Kimiya Nemoto

Influence of rapid heating with infrared radiation on RF magnetron-sputtered calcium phosphate coatings

This study evaluated the effect of rapid heating with infrared radiation on the physico-chemical and morphological properties of radio frequent (RF) magnetron-sputtered calcium phosphate (Ca-P) coatings. About 2.5 microm thick Ca-P coatings were deposited on titanium disks and cylinders. These specimens were left untreated or were heat treated by infrared radiation at 300, 400, 500, 600, and 700 degrees C for 4, 7, 11, 17, and 24 s. Subsequently, the specimens were immersed in simulated body fluid (SBF) for 1 day, 1 week, and 5 weeks. X-ray diffraction measurements showed that heating at 500 degrees C or higher resulted in an increase of coating crystallinity. In addition, FT-IR measurements revealed the appearance of OH peaks in the spectra of samples treated at 500-700 degrees C. Electron probe microanalysis showed that after 5 weeks of immersion about 40-50% of the coatings heat treated at 500 and 600 degrees C was maintained. The coatings heat treated at 700 degrees C showed no dissolution at all. On the other hand, as-coated and 300 degrees C treated films were dissolved within 1 day. Scanning electron microscopy of the samples showed that directly after heat treatment no apparent cracks were present in the coatings. On the basis of these findings, we conclude that rapid heating with infrared radiation around 600 degrees C is the best heat treatment for RF magnetron-sputtered coatings.

Characterization and protein-adsorption behavior of deposited organic thin film onto titanium by plasma polymerization with hexamethyldisiloxane.

Plasma polymerized hexamethyldisiloxane (HMDSO) thin film was deposited onto titanium using a radio-frequency apparatus for the surface modification of titanium. A titanium disk was first polished using colloidal silica at pH=9.8. Plasma-polymerized HMDSO films were firmly attached to the titanium by heating the titanium to a temperature of approximately 250 degrees C. The thickness of the deposited film was 0.07-0.35mum after 10-60min of plasma polymerization. The contact angle with respect to double distilled water significantly increased after HMDSO coating. X-ray photoelectron spectroscopy revealed that the deposited thin film consisted of Si, C, and O atoms. No Ti peaks were observed on the deposited surface. The deposited HMDSO film was stable during 2-weeks immersion in phosphate buffer saline solution. Fourier transform reflection-absorption spectroscopy showed the formation of Si-H, Si-C, C-H, and Cz.dbnd6;O bonds in addition to Si-O-Si bonds. Quartz crystal microbalance-dissipation measurement demonstrated that the deposition of HMDSO thin films on titanium has a benefit for fibronectin adsorption at the early stage. In conclusion, plasma polymerization is a promising technique for the surface modification of titanium. HMDSO-coated titanium has potential application as a dental implant material.

Influence of self-etching primer treatment on the adhesion of resin composite to polished dentin and enamel

OBJECTIVE This study investigated the effectiveness of the self-etching primer treatment on the adhesion of resin composite to both dentin and enamel. METHODS Two types of self-etching primer were prepared. One was an aqueous solution of 2-methacryloyloxyethyl phenyl hydrogen phosphate (Phenyl-P) and 2-hydroxyethyl methacrylate (HEMA), and the other was an aqueous solution of 10-methacryloxydecyl dihydrogen phosphate (MDP) and HEMA. Influence of the concentration of Phenyl-P and MDP, and that of the application time on the adhesiveness were examined by measuring the tensile bond strengths of resin composite to dentin and enamel. The data were analyzed using the analysis of variance and Scheffes test for multiple comparison among the means. RESULTS After the 20P and 30P treatment for 30 s, bond strengths to dentin were significantly higher than those after 5P and 10P treatment for 30 s. The 30M treatment of dentin for 15 s significantly increased the bond strength compared with 5P, 10P and 20P for 15 s. In enamel, bond strength with 30P for 60 s was significantly higher than with 5P for 60 s and 30P for 15 s. The 30M for 60 s resulted in significantly higher bond strength than for 15 s. The smear layers on the dentin and enamel were partially dissolved by the self-etching primer treatment. A hybrid layer with a thickness of 1-1.5 microns was formed in dentin-bonded specimens. SIGNIFICANCE The self-etching primer containing Phenyl-P or MDP showed good adhesion to dentin and enamel, and this primer is a promising material for resin composite restoration.

Trabecular bone response to surface roughened and calcium phosphate (Ca-P) coated titanium implants.

The influence of calcium phosphate (Ca-P) coating and surface roughness on the trabecular bone response of titanium implants was investigated. Four types of titanium implants, i.e. blasted with titanium powder, sintered with titanium beads, titanium powder blasted and provided with an additional Ca-P coating, and titanium beads with Ca-P coating, were prepared. The Ca-P coating was deposited by ion beam dynamic mixing method. The Ca-P coating was rapid heat-treated with infrared radiation at 700 degrees C. The implants were inserted into the trabecular bone of the left and right femoral condyles of 16 rabbits. After implantation periods of 2, 3, 4 and 12 weeks, the bone-implant interface was evaluated histologically and histomorphometrically. Histological evaluation revealed new bone formation around different implant materials after already 3 weeks of implantation. After 12 weeks, mature trabecular bone surrounded all implants. At 3 and 4 weeks of implantation, no difference existed in bone contact to the various implant materials. On the other hand, after 12 weeks of implantation the highest percentage of bone contact was found around the Ca-P coated beads implants. Supported by the results, we concluded that the combination of surface geometry and Ca-P coating benefits the implant-bone response during the healing phase.

Hydrolytic stability of methacrylamide in acidic aqueous solution

In order to develop a more effective self-etching primer, with a longer lasting shelf life, we designed a self-etching primer comprised of methacrylamide, N-methacryloyl glycine, NMGly. In this study, the hydrolytic stability of the amide portion in the NMGly was examined. The difference in the hydrolytic stability between the methacrylamide and the methacrylate, 2-hydroxyethyl methacrylate, HEMA was then discussed. The addition of an acid to an aqueous solution allows for the hydrolysis of the ester portion in the methacrylate and for the production of methacrylic acid, MA and ethylene glycol, EG. From our study, the data clearly demonstrated that, if the storage duration of a commercially available self-etching primer is prolonged, then the functional methacrylates constituting the self-etching primer will be altered upon use. However, the hydrolytic stability of the amide portion in the methacrylamide, NMGly, designed as an acidic and/or hydrophilic monomer for the self-etching primer, was greater than the results achieved with the methacrylate, HEMA.

Development of high-toughness resin for dental applications

OBJECTIVES The purpose of this study was to develop a heat-cured resin with improved toughness. Polyurethane dimethacrylate (PUDMA) with hard and soft segments in the chemical structure was synthesized using polyurethane diisocyanate and 2-HEMA. METHODS The bulk polymerization of PUDMA, Bis-GMA, TEGDMA and MMA was carried out in a glass tube with 0.5 wt% of BPO at 60 degrees C for 24 h and 110 degrees C for 3 h. The physical and mechanical properties of these polymers were measured, i.e., the polymerization shrinkage, water sorption, transverse strength, modulus of elasticity, deflection and Knoop hardness of these polymerized methacrylates were determined. RESULTS The volume shrinkage and the water sorption values of PUDMA were lower than those of Bis-GMA. The transverse strength and the modulus of elasticity of PUDMA were close to those of PMMA. The deflection of PUDMA, as determined by a bending test, was higher than any of the other cured resins tested. SIGNIFICANCE These results suggest that PUDMA is an excellent toughened polymer. The fracture toughness of PUDMA is sufficient for crown and bridge resins and dental composites.

A 13C NMR Study on the Adsorption Characteristics of HEMA to Dentinal Collagen

To develop a more effective primer, we must understand how 2-hydroxyethylmethacrylate, the HEMA primer, enhances bonding at the resin-dentin interface. In this study, to obtain an insight into the adhesion mechanisms of adhesive resin to etched dentin through HEMA, we examined the adsorption characteristics of HEMA to dentinal collagen by using the 13C NMR technique. The addition of dentinal collagen to the HEMA solution resulted in a decrease in T 1 values of carbons attributed to the HEMA, thus reflecting an interaction between HEMA and collagen. Specifically, a reduction in the T 1 value in the ester carbonyl carbon attributed to HEMA greater than that in the other carbons suggested the formation of a hydrogen bond between the ester carbonyl group in HEMA and the dentinal collagen.

Adhesion of N-Methacryloyl-ω-Amino Acid Primers to Collagen Analyzed by 13C NMR

Previously, we reported that the strength of the interaction between N-methacryloyl-w-amino acid (NMωA) primers and dentinal collagen exhibited a strong correlation with the bond strength of the resin to etched dentin. To determine the pertinent functional groups of the amino acid residues in the dentinal collagen, to which the amide and/or the carboxylic acid groups of the NMwAs are adsorbed, we used 13C NMR techniques-primarily through the observation of spin-lattice relaxation times, T i—to investigate the adsorption characteristics resulting from the interaction of NMwAs with a model oligopeptide for collagen, (PPG)5. The addition of NMωAs to a collagenous solution resulted in a decrease in the T 1 values of the carbonyl carbons attributed to the carboxylic acid of the C-terminal Gly and to the third amide of the N-terminal Pro residues in the (PPG)5 molecule, thus reflecting the formation of hydrogen-bonded interactions.

Adhesion mechanisms of resin to etched dentin primed with N‐methacryloyl glycine studied by 13C‐NMR

The origin of the pH-dependent bond strength of the resin to etched dentin treated with N-methacryloyl glycine (NMGly) primer was studied by 13C-nuclear magnetic resonance (NMR) including spin-lattice relaxation time, T1, observation. When the dentinal collagen was suspended in the NMGly solution at pH = 1.6, the T1 values of all the carbons attributed to the NMGly species were significantly decreased. This indicated the presence of an interaction between the NMGly and the dentinal collagen. To obtain detailed information of this interaction, the 13C-NMR spectra of the NMGly were measured in the presence of the model compound for the collagen, (Pro-Pro-Gly)5 at pH = 1.7. The 13C-NMR peaks of the carbonyl carbons of the amide and carboxylic acid in the NMGly species shifted to a higher field and the T1 values decreased. Furthermore, when the molar ratio of (Pro-Pro-Gly)5 to NMGly was decreased from 1:1 to 1:3, the T1 values of the carbonyl carbon attributed to the carboxylic acid in the C-terminal Gly residue of the oligopeptide decreased dramatically. It can be construed that this indicated the formation of a hydrogen bond between the amide, -NH and the carboxylic acid of the NMGly species and the carboxylic acid of the C-terminal Gly residue of the oligopeptide.

Distortion Behavior of Heat-activated Acrylic Denture-base Resin in Conventional and Long, Low-temperature Processing Methods

There have been many reports on fatal distortion of heat-activated acrylic denture-base resin which is still widely used in the field of removable prosthodontics. However, these reports have failed to report quantitatively on polymerization and thermal shrinkage factors. In the present study, we attempted to verify that the shrinkage of heat-activated acrylic denture-base resin was caused mainly by thermal contraction after processing. Furthermore, we examined the degree of distortion resulting from long, low-temperature processing, and compared the results with that of the conventional method. The strain gauge and thermocouple were embedded in a specimen at the time of resin packing. The measurement started from the beginning of processing and continued until the specimen was bench-cooled and immediately before and after it was de-flasked, as well as during seven-day immersion in water at 37°C. The resin expanded when processed by the conventional method. Meanwhile, mild shrinkage, possibly polymerization shrinkage, was observed when the resin was processed by the low-temperature method. This suggested that polymerization shrinkage was compensated for by thermal expansion during processing by the conventional method. Moreover, the shrinkage strains in the period from the completion of processing to immediately after de-flasking, in both the conventional and low-temperature methods, were identical to the theoretical value of thermal shrinkage which we obtained by multiplying the linear coefficients of thermal expansion by temperature differences. The shrinkage strain in the specimen processed by the low-temperature method, measured from the end of processing to immediately after de-flasking, averaged 64% of that in the specimen processed by the conventional method. The results revealed quantitatively that the shrinkage of heat-activated acrylic denture-base resin was mainly thermal shrinkage, and demonstrated the advantage of the low-temperature method in reducing thermal shrinkage.