S ZIRCONIA NHA KHOA.

PHN 1: BN CHT V NG DNG THC TIN

ThS. o Ngc Lm
B mn K thut Phc hnh rng,
Khoa Rng Hm Mt, i hc Y Dc TP.HCM

Vt liu s (ceramics) c ng dng trong nha khoa

t rt sm, bt u t nhng nm 1816, ca th k XIX, v c nhng c im ph hp vi nhu cu
thm m v phc hi nha khoa. S pht trin ca ng dng vt liu s trong ngnh y t ni chung v
trong nha khoa ni ring trong sut hn thp k qua chng minh c vai tr quan trng v tim
nng ca vt liu ny trong cc ng dng thc tin vo lnh vc chm sc sc khe chung. Ring trong
nha khoa, vt liu s c ng dng kh ph bin bi tnh tng thch sinh hc v tnh thm m ph
hp vi c tnh m hc ca rng, ng thi loi vt liu phc hi rng ny cng c nghin cu v
pht trin mt cch c h thng v lin tc theo c chiu rng v su. Theo dng lch s, vt liu s nha
khoa pht trin kh nhanh chng vi nhiu dng khc nhau v cc dng ny c chia thnh hai
nhm chnh nh sau:
- S khng c cu trc tinh th (Non crystalline ceramics) (Nhm I), l cc s ch c cu thnh bi
cc oxit phi kim, gm cc i din chnh nh s carbide, s nitride, s bohride
- S c cu trc tinh th (Crystalline ceramics) (Nhm II), l cc s ch c cu thnh bi cc oxit
kim loi, gm cc i din l s feldspar (Felsdpathic ceramics), s alumina (Alumina ceramics), s
spinnel (Spinnel ceramics), s zirconia (Zirconia ceramics), v.v[2], [5]
D nhin, thc t lun tn ti nhm lai hay cn gi l nhm vt liu s phc hp (Composite ceramics) (Nhm III), l cc nhm s c c cc c tnh ca nhm vt liu s khng c cu trc v nhm
vt liu s c cu trc. Tuy nhin, khc vi nhm vt liu thy tinh (Glass), trong nha khoa hin nay
thng s dng thut ng s thy tinh (Glass/glassy ceramics) ch mt nhm nh trong nhm s
lai ny. Trong phm vi ca bi vit ny, ch cp ch yu n nhm vt liu s c cu trc tinh th
v mt phn nh bin th ca nhm vt liu ny trong nhm s lai. S zirconia c xem l mt
trong nhng bc tin mi ca dng vt liu s nha khoa thuc Nhm II v Nhm III hin nay. Thc
t, dng vt liu ny c nhng im g khc bit v ni tri hn so vi cc dng vt liu s cng nhm
trc khng?. Phn ni dung k tip s cp n bn cht ca vt liu s v s Zirconia gip
chng ta c th gii p thc mc trong cu hi nu trn.
V thnh phn cu to, s c cu thnh bi ch yu cc oxide (oxides), bao gm c cc oxide kim
loi v cc oxide phi kim, c kt hp li da trn c ch cng bc v mt c - ha - l, gm: ngun
nhit (Heat), p sut (Pressure) v c im ca mi trng x l (ph gia hiu chnh c l, ph gia
c ha v ph gia hiu c ha l). S l kt qu sau khi lm ngui, sau thiu kt, qu trnh x l
nhit ca trng thi ban u (bt liu kh (powder) hay trng thi trung gian (paste - bt nho)).
V mt cu trc vt liu, s c chia thnh cc nhm chnh sau:

- Vt liu s khng c cu trc tinh th (Non crystalline ceramics) (Nhm I), l cc s ch c cu

thnh bi cc oxit phi kim, gm cc i din chnh sau: s carbide, s nitride, s bohride, s
- Vt liu s c cu trc thun tinh th (Crystalline ceramics) (Nhm II), l cc s ch c cu thnh
bi cc oxit kim loi, gm cc i din chnh sau: s feldspar, s alumina, s spinnel, s zirconia,
v.v
- Vt liu s nhm lai hay cn gi l nhm vt liu s phc hp (Composite ceramics) (Nhm III), l
cc nhm s va c cc c tnh ca nhm vt liu s khng c cu trc v ca nhm vt liu s c
cu trc.
Hin nay, trong nha khoa thng s dng thut ng s thy tinh (Glass/glassy ceramics) ch mt
nhm nh trong nhm s lai ny, vt liu s thy tinh c cu trc ch yu l v nh hnh dng phi
newton tng t nh trng thi cu trc ca pha thy tinh, tuy nhin, vt liu s khc hon ton v
bn cht so vi vt liu thy tinh (Glass).
Nhit thiu kt t trng thi th ban u ca vt liu s thng trong khong t 10000C 38000C,
i vi trng thi trung gian hay tin gia nhit (Pre-sintered/pre-heated) th nhit thiu kt nm trong
khong 8400C 18000C [3].
Trong nha khoa, s Zirconia c cu thnh ch yu bi cc thnh phn chnh sau:
- Oxide nn l zirconia (ZrO2)
- Cc ph gia gia cng c l nh: alumina (Al2O3), hay feldspar (K2O.Na2O), v mt s oxide kim
loi khc
- Cc ph gia hiu chnh ha l chnh, thng l cc oxide kim loi, nh: yttria (Y2O3), hay ceria
(Ce2O3), hay magnesia (MgO), hay calcia (CaO), hay hn hp potasia v natria (K2O.Na2O).
Trong , cc tnh cht c trng ca s Zirconia c quyt nh ch yu bi c tnh ca zirconia,
mt trong nhng thnh phn cu to chnh c quan tm nghin cu trong k thut vt liu s hin
i. Ni cch khc, c tnh ca s zirconia c c trng bi cu trc tinh th ca zirconia trong cu
trc vt liu ca s (xem Bng 1.0). bn ca s zirconia ph thuc rt nhiu vo thnh phn ca pha
zirconia trong cu trc ca s, do s zirconia cn c phn loi theo t l tinh th zirconia trong
s, gm hai nhm chnh [2]:
- Nhm vt liu s zirconia c thnh phn zirconia c bn cao, gm c cu trc tinh th dng hnh
hp ch nht v dng tinh th lp phng, cn c gi l nhm vt liu s Zirconia n nh khng
hon ton (PSZP = Partial Stabilized Zirconia Porcelain), thng t l thnh phn zirconia bn n
cao (TZC v PSZC) ~ (96,0 98,0) % .
- Nhm vt liu liu s zirconia ch yu thnh phn zirconia, cu trc tinh th dng hnh hp ch nht,
cn c gi l nhm vt liu s Zirconia tinh th hnh hp ch nht (TZP = Tetragonal Zirconia
Porcelain), thng t l thnh phn zirconia TZP ~ (96,0 99,9) % .
Bng 1.0. c tnh ca Zirconia
STT

Thng s c tnh vt liu

K hiu

Gi tr/ Ghi ch

n v
tnh

K hiu v tn gi theo IUPAC

Trng thi tn ti trong t

nhin

Sc mu nguyn thy

Khi lng mol ph n t

Khi lng ring

Nhit nng chy

Nhit si

Cng bn

Tnh tan

ZrO2

-Zirconium dioxide
-Zirconium(IV) oxide
- Khong Baddeleyite l
khong dng chnh tn ti trong
t nhin ca zirconia (ZrO2), kt
hp vi zirconium di sulfide
(ZrS2), titanium dioxed (TiO2)
va Hafnium dioxide (HfO2),
thng c mu xanh xm, en
nh kim, nu t, v.v ty theo
hm lng ca cc khong tp
km theo.
Mu trng

Mmol

123.218

g/mol

5.68

g/cm3

Tnc

2715

oC

Ts

4300

oC

Mpa
- Gn nh khng tan trong
nc.
- Tan trong dung dch HF v
dung dch H2SO4 nng, dung
dch HNO3 nng v dung dich
HCl nng.

10

Chit sut t i

nD

2.13

Zirconia tinh cht thng tn ti cu trc tinh th n t (hnh hp hnh bnh hnh) (Monoclithic
crystalline hay MZC = Monoclithic Zirconia Crystalline) nhit thng (iu kin tiu chun t 23
26 oC), khi nhit tng dn, cu trc pha tinh th ca zirconia chuyn bin ln lt thnh cc dng
pha cu trc sau (xem Hnh 1.1 [2]):
- Tinh th hnh hp ch nht (Tetragonal Crystaline hay TZC = Tetragonal Zirconia Crystalline).
- Tinh th lp phng (Cubic crystalline hay CZC = Cubic Zirconia Crystalline)
- V nh hnh (Amorphous phase hay AZS = Amorphous Zirconia Structure) trong trng thi cn nng
chy v nng chy (hay trong trng hp lm ngui nhanh).

(a) (b) (c)

Hnh 1.1. Cu trc tinh th ca zirconia (ZrO2) [2]:
(a) Tinh th lp phng (CZC)
(b) Tinh th hnh hp ch nht (TZC)
(c) Tinh th n t (MZC)
iu cng ng ngha l trong qu trnh lm ngui s lun tn ti hin tng lin tc gin n v th
tch trong sut qu trnh chuyn bin pha t cu trc v nh hnh ln lt thnh cu trc tinh th lp
phng, cu trc tinh th hnh hp hnh ch nht v cu trc tinh th n t, khi nhit gim dn n
nhit mi trng (nhit phng) (xem Hnh 1.2. [2]). cng chnh l nguyn nhn chnh gy ra
hin tng ph hy, do hiu ng ng sut d th tch trong qu trnh chuyn bin pha, trong qu trnh
x l cc phc hnh s zirconia. Trong , cu trc tinh th lp phng v cu trc tinh th t din c
bn c hc ng tnh theo cc phng cao hn so vi cu trc tinh th n. Do , trong vt liu s
zirconia, cc nh cng ngh lun tm cch lu gi cu trc tinh th mong mun (lp phng v t
din) bng cc ph gia hiu chnh ha l (dopants), nh: yttria (Y2O3), hay ceria (Ce2O3), hay magnesia (MgO), hay calcia (CaO), hay hn hp potasia v natria (K2O.Na2O), v.v [2], [3]

Hnh 1.2. th biu din mi quan h gia nng lng (E [eV/nguyn t]) (trc tung) v
th tch (V[A3/nguyn t]) (trc honh) tnh theo nguyn t ca
ba dng cu trc tinh th chnh ca zirconia (ZrO2):
lp phng (cubic), hp ch nht (tetragonal) v tinh th n t (monoclinic).
(a) th ca Stapper et al. (b) th ca Dewhurst and Lowthe [2]
Trong y t ni chung v nha khoa ni ring, cc ph gia hiu chnh yttria, ceria, calcia, magnesia, hn
hp natria va potasia c s dng nhiu nht v tnh tng thch v an ton sinh hc cao (theo tiu
chun ca FDA), theo mc hiu dng ln lt l:
- Yttria (Y2O3), cho t l v th tch ca cu trc tinh th hnh hp ch nht v tinh th lp phng
trong cu trc vt liu ca s zirconia (NZr/Mat) cao nht (thng dao ng trong khong t 98,0
99,9%).
- Yttria (Y2O3) kt hp magnesia (MgO) (NZr/Mat thng dao ng trong khong t 96,0 98,7%).

- Ceria (Ce2O3) kt hp magnesia (MgO) (NZr/Mat thng dao ng trong khong t 95,0 97,0%).
- Calcia (CaO) kt hp khong phc ca potasia v natria (K2O.Na2O) (NZr/Mat thng dao ng trong
khong t 93,0 96,0%)
S zirconia PSZP thng c to thnh bi s hin din v tc ng ca cc ph gia hiu chnh ha
l chnh c cha cc thnh phn ion nh Ca2+ (CaO), Mg2+ (MgO) hay phc Na+/K+ (Na2O.K2O) trong
thnh phn cu to ca s zirconia.
S zirconia TZP ch c to thnh khi v ch khi c s hin din v tc ng ca cc ph gia hiu
chnh ha l c cha cc ion nh Ce4+ (CeO2) v Y3+ (Y3O2).
S TZP c to thnh bi thnh phn ph gia Y2O3 v CeO2 ln lt c k hiu l (Y TZP) v
(Ce TZP), cn s PSZP c to thnh bi thnh phn ph gia MgO2 v CaO ln lt c k hiu
l (Mg PSZP) v (Ca PSZP).
T l zirconia trong s zirconia (gm c TZP v PSZP) c quyt nh bi hm lng ca cc ph gia
hiu chnh c tnh bng thnh phn phn trm mol, c bit trong cc ng dng v y t, t l ca cc
ph gia hiu chnh thng c kim sot trong gii hn nht nh do c nh hng n sc khe ca
c th. Theo quy nh ca FDA, thnh phn ca Ce4+ (CeO2) < 2 5%, Y3+ (Y2O3) < 5 - 8%, Mg2+
(MgO) < 8 10%, v.v Ni cch khc, cu trc tinh th ti u ca zirconia quyt nh bn ca s
zirconia, hay s TZP c bn c hc cao hn so vi s PSZP. Trong thnh phn chnh ca s zirconia TZP chnh l cu trc tinh th hnh hp ch nht TZC, nhng TZC cng chnh l mt trong cc
cu trc trung gian n nh dng meta (meta-stable structure) kh c bit. V c tnh, MCZ (3,5
5,0 GPa) c c tnh thp hn so vi TZC (5,5 15,0 GPa) v CZC (> 7,0 GPa) ty thuc vo t l
thnh phn cha trong s v kch thc ht to thnh ca cc cu trc, nhng th tch ring ca MCZ
cao hn so vi TZC v CZC.
Nh trnh by trn, qu trnh chuyn bin ny s dn n hiu ng gin n v th tch ring ca
cu trc ng k, ni cch khc qu trnh chuyn bin pha ny s lm chm qu trnh ph hy ti cc
vi nt (vi k), do hin tng ln p ca th tch gin n ny vi th tch khong trng ca cc vi nt
trong ni cu trc vt liu, to nn c ch hn c hc, p cc thnh ca cc vt nt li gn nhau,
trong mt s trng hp cc vt nt khi c khp kn ti cp n v cu thnh nn cu trc tinh th
th cc vt nt ny c xu hng t ti to/ phc hi cc lin kt trong cu trc tng t trng thi ban
u. Qu trnh ny c gi l c ch ha bn do chuyn bin pha (Transformer toughening mechanism) [2], [3], [5], [6](Xem Hnh 1.3.).

Hnh 1.3. C ch c ch ha bn do chuyn bin pha

(Transformer toughening mechanism) ca s zirconia TZP v PSZP [2], [3]
Tuy nhin, khi thnh phn cc ph gia hiu chnh ca s zirconia tng, th dn ca vt liu cng
tng t l thun, do thnh phn ca cc ph gia hiu chnh thng c gii hn v kim chng
bng thc nghim trong khong cho php ph hp vi yu cu ca cc ng dng trong nha khoa v y
t, theo thc nghim th khi % mol ca Y2O3 ln hn 10% (Xem Hnh 1.4.).

Hnh 1.4. Gin pha ca s zirconia Y TZP theo

nhit v thnh phn %mol ca ph gia hiu chnh ha l Yttira (Y2O3) [2], [3]
Theo thc nghim ca R.A. Cutler et al[9] v A. Bravo Leon et al[10], vi mt t l nht nh ca cu
trc tinh th TZC trong cu trc vt liu s TZP (Y-TZP), vi thnh phn %mol ca Y2O3 thp, khong
di (3,0 3,5) %, khi vt liu chu lc tc ng gy ra hin tng vi ph hy do hiu ng tp trung
ng sut (hiu ng mi nhn), nu kch thc ca cc ht to thnh trong cu trc s ln th hiu ng
vi nt do hin tng bin dng trt trn bin gii ht hay trn cc mt trt ca cu trc TZC trong
qu trnh chuyn bin pha cng c th ln gy ra cc ph hy ln m c ch ha bn do
chuyn bin pha (Transformer toughening mechanism) khng th kim sot hay khng ch c, hay
ni cch khc tc pht trin vt nt ln hn tc gin n th tch do qu trnh chuyn bin pha to
ra, khi ni ng sut d ca vt liu c gii phng thnh ni nng trong cu trc ca zirconia, cng
chnh l tc

Trong , tc lm ngui thng c hiu chnh v kim sot trong cc mi trng lu cht lm
ngui thch hp bng dng kh lu cng bc hay trong lu cht lng, tuy nhin p sut ca mi
trng lm ngui cng ng mt vai tr rt ln trong vic kim sot tc pht trin ht v kch thc
ht ca s trong qu trnh kt tinh, theo c ch cng bc v mt c hc thun ty. Kt qu thc
nghim chng thc iu ny thng qua hng lot cc nghin cu mang tnh c th ca Chiang et al
[11], R.A. Cutler et al [9], Bravo Leon et al [10], Richerson et al [13], bn mi ca TZP c ci thin
ng k trong iu kin kt tinh ph hp vi khong p sut mi trng lm ngui dao ng trong
khong (3.0 20.0) GPa, ng vi khong nhit dao ng trong khong (1050 - 1210)oC cho cc
mu th nghim Y TZP, vi %mol Y3O2 ~ (0,5 3,5)% (xem Hnh 1.6.). Tuy nhin theo nghin cu
chuyn su ca Richerson et al [13], s TZP c bn mi v bn c hc ni chung khng tt bng

s PSZP, tr cng v bn nn. T kt cc qu nghin cu trn, xu hng ca mt s nh nghin

cu hin nay, s zirconia l tng cho cc ng dng trong y nha khoa li l cc cu trc a tinh th
phi hp gia cu trc ca s zirconia TZP v s zirconia PSZP. Tuy nhin, theo thc nghim ca Desgreniers v Lagarec [14] v Stapper et al [4], cu trc tinh th TZC c xu hng bin dng thnh cu
trc tinh th hnh hnh hp y hnh thoi (OZC = Orthorhombic Zirconia Crystalline), l dng bin th
trung gian gia TZC v MZC, do OZC c c cc u im c trng v mt bn c hc ca c
TZC v MZC.

Hnh 1.5. Gin pha ca s zirconia Y TZP theo

nhit (oC) v thnh phn %mol ca ph gia hiu chnh ha l Yttira (Y2O3) [2]
Sau y l mt s thng s thc nghim v bn nn ca s zirconia theo cc dng cu trc tinh th
c hnh thnh trong trng hp l tng:
- S zirconia c cha thun ty cu trc MZC hay thun ty cu trc TZC thng c module n hi
nn, dao ng trong khong (150 200) GPa[9] v [10].
- S zirconia c cha thun ty cu trc CZC thng c module n hi nn, dao ng trong khong
(171 288) GPa [9] v [10].
- S zirconia c cha thun ty cu trc OZC I v cu trc OZC II (ng vi p sut mi trng ~
20GPa) (theo Ohtaka et al [15]) thng c module n hi nn ln lt dao ng trong cc khong (224
273) GPa v (254 444) GPa.

Hnh 1.6. Gin pha ca s zirconia theo

nhit (oK) v p sut mi trng lm ngui (GPa) [2]
Ty theo nh sn xut, s zirconia hin nay c chia thnh 3 nhm chnh da trn cu trc tinh th
c hnh thnh trong cu trc vt liu: nhm s zirconia PSZP, nhm s zirconia TZP v nhm s zirconia c cu trc a tinh hn hp gia PSZP v TZP.
bn nn ca mi loi s thng phm ng dng trong nha khoa hin nay thng khc nhau t nhiu
v dao ng trong khong gi tr kh rng: []nn = (450 1900) MPa. Tuy nhin, ngay c trong trng
hp thnh phn cu to ca cc sn phm s zirconia thng phm ging nhau hon ton cng c th
c cc bn c hc khc nhau, ph thuc rt nhiu vo quy trnh cng ngh x l v ch to vt liu
ca mi nh sn xut.
V thnh phn ca s zirconia, c nhng sn phm thng phm c t l TZP trong cu trc vt liu
s ln n 99,99% (c th c xem l gn nh nguyn cht l cu trc tinh th TZC), 0,01% cn li
thng l cc oxide khc nh Y2O3, Al2O3 v mt vi lng ca CaO, K2O.Na2O, cn phn ln cc s
thng phm khc c thnh phn c t l TZP trong cu trc vt liu s trong khong (96,0 98,0)%.
Trong lnh vc thng phm trong cng nghip y nha khoa, hn 90% th phn s zirconia l cc
thng phm s zirconia y nha khoa dng cho cc h thng cng ngh CAD/CAM v cng ngh
MAD/MAM, 1% th phn l cc sn phm ph trong cng ngh TCB (Thermal Coating Barrier/ Bonding) trn cc dng c gii phu y nha khoa hay cc chi tit cm ghp trong nha khoa nh cc dng imlant v abutment phc hnh dng lai c lm bng c hp kim/ kim loi v s zirconia (Hybrid implants and abutments), (3 5)% th phn dng trong sn xut mt s dng dng c gii phu v chi tit
cm ghp lm bng s zirconia hon ton. Trong phm vi phn tip theo, bi trnh by ny s tip tc

trnh by cc kin thc v quy trnh cng ngh dng ch to v sn xut mt s thng phm s zirconia v mt s cng ngh mi trong k thut vt liu ng dng trong nghin cu v ng dng s zirconia trong nha khoa.
TI LIU THAM KHO:
[1] Gio trnh Cng ngh vt liu & C kh ng dng trong K thut phc hnh rng, o Ngc
Lm, B mn K thut Phc hnh rng, Khoa Rng Hm Mt, i hc Y Dc TP.HCM (lu hnh ni
b).
[2] Ceramic and Glass Materials: Structure, Properties and Processing, James F. Shackelford & Robert H. Doremus, 1st Edition, ISBN 978-0-387-73361-6, p.168-197, Springer Science+Business Media
LLC, 2008.
[3] The Fundamentals of Material Sciences and Engineering, William D. Callister, Jr., 5th Edition,
ISBN 0-471-39551-X, John Wiley & Sons, Inc., 2001.
[4] - Ab initio study of structural and electronic properties of yttria-stabilized cubic zirconia, G. Stapper, M. Bernasconi, N. Nicoloso, and M. Parrinello, Phys. Rev. B, 59(2), 797810 (1999).
[5] - Relative stability, structure, and elastic properties of several phases of pure zirconia, J.K. Dewhurst and J.E. Lowther, Phys. Rev. B, 57(2), 741747 (1998).
[6] - Transformation Toughening of Ceramics, Green, D.J.; Hannink, R.; Swain, M.V., ISBN 0-84936594-5, Boca Raton: CRC Press (1989).
[7] - A historical perspective of synthetic ceramic and traditional feldspathic porcelain, Chu S, and Ahmad I., Pract Proced Aesthet Dent. 2005 Oct;17(9):593-8; quiz 600.
[8] - Development of dental ceramics: An historical perspective, Jones D.W., Dent Clin North Am.
1985 Oct;29(4):621-44.
[9] Sintering and characterization of polycrystalline monoclinic, tetragonal, and cubic zirconia,R.A.
Cutler, J.R. Reynolds, and A. Jones, J. Am. Ceram. Soc. 75(8), 21732183 (1992).
[10] Fracture toughness of nanocrystalline tetragonal zirconia with low yttria content, A. BravoLeon, Y. Morikawa, M. Kawahara, and M.J. Mayo, , Acta Mater. 50, 45554562 (2002).
[11] - Physical Ceramics Principles for Ceramic Science and Engineering, Y.-M. Chiang, D. Birnie III,
and W.D. Kingery, Wiley Inc., New York, 1997, p. 484.
[12] The microstructure and mechanical properties of yttria-stabilized zirconia prepared by arc-melting, T. Sakuma, Y.-I. Yoshizawa, and H. Suto, J. Mater. Sci. 20, 23992407 (1985).
[13] Modern Ceramic Engineering Properties, Processing, and Use in Design, D.W. Richerson, 3rd
Edition, Taylor and Francis Group, Boca Raton, 2006, pp. 275, 643.
[14] High-density ZrO2 and HfO2: Crystalline structures and equations of state, S. Desgreniers and K.
Lagarec, Phys. Rev. B, 59(13), 84678472 (1999)
[15] Stability field of cotunnite-type zirconia, O. Ohtaka, S. Kume, and E. Ito, J. Am. Ceram.
Soc.73(3), 744745 (1990).