7.4 Sintering of Multicomponent Systems
7.4 Sintering of Multicomponent Systems
7.4 Sintering of Multicomponent Systems
Sintering of multicomponent ~y."tcm~ 1n P/~f 1~ cnmrnun. ~,nee ir b unc nt rhc nll)'.'1{ tmpon.:r::
methods of forming alloy\ \tar1ing from clcrnenwl f)<)\\dl'r~. S111tenng of ek~mentJl J)'J" de" ·,
advantageous in n1any \vay~. for cxan1pk. H J\ cibY co con1pacr a nlL\tUrt· of ,ron Jnd i:arbor.
pcn-\·der~ rarher than ~1ntcn ng )tee l powder~ . ()rher L' xarnplc~ 1nL·IuJc hr~,~~ anJ bron1t' po'4dtr-
from elemental powder\. In the ,1nrcnng of n1uh1con1rxn1cnr :-,y~ccnh. the n1accnaf crao~~<.
,nechan ism~ involve ( 111 add1 tiun ro .\clt'-d1ft'u.-.,1on L·auscd hy l·apil la~ fon·c~ ,. ,nt(n.1iftlbutn ol
rhc components into om.: another (due to cc mccncr:tr1t ,11 gradient, rhruugh \ al·anl'} n1o~ement
------ --
such systems may also i -------- .._
---...._____
of - . . nvolve I -------
. ,ering consists of a low- me lting con, t 1c fllrn . . -- ---- Cham
51~reg~te (e g . W -Co, hard metal) Ponc111 Wh 1,n,c>n <lf . - ·--~ 7 s.,,
;1i~ en1ture . . o~c lllt.: lt1 11 " liq111<.1 n 1. •:rr'J -
cn1P • f g ~
l
cintenn_ g o Powder
:l ;;, Aggregates
i1111 ,, btt
,•wt,
,1 n,';'. . . . .
Ill, th~ 1· ,·~dc-r
1,4• formation "'1ith 1'-4o
'- 'lli(cr,
,'.)~
. - case, during si ntcring, diffusion oc liqllid p
1s .. 11 The extent of homogeni z, t · curs and ha~
In 11105 ,tio · . d ion d rnav
con1P • which in turn d e pends on particle .· epcncts <in -h re,u11 in h
ents. b size s·11 t e d·,-1 fu,10n .r,rn r1gtn1;,Jti,
~lef11 . ·tuents will not e equal, with on '· Hering te,
s11 t· . e comp nperat Coen, It) c,i
of c011 · 11 the case o 1ron-carbon mixtu. onent diff . Ure and t c1cnt, r1f •
nple, J • • I e, <.: arb . u~1ng I· irne I '~,('.
~~ar b O n This occun-ence ot Kirkendall t·t· on diffuses il:,tcr th· nterctitr'u
car · . e ect d · · rnuch f· iln tht: 1 ' in
,n[() , ri on which may cause pores to ap unng sintenn il\tcr 101 1)>ther 1--r,r
centra ' pear and g may I in,n 'h
con nt This pore growth may be offset b grow, in tu cad ti i tx . '· an 1run
rnpone · . • Y the h · rn caus1 1.:t--., \ Gn
co . of atoms mto vacancies. In many m 1 . s nnkage < f · ng the gro¼th 1.::
d,·ffusron II d d u ticompon J pore\ b , 1,f •t.
sometimes ca e as opants, is added int . ent systems . . ) the n1Jrrn:i1 ' ~
hase. • h ent1onall . · · il !->mall . '1<:l!
P JOO times . This p enomenon , known . Y to increase th d amount ()f ~u ,
about l'k as acr1var I . e ensrfic >nJ
. cory metals I e tungsten, molybdenum ta t ec. s1nrering i. . a1ton rate) b,
retrac . , n aIum haf · · s 1ounct t -'
d
·um as the activators. The significant im · nium and rhen u ()<.: cur ,0
Pal Ia 1 e of dopants has been attributed to the enh· provement 111 · . um w11h k
1
d . sintering char· . nit: ·el c1r
presenC . ance grai b actenstic~
resence of dopants at the gram boundaries of these ref n oundary d1ffus1on cau"C.d : th-:
p ractory metals. y the
d . prccip1tatwn proce.. .
ss· rn this stage, smaller particle~ ct· -.. . ·
. . ,~~rI
·t This causes the particle centres to appr · >vt fr
they ·,re in contac . . f (><1<.: h ,,.
areas w ie_rc ' . .. I ed material is carried away rom the contact , l:ili.J.,,.
densifica1ton. The disso v . arert., __ i
· · m larger particles. ~r
rcprec1p1tate t . ._ . ,
st the rate of densification slows and fi1 , ·
( j j j) Solid state si nten ng: I11 this age, _ . . _ nctlly \ltiv,
. _. _ . I' .d hase sinten ng w1 th 11 me and the progress of den ..
The dtf lercnr ~tcps ,~ iq_u1 p 6 This form of liquid-phase sintering, abo kSlfil4t1r~_
·1re shown schematically m Figure 7. . . I t· th W N. F no.,.,n ·.
' . . _. • • h been used extensive y or e - 1- e, W-M0 . ~-
'persistent l1qu1d phase smtenng as -Ni+t.
WC-Co and W-Cu systems.
Time --+
Figure 7.6 Stages in liquid phase sintering: (i) liquid flow stage, (ii) solution and reprecipitation stage, and
(iii ) solid state sintering stage.
In another form of liquid phase sintering known as transient liquid phase sintering, the
liquid formed is temporary in nature. In this case, the liquid continues to take the solid into
solution until it reaches a point when the solidus boundary is reached and the liquid resolidifies.
An example of such a system exhibiting transient liquid phase sintering is 90Cu-10Sn bronze
used in preparing self-lubricating bearings. During sintering, the tin melts first, forms solid
solution with copper and quickly resolidifies.
Liquid phase sintering will be effective only if the liquid phase completely penetrates
between solid particles. Liquid phase sintering involves transport of materials (atoms or ions)
from surfaces of higher energy to surfaces of lower energy (surfaces with small radii of convex
curvature have higher energy and surfaces with small radii of concave curvature will have
lower energy).
The mechanism of liquid phase sintering is complicated because chemical forces are also
acting during sintering. A solid skeleton forms similar to solid state sintering during the final
stage. In the mic~ostructure of the final product, two different phases can be clearly
distinguished. In this case, the solid particles are coated by the liquid in the initial stage. In
liquid phase sinte~in~, the grains (solid) are separated by a liquid film. Because of this, the
dihedral angle ( f!) 1s .important. ~onsider two particles in contact with a drop of liquid between
them as shown 111 Figure 7.7. Smee the driving force for diffusion is the reduction in surface
~-- u,1ace energy
. term is very import•ant. 1. .. . c.;hapte,-~ -S. .
1
rhe 5 ur) is given by the equation he surface , ntenng .
11'1'· ·d vapo energy f
.,i,fe:- (qt'' - cir the b
>1id- '
( 0 ::: Ys- /2v a ovc systern
' .f I 1- .r
Grain
Grain
r$
11 Schematic representation of dihedral angle between two sol'd
Figure • with them.
.
• part1c1es and liquid phase rn contact
friction leads to faster rearrangemen t of particles. resence o .11qu1d ph ase aid 'C.le
material flow and better packing. Sharp edges a nd corners are dissolved in the Ii s 1n
· m
resulting · eff..1c1ent
· pac k.mg. qu,d
th
(ii) Use of additives with lower melting temperatures an e base metal Powdth
enables sintering to take place at lower temperatu.r~s. . . . er
nd
(iii) Processing of difficult to sinter materials such as silicon nit e 15 possible. Do .
can also be done to lower the sintering temperatures, especially in the ca Ping
Se Of
ceramics.
The process also has certain disadvantages :
(i) Proper control is necessary. Too much of liquid phase may cause the collapse of
object under its own weight.
(ii) Enhanced kinetics can lead to grain growth.
(iii) Possibility of grain boundary segregation can lead to deterioration of c
reep
properties.
(iv) The control of microstructure is more difficult as the liquid phase tends to increase
grain growth .
(vi) The high -temperature properties of the sintered material are lowered due to the
presence of the liquid phase at the grain boundaries . Shrinkage is also more, though
may not be present throughout the sintering process.
The driving force for various material transport mechanisms operating during solid and
liquid phase sintering is summarized in Table 7.3.
Table 7.3 Summary of the Driving Force for Various Material Transport Mechanisms Operating During Solid
and Liquid Phase Sintering
------_:____:__:_:,:_
Viscous flow
Solution-precipitation
__ Surface tension
Surface tension No
~ ~ ~ ~ ~ -- - ~ ' . _ - - -
Yes
------
~s
7.
::::::--~;:---------------~C~h~a~p~fe:_r!_7~S~in~te~r~in~gJIUliijl
VARIABLES
■
~~
. variables
.
in sintering include the following .
Process Variables
7.s.1
(i) Sintering temperature: Increasing the sintering temperature greatly increases the rate
and magnitude ?f a~y changes occurring during sintering, due to increased diffusion.
(ii) Sinten~1g tzme: _The degree of sintering increases with increasing time, though the
effect is sn:all m companson to the effect of temperature. The loss of driving force with
increasing nme ~t an~ temp~rature is one of the reasons why it is so very difficult to remove
all porosity by smtenng. It is possible to achieve the desired properties of the sintered parts
by shorter sintering times and correspondingly higher temperatures. However, the maintenance
costs and energy consumption of a furnace increase when its operating temperature is raised.
Longer times may also result in grain coarsening, which affects the mechanical properties
adversely.
(iii) Sintering atmosphere: Sintering atmosphere plays a vital role in bonding of the
particles and hence in influencing the properties of the sintered part. Atmospheres not only
provide protection against oxidation, but also help to reduce surface oxides, thus, aiding the
sintering process.
The proper production, use and control of sintering atmospheres, which are essential for
the optimum use of the powder metallurgy process, are described in a later section.