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The inuence of grain size on low-temperature degradation of dental zirconia

Lubica Hallmann,1 Albert Mehl,2 Peter Ulmer,3 Eric Reusser,3 Johannes Stadler,4 zcan,1 Christoph H. F. Ha Renato Zenobi,4 Bogna Stawarczyk,1 Mutlu O mmerle1
1

Clinic of Fixed and Removable Prosthodontics and Dental Material Science, Center of Dental Medicine, University of Zu rich, Zurich, Switzerland 2 Clinic of Preventive Dentistry, Periodontology and Cariology, Computer Assisted Restorations, Center of Dental Medicine, University of Zu rich, Zurich, Switzerland 3 Institute of Geochemistry and Petrology, ETH Zu rich, Switzerland 4 Department of Chemistry and Applied Biosciences, ETH Zu rich, Switzerland Received 13 July 2011; revised 29 August 2011; accepted 6 September 2011 Published online 25 November 2011 in Wiley Online Library (wileyonlinelibrary.com). DOI: 10.1002/jbm.b.31969 Abstract: The purpose of this study was to evaluate the inuence of grain size and air abrasion on low-temperature degradation (LTD) of yttria stabilized tetragonal zirconia polycrystalline (Y-TZP). Disc-shaped specimens were sintered at 1350, 1450, and 1600 C. Air abrasion was performed with different abrasive particles. The specimens were stored for 2 h at 134 C under 2.3 bar water vapor pressure. All specimens were characterized by X-ray powder diffraction analysis (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and eld emission scanning electron microscopy (FESEM). Y-TZP sintered at a temperature of 1350 C did not undergo the tm phase transformation during accelerated aging. The diffusion-controlled tm phase transformation initiated with the specimens sintered at 1450 C. This transformation was remarkable for the specimens sintered at 1600 C. X-ray photoelectron spectroscopy (XPS) measurements did not conrm the generation of Zr-OH and Y-OH bonds. No increase of yttrium concentration on the grain boundaries of Y-TZP was detected, which could be responsible for the destabilization of dental zirconia ceramics. A slight increase of diffusion-controlled tm phase transformations was observed for all abraded specimens sintered at 1350 and 1450 C. The size of abrasive particles did not play a crucial role on LTD of Y-TZP. The retardation of diffusion-controlled tm phase transformation was evident for all abraded specimens sintered at 1600 C by comparison to non-abraded specimens. Conclusion: The LTD of Y-TZP can be suppressed when the sintering temperature is set C 2011 Wiley Periodicals, Inc. J Biomed between 1350 and 1450 C. V
Mater Res Part B: Appl Biomater 100B: 447456, 2012.

Key Words: dental zirconia (Y-TZP), degradation, grain size, air abrasion, tensile stress

zcan M, Ha How to cite this article: Hallmann L, Mehl A, Ulmer P, Reusser E, Stadler J, Zenobi R, Stawarczyk B, O mmerle CHF. 2012. The inuence of grain size on low-temperature degradation of dental zirconia. J Biomed Mater Res Part B 2012:100B:447456.

INTRODUCTION

Dental zirconia ceramic, consisting of 3 mol % yttria stabilized tetragonal polycrystalline zirconia (Y-TZP), has excellent mechanical, biomedical, aesthetic properties with its semitranslucent and radiopacity features.13 The development of CAD/CAM systems, the increase in aesthetic demand and, worries about metallic hypersensitivity have increased the application of Y-TZP in dentistry. Y-TZP has extraordinary strength and toughness due to the transformation from the tetragonal to the monoclinic polymorph when external stress is applied.4,5 For these reasons, Y-TZP is used to substitute the traditional metal-based xed dental prosthesis (FDPs). Zirconia full-ceramic copings, FDP frameworks, and implant suprastructures are introduced to replace the traditionally used metals.4 However, the failure
Correspondence to: L. Hallmann; e-mail: lubica.hallmann@zzm.uzh.ch

of a number of zirconia hip joints has drawn the attention of researchers to the behavior of Y-TZP ceramics in humid environments. Fractures are often associated with a large amount of monoclinic phase created during tetragonal monoclinic phase transformation in the human body.6,7 This transformation reduces the mechanical properties of Y-TZP and is known as low-temperature degradation (LTD).6 The spontaneous transformation from the tetragonal into monoclinic structure initiates on the surface of Y-TZP via a stress corrosion type mechanism and proceeds to the bulk of the ceramic.4,7 The principal mechanism of LTD is diffusion-controlled, while the tm modication transformation, once nucleated, is martensitic.4 The transformation proceeds most rapidly at temperatures of 200300 C.8 The destabilization of the tetragonal phase is accompanied by the

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formation of micro- and macrocracks and is dependent on the concentration of the stabilizer, and the grain size of ceramic.610,11 Y-TZP undergoes a stress-induced volume-expansion phase transformation during air abrasion. Flaws or microcracks can thereby be introduced in the Y-TZP surface.12,13 The pre-existing monoclinic phase on the air-abraded Y-TZP surface hinders the propagation of the diffusion-controlled transformation during accelerated aging.4 The aging of zirconia is a serious problem for the orthopedic community.4 In conventional dental applications, the zirconia core or framework is not in contact with the oral environment and hard dental tissues due to veneering and luting materials and the problem seems not to be predominant.4 However, the luting resin could absorb water via dental tubules and the zirconia core and framework exposed to water may suffer from aging degradation.4 Additionally, more and more fully ceramic zirconia restorations are inserted, where zirconia surfaces are directly opposed to the intraoral environment. Several theoretical causes have been proposed to explain the mechanism of LTD. Sato et al. suggested the chemical reaction of water with Zr-O-Zr bonds at the pre-existing surface aws.9 This reaction is associated with the formation of Zr-OH bonds, releasing the strain that stabilizes the tetragonal phase, thus promoting the tm phase transformation.9 The phase transformation starts at the surface and propagates into the interior.9 According to Lange et al., the water reacts with Y2O3 at the surface of the zirconia and clusters of Y(OH)3 are formed, leading to the depletion of stabilizers from the grains and the spontaneous tm transformation takes places in the grains.10 Yoshimura et al. explained the degradation of Y-TZP with the annihilation of oxygen vacancies and about 60% of these vacancies are occupied by OH anions.14 The OH anions would migrate faster than O2 because of less charge and similar size.14 These authors did not accept the depletion of yttrium as the result of Y(OH)3 formation or the dissolution of Y3 during hydrothermal treatment. According to Hughes et al., the generation of O2 is responsible for the rapid annealing of surface oxygen vacancies.15 The penetration of O2 into the lattice destabilizes the t-phase and the transformation or nucleation of the m-phase domains occurs.15 Oxygen vacancies play an important role in the stabilization of the metastable tetragonal and cubic structure.16 Fabris et al. employed a self-consistent tight-binding model to constrain that the stabilization of the cubic and tetragonal structure could be achieved by introducing oxygen vacancies into the zirconia lattice.17 Guo related the LTD with annihilation of oxygen vacancies that stabilize the metastable tetragonal phase through the OH group.18 Chevalier proposes that the lling of oxygen vacancies with O2 and not OH ions may be responsible for low-temperature degradation of zirconia.6 The O2 ions originate from the dissociation of water on the surface of Y-TZP ceramic.6 The processes of low-temperature degradation (LTD) can effectively be simulated at 134 C, under a water vapor pressure of 2 bar. One hour of this treatment corresponds roughly to 4 years of aging in human environment.7

Therefore, the purpose of the present study was to evaluate the effect of grain size, aws, and pre-existing monoclinic phase created during air abrasion on the lowtemperature degradation (LTD) of dental Y-TZP ceramic under above-mentioned conditions. One of the most important factors on LTD mechanism of dental zirconia is tensile strain, which is grain size dependant. An additional goal of this study was to test the idea that aws, micro-cracks, and pre-existing monoclinic phase play a certain role on the LTD of Y-TZP, but the most important factor is the critical grain size. An attempt was made to ascertain the proper mechanism of LTD during the accelerated aging of Y-TZP ceramic. The working hypothesis was that the resulting LTD of Y-TZP ceramic under hydrothermal condition is not primarily controlled by the concentration gradient of yttrium on grain boundaries and/or the Zr-OH and Y-OH bonds formation resulting from OH anion diffusion, but critically depends on the species that diffuse rapidly in the lattice of Y-TZP ceramic.
MATERIALS AND METHODS

Specimen preparation Y-TZP ceramic blanks (Cercon base, DeguDent, Hanau, Germany) (ZrO2, 5% Y2O3, < 2% HfO2, < 1% Al2O3 SiO2) were cut with a cutting machine (Precision Diamond Wire Saw, Well, Switzerland) into discs (diameter: 25 mm, thickness: 3 mm) under copious water (n 216). The specimens were sintered in a programmable oven (Cercon heat, DeguDent, the sinter temperature was set to 1350 C for 2 h). Other specimens were sintered at 1450 and 1600 C for 2 h with heating and cooling rates of 10 C/min (Nabertherm, Switzerland). The specimens were divided randomly into six main groups and each main group was divided into four subgroups (see Table I). The specimens were abraded with different air-borne particles (50 and 110 lm alumina, 30 and 110 lm silica-coated alumina particles) at a pressure of 2.5 bar for 15 s/cm2 from a distance of 10 mm (LEMAT NT4, Wassermann, Germany). After air abrasion, all specimens were rst air-blown at a pressure of 3 bar for 1 min and then ultrasonically cleaned in 99.8% isopropanol (Merck, Darmstadt, Germany) for 20 min (Brasonic Ultrasonic Cleaner, Danbury) at a frequency of 42 kHz. The acceleration aging of specimens was performed under autoclave conditions of 134 C and a water vapor pressure of 2.3 bar for a duration of 2 h (GETINGE industriv 5 SE-471 31 Ska rhamn, Sweden). Ceramic veneering simulation was performed in an oven (Austromat M, Dekema, Freilassing, Deutschland) at 830 C for 1 min. The heating rate was set to 55 C/min. Additional ceramic veneering simulations were conducted at 820, 810, and 800 C. The holding time for these temperature treatments was 1 min and the heating rate was 45 C/min. Phase transformation Tetragonal (t)monoclinic (m) phase transformations of YTZP ceramics were analyzed with X-ray powder diffraction technique (Bruker, AXS D8 Advance) using Cu Ka1 X-rays.

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TABLE I. Preparation of Specimens (72 Groups With Each n 3 Specimens) Specimens Y-TZP sintered at 1350, 1450, and 1600 C Treatment Main group a Subgroups: a0 control specimens a00 aged specimens a000 aged specimens rst ceramic veneering stimulation a0000 aged specimens fourth ceramic veneering stimulations Main group b Subgroups: b0 abraded specimens with 50 lm alumina particles b00 abraded specimens aging b000 abraded and aged specimens rst ceramic veneering stimulation b0000 abraded and aged specimens fourth ceramic veneering stimulations Main group c Subgroups: c0 abraded specimens with 110 lm alumina particles c00 , c000 , c0000 the specimens are treated as specimens of main group b Main group d Subgroups: d0 abraded specimens with 30 lm silica-coated alumina particles d00 , d000 , c0000 ; the specimens are treated as specimens of main Group b Main group e Subgroups: e0 abraded specimens with 110 lm silica-coated alumina particles e00 , e000 , c0000 the specimens are treated as specimens of main group b Main group f Subgroups: f0 abraded specimens with 110 lm alumina particles followed by 110 lm silica-coated alumina particles (Rocatec system) f00 , f000 , f0000 the specimens are treated as the specimens of main group b

Ceramic veneering simulation was performed at 830 C with heating rate of 55 C/min and 820, 810, and 800 C with heating rate of 45 C/min. The holding time was 1 min for each temperature.

The diffraction proles were acquired from 25.5 to 29 (2h) with a step size of 0.001 and counting time of 2 s/step, and from 25 to 37 (2h) with a step size of 0.006 and counting time of 2 s/step. Raman spectroscopy was additionally employed to investigate the tm phase transformation. High-resolution AFM and confocal Raman measurements were conducted on a combined confocal Raman system and AFM instrument (Spectra Ntegra upright, NTMDT, Russia) equipped with a 100 0.7 NA objective (Mitutoyo, Japan), a 632.8 nm HeNe laser (up to 3 mW), a 100 100 10 lm piezo scanner, and non-contact cantilever-based AFM probes (ATEC-NC, NanoSensors, Switzerland) for atomic force microscopy. Surface elemental composition The surface chemistry of the specimens was investigated by means of X-ray photoelectron spectroscopy (XPS). The analyses were performed with a PHI Quantera SXM (ULVAC-PHI, Chanhassen, MN) spectrometer. All XPS spectra were collected at an emission angle of 45 using a beam size of 200 lm with a power of 50 W in the constantanalyzer energy (CAE) mode. High-resolution spectra were acquired using a pass energy of 55 eV and a step size of 0.1 eV (fullwidth-at-half-maximum (FWHM) of the peak height for Ag 3d5/2 0 0.64 eV). Survey spectra were collected with a pass energy of 280 eV and a step size of 1 eV. A high-perform-

ance, oating-column ion gun, and an electron neutralizer were used for charge compensation. The residual pressure in the analysis chamber was below 5 107 Pa. The spectrometer was calibrated according to ISO 15472:2001 with an accuracy of 60.1 eV. Surface topography The topography of the Y-TZP ceramic surface before and after aging was investigated using AFM and FESEM. The images were acquired using a BRUKER N8 RADOS scanning probe microscope as follows: Aged specimens which were sintered at 1350 and 1600 C: N8 RADOS equipped with NANOS 806, 80 80 lm2 maximal scan area, 6 lm Z-range, active vibration isolation, acoustic enclosure. Sintered specimens at 1350 and 1600 C: N8 NEOS equipped with NANOS 806, (80 80 lm2) maximal scan area, 6 lm Z-range. Measurement Parameters: * Dynamic (intermittent contact) mode. * Free amplitude was varied between 10 and 170 nm. * Damping set point was varied 58 and 70%. * Scan speed: 0.5 line per second. The phase images were acquired simultaneously with the topography images.

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FIGURE 1. XRD patterns of YTZP specimens before and after aging at the range of 27.529 (2y). [Color gure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

FESEM experiments were carried out with a Carl Zeiss Supra 50 VP FESEM (Oberkochen, Germany). The acceleration voltage of the cathode was 530 kV. All specimens were palladium gold coated before FESEM examinations.
RESULTS

Phase identication Figure 1 displays the X-ray diffraction pattern (XRD) of YTZP sintered at various temperatures (1350, 1450, and 1600 C) over the range 27.529 (2h) before and after aging. The proles are zoomed in this range because the tm phase transformation can visually be identied. For specimens sintered at 1350 C, the tm phase transformation after aging for 2 h at 134 C and under water vapor pressure of 2.3 bar, was not observed [Figure 1(a), plot a00 ], whereas the specimens sintered at 1450 and 1600 C showed the tm transformation [Figure 1(b,c), plots a00 ]. After air abrasion with different air-borne particles, a detectable monoclinic peak with orientation m(11-1) was discernable [Figure 1(af), plots; b0 f0 ]. The intensity of this peak was increased after accelerated aging for abraded specimens [Figure 1(af), plots b00 f00 ]. In contrast, the intensity of these peaks decreased after the ceramic veneering simulation at 830 C for 1 min. [Figure 1(bf), plots a000 f000 ]. The highest extent of tm phase transformation was observed for Y-TZP sintered at 1600 C. A retardation of the

tm phase transformation was evident for all the abraded specimens sintered at 1600 C in comparison with nonabraded specimens [Figure 1(c,f)]. Figure 2 reveals the effect of low-temperature degradation (LTD) at 134 C under a water vapor pressure of 2.3 bar of Y-TZP ceramic sintered at different temperatures over a range of diffraction angles from 25 to 39 (2h). The X-ray diffraction patterns of non-aged and aged specimens sintered at 1350 C are similar and clearly indicate the missing of a tm phase transformation [Figure 2(a)]. The effects of accelerated aging on the tm phase transformation for YTZP ceramic sintered at 1450 and 1600 C are shown in Figure 2(c,e). Compared to the non-aged Y-TZP specimens, the aged Y-TZP specimens sintered at 1600 C contains the highest concentration of the monoclinic phase. The reverse m-t phase transformation took place after ceramic veneering simulation. The intensity of the m(11-1) peak in this case decreased accompanied by an increase of the t(111) peak intensity. However, a small proportion of monoclinic phase seems to be present in both cases, but for the specimen sintered at 1600 C the amount of non-transformed monoclinic phase was higher than for the specimen sintered at 1450 C [Figure 2(c,e) and plots a0 , a00 , and a000 ]. After air abrasion, the monoclinic peak m(11-1) and a remarkable t(111) peak broadening accompanied by the reversed intensity of the tetragonal t(002) and t(020) peaks were observed in all

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FIGURE 2. XRD pattern of YTZP specimens before and after aging at the range of 2537 (2y). [Color gure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

XRD patterns. After accelerated aging, the intensity of m(111) peak was only slightly increased for the abraded specimens sintered at 1350 C followed by the specimens sintered at 1450 C, whereas the specimens sintered at 1600 C resulted signicantly higher tm phase transformation [Figure 2(b,d,f,g)]. The intensity of the m(11-1) peak and the broadening of the t(111) peak were reduced for all specimens after the rths ceramic veneering stimulation. After that no intensity change of the m(11-1) and t(111)

peaks was evident after the fourth ceramic veneering stimulation. Figure 3 presents Raman spectra of Y-TZP ceramic. It is evident from the Raman spectra that major bands are located at 141, 255, 315, 462, and 641 cm1. The peak at 635 cm1 has a shoulder at 603 cm1. These peaks are characteristic for the tetragonal phase of Y-TZP ceramic.1922 The peaks at 175 and 373 cm1 are characteristic for a monoclinic structure.2325 The weak peak at 550 cm1 likewise is

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3d core level was not observed. Such a positive shift would be indicative for the formation of M-OH bonds. No remarkable change of the binding energy for the aluminium ion was detected from the Al 2p spectra [Figure 4(e)]. Figure 4(f) shows the energy binding of the O 1s core level before and after aging. The peak at low binding energy is assigned to oxygen in the metal-O-metal bond. The shoulder at higher binding energy 530.4531 eV (Table III) could be assigned to the OH bond, absorbed water, or oxygencarbon bonds.

FIGURE 3. Raman spectra of Y-TZP specimens before and after aging. [Color gure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

attributed to the monoclinic phase (Table II). Comparing plots 3a, b and c reveals that the distribution of the monoclinic phase for aged Y-TZP sintered at 1600 C was not homogenous.

Surface elemental composition The survey XPS spectra [Figure 4(a)] revealed that the elemental composition of the Y-TZP ceramic surface did not change after accelerated aging at a temperature of 134 C under a water pressure of 2.3 bar for 2 h. The C 1s peak of all the specimens resulted from an overlaying contaminating hydrocarbon layer, which was unavoidable during XPS measurement [Figure 4(b)]. Figure 4(c) compares the Zr 3d spectra obtained before and after accelerated aging for the Y-TZP sintered at three different temperatures. The binding energies of Zr 3d3/2 and Zr 3d5/2 were 183.2183.6 eV and 180.8182.2 eV, respectively (Table III). The binding energy of the Zr 3d core was shifted for 0.3 eV to negative values for aged specimens sintered at 1600 C. The Y 3d spectra are shown in Figure 4(d). The binding energy of Y 3d3/2 and Y 3d5/2 varied from 158.0 to 158.4 eV and 156.0 to 156.5 eV, respectively. The Y 3d core peaks were shifted for 0.4 eV to negative values for the samples sintered at 1600 C. A positive shift of binding energy for Zr 3d and Y

Surface topography Figure 5 shows the AFM images of surface morphology of YTZP ceramic, which was sintered at 1350 and 1600 C before and after aging. No change of the surface morphology and/or roughness of non-aged and aged Y-TZP ceramic, sintered at 1350 C, was not observable. The roughness for non-aged and aged Y-TZP ceramic surface was 10.37 and 8.97 nm, respectively. Figure 5(a0 d0 ) presents AFM images of the surface morphology of Y-TZP ceramic sintered at 1600 C, indicating that a change of grain topography occurred as the grain surfaces were not at after accelerated aging. The monoclinic phase precipitated as dispersed lenses in the tetragonal matrix phase. The roughness of YTZP ceramic surface increased after accelerated aging to 9.75 and 15.3 nm for non-aged and aged Y-TZP ceramic surfaces, respectively. Figure 6 displays the FESEM images of non-aged and aged Y-TZP ceramics, which were sintered at different temperatures. The average grain size was small (about 0.21 lm) and not homogenous for the specimens sintered at 1350 C. The same applied to the specimens sintered at 1450 and 1600 C, with a grain size of 0.3 and 0.72 lm, respectively. After accelerated aging, the grains of specimens sintered at temperature1350 and 1450 C appeared not to be uplifted in contrast to the specimen sintered at 1600 C. The surface of aged Y-TZP sintered at 1600 C was damaged as a result of volume increasing during tm phase transformation and holes were created [Figure 6(f)]. Figure 6(h) shows the precipitation of the monoclinic phase as dispersed lenses. The EDS measurements did not reveal any change in the yttrium concentration before and after accelerated aging of Y-TZP ceramic sintered at different temperatures. Screening of elemental composition for grain surface

TABLE II. Wave Number (in cm1) of Raman Vibration Bands for the Tetragonal and Monoclinic Structure of Y-TZP Ceramics Specimens Sintered specimen at 1350 C Aged specimen (sintered at 1350 C) Sintered specimen at 1450 C Aged specimen (sintered at 1450 C) Sintered specimen at 1600 C (a) Aged specimen (sintered at 1600 C) (b) Aged specimen (sintered at 1600 C) (c) Aged specimen (sintered at 1600 C) Specimens (b) Aged specimen (sintered at 1600 C (c) Aged specimen (sintered at 1600 C)


Tetragonal Phase 141 141 144 143 144 142 144 141 175 175 254 254 258 257 257 256 258 256 187 187 314 314 318 316 318 317 319 323 Monoclinic 377 374 458 458 462 462 462 460 464 466 Phase 601 601 604 604 604 604 604
sh sh sh sh sh sh sh

637 637 641 640 640 639 640 634

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FIGURE 4. XPS spectra of Y-TZP ceramic surfaces before and after aging. [Color gure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

and boundary concentration changes showed a homogenous distribution of yttrium across the surface and no concentration gradient in the grain-boundary region was observed (Table IV).
DISCUSSION

Low-temperature degradation (LTD) of dental zirconia by annealing in water vapor is dependent on several factors such as crystal structure, grain size, the amount of dopant, residual stress. In this study, the stress-induced tm phase transformation of Y-TZP started at a sintering temperature of 1450 C. The highest transformation rate observed for YTZP ceramic sintered at 1600 C can be explained by increased tensile stresses, as larger grain sizes correspond to a larger tensile stress (this work will be soon submitted). The grains of Y-TZP sintered at 1350 C were more spherical than the grains of Y-TZP sintered at 1450 C, while the grains of Y-TZP sintered at 1600 C were attened and enlarged. The stress distribution is more uniform for the spherical grains than for the at grains. The tensile and compressive stresses are present in the sintered ceramic, but the ratios

of these stresses depend of the sintering temperature. The slight increasing of the extent of the tm phase transformation observed for aged ceramic sintered at 1450 C implies that this ratio was changed in favor of tensile stress in comparison to the ceramic sintered at 1350 C. Some groups of Y-TZP ceramic surfaces in this study were abraded before accelerated aging. The aim was to investigate the effect of micro-cracks that were introduced on the Y-TZP ceramic surface during air abrasion. There are studies which relate the propagation of the tm phase transformation to the creation of micro-cracks during accelerated aging.26,27 Micro-cracks served as preferential paths for water diffusion inside the bulk of the Y-TZP ceramic.28 The air abrasion induced the tm phase transformation, plastic deformations, aws, grooves, cracks, and impinging of air-borne particles on the surface of the ceramic. The compressive stresses created during the air abrasion serve to inhibit micro-crack extension.4 Our study showed that the air abrasion was responsible for the retardation of diffusion controlled tm phase transformation for Y-TZP ceramic sintered at 1600 C. The slight increasing of the tm phase

TABLE III. Binding Energies (in eV) of Zr 3d, Y 3d, Al 2p, and O 1s Core Levels Specimens Sintered specimen at 1350 C Aged sintered specimen at 1350 C Sintered specimen at 1450 C Aged sintered specimen at 1450 C Sintered specimen at 1600 C Aged sintered specimen at 1600 C


Zr 3d3/2 183.2 183.2 183.5 183.4 183.6 183.3

Zr 3d5/2 180.8 180.8 181.2 181.1 181.2 180.9

Y 3d3/2 158.0 158.0 158.2 158.0 158.5 158.1

Y 3d5/2 156.0 156.0 156.2 156.0 156.5 156.2

Al 2p 73.0 73.1 73.2 73.1 73.5 73.5

O 1s 528.6 528.8 528.9 528.7 529.1 528.8

O 1s 530.0 530.5 530.8 531.0 531.2 531.2

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FIGURE 5. AFM images of Y-TZP ceramic surfaces before and after aging for specimens sintered at 1350 and 1600 C. [Color gure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

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FIGURE 6. FESEM images of the specimens sintered at 1350, 1450, and 1600 C before and after aging.

transformation for aged Y-TZP sintered at 1350 and 1450 C after air abrasion in comparison with non-abraded Y-TZP ceramic can be explained by the different stresses which predominate in these ceramics before and after air abrasion. After air abrasion, this ratio changed in favor of tensile stresses, which were responsible for contrasting behaviors of sintered and abraded ceramics sintered at these temperatures. The grain size of abrasive particles did not play a crucial role on LTD of Y-TZP sintered at different temperatures. The binding energy shift of a core-electron is related to the change of the chemical environment of the element. The negative shift of the Zr 3d binding energy for the specimen sintered at 1600 C after aging in this study indicates a change of the chemical state for the zirconium ion. Binding energy reduction of a metal ion is an indication for an increasingly covalent bond formation,29 whereas the formation of a Zr-OH bond shows a higher binding energy than that of ZrO2 for the same oxidation state.30 It may therefore be suggested that the partial reduction of Zr4 to Zr3 took place and the conversion of ZrO2 to suboxides ZrOx occurred during aging process.31 The lack of a positive shift for the zirconium and yttrium ions shown in this study indicated that Zr-OH and Y-OH bonds were not introduced into the Y-TZP lattice. The lack of concentration gradients for yttrium ions at the grain boundaries does not support the theory of LTD occurring through the depletion of yttrium ions from the lattice of Y-TZP ceramic.

The theoretical atomistic study of Kushima et al. conducted to explain the mechanism of oxygen anion transport in anion conducing ceramic reveled that the biaxial tensile lattice stress is a very important factor for the migration of oxygen vacancies by the hopping mechanism.28 The energy barrier of migrating vacancies is affected by the migration space, cation-oxygen bond strength, and additional factors. The increase of cationcation distances and the weakness of the cationoxygen bond strength decrease the migration energy barrier of vacancies. The oxygen ions migrate after the same mechanism as vacancies. These authors found that the macroscopic oxygen diffusivity increases exponentially in yttria stabilized zirconia up to a critical value of biaxial tensile stress, especially at lower temperatures. Beyond this critical value of lattice stress, the migration of oxygen decreases due to local relaxation.28 The higher tm phase transformation rate during accelerated aging observed for sintered Y-TZP at 1600 C in this study conrms their calculations. There is a debate32 about the species that are responsible for stress induced tm phase transformation of Y-TZP ceramic. The backward phase transformation m-t observed during the rst ceramic veneering simulation provides information about these species. This transformation took place very fast at the beginning and thereafter the reversible reaction is retarded. The full reversible reaction took place at higher temperatures only. This implies that the species that

TABLE IV. Elemental Compositions in wt % of Non-aged and Aged Y-TZP Ceramic in Terms of Zr and Y Zr (wt %) Grain Sintered zirconia at 1350 C Aged zirconia (sintered at 1350 C) Sintered zirconia at 1450 C Aged zirconia (sintered at 1450 C) Sintered zirconia at 1600 C Aged zirconia (sintered at 1600 C)


Y (wt %) Boundary 78.70 77.97 78.48 79.27 78.31 78.96 Grain 7.08 6.85 7.04 7.12 7.47 8.53 Boundary 7.12 6.91 7.35 7.21 7.78 7.78

78.55 78.37 78.63 79.35 78.45 78.69

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are involved in this transformation moved very fast at rst and after that, due to the alteration of the lattice stress, the migration barrier energy increased. The surface of Y-TZP serves as a catalyst for the dissociation of water into O2 and H ions. H ions, therefore, probably play a crucial role on LTD of Y-TZP. For a full understanding of the LTD mechanism, additional theoretical calculations at an atomistic scale are required. The biaxial tensile stress is one of the factors which control the diffusion of vacancies and oxygen into the lattice of Y-TZP. The role of hydrogen on the LTD mechanisms is not yet clear and request complementary measurements which are beyond the scope of this article.

CONCLUSION

1. The degradation of Y-TZP ceramic at the condition of accelerated aging is strongly dependent on the grain sizes. 2. When the grain size has achieved the critical value, which is about 0.3 lm, the tm phase transformation occurred. 3. Y-TZP sintered at 1600 C resulted the highest rate of degradation (average grain size was about 0.72 lm). 4. Flaws and cracks which were induced on the surface of Y-TZP through the air abrasion process were not an important factor for the LTD. The size of air-borne particles was not a crucial factor on the LTD. The retardation of LTD caused by air abrasion was observed for sintered specimens at 1600 C. 5. The formation of Y-OH and Zr-OH bonds was not observed. The concentration gradient of yttrium ions on the surface of grains or on the grain boundaries did not take place. 6. A stable Y-TZP can be achieved from a sintering temperature ranging between 1350 and 1450 C.
ACKNOWLEDGMENTS

The authors thank Prof. N. Spencer and Mr. F. Mangolini from the Surface & Science Technology, Department of ETH Zu rich for XPS measurements, Dr. Igor Nemeth Bruker Nano GmbH Berlin for AFM measurements, Dr. L Vo lkl of Degudent for the Y-TZP blanks, Prof. Gauckler from the Nonmetallic Inorganic Materials, Swiss Federal Institute of Technology, Department of Materials of ETH Zu rich for his advice.

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