Robert H. Doremus

Enhanced functions of osteoblasts on nanophase ceramics

Select functions of osteoblasts (bone-forming cells) on nanophase (materials with grain sizes less than 100 nm) alumina, titania, and hydroxyapatite (HA) were investigated using in vitro cellular models. Compared to conventional ceramics, surface occupancy of osteoblast colonies was significantly less on all nanophase ceramics tested in the present study after 4 and 6 days of culture. Osteoblast proliferation was significantly greater on nanophase alumina, titania, and HA than on conventional formulations of the same ceramic after 3 and 5 days. More importantly, compared to conventional ceramics, synthesis of alkaline phosphatase and deposition of calcium-containing mineral was significantly greater by osteoblasts cultured on nanophase than on conventional ceramics after 21 and 28 days. The results of the present study provided the first evidence of enhanced long-term (on the order of days to weeks) functions of osteoblasts cultured on nanophase ceramics; in this manner, nanophase ceramics clearly represent a unique and promising class of orthopaedic/dental implant formulations with improved osseointegrative properties.

Specific proteins mediate enhanced osteoblast adhesion on nanophase ceramics

Osteoblast, fibroblast, and endothelial cell adhesion on nanophase (that is, materials with grain sizes less than 100 nm) alumina, titania, and hydroxyapatite (HA) was investigated using in vitro cellular models. Osteoblast adhesion was significantly (p < 0.01) greater after 4 h on nanophase alumina, titania, and HA than it was on conventional formulations of the same ceramics. In contrast, compared to conventional alumina, titania, and HA, after 4 h fibroblast adhesion was significantly (p < 0.01) less on nanophase ceramics. Examination of the underlying mechanism(s) of cell adhesion on nanophase ceramics revealed that these ceramics adsorbed significantly (p < 0.01) greater quantities of vitronectin, which, subsequently, may have contributed to the observed select enhanced adhesion of osteoblasts. Select enhanced osteoblast adhesion was independent of surface chemistry and material phase but was dependent on the surface topography (specifically on grain and pore size) of nanophase ceramics. The capability of synthesizing and processing nanomaterials with tailored (through, for example, specific grain and pore size) structures and topographies to control select subsequent cell functions provides the possibility of designing the novel proactive biomaterials (that is, materials that elicit specific, timely, and desirable responses from surrounding cells and tissues) necessary for improved implant efficacy.

Hydroxylapatite synthesis and characterization in dense polycrystalline form

A new process is described for preparing dense, polycrystalline hydroxylapatite. This material has close to theoretical density and is free of fine pores and second phases. The best material has an average compressive strength of 917 MN m−2 (133×103 psi), and polished samples have an average tensile strength of 196 MN m−2 (28.4×103 psi). The material is highly translucent, and the degree of translucence depends upon processing conditions. The relationship between processing variables and microstructure, strength, and translucence is described. This dense hydroxylapatite has good promise for bone implants and dental applications.

Enhanced osteoclast-like cell functions on nanophase ceramics

Synthesis of tartrate-resistant acid phosphatase (TRAP) and formation of resorption pits by osteoclast-like cells, the bone-resorbing cells, on nanophase (that is, material formulations with grain sizes less than 100nm) alumina and hydroxyapatite (HA) were investigated in the present in vitro study. Compared to conventional (that is, grain sizes larger than 100 nm) ceramics, synthesis of TRAP was significantly greater in osteoclast-like cells cultured on nanophase alumina and on nanophase HA after 10 and 13 days, respectively. In addition, compared to conventional ceramics, formation of resorption pits was significantly greater by osteoclast-like cells cultured on nanophase alumina and on nanophase HA after 7, 10, and 13 days, respectively. The present study, therefore, demonstrated, for the first time, enhanced osteoclast-like cell function on ceramic surfaces with nanometer-size surface topography.

INTERDIFFUSION OF HYDROGEN AND ALKALI IONS IN A GLASS SURFACE

Experimental data on the interdiffusion of hydrogen and alkali ions in glass are examined using a concentration-dependent interdiffusion coefficient, taking into account surface dissolution. The comparisons between calculated and experimental concentration profiles and diffusion coefficients are more satisfactory than for a concentration-independent diffusion coefficient, and support the use of the interdiffusion coefficient.

Silicon oxycarbide glasses: Part II. Structure and properties

Silicon oxycarbide glass is formed by the pyrolysis of silicone resins and contains only silicon, oxygen, and carbon. The glass remains amorphous in x-ray diffraction to 1400 °C and shows no features in transmission electron micrographs (TEM) after heating to this temperature. After heating at higher temperature (1500–1650 °C) silicon carbide lines develop in x-ray diffraction, and fine crystalline regions of silicon carbide and graphite are found in TEM and electron diffraction. XPS shows that silicon-oxygen bonds in the glass are similar to those in amorphous and crystalline silicates; some silicons are bonded to both oxygen and carbon. Carbon is bonded to either silicon or carbon; there are no carbon-oxygen bonds in the glass. Infrared spectra are consistent with these conclusions and show silicon-oxygen and silicon-carbon vibrations, but none from carbon-oxygen bonds. 29 Si-NMR shows evidence for four different bonding groups around silicon. The silicon oxycarbide structure deduced from these results is a random network of silicon-oxygen tetrahedra, with some silicons bonded to one or two carbons substituted for oxygen; these carbons are in turn tetrahedrally bonded to other silicon atoms. There are very small regions of carbon-carbon bonds only, which are not bonded in the network. This “free” carbon colors the glass black. When the glass is heated above 1400 °C this network composite rearranges in tiny regions to graphite and silicon carbide crystals. The density, coefficient of thermal expansion, hardness, elastic modulus, index of refraction, and viscosity of the silicon oxycarbide glasses are all somewhat higher than these properties in vitreous silica, probably because the silicon-carbide bonds in the network of the oxycarbide lead to a tighter, more closely packed structure. The oxycarbide glass is highly stable to temperatures up to 1600 °C and higher, because oxygen and water diffuse slowly in it.

Hydration of soda-lime glass☆

Abstract The hydration of soda-lime glass is studied using resonant nuclear reactions to measure the hydrogen and sodium profiles of hydrated glasses. The rate of growth of the surface layer of hydrated glass is initially proportional to the square root of time as is characteristic of diffusion controlled processes. After longer exposure a steady-state hydration profile is observed, which indicates that in addition to the diffusion controlled reaction there is a slow etching of the glass surface. The measured hydration profiles are discussed in relationship to the Doremus model of interdiffusing ions, which is found to be in good agreement with the data. This model is also discussed in relationship to measured hydration profiles of vacuum heated samples of hydrated glass.

Silicon oxycarbide glasses: Part I. Preparation and chemistry

Silicone polymers were pyrolyzed to form silicon oxycarbides that contained only silicon, oxygen, and carbon. The starting polymers were mainly methyl trichlorosilane with a small amount of dimethyl dichlorosilane. NMR showed that the polymers had a silicon-oxygen backbone with branching and ring units. When the polymer was heated in hydrogen, toluene and isopropyl alcohol, used in production of the polymer, were given off in the temperature range 150 °C to 500 °C. Substantial decomposition of the polymer itself began only above about 700°by evolution of methane. The network of silicon-oxygen bonds and silicon-carbon bonds did not react and was preserved; the silicon-carbon bonds were linked into the silicon-oxygen network. The silicon oxycarbide was stable above 1000 °C, showing no dimensional changes above this temperature. The interior of the silicon oxycarbide was at very low effective oxygen pressure because oxygen diffused slowly in it. There was also a protective layer of silicon dioxide on the surface of the silicon oxycarbide.

Viscosity of silica

Experimental measurements of the viscosity of silica (SiO2) are critically examined; the best measurements show an activation energy of 515 kJ/mole above 1400 °C and 720 kJ/mole below this temperature. The diffusion of silicon and oxygen in silica have temperature dependencies close to that of the high temperature viscosity. Mechanisms of viscous flow and diffusion of silicon and oxygen in silica are proposed that involve motion of SiO molecules. Viscous flow is proposed to result from the motion of line defects composed of SiO molecules At temperatures below 1400 °C the fraction of SiO molecules in line defects changes with temperature. The relaxation of this fraction to an equilibrium value depends on the time. These proposed mechanisms are consistent with experimental measurements of silica viscosity.

The infrared transmission spectra of four silicate glasses before and after exposure to water

The infrared transmission spectra of four silicate glasses were investigated. By using blown glass films, 1–2 μm thick, detailed infrared transmission spectra were generated over the 4000–180 cm −1 range, both before and after the films were exposed to water. The water had little effect on the spectra of the 70SiO 2 –20Na 2 O–10Al 2 O 3 (mol %) and Pyrex compositions, but had a large effect on the spectra of the 70SiO 2 –30Na 2 O (mol %) and Corning 015 compositions. The Si–O nonbridged stretching band at ∼950 cm −1 and a largely overlooked bending band at ∼600 cm −1 were the bands most sensitive to hydration in the 70/30 and 015 compositions. Changes were also seen in the Si–O–Si bridged stretching bands at ∼1050 cm −1 and ∼770 cm −1 . The water, however, had no effect on the dominant Si–O–Si bending band at 460 cm −1 . It was also discovered that the 70/30 and 015 films reacted with the atmosphere to form a carbonate layer on their surface. This carbonate accounted for the 1450 cm −1 and 230 cm −1 bands seen in their infrared transmission spectra.