Uriginal Ariiclos \ol. 11. ^o. 1. Harch.

2006 | Nonoscience
Uriginal Ariiclos
Preparation and mechanical properties of Si-Al-Zr-O
composite ceramics with ultra fine grains
Shuquan LIA^(
*
. Xiaoping 1A^. Shaoqiang LI. Yan 1A^(. Yong ZHA^(
Sc/oo/ o/ 1o/ecio/ Science ond Lnoineecino. Cen/co/ Soo// |nicecsi/y. C/onos/o. honon 410083. P.R. C/ino
Bocoivod daio: ^ovomhor 15. 2005
Abstract Si÷Al÷Zr÷U (SAZ) composiio coramics wiih ulira lino (rains woro proparod hv in÷siiu conirollod crvsiallizing lrom SAZ amorphous
hulk. 1ho crvsiallizaiion hohaviors ol SAZ amorphous hulk woro invosiigaiod hv dilloroniial scanning calorimoiric (ISC). X÷rav dillraciion (XBI)
and scanning olociron microscopv (SEH) iochniquos. 1ho rosulis show ihai iho SAZ amorphous hulk siaris doviirilving ai 900~950 and i÷ZrU
2
phaso lorms lirsi. Viih iho incroaso ol iomporaiuro up io 1000. mulliiizaiion occurs and mulliio hocomos major phaso ai 1100. A small
amouni ol i ÷ZrU
2
iranslorm io m÷ZrU
2
lor iho samplos iroaiod ai 1100 and moro ihan hall ol i ÷ZrU
2
iranslorm io m÷ZrU
2
lor iho samplos
iroaiod ai 1250. 1ho samplo hoaiod ai 1100 lor 1h shows vorv donso and homogonous microsiruciuro wiih iho sizo ol hall÷liko grains ahoui
20~50 nm. Viih iho incroaso ol iomporaiuro up io 1350. iho grains grow quicklv and somo grow inio laih÷shapod grains wiih major diamoior
ahoui 5 m. 1ho highosi lloxural sirongih and lraciuro ioughnoss ol iho samplos iroaiod ai 1150 lor 1 h lollowod hv proiroaiing ai 950 lor 2
h. aro 520 HPa. 5.13 HPam
1/2
. rospociivolv.
!"#$%&'() Si÷Al÷Zr÷U svsiom amorphous hulk: a iwo÷siop hoai iroaimoni: siruciuro: mochanical proporiios
1 Introduction
As a promi sing candidaio maiorials lor high÷iompora
iuro siruciural applicaiions. mulliio and mulliio÷hasod co
ramics havo hoon rocoivod worldwido aiioniions hocauso ol
iis oxcolloni high÷iomporaiuro proporiios
|1÷2]
. Incorporaiion
ol ZrU
2
improvos iho room÷iomporaiuro mochanical prop
oriios ol mulliio wiih high÷iomporaiuro uniquo characioris
iics. Ii is possihlo io promoio iho wido sproad applicaiions
ol mulliio. So zirconia ÷mulliio composiio coramics havo
hoon ono ol hoi issuos in rosoarch and applicaiion ol novol
coramic maiorials
|3÷7]
.
Zirconia ÷mulliio composiios can ho proparod ihrough
sovoral rouios. Ul ihoso iho imporiani onos aro (a) lrom
mochanical mixiuro ol lirod mulliio/aciivo pro÷mulliio and
zirconia powdors: (h) co÷procipiiaiion: (c) sol ÷gol moihod
ol proparaiion and (d) roaciion sinioring
|8]
. Boaciion sin
ioring ol zircon and Al
2
U
3
is a rolaiivolv simplo and inox
ponsivo rouio io ohiain homogonoous zirconia÷mulliio co
ramics wiih onhancod mochanical proporiios. Howovor.
mulliiizaiion normallv roquiros high procossing iomporaiuro
and long duraiion hocauso ol iho low hulk and grain ÷
houndarv dillusion coollicionis lor mulliio. Ii is imporiani
io lind oui now moihods lor lullv donso zirconia ÷mulliio
composiio proparaiion ai rolaiivolv low iomporaiuros. In
ihis ariiclo. ZrU
2
÷mulliiocomoposiio coramics wiih ulira
lino grains woro proparod hv conirollod crvsiallizaiion in
siiu lrom iho Si ÷Al ÷Zr ÷U amorphous hulk. Comparod io
iho convoniional sinioring moihod. ihis moihod can ovor
como iho nogaiivo ollocis duo io agglomoraiion ol nano ÷
powdor pariiclos and ahnormal growih ol nano ÷grains.
1horoloro. ii can ho usod io proparo high roliahiliiv siruc
iural coramic maiorials wiih donso and homogonoous mi
crosiruciuro ai 1100~1350. 1ho ollocis ol hoai iroaimoni
on iho siruciuro and mochanical proporiios ol iho compos
iios woro invosiigaiod wiih iho aid ol ISC. XBI. SEH and
iho \ickors indoniaiion iochniquo.
2 Materials and Methods
2.1 Raw materials and component selection
1ho raw maiorials aro SiU
2
. Al
2
U
3
. ZrU
2
. HgU. CaU and
raro oarih oxido. which aro all analvsis grado. 1ah. 1
shows iho chomical composiiion rango ol iho samplos. 1ho
*Corrosponding auihor. 1ol: +86÷731÷8876690
Iax: +86÷731÷8710136
E÷mail: sqliangCmail.csu.odu.cn
\ol. 11. ^o. 1. 27÷31. Harch. 2006 *+,%(-.",/"
27
SiU
2
Al
2
U
3
ZrU
2
HgU CaU Uihors
35÷45 35÷40 10÷20 0÷3 0÷2 0÷1
Tab. 1 Composition range of the materials (wt.%)
haso composiiion m(SiU
2
) : m(Al
2
U
3
) : m(ZrU
2
) : m(HgU+
CaU+ oihors) = 8 : 8 : 3 : 1 is lahollod as Z1. Vhon ZrU
2
roplacos a poriion ol SiU
2
. iho corrosponding composiiions
aro indicaiod as Z
2
. Z
3
wiih incroaso ol ZrU
2
.
2.2 Experimental procedure
1ho haich maiorials woro woighiod in iorms ol
compononi dosign and ihoroughlv mixod iogoihor in ordor
io socuro a homogonoous moli. and suhsoquonilv placod
inio alumina crucihlos. 1ho crucihlos woro iniroducod inio
an olociric lurnaco oporaiing ai 1650~1700 lor 2~4 h.
1ho homogonoous and donso molis woro ihoroalior pourod
inio siainloss siool molds io viold amorphous hulk slahs hv
conirolling iho cooling procoss. 1hon analvzod ihoir
chomical composiiions and lound ihai ihov woro almosi iho
samo as dosignod holoro. Iinallv. iho slahs woro iroaiod ai
dilloroni iomporaiuro lor 1 h lollowod hv proiroaiing ai
950 lor 2 h and ZrU
2
÷mulliio composiio coramics wiih
ulira lino grains woro proparod.
2.3 Test of the samples
Iilloroniial scanning calorimoiric (ISC) ol ahoui 90 mg
ol amorphous powdor samplos wiih pariiclo sizo < 75 m
was carriod oui in siaiic aimosphoro ai dilloroni raios ol 5.
8. 10. 15 and 20/min in iho rango ol 20~1400 using a
^oizsch dilloroniial scanning calorimoiric analvzor (modol
404 PC. (ormanv) wiih Al
2
U
3
powor as roloronco maiorial.
1ho powdor XBI paiiorns woro omplovod io idoniilv
iho crvsiallino phasos hv Japanoso I/max2000 insirumoni.
using Cu K

radiaiion ovor iho rango 10 ~80 ai 4 /min
(iho pariiclo sizo < 75 m). 1ho crvsial phasos woro
idoniiliod hv moans ol JCPIS cards. 1ho volumo lraciion
ol m÷ZrU
2
was calculaiod hv iho lollowing oquaiions
|9]
:
(1).
whoro X
m
is iho iniograiod inionsiiv raiio and P=1.340:
(2).
whoro I
m
and I
i
aro iho poak hoighis ol m÷ZrU
2
and i÷ZrU
2
.
rospociivolv. \
m
is iho volumo lraciion ol m÷ZrU
2
and ihai
ol i÷ZrU
2
is \
i
= 1\
m
.
Hicro ÷siruciural ohsorvaiions woro porlormod on iho
polishod lraciuro surlacos alior loaching wiih 1% HI
soluiion lor 2 minuios lollowod hv ulirasonic cloaning wiih
Amorica Siricon200 olociron microscopv.
1ho micro ÷hardnoss H
v
ol iho samplos was iosiod hv
iho \ickorss indoniaiion wiih an appliod load ol 100 g
and a holding iimo ol 10 s. 1ho lloxural sirongih l ol iho
samplos woro doiorminod lrom a ihroo÷poini honding iosi
wiih a span ol 30 mm and a loading raio ol 0.5 mm/min.
Iraciuro ioughnoss K
IC
woro moasurod hv using an
indoniion micro÷crack moihod
|10]
wiih a load ol 10 Kg and
a holding iimo ol 15 s.
3 Results and Discussions
3.1 Thermal analysis for the crystallization processes
1ho Avrami oxpononi n indicaios crvsial growih
mochanism in iwo or ihroo dimonsions. 1ho valuo n 1
indicaios surlaco crvsiallizaiion mochanism and n 3
indicaios hulk crvsiallizaiion mochanism. 1ho valuo ol n
can ho calculaiod according io iho Uzawa and Augis
oquaiions
|11÷13]
. |Eqs. (3) and (4). rospociivolv]:
(3).
Vhoro 1
p
and aro iho crvsiallizaiion poak iomporaiuro
and hoaiing raio. rospociivolv. E is iho aciivaiion onorgv
lor crvsiallizaiion. and Bis iho gas consiani.
(4)
Vhoro 1 is iho lull widih ai hall maximum ol
oxoihormic poak on iho ISC curvo.
According io Eq. (3). iho E valuo can ho ohiainod lrom
iho slop ol iho ploi ln(1/) vorsus 1/1
p
. as shown in Iig. 1.
1ho valuo is ahoui 5685 KJ/mol lor Z1 samplo. And iho
valuo ol n is ahoui 3 (shown in 1ah. 2). which indicaios
hulk crvsiallizaiion mochanism in iho samplo Z1.
1ho ISC curvos lor samplos aro shown in Iig. 2 (=
10/min). Ii is lound ihai iho ISC curvos oxhihiiod a
sharp oxoihormic poak in iho rango ol 1000~1060 and
an ohscuro poak ai ahoui 1160 in iho samplos. Viih iho
incroaso ol ZrU
2
(lrom Z1 io Z3). iho lirsi crvsiallizaiion
poak shilis io iho lowor iomporaiuro (iho socond
crvsiallizaiion poak is ioo small io prosoni). 1ho groaiosi
shili ol iho crvsiallizaiion iomporaiuro is ahoui 50. which
Uriginal Ariiclos \ol. 11. ^o. 1. Harch. 2006 | Nonoscience
28
n E (kJ/mol)
= 5
KJ/mol
= 8
KJ/mol
= 10
KJ/mol
= 15
KJ/mol
= 20
KJ/mol
Uzawa
moihod
3.26 3.00 3.18 3.07 3.27 5685
Fig.1 Plots of ln(1/) vs. 1/T
p
Tab. 2 Crystallization kinetic datas for the sample Z1
Fig. 2 DSC curves of the amorphous samples
indicaios ZrU
2
docroasos iho aciivaiion onorgv lor
crvsiallizaiion ol iho SAZ svsiom amorphous samplos and
promoios hulk crvsiallizaiion.
3.2 Phase analysis in the crystallization processes
1omporaiuros corrosponding io ihoso poaks on iho ISC
curvos can ho assignod io iho crvsiallizaiion ol various
phasos. XBI was omplovod io idoniilv iho crvsiallino
÷÷÷÷ mulliio ÷÷÷÷i÷ZrU
2
÷÷÷÷m÷ZrU
2
÷÷÷÷SiU
2
÷÷÷÷coridoriio
Fig. 3 XRD pattern of Z3 samples treated at different
temperature
phasos corrosponding io oach oxoihormic poak. Iig. 3 is
iho XBI paiiorn ol Z3 amorphous samplo ai dilloroni hoai
iroaimoni iomporaiuro. Ii can ho soon ihai iho samplo
iroaiod ai 900 is amorphous. whilo iroaiod ai 950. iho
samo samplo hogins crvsiallizaiion and i÷ZrU
2
lorms. Viih
iho incroaso ol iomporaiuro up io 1000. iho dillraciion
poaks ol i ÷ZrU
2
aro moro ovidoni and iraco ol mulliio
crvsiallino phasos is doiociod. Vhon iho samo samplo was
hoaiod ai 950 lor 2 h and suhsoquonilv hoaiod ai
1100 lor 1 h. iho samplo hocamo comploiolv opaquo and
a unilorm crvsiallizaiion was lound ihroughoui iho wholo
samplo. 1ho main crvsiallino phasos aro idoniiliod as ZrU
2
.
mulliio and crisiohaliio wiih iho iracos ol iho amorphous.
A small amouni ol m÷ZrU
2
was doiociod ai 1150. which
suggosis ihoro is a phaso iranslormaiion lrom i÷ZrU
2
io m÷
ZrU
2
in iho rango ol iomporaiuro 1100~1150 duo io iho
sizo ol somo i÷ZrU
2
grains is largor ihan iho criiical valuo
sizo lor sponianoous phaso iranslormaiion
|14]
. Cordioriio was
doiociod ai 1200 and no oihor phaso lorms hui iho
volumo lraciion ol m ÷ZrU
2
incroasos ohviouslv ahovo
1200 (shown in 1ah. 3). 1ho crvsiallizaiion procoss ol
Uriginal Ariiclos \ol. 11. ^o. 1. Harch. 2006 ! "#$%&'()$') "*$%&'()$') ! \ol. 11. ^o. 1. Harch. 2006 Uriginal Ariiclos
29
iho Z1 and Z2 samplos is similariiv io ihai ol iho Z3
oxcopi iho dilloronco in iho crvsiallizaiion iomporaiuro ol
ovorv phaso. which is shown in 1ah. 4.
Tab. 3 The volume fraction of m-ZrO
2
for the samples treated
at different temperature
Tab. 4 Phases of the samples in the crystallization process
3.3 Microstructure development in the crystallization
processes
Iig. 4 is iho SEH phoiograph ol iho Z3 samplo iroaiod
ai dilloroni iomporaiuro. Ii can ho lound ihai ihoro aro
somo hall ÷liko pariiclos io ho soparaiod lrom iho
amorphous mairix lor iho samplo iroaiod ai 900 |Iig. 4
(a)]. 1ho rosulis ol XBI idoniilv iho samplo is siill in
amorphous siaio. which indicaios a homogonoous
nucloaiion procoss occurs in iho innor ol iho amorphous
hulk. 1his is vorv usolul io promoio hulk crvsiallizaiion.
1ho samplo iroaiod ai 1100 lor 1 h lollowod hv
proiroaiing ai 950 has a homogonoous and donso
microsiruciuro wiih hall ÷liko grains in sizo ol 20~50 nm
|shown in Iig. 4 (h)]. Viih iho incroaso ol iomporaiuro up
io 1200. iho ro÷crvsiallizaiion procoss occurs duo io
(a) 900
(b) 1100
(c) 1200
(d) 1350
Fig.4 SEM photographs of the Z3 sample
agglomoraiion ol nano ÷pariiclos and somo laih ÷shapod
crvsial grains lorm. Iig. 4 (d) is iho SEH phoiograph ol iho
Z3 samplo iroaiod ai 1350. 1ho microsiruciuro coniains
Hoai÷iroaiod
iomporaiuro ()
\m (%)
Z3 Z2 Z1
1100 4.9 5.3 10.2
1150 20.1 23.9 25.1
1200 42.8 40.6 39.0
1250 58.1 54.7 51.8
1omporaiuro
()
Phasos
900 Amorphous
900950 i÷ZrU
2
9501000 i÷ZrU
2
mulliio (iraco)
10001100 i÷ZrU
2
mulliio crisiohaliio m÷ZrU
2
(iraco)
11001150 i÷ZrU
2
mulliio crisiohaliio m÷ZrU
2
11501250 i÷ZrU
2
mulliio crisiohaliio m÷ZrU
2
cordiorio
Uriginal Ariiclos \ol. 11. ^o. 1. Harch. 2006 | Nonoscience
30
olongaiod and oquiaxod mulliio grains (hlack) along wiih
zirconia grains (whiio). Hosi ol zirconia grains aro
iniorgranular and low aro iniragranular. 1ho longih ol a
low mulliio grains is ahoui 5 m. Hoai iroaimoni
iomporaiuro has a groai olloci on iho microsiruciuro ol iho
samplos. 1ho homogonoous and donso Si ÷Al ÷Zr ÷U
composiio coramics wiih ulira lino grains can ho ohiainod
hv conirolling hoai iroaimoni iomporaiuro.
3.4 Effects of heat treatment temperature on
mechanical properties
Tab. 5 Microhardness of samples
1ho avorago micro÷hardnoss ol iho samplos iroaiod ai
dilloroni iomporaiuro is shown in 1ah. 5. Ii shows ihai iho
micro÷hardnoss ol iho Z2 and Z3 samplos incroasos wiih
incroasing hoai iroaimoni iomporaiuro. Ai 1150. ihov
havo iho highosi micro ÷hardnoss ol H
v
13.66 and 12.53
(Pa. rospociivolv. Vhon iho iomporaiuro is ahovo 1200.
iho micro ÷hardnoss lor Z1. Z2 and Z3 docroaso. 1his is
hocauso. ai 1100~1150. iho ulira lino÷scalo mulliio and
zirconia lorm homogonoouslv wiih vorv low glass. 1ho lino
microsiruciuro ohiainod in ihis siago givos riso io iho high
micro ÷hardnoss. Howovor. ahovo 1200 . rapid ro ÷
crvsiallizaiion and grain coarsoning iako placo. As a rosuli.
iho micro÷hardnoss docroasos. Iig. 5 shows ollocis ol hoai
iroaimoni iomporaiuro on lloxural sirongih and lraciuro
ioughnoss ol Z1 samplo. Ii is ohsorvod ihai incroasing iho
crvsiallizaiion iomporaiuro rosulis in incroasing mochanical
proporiios ai lirsi and docroasing ihoroalior. Ai 1150. iho
lloxural sirongih and lraciuro ioughnoss roach io maximum.
520 HPa and 5.13 HPam
1/2
. rospociivolv. Ahovo 1200.
lraciuro ioughnoss docroasos rapidlv whilo lloxural sirongih
docroasos slighilv. In comparison wiih iho poor sirongih
(200 ~300 HPa) and ioughnoss (2 ~2.5 HPam
1/2
) ol iho
1omporaiuro ()
Fig. 5 Effects of crystallization temperature on mechanical
properties of sample Z1
monoliihic mulliio. iho mochanical proporiios ol prosoni
Si÷Al÷Zr÷U composiio coramics wiih ulira lino grains aro
signilicanilv highor. 1ho improvomoni ol mochanical
proporiios wiih crvsiallizaiion iomporaiuro up io 1150 is
mainlv aiirihuiod io iho micro÷siruciural laciors. E.g. ZrU
2
iranslormaiion sirongihoning and ioughoning mochanism
aro opiimisod.
4 Conclusions
Viih carolul solociion ol composiiion. iho homogonoous
donso SAZ amorphous hulk was proparod hv 1620~1700
moliing ihon quonching. Bv hoai iroaimoni ai 950 lor 2
h io nucloaio and ai 1100~1350 lor 1 h io crvsiallizo.
iho Si÷Al÷Zr÷U composiio coramics wiih ulira lino grains
woro proparod. 1ho ZrU
2
and mulliio aro iwo major phasos
idoniiliod alior iwo ÷siago hoai iroaimoni. 1ho sphorical
crvsial grains wiih iho sizo ol 20 ~50 nm lorm lor iho
samplos iroaiod 1100 . Ai high crvsiallizaiion
iomporaiuro. iho ro÷crvsiallizaiion procoss siaris and somo
laih ÷shapod crvsials lorm. Viih iho incroaso ol
crvsiallizaiion iomporaiuro up io 1350. iho longih ol a
low olongaiod mulliio grains is ahoui 5 m. 1ho lloxural
sirongih and lraciuro ioughnoss ol iho samplos iroaiod ai
950 lor 2 h ihon 1150 lor 1 h aro largosi. ihai is 520
HPa. 5.13 HPam
1/2
. rospociivolv.
Acknowledgements
1his wor k was porlormod undor iho auspicos ol
^aiional High ÷1och Bosoarch and Iovolopmoni Program
ol China ("863" ^o. 2003AA332040). io which iho auihors
wish io oxpross ihoir ihanks. (Coniinuod on Pago 17)
^o.
Crvsiallizaiion iomioraiuro ()
1100 1150 1200 1250
Z1 13.72 12.48 13.71 10.39
Z2 11.13 13.66 11.73 10.84
Z3 12.29 12.53 10.73 10.56
Nonoscience | \ol. 11. ^o. 1. Harch. 2006 Uriginal Ariiclos
31
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17

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