K. van Dijk

Influence of annealing temperature on RF magnetron sputtered calcium phosphate coatings

The effect of different annealing temperatures on the characteristics of thin calcium phosphate coatings fabricated by radiofrequency magnetron sputtering was studied. Annealing of the as-sputtered films was necessary to change the amorphous coating to a crystalline coating. The films were annealed for 2 and 4 h at 400, 600, 800, 1000 and 1200 degrees C under dry argon or argon and water vapour flow. After annealing, the structure and the chemical composition of these films were characterized with incident light microscopy, Rutherford backscattering spectrometry (RBS), X-ray diffraction (XRD), and Fourier transform infrared absorption spectrometry (FTIR). Incident light microscopy showed cracks in the coatings annealed at a higher temperature than 400 degrees C. RBS revealed that the as-sputtered coatings had a high Ca/P ratio which decreased with increasing annealing temperature. After annealing at a temperature of 600 degrees C or more the XRD showed crystalline hydroxyapatite (HA) coatings. However, the second phase, present in the coatings, changed from tetra-calcium phosphate to calcium oxide to beta-tri-calcium phosphate with increasing annealing temperature. FTIR measurements showed the existence of OH- and PO- bonds in all coatings, although the PO- bonds varied for different annealed coatings, from the PO- bonds due to HA to PO- bonds due to other calcium phosphates. From the results of this study we suggest that 600 degrees C is probably the best annealing temperature to obtain a better characterization and understanding of the coating.

Influence of Ar pressure on r.f. magnetron-sputtered Ca5(PO4)3OH layers

Abstract Currently, medical and dental implants are often provided with thin calcium phosphate ceramic coatings (preferably Ca 5 (PO 4 ) 3 OH (HA)) to improve their biological behaviour. Previous studies have demonstrated that radio-frequency (r.f.) magnetron sputtering is a suitable technique for depositing such thin Ca−PO layers. Although X-ray diffraction showed that the deposited films had an HA structure, the Ca/P ratio of the layers was higher than the theoretical value of 1.67 for HA. In the present study the influence of the argon pressure and input power on the structure and chemical composition of the sputtered layers, especially the Ca/P ratio, is investigated. Rutherford backscattering spectrometry (RBS), stylus profilometer (alpha-step), X-ray diffraction spectrometry (XRD), and IR spectrometry (FTIR) were used to characterise the coatings. Although the Ca/P ratio became lower when sputtered at lower input power, it was still higher than the value of 1.67 for HA. The density measured for the films sputtered at 200 and 400 W did not show a simple relation with the argon pressure. For all the films after annealing XRD and FTIR showed an HA-like structure and HA bonds. However, the OH bond appeared to be dependent on the partial pressure of water vapour during sputtering.

Evaluation of plasma-spray and magnetron-sputter Ca-P-coated implants: An in vivo experiment using rabbits

The bone response to different plasma-spray and magnetron-sputter calcium phosphate (Ca-P)-coated implants was evaluated in a rabbit animal model. Four types of Ca-P coatings have been investigated: a plasma-spray Ca-P coating (HA-PS), a heat-treated plasma-spray Ca-P coating (HA-PS/ht), an amorphous magnetron-sputter coating (Ca-P-a), and a crystalline magnetron-sputter coating (CA-P-c). Seventy-two specially designed cylindrical implants were inserted in the lateral and medial femoral condyles of 18 New Zealand White rabbits. The four differently coated implants were positioned in one animal according to a split-plot design. After implantation periods of 3, 6, and 9 weeks, the bone-implant interface was evaluated histologically. Besides descriptive light microscopical evaluation, quantitative histomorphometrical measurements were done to determine bone contact and the amount of bone surrounding the implant-bone interface. Light microscopical examination revealed that all types of coatings followed the same process of bone healing. Measurements of bone contact at 6 and 9 weeks did not reveal significant differences between the various coatings. For the amount of bone, in a circular region at a certain distance from the implant, the Ca-P-c-coated implants showed a significantly greater amount of bone after 6 weeks of implantation than did the other three Ca-P coatings. At 9 weeks this difference could no longer be measured. On the basis of these findings we concluded that magnetron-sputtered Ca-P coatings show the same process of bone healing as the plasma-sprayed Ca-P coatings when inserted into the trabecular femoral bone of rabbits.

Mechanical and histologic evaluation of Ca-P plasma-spray and magnetron sputter-coated implants in trabecular bone of the goat

To aim of this study was to investigate the bone response to calcium phosphate (Ca-P) plasma-spray and radiofrequency magnetron sputter-coated implants with comparable roughness. Therefore, tapered conical screw designed implants were installed in the trabecular bone of the femurs of nine goats. They were provided with two types of coatings, a plasma-spray dual coating of fluorapatite and hydroxyapatite (FA/HA-PS) and a titanium plasma-spray coating, covered with an amorphous Ca-P magnetron sputtercoating (TPS/Ca-P-a). These implants were evaluated histologically and mechanically after 3 months of implantation. A well-controlled method to apply and measure a torsional force to load the screw-type implants to the point of failure was introduced. All implants healed uneventful and were well fixed. No significant difference (Student t test, p > 0.05) for the torsional failure force was measured for both type of coatings. Nevertheless, SEM revealed differently situated fracture planes. Light microscopy showed intimate bone-implanted contact for both types of coatings; original drill margins were still visible. A lamellar type of bone with some remodeling lacunae was shown. Histomorphometry revealed a higher percentage of bone contact for the FA/HA-PS-coated implants (students t test, p < 0.05). Measurement of the amount of bone revealed more bone mass around TPS/Ca-P-a-coated implants (analysis of variance and Turkey multiple comparison, p < 0.05).

Study of the influence of oxygen on the composition of thin films obtained by r.f. sputtering from a Ca5(PO4)3 OH target

Abstract In this paper we present a study of the influence of the presence of oxygen during sputter deposition on the properties of the films obtained from a Ca 5 (PO 4 ) 3 OH (HA) target. The films were characterised using X-ray diffraction, Fourier transform infrared spectroscopy and profilometer measurements. The composition of the deposited films was obtained by Rutherford backscattering spectrometry measurements. We found that an increase of the oxygen pressure resulted in a strong reduction of the growth rate of the films. Also a better stoichiometry of the films with respect to HA was obtained by intentional introduction of oxygen in the sputtering gas. Furthermore, we have shown that the average Ca/P ratio increases to a higher value than the Ca/P ratio of the target, with increasing film thickness and with increasing external negative bias on the substrate.

Measurement and control of interface strength of RF magnetron‐sputtered Ca‐PO coatings on Ti‐6Al‐4V substrates using a laser spallation technique

In previous studies, an RF magnetron sputter technique was developed for the production of thin calcium phosphate coating. Several deposition parameters were found to influence the growth rate and the stoichiometry of the coatings. For instance, deposition with additional oxygen pressure decreased the Ca to P ratio of the coatings to 1.67. For application of these coatings on actual Ti implants, it is important to know their adhesive tensile strength with the implant surface and how it varies with the deposition parameters. Motivated by these goals, the aim of this study was to measure the adhesive tensile strength of these coatings with Ti substrates and to study its variation with the deposition parameters. Since most mechanical characterization methods are incapable of providing a direct measure of the interfaces fundamental strength, a novel laser spallation experiment was used to accomplish this task. In this experiment, a compressive stress pulse is generated on the back side of a substrate by impinging a 3-ns long Nd:YAG laser pulse. The stress pulse propagates through the substrate and is reflected into a tensile stress wave from the free surface of the coating deposited on its front surface. The returning tensile pulse pries off the coating if its amplitude is high enough. The peak interface tensile stress is computed by using the optically recorded free surface displacement of the coating. Because interface decohesion is accomplished at a strain rate of almost 10(7) s-1, all inelastic processes essentially are suppressed and the measured value essentially is the intrinsic tensile strength of the interface. Tensile strength values in the range of 500-900 MPa were recorded for the interfaces between sputter-deposited calcium-phosphate coatings and Ti substrates. To confirm the locus of failure, the spalled spots were examined using SEM and EDS. The variation in the measured values was related to the changes in the deposition conditions.

A histological and histomorphometrical evaluation of screw type calciumphosphate (Ca-P) coated implants: an in vivo experiment in maxillary cancellous bone of goats

The bone response to different calcium phosphate (Ca-P) coated implants was evaluated in a goat animal model. Two types of plasma spray coatings were applied to a commercially pure titanium (cpTi) tapered, conical screw-design implant (BioComp®); hydroxyapatite (HA-PS) and a dual coating, consisting of FA and HA (FA/HA-PS). In addition an amorphous RF magnetron sputter coating (Ca-P-a) and uncoated implants were investigated. Forty-eight implants were inserted in the maxilla of 12 adult female goats. After implantation periods of 3 and 6 months, the bone implant interface was evaluated histologically and histomorphometrically. After both implantation periods all plasma spray coated implants were maintained. On the other hand three Ca-P-a and two cpTi implants were lost. Histological examination revealed a better bone response to both plasma spray coated implants. Histomorphometrical evaluation confirmed this finding. At 3 and 6 months significantly higher percentages of bone contact (p<0.001, ANOVA) were measured for both plasma spray coated implants than for the cpTi and Ca-P-a implants, while no significant difference (p<0.05) existed between both implantation periods. Degradation of both plasma spray coatings was observed. Supported by the results, it is concluded that, although Ca-P coatings can improve the performance of dental implants, the presence of a Ca-P coating is not the only important factor for bone healing around implants placed in low density trabecular bone.

A complete characterization of Ca5(PO4)3OH-sputter deposited films by ion beam analysis: RBS and ERD

RF magnetron sputter deposition was used to deposit thin calcium phosphate (hydroxyapatite) layers on titanium alloy substrate material. We determined the precise amount of calcium, phosphorus, oxygen, and hydrogen in these films by combining two ion-beam analysis techniques: Rutherford backscattering spectrometry (RBS) and elastic recoil detection (ERD). Variables were power level, partial oxygen pressure, or additional water vapor. Also examined was the influence of additional bias power to the substrates during deposition and the effect of annealing on the final composition of the deposited layers. Measurements showed that the Ca/P ratio decreased with increasing oxygen pressure or decreasing sputtering power. In addition, the Ca/P ratio increased when a bias was applied to the substrates. The O/P ratio of the films decreased with additional oxygen pressure but increased when additional water vapor was applied during deposition. All as-deposited films showed a higher hydrogen content than stoichiometric HA. The hydrogen content in the films deposited with water vapor was more than 7 times higher than in the films deposited under pure argon conditions. After annealing, the hydrogen content decreased to about 3.5 at % whereas in stoichiometric HA the hydrogen content amounts to 4.5 at %. After annealing, the oxygen concentration in the film also decreased. We assume that hydrogen disappears out of the film as H2O during annealing. For the targets used in these experiments, sputter deposition at 400 W, with additional water vapor and annealing at 500 degrees C, produced films with a stoichiometry closest to that of hydroxyapatite.