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Dilatometric Sintering Study of Titanium-Titanium Nitride Nano/nanocomposite Powders
Dilatometric Sintering Study of Titanium-Titanium Nitride Nano/nanocomposite Powders
To cite this article: V. V. Dabhade, T. R. Rama Mohan & P. Ramakrishnan (2007) Dilatometric
sintering study of titanium–titanium nitride nano/nanocomposite powders, Powder Metallurgy,
50:1, 33-39
Download by: [University of Saskatchewan Library] Date: 26 February 2016, At: 06:35
Dilatometric sintering study of titanium–
titanium nitride nano/nanocomposite
powders
V. V. Dabhade1, T. R. Rama Mohan2 and P. Ramakrishnan2
The sintering behaviour of titanium–titanium nitride nano/nanocomposite powders has been
investigated by dilatometry. The nanosized titanium powders (40 nm) were produced by the
attrition milling of micron sized titanium powders (12 mm) in Ar atmosphere while the nanosized
titanium nitride powders (50 nm) were as procured. Two compositions of the nano/nanocomposite
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powders, i.e. Ti–8TiN and Ti–15TiN (wt-%) were produced by physical mixing and ultrasonifica-
tion. Dilatometry was carried out at a constant rate of 10 K min21 heating to various temperatures
in the range of 450–1250uC followed by holding for 1 h. The effect of nanoTiN reinforcement on
the sintering onset temperature, linear shrinkage, shrinkage rate, activation energy for sintering,
microstructure and grain growth has been reported and discussed.
Keywords: Nano/nanocomposite, Dilatometry, Sintering, Activation energy, Grain growth
1 Photograph (TEM) and selected area electron diffrac- 3 DTA and TG plots of nanoTi
tion (SAED) pattern of nanoTi
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nitride nano/nanocomposite powders by dilatometry. instrument (9900 model) using a-alumina as the
The effect of nanosized titanium nitride reinforcement reference, while the TG was carried out in a Shimadzu
on the sintering onset temperature, linear shrinkage, thermal analyser (DT-40). Both DTA and TG were
shrinkage rate and activation energy, microstructure carried out employing a heating rate of 10 K min21 in
and grain growth of nanosized titanium has been high purity Ar atmosphere, passed over heated (1000uC)
investigated. titanium getter to remove the traces of oxygen. The
heating rate and the atmosphere were similar to that
employed during the dilatometry. The chemical analysis
Experimental of the powder as obtained by the inductively coupled
Raw material plasma atomic emission spectroscopy (ICPAES) showed
major impurities to be that of 0.62Fe, 0.16Cr, 0.1Ni and
Synthesis of nanosized Ti was carried out on a
0.1Mn (wt-%). A Plasmalab 8440, Labtam Ltd, instru-
laboratory scale by the attrition milling of micron sized
ment was used for the ICPAES analysis.
Ti for 40 h under high purity Argon, as reported earlier
In the present investigation, nanosized TiN powders
in a separate study.22 The average particle size of the
of average particle size of 50 nm were used. The particle
40 h milled nanosized Ti powder produced was y40 nm
size was determined by TEM (Fig. 4) as explained
as determined from TEM (Fig. 1). The particle sizes of
above. The XRD pattern of the nanosized TiN powder
over 100 particles were determined individually from the
is shown in Fig. 5. The chemical analysis of the powder
TEM, and their average was taken as the average
as obtained by ICPAES indicated no impurities in the
particle size. A Philips (CM 200) make instrument was
detectable limits (,0.01 wt-%).
used for the TEM analysis. The XRD pattern of the
nanosized Ti powder is shown in Fig. 2. A Philips make Compaction and Sintering procedure
X-pert pro XRD with X’celerator instrument was used Since nanosized powders were involved, extra precau-
in the present investigation with Cu target (l51.54 Å). tions were taken during powder mixing to ensure that
Figure 3 shows the differential thermal analysis (DTA) proper mixing of the reinforcement powder took place
and thermo gravimetric (TG) curves of nanosized Ti
powder. The DTA was carried out in a Du pont
2 X-ray diffraction pattern of nanoTi 4 Photograph (TEM) and SAED pattern of nanoTiN
6 Variation of linear shrinkage (%) with temperature dur- 8 Variation of linear shrinkage (%) with temperature dur-
ing constant rate of heating at 10 K min21 (left side)
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was determined from the point at which deviation from right side portion represents dilatometric data during
linearity during thermal expansion occurred in the holding at sintering temperature.
dilatometric curves. The reported onset temperatures It can be noticed that during CRH, the observed
are the average of all the samples heated in the shrinkage for all the specimens showed two distinct
temperature range of 450–1250uC. The addition of slopes. The slope in the first region (450–550uC)
nanoTiN in nanoTi led to an increase in the sintering corresponds to a-Ti where the shrinkage was lower,
onset temperature, which could be attributed to the and the slope in the second region (575–1250uC)
lower sinterability of the nanoTiN as compared with corresponding to b-Ti where the shrinkage was higher.
that of nanosized Ti. This is most likely due to the open structure of the b-Ti
phase (bcc) compared with the a-Ti phase (hcp) which is
Linear shrinkage and shrinkage rate close packed.
During the constant rate of heating (CRH) the linear All powders, i.e. nanoTi, nanoTi–8TiN and nanoTi–
shrinkage was determined as a function of temperature 15TiN, showed considerably large amount of shrinkage
while during isothermal holding it was determined as a during CRH than that during isothermal holding.
function of time. Figures 6, 8 and 9 show the dilato- Figures 6, 8 and 9 indicate that for nanoTi, nanoTi–
metric curves obtained for heating at a constant rate of 8TiN and nanoTi–15TiN specimens, the shrinkage rate
10 K min21 up to various sintering temperatures during CRH varied with respect to temperature and
followed by holding at that temperature for 1 h for therefore this parameter was plotted as a function of
specimens of nanoTi, nanoTi–8TiN and nanoTi–15TiN temperature. Since the individual curves shown in
respectively. The left portion of Figs. 6, 8 and 9
represents the dilatometric data during CRH while the
The activation energy values, although are valuable, compacts are nanocrystalline even after the sintering
cannot point out the mechanisms responsible for process.
sintering. The latter are studied with the help of sintering
models suggested by Johnson and co-workers in another Conclusions
study by the same research group.25
The onset of sintering temperature for nanoTi powder
Microstructure and grain growth was found to decrease with the addition of nanoTiN
which has been attributed to the poorer sinterability of
Figures 11 and 12 show the SEM photographs of
the nanoTiN powder at lower temperatures. The linear
nanoTi–8TiN and nanoTi–15TiN compacts sintered at
shrinkage as well as the shrinkage rate during CRH was
1000uC respectively. The microstructure of both the
found to decrease with the addition of nanoTiN to
compacts at lower magnification shows a well densified
nanoTi. The addition of nanoTiN in nanoTi led to a
structure while that at higher magnification shows a
decrease followed by an increase in the activation
structure of sintered agglomerates and clusters (agglom-
energy. The microstructure showed a structure of
erates of agglomerates). Porosity is also seen between
sintered agglomerates and clusters (agglomerates of
the agglomerates and clusters in the structure in the agglomerates) with porosity between the agglomerates
form of inter agglomerate space. It was not possible to and clusters in the form of inter agglomerate space. The
distinguish the nanoTiN reinforcement phase in the addition of nanoTiN reinforcement in nanoTi did not
microstructure possibly owing to lower magnifications affect the grain size of the nanoTi.
involved.
Figure 13 shows the variation of grain size (obtained Acknowledgements
from X-ray line broadening) with sintering temperature
for nanoTi, nanoTi–8TiN and nanoTi–15TiN. The The author, V. V. Dabhade, wishes to acknowledge Dr
slight drop in the grain size up to 700uC may be due B. B. Panigrahi and Professor M. M. Godkhindi for
to recrystallisation, as the nanoTi powder is in a highly their help in carrying out the dilatometric experiments at
cold worked state owing to the attrition milling. Grain the Department of Metallurgical and Materials Engineer-
growth takes place beyond 700uC (0.5Tm) for all the ing, Indian Institute of Technology, Kharagpur, India.
powders and reaches a maximum of y88 nm at 1200uC.
The addition of nanoTiN reinforcement in nanoTi does References
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