOn Steel Inst., 196, 64(1961).

28.

w. A. Fischer, K. Lorenz, H. Fabrltius, and D. Schlegel, Arch. Eisenhuttenwes.,3,

29.

489 (1970).

R. J. Hawkins, lfChemicalMetallurgy of Iron and Steel", Iron Steel Inst., London, p.310 (1973).

30.

L. Kaufman and H. Nesor, CALPHAD, 1, 55 (1978).

223

L. KAUFMAN

224

31.

M. Hillert and L. I Staffansson, Acta Chem.Scand., 24, 3618 (1970).

32.

L. Kaufman and H. Nesor CALPHAD 2, 325,(1978).

33.

L. Kaufman CALPHAD 1, 7 (1979).

34.

L. Kaufman, CALPHAD 3, 45, (1979).

35.

T. G. Chart, F. Putland and A. Dinsdale, CALPHAD 'I, 27, (1980).

36.

E. I. Gladyshevskl and L. K. Borushevlch, J. Neorg, Khlml 8, 1915 (1963).

37.

L. A. Mloroshnlkov, F. A. Sidorenko and A. N. Bortnlk, Tr. Ural'sk Polltekhn In-Ta No. 186, 44, (1970).

38.

l~Equlllbrlum Diagrams of Alumlnlum Alloy System, The Alumlnlum Development Assoclaton, Inf. Bull. a,

(19611, London, U. K.

39.

D. A. Petrov and N. D. Nagorskaya, Jlmmz, 274 (1977).

40.

T. Yokokawa and K. Nlwa, trans. Jap. Inst. Metals 2,

41.

P. L. Lin and A. D. Pelton, Met. Trans. E,

42.

H. Flood and W. J. Knapp, J. Am. Ceram. Sot. 5,

43.

T. Furukawa, S. A. Brawer and W. B. White, J. Mater. Scl. 2,

3(1969).

667(1979). 61, (1963). 268,

(1978). 44.

Bjorkman, B., Eriksson, G. and Rosen, E. Metall. Trans. @, (19841, 511-16.

45.

Bjorkman, B., CALPHAD 9 273 (1985).

46.

J. E. Morral, Scrlpta Met., 18, 407(1984).

47.

T. R. Bramblett,

and J. E. Morral; Bull. Alloy Phase Diagrams, 2

433 (1984). 48.

B. Sundman, B. Jansson, J. 0. Andersson, CALPHAD 2, 14g-185(1985).

49.

B. Sundman and J. Agren, J. Phys. Chem. Solids, 42, 297 (1981).

50.

M. Hlllert and M. Jarl, CALPHAD, 2, 227 (1978).

51.

M. Hlllert, B. Jansson, B. Sundman and J. Agren, TRITA-MAC 218 Royal Institute of Technology, Stockholm, Sweden (1984).

52.

C. Chatlllon and C. Bernard to be published in J. of Crystal Growth.

53

A. Gabriel, C. Chatillon and I. Ansara, to be published.

SUMMARY OF THE PROCEEDINGS OF THE FOURTEENTH CALPHAD MEETING

54.

225

G. Lehnert and H. Melnhardt, Electrodeposition and Surface Treatment. 1, 71 (1972).

55.

L. Kaufman and H. Nesor, CALPHAD 2, 325 (1978).

56.

R. Hultgren, P. Desal et al "Selected Values Of The Thermodynamic Properties Of Binary Alloys IIASM Metals Park Ohio 44073

57.

(1973).

J. Major* and W. L. Worrell, unpublished research, University of Pennsylvania (1979) referenced in W. L. Worrell and T. A. Ramanarayanan, chemical Metallurgy-A Trlbute to Carl Wagner, N. A. Gokcen Ed., A.I.M.E. Warendale PA

58.

(1981).

J. N. Pratt, A. W. Bryant and D. T. Underhill, "Calorimetric studies of the Intermediate Compounds Pt2A13, RhAl, NiAl, and PdGa ttTechnlcal Report, University

of

Birmingham Contract DAJA37-70-C-0632 January 1971. 59.

D. Blrnle, E. S. Machlln, L. Kaufman and K. Taylor, CALPHAD 6, 93. (1982).

60.

L. Kaufman, B. Uhrenlus, D. Birnle and K. Taylor,

CALPHAD I,25

(1983). 61.

T. Chart, F. Putland and a. Dinsdale, CALPHAD 8, 75,(1980).

62.

J. Pratt and I. P. Jones, CALPHAD 5, 75 (1984).

63.

L. Kaufman and H. Bernstein Computer Calculation of

Phase

Diagrams Academic Press N.Y. (1970). 64.

J. Murray, Bulletin of Alloy Phase Diagrams 2, 48 (1981).

65.

J. F. Smith, D. M. Bailey and 0. N. Carlson, Bulletin of Phase Diagrams 2, 469 (198.2).

66.

J. 0. Andersson, CALPHAD, 1, 305 (1983).

67.

F. Hayes, CALPHAD XIII, Grenoble, France May (1984)

68.

J. F. Smith and 0. N. Carlson, Bulletin of Alloy Phase Diagrams 2, 348 (1981).

Alloy

L. KAUFMAN

226

69.

T. Ichlkawa, and S. Chang, ed. 1984 IEEE Computer society Workshop on Visual Languages, December 6-8, 1984

Hiroshima,

Japan. 70.

A. Algner, CombinatorialTheory. Springer-Verlag,New York. p. 138-151

(1979).

71.

M. Hoch, Calphad 2

72.

H. Ruppersberg and J. Schlrmacher, J. Phys. F: Metal Physics -14 2787

59 (1985).

(1984).

73.

N. Saunders, CALPHAD 2 301 (1985).

74.

H. Holleck, "Binary and Ternary Transitions Metal Carbide and Nitride Systems" Gebr. Borntraeger Verlag Berlin, Stuttgart (1984).

75.

H. Okamoto and T. B. Massalskl, Bull. Alloy Phase Diagrams 4, 401, (1981).

76.

Ibid, 2, 276, (1984).

77.

B. Zimmerman, Thesis-Universityof Stuttgart (1976).

78.

D. M. Kundrat, M. Chochol and J. F. Elliot, Met Tr. 15B 663 (1984).

79.

M. Hlllert, B. Jansson, B. Sundman and J. Agren, Met. (1985).

Tr. 16A 261