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p
P
l
r
l
2
4 T
4
T
4
a
_ _
_ _
;
T
m
;
T
a
3r
l
2
p
c
p
r
p
v
l
p
P
l
r
l
2
4 T
4
T
4
a
_ _
_ _
;
Q
in
bQ
1
Q
1
Q
in
Q
2
Q
in
NQ
2
_
_
4
where, a
p
is the laser absorption coefcient of powder; is the Stefan
Boltzmannconstant; is the radiation emissivity; v
l
is the laser scanning
velocity; T
a
is the environment temperature; and P(x(t), z(t)) is the dis-
tribution of laser source. c, l
P
, and T
m
are specic heat, latent heat of fu-
sion and melting temperature of metal particles respectively.
FromEq. (4), it can be foundthat powder heating is dependent on its
own characteristics (melting temperature, specic heat and thermal ab-
sorption) and the laser treating time. Every powder particle could ob-
tain its corresponding temperature. The powder particle will melt
when this corresponding temperature reaches the melting temperature
(Fig. 3c). On the contrary, the powder particle may melt partially or not
melt (Fig. 3a and b).
Table 1
Compositions of three powder systems with variation of Ni contents.
Powder system W powder (wt.%) Ni powder (wt.%)
A 90 10
B 80 20
C 60 40
16 D.Q. Zhang et al. / Int. Journal of Refractory Metals and Hard Materials 45 (2014) 1522
Phase transformation
Figs. 5 and 6 depict the typical X-ray diffraction spectrum of WNi
powders A, B and C and the respective SLMsamples produced. The pow-
ders mainly consisted of matrix metal Wand Ni, while Ni peaks became
higher when its relative content increases (Fig. 5c). After the SLM
process, the diffraction peaks of W, Ni and Ni
4
W could be observed
(Fig. 6). Furthermore, Fig. 6 reveals the presence of an intermetallic
compound phase, Ni
4
W, after the SLM process. Some Ni peaks were
also observed to be missing after the SLMprocess and this was because
a large amount of Ni powder melted due to its lower melting point rel-
ative to W. On the other hand, reaction of Wphase may also occur after
the temperature has reached about 970 C to form Ni
4
W phase accord-
ing to the WNi phase diagram shown in Fig. 7 [21]. As the Ni content
increased from 10 wt.% to 20 wt.% to 40 wt.% for SLM specimens A, B
and C respectively, the corresponding diffraction peaks of Ni
4
W phase
increased accordingly.
Zhou Y et al. [9] reported that there was a weak WNi phase
(040) peak that appeared in WNi sintered samples through micro-
wave sintering process. This illustrated that the Ni
4
W phase was
formed after the sintering process because at 1450 C, the liquid Ni
phase dissolved a large amount of W. While the LPS process in
SLM of WNi is similar to LPS process in microwave sintering of
WNi, only Ni
4
W was observed and not WNi. Instead, W dendrites
were observed. Therefore, this evidence strongly indicated that
some W particles experienced melting and formed dendrites upon
solidication while the remaining W particles were sintered togeth-
er with Ni.
Microstructure evolution
The resultant microstructures of SLM specimens A, B and C are
shown in Fig. 8. As the Ni content increased from 10 wt.% to
20 wt.% to 40 wt.%, the microstructures evolved from bar shaped
structures to dendrites to honeycomb structures. The forming mech-
anism of SLM process is not the same as LPS in powder metallurgy
Fig. 1. Morphology of powder systems with various contents of Ni powder: (a) powder A, (b) powder B, and (c) powder C.
Fig. 2. Image of WNi alloy SLM specimen.
17 D.Q. Zhang et al. / Int. Journal of Refractory Metals and Hard Materials 45 (2014) 1522
and, in some area, Wparticles experience melting/solidication dur-
ing the SLM process (Fig. 9). The experimental results demonstrated
that the content of Ni element played an important role in the micro-
structures of WNi SLM parts. Adding Ni element in the powder sys-
temcould decrease the temperature gradient of powder bed because
of the relatively lower melting temperature of Ni. Based on dendrite
growth theory [22], primary dendritic space would augment with
the fall of temperature gradient. Hence, a larger Ni content of
40 wt.% combined with the decreasing of temperature gradient in
SLM process along Z direction, and the microstructures evolved
from bar shaped structures to dendrites to honeycomb structures
accordingly.
Fig. 10 shows the EDS results of SLM samples using powder A.
The results revealed that the grey phase contained a large W con-
tent (91.88 wt.%) and the dark matrix contained a large Ni content
(51.81 wt.%). Similarly, the EDS results of SLM sample using
Fig. 3. Surface morphologies of SLM-fabricated specimens using: (a) sample A (90 WNi), (b) sample B (80 WNi), and (c) sample C (60 WNi).
Fig. 4. Coordinate system of powder heating model.
Fig. 5. X-ray diffraction peaks of WNi powder systems: (a) powder A; (b) powder B; and
(c) powder C.
18 D.Q. Zhang et al. / Int. Journal of Refractory Metals and Hard Materials 45 (2014) 1522
powder B (Fig. 11a and b) demonstrated that the grey phase
contained a large W content and the dark matrix contained a
large Ni content. Based on metal solidication theory [22,23],
supercooling rate is usually considered with regard to its solidica-
tion conditions, initiation grain of crystallization and the growth of
crystal. For SLM of WNi alloys, the heating effect of powder par-
ticles was determined by the thermal conditions of powder bed.
Since the Ni particles melted rst during the SLM process, the W
particles were rearranged by the capillary force. With the increase
of Ni content, the WNi powder experienced a near rapid melting-
solidication process with the composition undercooling as the
primary factor. Under a positive temperature gradient
dT x
x
0 N0
_ _
,
the structural features of the dendrites varied according to the
composition undercooling of the WNi powder. The structural
features of the dendrites transited from cellular crystals to colum-
nar crystals to free dendrites with the increase in undercooling
[24] as shown in Fig. 9ac.
Inuence of Ni content during SLM process
Liu et al. [25] systematically studied the microwave sintering prop-
erties of WNiFe and sintering parameters of tungsten-based alloy
[8]. Zhou et al. [26] also investigated the forming process of high
performance tungsten through microwave sintering. Their results
showedthat the mainfactor of activationmechanismby adding alloy el-
ement could be regarded as volume diffusion through the crystalline
lattice and via short-circuit paths such as particle surfaces and grain
boundaries.
When the surface of the matrix is covered with a metal lm of
high diffusion coefcient, a large amount of vacancy and micro
pores appeared on the surface of metal particles. This resulted from
the diffusion of metal atoms from the metal lm into the matrix.
The nature of diffusion during sintering can be considered as the mo-
tion of lattice vacancies in the material. Adding Ni element is a prom-
ising approach for the sintering of W since it promotes particle
diffusion and reduces viscosity. As a result, the sintering process is
improved.
In SLM, the main driving force in molten pool can be regarded as the
convection applied by the combination of buoyancy, surface tension
gradient and viscous shear stress. Gu and Shen [27] developed a multi
component Cu powder and studied the microstructure during the SLM
process. Averyanova et al. [28] also investigated the inuence of initial
powder characteristics on nal parts. From their work, it is believed
that the mutual solubility of chemical composition and the possible
chemical reaction have inuenced the density and microstructure of
SLM samples. In the present research, the carbonyl nickel powders
(purity 99%, with a mean particle size of 2.3 m) were used to prepare
the WNi composite powder. Owing to the high specic surface area
and low melting point, the composite powder system can enhance the
absorption of laser energy so as to benet the characteristics of sintering
kinetics.
Under the radiation of the laser beam, there was a temperature gradi-
ent in the melt in every direction. Furthermore, the evaporation of mate-
rial at certainlocations as well as the chemical potential gradient of solute
elements resulted from the thermal gradients; the direction of surface
tension gradient and the orientation of liquid ow were codetermined
by these effects. During the SLM forming process of WNi alloy, the
melt consisted of both liquid phase and solid phase. Moreover, under
the force of thermal capillary, the effect of the liquid content to the
melt viscosity () can be dened by [29]:
0
1
1
l
s
_ _
2
5
where,
0
is the basic viscosity value,
l
and
s
are the volume fraction of
liquid and critical solid phase volume fraction, respectively. The weight
percentage increase of Ni could enlarge the liquid content in molten
pool and cause the reduction of the melt viscosity resulting in a better
ow ability and stability of the molten tracks.
During SLM, laser scanning is performed line-by-line, followed by
layer-by-layer over the powder bed. Furthermore, there were some re-
search works on the melting process of metal powder in SLM. For in-
stance, Gusarov et al. [29] worked on the radiation and heat transfer
in laser-powder interface of SLM. Niu and Chang [30] also investigated
the instability of scan tracks of high speed powder in SLM. Shen et al.
[31] developed a porous 316 L with controllable microcellular in SLM.
Their research showed that the surface tension of the liquid phase can
be regarded as the main factor which controlled the resistance of defor-
mation capacity due to the contraction of the liquid phase.
Based on the research by Simchi and Pohl [32], the instability of the
molten tracks can be considered by:
ND 6
Fig. 6. X-ray diffraction peaks of WNi SLM-fabricated samples: (a) sample A, (b) sample
B, and (c) sample C.
Fig. 7. Binary phase diagrams of WNi alloy.
19 D.Q. Zhang et al. / Int. Journal of Refractory Metals and Hard Materials 45 (2014) 1522
where is the laser wavelength, and Dis the diameter of continues mol-
ten tracks. It should be pointed out that, under the xed laser wave-
length, large D value had better ability for attaining a continuous
molten track. The increase of Ni weight percentage could prevent the
molten tracks from breaking up due to the decrease in surface tension.
This was consistent with what was observed in Fig. 4ac where the in-
crease of Ni content was benecial to the thermal uidity of the molten
tracks.
Inuence of Ni content on hardness value
Fig. 12 depicts the microhardness variation on the cross-sections of
SLMsamples A, B andC. Generally, the hardness decreased withincreas-
ing Ni content as W content decreases. In addition, the hardness de-
creased along the building direction. Another reason for the hardness
variation was due to the solidication shrinkage of loose powder bed
that resulted in a larger real layer thickness. Based on our previous
Fig. 8. Microstructures of SLM-fabricated samples: (a) sample A, (b) sample B, and (c) sample C.
Fig. 9. Forming mechanism schematic illustration for WNi powder system during SLM.
20 D.Q. Zhang et al. / Int. Journal of Refractory Metals and Hard Materials 45 (2014) 1522
research [33], the total shrinkage of metal powder layer sharply in-
creased in the initial layers and then reached to a plateau value with
the increased processing layers. This value was dened by the ratio of
sliced layer thickness (h) to relative density (k) during the SLMprocess.
The real powder thickness (h
real
= H
layernumber
) variation could be
calculated as:
H
max
h a
n
h h 1k =k h=k h
m
=
l
5
where
m
is the density of the solid parts and
l
is the density of loose
powder.
Eq. (5) showed that there was a gradual increase of the real layer
thickness during SLM process, which could result in a decrease of the
microhardness along the Z direction.
On the other hand, the laser energy gradient distribution along the
powder layer thickness direction could induce the uctuation hardness
values between each scan layer.
Conclusions
WNi specimens with different Ni content were successfully pro-
duced by SLM. The microstructure evolution was characterized and
the microhardness was measured. The results can be concluded as
follows:
(1) The forming mechanism of WNi powder mixture in SLM was
characterized by LPS and partial melting of Wwhere Ni particles
melted to form the liquid to wet the solid W particles pull the
grains together through capillary force. W dendrite was also
found in the melted specimens. This illustrated that partial W
particles also underwent the melting/solidication process.
(2) Under the same forming parameters, SLM specimens with dif-
ferent Ni content manifested different microstructure. The mi-
crostructure evolved from bar shaped structure to dendrites
to honeycomb structure for specimens with a Ni content of
10 wt.%, 20 wt.% and 40 wt.% respectively. This indicated an
increase of temperature in powder bed combined with a
decrease of solidication rate.
(3) The different microstructural features were concluded to be a
result of constitutional supercooling of the powder systems.
Increasing Ni content promoted uniformity of melting samples
and decreased the melt viscosity.
(4) The hardness decreased along the building direction which
resulted from the shrinkage of loose powder bed.
Fig. 10. EDS analyses showing elemental distribution of sample A: (a) elemental distribution of point A; and (b) elemental distribution of point B.
Fig. 11. (a) Microstructure morphology of sample B and (b) EDS analysis along line AB.
21 D.Q. Zhang et al. / Int. Journal of Refractory Metals and Hard Materials 45 (2014) 1522
Acknowledgements
The authors would like to thank the open fund of state key laboratory
of powder metallurgy of Central SouthUniversity of China (2008112022).
The authors would like to acknowledge the National Natural Science
Foundation of China (61078078).
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22 D.Q. Zhang et al. / Int. Journal of Refractory Metals and Hard Materials 45 (2014) 1522