Powder Metallurgy

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Quantitative Assessment of Enhanced Sintering

Concepts

D. S. Madan & R. M. German

To cite this article: D. S. Madan & R. M. German (1990) Quantitative Assessment of Enhanced
Sintering Concepts, Powder Metallurgy, 33:1, 45-52, DOI: 10.1179/pom.1990.33.1.45

To link to this article: http://dx.doi.org/10.1179/pom.1990.33.1.45

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 Quantitative assessment of enhanced
sintering concepts
D. S. Madan and R. M. German
The theories of enhanced sintering identify three
criteria for a sintering enhancer; high solubility of
base material in the second phase, segregation of the
additive at the interparticle boundaries, and easy
diffusion of the base material through the segre-
gated phase. Although these qualitative ideas are
valuable in the selection of a sintering enhancer, a
quantitative assessment would render them more
Downloaded by [Monash University Library] at 10:37 02 July 2016
meaningful. This study proposes a figure of merit
relating to thermodynamic quantities, capable of
identifying a sintering enhancer reliably. This figure
of merit is defined as a weighted sum of solubility,
segregation, and diffusion terms. It is a dimension-
less quantity, and can easily be calculated from
phase diagram features. The proposed figure of
merit has been used successfully to identify effective
sintering enhancers for iron, and the results have
been compared with sintered density values
obtained from a controlled experiment and from the
literature. PM/0493
© 1990 The Institute of Metals. Manuscript received 13
April 1989; in final form 14 August 1989. Dr Madan is at
Elkem Metal Company, Niagara Falls, NY, USA and
Professor German is in the Rensselaer Polytechnic
Institute, Troy, NY.
Enhanced sintering involves the addition of an alloy addi-
tive to the base material to increase the sintering rate by
providing a short circuit mass transport path for rapid
diffusion.I-3 This short circuit path is generally through a
segregated second phase at the interparticle boundaries.
Rapid diffusion of the base atoms through this layer results
in enhanced sintering, leading to densification of the
compact. The segregated phase may exist either as a solid
or a liquid, hence the term 'enhanced sintering' embraces
both liquid phase and activated sintering.
Figure 1 schematically illustrates a simple model for
enhanced sintering.2 The major component is designated
as the base material, 'B', and the minor component is an
addition, 'A'. In the pressed condition, 'A' is dispersed
among the particles of 'B' and, on heating, an effective
additive segregates to the particle boundaries as a second
phase. This second phase may be the additive itself, a solid
solution, a product of a reaction between the additive and
the base, or even a liquid phase.
'A' should form a segregated phase at the interparticle
boundaries of 'B', so as to remain effective as a sintering
enhancer during the entire sintering cycle. Low solubility
(XA) of 'A' in 'B' and high solubility (XB) of 'B' in the
segregated second phase ensure segregation of an additive
rich activator layer. This unipolar solubility condition also
minimises the amount of additive needed to maximise
densification.
As an example of these concepts, consider the sintering
of iron. Solubilities of various additives in iron, solubility
of iron in the additives, and relevant phase diagram
features of the iron-additive binary are listed in Table 1.4,5
The strength, ductility, and density of these iron-additive
binary systems, with the alloy addition (wt-%), processing
parameters, and references are listed in Table 2.3,6-12
Additives such as boron, carbon, phosphorus, and tita-
nium, which have a higher value of XFe than XA increase
the sintered density of iron. Boron, carbon, and phospho-
rus form iron rich intermetallics, which form a eutectic
phase with iron, resulting in high solubility of iron in the
liquid phase. On the other hand, elements such as tanta-
lum and silicon have a lower value of XFe than XA and tend
to lower the sintered density of iron. Cobalt and nickel
show only marginal differences between the values of XFe
and XA, and consequently do not affect the densification
of iron, as seen in Tables 1 and 2. Although copper
has comparable values of XFe and XA, it can densify iron
due to the formation of a liquid phase under certain
conditions.
The real effect of the additive is assessed by its influence
on diffusivity. Faster diffusion of the base metal in the
segregated phase is the primary mechanism of enhanced
sintering. Hence, the alloy or intermetallic layer formed at
the interparticle boundaries should offer minimal resist-
ance to the diffusing base metal atoms. In addition, the
stabilisation of a crystallographically more open structure
for the base material would enhance its selfdiffusivity.13 A
liquid phase permits faster atomic diffusion than a' solid
phase, resulting in faster sintering rates.
Appropriate diffusion data, if available, are the best
guide in selecting a sintering enhancer. Usually these data
are not available, and melting behaviour is a first good
approximation to the activation energy of diffusion. 14,15
Phase diagrams with low eutectic or peritectic tempera-
tures are most favourable for a high diffusivity of the base
in the activator. A low liquidus temperature is an indicator
of a low bond strength, low activation energy, and hence
more rapid diffusion than in the unalloyed base material.
Sintering enhancers which form a low melting point liquid
phase with iron have been identified in Table 1, which also
lists the melting points of the second phase Tm, p. Additives
for which iron based phase diagrams indicate the forma-
tion of a liquid phase, and which have a unipolar solubility
of iron in the additive, or at least comparable solubilities,
alloy diffusion
A
additive lux path
pressed sintering
1 Schematic model for enhanced sintering: see Ref. 2
Powder Metallurgy 1990 Vol. 33 No. 1 45
 46 Madan and German Quantitativeassessmentof enhanced sinteringconcepts

Table 1 Features of iron based phase diagrams at 1200°C (Refs. 4, 5, 23-25)

Additive Phase field Phase diagram features XA, at.-% XFe, at.-% Tm,p, K

B y+L Fe-FezB eutectic, 17 at.-%, 1170°C 0·01 83·0 1450

C y+L Fe-Fe3C eutectic, 17·1 at.-%, 1155°C 9·23 82·9 1426
Co y y-Fe solid solution 100·00 100·0 1800
Cu y+L Peritectic, 95·2 at.-%, 1094°C 7·50 7·0 1367
Mo a a at >2·2 at.-% Mo 14·00 6·0 1800
Ni y y solid solution 100·00 100·0 1800
P a+L Fe-Fe3P eutectic, 16·9 at.-%, 1050°C, 4·52 83·1 1321
a >1·2 at.-% P
Si a a-Fe at >3·8 at.-% Si 17·50 0·0 1770
Sn a a-Fe> 1·48 at.-%; 8·30 31·0 1586
transient eutectic, 32 at.-%, 1130°C
Ta y y-Fe solid solution 0·80 4·0 1770
Ti a a-Fe >1·4 at.-%; 7·00 22·0 1560
transient eutectic, 71 at.-%, 1085°C

Table 2 Properties of iron based· binary alloys

Addition, Strength, Ductility, Density,
Element wt-% Processing condition MNmz % g cm-3 Reference
Downloaded by [Monash University Library] at 10:37 02 July 2016

Base
Fe 1200°C, 1h, Hz 162 20 6·7 7
Additive
B 0·20 1200°C, 1h, Hz 200 10 7·8 3
C 1·00 1175°C, 0·5h, Hz 550 10 7·2 11
Co 4·00 1200°C, 1h, Hz 6·8 10
Cu 7·50 1100°C,3h 426 20 7·7 8
Mo 5·00 1200°C, 1h, Hz 250 10 7·0 10
Ni 6·00 1200°C, 1h, Hz 6·8 10
P 0·45 1120°C, 0·5h 405 10 7·1 6
Si 1·00 1200°C, 1h, Hz 6·6 10
Sn 1·00 1100°C 230 5 6·6 9
Ta 1·00 1200°C, lh, Hz 6·6 10
Ti 3·50 1300°C, lh, Hz 350 18 7·4 12

tend to increase the sintered density of iron. For example,
boron, carbon, phosphorus, and titanium satisfy the segre-
gation and solubility criteria, form a low melting liquid
phase with iron, and enhance the sintering of iron. On the
other hand,. silicon and tin can form a low melting liquid
phase when alloyed with iron, but do not satisfy the
segregation and solubility criteria and hence do not
enhance the sintering of iron.
An ideal model binary phase diagram for a sintering
enhancer, shown in Fig. 2,2,16 exhibits all the features
discussed above. The base 'B' has a high solubility in the
additive' A' , and the reverse solubility is low. This satisfies
the unipolar solubility criterion. The diagram has decreas-
TI
1 L
ing solidus and liquidus lines as 'B' is alloyed with 'A', thus
satisfying the segregation criterion. The deep eutectic in
the diagram satisfies the diffusion criterion. The features
of a few iron based phase diagrams are outlined in Table
1.4,5 Enhanced sintering by the additive mentioned above
is indicated by the high sintered densities in Table 2.
Examination of the data given in Table 1 indicates that
boron satisfies all the criteria for a good sintering enhancer
for iron, and Table 2 shows that sintered densities ----99%
of theoretical density can be obtained for iron compacts
containing 0·2 wt-%B and sintered at 1200°C for 1 h in dry
hydrogen.3
Thus, the theories of enhanced sintering identify the
following main criteria for selection of an appropriate
sintering enhancer:
(i) high solubility of the base in the second phase
(ii) segregation of the additive at the interparticle
boundaries
I
I (iii) easy diffusion of the base material through the
,
I
segregated phase.
'LARGE: A qualitative assessment of these criteria based on phase
: 6Trn

,
I
diagram considerations has been reported by German and
I
coauthors. 1-3, 16, 17 Although these qualitative techniques
I provide a valuable tool, a quantitative assessment would
LIQUID
ENHANCED
PHASE
SINTER'NG
i make selection easier and more meaningful. The aim of
this investigation has been to combine the selection cri-
LOWS,6,
teria into a single figure of merit by which to judge
CI
sintering enhancers. Miodownik's figure of merit18 is ex-
amined, its application to iron based alloys is discussed,
and a new figure of merit is proposed.

A B MIODOWNIK'S FIGURE OF MERIT (})

AOOfTIVE BASE
Miodownik attempted to quantify the criteria for the
2 Phase diagram for ideal additive: see Ref. 2 selection of an additive for enhanced sintering18 by

Powder Metallurgy 1990 Vol. 33 NO.1

 Madan and German Quantitative assessment of enhanced sintering concepts 47

Table 3 Data for calculating <Il for iron19-21 taken as the surface energy of iron for the calculations.
213
The terms I1H}, 11Hz, I1H3, and <PFe were calculated as
tlRFeinA, tlRAinFe, YS,A, V A, tlH~,
discussed above, and are listed in Table 4.
Additive kJ mol-l kJ mol-l J m-z cmz kJ mol-l
A high positive value of <PFe indicates that the additive is
B -65 2·27 2·80 73 a good sintering enhancer for iron. Table 4 also compares
C -28 2·41 1·80 50 the values of <PFe with the experimental sintered densities
Co -2 -2 2·55 3·55 127 Ps obtained f!?m Table 2. Ranks Rep and Rp were assigned
Cu 53 50 1·85 3·70 100 to the additIves based on <PFe and Ps respectively.
Mo -7 -9 2·95 4·45 185 Standards of 'good', (G), or 'bad', (B), were assigned to
Ni -6 -6 2·45 3·52 122 R<I>,depending on whether <PFe was greater than or less
P -156 1·53 4·15 73 than -100. Similarly, either G or B was assigned to R
Si -67 -75 1·29 4·20 64
depending on whether Ps was greater than or less th;~
Sn 34 56 0·71 6·43 53
Ta -54 -67 3·05 4·89 214 7·0 g C~-3. A statistical correlation test was performed on
Ti -62 -74 2·05 4·82 141 these eight data points by assigning values of G = 1 and
B = 0, which showed a correlation coefficient of 0·15 and a
* Insufficient data significance of <30%• There is therefore no correlation
between the predictions based on <PFe and the experimen-
tal sintered densities. For example, the figure of merit
combining them into a figure of merit <P given by predicts that sili.con and tin are good sintering enhancers,
<P = I1H1 + 11Hz + I1H3 (1) although expenmental results show that they do not
densify iro~. Elements such as boron, carbon, and phos-
where I1H}, 11Hz, and I1H3 are thermodynamic terms
phorus, which are known to enhance the sintering of iron,
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related to solubility, segregation, and diffusion criteria

cou~d ~ot be evaluated in terms of <PFe due to non-
respectively. Miodownik related solubility to the partial
availability of data.
heat of solution of one component in another, assuming
. Miodownik's figure of merit fails to quantify the enhanc-
that the formation of a compound did not limit the solu-
i~g P?~er of additives for iron because solubility and
bility and that the heat of solution was independent of
diffusivity of the base in the additive itself are considered
temperature. Thus, the criterion of unipolar solubility of
for the purpose of the analysis. Theories of enhanced
the base in the additive was related to the negative of the
sintering suggest that the additive should form a second
partial heat of solution of the base 'B' in the additive 'A'
phase at the interparticle boundaries. This second phase
I1H B in A. Diffusion was characterised by the energy
can be the additive itself, a solid solution of the addi:~ve
required for the formation of a single vacancy I1H~ in the
and the base, a reaction product, or even a liquid phase.
additive, and was related to the surface energy of the
The solubility and diffusion of the base in the second phase
additive.
govern the sintering process. Thus, the partial heat of
Miodownik calculated <P for various sintering enhancers
solution of the base in the -second phase and the heat of
of tungsten, using thermodynamic data based on
formation of a mono vacancy in the second phase would
Miedema's formulations.19-Z1 His results were in good
truly represent the solubility and diffusion criterion re-
agreement with the qualitative estimates of the enhancing
spectively. Unfortunately, these data are not always avail-
power of these additives by Zovas et al.l However,
able: formulation of a new figure of merit, that will
Miodownik's predictions are reliable only when the addi-
acco?nt for the presence of the segregated second phase, is
tives are close to the base metal in the periodic table. requued.
Miodownik's figure of merit for iron cIlFe
An attempt was made to apply Miodownik's figure of
merit to the identification of effective sintering enhancers NEW FIGURE OF MERIT Q
for iron. Values for partial heats of solution, surface The new figure of merit Q, based on phase diagram
energies, molar volumes, and enthalpies of monovacancy features, has been defined as
formation for some alloy additives to iron are given in Q = clal + czaz + C3a3 (2)
Table 3, based on Miedema's formulations and ~here aI, az, and a3 are terms related to solubility, segrega-
tabulations.19-z1 For certain additives, the values of Ys, A tIon, and diffusion criteria respectively, and c}, Cz, and C3
and I1H~ were calculated using relations~ips outlined by are constants. As a first approximation it was assumed that
Miodownik, where YS,A is the surface energy of the addi- CI =CZ=C3= 1.
tive. Unfortunately, I1HFeinA values for boron, carbon, Miodownik based the figure of merit <P on thermo-
and phosphorus were not available, and their figure of dynamic quantities, therefore <P was expressed in units of
merit could not be calculated. A value of 2·55 J m-z was energy. The partial heats of solution were related to
solubility. Unfortunately, I1H values for compounds and
Table 4 Figure of merit <IlFe solid solutions are difficult to estimate. The present study
assumes that the binary alloys form regular solutions and
tlHb tlHz, tlH3, that the partial heat of formation of the solution can be
Additive kJ mol-1 kJ mol-l kJ mol-l <I>
Fe expressed as
B -5 -73 7·8 G I1Hi = - RTxf (3)
C -3 -50 7·2 G where Xi is the atomic fraction of the species i, T is the
Co 2 -1 -127 -126 6·8 B B temperature under consideration, and R is the universal
Cu -53 46 -100 -107 7·7 B G
-25 -185 -203 7·0
gas constant. Thus, for a given sintering temperature, the
Mo 7 B B
Ni 6 3 -123 -114 6·8 B B
partial heat of solution can be related to the square of the
P 18 -73 7·1 G solubility of the species under consideration.
Si 67 51 -64 54 6·6 G B
Sn -34 167 -53 80 6·6 G B Solubility criterion
Ta 54 -48 -214 -208 6·6 B B
The solubility criterion dictates that the base metal should
Ti 62 14 -141 -66 7·4 G G
have a high solubility in the segregated phase, i.e. a high
* Insufficient data value of X B. The phase diagram can be used to identify the

Powder Metallurgy 1990 Vol. 33 NO.1

 48 Madan and German Quantitative assessment of enhanced sintering concepts
second phase and to determine the atomic fraction XB for
any given sintering temperature. The term which
represents the solubility criterion can be expressed as
al = 100 (X~) (4)
Although al is proportional to the heat of solution of the
base in the additive phase, it is a dimensionless quantity.
The atomic fraction X B can vary between a minimum of 0
and a maximum of 1, therefore al can vary between 0 and
100. A high value of XB implies a high value of at, and
represents the fulfilment of the solubility criterion.
Segregation criterion
A low solubility of the additive in the base metal X A would
ensure that the additive remains segregated at the particle
boundaries. The maximum solubility of the additive in the
base, when heating from room temperature to the sinter-
ing temperature, is selected as a conservative estimate of
X A. The term az can be expressed as
az = 100(1- XA)2 (5)
The term az is related to a thermodynamic quantity, but
Downloaded by [Monash University Library] at 10:37 02 July 2016
again it is a dimensionless quantity. The atomic fraction of
the additive that is soluble in the base can vary between 0
and 1, thus the term az can vary between 0 and 100. A low
value of XA implies a high value of (1- XA)Z, therefore a
high value of az. Additives which satisfy the segregation
criterion possess a high value of az.
Diffusion criterion
The diffusion criterion term, a3 can be expressed as
~=d+n (~
where d relates to the relative diffusivity of the base metal
in the segregated phase and n relates to the relative
activation energy for selfdiffusion in the stable crystal
structure of the base.
The heat of formation of a monovacancy can be related
to the melting point of the segregated phase Tm, P as1,20
~H~ = C(Tm, p) (7)
where C is the proportionality constant. The ease of
diffusion of the base atoms through the segregated phase is
therefore governed by the difference between the melting
points of the base metal and the segregated phase. Thus, a
dimensionless factor d based on thermodynamic concepts
can be defined as
d = 100 [(Tm,B - Tm,p )/Tm,B] (8)
or
d = 100[1- (Tm,pITm,B)] (9)
where Tm, B is the melting point of the base metal. The
term d equals zero when Tm, p = Tm, B, and theoretically
d = 100 when Tm, p = 0 K. In most practical situations Tm, P
is greater than -t Tm, B, thus a practical maximum value of d
is ----50.On the other hand, d is less than zero when
Tm, p > Tm, B· Again, practically, T m, P is· seldom >+ Tm, B,
and therefore d can be assumed to vary between - 50 and
50. The lower the melting point of the segregated phase,
the higher the value of d.
Some base metals can exhibit different crystal structures
at different temperatures or in the presence of alloying
elements. The stabilisation of a crystallographically more
open structure increases the selfdiffusivity of the base
material, leading to better densification. Consider a base
metal 'B', which at the sintering temperature has a stable
crystal structure y in its pure state and a stable crystal
structure a when alloyed with the additive' A'. A dimen-
sionless parameter n can be defined as
n = 100 [(Q - Qa)/Qy] (10)
or
. (11)
Powder Metallurgy 1990 Vol. 33 NO.1
where Qy and Qa are the activation energies of self-
diffusion of 'B' in the y and a phases respectively. If the
additive does not influence the crystal structure of the base
metal, then Q y = Q a and n = O. If the additive stabilises a
more closely packed crystal structure of the base metal,
then Qy< Qa and n is a negative contribution to the a3
term. On the other hand, if the additive stabilises a
crystallographically more open structure of the base metal,
then Qy> Qa and n is a positive quantity. In most practical
situations Qa and Qy would differ by 25% at most, hence n
can be assumed to vary between - 25 and 25. If a and y
coexist at the sintering temperature, an average value of n
can be assumed for the analysis.
As shown in equation (6), the net diffusion criterion
term a3 is expressed as the sum of the d and n terms. It can
be assumed to vary between -75 and 75. Higher values of
d and n imply a higher value of a3, indicating that the
additive satisfies the diffusion criterion.
Application of new figure of merit Q
The terms ab az, and a3 are all based on thermodynamic
concepts and are dimensionless quantities, giving the
figure of merit Q as in equation (2). The new figure of
merit is based on binary phase diagram features, and is
fairly easy to estimate. As a first approximation, the
constants Ct, Cz, and C3can be assumed to be unity. The
solubility values needed for the terms a1 and az can be
obtained from the equilibrium phase diagram for any
given sintering temperature and phase field. The melting
point of the second phase can also be obtained from the
phase diagram. The activation energies for selfdiffusion
are available in the literature. zz The figure of merit thus
calculated can provide an accurate evaluation of the
enhancing powers of various alloy additives. Higher values
of Q imply that the additive is a good sintering enhancer
for the base metal. In most practical situations, Q can be
assumed to vary between -75 and 275. It can also be used
to compare the enhancing power of an additive at different
sintering temperatures and alloy compositions. For exam-
ple, in the iron-carbon binary system, a composition of
1·5 at.-%C places the alloy in the y-Fe phase field when
sintered at either 1150°C or 1200°C. This alloy is expected
to have a very low value of Q and will not densify iron at
either sintering temperature. On the other hand, a compo-
sition of 2·0 at.-%C places the alloy in the y + L phase field
at 1200°C and in the y + Fe3C phase field at 1150°C. This
alloy will have a high value of Q, and is expected to have a
high density when sintered at 1200°C, whereas it will have
a low Q and a low sintered density when sintered at
1150°C.
NEW FIGURE OF MERIT FOR IRON QFe
The new figure of merit Q was used to predict effective
sintering enhancers for iron. The relevant iron binary
phase diagramsZ3-25 were studied to identify the possible
phase fields and alloy compositions at the sintering tem-
perature of 1200°C. The values of the solubility of iron in
the second phase XFe, the maximum solubility of the
additive in iron XA, and the melting point of the second
phase T m, P, were obtained from the phase diagrams for a
sintering temperature of 1200°C. These values are listed in
Table l.
Additives such as boron, phosphorus, and carbon each
form a eutectic with iron at temperatures below the sinter-
ing temperature, and can effectively densify iron if an alloy
composition in the iron-liquid two phase field is selected.
The eutectic liquid can be an effective second phase,
resulting in liquid phase sintering. In these cases X Fe and
Tm, P were selected as the eutectic composition and tem-
perature respectively. Unless otherwise indicated, XA for
all additives was selected as the maximum solubility of the
 Madan and German Quantitative assessment of enhanced sintering concepts 49

Table 5 Evaluation of figure of merit QFe at Ts = 1200°C

-3
Additive Phase field h d at a2 a3 VFe ps,gcm Rv Rp

B g+L 0 20 69 100 20 189 7·8 G G

C g+L 0 21 69 82 21 172 7·2 G G
Co g 0 1 100 0 1 101 6·8 B B
Cu g+L 0 24 1 86 24 111 7·7 B G
Mo a 10 1 0 74 11 85 7·0 B B
Ni g 0 1 100 0 1 101 6·8 B B
P a+L 10 27 69 91 37 197 7·1 G G
Si a 10 2 0 68 12 80 6·6 B B
Sn a 10 2 10 84 12 106 6·6 B B
Ta g 0 2 0 98 2 100 6·6 B B
Ti a 10 6 5 87 16 108 7·4 B G

additive in iron when heating from room temperature to
the sintering temperature. Copper reacts peritectically
with iron and alloys containing this additive can be sin-
tered in the y + L two phase region. Again, the liquid
phase can be an effective second phase. Thus, for iron
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Calculation of QFe at 1200°C
Iron has two crystallographic forms, a-Fe and y-Fe. The a-
Fe has a bcc structure, whereas y-Fe has the more closely
packed fcc structure. The activation energy for the selfdif-
fusion of a-Fe and y-Fe are Qa=255 and Qy=284KJ

alloyed with copper, X Fe and X A were calculated based on
the tie line in the y- L phase field at the sintering tempera-
ture, and Tm. P was selected as the peritectic reaction
temperature.
Iron based binary phase diagrams of molybdenum, sili-
con, tin, and titanium indicate that at 1200°C a practical
alloy composition could be sintered in the a-Fe phase
field. These additives enhance the sintering of iron by
increasing the selfdiffusivity of the a-Fe. For molybdenum
or silicon containing alloys, X Fe was selected as the solubi-
lity of iron in the respective additives, and T m. P was
selected as an average of the liquidus and solidus tempera-
tures for a typical iron rich composition. For example, an
iron alloy containing 3·8 wt-OloSi has liquidus and solidus
temperatures of 1783 and 1758 K respectively, resulting in
an average T m, P value of 1770 K for this alloy. In addition
to a-Fe stabilisation, tin and titanium have potential to
form a transient eutectic liquid phase with iron. The iron
would dissolve into the liquid that forms on heating, and
eventually the liquid phase would disappear. While the
liquid is present at the particle boundaries, it can allow
easy diffusion of the iron atoms. Thus, the eutectic compo-
sition was selected as XFe, and Tm•p as the average of the
eutectic temperature and the melting point of an iron rich
composition.
Cobalt and nickel form a y-Fe solid solution at 1200°C
for all compositions of the additive. Hence, XFe =
100 a1.-olo, and T m, p was selected as an average of the
liquidus and solidus temperatures for a typical iron rich
composition. Iron-tantalum alloys can be sintered in the
y-Fe-Fe2Ta two phase field. Unfortunately, the melting
point of Fe2Ta is 1775°C, 237 K higher than iron, therefore
Tm, p would be a negative quantity. It would thus be best to
sinter tantalum containing iron compacts in the y-Fe phase
field. X Fe was selected as the solubility of iron in tantalum
at 1200°C and T m, p as an average of the liquidus and
solidus temperatures for a typical iron rich composition.
mol-1 respectively. From equation (11), it can be seen that
1] = 0 or 1] = 10, depending on whether the additive stabi-
lises y-Fe or a-Fe. In cases where y- and a-Fe coexist, an
average value of 1] = 5 can be assumed. The term <5 was
calculated using equation (9), the values of Tm, p listed in
Table 1, and a value of T m, B = T m, Fe = 1536°C = 1809 K.
The terms at. a2, a3, and the figure of merit QFe were
calculated using· the data in Table 1, and equations (4),
(5), (6), and (2) respectively. The results are given in
Table 5. A high value of Q implies that the additive is a
good sintering enhancer.
Table 5 compares the figure of merit QFe to the experi-
mental sintered densities compiled from an extensive liter-
ature survey and summarised in 'fable 2. The additives
were assigned ranks, RQ and Rp, based on the figure of
merit QFe and the sintered density PS' Standards of 'good'
(G) or 'bad' (B) were assigned to RQ, depending on
whether QFe was greater than or less than 170. Similarly,
an assignment of G or B to R p was undertaken depending
on whether Ps was greater than or less than 7·0 g cm -3. A
statistical correlation test was performed on these 12 data
points by assigning values of G = 1 and B = 0, resulting in a
correlation coefficient of 0·68 and a significance of
>98·50/0. Use of the figure of merit Q is therefore a
reliable technique for predicting the enhancing power of
an alloy additive.
This technique predicted boron, carbon, and phos-
phorus to be good sintering enhancers; this was corrobor-
ated by the experimental sintered densities given in Table
5. The additives cobalt, molybdenum, nickel, silicon, tin,
and tantalum were predicted to be bad sintering
enhancers: this was also in agreement with the experimen-
tal observations. The figure of merit predictions regarding
titanium and copper did not agree with the sintered densit-
ies of iron alloyed with these elements: they were pre-
dicted to be bad sintering enhancers, but were found to
densify iron compacts.

Table 6 Figure of merit QFe for sintering conditions in Table 2

Phase XA, XFe, Tm,p,
Additive field at.-% at.-% K 0 at a2 a3 QFe
Ts'oC 1]

C 1175 y 9·23 82·9 1563 0 14 69 82 14 165

Cu 1100 y+L 6·00 4·5 1367 0 24 0 88 24 112
P 1120 a+y 4·52 83·1 1510 5 17 69 91 22 182
Si 1200 Y 17·50 0·0 1770 0 2 0 68 2 70
Sn 1100 y 8·30 17·5 1770 0 2 3 84 2 89
Ti 1300 a 9·00 84·0 1631 10 10 71 83 20 174

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 50 Madan and German Quantitative assessment of enhanced sintering concepts

Table 7 Evaluation of QFe for sintering conditions in ing temperatures of the alloys ?ased ?n the .add~tion of
Table 2 carbon, copper, phosphorus, silIcon, tIn, or tItanIum are
listed in Table 2. The values of XA, XFe, Trn,p, and the
Phase phase field for these additives ~ere ~etermined from
Additive field QFe* Ps, g cm-3 RQ Rp binary phase diagrams and are lIsted In Table 6. The
values of 6, 1], ab a2, a3, ,and QFe were calculated as above,
B y+L 189 7·8 G G
and are also listed in Table 6. Table 7 compares the
C y 165 7·2 G G
y 101 6·8 B B
recalculated figure of merit with the experimental sintered
Co
Cu y+L 112 7·7 B G densities. The figure of merit for carbon, copper, phos-
Mo a 85 7·0 B B phorus, silicon, and tin did not change appreciably, and
Ni Y 101 6·8 B B ranks RQ were unchanged. On the other hand, the figure
P a+y 182 7·1 G G of merit for titanium increased from 108 to 174: titanium
Si y 70 6·6 B B could now be classified as a good sintering enhancer. This
Sn y 89 6·6 B B was in agreement with the experimenta~ re~ults given in
Ta y 100 6·6 B B Table 2. After changing the rank RQ for tItanIum to G, the
Ti a 174 7·4 G G
statistical analysis was repeated and yielded a correlation
* At varying temperatures (see Table 2)
coefficient of 0·84, with a significance >99.9%. .
The only additive incorrectly predicted was copper: thIS
was because Lenel and Hwang8 used a fine iron powder
The values of sintered density obtained by various and sintered the compacts for a relatively long time (3 h).
authors are listed in Table 2, with the sintering conditions. Apparently, some additives like copper which have a hi~h
The studies differ in the type of iron powder used, average diffusivity term a3, but an overall low value of Q can stIll
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particle size, the size distribution of powders, sinter~ng
cycle, and compaction conditions. For exampl~, the tIta-
nium additions to iron were sintered at 1300°C; Iron alloys
containing copper, phosphorus, or tin at ,....., 1100°C; iron
compacts containing carbon at 1175°C; and the rem~i~ing
alloys at 1200°C. In addition, some of the composItIons
listed in Table 2 place the alloy in a different phase field
from that assumed for the QFe calculations. For example,
the carbon, silicon, and tin contents given in Table 2 place
these iron based alloys in the y phase field, whereas phase
fields y + L, a, and a, respectively, were assumed for the
calculation of the figure of merit for these additives.
Similarly, an addition of 0·45 wt_%P places this alloy in
the a + y phase field, whereas a phase field of y was
assumed for the QFe calculations. These variations in the
process variables and sintering conditions can. influence
the sintered densities. A more rigorous evaluatIon of the
figure of merit would require its comp.arison .with sin~~red
densities of one type of iron alloyed wIth vanous addItIves
and sintered under identical conditions. The additives
should have similar size distributions and average particle
sizes. Also, the alloy composition selected for comparison
should place the alloy in the same phase field duri~g
sintering as the phase field assumed for the figure ?f men.t.
Unfortunately, experimental data were not avaIlable In
the literature.
Calculation of QFe in varying conditions
Fortunately, the new figure of merit Q can be used to
compare the enhancing potential of an additive under
various sintering conditions. The compositions and sinter-
densify iron if the sintering time is increased.
Experimental verification of QFe at 1200°C
A more rigorous evaluation of the figure of merit requires
its comparison with sintered densities of a single type of
iron alloyed with different additives and sintered under
identical conditions. The water atomised A1000B iron
powder was selected for the study. The powder sources,
average particle size, and particle sizes than which 50 and
900/0 were smaller are listed in Table 8. The additives
selected had an average particle size of less than 25 !lm and
a median of ,.....,20!lm; all were less than 40 !lm. The
alloying additions are listed in Table 9; these values
correspond to ,.....,5vol._% of the additive. The stable
phases at the sintering temperature were determined from
phase diagrams for each alloy composition, and are given
in Table 9. The volume fraction of each component for
100 g of the alloy was calculated, and the sum of the
volumes was used to calculate the theoretical density of
the binary alloy. Cylindrical samples were compacted to
± 1% of theoretical density using die wall lubrication.
,.....,81
Compacts were sintered at 1200°C for 1 h in dry hydrogen
(dew point -55 ± 5°C). The sintered densities of the com-
pacts were measured and are given in Table 9.
The compacts containing boron, phosphorus, and car-
bon densified to 96%, 90%, and 88% of theoretical
density respectively. The compacts alloyed with carbon
lost some carbon during sintering. A compact containing
enough graph1te to compensate for the carbon loss would
have sintered to higher densiti~s. Thus, boron, phos-
phorus, and carbon can be regarded as good sintering

Table 8 Particle size and source of additives for evaluation of figure of merit
Mean Particle size than Particle size than
size, which 50% are which 90% are
Additive Source !lm smaller, !lm* smaller, !lm

B AlfaProducts, as received 5 3 9
C Alfa Products, as received 9 8 17
Co Pfizer Corp., as received 11 10 19
Cu SCM Metals, - 325 fractiop 22 20 35
Mo AMAX Corp., -325 fraction 11 10 21
Ni INCa Corp., as received 13 10 25
P Alfa Products, -325 fraction 21 18 40
Si Alfa Products, - 325 fraction 13 10 30
Sn AMAX Corp., -325 fraction 9 8 27
Ta Alfa Products, - 325 fraction 19 15 40
Ti Timet Corp., -325 fraction 25 20 40

* Median

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 Madan and German Quantitative assessment of enhanced sintering concepts 51

Table 9 Experimental evaluation of figure of merit QFe

and QFevised at 1200°C 1:

v
300 Original

Phase Addn, QFe Qrevised 8 200

Fe •....
Additive field wt-% Pg Ps 1200°C RQ Rp 1200°C o good

B y+L 1·6 80 96 189 G G 245 a

V
100
---

C y+L 2·0 82 88 172 G G 232 .~

•....
Co y 5·6 81 84 101 B B 104
Cu y+L 13·3 82 78 110 B B 181
Mo a 6·4 81 83 85 B B 114
Ni y 5·6 82 84 101 B B 104
P a+L 2·2 81 90 197 G G 308 .~
-' 300 Revised
Si a 2·0 80 83 80 B B 113 v
Sn a 4·7 82 84 106 B B 138 8 200
good

Ta y 10.0 82 82 100 B B 99 •....

o bad
Ti a 2·9 81 80 108 B B 152 v
a
tID
100

;;:
enhancers on this experimental evidence. On the other
hand, the remaining additives did not densify the A1000B B C Co Cu Mo Ni P Si Sn Ta Ti
iron powder, giving <84% theoretical density. The addi- Element
tives were ranked as before and the ranks are listed in
Table 9. The ranking based on this experimental study 3 Figure of merit of various sintering enhancers for iron,
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accords with that based on the calculated figure of merit. 1200°C

Statistical determination of c., C2, and C3

The constants c}, Cz, and C3 in equation (2) have so far been
assumed to be unity. An attempt was made to estimate the
values of c}, C2, and C3 using a multiple regression model.
The terms aI, az, and a3 were defined as independent
variables, and the figure of merit Q as the dependent
variable. It should be noted that Q values were calculated
using the independent variables: they were not measured
quantities. Thus, when all three terms, a}, az, and a3, are
simultaneously entered in the regression equation, the
analysis yields a value of unity for the coefficients a}, a2,
and a3. The regression analysis was therefore performed in
three steps. At each step one of the independent variables
ai was entered into the regression equation, and the
coefficient Ci determined. The three coefficients were nor-
malised with respect to Cl and a revised figure of merit
Qrevised was measured for each element using equation (2).
Next, the new figure of merit was treated as the dependent
variable and the regression analysis was repeated to obtain
another set of values for the three coefficients. The analy-
sis was repeated six times in all; the coefficients obtained
are given in Table 10. At the end of six iterations the
values of c}, C2, and C3 converged to 1·0, 0·92, and 4·2
respectively. The revised figure of merit can therefore be
represented as
Qrevised = al + 0·92 az+ 4·2 a3 . (12)
For the final iteration the analysis indicated correlation
coefficients of 0·714, 0·913, and 0·950 for the terms a}, az,
and a3 respectively. This corresponds to a significance
>99% for the 11 data points. The correlation coefficients
for the segregation and diffusion terms had a significance
>99·9%.
As seen in equation (12), the diffusion term a3 is the
most important in determining the effectiveness of a sin-
Table 10 Statistical determination of Cl, C2,
Iteration CI Cz
0 1·0 1·0
1 1·0 0·85
2 1·0 0·89
3 1·0 0·91
0·92
4 1·0
5 1·0 0·92
6 1·0 0·92
Qrevised = at + 0.92 az + 4.2 a3
tering enhancer, the solubility and segregation terms hav-
ing coefficients approximating to unity. Thus, additives
which form an easy diffusion path for the base metal atoms
are best for enhancing the sintering kinetics.
Table 9 compares the figures of merit for iron, QFe and
QF~vised. As seen in Fig. 3 and Table 9, the revised figure of
merit is a better differentiator of 'good' and 'bad' sintering
enhancers.
DISCUSSION
The new figure of merit Q provides a reasonably accurate
technique to evaluate the enhancing power of alloy addi-
tives for iron. It is based on equilibrium phase diagram
features, and is easy to calculate and understand. It can be
used to evaluate the effectiveness of different alloy addi-
tives for any given sintering condition, and to evaluate the
same additive under different sintering conditions. This
technique does not consider non-equilibrium features such
as extremely high heating rates, which can influence such
parameters as solubility of the additive in the base.
Although Q gives a good estimate of the enhancing poten-
tial of an additive, it would be unwise to discard entirely
additives with mediocre Q values. Closer examination of
the solubility, segregation, and diffusion terms can suggest
possible manipulations of process variables to assist the
additive in enhancing the sinterability of the base metal.
Boron, carbon, and phosphorus were identified as good
sintering enhancers for iron. All three additives have
relatively low solubility in iron and form a low melting
eutectic; iron has a high solubility in the eutectic liquid.
Also, all three additives have an electron configuration
very different from that of iron. Additives which have an
electron structure similar to that of iron had relatively low
values of the figure of merit. Kipphut and GermanZ6
and C3 suggest that the electron structure of a phase, which is
related to the regular solution interaction parameter, can
C3 be linked to the phase diagram criteria for liquid phase
sintering. A favourable system would have the greatest
1·0 thermodynamic stability or a relatively low interaction
3·72 parameter associated with the liquid, and the least stability
4·08 or a relatively high interaction parameter for the base. A
4·17
4·18
different electron structure implies a desirable electron
4·20 exchange between the base and the eutectic liquid phase.
4·20 This favours the solubility and diffusion of the base
through the liquid phase.z6 Among the additives con-
sidered, boron had an electron structure differing most

Powder Metallurgy 1990 Vol. 33 NO.1

 52 Madan and German Quantitative assessment of enhanced sintering concepts

from that of iron. It forms a low temperature liquid phase 2. R. M. GERMAN and B. H. RABIN: Powder Metall., 1985,28, (1),
with a high solubility for iron, and results in electron 7-12.
transfer due to a strong compound forming tendency. In 3. D. S. MADAN and R. M. GERMAN: in 'Modern developments in
addition, the iron atoms have a high diffusivity through the powder, metallurgy', (ed. E. N. Aqua and C. I. Whitman),
iron-boron eutectic phase. The predictions based on Vol. 15,441-445; 1986, Princeton, NJ, MPIF.
4. 'Metals handbook', 8th edn, Vol. 8, 270-307; 1975, Metals
the figure of merit seem to accord with the interaction Park, OH, ASM.
parameter theory proposed by Kipphut and German. 5. M. HANSEN and K. ANDERKO: 'Constitution of binary alloys',
Boron had a high value of the figure of merit, and is a 2nd edn; 1958, New York, McGraw-Hill.
potential sintering enhancer for iron. According to the 6. M. J. KOCZAK and P. AGGARWAL: in 'Progress in powder
phase diagram, at the sintering temperature of l200°C metallurgy' Vol. 36, 113-132; 1979, Princeton, NJ, APMI.
boron is expected to form a eutectic liquid phase with iron. 7. D. S. MADAN, R. M. GERMAN, and c. LALL: in 'Progress in
Thus, at the sintering temperature, the segregated phase powder metallurgy', Vol. 41, 307-326; 1986, Princeton, NJ,
would be the eutectic liquid phase. The iron-boron phase APMI.
8. F. V. LENEL and K. S. HWANG: Powder Metall. Int., 1980, 12,
diagram indicates that at the sintering temperature iron
88-90.
has a high solubility of 96 wt_% in the eutectic liquid 9. F. J. ESPER, K. H. FRIESE, and R. ZELLER: Int. J. Powder
phase. Also, boron has a very low solubility of 0·005 wt_% Metall., 1969, 5, (3), 19-32.
in iron and would remain segregated at the particle boun- 10. K. S. HWANG and R. M. GERMAN: in 'Processing of metals
daries. Thus, boron has a high al value (69), and a high a2 and ceramic powders', (ed. R. M. German and K. W. Lay),
value (100). 245-310; 1982, Warrendale, PA, The Metallurgical Society of
The experimental results of a comprehensive study on AIME.
the iron-boron system27 are in excellent agreement with 11. T. T. LAM: 'High density sintering of iron-carbon alloys via
the prediction based on the new figure of merit, and transient liquid phase', Report LBL-8001, 1978, Berkeley,
Downloaded by [Monash University Library] at 10:37 02 July 2016

CA, University of California.

provide a verification of the concept of enhanced sintering.
12. R. M. GERMAN, W. H. BAEK, and J. W. DUNLAP: in 'Progress in
powder metallurgy', Vol. 41,765-790; Princeton, NJ, APMI.
CONCLUSIONS 13. R. M. GERMAN and K. A. D'ANGELO: Int. Met. Rev., 1984, 29,
An evaluation of Miodownik's figure of merit showed that 249-272.
it did not successfully quantify the enhancing power of 14. L. E. TOTH and A. W. SEARCY: Trans. TMS-AIME, 1977,22,
sintering aids for iron. The new figure of merit proposed in 262-301.
this study combines the qualitative enhanced sintering 15. A. M. BROWN and M. F. ASHBY: Acta Metall., 1980, 28,
criteria of solubility, segregation, and diffusion in a single 1085-1101.
16. R. M. GERMAN: in 'Modern developments in powder metal-
quantitative model. It is defined as a dimensionless quan-
lurgy', (ed. E. N. Aqua and C. I. Whitman), Vol. 15,
tity relating to thermodynamic concepts, and can easily be 253-273; 1986, Princeton, NJ, MPIF.
calculated from phase diagram features. It has been shown 17. R. M. GERMAN: in 'Progress in powder metallurgy', Vol. 42,
to predict, reliably and accurately, the effectiveness of 235-248; 1986, Princeton, NJ, MPIF.
sintering enhancers at any given sintering temperature and 18. A. P. MIODOWNIK: Powder Metall., 1985,28, (1), 151-154.
alloy composition. The model predicts boron to have most 19. A. K. NIESSEN, F. R. DE BOER, R. BOOM, P. F. DE CHATEL,

potential as a sintering enhancer for iron. The new figure W. C. M. MATIENS, and A. R. MIEDEMA: Calphad, 1983, 7,
of merit provides a verification of the concepts of 51-70.
20. A. R. MIEDEMA: Z. Metallkd., 1979, 70, (6), 345-353.
enhanced sintering.
21. A. R. MIEDEMA: Z. Metallkd., 1978, 69, 287-292.
22. c. J. SMITHELLS: 'Smithells metal reference book', (ed. E. A.
ACKNOWLEDGMENTS Brandes); 1983, London, Butterworth.
This study was conducted in the Materials Research 23. T. B. MASSALSKI: 'Binary alloy phase diagrams', Vol. 1; 1987,
Center at Rensselaer Polytechnic Institute, Troy, NY. Metals Park, OH, ASM.
One of the authors was supported by a Hoeganaes 24. T. B. MASSALSKI: 'Binary alloy phase diagrams', Vol. 2; 1987,
Corporation Fellowship for the duration of the study. The Metals Park, OH, ASM.
authors wish to thank the Hoeganaes Corporation, 25. o. KUBASCHEWSKI: 'Iron binary phase diagrams', 15-18;
Riverton, NJ for donating the AlOOOBiron powder. 1982, Dusseldorf, FRG, Springer-Verlag.
26. c. M. KIPPHUT and R. M. GERMAN: Sci. Sinter., 1988, 20, (1),
31-41.
REFERENCES 27. D. S. MADAN: PhD thesis, Rensselaer Polytechnic Institute,
1. P. E. ZOVAS, R. M. GERMAN, K. S. HWANG, and c. J. u: J. Met., Troy, NY, 1988.
1983, 35, (1), 28-33.

Powder Metallurgy 1990 Vol. 33 NO.1