Isao Kawashima

Mechanical behavior at different temperatures and stresses for superelastic nickel-titanium orthodontic wires having different transformation temperatures.

OBJECTIVE The purpose of this study was to investigate the mechanical properties of superelastic nickel-titanium orthodontic wires under controlled stress and temperature. METHODS Three different superelastic nickel-titanium wires were examined using differential scanning calorimetry (DSC), three-point bending test and micro X-ray diffraction (micro-XRD). The three-point bending test was carried out at constant temperature (23, 37 and 60 degrees C) and stepwise temperature changes (37-60 degrees C and to 37 degrees C) (37-2 degrees C and to 37 degrees C). Five specimens of each wire were tested. Micro-XRD spectra were measured at the tension side of the wire when the temperature changed from 37 to 60 degrees C or 2 degrees C. RESULTS The load during the stepwise temperature changes (37-2 degrees C and to 37 degrees C) was consistent with that measured at a corresponding constant temperature. The micro XRD spectrum clearly showed that the austenite phase was transformed to martensite phase when the temperature is decreased from 37 to 2 degrees C. In a stepwise temperature change (37-60 degrees C and to 37 degrees C), the load became higher than the original load at each corresponding constant temperature. However, there was no detectable change in the micro-XRD spectrum when the temperature was increased from 37 to 60 degrees C. SIGNIFICANCE The superelastic nickel-titanium wires exhibited complicated and unexpected mechanical properties under stepwise temperature change. This study shows the possibility of qualitative analysis using micro-XRD to understand mechanical properties of these nickel-titanium wires.

Micro X-ray diffraction study of superelastic nickel-titanium orthodontic wires at different temperatures and stresses.

The phase transformation behavior in three commercial nickel-titanium orthodontic wires having different transformation temperatures was studied by micro X-ray diffraction (micro-XRD). Micro-XRD spectra were obtained at three different included bending angles (135 degrees, 146 degrees and 157 degrees) and three different temperatures (25 degrees C, 37 degrees C and 60 degrees C). The regions analyzed by micro-XRD were within the separate areas of a given wire specimen that experienced only tensile or compressive strain. The intensity ratio (M002/A110) between the 002 peak for martensitic NiTi and the 110 peak for austenitic NiTi was employed as the index to the proportions of the martensite and austenite phases. The ratio of martensite to austenite increased in all three nickel-titanium wires with decreasing included bending angle (greater permanent bending deformation), and was lower within the compression area for all wires at all bending angles than within the tension area. Micro-XRD provides an effective method for quantitative evaluation of the proportions of these two phases in nickel-titanium orthodontic wires, even though considerable preferred crystallographic orientation exists because of the wire drawing process.

Micro-X-ray diffraction observation of nickel–titanium orthodontic wires in simulated oral environment

A micro-X-ray diffraction (micro-XRD) technique has been employed to determine the phases in two superelastic nickel-titanium orthodontic wires that exhibit shape memory in the oral environment and one superelastic nickel-titanium wire that does not exhibit shape memory in vivo. The micro-XRD analyses were performed over the clinically relevant temperature range of 0-55 degrees C, which corresponds to the ingestion of cold and hot liquids, and both straight and bent (135 degrees ) test samples were analyzed. The results showed that for straight (as-received) test samples, the rhombohedral phase (R-phase) was definitely present in one shape memory wire product and perhaps in the other shape memory wire product, but was apparently absent in the superelastic wire product that did not display shape memory. Martensite was observed in all three wire products after bending. Phase transformations occurred with temperature changes simulating the oral environment for straight test samples of the two shape memory wires, but the micro-XRD pattern changed minimally with temperature for straight test samples of the superelastic wire and for bent test samples of all three wire products. The phase transformations revealed by micro-XRD were consistent with results recently found by temperature-modulated differential scanning calorimetry.

Electrochemical characteristics of high-Pd alloys in relation to Pd-allergy

OBJECTIVE The aim of this study was to determine whether the Pd-Cu-based dental ceramic alloys possess any electrochemical characteristics distinguishable from that of other Pd-containing alloys. Of all Pd-containing alloys, this particular alloy group has been linked to frequent incidence of allergy and hypersensitivity reactions. Electrochemical corrosion may instigate these reactions. METHODS Four groups of alloys, Pd-Cu, Pd-Ga-(with and without Ag), Pd-Ag, and Au-Pd, were evaluated by traditional corrosion measurement techniques in a phosphated buffer saline solution at 20 degrees C. The electrochemical characteristics measured were: (1) 20 h open circuit potential (OCP); (2) 20 h corrosion rate (Icorr); and (3) anodic polarization (E-i) curves. RESULTS The OCP values (232 +/- 25 mV) of the Ag-free Pd-Ga and Pd-Cu-based alloys were higher than and distinctly different from that (144 +/- 52 mV) of the Ag-containing alloys. The Icorr values of different alloys, despite varied compositions, were indistinguishable from one another. The E-i curves of all alloys were essentially similar, with the Ag-containing (> 5 wt%) alloys showing a subtle difference in their anodic slope within 100 mV above their corrosion potentials. SIGNIFICANCE The OCP values of Pd-Cu alloys and the Ag-free Pd-Ga alloy are comparable to that reported for pure Pd (239 +/- 21 mV), which indicates that during corrosion these alloys undergo dealloying and consequent Pd-enrichment on their surface. Such a condition is conducive to the release of allergenic Pd++ ions and offers a plausible explanation for the frequent incidence of hypersensitivity reactions associated with the Pd-Cu alloys. The OCP values in other alloys are attributed to dealloying followed by surface enrichment with Ag and/or Au and the possible formation of an insoluble AgCl surface film on the respective alloy surfaces. These events have the potential to suppress or prevent Pd++ ion release. Alloys showing these characteristics have seldom been linked to allergic reactions.

Effect of Pd or Au addition on age-hardening in AgMn-based alloys

OBJECTIVE The objective of this research was to characterize the age-hardening behavior of AgMn alloys modified with Au or Pd. These alloys are being studied as possible alternatives to Type III dental alloys. METHODS The age-hardening reactions in Ag-37 at % Mn alloys with 5 at% Au or Pd were investigated by optical microscopy, electrical resistivity, X-ray diffraction and hardness tests. RESULTS Optical microscopy showed no grain boundary precipitates formed after overaging. The maximum hardness reached by aging in all alloys is about 260 (Hv) and identical to that of traditional AgPdCu dental alloys. The precipitation reactions were retarded with the addition of 5 at% Au or Pd. X-ray diffraction studies suggest a fine precipitate, alpha-Mn, is dispersed within the grain interior. The activation energy for the precipitation reaction is 114 kJ/mol for the AgMn and AgMnAu alloys. This value is about one-half of the activation energy for volume diffusion of manganese in AgMn alloys. SIGNIFICANCE The age-hardenable AgMn-based alloys modified with Au or Pd can achieve hardness values comparable to those of traditional AgPdCu alloys. Provided the in vivo corrosion resistance of these alloys is adequate, they show promise as a Cu-free alternative material for cast restorations.

Elemental Release from CoCr and NiCr Alloys Containing Palladium

PURPOSE An entirely new subclass of casting alloy composition whereby palladium (∼approximately 25 wt%) is added to traditional base metal alloys such as CoCr and NiCr was recently introduced to the market. The purpose of this study was to evaluate the elemental release of new CoPdCr and NiPdCr alloys and compare them to traditional CoCr and NiCr alloys. MATERIALS AND METHODS Five casting alloys were investigated: CoPdCr-A (NobleCrown NF, The Argen Corporation), CoPdCr-I (Callisto CP+, Ivoclar Vivadent), NiPdCr (NobleCrown, Argen), CoCr (Argeloy N.P. Special, Argen), and NiCr (Argeloy N.P. Star, Argen). Rectangular specimens (n = 6/alloy) were prepared and immersed in a lactic acid/NaCl solution at 37°C for 7 days according to ISO 10271. Solutions were analyzed with ICP-AES to determine elemental release. The concentrations of major ions (cobalt, nickel, palladium, chromium, and molybdenum) were compared using a generalized linear model (p < 0.05). Representative specimens were examined with optical microscopy before and after immersion. RESULTS The CoPdCr alloys released a significantly greater amount of respective ions (Co, Cr, Mo, and total ions) compared to the traditional CoCr alloy. No significant differences in elemental release were noted between NiPdCr and NiCr. Optical microscopic examination showed abundant areas of corrosion in the palladium-containing CoCr alloys after immersion, whereas little difference was observed for the other alloys. CONCLUSIONS Corrosion resistance measured via elemental release was compromised when CoCr was alloyed with palladium, but this effect was not observed with NiCr.

Metal-ceramic interface evaluation of a gold-infiltrated alloy.

PURPOSE The success of metal-ceramic systems partially depends on the formation of a stable bond between metal and porcelain. The purpose of this study was to investigate the porcelain/metal interface and the mechanism of interfacial bonding in a gold-infiltrated alloy (Captek). MATERIALS AND METHODS Captek specimens with feldspathic porcelain were evaluated by optical microscopy, scanning electron microscopy (SEM), electron probe microanalysis (EPMA), X-ray diffraction (XRD), and the Schwickerath crack initiation test for metal-ceramic bond compatibility. Specimens were processed with or without Capbond, a bonding agent. A traditional metal-ceramic alloy was also analyzed with microscopy for comparative purposes. RESULTS Optical and scanning electron micrographs of Captek specimens processed with Capbond revealed close adaptation of porcelain to the surface of the metal with sporadic nodules extending from the Captek surface. In contrast, the specimens of Captek without Capbond showed a much flatter porcelain/metal interface. Comparatively, the porcelain/metal interface of the traditional metal-ceramic crown showed greater surface roughness than the Captek specimens. No metal oxides were observed at the porcelain/metal interface of the Captek specimens with XRD. During the Schwickerath test, the Captek specimens permanently deformed, not allowing for crack initiation at the porcelain/metal interface. CONCLUSIONS Microscopy and XRD analysis showed that micromechanical interlocking is the primary mechanism of porcelain adherence to Captek metal. The use of Capbond prior to porcelain application to Captek results in gold nodules on the surface to aid retention. Existing metal-ceramic bond compatibility standardized tests are not sufficient for evaluating Captek, primarily due to the flexibility of the material.

Retardation of grain boundary reactions in Ag-Pd-Cu alloys by additions of small amounts of other elements

The grain-boundary reactions in Ag-25 mass% Pd-10 mass% Cu alloys with 1 mass% aluminium, cobalt, tin, chromium or indium, were investigated by optical microscopy, electrical resistivity, and hardness tests. Addition of tin and chromium retarded grain-boundary reactions. The growth rate of nodules with tin addition was 1/18 of the alloy without additons. Grain-interior reactions are accelerated with chromium, tin and indium addition, with chromium the most effective. The activation energies for the grain-interior and grain-boundary reactions are 192 to 196 and 144 to 208 kJ mol−1, respectively. Additions retard the growth but not the nucleation at the grain boundary. It is concluded that elements which form stable precipitates in the grains retard the grain-boundary reaction.

Corrosion of three experimental AgMn-based casting alloys

OBJECTIVE Alloys based on AgMn are being evaluated in our laboratory for their possible use as an alternative to Type III dental alloys. They respond to heat treatment and develop hardness values comparable to that of Type III alloys. The objective of the present research was to evaluate their corrosion characteristics. METHODS The three experimental silver-based alloys of the following composition (at%): (1) 63Ag37Mn, (2) 60Ag35Mn5Au and (3) 60Ag35Mn5Pd, were tested in their peak-hardened condition. Following 0.5 h open-circuit potential (OCP) measurement of each alloy in a phosphated buffer saline (PBS) solution, its current-potential profile was generated by the cyclic voltammetry technique within -1300 and +200 mV (SCE) at 1 mV s-1. In a separate test, the OCP of each alloy was monitored over a 24 h period. RESULTS Each of the three alloys showed ennoblement of their OCP over time due to dissolution of Mn and consequent enrichment with Ag (Au or Pd). At 24 h, the two ternary alloys were the most noble followed by the binary alloy. With respect to the cyclic voltammetry, oxidation of Ag was noted during forward scans at around 0 mV. The reverse scan was associated with a reduction current peak between -37 and -128 mV. The values for this peak, which is a measure of Ag oxidation, were highest (11.5 mA cm-2) for the binary alloy followed by the Au- (2.9 mA cm-2) and Pd-containing (0.04 mA cm-2) alloys, respectively. This indicates that, for equivalent concentration, Pd is more effective in reducing Ag corrosion than Au. SIGNIFICANCE Alloys based on the AgMn system are as hard as Type III dental alloys. Information on the corrosion characteristics of the AgMn-based alloys presented here is of value in further development of this alloy system.

Effect on the grain interior and grain boundary reactions by Cr addition to low gold content alloys

The effect on grain interior and grain boundary reactions by Cr addition to low gold content alloys were investigated by electric resistivity measurements, hardness tests, optical microscopic observations, and TEM observations. The grain interior reactions were accelerated by the chromium addition while grain boundary reactions were retarded. The formation of AuCu l type ordered phase in the grain interior was accelerated, and the T-T-T curve of AuCu l type ordered phase shifted to higher temperatures and shorter times with increasing chromium content.