Effect of framework soldering on the deformation of implant abutments after framework seating: a study with strain gauges

Introduction: Passive fit has been considered an important requirement for the longevity of implant-supported prostheses. Among the different steps of prostheses construction, casting is a feature that can influence the precision of fit and consequently the uniformity of possible deformation among abutments upon the framework connection. Purpose: This study aimed at evaluating the deformation of abutments after the connection of frameworks either cast in one piece or after soldering. Materials and Methods: A master model was used to simulate a human mandible with 5 implants. Ten frameworks were fabricated on cast models and divided into 2 groups. Strain gauges were attached to the mesial and distal sides of the abutments to capture their deformation after the framework’s screw retentions were tightened to the abutments. Results: The mean values of deformation were submitted to a 3-way analysis of variance that revealed significant differences between procedures and the abutment side. The results showed that none of the frameworks presented a complete passive fit. Conclusion: The soldering procedure led to a better although uneven distribution of compression strains on the abutments.

Análise tomográfica para colocação de parafusos em C2 nos pacientes com artrite reumatoide

OBJETIVO: A análise morfológica da estrutura óssea de C2, em pacientes com artrite reumatoide, com o objetivo de aumentar a segurança de procedimentos de estabilização desta vértebra. MÉTODOS: Analisamos retrospectivamente 20 tomografias de coluna cervical realizadas em pacientes com artrite reumatoide, foram medidos os seguintes parâmetros: o ângulo espinolaminar, espessura e comprimento da lâmina de C2. RESULTADOS: Os valores médios encontrados são: espessura das lâminas direita 5,92mm e esquerda 5,87mm; comprimento das lâminas direita 27,75mm e esquerda 27,94mm e ângulo espinolaminar 44,7(0). CONCLUSÃO: Os valores obtidos são compatíveis com os de estudos realizados em indivíduos normais publicados por outros autores, não havendo aparente necessidade de alteração na técnica para colocação dos parafusos. Nível de Evidência IV, Série de casos.

Accuracy, precision and robustness of different methods to obtain samples from silages in fermentation studies

The objective of this study was to evaluate accuracy, precision and robustness of two methods to obtain silage samples, in comparison with extraction of liquor by manual screw-press. Wet brewery residue alone or combined with soybean hulls and citrus pulp were ensiled in laboratory silos. Liquor was extracted by a manual screw-press and a 2-mL aliquot was fixed with 0.4 mL formic acid. Two 10-g silage samples from each silo were diluted in 20 mL deionized water or 17% formic acid solution (alternative methods). Aliquots obtained by the three methods were used to determine the silage contents of fermentation end-products. The accuracy of the alternative methods was evaluated by comparing mean bias of estimates obtained by manual screw-press and by alternative methods, whereas precision was assessed by the root mean square prediction error and the residual error. Robustness was determined by studying the interaction between bias and chemical components, pH, in vitro dry matter digestibility (IVDMD) and buffer capacity. The 17% formic acid method was more accurate for estimating acetic, butyric and lactic acids, although it resulted in low overestimates of propionic acid and underestimates of ethanol. The deionized water method overestimated acetic and propionic acids and slightly underestimated ethanol. The 17% formic acid method was more precise than deionized water for estimating all organic acids and ethanol. The robustness of each method with respect to variation in the silage chemical composition, IVDMD and pH is dependent on the fermentation end-product at evaluation. The robustness of the alternative methods seems to be critical at the determination of lactic acid and ethanol contents.

Morse taper implants at different bone levels: a finite element analysis of stress distribution

AIM: To explore the biomechanical effects of the different implantation bone levels of Morse taper implants, employing a finite element analysis (FEA). METHODS: Dental implants (TitamaxCM) with 4x13 mm and 4x11 mm, and their respective abutments with 3.5 mm height, simulating a screwed premolar metal-ceramic crown, had their design performed using the software AnsysWorkbench 10.0. They were positioned in bone blocks, covered by 2.5 mm thickness of mucosa. The cortical bone was designed with 1.5 mm thickness and the trabecular bone completed the bone block. Four groups were formed: group 11CBL (11 mm implant length on cortical bone level), group 11TBL (11 mm implant length on trabecular bone level), group 13CBL (13mm implant length on cortical bone level) and group 13TBL (13 mm implant length on trabecular bone level). Oblique 200 N loads were applied. Von Mises equivalent stresses in cortical and trabecular bones were evaluated with the same design program. RESULTS: The results were shown qualitatively and quantitatively by standard scales for each type of bone. By the results obtained, it can be suggested that positioning the implant completely in trabecular bone brings harm with respect to the generated stresses. Its implantation in the cortical bone has advantages with respect to better anchoring and locking, reflecting a better dissipation of the stresses along the implant/bone interfaces. In addition, the search for anchoring the implant in its apical region in cortical bone is of great value to improve stabilization and consequently better stress distribution. CONCLUSIONS: The implant position slightly below the bone in relation to the bone crest brings advantages as the best long-term predictability with respect to the expected neck bone loss.

Assessment of changes in smile after rapid maxillary expansion

INTRODUCTION: This study evaluated changes in the smile characteristics of patients with maxillary constriction submitted to rapid maxillary expansion (RME). METHODS: The sample consisted of 81 extraoral photographs of maximum smile of 27 patients with mean age of 10 years, before expansion and 3 and 6 months after fixation of the expanding screw. The photographs were analyzed on the software Cef X 2001, with achievement of the following measurements: Transverse smile area, buccal corridors, exposure of maxillary incisors, gingival exposure of maxillary incisors, smile height, upper and lower lip thickness, smile symmetry and smile arch. Statistical analysis was performed by analysis of variance (ANOVA), at a significance level of 5%. RESULTS: RME promoted statistically significant increase in the transverse smile dimension and exposure of maxillary central and lateral incisors; maintenance of right and left side smile symmetry and of the lack of parallelism between the curvature of the maxillary incisal edges and lower lip border. CONCLUSIONS: RME was beneficial for the smile esthetics with the increase of the transverse smile dimension and exposure of maxillary central and lateral incisors.

cis-Bis(1,10-phenanthroline-j2N,N0)bis-(pyridin-4-amine-jN1)ruthenium(II) bis(hexafluoridophosphate)

In the title complex, [Ru(C12H8N2)2(C5H6N2)2](PF6)2, the RuII atom is bonded to two -diimine ligands, viz. 1,10- phenanthroline (phen), in a cis configuration, in addition with with two 4-aminopyridine (4Apy) ligands, resulting in a distorted octahedral coordination geometry. N—H F hydrogen-bonding interactions play an important role in the crystal assembly: 21-screw-axis-related complex molecules and PF6 counter-ions alternate in helical chains formed along the a axis by means of these contacts. N—H contacts (H centroid = 3.45 A ° ) are responsible for cross-linking between the helical chains along [001].

A control and automation system for wave basins

This paper presents the new active absorption wave basin, named Hydrodynamic Calibrator (HC), constructed at the University of São Paulo (USP), in the Laboratory facilities of the Numerical Offshore Tank (TPN). The square (14 m 14 m) tank is able to generate and absorb waves from 0.5 Hz to 2.0 Hz, by means of 148 active hinged flap wave makers. An independent mechanical system drives each flap by means of a 1HP servo-motor and a ball-screw based transmission system. A customized ultrasonic wave probe is installed in each flap, and is responsible for measuring wave elevation in the flap. A complex automation architecture was implemented, with three Programmable Logic Computers (PLCs), and a low-level software is responsible for all the interlocks and maintenance functions of the tank. Furthermore, all the control algorithms for the generation and absorption are implemented using higher level software (MATLAB /Simulink block diagrams). These algorithms calculate the motions of the wave makers both to generate and absorb the required wave field by taking into account the layout of the flaps and the limits of wave generation. The experimental transfer function that relates the flap amplitude to the wave elevation amplitude is used for the calculation of the motion of each flap. This paper describes the main features of the tank, followed by a detailed presentation of the whole automation system. It includes the measuring devices, signal conditioning, PLC and network architecture, real-time and synchronizing software and motor control loop. Finally, a validation of the whole automation system is presented, by means of the experimental analysis of the transfer function of the waves generated and the calculation of all the delays introduced by the automation system.

Ricostruzione degli sforzi in elementi finiti di piastra

Nell’ambito dell’analisi computazionale delle strutture il metodo degli elementi finiti è probabilmente uno dei metodi numerici più efficaci ed impiegati. La semplicità dell’idea di base del metodo e la relativa facilità con cui può essere implementato in codici di calcolo hanno reso possibile l’applicazione di questa tecnica computazionale in diversi settori, non solo dell’ingegneria strutturale, ma in generale della matematica applicata. Ma, nonostante il livello raggiunto dalle tecnologie ad elementi finiti sia già abbastanza elevato, per alcune applicazioni tipiche dell’ingegneria strutturale (problemi bidimensionali, analisi di lastre inflesse) le prestazioni fornite dagli elementi usualmente utilizzati, ovvero gli elementi di tipo compatibile, sono in effetti poco soddisfacenti. Vengono in aiuto perciò gli elementi finiti basati su formulazioni miste che da un lato presentano una più complessa formulazione, ma dall’altro consentono di prevenire alcuni problemi ricorrenti quali per esempio il fenomeno dello shear locking. Indipendentemente dai tipi di elementi finiti utilizzati, le quantità di interesse nell’ambito dell’ingegneria non sono gli spostamenti ma gli sforzi o più in generale le quantità derivate dagli spostamenti. Mentre i primi sono molto accurati, i secondi risultano discontinui e di qualità scadente. A valle di un calcolo FEM, negli ultimi anni, hanno preso piede procedure di post-processing in grado, partendo dalla soluzione agli elementi finiti, di ricostruire lo sforzo all’interno di patch di elementi rendendo quest’ultimo più accurato. Tali procedure prendono il nome di Procedure di Ricostruzione (Recovery Based Approaches). Le procedure di ricostruzione qui utilizzate risultano essere la REP (Recovery by Equilibrium in Patches) e la RCP (Recovery by Compatibility in Patches). L’obbiettivo che ci si prefigge in questo lavoro è quello di applicare le procedure di ricostruzione ad un esempio di piastra, discretizzato con vari tipi di elementi finiti, mettendone in luce i vantaggi in termini di migliore accurattezza e di maggiore convergenza.

Estimating crustal deformation from geodetic data

By the end of the 19th century, geodesy has contributed greatly to the knowledge of regional tectonics and fault movement through its ability to measure, at sub-centimetre precision, the relative positions of points on the Earth’s surface. Nowadays the systematic analysis of geodetic measurements in active deformation regions represents therefore one of the most important tool in the study of crustal deformation over different temporal scales [e.g., Dixon, 1991]. This dissertation focuses on motion that can be observed geodetically with classical terrestrial position measurements, particularly triangulation and leveling observations. The work is divided into two sections: an overview of the principal methods for estimating longterm accumulation of elastic strain from terrestrial observations, and an overview of the principal methods for rigorously inverting surface coseismic deformation fields for source geometry with tests on synthetic deformation data sets and applications in two different tectonically active regions of the Italian peninsula. For the long-term accumulation of elastic strain analysis, triangulation data were available from a geodetic network across the Messina Straits area (southern Italy) for the period 1971 – 2004. From resulting angle changes, the shear strain rates as well as the orientation of the principal axes of the strain rate tensor were estimated. The computed average annual shear strain rates for the time period between 1971 and 2004 are γ˙1 = 113.89 ± 54.96 nanostrain/yr and γ˙2 = -23.38 ± 48.71 nanostrain/yr, with the orientation of the most extensional strain (θ) at N140.80° ± 19.55°E. These results suggests that the first-order strain field of the area is dominated by extension in the direction perpendicular to the trend of the Straits, sustaining the hypothesis that the Messina Straits could represents an area of active concentrated deformation. The orientation of θ agree well with GPS deformation estimates, calculated over shorter time interval, and is consistent with previous preliminary GPS estimates [D’Agostino and Selvaggi, 2004; Serpelloni et al., 2005] and is also similar to the direction of the 1908 (MW 7.1) earthquake slip vector [e.g., Boschi et al., 1989; Valensise and Pantosti, 1992; Pino et al., 2000; Amoruso et al., 2002]. Thus, the measured strain rate can be attributed to an active extension across the Messina Straits, corresponding to a relative extension rate ranges between < 1mm/yr and up to ~ 2 mm/yr, within the portion of the Straits covered by the triangulation network. These results are consistent with the hypothesis that the Messina Straits is an important active geological boundary between the Sicilian and the Calabrian domains and support previous preliminary GPS-based estimates of strain rates across the Straits, which show that the active deformation is distributed along a greater area. Finally, the preliminary dislocation modelling has shown that, although the current geodetic measurements do not resolve the geometry of the dislocation models, they solve well the rate of interseismic strain accumulation across the Messina Straits and give useful information about the locking the depth of the shear zone. Geodetic data, triangulation and leveling measurements of the 1976 Friuli (NE Italy) earthquake, were available for the inversion of coseismic source parameters. From observed angle and elevation changes, the source parameters of the seismic sequence were estimated in a join inversion using an algorithm called “simulated annealing”. The computed optimal uniform–slip elastic dislocation model consists of a 30° north-dipping shallow (depth 1.30 ± 0.75 km) fault plane with azimuth of 273° and accommodating reverse dextral slip of about 1.8 m. The hypocentral location and inferred fault plane of the main event are then consistent with the activation of Periadriatic overthrusts or other related thrust faults as the Gemona- Kobarid thrust. Then, the geodetic data set exclude the source solution of Aoudia et al. [2000], Peruzza et al. [2002] and Poli et al. [2002] that considers the Susans-Tricesimo thrust as the May 6 event. The best-fit source model is then more consistent with the solution of Pondrelli et al. [2001], which proposed the activation of other thrusts located more to the North of the Susans-Tricesimo thrust, probably on Periadriatic related thrust faults. The main characteristics of the leveling and triangulation data are then fit by the optimal single fault model, that is, these results are consistent with a first-order rupture process characterized by a progressive rupture of a single fault system. A single uniform-slip fault model seems to not reproduce some minor complexities of the observations, and some residual signals that are not modelled by the optimal single-fault plane solution, were observed. In fact, the single fault plane model does not reproduce some minor features of the leveling deformation field along the route 36 south of the main uplift peak, that is, a second fault seems to be necessary to reproduce these residual signals. By assuming movements along some mapped thrust located southward of the inferred optimal single-plane solution, the residual signal has been successfully modelled. In summary, the inversion results presented in this Thesis, are consistent with the activation of some Periadriatic related thrust for the main events of the sequence, and with a minor importance of the southward thrust systems of the middle Tagliamento plain.

Sulla energia dissipata in alcuni organi di macchina

Questa tesi riguarda l'analisi delle trasmissioni ad ingranaggi e delle ruote dentate in generale, nell'ottica della minimizzazione delle perdite di energia. È stato messo a punto un modello per il calcolo della energia e del calore dissipati in un riduttore, sia ad assi paralleli sia epicicloidale. Tale modello consente di stimare la temperatura di equilibrio dell'olio al variare delle condizioni di funzionamento. Il calcolo termico è ancora poco diffuso nel progetto di riduttori, ma si è visto essere importante soprattutto per riduttori compatti, come i riduttori epicicloidali, per i quali la massima potenza trasmissibile è solitamente determinata proprio da considerazioni termiche. Il modello è stato implementato in un sistema di calcolo automatizzato, che può essere adattato a varie tipologie di riduttore. Tale sistema di calcolo consente, inoltre, di stimare l'energia dissipata in varie condizioni di lubrificazione ed è stato utilizzato per valutare le differenze tra lubrificazione tradizionale in bagno d'olio e lubrificazione a “carter secco” o a “carter umido”. Il modello è stato applicato al caso particolare di un riduttore ad ingranaggi a due stadi: il primo ad assi paralleli ed il secondo epicicloidale. Nell'ambito di un contratto di ricerca tra il DIEM e la Brevini S.p.A. di Reggio Emilia, sono state condotte prove sperimentali su un prototipo di tale riduttore, prove che hanno consentito di tarare il modello proposto [1]. Un ulteriore campo di indagine è stato lo studio dell’energia dissipata per ingranamento tra due ruote dentate utilizzando modelli che prevedano il calcolo di un coefficiente d'attrito variabile lungo il segmento di contatto. I modelli più comuni, al contrario, si basano su un coefficiente di attrito medio, mentre si può constatare che esso varia sensibilmente durante l’ingranamento. In particolare, non trovando in letteratura come varia il rendimento nel caso di ruote corrette, ci si è concentrati sul valore dell'energia dissipata negli ingranaggi al variare dello spostamento del profilo. Questo studio è riportato in [2]. È stata condotta una ricerca sul funzionamento di attuatori lineari vite-madrevite. Si sono studiati i meccanismi che determinano le condizioni di usura dell'accoppiamento vite-madrevite in attuatori lineari, con particolare riferimento agli aspetti termici del fenomeno. Si è visto, infatti, che la temperatura di contatto tra vite e chiocciola è il parametro più critico nel funzionamento di questi attuatori. Mediante una prova sperimentale, è stata trovata una legge che, data pressione, velocità e fattore di servizio, stima la temperatura di esercizio. Di tale legge sperimentale è stata data un'interpretazione sulla base dei modelli teorici noti. Questo studio è stato condotto nell'ambito di un contratto di ricerca tra il DIEM e la Ognibene Meccanica S.r.l. di Bologna ed è pubblicato in [3].

Riabilitazione protesica ed implanto-protesica di pazienti in età evolutiva affetti da Displasia Ectodermica

Introduction. Ectodermal Dysplasias are a heterogeneous group of inherited disorders characterized by dysplasia of tissues of ectodermal origin (hair, nails, teeth, skins and glands). Clinically, it may be divided into two broad categories: the X-linked hypoidrotic form and the hidrotic form. Hypohidrotic Ectodermal Dysplasia (H.E.D) is characterized by the triad oligo-anodontia, hypotricosis, hypo-anhydrosis (Christ-Siemens-Tourane syndrome). The incidence of HED is about 1/100,000. Mutation in the actodysplasin-A (EDA) and ectodysplasin-A receptor (EDAR) genes are responsible for X-linked and autosomal HED. The clinical features include sparse, fine hair, missing or conical-shaped teeth, decreased sweat and mucous glands, hypoplastic skin, and heat intolerance with exercise or increased ambient temperature. Complete or partial anodontia and malformation of teeth are the most frequent dental findings. Incisors and canines are often conical-shaped while primarily second molars, if present, are mostly affected by taurodontism. Treatment is supportive and includes protection from heat exposure, early prosthetic rehabilitation, skin, hair ear, nose and nail care, and genetic counseling for family planning. The diagnosis of HED in the neonatal and early infancy period may be difficult since sparse hair and absent teeth are normal finding at this age. In childhood the diagnosis is more easily made on the basis of history and clinical examination. Dental abnormalities are the most common complaint. Prosthetic rehabilitation has been recommended as an essential part of the management of HED because is important from functional, esthetic, and psychological standpoint. A team approach that includes input from a pediatric dentist, an orthodontist, a prosthodontist, and an oral and maxillofacial surgeon is necessary for a successful outcome. Conventional prosthodontic rehabilitation in young patient is often difficult because of the anatomical abnormalities of existing teeth and alveolar ridges. The conical shaped teeth and “knife-edge” alveolar ridges result in poor retention and instability of dentures. Moreover, denture must permit jaws expansion and a correct pattern of growth. Materials and Methods. Complete removable dentures were provided to allow for normal physiological development and a corrected masticatory function. Initial maxillary and mandibular impressions were made with smallest stock trays and irreversible hydrocolloid and then final impressions ware made with light-bodied polysulfide rubber base impression material. A base of autopolymerizing resin was constructed and a wax rim was added to the base. The patient’s vertical dimension of occlusion was established by assessing phonetic and esthetic criteria. Preliminary occlusal relations were recorded, and the mandibular cast was mounted on the articulator. Acrylic resin teeth specific for children dentures were selected and mounted. The dentures were tried in and, after proper adjustments, were inserted. The patients were monitored clinically every month to fit prostheses. Cephalometric radiographs were taken every 6 month with the prostheses in place in order to evaluate correct pattern of growth. Cephalometric measurements were realized and used to evaluate the effect of rehabilitation on craniofacial growth. Cephalometric measurements of sound patients were compared with ED patients. After two month expander screws (three-way screw in the upper denture and two-way the lower one)were inserted in each denture in order to permit the expansion of the denture and the jaws growth. Where conical teeth were present, composite crown were realized and luted to improve the esthetic and phonesis. In order to improve retention the placement of endosseous implants was carried out. TC 3D Accuitomo was performed and a resin model of mandibular bone of the patient was realized. At the age of 11 years two implants were inserted into anterior mandible in a child with anodontia. Despite a remarkable multi-dimensional atrophy of the mandibular alveolar process, the insertion of two tapered screw implants (SAMO Smiler, diameter 3.8, length 10 mm). After a submerged healing period of two-three month, the implants were exposed. Implants were connected with an expansion guide that permits mandibular growth and prosthetic retention. The amount of mandibular growth was also evaluate dusing the expansion guide. Results. Early oral rehabilitation improve oral function, phonesis and esthetic, reducing social impairment. Treated patients showed normal cephalometric measurement. Early rehabilitation is able to prevent the prognatissm of the mandibula . The number of teeth was significantly related to several changes in craniofacial morphology. Discussion. In the present study the 5,3% of ED patients showed hypodontia, the l’89,4% di oligodontia, and the 5,3% di anodontia. The cephalometric analysis supports that ED patients showed midface hypoplasia. ED groups showed an increased pogonion to nasion measurement than sound patients, indicative of class III tendency. The present study demonstrated that number of teeth was significantly correlated with deviation of cephalometric measurements from normality. Oligoanodontia is responsible for changing of cephalometric measuraments also on sagittal plane with a class III tendency. Maxillary jaw showed a retrused position related to the presence of hypodontia.

Funzionalizzazione della mandibola dopo ricostruzione con lembo libero rivascolarizzato di fibula "single strut". Al di là del deficit di verticalità.

Obiettivi: Valutare la modalità  più efficace per la riabilitazione funzionale del limbo libero di fibula "single strut", dopo ampie resezioni per patologia neoplastica maligna del cavo orale. Metodi: Da una casistica di 62 ricostruzioni microvascolari con limbo libero di fibula, 11 casi sono stati selezionati per essere riabilitati mediante protesi dentale a supporto implantare. 6 casi sono stati trattati senza ulteriori procedure chirurgiche ad eccezione dell'implantologia (gruppo 1), affrontando il deficit di verticalità  della fibula attraverso la protesi dentaria, mentre i restanti casi sono stati trattati con la distrazione osteogenetica (DO) della fibula prima della riabilitazione protesica (gruppo 2). Il deficit di verticalità  fibula/mandibola è stato misurato. I criteri di valutazione utilizzati includono la misurazione clinica e radiografica del livello osseo e dei tessuti molli peri-implantari, ed il livello di soddisfazione del paziente attraverso un questionario appositamente redatto. Risultati: Tutte le riabilitazioni protesiche sono costituite da protesi dentali avvitate su impianti. L'età  media è di 52 anni, il rapporto uomini/donne è di 6/5. Il numero medio di impianti inseriti nelle fibule è di 5. Il periodo massimo di follow-up dopo il carico masticatorio è stato di 30 mesi per il gruppo 1 e di 38.5 mesi (17-81) di media per il gruppo 2. Non abbiamo riportato complicazioni chirurgiche. Nessun impianto è stato rimosso dai pazienti del gruppo 1, la perdita media di osso peri-implantare registrata è stata di 1,5 mm. Nel gruppo 2 sono stati riportati un caso di tipping linguale del vettore di distrazione durante la fase di consolidazione e un caso di frattura della corticale basale in assenza di formazione di nuovo osso. L'incremento medio di osso in verticalità è stato di 13,6 mm (12-15). 4 impianti su 32 (12.5%) sono andati persi dopo il periodo di follow-up. Il riassorbimento medio peri-implantare, è stato di 2,5 mm. Conclusioni: Le soluzioni più utilizzate per superare il deficit di verticalità  del limbo libero di fibula consistono nell'allestimento del lembo libero di cresta iliaca, nel posizionare la fibula in posizione ideale da un punto di vista protesico a discapito del profilo osseo basale, l'utilizzo del lembo di fibula nella versione descritta come "double barrel", nella distrazione osteogenetica della fibula. La nostra esperienza concerne il lembo libero di fibula che nella patologia neoplastica maligna utilizziamo nella versione "single strut", per mantenere disponibili tutte le potenzialità  di lunghezza del peduncolo vascolare, senza necessità  di innesti di vena. Entrambe le soluzioni, la protesi dentale ortopedica e la distrazione osteogenetica seguita da protesi, entrambe avvitate su impianti, costituiscono soluzioni soddisfacenti per la riabilitazione funzionale della fibula al di là  del suo deficit di verticalità . La prima soluzione ha preso spunto dall'osservazione dei buoni risultati della protesi dentale su impianti corti, avendo un paragonabile rapporto corona/radice, la DO applicata alla fibula, sebbene sia risultata una metodica con un numero di complicazioni più elevato ed un maggior livello di riassorbimento di osso peri-implantare, costituisce in ogni caso una valida opzione riabilitativa, specialmente in caso di notevole discrepanza mandibulo/fibulare. Decisiva è la scelta del percorso terapeutico dopo una accurata valutazione di ogni singolo caso. Vengono illustrati i criteri di selezione provenienti dalla nostra esperienza.

Polymer controlled mineralization of zinc phosphate hydrates and applications in corrosion protection, catalysis and biomedicine

ZUSAMMENFASSUNG Die Tauglichkeit von Hybridmaterialien auf der Basis von Zinkphosphathydrat-Zementen zum Einsatz als korrosionshemmende anorganische Pigmente oder zur prothetischen und konservierenden Knochen- und Zahntherapie wird weltweit empirisch seit den neunziger Jahren intensiv erforscht. In der vorliegenden Arbeit wurden zuerst Referenzproben, d.h. alpha-und beta-Hopeite (Abk. a-,b-ZPT) dank eines hydrothermalen Kristallisationsverfahrens in wässerigem Milieu bei 20°C und 90°C hergestellt. Die Kristallstruktur beider Polymorphe des Zinkphosphattetrahydrats Zn3(PO4)2  4 H2O wurde komplett bestimmt. Einkristall-strukturanalyse zeigt, daß der Hauptunterschied zwischen der alpha-und beta-Form des Zinkphosphattetrahydrats in zwei verschiedenen Anordnungen der Wasserstoffbrücken liegt. Die entsprechenden drei- und zweidimensionalen Anordnungen der Wasserstoffbrücken der a-und b-ZPT induzieren jeweils unterschiedliches thermisches Verhalten beim Aufwärmen. Während die alpha-Form ihr Kristallwasser in zwei definierten Stufen verliert, erzeugt die beta-Form instabile Dehydratationsprodukt. Dieses entspricht zwei unabhängigen, aber nebeneinander ablaufenden Dehydratationsmechanismen: (i) bei niedrigen Heizraten einen zweidimensionalen Johnson-Mehl-Avrami (JMA) Mechanismus auf der (011) Ebene, der einerseits bevorzugt an Kristallkanten stattfindet und anderseits von existierenden Kristalldefekten auf Oberflächen gesteuert wird; (ii) bei hohen Heizraten einem zweidimensionalen Diffusionsmechanismus (D2), der zuerst auf der (101) Ebene und dann auf der (110) Ebene erfolgt. Durch die Betrachtung der ZPT Dehydratation als irreversibele heterogene Festkörperstufenreaktion wurde dank eines „ähnlichen Endprodukt“-Protokolls das Dehydratationsphasendiagramm aufgestellt. Es beschreibt die möglichen Zusammenhänge zwischen den verschiedenen Hydratationszuständen und weist auf die Existenz eines Übergangszustandes um 170°C (d.h. Reaktion b-ZPT  a-ZPT) hin. Daneben wurde auch ein gezieltes chemisches Ätzverfahren mit verdünnten H3PO4- und NH3 Lösungen angewendet, um die ersten Stufe des Herauslösens von Zinkphosphat genau zu untersuchen. Allerdings zeigen alpha- und beta-Hopeite charakteristische hexagonale und kubische Ätzgruben, die sich unter kristallographischer Kontrolle verbreitern. Eine zuverlässige Beschreibung der Oberfächenchemie und Topologie konnte nur durch AFM und FFM Experimente erfolgen. Gleichzeitig konnte in dieser Weise die Oberflächendefektdichte und-verteilung und die Volumenauflösungsrate von a-ZPT und b-ZPT bestimmt werden. Auf einem zweiten Weg wurde eine innovative Strategie zur Herstellung von basischen Zinkphosphatpigmenten erster und zweiter Generation (d.h. NaZnPO4  1H2O und Na2ZnPO4(OH)  2H2O) mit dem Einsatz von einerseits oberflächenmodifizierten Polystyrolatices (z.B. produziert durch ein Miniemulsionspolymerisationsverfahren) und anderseits von Dendrimeren auf der Basis von Polyamidoamid (PAMAM) beschritten. Die erhaltene Zeolithstruktur (ZPO) hat in Abhängigkeit von steigendem Natrium und Wassergehalt unterschiedliche kontrollierte Morphologie: hexagonal, würfelförmig, herzförmig, sechsarmige Sterne, lanzettenförmige Dendrite, usw. Zur quantitativen Evaluierung des Polymereinbaus in der Kristallstruktur wurden carboxylierte fluoreszenzmarkierte Latices eingesetzt. Es zeigt sich, daß Polymeradditive nicht nur das Wachstum bis zu 8 µm.min-1 reduzierten. Trotzdem scheint es auch als starker Nukleationsbeschleuniger zu wirken. Dank der Koordinationschemie (d.h. Bildung eines sechszentrigen Komplexes L-COO-Zn-PO4*H2O mit Ligandenaustausch) konnten zwei einfache Mechanismen zur Wirkung von Latexpartikeln bei der ZPO Kristallisation aufgezeigt werden: (i) ein Intrakorona- und (ii) ein Extrakorona-Keimbildungsmechanismus. Weiterhin wurde die Effizienz eines Kurzzeit- und Langzeitkorrosionschutzes durch maßgeschneiderte ZPO/ZPT Pigmente und kontrollierte Freisetzung von Phosphationen in zwei Näherungen des Auslösungsgleichgewichts abgeschätzt: (i) durch eine Auswaschungs-methode (thermodynamischer Prozess) und (ii) durch eine pH-Impulsmethode (kinetischer Prozess. Besonders deutlich wird der Ausflösungs-Fällungsmechanismus (d.h. der Metamorphismus). Die wesentliche Rolle den Natriumionen bei der Korrosionshemmung wird durch ein passendes zusammensetzungsabhängiges Auflösungsmodell (ZAAM) beschrieben, das mit dem Befund des Salzsprühteste und der Feuchtigkeitskammertests konsistent ist. Schließlich zeigt diese Arbeit das herausragende Potential funktionalisierter Latices (Polymer) bei der kontrollierten Mineralisation zur Herstellung maßgeschneiderter Zinkphosphat Materialien. Solche Hybridmaterialien werden dringend in der Entwicklung umweltfreundlicher Korrosionsschutzpigmente sowie in der Dentalmedizin benötigt.

Kinematics of the Sicily and Calabria Subduction System from Elastic Block Modeling of GPS Data

We use data from about 700 GPS stations in the EuroMediterranen region to investigate the present-day behavior of the the Calabrian subduction zone within the Mediterranean-scale plates kinematics and to perform local scale studies about the strain accumulation on active structures. We focus attenction on the Messina Straits and Crati Valley faults where GPS data show extentional velocity gradients of ∼3 mm/yr and ∼2 mm/yr, respectively. We use dislocation model and a non-linear constrained optimization algorithm to invert for fault geometric parameters and slip-rates and evaluate the associated uncertainties adopting a bootstrap approach. Our analysis suggest the presence of two partially locked normal faults. To investigate the impact of elastic strain contributes from other nearby active faults onto the observed velocity gradient we use a block modeling approach. Our models show that the inferred slip-rates on the two analyzed structures are strongly impacted by the assumed locking width of the Calabrian subduction thrust. In order to frame the observed local deformation features within the present- day central Mediterranean kinematics we realyze a statistical analysis testing the indipendent motion (w.r.t. the African and Eurasias plates) of the Adriatic, Cal- abrian and Sicilian blocks. Our preferred model confirms a microplate like behaviour for all the investigated blocks. Within these kinematic boundary conditions we fur- ther investigate the Calabrian Slab interface geometry using a combined approach of block modeling and χ2ν statistic. Almost no information is obtained using only the horizontal GPS velocities that prove to be a not sufficient dataset for a multi-parametric inversion approach. Trying to stronger constrain the slab geometry we estimate the predicted vertical velocities performing suites of forward models of elastic dislocations varying the fault locking depth. Comparison with the observed field suggest a maximum resolved locking depth of 25 km.

Solid-state NMR investigation of phosphonic acid based proton conducting materials

In this work, new promising proton conducting fuel cell membrane materials were characterized in terms of their structure and dynamic properties using solid-state nuclear magnetic resonance (NMR) spectroscopy and X-ray diffraction. Structurally different, phosphonic acid (PA) containing materials were systematically evaluated for possible high-temperature operation (e.g. at T>100°C). Notably, 1H, 2H and 31P magic angle spinning (MAS) NMR provided insight into local connectivities and dynamics of the hydrogen bonded network, while packing arrangements were identified by means of heteronuclear dipolar recoupling techniques.rnThe first part of this work introduced rather crystalline, low molecular weight ionomers for proton conducting membranes, where six different geometries such as line, triangle, screw, tetrahedron, square and hexagon, were investigated. The hexagon was identified as the most promising geometry with high-temperature bulk proton conductivities in the range of 10-3 Scm-1 at a relative humidity of 50%. However, 2H NMR and TGA-MS data suggest that the bulk proton transport is mainly due to the presence of crystal water. Single crystal X-ray data revealed that in the tetrahedron phosphonic acids form tetrameric clusters isolating the mobile protons while the phosphonic acids in the hexagon form zigzag-type pathways through the sample.rnThe second part of this work demonstrates how acid-base pairing and the choice of appropriate spacers may influence proton conduction. Different ratios of statistical copolymers of poly (vinylphosphonic acid) and poly (4-vinylpyridine) were measured to derive information about the local structure and chemical changes. Though anhydrous proton conductivities of all statistical copolymers are rather poor, the conductivity increases to 10-2 S cm-1 when exposing the sample to relative humidity of 80%. In contrast to PVPA, anhydride formation of phosphonic acids in the copolymer is not reversible even when exposing the sample to a relative humidity of 100%.rnIn addition, the influence of both spacers and degree of backbone crystallinity on bulk proton conductivity was investigated. Unlike in systems such as poly benzimidazole (PBI), spacers were inserted between the protogenic groups along the backbone. It was found that dilution of the protogenic groups decreases the conductivity, but compared to PVPA, similar apparent activation energies for local motions were obtained from both variable temperature 1H NMR and impedance spectroscopy data. These observations suggest the formation of phosphonic acid clusters with high degrees of local proton motion, where only a fraction of motions contribute to the observable bulk proton conductivity. Additionally, it was shown that gradual changes of the spacer length lead to different morphologies.rnIn summary, applying advanced solid-state NMR and X-ray analysis, structural and dynamic phenomena in proton conducting materials were identified on a molecular level. The results were discussed with respect to different proton conduction mechanisms and may contribute to a more rational design or improvement of proton conducting membranes.rn