Timo Peltola

Calcium phosphate induction by sol-gel-derived titania coatings on titanium substrates in vitro

Titanium and its alloys are used widely in the manufacture of orthopedic and dental implants. Sol-gel-prepared titania is able to stimulate bone-like apatite formation in in vitro and in vivo cultures. These materials can be used, for example, as coatings on dental and orthopedic implants. However, the processes that lead to apatite formation are not fully understood. In this study different kinds of titania coatings on commercially pure titanium (c.p. Ti) were tested for apatite-forming ability. The rate of apatite formation is considered to be descriptive of a materials bioactive (bone-bonding) potential. Apatite-forming tests were done in simulated body fluid (SBF). Apatite-forming ability was highest with the addition of valeric acid to sol (600 degrees C) or with sintering sol-gel coatings at 450 degrees-550 degrees C. At that temperature range calcium phosphate forms on the coatings in 1 week. Calcium phosphate forming is observed in 1 day on standard coatings sintered at 500 degrees C.

Influence of sol and surface properties on in vitro bioactivity of sol-gel-derived TiO2 and TiO2-SiO2 films deposited by dip-coating method

Different sol-gel-derived titania and titania-silica films were prepared and their properties related to in vitro bioactivity. The films were prepared by depositing the sols on the substrate surface using a dip-coating method. The sols were monitored carefully as a function of time, using rheological techniques and dynamic light scattering. The topography of the films was characterized using atomic force microscopy, and thicknesses and refractive indexes of the films were evaluated by fitting transmittance spectra measured in a wave length region of 370-1100 nm with a spectrophotometer. The in vitro bioactivity tests were performed in simulated body fluid. Surface topography was found to be of great importance with respect to the bioactivity of the studied films.

Calcium phosphate formation on porous sol-gel-derived SiO2 and CaO-P2O5-SiO2 substrates in vitro.

Sol-gel-derived SiO2 and CaO-P2O5-SiO2 have been shown to be bioactive and bone bonding. In this study bioactive sol-gel-derived SiO2 and CaO-P2O5-SiO2 systems were tested for in in vitro bioactivity. The calcined ceramic monoliths were immersed in a simulated body fluid and analyzed to follow the hydroxyapatite formation on the ceramic surface. Apatite-forming ability was investigated in terms of structural changes by changing the composition and the preparation method. The role of Ca and P dopants in the substrate structure is complicated, and careful characterization is needed. The composition and structure together determine the in vitro bioactivity. The pore structure was analyzed using N2-adsorption/desorption isotherms. The results indicate that a great mesopore volume and a wide mesopore size distribution favor hydroxycarbonate apatite nucleation and a great surface area is not needed. The performed preparation process for silica in a basic environment provides a convenient way to prepare a mesoporous material.

Effect of aging time of sol on structure and in vitro calcium phosphate formation of sol-gel-derived titania films.

Titanium and its alloys have been used successfully in the manufacture of orthopedic and dental implants to replace damaged bone tissue. In this study, different sol-gel-derived TiO(2) coatings were produced on titanium substrates using different aging times (5, 10, 24, or 48 h) of the sol before dipping the coatings and varying numbers (one, three, or five) of coating layers. The influence of the aging time of the sol on the structure of the titania coatings with respect to in vitro bioactivity was investigated. The in vitro bioactivity tests were done in a simulated body fluid (SBF). The sol properties were monitored using a capillary viscometer and dynamic light scattering to determine the viscosity and particle size, respectively. The topography of the films was characterized using atomic force microscopy. The various sol aging times and numbers of layers produced differences in the topography of the titania films. For the coatings with one and three layers, the aging of the sols had an influence on the height of the peaks (lower with longer aging times) although the peak distance was about the same. The number of coating layers had a stronger influence. The distribution of the peak distances became narrower with an increasing number of coating layers. The coating with three layers (top coating prepared after 24 h of sol aging) and the coatings with five layers had a similar distribution of peak distances (15-50 nm), which was favorable for calcium phosphate formation. On these substrates, calcium phosphate formation started within 3-6 days of immersion in SBF. The aging time of the titania sol and the number of coating layers were found to have a strong influence on the surface topography in the nanometer scale of the titania films. The results indicate that the topography of the outermost surface is of importance for in vitro bioactivity.

Surface properties of in vitro bioactive and non-bioactive sol-gel derived materials.

The acid-base properties of several in vitro bioactive (able to form bone mineral-like calcium phosphate on their surfaces) and non-bioactive sol-gel processed oxides are studied. The amount of Lewis acid sites was calculated from the pyridine adsorption using the Langmuir adsorption model. The Henry adsorption model was used in cases where no specific affinity between the adsorbent and the probe molecule was observed. The results were used to calculate the specific amounts of acidic and basic sites on SiO2- and TiO2-based materials. The zeta potential was measured for dip-coated TiO2 films, calcium- and phosphate-doped TiO2 films and for a non-bioactive Al2O3 film. Also, the calcium phosphate formation in simulated body fluid on in vitro bioactive TiO2 film was studied with zeta potential measurements. The results showed dependence on the negative surface charge and the important role of calcium adsorption in the beginning of the calcium phosphate formation. Surface topography of the films was investigated with atomic force microscopy, including a detailed analysis of the peak heights and distribution over cross sections. It was observed that in vitro bioactivity was strongly dependent on the nanoscale dimensions. Consequently, the in vitro calcium phosphate formation seems to be due to both the chemical interactions and the surface structure.

Osteoblast differentiation of bone marrow stromal cells cultured on silica gel and sol-gel-derived titania.

Primary cultures of osteogenic precursor cells derived from rat bone marrow stroma were performed on commercially available pure titanium discs (Ti c.p.) and surface modified Ti c.p.using a sol-gel technique (Ti sol). In separate repeated experimental runs, cell behavior and in vitro mineralization were compared with cultures on silica gel bioactive glass discs (S53P4). All substrates were incubated in simulated body fluid prior to the experiment. Overall, variable effects between experimental runs were seen. Apparently, this was due to the heterogeneous nature of the used cell population. Therefore, only careful conclusions can be made. Initial cell adhesion and growth rates between 3 and 5 days of culture--analyzed by cell numbers--were in general comparable for the two titanium substrates, while initial growth up to day 3 is suggested to be higher in Ti c.p. compared to Ti sol. Although initial cell adhesion on the S53P4 glass discs was lower than the titanium substrates, cell growth rates appeared to be higher on the silica gel compared to the two titanium substrates. Further, there were some indications that the early and late osteoblast differentiation markers, alkaline phosphatase and osteocalcin, monitored up to day 24, were elevated in Ti c.p cultures compared to Ti sol cultures. There were no differences observed in in vitro mineralization between the titanium groups. S53P4 seemed to display a substantially higher differentiating capacity for both osteogenic cell markers as well as in vitro mineralization compared to the two titanium substrates.

Effect of Hydroxyapatite and Titania Nanostructures on Early In Vivo Bone Response

PURPOSE Hydroxyapatite (HA) or titania nanostructures were applied on smooth titanium implant cylinders. The aim was to investigate whether nano-HA may result in enhanced osseointegration compared to nano-titania structures. MATERIALS AND METHODS Surface topography evaluation included detailed characterization of nano-size structures present at the implant surface combined with surface roughness parameters at the micro- and nanometer level of resolution. Microstructures were removed from the surface to ensure that bone response observed was dependent only on the nanotopography and/or chemistry of the surface. Early in vivo histological analyses of the bone response (4 weeks) were investigated in a rabbit model. RESULTS In the present study, nano-titania-coated implants showed an increased coverage area and feature density, forming a homogenous layer compared to nano-HA implants. Bone contact values of the nano-titania implants showed a tendency to have a higher percentage as compared to the nano-HA implants (p = .1). CONCLUSION Thus, no evidence of enhanced bone formation to nano-HA-modified implants was observed compared to nano-titania-modified implants. The presence of specific nanostructures dependent on the surface modification exhibiting different size and distribution did modulate in vivo bone response.

Bonding Strengths of Titania Sol-Gel Derived Coatings on Titanium

Bioactive ceramic coatings have had poor adhesion to substrate. In this study, the bond strength (tensile strength) of titania gel coating to titanium substrate was studied. In the experiments three different pretreatments were used, namely sodium hydroxide corroding, plasma cleaning and titanium nitride coating. Also the effects of heating temperature, heating in vacuum and titanium surface roughness were studied. The sol properties were altered with valeric acid addition. Samples were analysed by SEM-EDX, AES, AFM and tested by bond strength gauge. Those samples in which the titanium surface was precorroded one hour in sodium hydroxide, predeposited by titanium nitride or ground improved the bonding strengths of titania coatings to over 24 MPa. In these samples a fracture occurred at the glue-coating interface.

Influence of sol and stage of spinnability on in vitro bioactivity and dissolution of sol-gel-derived SiO2 fibers.

The ability of the sol-gel-derived green state silica fibers to induce the formation of bone-like calcium phosphate (HCA) on their surfaces has not been studied earlier. Bioactive silica fibers provide alternatives for the design of novel products, e.g., as implants used in tissue guiding or bone repairs. In this study, dry spinning was used to prepare the sol-gel fibers. Different fibers with different bulk structures were prepared by changing the composition and controlling the stage of spinnability. Additionally, the influence of the aging time of the fibers on the bulk structure of the samples was investigated. Furthermore, the ability to form calcium phosphate was investigated in vitro in the simulated body fluid (SBF). Transmission electron microscopy was used to illustrate the bulk structure of the green state fibers and scanning electron microscopy to illustrate the formed calcium phosphate layer on the fibers. The fibers were additionally characterized by measuring the dissolution of the silica in the SBF. In vitro bioactive silica fibers were successfully prepared. The calcium phosphate layer was formed within 1-5 days in the best case. The structural stability and the in vitro bioactivity varied with the aging time expect in one case where practically stable fibers could be prepared. The concentration of silica released in the SBF had no direct connection with the HCA formation. The silica-rich gel layer was not observed on the fibers, but the structure of the fibers was suggested to have an important role in the HCA formation.

RELATION BETWEEN AGGREGATION AND HETEROGENEITY OF OBTAINED STRUCTURE IN SOL-GEL DERIVED CAO-P2O5-SIO2

Potentially bioactive sol-gel derived CaO-P2O5-SiO2 systems are studied and the influence of aggregation mechanism on the gel structure is discussed. A rheological measuring technique is used to monitor the aggregation process and the results are related to heterogeneity of the obtained gel structure. The results indicate that heterogeneity is produced in the sol-gel transition when calcium nitrate and phosphoric acid are used as precursors of CaO and P2O5. This destroys the correlation between bioactivity and the calcium and phosphorus content of the gel derived glasses.