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JournaloftheEuropeanCeramicSociety35(2015)477486

SparkplasmasinteringofSiCpowdersproduced
bydifferentcombustionsynthesisroutes
a

DmitryO.Moskovskikh ,YaChengLin ,AlexanderS.Rogachev

b

PaulJ.McGinn ,AlexanderS.Mukasyan

a,c

b,

CenterofFunctionalNanoCeramics,NationalUniversityofScienceandTechnology,MISIS,Moscow119049,Russia
b
DepartmentofChemicalandBiomolecularEngineering,UniversityofNotreDame,IN46556,USA
c
InstituteofStructuralMacrokineticsandMaterialsScienceRussianAcademyofSciences(ISMAN),Chernogolovka,MoscowRegion142432,Russia
Received26May2014;receivedinrevisedform7September2014;accepted8September2014
Availableonline23September2014

Abstract
Inthisworksiliconcarbide(SiC)submicronpowdersweresynthesizedusingfourdifferentcombustionroutes,whichincludethefollowing
reactivesystems:Si/C/Teflon(T);Si/C/N2(N);Si/Cmechanicallyactivatedcompositeparticles(MA)andreductionSiO 2/Mg/Creaction(R).
ThespecificsurfaceareaoftheassynthesizedSiC T,SiCN,SiCMAandSiCRpowdersare:40.5;172;202and1455m2/grespectively.
Thesepowdersweresubjectedtosparkplasmasintering(SPS)withoutanyadditivesat2073Kfor10min.Thedensificationkineticsforeach
powderweremeasuredanddiscussed.Theobtainedceramicspossessarelativedensityintherange8095%andVickersmicrohardness( Hv)
from7to20GPa.Toillustratethecapabilityofthemethod,essentiallyporefreeceramicswerepreparedfromSiC MA powderby1hSPS
withoutadditivesat2273K,withHv=24GPaandfracturetoughnessK1C=35MPam1/2.
2014ElsevierLtd.Allrightsreserved.
Keywords:Sparkplasmasintering;SiC;Combustionsynthesis;Vickersmicrohardness;Fracturetoughness
http://dx.doi.
org/10.1016/
1.Introduction
j.jeurcerams
oc.2014.09.0
Siliconcarbide(SiC)isanimportantceramicmaterialthatis 140955
widelyusedinmanyengineeringandindustrialprocesses.The 2219/2014
ElsevierLtd.
set of unique physical/mechanical/thermal properties such as
Allrights
lowdensityandhighhardness,highstrengthatelevatedtem reserved.

peratures, excellent thermal conductivity, and good wear and

corrosionresistancemakeSiCahighlyattractivematerialfora
variety of applications including power devices and sensors,
heating and corrosion protective elements in the nuclear and

atomic industries, and structural ceramics in combat fields.

However,itisnotaneasytasktomanufacturefullydensebulk
SiCspecimensbyconventionalsintering,whichrequireshigh
temperatures(>2000K)andlongdurationoftheconsolidation
process.

Correspondingauthor.Tel.:+15746319825;fax:+15746318366.E
mailaddresses: amoukasi@nd.edu, zekelin2008@gmail.com,

ylin5@nd.edu(A.S.Mukasyan).

To overcome this
shortcoming, researchers have
reportedthatthroughtheuseof
sinteringadditives(i.e.,boron,
carbon) SiC sintering
temperaturescanbedecreased
whileahigherbulkdensityis
2

achieved. Another promising

way to obtain porefree bulk
SiCceramicsisbyusingnano
powders.Itisageneralbelief
that use of submicron (i.e.,
nanoscale) SiC powders may
yieldasignificantreductionof
sintering temperature and
duration needed to produce
porefree ceramics while
increasing the mechanical
properties. Examples include
the application of such
conventional

sintering
techniques as pressureless

3
sintering, hot pressing or hot isostatic pressing. Finally, an Combustionsynthesis(CS),
alsoknownasselfpropagating
advanced technique, such as spark plasma sintering (SPS) that
high temperature synthesis
combinesaxialpressurewithheatingbypulsesofelectriccurrent
(SHS),isanenergysavingand
passing through the die and the green powder body, may also
attractive method for
4
shortensinteringtemperaturesandtimes.
production of a variety of

advanced micron and nano

scale materials withproperties
that are superior to those
manufactured by conventional
5

methods. Recent

478

D.O.Moskovskikhetal./JournaloftheEuropeanCeramicSociety35(2015)477486

synthesis of SiC, when

(922 K and 1363 K,

developmentsandbreakthroughswithinthe magnesium(Mg)isused
correspondingly),aswell
CS field have shown its high level of as a reducing element,
as the m.p. of silicon
diversity.InaconventionalSHSscheme,a canbewrittenasfollows:
(1683 K) and silicon
oxide(1923K),butwell
reactivemixtureofsolidpowders(e.g.,Si+
below the m.p. of MgO
C) is ignited at one end and a high SiO2+2Mg+C=SiC+2MgO
(3073 K) and carbon
temperature combustion wave self Thermodynamicanalysis
(4093 K). It was also
propagatesthroughthemedia,convertingthe allows calculating the
adiabatic

combustion
provedthattheamountof
precursors to the desired product. Some
gaseous products (which
temperature

(T
)

and
ad
unique characteristics of CS include: (i)
equilibrium products for
includes Mg, CO and
short (seconds) reaction time, (ii) energy reaction(2)asafunctionof
SiO)canbesignificantly
efficiency, since the internal system the inert gas (argon)
decreasedbyanincrease
chemical energy is primarily used for pressure(P)inthereaction
of inert gas pressure in
chamber.Itwasshownthat
materials production, (iii) simple
the reaction chamber,
T

increases

and

the
technologicalequipment,and(iv)anability ad
sincehigherPsuppresses
amount of gas phase
toproducehighpurityproductswithahigh products decreases, with
the metalgasification
production rate. The selfpurification effect increase of inert gas pres
7
processes.
occursduetoanextremelyhighcombustion sure. Also the absolute
A number of
temperature that burns off most of the value of Tad exceeds 2000
publications

are
K, which is above the
impurities.
melting (m.p.) and boiling

Inthecaseofcombustionsynthesisof (b.p.)pointsofmagnesium
siliconcarbidefromelementsthereaction
canbewrittenasfollows:
Table1
Si+C=SiC+73kJ/mol
Thereaction(1)hasamoderateenthalpy
ofproductformation(comparedto H273 =
230kJ/molforTiCsystem)andtherefore
a relatively low adiabatic combustion
temperature(Tad =1860K;comparedwith
3290 K for TiC reaction). Thus it is not
easy to accomplish a selfsustained SHS
processinthissystem.However,almostall
availableliteratureonCSofsiliconcarbide
6
isrelatedtothischemicalpathway. Several
approacheshavebeendevelopedtoenhance
thereactivityofSiCsystem.Theycanbe
subdividedinfivemajorgroups:

(1) CSwithpreliminarypreheatingofthe

reactivemedia
(2) CSwithadditionalelectricalfield
(3) ChemicalactivationoftheCSprocess
(4) SHS synthesis in SiCair/nitrogen
systems
(5) Mechanical activation of the initial
mixture

The use of one or another approach

dependsonthedesiredproductproperties,
e.g.purity,particlesizedistribution,mor
phology and yield, as well as cost
considerations. The other way to
synthesize SiC in combustion way is to
use reduction route. The overall
combustion reaction for reduction

Specificsofpowderprecursors
utilizedinthiswork.

dedicated specifically to
sinteringofSiCmicron
and nanosized powders,
and are the subject of a
8

recent review. In this

work special attention
hasbeenpaidtoproduce
SiC powders using four
different combustion
routes,allofwhichallow
scaledup production of
such nanopowders at
much lower costs. The
XRD, BET and SEM
analysesofSiCprepared
by each method have
beencarriedout andthe
resultsarediscussed.All
assynthesized SiC
powders were subjected
tosparkplasmasintering
(SPS) under similar
conditions: 200 K/min
heating rate to a desired
temperature(i.e.,2073K)
and holding for 10 min.
Theevolutionofrelative
density, densification
rate and porosity of the
materials during SPS
were investigated. The
mechanical properties of
the obtained ceramics
including

fracture
toughness (K1C) and
hardness were measured
for all produced
materials.

The
correlations between
microstructure of the

initial powders and their sinterability are abbreviated as SiCT,

discussed.
SiCMA,SiCN,andSiCR,
respectively.Theprecur
sor powders utilized in
2.Materialsandmethods
this work include Si
In this work silicon carbide (SiC) (300 mesh, 99.5%,
powdersweresynthesizedbyfourdifferent China), Si (325 mesh,
combustionbased routes: (i) chemical99.5%, Alfa Aesar,
activation of reaction (1) by adding ofUSA), C (100 nm,

Fisher
polytetrafluoroethylene (Teflon), (ii)lampblack,
mechanical activation of SiC powderScientific,

USA),
mixture,(iii)internarySiCN2system,andpolytetrafluoroethylene
(710 m, Alfa Aesar,
(iv)reductionreaction(2).
Specificsofthepowderprecursorsare USA),SiO2 (325mesh,
summarizedin Table1,withthefourasCeracInc.,USA)andMg
synthesized SiC powders being(325mesh,99.8%,Alfa
Aesar,USA).

The SiC powder

preparation procedures
and combustion syn
thesisofeachsystemare
brieflydescribedbelow.
2.1.Route1:Si/C/Teflon
(SiCT)
Milling of the as
receivedSipowder(325
mesh) to reach the
average particle size of
5 m with 90% of less
than10m

System

Siliconprecursor

InitialSiparticlesize(mesh)

Si/C/Teflon
Si,China
300
325
Si/C,MA
Si,USA
300
Si/C/N2
Si,China
SiO2/Mg/C
SiO2,USA
325
D.O.Moskovskikhetal./JournaloftheEuropeanCeramicSociety35(2015)
477486

0.2 MPa. The milling

isnecessarypriortosynthesisbecausethe ball (2 mm) to powder

combustionfront cannotselfpropagateifratio was 40:1 and the
precursor particle sizes are not in therotation speed (planetary
desired range. Therefore, powder millingball mill Retsch PM100,
wasperformedinasinglestationplanetaryGermany) was 650 rpm
ballmill(RetschPM100,Germany).The and the process duration
ratio of steel milling balls (10 mm) to was1h.Afterballmilling
powder was 10:1 and the rotation speed thejarwasallowedtocool
was 200 rpm. The 1 h duration millingdowntoroomtemperature
process was carried out in an argon and then the prepared
powders were collected.
atmosphere(0.2MPa).
The Si/C/Teflon powder mixingCombustion synthesis of
procedure involved two steps. The first themechanicallyactivated
stepwastomixasmilledSipowderwith mixturewascarriedoutby
carbon lampblack powder for 6 h in ausingthesameprocedure,
rotary mixer; while the second stepasdescribedforroute1.
included12hmixingoftheSi+Cpowder
mixture with Teflon (18 wt.%). After2.3.Route3:Si/C/N
mixing the powder was collected and (SiCN)
cylindricalsamples(5mmD15mmH)
werepreparedbyauniaxialpressunder1 Similar experimental
tonload.
procedures, as described
Sample ignition was accomplishedfor route 1, were
insideaSHSreactorinapressurizedargon performedforthisroute.
atmosphere.ThepressedcylindricalsamHowever, the following
ple was placed in a stainless steel SHS mixing conditions were
combustionchamber,whichwasequipped
used: milling ball to
withtransparentwindowsformonitoring
powderratio5:1,rotation
the reaction process. The reactor was
speed 300 rpm and
5
sealed,evacuatedto Pi =10 MPa,andprocessduration30min.
filled with argon gas (99.998%; Praxair Also, instead of argon,
DistributionInc.,USA)to2MPa.Ashort nitrogen (99.998%;
dc pulse (I = 10 A, U = 20 V) passedPraxairDistributionInc.,
through a tungsten wire located close to USA) gas was used and
the topsurfaceofthepellettoinitiatethe the reactor was
reaction. After combustion synthesis thepressurizedupto3MPa
reactorwasallowedtocooldowntoroom beforereactioninitiation.
temperature before collecting the as
synthesized powder. The assynthesized
2.4.Route4:SiO2/C/Mg
SiCsamplepelletwasthenpulverizedby
agate mortar and pestle for 5 min and (SiCR)
subjectedtoanalyses,asdescribedbelow.
2.2.Route2:Si/C(mechanicalactivation)
(SiCMA)

The desired ratio

(1:2:1) of SiO2, Mg and
carbonlampblack(SiO2 +

Astoichiometricratio(1:1)ofsiliconand 2Mg+C2MgO+SiC)
carbonlampblackpowderswasusedasthe powdersweremixedinan
reactants.Afterthemillingjarwassealed,itethanolbath(100ml)for
wasoutgassedandpurgedwithargongasto

Carbonprecursor

Other

Abbreviation

Lampblack
Lampblack
Lampblack

Teflon
N/A
Nitrogen

Lampblack

Magnesium

SiCT
SiCMA
SiCN
SiCR
479

6 h and then filtered and

collected,

of the assynthesized SiC

powders were examined
by different material
characterization
techniques including field
emissionscanningelectron
microscopy (FESEM,
Magellan 400L, FEI
company, USA), energy
dispersive spectroscopy
(INCAxsightmodel7636;
Oxford Instruments,
USA), Xray diffraction
(Scintag X1 advanced
diffraction system with
CuK radiation of
wavelength

1.54056 A, Scintag Inc.,

USA). The BET specific
Fig.1.Schematicillustrationofsparkplasma
surface area (SSA) was
sinteringdevice.
measured on a Coulter
SA3100analyzerat77K,
whichusednitrogenasthe
followedbyovernightovendryingat330adsorbent gas. Samples
K.Theloosepowdermixtureswerethen weregroundwithanagate
placedinaquartztubeintheSHSreactor, mortar and pestle and
followedbyreactioninitiationinanargon placed in BET tubes, fol
lowed by outgassing at
atmosphere (2 MPa). The assynthesized
298Kfor4hbeforeSSA
productwasthensubjectedtoaleaching
measurement.
processindilutedhydrochloricacid(5%)

schematic
for 12 h to completely eliminate the A
representationofthespark
undesired MgO phase, followed by
plasmasinteringdevice is
filteringanddryinginanovenat373K.
shownin Fig.1.TheSiC
The morphology and phase composition

powderswereplacedintoa
cylindrical graphite die
with dimensions of 15.4
mm(ID) 30mm(OD)
30mm(H).Thesample
was wrapped in graphite
tape(0.2mminthickness).
Auniaxialpressureof50
MPa was then applied
throughthetopandbottom
plungers.Eachplungerhas
adiameterof15mmanda
length of 20 mm. The
samples were sintered
using a spark plasma
sintering system (Labox
650,SinterLand,Japan)to

2073 K (1800 C) with a

heatingrateof200K/min
in an argon atmosphere.
Sampleswerethenheldat
the constant temperature
for 10 min. The exper
imental parameters of
temperature, applied
pressure, current, voltage,
and sample displacement
(i.e.,shrinkage)weremea
sured continuously during
the consolidation cycle.
Temperatures

were
recorded by an optical
pyrometeronaholedrilled
into the die surface to a
depth of 4.5 mm. An
emissivityof0.9wasused

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