Thermodynamic self-consistency issues related to the Cluster Variation Method: The case of the BCC Cr-Fe (Chromium-Iron) system

The Cluster Variation Method (CVM), introduced over 50 years ago by Prof. Dr. Ryoichi Kikuchi, is applied to the thermodynamic modeling of the BCC Cr-Fe system in the irregular tetrahedron approximation, using experimental thermochemical data as initial input for accessing the model parameters. The results are checked against independent data on the low-temperature miscibility gap, using increasingly accurate thermodynamic models, first by the inclusion of the magnetic degrees of freedom of iron and then also by the inclusion of the magnetic degrees of freedom of chromium. It is shown that a reasonably accurate description of the phase diagram at the iron-rich side (i.e. the miscibility gap borders and the Curie line) is obtained, but only at expense of the agreement with the above mentioned thermochemical data. Reasons for these inconsistencies are discussed, especially with regard to the need of introducing vibrational degrees of freedom in the CVM model. (C) 2008 Elsevier Ltd. All rights reserved.

Precipitation of Laves phase in a 28%Cr-4%Ni-2%Mo-Nb superferritic stainless steel

The main objective of the present work was to study the precipitation of the Laves phase in the X1 CrNiMoNb 28 4 2 (Werkstoff-Nr. DIN 1.4575) superferritic stainless steel employing several complementary techniques of microstructural analysis. The phase that precipitated in largest quantity in the DIN 1.4575 steel was the sigma (sigma) phase. However, along grain boundaries, after aging at 850 degrees C, a Laves phase of the MgZn2 type, with a hexagonal C14 crystal structure and chemical composition (Fe,Cr,Ni)(2)(Nb,Mo,Si), was also identified. Growth of the Laves phase is curtailed by exhaustion of niobium of the matrix and by the presence of the sigma phase, which also precipitates in the vicinity of the grain boundaries, however in larger amounts. No chi (chi) or austenite phases were detected in the temperature range studied. (C) 2007 Elsevier Inc. All rights reserved.

Ecophysiological responses of water hyacinth exposed to Cr(3+) and Cr(6+)

Due to its wide industrial use, chromium (Cr) is considered a serious environmental pollutant of aquatic bodies. in order to investigate the ecophysiological responses of water hyacinth [Eichhornia crassipes (Mart.) Solms] to Cr treatment, plants were exposed to 1 and 10 mM Cr(2)O(3) (Cr(3+)) and K(2)Cr(2)O(7) (Cr(6+)) concentrations for two or 4 days in a hydroponic system. Plants exposed to the higher concentration of Cr(6+) for 4 days did not survive, whereas a 2 days treatment with 1 mM Cr(3+) apparently stimulated growth. Analysis of Cr uptake indicated that most of the Cr accumulated in the roots, but some was also translocated and accumulated in the leaves. However, in plants exposed to Cr(6+) (1 mM), a higher translocation of Cr from roots to shoots was observed. it is possible that the conversion from Cr(6+) to Cr(3+), which immobilizes Cr in roots, was not total due to the presence of Cr(6+), causing deleterious effects on gas exchange, chlorophyll a fluorescence and photosynthetic pigment contents. Chlorophyll a was more sensitive to Cr than chlorophyll b. Cr(3+) was shown to be less toxic than Cr(6+) and, in some cases even increased photosynthesis and chlorophyll content. This result indicated that the F(v)/F(0) ratio was more effective than the F(v)/F(m) ratio in monitoring the development of stress by Cr(6+). There was a linear relationship between qP and F(v)/F(m). No statistical differences were observed in NPQ and chlorophyll a/b ratio, but there was a tendency to decrease these values with Cr exposure. This suggests that there were alterations in thylakoid stacking, which might explain the data obtained for gas exchanges and other chlorophyll a fluorescence parameters. (C) 2008 Elsevier B.V. All rights reserved.

Photochemical cleavage of nitrate ion coordinated to a Cr(III) porphyrin#

Photolysis of the nitrato chromium(III) tetraphenylporphyrinato compound Cr(TPP)(NO(3)) (TPP, tetraphenylporphyrin) in toluene solution clearly leads to the formation of the Cr(IV) oxo complex Cr(TPP)(O) with a quantum yield of 0.011. The other product, NO(2), was detected quantitatively by its reaction with the spin trapping agent 2,2,6,6-tetramethyl-piperidine-1-oxyl.

Validation of plasma clearance of (51)Cr-EDTA in adult renal transplant recipients: comparison with inulin renal clearance

Plasma clearance of (51)Cr-EDTA ((51)Cr-EDTA-Cl) is an alternative method to evaluate glomerular filtration rate (GFR). This study aimed to investigate the concordance between (51)Cr-EDTA-Cl and renal inulin clearance (In-Cl) in renal transplant recipients as well to determine the repeatability of (51)Cr-EDTA-Cl in kidney donors. Forty four kidney recipients and 22 kidney donors were enrolled. Simultaneous measurements of (51)Cr-EDTA-Cl and In-Cl were performed. A single dose of 3.7MBq of (51)Cr-EDTA was injected and the plasma disappearance curve was created by taking blood samples at 2, 4, 6 and 8 h after injection. Bland and Altman statistical approach was used to quantify the agreement between In-Cl and (51)Cr-EDTA-Cl and to determine the better concordance between all possibilities of measure for the (51)Cr-EDTA-Cl. The mean of In-Cl was 44.5 +/- 17.9 ml/min/1.73 m(2). There was a positive correlation between In-Cl and all possible measurements of (51)Cr-EDTA-Cl. (51)Cr-EDTA-Cl with two samples taken at 4 and 8 h or at 4 and 6 h presenting the narrow limits of agreement and a difference (bias) of 2.8 and 2.7 ml/min, respectively. Two plasma sampling for (51)Cr-EDTA-Cl was a reliable method to measure GFR compared with In-Cl and comprises a suitable method to be used in kidney transplanted patients.

In Vitro Microleakage of Composite Restorations Prepared by Er:YAG/Er,Cr:YSGG Lasers and Conventional Drills Associated with Two Adhesive Systems

Purpose: The objective of this in vitro study was to compare the degree of microleakage of composite restorations performed by lasers and conventional drills associated with two adhesive systems. Materials and Methods: Sixty bovine teeth were divided into 6 groups (n = 10). The preparations were performed in groups 1 and 2 with a high-speed drill (HID), in groups 3 and 5 with Er:YAG laser, and in groups 4 and 6 with Er,Cr:YSGG laser. The specimens were restored with resin composite associated with an etch-and-rinse two-step adhesive system (Single Bond 2 [SB]) (groups 1, 3, 4) and a self-etching adhesive (One-Up Bond F [OB]) (groups 2, 5, 6). After storage, the specimens were polished, thermocycled, immersed in 50% silver nitrate tracer solution, and then sectioned longitudinally. The specimens were placed under a stereomicroscope (25X) and digital images were obtained. These were evaluated by three blinded evaluators who assigned a microleakage score (0 to 3). The original data were submitted to Kruskal-Wallis and Mann-Whitney statistical tests. Results: The occlusal/enamel margins demonstrated no differences in microleakage for all treatments (p > 0.05). The gingival/dentin margins presented similar microleakage in cavities prepared with Er:YAG, Er,Cr:YSGG, and HD using the etch-and-rinse two-step adhesive system (SB) (p > 0.05); otherwise, both Er:YAG and Er,Cr:YSGG lasers demonstrated lower microleakage scores with OB than SB adhesive (p < 0.05). Conclusion: The microleakage score at gingival margins is dependent on the interaction of the hard tissue removal tool and the adhesive system used. The self-etching adhesive system had a lower microleakage score at dentin margins for cavities prepared with Er:YAG and Er,Cr:YSGG than the etch-and-rinse two-step adhesive system.

Different air-water spray regulations affect the healing of Er,Cr:YSGG laser incisions

Surgeries performed with high-intensity laser devices may be improved with accurate protocols, including the air-water spray regulation. Thus, this study sought to investigate the healing process of wounds made on the dorsum of rat tongues using an Er,Cr:YSGG laser device with different air-water spray regulations. The incisions were made on the dorsum of Wistar rat tongues using an Er,Cr:YSGG laser with three different air-water spray regulations (100/0%, 50/50%, 11/7%). Scalpel incisions functioned as controls. The sacrifices occurred between 0 and 14 days after surgery. Morphological, histological, and immunohistochemical (fibronectin and type III collagen) analysis of the wounds were performed. The air-water spray regulation influenced wound healing and the inflammatory response, especially in the earlier stages. Incisions performed using the 100/0% air/water spray regulation had the worst results, expressing a greater amount of fibronectin and type III collagen. The 50/50% air/water spray regulation brought in a non-clear surgical field and poor laser interaction with the tissue. The 11/7% air/water spray regulation showed the best clinical results and less pronounced histological events. According to the results encountered, the air-water spray should be regulated to improve surgery.

Modified section method for laser-welding of ill-fitting cp Ti and Ni-Cr alloy one-piece cast implant-supported frameworks

P>This study aimed to verify the effect of modified section method and laser-welding on the accuracy of fit of ill-fitting commercially pure titanium (cp Ti) and Ni-Cr alloy one-piece cast frameworks. Two sets of similar implant-supported frameworks were constructed. Both groups of six 3-unit implant-supported fixed partial dentures were cast as one-piece [I: Ni-Cr (control) and II: cp Ti] and evaluated for passive fitting in an optical microscope with both screws tightened and with only one screw tightened. All frameworks were then sectioned in the diagonal axis at the pontic region (III: Ni-Cr and IV: cp Ti). Sectioned frameworks were positioned in the matrix (10-Ncm torque) and laser-welded. Passive fitting was evaluated for the second time. Data were submitted to anova and Tukey-Kramer honestly significant difference tests (P < 0 center dot 05). With both screws tightened, one-piece cp Ti group II showed significantly higher misfit values (27 center dot 57 +/- 5 center dot 06 mu m) than other groups (I: 11 center dot 19 +/- 2 center dot 54 mu m, III: 12 center dot 88 +/- 2 center dot 93 mu m, IV: 13 center dot 77 +/- 1 center dot 51 mu m) (P < 0 center dot 05). In the single-screw-tightened test, with readings on the opposite side to the tightened side, Ni-Cr cast as one-piece (I: 58 center dot 66 +/- 14 center dot 30 mu m) was significantly different from cp Ti group after diagonal section (IV: 27 center dot 51 +/- 8 center dot 28 mu m) (P < 0 center dot 05). On the tightened side, no significant differences were found between groups (P > 0 center dot 05). Results showed that diagonally sectioning ill-fitting cp Ti frameworks lowers misfit levels of prosthetic implant-supported frameworks and also improves passivity levels of the same frameworks when compared to one-piece cast structures.

Influence of Er,Cr : YSGG laser treatment on the microtensile bond strength of adhesives to dentin

Purpose: In light of the concept of minimally invasive dentistry, erbium lasers have been considered as an alternative technique to the use of diamond burs for cavity preparation. The purpose of this study was to assess the bonding effectiveness of adhesives to Er,Cr:YSGG laser-irradiated dentin using irradiation settings specific for cavity preparation. Materials and Methods: Fifty-four midcoronal dentin surfaces, obtained from sound human molars, were irradiated with an Er,Cr:YSGG laser or prepared with a diamond bur using a high-speed turbine. One etch-and-rinse (Optibond FL/Kerr) and three self-etching adhesives (Adper Prompt L-Pop/3M ESPE, Clearfil SE Bond/Kuraray, and Clearfil S-3 Bond/Kuraray) were used to bond the composite to dentin. The microtensile bond strength (mu TBS) was determined after 24 h of storage in water at 37 degrees C. The Kruskal-Wallis test was used to determine pairwise statistical differences (p < 0.05). Prepared dentin surfaces, adhesive interfaces, and failure patterns were analyzed using a stereo microscope and Field-emission gun Scanning Electron Microscopy (Feg-SEM). Results: Significantly lower mu TBS was observed to laser-irradiated than to bur-cut dentin (p < 0.05), irrespective of the adhesive employed. Feg-SEM photomicrographs of lased dentin revealed an imbricate patterned substrate and the presence of microcracks at the dentin surface. Conclusion: Morphological alterations produced by Er,Cr:YSGG laser-irradiation adversely influence the bonding effectiveness of adhesives to dentin. Keywords: dentin, adhesion, adhesives, laser, ErCr:YSGG.

Relaxation of the electrical resistivity in Cr-doped Nd(0.5)Ca(0.5)MnO(3) single crystals

We have performed a systematic study of the time and temperature dependencies of the electrical resistivity (rho(T, t)) inNd(0.5)Ca(0.5)Mn(1-x)Cr(x)O(3) single crystals with x = 0.02 and 0.07 in order to examine the dynamics of the phase separation. The relaxation effects can be described by the combination of a rapid exponential increase/decrease with a slower logarithmic contribution at longer times. The experimental results suggest the existence of a large temperature window in which huge relaxation effects occur, and the relative fraction of the coexisting phases rapidly changes as a function of time, depending on the initial magnetic state of the sample. The rho(T, t) relaxation measurements were shown to be a suitable tool for probing the dynamical nature of the phase separation, in which magnetically distinct phases compete against each other in a wide temperature range. In addition, the features observed in the rho(T, t) curves were found to be in excellent agreement with both the magnetic properties and the structural transitions observed in these manganites.

Effect of Ti-C and Cr Additions on Magnetic Properties of Nanocrystalline (Pr,Nd)-Fe-B Alloys

The addition of both Ti-C and Cr as grain refiners in Nd-Fe-B nanocomposites substantially increases the coercive field Hc. This motived our investigation of the effect of Ti-C and Cr on Pr-Fe-B nanocomposites. Melt-spun ribbons of composition (Pr(9.5)Fe(84.5)B(6))(0.97-x)Cr(x)(TiC)(0.03)(x = 0; 0.25; 0.5; 0.75; 1) and (Nd(9.5)Fe(84.5)B(6))(0.97-x)Cr(x)(TiC)(0.03)(x = 0.5 and 1) were produced for study. For a Pr nanocomposite with 1% Cr, Hc = 12.5 kOe. However, the energy product was limited to 13.6 MGOe by the remanence value. Rietveld analysis of X-ray spectra showed the ribbons to consist of predominantly hard (similar to 70 wt%) R(2)Fe(14)B, the soft phase being (similar to 30 wt%) alpha-Fe. Mossbauer measurements at 300 K are consistent with a reduced hyperfine field for the hard magnetic phase due to the Cr addition. Analysis of transmission electron microscopy images showed the Pr nanocomposite with 1% Cr to have an increased average grain size.

Pseudo-nonlinear and athermal lensing effects on transverse properties of Cr(3+) based solid-state lasers

Several experiments (time-resolved Z-scan experiments based on pulsed and CW pump lasers, time-resolved divergence diagnostics) have been performed to examine and clarify the question of the converging or diverging population lensing effect occurring in a Cr(3+):Al(2)O(3) ruby laser. The dynamics of the laser far-field divergence of such a laser indeed indicated initially a diverging effect while Z-scan measurements conclude to a converging one. The origin of this discrepancy is thus analysed and elucidated here by introducing the general concept of correlation collapse between the centre and the wings of a laser beam having some clipping. (C) 2010 Elsevier B.V. All rights reserved.

Major- and trace-element composition of olivine, perovskite, clinopyroxene, Cr-Fe-Ti oxides, phlogopite and host kamafugites and kimberlites, Alto Paranaiba, Brazil

An integrated whole-rock petrographic and geochemical study has been carried out on kamafugites and kimberlites of the Late Cretaceous Alto Paranaiba igneous province, in Brazil, and their main minerals, olivine, clinopyroxene, perovskite, phlogopite, spinels and ilmenite. Perovskite is by far the dominant repository for light lanthanides, Nb, Ta, Th and U, and occasionally other elements, reaching concentrations up to 3.4 x 10(4) chondrite values for light lanthanides and 105 chondrite for Th. A very strong fractionation between light and heavy lanthanides (chondrite-normalized La/Yb from similar to 175 to similar to 2000) is also observed. This is likely the first comprehensive dataset on natural perovskite. Clinopyroxene has variable trace-element contents. likely due to the different position of this phase in the crystallization sequence; Sc reaches values as high as 200 ppm whereas the lanthanides show very variable enrichment in light over heavy REE, and commonly show a negative Eu anomaly. The olivine, phlogopite (and tetra-ferriphlogopite), Cr-Ti oxide and ilmenite are substantially barren minerals for lanthanides and most other trace elements, with the exception of Ba, Cs and Rb in mica, and V, Nb and Ta in ilmenite. Estimated mineral/whole-rock partition coefficients for lanthanides in perovskite are similar to previous determinations, though much higher than those calculated in experiments with synthetic compositions, testifying once more to the complex behavior of these elements in a natural environment. The enormous potential for exploitation of lanthanides, Th, U and high-field-strength elements in the Brazilian kamafugites, kimberlites and related rocks is clearly shown.

Feasibility of using in situ fusion for the determination of Co, Cr and Mn in Portland cement by direct solid sampling graphite furnace atomic absorption spectrometry

In situ fusion on the boat-type graphite platform has been used as a sample pretreatment for the direct determination of Co, Cr and Mn in Portland cement by solid sampling graphite furnace atomic absorption spectrometry (SS-GF AAS). The 3-field Zeeman technique was adopted for background correction to decrease the sensitivity during measurements. This strategy allowed working with up to 200 mu g of sample. The in situ fusion was accomplished using 10 mu L of a flux mixture 4.0% m/v Na(2)CO(3) + 4.0% m/v ZnO + 0.1% m/v Triton (R) X-100 added over the cement sample and heated at 800 degrees C for 20 s. The resulting mould was completely dissolved with 10 mu L of 0.1% m/v HNO(3). Limits of detection were 0.11 mu g g(-1) for Co, 1.1 mu g g(-1) for Cr and 1.9 mu g g(-1) for Mn. The accuracy of the proposed method has been evaluated by the analysis of certified reference materials. The values found presented no statistically significant differences compared to the certified values (Student`s t-test, p<0.05). In general, the relative standard deviation was lower than 12% (n = 5). (C) 2009 Elsevier B.V. All rights reserved.

Correlation between margin fit and microleakage in complete crowns cemented with three luting agents

Microleakage can be related to margin misfit. Also, traditional microleakage techniques are time-consuming. This study evaluated the existence of correlation between in vitro margin fit and a new microleakage technique for complete crowns cemented with 3 different luting agents. Thirty human premolars were prepared for full-coverage crowns with a convergence angle of 6 degrees, chamfer margin of 1.2 mm circumferentially, and occlusal reduction of 1.5 mm. Ni-Cr cast crowns were cemented with either zinc phosphate (ZP) (S.S. White), resin-modified glass-ionomer (RMGI) (Rely X Luting Cement) or a resin-based luting agent (RC) (Enforce). Margin fit (seating discrepancy and margin gap) was evaluated according to criteria in the literature under microscope with 0.001 mm accuracy. After thermal cycling, crowns were longitudinally sectioned and microleakage scores at tooth-cement interface were obtained and recorded at ×100 magnification. Margin fit parameters were compared with the one-way ANOVA test and microleakage scores with Kruskal-Wallis and Dunn's tests (alpha=0.05). Correlation between margin fit and microleakage was analyzed with the Spearman's test (alpha=0.05). Seating discrepancy and marginal gap values ranged from 81.82 µm to 137.22 µm (p=0.117), and from 75.42 µm to 78.49 µm (p=0.940), respectively. Marginal microleakage scores were ZP=3.02, RMGI=0.35 and RC=0.12 (p<0.001), with no differences between RMGI and RC scores. The correlation coefficient values ranged from -0.27 to 0.30 (p>0.05). Conclusion: Margin fit parameters and microleakage showed no strong correlations; cast crowns cemented with RMGI and RC had lower microleakage scores than ZP cement.