Control of phase composition in hydroxyapatite/tetracalcium phosphate biphasic thin coatings for biomedical applications.

Biphasic calcium phosphates comprising well-controlled mixtures of nonresorbable hydroxyapatite and other resorbable calcium phosphate phases often exhibit a combination of enhanced bioactivity and mechanical stability that is difficult to achieve in single-phase materials. This makes these biphasic bioceramics promising substrate materials for applications in bone tissue regeneration and repair. In this paper we report the synthesis of highly crystalline, biphasic coatings of hydroxyapatite/tetracalcium phosphate with control over the weight fraction of the constituent phases. The coatings were produced by pulsed laser deposition using ablation targets of pure crystalline hydroxyapatite. The fraction of tetracalcium phosphate phase in the coatings was controlled by varying the substrate temperature and the partial pressure of water vapor in the deposition chamber. A systematic study of phase composition in the hydroxyapatite/tetracalcium phosphate biphasic coatings was performed with X-ray diffraction. Tetracalcium phosphate in the coatings obtained at high substrate temperature is not formed by partial conversion of previously deposited hydroxyapatite. Instead, it is produced by nucleation and growth of tetracalcium phosphate itself from the ablation products of the hydroxyapatite target or by accretion of tetracalcium phosphate grains formed during ablation. This finding was confirmed by formation of calcium oxide, not tetracalcium phosphate, after annealing of pure hydroxyapatite coatings at high temperatures of 700-850 degrees C.

Interaction between topography and coating in the formation of bone nodules in culture for hydroxyapatite- and titanium-coated micromachined surfaces.

Rat osteoblast cultures were maintained from 24 h to 6 weeks on hydroxyapatite (HA)- or titanium (Ti)-coated smooth and micromachined grooved substrata in medium supplemented with L-ascorbic acid-2-phosphate and beta-glycerophosphate to promote mineralization. The HA coatings, approximately 1 microm thick, were characterized using X-ray diffraction, surface roughness, and scanning electron microscopy (SEM). Osteoblasts elongated, aligned, and moved in the direction of the grooves on both Ti and HA grooved surfaces. HA surfaces produced significantly more bone-like nodules than Ti surfaces. All grooved substrata produced significantly more nodules than smooth surfaces. These results are consistent with the hypothesis that substrata can increase osteogenesis by formation of an appropriate microenvironment. There was also a statistically significant interaction between topography and chemistry in the formation of mineralized nodules. A strong correlation (r = 0.958) between alkaline phosphatase (Alk-P) at 2 weeks and nodule counts at 6 weeks was observed, suggesting that Alk-P may possibly be used as a leading indicator of osteogenesis on microfabricated surfaces. The results of this study indicate that surface topography and chemistry can affect osteogenesis, and that interactions between chemistry and topography can occur.

Orthodontic in vivo bond strength: comparison with in vitro results.

The purpose of the present study was to test a new in vivo debonding device and compare in vivo bond strengths recorded by this device with in vitro bond strengths recorded by a universal testing machine such as the Instron. For the in vitro part of the study, 60 extracted premolar teeth were divided into 2 groups of 30 each. Both groups of 30 teeth had 3M Unitek Victory Twin brackets, precoated with Transbond XT composite resin, bonded to them. Shear bond strength tests were carried out in vitro using the universal testing machine on one group of 30 teeth while the debonding device was used on the other group of 30 teeth. The mean shear bond strength of the group debonded using the universal machine was 11.02 MPa and that of the group debonded with the debonding device was 12.82 MPa. For the in vivo part of the study, 8 patients randomly assigned to the research clinician from patients in The University of Alabama School of Dentistry, Department of Orthodontics, had a total of 60 premolar teeth bonded with 3M Unitek Victory Twin brackets. Following comprehensive orthodontic treatment (average time of 23 months), shear bond strength tests were carried out using the debonding device, which can measure debonding forces in vivo. The mean shear bond strength recorded in vivo was 5.47 MPa. Statistically significant differences were found between all 3 groups tested. The results appear to indicate that mean bond strengths recorded in vivo following comprehensive orthodontic treatment are significantly lower than bond strengths recorded in vitro.

Structural and morphological study of pulsed laser deposited calcium phosphate bioceramic coatings: influence of deposition conditions, laser parameters, and target properties.

Calcium phosphate (CaP) bioceramics, especially hydroxyapatite (HA), have been used as coatings on implants owing to their biocompatible properties. The commercial practice for applying HA coating, plasma spraying, has some disadvantages which limit the long-term stability of the implants. Pulsed laser deposition (PLD) is being investigated as an alternative technique. The purpose of this research was to systematically study the effect of various parameters of the PLD process on the properties of CaP coatings. In this study, three types of HA targets and two laser wavelengths were used to make six categories of coatings. Predominantly crystalline HA coatings were produced under all six categories at optimum conditions, although small amounts of minor phases sometimes were found. Sufficient coating/substrate bond strength was also obtained. A wide variety of coating morphologies was obtained, from rather dense and uniform to rough and porous. The important factors that affected the morphology included target properties, vacuum level, deposition temperature, and laser wavelength and energy density. PLD's ability to produce both amorphous and crystalline, and both smooth/dense and rough/porous coatings may be a unique advantage.

The study of surface transformation of pulsed laser deposited hydroxyapatite coatings.

Hydroxyapatite (HA) coatings generally exhibit very good biocompatibility owing to their compositional resemblance to the natural hard tissue and to bioactive properties that are directly related to surface transformations in physiological fluids. In this study, two types of porous HA coatings produced with pulsed laser deposition were tested with respect to their dissolution/reprecipitation in a semidynamic simulated physiological solution. Coatings with higher porosity produced with a 355-nm wavelength laser exhibited significant reprecipitation earlier than those produced with a 266-nm wavelength laser. The dissolution of the non-HA phases played a major role in the reprecipitation of HA-like material as indicated by X-ray diffraction (XRD). The coatings' Ca/P ratio became closer to the theoretical value of HA. The newly formed HA had imperfect crystal structure and/or small crystal size as suggested by XRD. The reprecipitation resulted in a very dense morphology as shown by scanning electron microscopy, suggesting a mechanically strong structure after reprecipitation. Despite undergoing dissolution and reprecipitation, the coatings showed sufficient stability in the solution, as XRD and energy-dispersive X-ray studies indicated no significant loss of the coatings. The stability of these HA coatings and their ability to cause reprecipitation of HA in the simulated physiological solution showed the potential of these coatings for clinical applications.

XPS, EDX and FTIR analysis of pulsed laser deposited calcium phosphate bioceramic coatings: the effects of various process parameters.

Many techniques have been used to produce calcium phosphate, especially hydroxyapatite (HA), coatings on metallic implant surfaces for improved biocompatibility. Although some techniques have produced coatings used clinically, the long-term stability of the coating/implant is still questionable. As a new technique for making HA coatings, pulsed laser deposition (PLD) shows some advantages in controlling the coatings' crystal structure and composition. In this study, three types of HA target and two wavelengths of laser were used to produce calcium phosphate coatings. Despite PLDs ability to improve the crystal structure by incorporating water vapor into the deposition process, the characterization with EDX and XPS showed that coatings had different Ca/P ratios from that of the pure HA targets, which almost assured the presence of non-HA phases. FTIR spectra also showed differences in phosphate bands of coatings and targets although the difference in data collecting modes might have been a factor. The observed differences might be related to the differences between the surface and bulk chemistries of the coatings. Nevertheless, when evaluating the suitability of the PLD technique for making HA coatings, the possibility of the formation of non-HA phases cannot be excluded, although it may not necessarily be a negative factor.

Bond strength of prosthodontic luting materials to titanium after localized cyclic loading.

PURPOSE: To establish an in vitro analysis system to evaluate the effect of cyclic loading on the bond strengths and durability of luting materials bonded to titanium. MATERIALS AND METHODS: Machine-milled titanium disks were finished with 600 grit silicon-carbide paper and pairs of disks were bonded together using the five different luting materials. A stainless steel stylus was vertically loaded at a center position (Model 1) or at the border (Model 2) of the specimens with a force of 75.6 N at 7500 cycles/hr. When the stylus contacted the specimen surface through the water slurry of poly(methyl methacrylate) beads, it rotated clockwise up to 15 degrees and counter-rotated. Shear bond strengths were determined 1 hr after bonding, after storage in water at room temperature for 24 hr, and after the loading for 100,000 cycles. RESULTS: The bond strengths of the unfilled adhesive resin and resin-based composite cement (RBC) were significantly higher than those of the glass-ionomer cements. Zinc phosphate cement demonstrated no bonding ability to titanium. After 100,000 cycles, peripheral loading in Model 2 significantly reduced the bond strength of the RBC and glass-ionomer cements, while Model 1 loading did not. The highest and the most durable bonds were obtained with the unfilled adhesive resin in both models.

An in vitro evaluation of a metal reinforced orthodontic ceramic bracket.

The objectives of the present study were to measure and compare the bond strength and failure sites of a currently available ceramic bracket (Transcend 3M-Unitek) with the new metal reinforced ceramic bracket (Clarity 3M-Unitek) and to evaluate the amount of composite left on the tooth using the Adhesive Remnant Index in the teeth that were debonded with pliers recommended for this purpose. In addition, the presence or absence of enamel damage after debonding was also assessed. One hundred and twenty extracted premolar teeth were divided into 4 groups of 30 each. Two groups of 30 teeth had Transcend 6000 brackets bonded, and the other 2 groups had Clarity brackets bonded. Shear bond strength was carried out on 30 Transcend 6000 brackets and 30 Clarity brackets, whereas the other 2 groups of 30 teeth bonded with Transcend 6000 and Clarity brackets were debonded with debonding pliers recommended by the manufacturer of both ceramic brackets. The mean shear bond strength of the Clarity brackets was 13.27 MPa, whereas that of the Transcend 6000 was 21.19 MPa. Both brackets failed mostly at the bracket-adhesive interface (75%), indicating a possible reduction of the chances of enamel damage. Six of the premolars, bonded with Transcend 6000 brackets and debonded with the plier, showed an increase in the number or length of enamel cracks as evaluated by an optical microscope (Micro-Vu); one premolar, bonded with Clarity brackets and debonded with the pliers, showed an increased enamel crack length. Gross enamel damage, assessed by enamel dislodgment, was not evident in any specimen. Results of this study suggest that the new metal reinforced ceramic bracket (Clarity) may be recommended for clinical use because of its acceptable shear bond strength and possible reduced chances of enamel damage during bracket removal.

Dissolution/reprecipitation of calcium phosphate thin films produced by ion beam sputter deposition technique.

The dissolution, reprecipitation and protein adsorption properties of amorphous CaP bioceramic thin films produced with an ion beam sputter deposition technique using hydroxyapatite (HA) and fluorapatite (FA) as starting materials were studied using Fourier transform infrared spectroscopy (FTIR) with attenuated total internal reflectance (ATR). Our studies showed that these amorphous CaP coatings dissolved to a greater extent when exposed to bovine serum albumin (BSA) in saline solution when compared to a protein free saline solution. Analysis of changes in infrared spectra revealed that coatings exposed to BSA solution exhibited a higher degree of crystalline structure after dissolution/reprecipitation than those exposed to saline alone. There was the indication that the association of inorganic and organic contents was achieved on the coating surface in BSA solution. We could detect no significant difference between the coatings produced from HA and FA targets.

Analysis of bovine serum albumin adsorption on calcium phosphate and titanium surfaces.

The protein adsorption behavior of thin films of calcium phosphate (CaP) bioceramic and titanium (Ti) was studied in this research. The thin films were produced with an ion beam sputter deposition technique using targets of hydroxyapatite (HA), fluorapatite (FA) and titanium (Ti). Fourier transform infrared spectroscopy (FTIR) with attenuated total internal reflectance (ATR) was used to evaluate protein adsorption on these surfaces. This study showed that surface composition and structure influenced the kinetics of protein adsorption and the structure of adsorbed protein. CaP surfaces adsorbed greater amount of protein than the Ti surface, and caused more alteration of the structure of adsorbed BSA than did the Ti surface. The differences in protein adsorption behavior could result in very different initial cellular behavior on CaP and Ti implant surfaces.

Materials characteristics of uncoated/ceramic-coated implant materials.

In this paper, the biocompatibility of dental implant materials is discussed in the context of both the mechanical characteristics of the materials and the type of surface presented to the surrounding tissues. The proper functioning of the implant depends on whether it possesses the strength necessary to withstand loading within the expected range, with other properties such as elongation being of importance in some instances. A suitable modulus of elasticity may be of major importance in situations when optimum load transmission from the implant into the surrounding bone is key to the successful functioning of the device. Dental implants present a wide range of surfaces to the surrounding tissues based on surface composition, texture, charge energy, and cleanliness (sterility). Metallic implants are characterized by protective oxide layers, but ion release is still common with these materials, and is a function of passivation state, composition, and corrosion potential. An effective surface treatment for titanium appears to be passivation or anodization in a suitable solution prior to implantation. Inert ceramic surfaces exhibit minimal ion release, but are similar to metals in that they do not form a high energy bond to the surrounding bone. Some of the newly developed dental implant alloys such as titanium alloys, which contain zirconium and niobium, and high-strength ceramics such as zirconia may offer some advantages (such as lower modulus of elasticity) over the conventional materials. Calcium phosphate ceramic coatings are commonly used to convert metallic surfaces into a more bioactive state and typically cause faster bone apposition. There is a wide range of ceramic coatings containing calcium and phosphorus, with the primary difference in many of these materials being in the rate of ion release. Although their long-term success rate is unknown, the calcium phosphate surfaces seem to have a higher potential for attachment of osteoinductive agents than do uncoated titanium and other more inert implant materials.

Current status of ceramic coatings for dental implants.

There are various ceramic coatings available for dental implants. From a commercial standpoint, plasma-sprayed hydroxyapatite (HA) is the most popular. These coatings are typically partially amorphous after processing and contain crystalline phases other than HA. Plasma-sprayed HA and the other bioactive ceramic coating materials have been shown to enhance bone apposition as compared with uncoated metal implants. Some of the other available materials include the bioglasses, other calcium phosphates such as fluorapatite and tricalcium phosphate, and the inert ceramics such as alumina. The plasma-spray process is not optimum for all types of ceramic coatings, because it is not suitable for coating porous surfaces; the exact control of structure and chemistry is difficult with this process, and bond strength is not as high as is desired for some applications. Alternative methods for coating include sol-gel processing, ion beam and radio frequency (RF) sputtering, pulsed laser deposition, hot isostatic pressing, and electrophoretic deposition. The use of osteoinductive agents in conjunction with ceramic-coated implants is of current interest, and the degree and type of bonding of these agents appear to vary with the composition of the ceramic coating. Because there seems to be no satisfactory means of incorporating osteoinductive agents into ceramic coatings during any of the conventional coating procedures, the best approach seems to be to diffuse the agents into the coating after processing. Other possibilities include the tethering of the agents to the surface of the ceramic by suitable organic molecules or the placing of the agent in some carrier material such as a cement, which is placed around the implants.

Evaluation of wear: enamel opposing three ceramic materials and a gold alloy.

STATEMENT OF PROBLEM: The wear of human enamel and of the restorative material is often a critical concern when selecting a restorative material for any given clinical restorative treatment. PURPOSE: This in vitro wear investigation evaluated three ceramic restorative materials and one type III gold (the control) opposing enamel. MATERIAL AND METHODS: The area of enamel lost at specified time intervals, the stylus area lost, and the combined stylus and enamel vertical height lost were evaluated. RESULTS: Enamel wear opposing one type III gold was statistically similar to that of Dicor MGC, which was lower than that of Vita Mark II and IPS Empress, which were also statistically similar in value. CONCLUSIONS: The total vertical height lost from the type III gold specimens and opposing enamel was statistically lower than that of Dicor MGC and IPS Empress (alpha < 0.05).

Interfacial shear strength and histology of plasma sprayed and sintered hydroxyapatite implants in vivo.

The interfaces of bone with sintered hydroxyapatite (SHA) and plasma sprayed hydroxyapatite-coated (HAC) implants in the femora of six dogs were examined by light microscopy, scanning electron microscopy, energy dispersive X-ray analysis, and push-out tests. The results demonstrated that there was no significant difference at 12 and 24 weeks after insertion between the interfacial shear strengths with bone for the two types of implants, however, the histological characteristics of the bone around the plasma sprayed HA could be distinguished from that of the sintered HA. The HAC implants showed an early surface biodegradation as compared with the SHA implants. The observed differences in the interfacial zones may be attributed to different bone cell activities and variations in the dynamics of bone formation, possibly resulting from a higher level of dissolution/reprecipitation along the plasma sprayed HA surface.

Hydroxyapatite/metal composite coatings formed by electrocodeposition.

Early bone infusion by cementless fixation of composite orthopedic and dental implants consisting of metallic substrates and bioceramics is well documented. Calcium phosphate ceramics in general and hydroxyapatite (HA) in particular have been the most popular of the bioceramics used for coating metals. Here, a non-line of sight coating procedure by electrocodeposition is reported for mechanically fixing HA particles in a metal matrix. Analyses of the coating showed excellent adhesion to the substrate and no structural transformation in either crystallinity or stoichiometry. Adhesion and surface coverage of HA depended upon the particle size. As a demonstration of the coating procedure's non-line of sight applicability, it was successfully used to coat titanium rods sintered with small titanium spheres.

Dipyridamole directly inhibits vascular smooth muscle cell proliferation in vitro and in vivo: implications in the treatment of restenosis after angioplasty.

OBJECTIVES: The effect of dipyridamole on smooth muscle cell proliferation and prevention of intimal thickening after arterial injury was investigated. BACKGROUND: In addition to antiplatelet activity, dipyridamole also inhibits cell proliferation. We examined whether the antiproliferative action of dipyridamole on smooth muscle cells, as demonstrated here, has a direct effect on intimal thickening after vascular injury. METHODS: Cell proliferation was determined by measuring deoxyribonucleic acid (DNA) synthesis and by cell counting. The in vivo effect of locally delivered dipyridamole was determined in a rabbit model with carotid or femoral artery injury. RESULTS: Dipyridamole produced a dose-dependent inhibition of smooth muscle cell proliferation, producing 50% inhibition at 7 micrograms/ml. Structural analogues SH-869 and mopamidol were 10 to 100 times less effective than dipyridamole, suggesting that cell growth inhibition may be unrelated to the antiplatelet activity of dipyridamole. Inhibition of cell proliferation by dipyridamole was attenuated by increasing the serum concentration in the culture medium. Bypassing serum by local delivery of dipyridamole at the periadventitial site produced 63% inhibition (p < 0.05) of cell replication in balloon-injured arteries. Locally delivered dipyridamole also inhibited intimal thickening (20%, p < 0.05) after balloon injury. CONCLUSIONS: Dipyridamole inhibited smooth muscle cell proliferation in vitro. This activity was attenuated by serum proteins. Locally delivered dipyridamole inhibited cell replication in arteries and intimal thickening after balloon injury. These results suggest that although systemic treatment with dipyridamole may not be efficacious because of inadequate serum levels, its antiproliferative action on smooth muscle cells may reduce restenosis when the drug is delivered locally after coronary angioplasty.

Structure and integrity of a plasma sprayed hydroxylapatite coating on titanium.

Plasma sprayed hydroxylapatite (HA) coatings on titanium substrates were analyzed for process-induced compositional and structural changes. The HA starting powder and the resulting HA coatings were characterized using x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and Raman spectroscopy. The integrity of the ceramic-to-substrate bond strength was also determined, by subjecting plasma sprayed HA coatings to shear/cantilever bond testing. The ceramic coatings retained the basic apatitic crystal structure of the starting powder; however, a considerable amount of amorphous material was created during the plasma spray process. FTIR and Raman spectroscopy revealed that the resulting coatings were partially dehydroxylated. Both XRD and FTIR spectroscopy results also suggested that amorphous material, as well as additional calcium phosphate phases such as alpha-tricalcium phosphate (TCP) not in the starting powder, were present in the HA coating. Average bond strengths of the HA coatings to Ti were determined to be 14.8 MPa +/- 3.5, with fracture occurring at the interface and within the coating itself.

An evaluation of three methods of bonding resin composite to stainless steel.

Three bonding agents were evaluated to determine which were most effective in enhancing the bond of resin composite to stainless steel. A light-activated resin composite was bonded to a total of 60 stainless steel specimens using Panavia, Cover-Up, or Silicoating. Tensile bond strength measurements revealed that all three agents provide a satisfactory means of increasing adherence of the esthetic veneer without decreasing bonding through thermocycling of the specimens. Panavia and Cover-Up were significantly more effective than Silicoating and appear to be easier to use.

Enamel roughness after air-powder polishing.

The purpose of this study was to quantify differences in enamel surface roughness following treatment with an air abrasive system when compared to a rubber cup and pumice. The coronal portion of 40 bovine teeth were tested. Half of the teeth were placed in a control group and cleansed with a rubber cup and pumice, the other half or "test" group were treated with an air-powder polisher. All teeth were exposed to the given cleansing agent for a time equivalent to a 15-year recall program. Pre- and post-treatment surface evaluation was completed using a surface profilometer. In addition, representative samples were evaluated before and after cleansing under the scanning electron microscope (SEM). The results of this study showed no statistically significant increase in enamel surface roughness in teeth cleansed with the air polisher when compared to the roughness of the control teeth. This was confirmed visually by use of SEM taken at magnifications of up to x1000. The findings of this study indicate there is no significant alteration of the enamel surface when a tooth is treated with an air-powder polisher for the equivalent of a 15-year recall program.