George R. Baran

The role of surface functional groups in calcium phosphate nucleation on titanium foil: a self-assembled monolayer technique

Surface functional groups play important roles in nucleating calcium phosphate deposition on surgical titanium implants. In this study, various functional groups were introduced onto the surface of commercially pure titanium foils using a self-assembled monolayer (SAM) technique. An organic silane, 7-oct-1-enyltrichlorosilane (OETS) was used and -OH, -PO4H2, -COOH groups were derived from its unsaturated double bond. Ti foils were first oxidized in concentrated H2SO4/H2O2. ESCA and contact angle measurements were used to characterize the SAM surfaces and confirm the presence of various functional groups. A fast calcium phosphate deposition experiment was carried out by mixing Ca2+- and (PO4)(3-)-containing solutions in the presence of the surface-modified Ti samples at pH 7.4 at room temperature in order to verify the nucleating abilities of these functional groups. SEM, Raman spectroscopy, XRD and ATR-FTIR results showed that poorly crystallized hydroxyapatite (HA) can be deposited on the SAM surfaces with -PO4H2 and -COOH functional groups, but not onto the SAM with -CH=CH2 and -OH. -PO4H2 exhibited a stronger nucleating ability than that of -COOH. The oxidized Ti sample also showed some calcium phosphate deposition but to a lesser extent as compared to SAM surfaces with -PO4H2 and -COOH. The pre-deposited HA can rapidly induce biomimetic apatite layer formation after immersion in 1.5 SBF for 18 h regardless of the amount of pre-deposited HA. The results suggested that the pre-deposition of HA onto these functionalized SAM surfaces might be an effective and fast way to prepare biomimetic apatite coatings on surgical implants.

Silane treatment effects on glass/resin interfacial shear strengths

OBJECTIVE Methacrylic resin-based dental composites normally use a bifunctional silane coupling agent with an intermediary carbon connecting segment to provide the interfacial phase that holds together the organic polymer matrix with the reinforcing inorganic phase. In this study, fiber pull-out tests were used to measure the interfacial bond strength at the fiber-matrix interface. METHODS Glass fibers (approximately 30 microm diameter, 8 x 10 (-2)m length, MoSci) were silanated using various concentrations (1, 5 and 10%) of either 3-methacryloxypropyl-trimethoxysilane (MPS) or glycidoxypropyltrimethoxy-silane (GPS) in acetone (99.8%). Rubber (poly(butadiene/acrylonitrile), amine terminated, M(w) 5500) molecules were also attached to the fiber surface via GPS molecules. The resin was comprised of a 60/40 mixture of Bis-phenol-A bis-(2-hydroxypropyl)-methacrylate (BisGMA) and tri (ethylene glycol) dimethacrylate (TEGDMA). A bead of resin approximately 2-4 x 10(-3)m in embedded length was placed on the treated fibers and light cured. The load required to pull the fiber out of the resin was converted to shear bond strength. RESULTS Interfacial shear strengths were greater for silanated specimens compared with unsilanated, and for MPS compared with GPS. The same set of samples soaked in 50:50 (v/v) mixtures of ethanol and distilled water for a period of 1 month showed a decrease in properties. SIGNIFICANCE A positive correlation was found between the amount of silane on the filler surface and the property loss after soaking. Rubber treatment provided improvement in interfacial strength. 5% MPS samples had the highest strength both in soaked as well as unsoaked samples.

Fatigue of Restorative Materials

Failure due to fatigue manifests itself in dental prostheses and restorations as wear, fractured margins, delaminated coatings, and bulk fracture. Mechanisms responsible for fatigue-induced failure depend on material ductility: Brittle materials are susceptible to catastrophic failure, while ductile materials utilize their plasticity to reduce stress concentrations at the crack tip. Because of the expense associated with the replacement of failed restorations, there is a strong desire on the part of basic scientists and clinicians to evaluate the resistance of materials to fatigue in laboratory tests. Test variables include fatigue-loading mode and test environment, such as soaking in water. The outcome variable is typically fracture strength, and these data typically fit the Weibull distribution. Analysis of fatigue data permits predictive inferences to be made concerning the survival of structures fabricated from restorative materials under specified loading conditions. Although many dental-restorative materials are routinely evaluated, only limited use has been made of fatigue data collected in vitro: Wear of materials and the survival of porcelain restorations has been modeled by both fracture mechanics and probabilistic approaches. A need still exists for a clinical failure database and for the development of valid test methods for the evaluation of composite materials.

Filler‐coupling agent‐matrix interactions in silica/polymethylmethacrylate composites

The interactions of the silane coupling agent methacryloxypropyltrimethoxysilane (MPS) with both fumed silica and a polymethylmethacrylate (PMMA) resin matrix were investigated using thermogravimetric analysis and Fourier transform infrared spectroscopy. OX 50 fumed silica was silanated with MPS at concentrations of 1% and 5% in aqueous ethanol (95%), acetone, and anhydrous toluene. Methyl methacrylate was polymerized with the silanated fumed silica (5% wt/wt) to form composites. The amount of MPS adsorption on the fumed silica and the amount of PMMA attached to the silanated fumed silica were determined by thermogravimetric analysis. MPS could be removed from the fumed silica after washing with methanol, but not after it underwent a drying process at 25 degrees C under vacuum. After vacuum drying at 25 degrees C, two types of adsorbed silane were found, i.e., firmly adsorbed and loosely adsorbed silane. The loosely adsorbed silane could desorb from silica and be incorporated into the polymer matrix through copolymerization with monomeric methyl methacrylate, resulting in crosslinking of the matrix. When the silanated silica was dried at 110 degrees C for 2 h, the loosely adsorbed silane was removed and the amount of firmly adsorbed silane increased. There was a positive correlation between the amount of firmly adsorbed MPS and the amount of PMMA attachment. The highest efficiency for PMMA attachment was found when MPS was adsorbed as a monolayer, because the loosely adsorbed silane did not contribute to the bonding of PMMA, and this suggested that not all of the double bonds of the MPS were accessible for reaction with the methacrylate monomer. Drying at 110 degrees C may also decrease the number of unsaturated double bonds of MPS.

The role of adsorbed endotoxin in particle-induced stimulation of cytokine release.

Numerous in vitro models have demonstraed the capacity of wear particles to stimulate the release of soluble pro‐inflammatory products with the ability to induce local bone resorption. Recent observations have demonstrated that binding of lipopolysaccharide (LPS) to particulate wear deris can significantly modulate the pattern of cell response in the in vitro models. These findings raise concerns over the possible role of LPS in the athogenesis of aseptic looseing after total joint replacements, and also indicates the importance of controlling for possible confounding effects of LPS contamination in the in vitro models used to study the reactive nature of wear debris. Our studies were undertaken to rigorously analyze the effects of particle‐associated LPS on cell responses and to assess the efficacy ofdifferent treatment protocols to inactivate LPS associated with different particulate materials. Particles of cobalt‐chrome alloy, titanium‐6‐aluminum‐4‐vanadium, titanium nitride and silica were pretreated with LPS and exposed to multiple treatment protocols. When cells were treated with „as‐received”︁ particles prepared by washing in ethanol, small amounts of TNF‐α, IL‐1β, and IL‐1α were detected. In contrast, all particle species pretreated with LPS produced marked increases in TNF‐α, IL‐1α, and IL‐1β release, as well as upregulation of corresponding mRNa levels even after ethanol washing. Boiling the LPS‐pretreated particles in 1% acetic acid or autoclaving and baking the particles also markedly reduced and in some instances abolished the effect of the LPS‐pretreatment. This indicates that LPS binds to the surface of particles of diverse composition and that the bound LPS is biologically active. Treatment protocols to inactivate particle‐associated LPS demonstrated significant differences in effcacy. When the most rigorous treatments were utilized, essentially all LPS activity could be eliminated. Particles treated with these methods retained some capacity to stimulated cytokine release, but activities were markedly reduced. These results provide further evidnce indicating that LPS contamination of particulate materials can markedly enhance their biological activity. This potential confounding effect needs to be carefully monitored and controlled in the in vitro model systems systems used to evaluate wear particles. Furthermore, the presence of particle‐associated endotoxin at the bone‐implant interface in vivo could markedly enhance the adverse biological activity of particulate wear debris.

Determination of the degree of cure of dental resins using Raman and FT-Raman spectroscopy

FT-IR spectroscopy has traditionally been used to determine the degree of conversion of dental resins. FT-Raman scattering provided an alternate method of obtaining degrees of conversion for these systems and was particularly useful for measuring spectra of materials without any sample preparation. Raman and FT-Raman spectroscopy gave identical results, but the latter technique was preferred for the highly fluorescent samples often encountered in commercial composites. Linear calibration curves were obtained for the aromatic mixtures Bis-GMA/TEGDMA and Bisphenol-A/TEGDMA using C = C/phi, and for the wholly aliphatic mixture EGDMA/EGDA using C = C/C = O, over a wide range of mole ratios. If both the mole and intensity ratios [C = C/phi or C = C/C = O] were known for an uncured dental resin, then the degrees of conversion could be obtained for the cured materials using Raman spectroscopy. However, if the mole ratios for the uncured resin were unknown, then the degree of conversion depended on the calibration curve, since the Raman scattering cross section of the vibrational modes depended on the molecules to which they were attached.

The metallurgy of Ni-Cr alloys for fixed prosthodontics

Ni-Cr alloys continue to be an important part of dental restorative materials. It behooves those interested to study these alloys and develop an understanding of their chemical and physical characteristics. Introduction of new alloys almost monthly presents an educational challenge to the entire profession. Many dental schools do not use Ni-Cr alloys for fixed prosthodontics because questions exist about the efficacy and performance of such alloys. These doubts may be resolved by continued research. Concern about mechanical properties can be alleviated if an understanding of the requirements for successful use, for example, casting, burnishing, polishing, and stresses encountered in service, is achieved. Information on the nature of corrosion intraorally is needed, particularly with regard to correlating in vitro testing with in vivo performance. Further studies of porcelain-alloy compatibility are indicated to understand properties affecting compatibility. Performance of high-temperature porcelain-alloy systems could influence processing techniques so that specific materials could be used more appropriately. In addition, the nature of porcelain-to-alloy bonding may be revealed by use of advanced chemical analysis techniques to identify processes occurring at the atomic level, with identification of oxides and reacted zone produces may also provide data for design of new alloys for porcelain-metal systems. Finally, factors related to the clinical performance of nickel-based alloys, including their allergenic potential, have not been considered in this report.

Nanoindentation studies of titanium single crystals.

Titanium single crystal planes of different atomic density have been reported to show different oxidation characteristics. The differences in oxide characteristics have further been demonstrated to lead to differences in osteoblast attachment. Investigations of the preferred crystallographic planes of titanium for osteoblast attachment can be used to optimize the surfaces of single crystal and polycrystalline titanium implants for anchoring various prostheses. Nanoindentation techniques were used to determine mechanical properties of two crystallographic planes of titanium of different atomic density. Modulus of elasticity of 128 +/- 10 GPa was obtained for polycrystalline titanium and 123 +/- 5 and 124 +/- 6 GPa for the basal plane and pyramidal planes, respectively. The variation of modulus with crystal orientation was not greater than the statistical variation in the data. Surface hardness values were 2.1 +/- 0.1 GPa for the polycrystalline sample and 1.6 +/- 0.1 and 1.9 +/- 0.1 GPa, respectively, for the basal and pyramidal planes. Curves of hardness as a function of depth (0-2000 nm) obtained from electrochemically polished surfaces showed a sharp increase at shallow depths and may reflect changes caused by oxidation of the titanium surfaces.

The use of a transition rod may prevent proximal junctional kyphosis in the thoracic spine after scoliosis surgery: a finite element analysis.

Study Design. Finite element analysis. Objective. Via finite element analysis: (1) to demonstrate the abnormal forces present at the top of a scoliosis construct, (2) to demonstrate the importance of an intact interspinous and supraspinous ligament (ISL/SSL) complex, and (3) to evaluate a transition rod (a rod that has a short taper to a smaller diameter at one end) as an implant solution to diminish these pathomechanics, regardless of the integrity of the ISL/SSL complex. Summary of Background Data. The pathophysiology of increased nucleus pressure and increased angular displacement may contribute to proximal junctional kyphosis. Furthermore, high implant stress can be demonstrated at the upper end of the construct, possibly leading to the risk of implant failure. Methods. A finite element model was constructed to simulate a thoracic spinal fusion. The model was altered to remove the ISL/SSL complex at the level above the construct. Then, the model was altered again by extending the construct one level superior with a transition rod. The angular displacement, the maximum pressure in the nucleus, and stress within the implant were extracted from computational results under 2 conditions: load control and displacement control. The testing was performed with both titanium and stainless steel implants. Results. Pressure in the nucleus and angular displacement are all increased when the ISL/SSL complex is removed immediately above the instrumented levels, whereas the screw pullout force and maximum stress within the screw are decreased. The nucleus pressure increases by more than 50%. The angular displacement increases by 19% to 26%. This absence of the ISL/SSL complex simulates the clinical scenario that occurs when these structures are iatrogenically detached. Abnormal mechanics can be restored to normal level by extending the construct rostral one level with a transition rod. Furthermore, the elevated nucleus pressure and angular displacement noted even when the ISL/SSL complex is intact can be avoided with the use of a transition rod. Under the same bending moment (3 Nm), the nucleus pressure at the level immediately cephalad is up to 23% lower than the pressure in a standard construct. The angular displacement is 18% to 19% less than the standard construct. The maximum implant stress is also decreased by as much as 60%. Conclusion. Finite element modeling suggests that the pathomechanics at the proximal end of a scoliosis construct may be diminished by preserving the ISL/SSL complex and possibly completely eliminated with the use of rods with a diameter transition at the most proximal level.

Predictive modeling of elastic properties of particulate-reinforced composites

The Youngs modulus and Poissons ratio of isotropic composites made of particulate glass fillers in a BISGMA/TEGDMA resin matrix are determined using an axisymmetric spherical cell finite-element model developed by Guild and co-authors for modeling the elastic properties of rubber particles/epoxy composites with volume fractions of less than 0.5. Here, we have used this method to calculate the elastic properties of particulate-filled composites with a range of filler volume fractions, including those with filler fractions above 0.5, which are of primary interest for dental clinical applications. We have also conducted modeling studies on the influence of imperfect interfaces and thin interlayers on the elastic properties of composites with low and high filler volume fractions. Finally, we have conducted experimental tensile tests in order to compare theoretical predictions with experimental data. The predictions from the current model agree well with the test results for a range of volume fraction up to 0.53.