Combustion, Explosion, and Shock Waves, Vol. 35, No.

2, 1999
Condi t i ons for SHS of I nt ermet al l i c Co mp o u n d s wi t h Sel ect i ve Laser
Si nt eri ng o f Powde r e d Co mpo s i t i o ns
I. V. Shi s hko v s ki i , 1 A. G. Ma ka r e nko , 2 and A. L. Pe t r o v I
UDC 621.373.826:536.46
Translated from Fizika Goreniya i Vzryva, Vol. 35, No. 2, pp. 59-64, Mach-April 1999.
Original article submitted January 1, 1998; revision submitted July 15, 1998.
The sel ect i ve l aser si nt eri ng of powder ed mi xt ur es t r adi t i onal l y used i n hi gh-
t e mpe r a t ur e synt hesi s t echnol ogy is st udi ed. It is s hown t hat a cont r ol l ed exot her mi c
combust i on r eact i on can be set up in t he focal spot of a CW Nd- YAG laser. The re-
qui red l aser i nt er act i on par zmet er s (power, scan r at e, a nd laser beam di amet er ) and
di sper si t y and composi t i on of t he powder composi t i on ar e det er mi ned for t hi s mode
of pr epar i ng t hr ee di mensi onal s~mples of i nt er met al l i c compounds by sel ect i ve l aser
si nt eri ng.
I NTRODUCTI ON
Selective laser sintering of powdered composi-
tions is a widespread method for creating three di-
mensional objects, material copies of models of ma-
chine parts, in the rapidly developing technology of
laser synthesis of three dimensional pieces. An over-
all view of the model and cross sections of its layers,
according to which the object will be synthesized-
grown layer-by-layer on a vertically moving plat-
form, are first stored in the memory of a personal
computer using standard graphics packages. The
computer then controls the entire engineering pro-
cess. The existing production equipment for selective
laser sintering is traditionally intended for wax, ny-
lon, polycarbonate, and acryl butadiene styrene. The
three dimensional copies created out of these mate-
rials can only serve as models and are used, e.g., for
precise casting in meltable molds, which greatly ease
the work of designers and reduce the time required
to bring new technologies into production. Here the
casting molds can only be used a limited number
of times. The problem of fabricating single copies of
complicated models in such areas of human activity
as prosthesis and restoration is also pressing. Thus,
an intense search is under way for promising powder
media for selective laser sintering in the technology of
laser synthesis of three dimensional pieces and stud-
1Samara Branch of the Lebedev Physics Institute,
Russian Academy of Sciences, Samara 443011.
2Samara State Technical University, Saznara 443010.
ies are being made of the physical processes which
take place when laser light interacts with powdered
media. It has already been found t hat metal pow-
ders coated with a polymer, as well as powders of
bimetals or ceramic materials can be used for three
dimensional prototype production [1-4].
The choice of promising powder compositions
for selective laser sintering is mainly based on the
possibility of realizing liquid phase sintering during
laser interaction. In these cases the composition is a
mixture of two or more powders with substantially
different melting points. During sintering, the easily
melted phase flows over the grains of the refractory
phase and, on crystallizing, serves as a binder which
imparts a durability to the laser processed sintering
region. Three dimensional objects grown by layer-
by-layer synthesis are semifinished products that re-
quire further work (e.g., annealing in an oven, infil-
tration of a filler, etc.). The need for initial prepara-
tion of the powder and for monitoring the surround-
ing atmosphere and the temperature of the pow-
dered medium on the platform where the sintering
takes place make selective laser sintering relatively
long and complicated. This reduces the advantages
of this method compared to other methods for laser
synthesis of three dimensional pieces (such as laser
stereolithography). Thus, besides searching for new
possibilities for selective laser sintering of powdered
systems and expanding the functional prospects for
the synthesized pieces, it seems reasonable to pro-
ceed to the use of new gradient composite materi-
als, as well as to combinations of laser sintering with
166 0010-5082/99/3502-0166 $22.00 (~ 1999 Kluwer Academic/Plenum Publishers
Condi t i ons for SHS of Int ermet aUi c Compounds wi t h Selective Laser Si nt er i ng 167
TABLE 1
Powders
Al umi num (ASD3, 4)
Fi l l er powder (PG-SR4)
Ti t ani um ( PTKh- 6)
Properties of the Powdered Materials Used [4, 6, 7]
D, ~m p, g/ c m 3 ps, g/ cm3 r Tin, ~
10--50 1.25 2.7 0.54 660
50-160 4.7 ~8. 8 0.47 ~1200
30-60 1.23 4.5 0.73 1668
Q,.n, k J / mol e ~ K
10.8 27 3
17.5 59 ]" 1/ 3 1
15.5 48 1
Not e s . D is the fract i on size, p is the bul k density, ps is t he solid density, ~ -- 1 - p/p~ is t he porosi t y, Trn is t he
mel t i ng t emper at ur e, Qrn is t he l at ent heat of fusion, ~ is t he at omi c mass, and K is t he st oi chi omet ri c coefficient.
In t he l ast col umn t he upwar d arrow i ndi cat es t hat one mass por t i on of the filler powder was mi xed wi t h three
por t i ons of al umi num and a downward arrow, t hat t hree mass por t i ons of the same powder were mi xed wi t h one
por t i on of t i t ani um.
other processes. Thus, combining laser sintering with
soldering [3, 5] makes it possible to produce three di-
mensional models out of bimetals in which the high
adhesion of the solder melt to the metallic phase im-
proves the mechanical properties of the piece.
In this paper, we study the possibility of us-
ing powdered exothermic mixtures, which are tradi-
tionally used in the technology of self-propagating
high-temperature synthesis (SHS), for selective laser
sintering, in particular mixtures based on stoichio-
metric and nearly stoichiometric Ni-Al and Ni-Ti
systems. Here it must be shown that a controlled
exothermic combustion reaction takes place precisely
in the laser focal spot as the beam is scanned over the
surface of the powdered composite, since the shape
of the synthesized model can be maintained only by
high-resolution spatially selective sintering. The use
of selective laser sintering for SHS processes makes it
possible, both to obtain more durable material copies
of complicated pieces, and to extend the functional
characteristics of these three dimensional objects by
synthesizing intermetallic compounds.
MATERI ALS AND EQUI PMENT
Selective laser sintering is performed with the
aid of a scanning laser beam from a computer con-
trolled CW Nd-YAG laser. Two standard lenses with
focal lengths f = 149 and 336 mm are used with the
KVANT-60 laser system (the focal spot diameters
of the laser beam are d = 50 and 100/zm, respec-
tively). The laser power was varied over P = 1-16
W and was monitored with an IMO-2A system at
the powder surface. The laser beam was scanned by
the computer over any previously specified profile to
reproduce, layer-by-layer, a three dimensional object
within fields of 50 x 50 mm and 100 x 100 mm (i.e.,
1024 x 1024 pixels) using mechanical deflectors. The
scanning speed depends on the time to shift the beam
from point to point and on the time the deflectors
TABLE 2
T h e r m a l and Physi cal Pr o p e r t i e s o f t h e N i - A I System [ 6 - 8 ]
Phas e Ti, ~ E, kJ / mol e Q, J / kg
Ni2AI3 - - - - 1.9 9 106
NiA1 637 4- 25 135 4- 27 9.7 9 10 s
Ni3A1 652 4- 16 115 4- 25 2.4 9 106
Mel t
(Ni-FA1) - - 48.24 1. 3. 106
dwell on a point. It could be varied by the device
over wide limits.
The powders listed in Table 1 were used to
prepare the SHS mixtures [4, 6, 7]. The PG-SR4
(GOST 9722-79) filler powder contains 2.8-3.8% B,
0.6-1.0% C, 3.0-4.5% Si, 15-18% Cr, ~<5.0% Fe,
0.04% P, and 0.04% S, and the rest Ni. The size of the
powder fractions was determined using mesh analysis
and by a NEOPHOT-30 optical microscope. In prin-
ciple, it was possible to choose the size of the process
fraction to be smaller than the laser spot size, so that
the beam overlapped and processed several particles
of the powder composition at once as it scanned the
powder surface. Powder composites were prepared to
yield the following exothermic reactions:
3Ni + A1 , NiaA1 + Qt, (1)
Ni + 3Ti , TiaNi + Q2, (2)
where Q1 and Q2 are the heats of reaction. These
systems are widely used in SHS technology. Their
basic thermal and physical characteristics (ignition
temperature ~, activation energy E for the chemical
reaction, and heats of reaction Q1 and Q2 per mole
of Ni) are known [6-9] and are listed here in Table 2
and Fig. 1.
168 Shi shkovskl l , Makarenko~ and Pet r ov
Fig. 1. Equilibrium diagram of the Ni-A1 system [9]: 7-, 6-,
and e-phase refer to Ni2AI3, NiAI, and Ni3A1, respectively.
EXPERI MENTAL RESULTS
AND DI SCUSSI ON
The powders to be processed were poured freely
into a volume clearly greater than the sintering depth
of a monolayer. The conditions for combined selec-
tive laser sintering and controlled SHS processing
in a single pass of the laser beam were studied as
functions of the laser power, spot diameter, scanning
rate, and powder composition. A controlled regime is
taken to mean execution of the SHS exothermic reac-
tion precisely at the working point (the so-called dif-
fusion SHS mode). The range of the sintering depth
h of a single monolayer for minimal distortion of this
layer was determined.
Figure 2 shows plots of the experimentally ob-
served effect of the laser interaction on a powdered
composite based on a stoichiometric Ni-Al system.
For P < 7 W and scan speeds v > 25 cm/sec, the sin-
tering depths are shallow. The sintered monolayers
disintegrate upon contact. As the power is raised and
the scan speed is reduced, the monolayers become
thicker. For P .~ 8.4-8.8 W (Fig. 2a) and v ~ 2.9-8.6
cm/sec (Fig. 2b), a controlled exothermic combus-
tion reaction is observed visually precisely at the
laser focal spot. Finally, for P > 8.8 W and v -- 25
cm/sec (Fig. 2a) and P -- 8.8 W and v < 2.9 cm/sec
(Fig. 2b), the exothermic reaction leading to forma-
tion of the intermetallic compound enters a front
combustion regime in which the reaction front prop-
agates through the entire side, independently of the
location of the laser spot. These regimes can be re-
garded as critical for t he case where, in accordance
with the theory of SHS, diffusion synthesis of the in-
termetallic compounds transforms to front combus-
tion of the powder mixture. In Fig. 2, this is indi-
cated with a dashed curve, since beyond that the sin-
tering depth can no longer be determined reliably. It
should be noted that, according to Fig. 1, the follow-
ing phases can be observed in the different stages of
heating and cooling [9]. During heating to a tempera-
ture below Te = 640~ the 7-phase Ni2Al3 nucleates
and grows; with further heating, the 7- and 6-phases
coexist; at temperatures 1132 < T < 1638~ the
7-phase melts and only the 6-phase NiAl remains;
and, only after the melting temperature of the NiA1
intermetallide is attained (T3 = 1638~ the inter-
metallide NiA1 first develops and then the e-phase
Ni3A1 forms with subsequent cooling. Therefore, de-
pending on the chosen laser parameters and the com-
position of the powder mixture, the laser energy may
be sufficient, or not, to reach the corresponding tem~
peratures and to obtain the phases inferred from the
equilibrium phase diagram in a model synthesized
by the selective laser sintering method.
The experiments showed that when the scatter
in the particle fractions was increased substantially
(from a set size of 30-50/zm to 30-150/Jm in an Ni-
A1 mixture of composition 3 : 1), intermetallides are
not formed when the powders are processed by the
KVANT-60 laser (d ~ 50/~m), since the SHS process
was not observed. On the other hand, the scatter in
the size fractions has less effect on the formation of
intermetallides when the diameter of the laser spot is
increased. This effect was made more precise on an-
other laser system. Thus, processing the same pow-
der mix with a spot diameter d ~ 0.5 mm on an
LTN-103 system indicated a coincidence of the se-
lective laser sintering and SHS processes. Equivalent
processing on the LTN-103 laser system was ensured
by setting the laser energy flux (4P/~rd 2) in the spot
equal to that for the KVANT-60 laser system. The
same effect owing to the size distribution was ob-
served in the Ni-Ti system.
Ni-Al systems with compositions 1 : 1, 2 : 1, and
4 : 1 were also studied. The experiments showed that
a deviation from the Ni3A1 stoichiometry greatly
narrows the range for optimum processing, so that
in some cases the selective laser sintering and SHS
processes cannot be combined, while in others, the
low durability of the monolayers causes their embrit-
tlement.
For powder compositions in the Ni-Ti system
(exothermic reaction (2)), the selective laser sinter-
ing and SHS processes were observed to combine for
v = 2.6 cm/sec and P = 7.2-8.8 W. However, the
sintered monolayers were less durable than for the
Ni-A1 powder composition. Adding a powdered ma-
terial with a lower melting temperature to the Ni-Ti
composite [PG-19M-01 bronze powder (TU 48-4206-
Condi t i ons f or SHS of I nt er met aUi c Compounds wi t h Sel ect i ve Laser Si nt er i ng 169
Fi g. 2. Sintering dept h as a function of laser power (a) and laser scanning speed (b) for an Ni-AI system.
156-82)] increased the durability of the monolayers.
The experiments made it possible to estimate
the time tLR = d/v during which the laser radia-
tion acts on the powder medi um and the transition
from a diffusion regime for formation of the inter-
metallides to front combustion of the powder mix-
ture takes place. For Fig. 2a (with P > 8.8 W),
tLR --" 0. 2 Il l sec, and for Fig. 2b (with v < 2.9 m/sec),
tI, R = 1.7 msec. The modern theory of ignition and
combustion [10] can be used to calculate some pa-
rameters of the SHS process which are fairly close to
the actual situation. Thus, in the theory of ignition
the i mport ant parameter is the adiabatic induction
period
c RT~ E
rind -- Qk0 --E-- exp RTi' (3)
which has the significance of the time LLR introduced
above and should obey the relation rind ~ tLN- In Eq.
(3), k0 is the preexponential factor, c is the specific
heat, Ti is the ignition temperature, and R is the
universal gas constant. The other parameter in the
theory is the width of the exothermic reaction zone
at the time of ignition, which is given by
Li = Q ko E exp , (4)
where A is the thermal conductivity.
Let us compare the experimentally determine
time t a r with the theoretical ~ind. Equation (3)
for the NiA1 and Ni3Al phases gives tin d = 41
and 0.74 msec, respectively. This calculation used
the dat a of Tables 1 and 2, as well as the values
CNi = 462 J / ( kg- K) and Chl = 879 J / ( kg. K)
from [8] and ANiAI : (9 4- 1) W/ ( m- K), ANi3AI ----
(11 -4- 1.3) W/ ( m. K), (Qko)Nih, = (14 4- 2). 10 I"
W/ m 3, and (Qk0)Ni3hl ---- (57 =k 8) 9 1016 W/ m 3
from [6]. It is clear t hat the calculated induction pe-
riods for both phases are of the same order of mag-
nitude as tLR. In addition, rind for the intermetallic
compound Ni3A1 lies within the experimentally de-
termined range, 0.2-1.7 msec, i.e., over the time of
the laser interaction it is possible, with a high prob-
ability, to obtain the Ni3A1 phase under conditions
such t hat the selective laser sintering and SHS pro-
cesses are combined. Equation (4) gives (Li)NiAl =
428.8 /zm and (Li)Ni3AI ---- 61 #m. These values are
also important, since spatial selectivity of the laser
radiation is necessary. This estimate shows that, for
the Ni3A1 phase, the width of the reaction zone is
comparable to the diameter of the laser focal spot
d -- 50 pm and to the size of the powder fraction
t hat was used. This confirms, once again, that we
can count on an optimal combination of the selective
laser sintering and SHS processes for the creation of
actual copies of three dimensional objects only when
synthesizing the intermetallide Ni3A1. The adiabatic
induction period for the thermodyanamically more
favorable NiA1 phase is much longer t han fLR; t hat
is, the conditions for formation of this phase are most
favorable for v = d/~ind ~ 0.12 cm/sec, when the
mixture experiences frontal combustion under our
conditions and is no longer controlled by the selec-
tive laser sintering process (see Fig. 2b). The need
for a large width (L/)NiAI of the reaction zone (..~8-9
times the diameter of the laser beam) confirms this
conclusion.
The simplest three dimensional objects (cube,
spheroid, etc.) have been synthesized from a powder
composition based on a 3 : 1 stoichiometric Ni-A1
system. In the future, it is planned to st udy the phys-
ical properties, phase composition, and structure of
the three dimensional pieces.
170 Sh i s h k o v s k i i , Ma k a r e n k o , a n d P e t r o v
C O N C L U S I O N
1. Combi ned sel ect i ve l aser si nt eri ng and SHS
have been realized for t he fi rst t i me in a single engi-
neeri ng process using powder ed composi t i ons based
on st oi chi omet ri c Ni-A1 and Ni - Ti syst ems wi t h a
CW Nd-YAG laser. Th r e e di mensi onal sampl es of
pieces made of t he compos i t e mat eri al s have been
obt ai ned.
2. The opt i mum l aser par amet er s for mai nt ai n-
ing a controlled exot her mi c r eact i on preci sel y at t he
laser focal spot have been det er mi ned.
3. A comparison of t he laser i nt er act i on t i me
wi t h t he t heoret i cal l y cal cul at ed i nduct i on per i od for
t he exper i ment al l y de t e r mi ne d par amet er s P, v, and
d showed t hat this t i me is sufficient for synt hesi s of
t he i nt ermet al l i c Ni3A1 phas e ri ght at t he laser focal
spot .
4. Good sel ect i vi t y can be achieved by combi n-
i ng t he selective laser s i nt er i ng and SItS processes.
The 61 #m width of t he exot her mi c r eact i on zone is
compar abl e to the di a me t e r of t he laser focal spot
and t o t he dispersity of t he powder mi xt ur e.
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