Functionalization of microstructured open-porous bioceramic scaffolds with human fetal bone cells.

Bone substitute materials allowing trans-scaffold migration and in-scaffold survival of human bone-derived cells are mandatory for development of cell-engineered permanent implants to repair bone defects. In this study, we evaluated the influence on human bone-derived cells of the material composition and microstructure of foam scaffolds of calcium aluminate. The scaffolds were prepared using a direct foaming method allowing wide-range tailoring of the microstructure for pore size and pore openings. Human fetal osteoblasts (osteo-progenitors) attached to the scaffolds, migrated across the entire bioceramic depending on the scaffold pore size, colonized, and survived in the porous material for at least 6 weeks. The long-term biocompatibility of the scaffold material for human bone-derived cells was evidenced by in-scaffold determination of cell metabolic activity using a modified MTT assay, a repeated WST-1 assay, and scanning electron microscopy. Finally, we demonstrated that the osteo-progenitors can be covalently bound to the scaffolds using biocompatible click chemistry, thus enhancing the rapid adhesion of the cells to the scaffolds. Therefore, the different microstructures of the foams influenced the migratory potential of the cells, but not cell viability. Scaffolds allow covalent biocompatible chemical binding of the cells to the materials, either localized or widespread integration of the scaffolds for cell-engineered implants.

Engineering macroporous composite materials using competitive adsorption in particle-stabilized foams.

The high absorption energies of partially wetted particles at fluid interfaces allow the production of macroporous composite materials from particle-stabilized foams. Competition between the different particle types determines how they are distributed in the foam lamella and allow the phase distribution to be controlled; a technique that is useful in the design and engineering of porous composites. Here, we report details on the effects of preferential and competitive adsorption of poly(vinylidene fluoride) (PVDF) and alumina (Al(2)O(3)) particles at the foam interfaces on the consolidated macroporous composite materials. By varying the relative composition and surface energies of the stabilizing particles, macroporous composite materials with a broad range of phase distributions are possible.

Dealloying of platinum-aluminum thin films: dynamics of pattern formation.

The application of focused ion beam (FIB) nanotomography and Rutherford backscattering spectroscopy (RBS) to dealloyed platinum-aluminum thin films allows for an in-depth analysis of the dominating physical mechanisms of nanoporosity formation during the dealloying process. The porosity formation due to the dissolution of the less noble aluminum in the alloy is treated as result of a reaction-diffusion system. The RBS and FIB analysis yields that the porosity evolution has to be regarded as superposition of two independent processes, a linearly propagating diffusion front with a uniform speed and a slower dissolution process in regions which have already been passed by the diffusion front. The experimentally observed front evolution is captured by the Fisher-Kolmogorov-Petrovskii-Piskounov (FKPP). The slower dissolution is represented by a zero-order rate law which causes a gradual porosity in the thin film.

Unifying model for the electrokinetic and phase behavior of aqueous suspensions containing short and long amphiphiles.

Aqueous suspensions containing oppositely charged colloidal particles and amphiphilic molecules can form fluid dispersions, foams, and percolating gel networks, depending on the initial concentration of amphiphiles. While models have been proposed to explain the electrokinetic and flotation behavior of particles in the presence of long amphiphilic molecules, the effect of amphiphiles with less than six carbons in the hydrocarbon tail on the electrokinetic, rheological, and foaming behavior of aqueous suspensions remains unclear. Unlike conventional long amphiphiles (≥10 carbons), short amphiphiles do not exhibit increased adsorption on the particle surface when the number of carbons in the molecule tail is increased. On the basis of classical electrical double layer theory and the formerly proposed hemimicelle concept, we put forward a new predictive model that reconciles the adsorption and electrokinetic behavior of colloidal particles in the presence of long and short amphiphiles. By introducing in the classical Gouy-Chapman theory an energy term associated with hydrophobic interactions between the amphiphile hydrocarbon tails, we show that amphiphilic electrolytes lead to a stronger compression of the diffuse part of the electrical double layer in comparison to hydrophilic electrolytes. Scaling relationships derived from this model provide a quantitative description of the rich phase behavior of the investigated suspensions, correctly accounting for the effect of the alkyl chain length of short and long amphiphiles on the electrokinetics of such colloidal systems. The proposed model contributes to our understanding of the stabilization mechanisms of particle-stabilized foams and emulsions and might provide new insights into the physicochemical processes involved in mineral flotation.

Controlling phase distributions in macroporous composite materials through particle-stabilized foams.

Aqueous foams stabilized by ceramic and thermoplastic polymeric particles provide a general method for producing novel porous materials because their extraordinary stability against disproportionation and drainage allows them to be dried and sintered into solid materials. Here, we report the different microstructures that can be obtained from liquid foams stabilized by binary mixtures of particles when the interfacial energies between the particles and the air-liquid interfaces are manipulated to promote either preferential or competitive self-assembly of the particles at the foam interface. Modification of the interfacial energies was accomplished through surface modification of the particles or by decreasing the surface tension of the aqueous phase. Materials derived from liquid foams stabilized by poly(vinylidene fluoride) (PVDF) and alumina (Al(2)O(3)) particles are investigated. However, as is shown, the method can be extended to other polymeric and ceramic particles and provides the possibility to manufacture a wide range of porous composite materials.

Contact angle and adsorption behavior of carboxylic acids on α-Al2O3 surfaces.

The hydrophilic character of aluminum oxide surfaces may be altered through coating such surfaces with carboxylic acids. The initially hydrophilic nature of the solid substrate changes towards a less hydrophilic character as the bulk concentration and the chain length of the acids increases. The acids employed in this work (propionic, valeric and enanthic) show a certain affinity to the liquid-gas, solid-liquid and solid-gas interfaces, being the relative adsorption on them competitive. The adsorption behavior of these carboxylic acids is experimentally investigated combining pendant drop tensiometry, contact angle measurements on α-Al(2)O(3) polycrystalline ceramics and adsorption on particles in aqueous suspensions, as a function of the hydrocarbon chain length of the acids and their bulk concentration, at pH equal to the acids' pKa. The hydrophilic character of the coated alumina decreases with the acids concentration upon a certain concentration beyond that, it increases. The minimum of hydrophilicity is reached right before bi-layer arrangements on the adsorption pattern of the acids on the solid substrates take place.

Electrical conductivity and crystallization of amorphous bismuth ruthenate thin films deposited by spray pyrolysis.

Amorphous oxide thin films with tailored functionality will be crucial for the next generation of micro-electro-mechanical-systems (MEMS). Due to potentially favorable electronic and catalytic properties, amorphous bismuth ruthenate thin films might be applied in this regard. We report on the deposition of amorphous bismuth ruthenate thin films by spray pyrolysis, their crystallization behavior and electrical conductivity. At room temperature the 200 nm thin amorphous films exhibit a high electrical conductivity of 7.7 × 10(4) S m(-1), which was found to be slightly thermally activated (E(a) = 4.1 × 10(-3) eV). It follows that a long-range order of the RuO(6) octahedra is no precondition for the electrical conductivity of Bi(3)Ru(3)O(11). Upon heating to the temperature range between 490 °C and 580 °C the initially amorphous films crystallize rapidly. Simultaneously, a transition from a dense and continuous film to isolated Bi(3)Ru(3)O(11) particles on the substrate takes place. Solid-state agglomeration is proposed as the mechanism responsible for disintegration. The area specific resistance of Bi(3)Ru(3)O(11) particles contacted by Pt paste on gadolinia doped ceria electrolyte pellets was found to be 7 Ω cm(2) at 607 °C in air. Amorphous bismuth ruthenate thin films are proposed for application in electrochemical devices operating at low temperatures, where a high electrical conductivity is required.

Engineering disorder in precipitation-based nano-scaled metal oxide thin films.

Distinctive microstructure engineering of amorphous to nanocrystalline functional metal oxide thin films for MEMS devices is of high relevance to allow for new applications, quicker response times, and higher efficiencies. Precipitation-based thin-film techniques are first choice. However, these often involve organic solvents in preparation. Their relevance on the disorder states of amorphous to fully crystalline metal oxides is unclear, especially during crystallization. In this study the impact of organic solvents on the as-deposited amorphous state and crystallization of the metal oxide, CeO(2), is reported for thin-film preparation via the precipitation-based method spray pyrolysis. The choice of organic solvent for film preparation, i.e. glycols of different chain lengths, clearly affects the structural packing and Raman bond length of amorphous states. Organic residues act as space fillers between the metal oxide molecules in amorphous films and affect strongly the thermal evolvement of microstructure, i.e. microstrain, crystallization enthalpy, crystallographic density, grain size during crystallization and grain growth. Once the material is fully crystalline, equal near- and long-range order characteristics result independent of organic solvent choice. However, the fully crystalline films still show decreased crystallographic densities, presence of microstrain, and lower Raman shifts compared to microcrystalline bulk material. The defect state of amorphous and fully crystalline thin-film microstructures can actively be modified via explicit use of organic glycols with different chain lengths for metal oxide films in MEMS.

Quantification of the heterogeneity of particle packings.

The microstructure of coagulated colloidal particles, for which the interparticle potential is described by the Derjaguin-Landau-Verweg-Overbeek theory, is strongly influenced by the particles' surface potential. Depending on its value, the resulting microstructures are either more "homogeneous" or more "heterogeneous," at equal volume fractions. An adequate quantification of a structure's degree of heterogeneity (DOH), however, does not yet exist. In this work, methods to quantify and thus classify the DOH of microstructures are investigated and compared. Three methods are evaluated using particle packings generated by Brownian dynamics simulations: (1) the pore size distribution, (2) the density-fluctuation method, and (3) the Voronoi volume distribution. Each method provides a scalar measure, either via a parameter in a fit function or an integral, which correlates with the heterogeneity of the microstructure and which thus allows to quantitatively capture the DOH of a granular material. An analysis of the differences in the density fluctuations between two structures additionally allows for a detailed determination of the length scale on which differences in heterogeneity are most pronounced.

General route for the assembly of functional inorganic capsules.

Semipermeable, hollow capsules are attractive materials for the encapsulation and delivery of active agents in food processing, pharmaceutical and agricultural industries, and biomedicine. These capsules can be produced by forming a solid shell of close packed colloidal particles, typically polymeric particles, at the surface of emulsion droplets. However, current methods to prepare such capsules may involve multistep chemical procedures to tailor the surface chemistry of particles or are limited to particles that exhibit inherently the right hydrophobic-hydrophilic balance to adsorb around emulsion droplets. In this work, we describe a general and simple method to fabricate semipermeable, inorganic capsules from emulsion droplets stabilized by a wide variety of colloidal metal oxide particles. The assembly of particles at the oil-water interface is induced by the in situ hydrophobization of the particle surface through the adsorption of short amphiphilic molecules. The adsorption of particles at the interface leads to stable capsules comprising a single layer of particles in the outer shell. Such capsules can be used in the wet state or can be further processed into dry capsules. The permeability of the capsules can be modified by filling the interstices between the shell particles with polymeric or inorganic species. Functional capsules with biocompatible, bioresorbable, heat-resistant, chemical-resistant, and magnetic properties were prepared using alumina, silica, iron oxide, or tricalcium phosphate as particles in the shell.

Nanoporous Ni-Ce0.8Gd0.2O1.9-x thin film cermet SOFC anodes prepared by pulsed laser deposition.

Nickel oxide-gadolinia-doped ceria thin films with a ceria composition of 80 at% Ce and 20 at% Gd were grown by pulsed laser deposition on sapphire and SiO2/Si wafers as well as on yttria stabilized zirconia polycrystalline substrates. Upon reduction of the NiO phase in a H2/N2 atmosphere at 600 degrees C, a stable three-phase, 3-D interconnecting microstructure was obtained of metallic Ni, ceramic, and pores. Coarsening and segregation of the Ni to the surface of the film was observed at higher temperatures. The kinetics of this process depend strongly on the microstructures that can be developed in situ during deposition or post-deposition heat treatments. In situ minimization of Ni-coarsening can be achieved at temperatures as low as 500 degrees C when the deposition pressure does not exceed 0.02 mbar. For films deposited at higher pressure and at temperatures below 800 degrees C, coarsening can be minimized post deposition by annealing in air at 1000 degrees C. The films showed very good metallic conductivity and stability upon thermal cycling in a reducing atmosphere. Redox cycles performed at 600 degrees C between air and H2 induced a loss of connectivity of the metallic phase and consequent degradation of the conductivity. After 16 cycles, corresponding to 65 hrs, the conductivity is reduced by one order of magnitude.

Oxidation states of Co and Fe in Ba(1-x)Sr(x)Co(1-y)Fe(y)O(3-delta) (x, y = 0.2-0.8) and oxygen desorption in the temperature range 300-1273 K.

Four compositions of Ba(1-x)Sr(x)Co(1-y)Fe(y)O(3-delta) were studied for phase, oxygen uptake-release, and transition metal (TM) oxidation states after solid state processing and with in situ heating from 300 to 1273 K in air. X-Ray diffraction showed that all compositions except one had the cubic perovskite structure at all temperatures; that with x, y = 0.2 was a mixture as prepared, becoming predominantly cubic at high temperature. Thermogravimetry showed a reversible oxygen absorption-desorption of approximately +/-1% from 700 to 1273 K. X-Ray absorption and Mössbauer spectroscopy showed a majority TM(3+) valence, with at most 40% TM(4+). Up to a temperature of 1073 K, the TM(4+) was reduced to TM(3+). Further heating of the composition with x, y = 0.2 to 1233 K resulted in the reduction of Co(3+) to Co(2+). Results from room temperature measurements confirm the thermally activated carrier hopping mechanism with charge fluctuations, while the high temperature delocalized carrier conductivity occurs with a small amount of TM reduction and without phase change for the initially cubic samples.

Stabilization of oil-in-water emulsions by colloidal particles modified with short amphiphiles.

Emulsions stabilized through the adsorption of colloidal particles at the liquid-liquid interface have long been used and investigated in a number of different applications. The interfacial adsorption of particles can be induced by adjusting the particle wetting behavior in the liquid media. Here, we report a new approach to prepare stable oil-in-water emulsions by tailoring the wetting behavior of colloidal particles in water using short amphiphilic molecules. We illustrate the method using hydrophilic metal oxide particles initially dispersed in the aqueous phase. The wettability of such particles in water is reduced by an in situ surface hydrophobization that induces particle adsorption at oil-water interfaces. We evaluate the conditions required for particle adsorption at the liquid-liquid interface and discuss the effect of the emulsion initial composition on the final microstructure of oil-water mixtures containing high concentrations of alumina particles modified with short carboxylic acids. This new approach for emulsion preparation can be easily applied to a variety of other metal oxide particles.

Bioinspired design and assembly of platelet reinforced polymer films.

Although strong and stiff human-made composites have long been developed, the microstructure of today's most advanced composites has yet to achieve the order and sophisticated hierarchy of hybrid materials built up by living organisms in nature. Clay-based nanocomposites with layered structure can reach notable stiffness and strength, but these properties are usually not accompanied by the ductility and flaw tolerance found in the structures generated by natural hybrid materials. By using principles found in natural composites, we showed that layered hybrid films combining high tensile strength and ductile behavior can be obtained through the bottom-up colloidal assembly of strong submicrometer-thick ceramic platelets within a ductile polymer matrix.

Five-year clinical results of zirconia frameworks for posterior fixed partial dentures.

PURPOSE: The aim of this prospective clinical cohort study was to determine the success rate of 3- to 5-unit zirconia frameworks for posterior fixed partial dentures (FPDs) after 5 years of clinical observation. MATERIALS AND METHODS: Forty-five patients who needed at least 1 FPD to replace 1 to 3 posterior teeth were included in the study. Fifty-seven 3- to 5-unit FPDs with zirconia frameworks were cemented with 1 of 2 resin cements (Variolink or Panavia TC). The following parameters were evaluated at baseline, after 6 months, and 1 to 5 years after cementation at test (abutments) and control (contralateral) teeth: probing pocket depth, probing attachment level, Plaque Index, bleeding on probing, and tooth vitality. Intraoral radiographs of the FPDs were taken. Statistical analysis was performed using descriptive statistics, Kaplan-Meier survival analysis, and the McNemar test. RESULTS: Twenty-seven patients with 33 zirconia FPDs were examined after a mean observation period of 53.4 +/- 13 months. Eleven patients with 17 FPDs were lost to follow-up. After the 3-year recall visit, 7 FPDs in 7 patients were replaced because they were not clinically acceptable due to biologic or technical complications. After 5 years of clinical observation, 12 FPDs in 12 patients had to be replaced. One 5-unit FPD fractured as a result of trauma after 38 months. The success rate of the zirconia frameworks was 97.8%; however, the survival rate was 73.9% due to other complications. Secondary caries was found in 21.7% of the FPDs, and chipping of the veneering ceramic in 15.2%. There were no significant differences between the periodontal parameters of the test and control teeth. CONCLUSIONS: Zirconia offers sufficient stability as a framework material for 3- and 4-unit posterior FPDs. The fit of the frameworks and veneering ceramics, however, should be improved.

Tailoring the microstructure of particle-stabilized wet foams.

Inorganic colloidal particles which are in situ hydrophobized upon adsorption of short-chain amphiphilic molecules can be used as foam stabilizers. In this study, we tailor the microstructure of particle-stabilized wet foams, namely, the foam air content, average bubble size, and bubble size distribution, by changing the composition of the initial colloidal suspension. Wet foams featuring average bubble sizes between 10 and 200 microm and air contents between 45% and 90% were obtained by adjusting the amphiphile and particle concentration, pH, ionic strength, and particle size in the initial suspension. The influence of these parameters on the bubble size was satisfactorily described in terms of a balance between the shear stress applied during mixing and the counteracting Laplace pressure of the air bubbles. This model, originally developed for oil droplets in emulsions, can therefore be used to deliberately tailor the microstructure of particle-stabilized wet foams.

Colloidal stabilization of nanoparticles in concentrated suspensions.

The stabilization of nanoparticles in concentrated aqueous suspensions is required in many manufacturing technologies and industrial products. Nanoparticles are commonly stabilized through the adsorption of a dispersant layer around the particle surface. The formation of a dispersant layer (adlayer) of appropriate thickness is crucial for the stabilization of suspensions containing high nanoparticle concentrations. Thick adlayers result in an excessive excluded volume around the particles, whereas thin adlayers lead to particle agglomeration. Both effects reduce the maximum concentration of nanoparticles in the suspension. However, conventional dispersants do not allow for a systematic control of the adlayer thickness on the particle surface. In this study, we synthesized dispersants with a molecular architecture that enables better control over the particle adlayer thickness. By tailoring the chemistry and length of these novel dispersants, we were able to prepare fluid suspensions (viscosity < 1 Pa.s at 100 s-1) with more than 40 vol % of 65-nm alumina particles in water, as opposed to the 30 vol % achieved with a state-of-the-art dispersing agent. This remarkably high concentration facilitates the fabrication of a wide range of products and intermediates in materials technology, cosmetics, pharmacy, and in all other areas where concentrated nanoparticle suspensions are required. On the basis of the proposed molecular architecture, one can also envisage other similar molecules that could be successfully applied for the functionalization of surfaces for biosensing, chromatography, medical imaging, drug delivery, and aqueous lubrication, among others.

Fatigue of zirconia under cyclic loading in water and its implications for the design of dental bridges.

OBJECTIVES: The aim of this study was to evaluate the cyclic fatigue behavior of zirconia (3Y-TZP) in water and derive guidelines for the design of zirconia-based dental bridges with extended lifetime. METHODS: The subcritical crack growth parameters under aqueous and cyclic loading conditions were determined from Weibull distributions of the initial mechanical strength and of the lifetime of TZP specimens. The strength and lifetime data were obtained using a specially designed bending machine under simple and oscillatory loading conditions, respectively. RESULTS: The TZP components submitted to cyclic loading in water exhibited subcritical crack propagation at stress levels significantly ( approximately 50%) lower than the critical stress intensity factor (K(IC)=5.6 MPam(1/2)). In spite of this susceptibility to subcritical crack growth, calculations based on the fatigue parameters and on the stress applied on the prosthesis indicate that posterior bridges with zirconia frameworks can exhibit lifetimes longer than 20 years if the diameter of the bridge connector is properly designed. SIGNIFICANCE: This in vitro study indicates that partially stabilized zirconia (3Y-TZP) can withstand the severe cyclic loading and wet conditions typically applied in the molar region of the mouth and is therefore an appropriate material for the fabrication of all-ceramic multi-unit posterior bridges.

Mechanical and fracture behavior of veneer-framework composites for all-ceramic dental bridges.

OBJECTIVES: High-strength ceramics are required in dental posterior restorations in order to withstand the excessive tensile stresses that occur during mastication. The aim of this study was to investigate the fracture behavior and the fast-fracture mechanical strength of three veneer-framework composites (Empress 2/IPS Eris, TZP/Cercon S and Inceram-Zirconia/Vita VM7) for all-ceramic dental bridges. METHODS: The load bearing capacity of the veneer-framework composites were evaluated using a bending mechanical apparatus. The stress distribution through the rectangular-shaped layered samples was assessed using simple beam calculations and used to estimate the fracture strength of the veneer layer. Optical microscopy of fractured specimens was employed to determine the origin of cracks and the fracture mode. RESULTS: Under fast fracture conditions, cracks were observed to initiate on, or close to, the veneer outer surface and propagate towards the inner framework material. Crack deflection occurred at the veneer-framework interface of composites containing a tough framework material (TZP/Cercon S and Inceram-Zirconia/Vita VM7), as opposed to the straight propagation observed in the case of weaker frameworks (Empress 2/IPS Eris). SIGNIFICANCE: The mechanical strength of dental composites containing a weak framework (K(IC)<3 MPam(1/2)) is ultimately determined by the low fracture strength of the veneer layer, since no crack arresting occurs at the veneer-framework interface. Therefore, high-toughness ceramics (K(IC)>5 MPam(1/2)) should be used as framework materials of posterior all-ceramic bridges, so that cracks propagating from the veneer layer do not lead to a premature failure of the prosthesis.

Cyclic fatigue in water of veneer-framework composites for all-ceramic dental bridges.

OBJECTIVES: Ceramic materials applied in dentistry may exhibit significant subcritical crack growth due to the severe cyclic loading in the aqueous environment encountered in the mouth during mastication. The authors report on the subcritical crack growth behavior of three dental restoration systems (Empress 2/IPS Eris, TZP/Cercon S and Inceram-Zirconia/Vita VM7) under cyclic loading in water, in order to establish guidelines for the use and design of long-lifetime all-ceramic posterior bridges. METHODS: Inert strength and lifetime tests under cyclic loading in an aqueous environment were performed in a mechanical bending apparatus and evaluated with Weibull statistics. RESULTS: Subcritical crack growth occurred predominantly in the outer veneer layer of the veneer-framework composites. The apatite-based veneer (IPS Eris) was more susceptible to subcritical crack propagation compared to the feldspathic glass veneers (Cercon S and Vita VM7). SIGNIFICANCE: Dental restoration systems containing apatite-based veneers and weak frameworks (Empress 2/IPS Eris) are not recommended for the fabrication of all-ceramic bridges in the molar region. Conversely, veneer-framework systems consisting of feldspathic glass veneers and tough zirconia-based frameworks (TZP/Cercon S and Inceram-Zirconia/Vita VM7) may exhibit lifetimes longer than 20 years if the bridge connector is properly designed.