Size-dependent phase transitions in nanostructured zirconia-scandia solid solutions.

Size effects on phase stability and phase transitions in technologically relevant materials have received growing attention. Several works reported that metastable phases can be retained at room temperature in nanomaterials, these phases generally corresponding to the high-temperature polymorph of the same material in bulk state. Additionally, size-dependent shifts in solubility limits and/or in the transition temperatures for on heating or on cooling cycles have been observed. ZrO2-Sc2O3 (zirconia-scandia) solid solutions are known to exhibit very high oxygen ion conductivity provided their structure is composed of cubic and/or pseudocubic tetragonal phases. Unfortunately, for solid zirconia-scandia polycrystalline samples with typical micrometrical average crystal sizes, the high-conductivity cubic phase is only stable above 600°C. Depending on composition, three low-conductivity rhombo-hedral phases (β, γ and δ) are stable below 600°C down to room temperature, within the compositional range of interest for SOFCs. In previous investigations, we showed that the rhombohedral phases can be avoided in nanopowders with average crystallite size lower than 35 nm.

Sintesi e caratterizzazione di nanopolveri composite allumina-zirconia

Il presente lavoro di tesi riguarda la sintesi di nanopolveri allumina-zirconia, seguendo tre differenti metodologie (sintesi per coprecipitazione, sintesi con il metodo dei citrati, sintesi idrotermale assistita da microonde) e il trattamento termico (calcinazione) delle polveri ottenute, mediante tecniche di riscaldamento convenzionali ed alternative (microonde). Lo scopo del lavoro è consistito nell’individuare, tra le tecniche esaminate, quella più idonea e conveniente, per la preparazione di nanopolveri cristalline 95 mol% Al2O3 – 5 mol% ZrO2 e nell’esaminare gli effetti che la calcinazione condotta con le microonde, ha sulle caratteristiche finali delle polveri, rispetto ai trattamenti termici convenzionali. I risultati ottenuti al termine del lavoro hanno evidenziato che, tra le tecniche di sintesi esaminate, la sintesi idrotermale assistita da microonde, risulta il metodo più indicato e che, il trattamento termico eseguito con le microonde, risulta di gran lunga vantaggioso rispetto a quello convenzionale. La sintesi idrotermale assistita da microonde consente di ottenere polveri nano cristalline poco agglomerate, che possono essere facilmente disaggregate e con caratteristiche microstrutturali del tutto peculiari. L’utilizzo di tale tecnica permette, già dopo la sintesi a 200°C/2ore, di avere ossido di zirconio, mentre per ottenere gli ossidi di alluminio, è sufficiente un ulteriore trattamento termico a basse temperature e di breve durata (400°C/ 5 min). Si è osservato, inoltre, che il trattamento termico condotto con le microonde comporta la formazione delle fasi cristalline desiderate (ossidi di alluminio e zirconio), impiegando (come per la sintesi) tempi e temperature significativamente ridotti. L’esposizione delle polveri per tempi ridotti e a temperature più basse consente di evitare la formazione di aggregati duri nelle nanopolveri finali e di contrastare il manifestarsi di fenomeni di accrescimento di grani, preservando così la “nanostruttura” delle polveri e le sue caratteristiche proprietà.

Tris(trimethylsilyl)silyl stabilized phosphorus and lead clusters

Die Hypersilylgruppe (Me3Si)3Si stellt einen sehr sperrigen, Elektronen liefernden Substituenten dar und kann zur Stabilisierung niedriger Oxidationsstufen sowie ungewöhnlicher Strukturelemente dienen. Durch Reaktionen der base-freien Hypersilanide der Alkalimetalle sowie des Dihypersilylplumbandiyls mit unterschiedlichsten phosphorhaltigen Reagenzien konnten eine Reihe hypersilyl-stabilisierter Phosphor- und Bleicluster-Verbindungen erhalten werden. Kaliumhypersilanid reagiert in Toluol glatt mit weißem Phosphor bei Raumtemperatur in Toluol unter quantitativer Bildung von rotem Kalium-bis(hypersilyl)tetraphosphenid [(Me3Si)3Si]2P4K2 (1), einem Kaliumsalz des Tetraphosphens (Me3Si)3Si-PH-P=P-PH-Si(SiMe3)3. In Benzol oder Toluol steht 1 im Gleichgewicht mit dem dimeren Octaphosphanid [(Me3Si)3Si]4P8K4 (2). Bei längerem Stehen der toluolischen Lösungen zerfällt 1 langsam vermutlich in Folge einer Protolyse zum gelben Pentaphosphanid [(Me3Si)3Si]3P5K2 (4). Aus benzolischer Lösung konnte hingegen ein weiteres Oktaphosphanid, [(Me3Si)3Si]3P8K3 (5), isoliert werden. Führt man die Reaktion Kaliumhypersilanid mit P4 in stärker koordinierenden Lösungsmitteln wie Diethylether durch, so entstehen neben 1 größere Mengen des Triphosphenids [(Me3Si)3Si]2P3K (3); dieses enthält ein Triphosphaallyl-Anion mit partieller P-P-Doppelbindung. Setzt man Lithiumhypersilanid mit weißem Phosphor um, so beobachtet man eine vollständig andere Produktpallette. Als Hauptprodukte lassen Polyphosphane wie beispielsweise [(Me3Si)3Si]2P4 (6) nachweisen, das zu 1 analoge [(Me3Si)3Si]2P4Li2 (7) entsteht nur in vergleichsweise kleinen Mengen. In der Gegenwart von Hexahydro-1,3,5-trimethyl-S-triazin, entsteht aus Lithiumhypersilanid und P4 hingegen im wesentlichen [(Me3Si)3Si]2P3Li (8) neben beträchtlichen Mengen von (Me3Si)4Si. Dessen Bildung erfordert eine Si-Si-Bindungsspaltung im Verlauf der Reaktion. Die Reaktion von Natriumhypersilanid mit P4 verläuft sehr unübersichtlich, das Pentaphosphanid [(Me3Si)3Si]3P5Na2 (9) ist das einzige isolierbare Produkt. Setzt man 1 mit [(Me3Si)2Si]2Sn um, so bilden sich überraschenderweise, je nach verwendetem Solvens [(Me3Si)3Si]3P4SnK (10) oder [(Me3Si)3Si]2[(Me3Si)2N]P4SnK (11). Alle neuen Verbindungen wurden NMR-spektroskopisch charakterisiert, die Phosphenide 1, 7, 8 sowie die Phosphanide 2, 4, 5, 9, 10 darüber hinaus durch Kristallstrukturanalysen. Dihypersilylplumbandiyl und -stannandiyl reagieren bei tiefer Temperatur mit P4, MPH2 (M=Li, K), PMe3, and PH3 zu formalen Lewis-Säure-Base-Addukten. Die Addukte {[(Me3Si)3Si]2PbPH2}M [M = Li (15), K (18)], {{[(Me3Si)3Si]2Pb}2PH2}M [M = Li (19), K (20)], und [(Me3Si)3Si]2EPMe3 [E = Pb (21), Sn (22)] wurden als kristalline Feststoffe erhalten und konnten vollständig charakterisiert werden. Die metastabilen Addukte {[(Me3Si)3Si]2E}4P4 (E = Pb, Sn) und [(Me3Si)3Si]2PbPH3 konnten lediglich NMR-spektroskopisch nachgewiesen werden. Bei Raumtemperatur entstehen in Folge von Ligandenaustausch-Prozessen die kristallographisch charakterisierten Heterokubane [(Me3Si)3Si]4P4E4 [E = Pb (12), Sn (14)], das Diphosphen (Me3Si)3SiP=PSi(SiMe3)3 (13) sowie der Pb2P2-Heterocyclus [(Me3Si)3SiPbP(H)Si(SiMe3)3]2 (17). Bei tiefer Temperatur wird aus einer sehr langsamen Reaktion von Dihypersilylplumbandiyl und PH3 in sehr kleinen Ausbeuten ein weiteres, völlig unerwartetes Produkt gebildet: der Bleicluster [(Me3Si)3Si]6Pb12 (23). Er weist ein verzerrt ikosaedrisches, zentrosymmetrisches Pb12-Gerüst auf. Nach jetzigen Erkenntnissen läuft seine Bildung über das nicht fassbare Hydridoplumbandiyl HPbSi(SiMe3)3, das intermediär durch Substituentenaustausch zwischen Pb[Si(SiMe3)3]2 and PH3 entsteht. Der Ersatz des Phosphans durch andere Hydridquellen wie (Ph3PCuH)6, (iBu)2AlH, and Me3NAlH3 führt ebenfalls zur Bildung von Bleiclustern, allerdings ist jetzt der Cluster [(Me3Si)3Si]6Pb10 (24) das Hauptprodukt. Beide Cluster, 23 und 24, gehorchen den Wade-Regeln.

Are endodontically treated incisors reliable abutments for zirconia-based fixed partial dentures in the esthetic zone?

This ex vivo pilot study tested the influence of defect extension and quartz-fiber post placement (QFP) on the ex vivo survival rate and fracture resistance of root-treated upper central incisors served as abutments for zirconia 2-unit cantilever fixed partial dentures (2U-FPDs) exposed to 10 years of simulated clinical function.

Changes in retention force with electroplated copings on conical crowns: a comparison of gold and zirconia primary crowns

The aim of this study was to examine the wear behavior of conical crowns with electroplated gold copings that are used to connect implants and teeth to a removable denture. Gold alloy and zirconium dioxide ceramic crowns were compared.

Five-year results of a randomized controlled clinical trial comparing zirconia and titanium abutments supporting single-implant crowns in canine and posterior regions

OBJECTIVES: To test the survival rates, and the technical and biological complication rates of customized zirconia and titanium abutments 5 years after crown insertion. MATERIAL AND METHODS: Twenty-two patients with 40 single implants in maxillary and mandibular canine and posterior regions were included. The implant sites were randomly assigned to zirconia abutments supporting all-ceramic crowns or titanium abutments supporting metal-ceramic crowns. Clinical examinations were performed at baseline, and at 6, 12, 36 and 60 months of follow-up. The abutments and reconstructions were examined for technical and/or biological complications. Probing pocket depth (PPD), plaque control record (PCR) and Bleeding on Probing (BOP) were assessed at abutments (test) and analogous contralateral teeth (control). Radiographs of the implants revealed the bone level (BL) on mesial (mBL) and distal sides (dBL). Data were statistically analyzed with nonparametric mixed models provided by Brunner and Langer and STATA (P < 0.05). RESULTS: Eighteen patients with 18 zirconia and 10 titanium abutments were available at a mean follow-up of 5.6 years (range 4.5-6.3 years). No abutment fracture or loss of a reconstruction occurred. Hence, the survival rate was 100% for both. Survival of implants supporting zirconia abutments was 88.9% and 90% for implants supporting titanium abutments. Chipping of the veneering ceramic occurred at three metal-ceramic crowns supported by titanium abutments. No significant differences were found at the zirconia and titanium abutments for PPD (meanPPD(ZrO2) 3.3 ± 0.6 mm, mPPD(T) (i) 3.6 ± 1.1 mm), PCR (mPCR(Z) (rO) (2) 0.1 ± 0.3, mPCR(T) (i) 0.3 ± 0.2) and BOP (mBOP(Z) (rO) (2) 0.5 ± 0.3, mBOP(T) (i) 0.6 ± 0.3). Moreover, the BL was similar at implants supporting zirconia and titanium abutments (mBL(Z) (rO) (2) 1.8 ± 0.5, dBL(Z) (rO) (2) 2.0 ± 0.8; mBL(T) (i) 2.0 ± 0.8, dBL(T) (i) 1.9 ± 0.8). CONCLUSIONS: There were no statistically or clinically relevant differences between the 5-year survival rates, and the technical and biological complication rates of zirconia and titanium abutments in posterior regions.

Acid and alkali etching of grit blasted zirconia: Impact on adhesion and osteogenic differentiation of MG63 cells in vitro

There is a need for evaluating zirconia surface modifications and their potential impact on the biological response of osteogenic cells. Grit blasted zirconia discs were either left untreated or underwent acid or alkaline etching. Adhesion and osteogenic differentiation of MG63 cells was determined after one week of culture. The macro-scaled roughness of the grit blasted zirconia discs, independent of the surface treatment, was within a narrow range and only slightly smoother than titanium discs. However, the alkaline- and acid-etching led to an increase of the micro-roughness of the surface. The surface modifications had no effect on cell spreading and did not cause significant change in the expression of differentiation markers. Thus, in this respective setting, morphologic changes observed upon treatment of grit blasted zirconia discs with acid or alkaline do not translate into changes in MG63 cell adhesion or differentiation and are comparable to findings with anodized titanium discs.

Effect of zirconia surface treatments on the shear strength of zirconia/veneering ceramic composites

Aim of the investigation was to assess the effect of different surface treatments on the bond strength of veneering ceramics to zirconia. In a shear test, the influences of polishing, sandblasting, and silica-coating of the zirconia surface on bonding were assessed with five different veneering ceramics. In addition the effect of liner application was examined. With one veneering ceramic, the impact of regeneration firing of zirconia was also evaluated. Statistical analysis was performed with one-way ANOVA and post hoc Scheffé's test. Failure in every case occurred in the veneering ceramic adjacent to the interface with a thin layer of ceramic remaining on the zirconia surface, indicating that bond strength was higher than the cohesive strength of the veneering ceramic. Shear strength ranged from 23.5 +/- 3.4 MPa to 33.0 +/- 6.8 MPa without explicit correlation to the respective surface treatment. Regeneration firing significantly decreased the shear strength of both polished and sandblasted surfaces. Findings of this study revealed that bonding between veneering ceramics and zirconia might be based on chemical bonds. On this note, sandblasting was not a necessary surface pretreatment to enhance bond strength and that regeneration firing was not recommended.

Zirconia for teeth and implants

This case series reports on the use of nonsilica-based high-strength full ceramics for different prosthetic indications. Fifty-two consecutive patients received tooth- or implant-supported zirconia reconstructions during a 2-year period. The observation period for reexamination was 12 to 30 months. The most frequent indications were single crowns and short-span fixed partial dentures. A few implant superstructures were screw-retained, whereas all remaining restorations were cemented on natural teeth or zirconia implant abutments. Clinical examination included biologic (probing depths, bleeding on probing) and esthetic (Papilla Index) parameters, as well as technical complications. No implant was lost or caused any problems, but two teeth were lost after horizontal fracture. Overall, the periodontal parameters were favorable. Fractures of frameworks or implant abutments were not observed. Abutment-screw loosening occurred once for one premolar single crown. Furthermore, five implant crowns in the posterior region exhibited chipping of the porcelain veneering material. With regard to esthetics, no reconstructions were considered unacceptable, but three crowns were remade shortly after delivery. In this short-term study, it was observed that biologic, esthetic, and mechanical properties of zirconia were favorable, and the material could be used in various prosthetic indications on teeth or implants.

[Zirconia and removable partial dentures]

The present paper deals with the double crown technique in removable prosthodontics. New ceramic materials like zirconia are increasingly used in combination with CAD/CAM technologies for framework fabrication of fixed prosthesis, tooth- or implant-supported. However, zirconia is also a newly accepted material in removable prosthodontics. It replaces gold alloys for the fabrication of primary telescopic crowns. The Galvanoforming technology is preferably used to fabricate the secondary crowns. The combination of both techniques and materials results in a prosthetic reconstruction of high quality, optimum fit and good biocompatibility.

[Rehabilitation of a periodontally compromised dentition with implant-supported zirconia bridges. Case report]

Clinical aspects of reconstruction with fix prosthesis and dental implants in a patient with a history of periodontitis is shown. A successful stabilization and rehabilitation of the periodontally involved dentition can be achieved with tooth-worn crown and bridge reconstructions. From a functional and aesthetic point of view the result may not be satisfying due to mobility and overlength of the teeth and open approximal spaces. Today, dentist and patient have often to weigh if teeth shall be maintained or replaced by dental implants. Thereby, both must be aware of the fact that in complex cases long-term success and aesthetic outcome may be difficult to predict. An intense discussion with the patient on his expectations, invasive treatment, risks with regard to biologic and prosthetic aspects is mandatory and must be based on the best scientific evidence available. The present case report shows different considerations and describes a radical solution which meets the patient's needs and is based on modern CAD-CAM technology.

Marked Silence, Neo-Feudalistic Reactions and the Stabilized Moral Regime – The Current De- and Reformation of „the Social“

The German chancellor and leader of the German conservative party, Angela Merkel, said in an interview a few weeks ago: “Nobody could have imagined a few months ago to what extent we would be pushed into state intervention programs. Of course, Merkel spoke on, this intervention is not easy for anybody. Therefore, she recommended turning back to the former course as soon as possible” (tagesschau.de, 11. März 2008, zit. nach Bildzeitungsinterview mit Angela Merkel, own translation). The worldwide celebrated new president of the United States, Barack Obama, said in an interview on CBS-News a few weeks before Merkel: “(...) there's no doubt that we have not been able yet to reset the confidence in the financial markets and in the consumer markets and among businesses that allow the economy to move forward in a strong way. And my job as president is gonna be to make sure that we restore that confidence“ (CBS News, 16. November 2008, Obama On Economic Crisis, Transition; http://www.cbsnews.com/stories/2008/11/16/60minutes/main4607893.shtml; Stand: 16. April 2009).

Are implants more reliable than severely compromised endodontically treated teeth as abutments for zirconia-based FPDs? : In vitro results of long-term preclinical load simulation

OBJECTIVES The aim was to study the impact of the defect size of endodontically treated incisors compared to dental implants as abutments on the survival of zirconia two-unit anterior cantilever-fixed partial dentures (2U-FPDs) during 10-year simulation. MATERIALS AND METHODS Human maxillary central incisors were endodontically treated and divided into three groups (n = 24): I, access cavities rebuilt with composite core; II, teeth decoronated and restored with composite; and III as II supported by fiber posts. In group IV, implants with individual zirconia abutments were used. Specimens were restored with zirconia 2U-FPDs and exposed to two sequences of thermal cycling and mechanical loading. Statistics: Kaplan-Meier; log-rank tests. RESULTS During TCML in group I two tooth fractures and two debondings with chipping were found. Solely chippings occurred in groups II (2×), IV (2×), and III (1×). No significant different survival was found for the different abutments (p = 0.085) or FPDs (p = 0.526). Load capability differed significantly between groups I (176 N) and III (670 N), and III and IV (324 N) (p < 0.024). CONCLUSION Within the limitations of an in vitro study, it can be concluded that zirconia-framework 2U-FPDs on decoronated teeth with/without post showed comparable in vitro reliability as restorations on implants. The results indicated that restorations on teeth with only access cavity perform worse in survival and linear loading. CLINICAL RELEVANCE Even severe defects do not justify per se a replacement of this particular tooth by a dental implant from load capability point of view.