Use of x-ray photoelectron spectroscopy and cyclic polarization to evaluate the corrosion behavior of six nickel-chromium alloys before and after porcelain-fused-to-metal firing

STATEMENT OF PROBLEM: Nickel-chromium casting alloys rely on a surface oxide layer for corrosion resistance to the oral environment. Porcelain-fused-to-metal (PFM) firing procedures may alter the surface oxides and corrosion properties of these alloys. Changes in alloy corrosion behavior affect metal ion release and therefore local and/or systemic tissue responses. PURPOSE: The aim of this study was to evaluate changes in alloy surface oxides and electrochemical corrosion properties after PFM firing. MATERIAL AND METHODS: The electrochemical corrosion behavior of 6 commercial nickel-chromium alloys was evaluated in the as-cast/polished and PFM fired/repolished states. Surface chemistries of the alloys were analyzed by x-ray photoelectron spectroscopy. RESULTS: Results indicated an increase in corrosion rates after PFM firing and repolishing for alloys containing 14% to 22% Cr and 9% to 17% Mo. This increase in corrosion rates was attributed to a decrease, caused by the PFM and repolishing process, in the Cr and Mo levels in the surface oxides of these alloys. The PFM firing and repolishing process did not alter the corrosion behavior of the alloys containing lower levels of Cr and Mo and/or Be additions in their bulk composition. These alloys exhibited low levels of Cr and Mo surface oxides in both test conditions. Si particles became embedded in the surfaces of the fired alloys during repolishing and may have contributed to the changes in surface oxides and the corrosion behavior of some alloys. CONCLUSION: The effects of PFM firing and repolishing on Ni-Cr dental casting alloy surface oxides and corrosion properties appear to be alloy dependent.     

Corrosion behaviour and surface analysis of a Co-Cr and two Ni-Cr dental alloys before and after simulated porcelain firing

This study evaluated the corrosion behaviour and surface properties of a commercial cobalt-chromium (Co-Cr) alloy and two nickel-chromium (Ni-Cr) alloys [beryllium (Be)-free and Be-containing] before and after a simulated porcelain-firing process. Before porcelain firing, the microstructure, surface composition and hardness, electrochemical corrosion properties, and metal-ion release of as-cast alloy specimens were examined. After firing, similar alloy specimens were examined for the same properties. In both as-cast and fired conditions, the Co-Cr alloy (Wirobond C) showed significantly more resistance to corrosion than the two Ni-Cr alloys. After firing, the corrosion rate of the Be-free Ni-Cr alloy (Stellite N9) increased significantly, which corresponded to a reduction in the levels of Cr, molybdenum (Mo), and Ni in the surface oxides and to a reduction in the thickness of the surface oxide film. The corrosion properties of the Co-Cr alloy and the Be-containing Ni-Cr alloy (ChangPing) were not significantly affected by the firing process. Porcelain firing also changed the microstructure and microhardness values of the alloys, and there were increases in the release of Co and Ni ions, especially for Ni from the Be-free Ni-Cr alloy. Thus, the corrosion rate of the Be-free Ni-Cr alloy increased significantly after porcelain firing, whereas the firing process had little effect on the corrosion susceptibility of the Co-Cr alloy and the Be-containing Ni-Cr alloy.     

三种口腔铸造合金耐蚀性及表面氧化膜的比较

目的 探讨3种常用口腔铸造合金模拟烤瓷前后的耐蚀性差异及氧化膜成分,以期为临床合理选择非贵金属合金提供依据.方法 用电感耦合等离子体原子发射光谱法(inductively coupled plasma atomic emission spectroscopy,ICP-AES)检测模拟烤瓷前后3种常用烤瓷非贵金属合金(镍铬合金、钴铬合金、镍钛合金)在达尔伯克改良伊格尔培养液中浸泡30 d后离子析出的种类和含量.同时用X射线光电子能谱(X-ray photoelectron spectroscopy,XPS)对模拟烤瓷后合金表面生成的氧化膜进行分析,扫描电镜(SEM)对合金表面腐蚀形态进行观察.结果 模拟烤瓷前3种合金离子总质量浓度由大到小依次为镍铬合金[(2.829±0.694)mg/L]、钴铬合金[(2.120±0.418)mg/L]、镍钛合金[(1.211±0.101)mg/L];镍铬合金组镍的质量浓度[(1.531±0.392)mg/L]＞镍钛合金组[(0.830±0.052)mg/L],钴和钼离子质量浓度由大到小为钴铬合金组[钴:(0.048±0.011)mg/L;钼:(1.562±0.333)mg/L]、镍铬合金组[钴:(0.034±0.002)mg/L;钼:(1.264±0.302)mg/L]、镍钛合金组[钴:(0.013±0.006)mg/L;钼:(0.151±0.026)mg/L],差异有统计学意义(P＜0.05).模拟烤瓷后3种合金离子析出总量[镍铬合金:(0.861±0.054)mg/L;钴铬合金:(0.695±0.327)mg/L;镍钛合金:(0.892±0.115)mg/L]均比未模拟烤瓷处理的合金离子析出总量少,差异有统计学意义(P＜0.05).XPS分析显示,模拟烤瓷后3种合金表面Cr2O3和钼、镍氧化物的含量增加.结论 3种常用烤瓷铸造合金中镍铬合金的离子析出量最大,耐蚀性最差;烤瓷加热处理可促进这3种合金生成连续的Cr2O3氧化膜,使合金的耐蚀性增强.

Abstract：

Objective To evaluate the types and compositions of oxide films formed during porcelain-fused-to-metal( PFM ) firing on three kinds of dental casting alloys, and to investigate the corrosion property of these alloys in Dulbecco's modification of Eagle's medium( DMEM ) cell culture fluid, before and after PFM firing. Methods Specimens of three dental casting alloys( Ni-Cr, Co-Cr and Ni-Ti) before and after PFM firing were prepared, and were immersed in DMEM cell culture fluid. After 30 days, the type and concentration of released metal ions were measured using inductively coupled plasma atomic emission spectroscopy(ICP-AES). X-ray photoelectron spectroscopy(XPS) and scanning electron microscope( SEM )were used for analysis of oxide film on the alloys. One way-ANOVA was adopted in data analysis. Results The total amount of metal ions released from the three dental alloys was found to be highest in Ni-Cr alloy [(2.829±0.694) mg/L], followed by Co-Cr[(2. 120 ±0.418) mg/L]and Ni-Ti alloy[(1.211 ±0. 101 ) mg/L]. The amount of Ni ions released from Ni-Cr alloys[( 1. 531 ± 0. 392) mg/L]was higher than that from Ni-Ti alloys[(0. 830 ±0. 052) mg/L]. The amount of Cr, Mo ions released from Co-Cr alloy [Cr: (0. 048 ± 0. 011 ) mg/L, Mo: ( 1. 562 ± 0. 333 ) mg/L]was higher than that from Ni-Cr alloy[Cr:(0. 034 ±0. 002) mg/L, Mo: ( 1. 264 ±0. 302) mg/L]and Ni-Ti alloy[Cr: (0. 013 ±0. 006) mg/L, Mo:(0. 151 ±0. 026) mg/L](P ＜0. 05). After PFM firing, the total amount of metal irons released from the three dental alloys decreased[N i-Cr: (0. 861 ± 0. 054 ) mg/L, Co-Cr: (0. 695 ± 0. 327 ) mg/L, Ni-Ti:(0. 892 ±0. 115) mg/L](P ＜ 0. 05). In addition, XPS showed increase of Cr2O3 and Mo-Ni oxide on the surface of all the alloys after PFM firing. Conclusions The amount of ions released from Ni-Cr alloy was the highest among the three dental casting alloys, this means Ni-Cr alloy is prone to corrode. The PFM firing process changed the alloys' surface composition. Increased Ni, Cr and Mo were found in oxide film, and the increase in Cr2O3 can improve the corrosion-resistance of alloys.     

表没食子儿茶素没食子酸酯对镍铬合金电化学腐蚀后表面结构和性能的影响

目的:研究表没食子儿茶素没食子酸酯(epigallocatechin gallate, EGCG)对镍铬合金电化学腐蚀后表面结构和性能的影响。方法:采用体视显微镜和扫描电镜,观察经0 g/L和1.0 g/L EGCG人工唾液电化学腐蚀后镍铬合金的表面形貌,并运用光电子能谱仪分析经0 g/L和1.0 g/L EGCG人工唾液电化学腐蚀后镍铬合金的表面腐蚀产物。结果:经0 g/L和1.0 g/L EGCG人工唾液电化学腐蚀后,镍铬合金表面均有不同程度的腐蚀,在0 g/L EGCG人工唾液中,出现的点蚀坑直径较小,基本未影响合金表面的枝晶结构;而在1.0 g/L EGCG人工唾液中,镍铬合金表面发生了较为严重的腐蚀,点蚀坑直径较大,枝晶区间开始融合、变得模糊不清。此外,经0 g/L EGCG和1.0 g/L EGCG人工唾液电化学腐蚀后,镍铬合金表面溅射120 s后均检测到了O、Ni、Cr、Be、C及Mo元素,表面氧化物均主要为NiO和Cr2O3。与0 g/L EGCG人工唾液相比,镍铬合金在1.0 g/L EGCG人工唾液电化学腐蚀后表面O元素、NiO和Cr2O3的含量较低。结论:经EGCG人工唾液电化学腐蚀后,镍铬合金表面形貌和表面腐蚀产物结果一致,提示1.0 g/L EGCG促使镍铬合金表面耐腐蚀性能变差,表面腐蚀产物中氧化物含量也降低。     

Corrosion of nickel-based dental casting alloys.

OBJECTIVES: To study the microstructure, corrosion behaviour and cell culture response of two nickel-based dental casting alloys before and after a heat treatment to simulate porcelain firing. METHODS: The microstructure was studied using scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX). Corrosion behaviour was evaluated by electrochemical measurements in artificial saliva at different values of pH in the presence of a crevice. 3T3 mouse fibroblasts were exposed indirectly to alloy specimens and the number of viable cells counted after 3 and 6 days compared to a control culture. RESULTS: Small changes in microstructure were observed after heat treatment but had a negligible effect on the corrosion properties in the conditions tested. The alloy with a lower bulk level of Cr (12.6 wt.%) showed lower corrosion resistance, indicated by an increased passive current density and this stability was greatly reduced at pH 2.5, where crevice corrosion was observed. Selective dissolution occurred at regions within the microstructure containing lower levels of Cr and Mo. Furthermore, the proliferation of 3T3 mouse fibroblasts was reduced (p<0.05) when exposed indirectly to this alloy. The alloy containing a higher level of Cr (25 wt.%) showed superior corrosion resistance, which was associated with a more uniform distribution of Cr in the alloy microstructure. SIGNIFICANCE: The presence of crevices combined with an inhomogeneous distribution of Cr in the microstructure can lead to accelerated corrosion of Ni-based alloys with lower Cr contents. This effect can be avoided by increasing the Cr content of the alloy.     

Surface characteristics and corrosion properties of selective laser melted Co–Cr dental alloy after porcelain firing

Objective

We examined the surface characteristics and corrosion properties of selective laser melted (SLM) cobalt–chromium (Co–Cr) dental alloys before and after porcelain-fused-to-metal (PFM) firing.

Methods

Samples were manufactured utilizing SLM techniques and control specimens were fabricated using traditional casting methods. The microstructure and surface composition were examined using metallographic microscopy, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Corrosion properties were evaluated using electrochemical impedance spectroscopy. Student's t-test was used to evaluate differences in numerical results of electrochemical corrosion tests between SLM and cast specimens before or after PFM firing. The results of electrochemical corrosion tests of the SLM and cast samples before and after firing were analyzed using one-way ANOVA.

Results

Although PFM firing altered the microstructure of the SLM specimens, they still exhibited a compact and homogeneous structure, and XPS analysis indicated that there were no significant differences in the surface composition of the specimens after firing. In artificial saliva at pH 5, the R_p value of the SLM specimens was 6.21 MΩ cm⁻² before firing and 2.84 MΩ cm⁻² after firing, suggesting there was no significant difference in electrochemical corrosion properties (P > 0.05). In artificial saliva at pH 2.5, the R_p value of the SLM group was 4.80 MΩ cm⁻² before firing and 2.88 MΩ cm⁻² after firing, again indicating no significant difference in electrochemical corrosion properties (P > 0.05). At pH 2.5, there was a significant difference in corrosion behavior between the cast and SLM groups, with the R_p value of the cast group being 0.78 MΩ cm⁻² vs. 2.88 MΩ cm⁻² for the SLM group.

Significance

The improved post-firing corrosion resistance of SLM specimens provides further support for their use in prosthodontic applications, as the oral environment may become temporarily acidic following meals.     

牙用烤瓷支架钴铬钼合金的研制及机械性能的测试

目的　研究一种能同时用于烤瓷修复和可摘局部义齿铸造支架的新型钴铬钼合金。方法　设计合金的多元配方,使用真空感应电炉熔炼合金。通过机械性能测试、硬度测试、密度及熔点范围测试、铸造性能测试、显微结构观察及X射线衍射分析进行筛选。结果　①合金的成份为Co 54%~67%、Cr 21%~26%、Mo 5%~8%、W5% ~8%、Si 1%~3%、Mn 0·1%~0·25%、其他微量元素。②合金的屈服强度为584 MPa;抗拉强度为736 MPa;延伸率为15·0%;维氏硬度为322 HV;铸流率为100%。结论　所研制的钴铬钼合金DA9-4的各项机械性能指标接近或达到国外同类产品的性能,能够满足临床要求。     

选择性激光熔融技术成形牙科钴铬合金性能的初步研究

目的:通过测试选择性激光熔融(selective laser melting,SLM)技术制作的牙科钴铬(Co-Cr)合金的部分机械性能、表面显微结构、瓷熔附后的界面情况,以期为该技术的应用提供基础资料。方法:使用SLM技术制作牙科钴铬合金样品,用扫描电镜观察样品的表面形貌和显微结构、测试样品的密度和硬度;将样品经过除气-预氧化处理,用扫描电镜观察样品表面氧化膜的形貌和显微结构;将经过除气-预氧化处理的样品进行瓷熔附,用扫描电镜观察样品金-瓷界面的显微结构。结果:SLM制作的钴铬合金的硬度明显高于铸造钴铬合金;经过除气-预氧化处理后的氧化膜细密均匀;两种方法制作的合金在瓷熔附处理后的金-瓷界面均没有发现明显裂纹。结论:SLM技术比传统铸造技术具有一定的优越性,技术细节有待深入研究。     

3种烤瓷铸造合金的离子析出研究

目的 研究3种常用烤瓷非贵金属合金模拟烤瓷前、后在体外细胞培养液中离子析出的量及种类。方法 用失蜡法铸造3种常用烤瓷非贵金属合金试件,镍铬合金、钴铬合金、镍钛合金,置于DMEM体外细胞培养液中30 d后重新打磨,模拟烤瓷加热过程,之后放回DMEM体外细胞培养液中浸泡30 d,用电感耦合等离子发射光谱法(ICP-AES)观察烤瓷处理前、后3种合金离子的析出的改变,扫描电镜(SEM)对表面形态观察。结果 (1)3种合金离子析出总量依次为镍铬合金>钴铬合金>镍钛合金,(2)模拟烤瓷程序后3种合金离子析出总量减少,差异具有统计学意义(P<0.05)。结论 3种常用烤瓷非贵金属合金中,镍铬合金的离子析出量最大,生物相容性最差;烤瓷过程会促进这3种合金表面氧化膜的生成,使合金的耐腐蚀性有所增强。     

Oxide adherence to a Ni-Cr-Mo ternary alloy

The success of a porcelain-fused-to-metal (PFM) restoration depends upon the quality of the porcelain-metal bond. Oxide adherence to commercial PFM alloys has been previously shown to vary widely and to correspond to porcelain-bonding behavior. Most non-precious PFM alloys are based upon a Ni?Cr?Mo ternary alloy and contain small amounts of other elements. The purpose of the present study was to evaluate the oxide adherence of a 76Ni?19Cr?5Mo ternary alloy similar to dental PFM alloys, yet without the additional elements found in these alloys. The outer oxide (NiO) on both polished and cold-worked specimens was found to delaminate at a stress of about 1 MPa. The darkened underlayer thus revealed was found to be enriched in Cr and Mo and appeared to be an internal oxide layer. The oxide adherence to this unmodified Ni?Cr?Mo ternary was substantially lower than any of the commercial alloys tested previously. Cold work was not found to improve the oxide adherence. These results indicate that the alloying elements present in commercial Ni?Cr?Mo alloys exert a pronounced influence on their oxide adherence. Measurement of the effects of various alloying additions on oxide adherence is planned for future work.     

临床常用4种烤瓷合金耐蚀性的比较

目的比较临床上4种常用烤瓷合金(Ni-Cr、Ni-Cr-Ti、Co-Cr合金和高贵Au合金)的耐腐蚀特性。方法模拟临床烤瓷修复体的制作,将4种受试合金分别与口腔茸毛链球菌共同培养10周后,用电化学方法对合金行动电位极化扫描,corrview2腐蚀分析软件分析自腐蚀电位(Ecorr)和临界破裂电位(Etp)。结果各合金相比,空白组和实验组Ecorr从大到小顺序分别为Au>Ni-Cr>Ni-Cr-Ti、Co-Cr以及Au>Co-Cr>Ni-Cr、Ni-Cr-Ti,Etp从大到小顺序分别为Au>Co-Cr>Ni-Cr>Ni-Cr-Ti和Au>Co-Cr>Ni-Cr-Ti>Ni-Cr,差异显著(P<0.05)。结论高贵Au合金耐蚀性明显优于非贵金属合金,Co-Cr合金优于Ni-Cr-Ti和Ni-Cr合金。     

Effects of chemical composition on the corrosion of dental alloys

The aim of this study was to determine the effect of the oral environment on the corrosion of dental alloys with different compositions, using electrochemical methods. The corrosion rates were obtained from the current-potential curves and electrochemical impedance spectroscopy (EIS). The effect of artificial saliva on the corrosion of dental alloys was dependent on alloy composition. Dissolution of the ions occurred in all tested dental alloys and the results were strongly dependent on the general alloy composition. Regarding the alloys containing nickel, the Ni-Cr and Ni-Cr-Ti alloys released 0.62 mg/L of Ni on average, while the Co-Cr dental alloy released ions between 0.01 and 0.03 mg/L of Co and Cr, respectively.The open-circuit potential stabilized at a higher level with lower deviation (standard deviation: Ni-Cr-6Ti = 32 mV/SCE and Co-Cr = 54 mV/SCE). The potenciodynamic curves of the dental alloys showed that the Ni-based dental alloy with >70 wt% of Ni had a similar curve and the Co-Cr dental alloy showed a low current density and hence a high resistance to corrosion compared with the Ni-based dental alloys. Some changes in microstructure were observed and this fact influenced the corrosion behavior for the alloys. The lower corrosion resistance also led to greater release of nickel ions to the medium. The quantity of Co ions released from the Co-Cr-Mo alloy was relatively small in the solutions. In addition, the quantity of Cr ions released into the artificial saliva from the Co-Cr alloy was lower than Cr release from the Ni-based dental alloys.     

Cobalt–chromium alloys fabricated with four different techniques: Ion release,toxicity of released elements and surface roughness

ObjectiveTo investigate the metal ion release, surface roughness and cytoxicity for Co–Cr alloys produced by different manufacturing techniques before and after heat treatment. In addition, to evaluate if the combination of materials affects the ion release.MethodsFive Co–Cr alloys were included, based on four manufacturing techniques. Commercially pure titanium, CpTi grade 4 and a titanium alloy were included for comparison. The ion release tests involved both Inductive Coupled Plasma Optical Emission Spectrometry and Inductive Coupled Plasma Mass Spectrometry analyses. The surface analysis was conducted with optical interferometry. Cells were indirectly exposed to the materials and cell viability was evaluated with the MTT (3-(4.5-dimethylthiazol-2-yl)-2.5-diphenyltetrazolium bromide) method.ResultsAll alloys showed a decrease of the total ion release when CpTi grade 4 was present. The total ion release decreased over time for all specimens and the highest ion release was observed from the cast and milled Co–Cr alloy in acidic conditions.The cast and laser-melted Co–Cr alloy and the titanium alloy became rougher after heat treatment. All materials were within the limits of cell viability according to standards.SignificanceThe ion release from Co–Cr alloys is influenced by the combination of materials, pH and time. Surface roughness is influenced by heat treatment. Furthermore, both ion release and surface roughness are influenced by the manufacturing technique and the alloy type. The clinical implication needs to be further investigated.     

pH值对烤瓷工艺处理后的合金耐腐蚀性能的影响

目的研究不同pH值对经过烤瓷处理过的烤瓷合金的耐腐蚀性能的影响。方法制作金合金、纯钛、钴铬合金、镍铬合金试件,常规临床烤瓷,分别置于不同的pH值溶液中,应用电化学综合测试系统和腐蚀分析软件对受试合金行动电位极化扫描,绘制合金在人工唾液中的极化曲线,获得并分析材料的自腐蚀电位(Ecorr)和腐蚀电流密度(Icorr)。结果4种合金临床烤瓷加工后在同一pH值人工唾液中自腐蚀电位负值增加的排序为金合金、纯钛、钴铬合金、镍铬合金;4种合金在pH为5.6±0.04、pH=为.6±0.04人工唾液中均比pH为6.8±0.04中自腐蚀电流密度增大,自腐蚀电位负值增大。结论纯钛与金合金耐腐蚀性能好于钴铬合金,镍铬合金,随pH值下降,非贵金属耐腐蚀性能下降明显。     

Effects of recasting on the chemical composition, microstructure, microhardness, and ion release of 3 dental casting alloys and titanium

This study evaluated the effects of recasting on high noble, noble, and nickel-based alloys, as well as on titanium. Four specimens of each material were cast and recast 7 times. Chemical composition, microstructure, microhardness, and ion release were determined before and after the first cast and following each recast. Zinc and tin concentrations in the high noble alloy decreased significantly with recasting; consequently, the release of these ions decreased as well. A significant increase in Vickers hardness appeared in the fifth recast in both the high noble alloy and titanium. The noble alloy and the nickel-based alloy demonstrated great stability after 7 recasts. The results suggest not recasting titanium.     

人工唾液中氯化钠浓度对钴铬、镍铬、含钛镍铬合金腐蚀行为的影响

目的：在人工唾液中氯化钠浓度升高的条件下,用电化学阻抗谱研究3种牙科常用合金（钴铬、镍铬、含钛镍铬合金）腐蚀行为的变化。方法：测定在人工唾液中氯化钠浓度分别为0.9%、2%、3%的条件下,3种合金的电化学阻抗谱,将各体系中合金界面电容和电荷转移电阻拟合,分析其腐蚀机制和耐腐蚀性能的变化。结果：随着氯化钠浓度升高,3种合金的界面电荷转移电阻（Rt值）都分别减小,界面电容（Qdl）增大,腐蚀反应过程加剧,抗蚀能力降低。但钴铬合金的Rt值是最大的。结论：在高氯环境中,3种合金腐蚀反应加快,抗腐蚀能力均降低,但钴铬合金抗腐蚀能力相对较强,这将影响它们的使用寿命。     

Corrosion properties of soldered joints. Part I: Electrochemical action of dental solder and dental nickel-chromium alloy

The corrosion properties of contact between six Ni-Cr alloys and two dental solders were evaluated. Ni-Cr alloys with low Cr content coupled with silver solder induced continuous galvanic current, whereas Ni-Cr alloys with high Cr and some Mo content coupled with silver or gold solder induced galvanic current for a short time. Six Ni-Cr alloys were divided into two groups according to the dissolution of Ni, one with low resistance and the other with high resistance. The initial equilibrium was induced between high resistance Ni-Cr alloys and both solders by less current density, which implies a smaller degree of corrosive current than that in low-resistance alloys. Corrosion was observed in the silver solder coupled with high-resistance Ni-Cr alloy, but was not found in the gold solder coupled with both alloys. In soldering Ni-Cr alloy, it is better to use a gold solder and a high-resistance Ni-Cr alloy for corrosion resistance.     

Long-term corrosion studies in vitro of gold, cobalt-chromium, and nickel-chromium alloys in contact

Specimens of various types of dental casting alloys were stored in phosphate-buffered 0.9% NaCl solution for 35 weeks. Every 7 weeks the solutions were changed and analyzed with regard to elements released from the alloys. The release of Cu from type III gold alloy increased in contact with gold alloys for metallo-ceramic use in a 1:2 area relation. However, when the area relation was reversed, no difference in the amounts of elements released was observed. Crevice corrosion was initiated with one of the Co-Cr alloys in contact with type III gold alloy. The crevice corrosion increased the amounts of Co and Cr released into the solutions. The release of Ni and Cr from the Ni-Cr alloys was prominent. These alloys were very susceptible to crevice corrosion. With one of the Ni-Cr alloys the release of elements increased in contact with type III gold alloy.     

Dealloying and electroformation in high-Pd dental alloys.

OBJECTIVE: The corrosion of high-Pd dental alloys, depending on their composition, is postulated to be associated with dealloying and electroformation. The aim of this study was to obtain additional information to support these postulations. METHODS: The corrosion characteristics of two commercial high-Pd alloys, Naturelle (79Pd-10Cu-2Au-9Ga wt%) and Rx 91 (54Pd-37Ag-9Sn), and their elemental components were evaluated in a phosphated buffer saline (PBS) solution. Indium, a common element in high-Pd alloys, was also included. The corrosion characteristics measured for each material were the 24 h open circuit potential (OCP) and the potentiodynamic anodic polarization curve. Additionally, the surface composition of the two alloys, before and after immersion corrosion in PBS for 2 months, was analyzed by X-ray photo electron spectroscopy (XPS). RESULTS: Of the pure metals, Ga had the most electroactive OCP followed in order by In, Sn, Cu, Ag, Au, and Pd. The anodic polarization data showed all base metals to be unstable in PBS. The electroformation of AgCl was evidenced in the polarization curve of pure Ag. Both electrochemical characteristics of the PdCu-based alloy were very similar to that of pure Pd. The PdAg-based alloy displayed corrosion behavior resembling that of Ag. XPS data showed that the corrosion of the PdCu-based alloy was associated with a decrease in surface content of Cu and Ga but an increase in Pd and Au. The PdAg-based alloy surface during corrosion showed a decrease in Sn, an increase in Ag, and an unaltered Pd content. The behavior of the PdCu-based alloy is attributed to the operation of a galvanic interaction that causes dissolution of base metals and surface enrichment with primarily Pd. Dealloying, Ag-enrichment, and AgCl formation are thought to have contributed to the observed behavior of the PdAg-based alloy. These mechanisms are consistent with data from published ion release studies. SIGNIFICANCE: The allergenic potential of any Pd alloy is dependent on its propensity to develop a Pd-rich surface and thus release Pd+2 ions. The present study, though limited, has shown that electrochemical characteristics, namely OCP and polarization curves, can be used to identify such alloys. Further studies are warranted to evaluate the widespread applicability of these characteristics in distinguishing between Pd alloys that are biologically safe and those that are not.     

镍铬合金在人工唾液中的电化学腐蚀行为

目的 本项研究旨在探讨镍铬合金在体外的电化学腐蚀行为。方法 实验应用极化曲线方法，将镍铬合金浸泡在人工唾液中，温度为36．5℃，pH值为7．0，测量试样的腐蚀电位和自腐蚀电流密度。应用X射线光电子能谱(X-ray photoelectron spectroscopy，XPS)，分析试样表面的元素成分变化。结果 实验结果表明，镍铬合金的点蚀电位为-390mV，钝化电位为-160mV，活性溶解区从-160mV到-270mV。它的自腐蚀电流密度为0．262μAcm^-2。极化曲线试验后，对试片表面进行XPS能谱分析，所得原子峰高图发现，随着氩离子刻蚀的由浅入深，金属元素镍(Ni)、铬(Cr)、钼(Mo)、铁(Fe)的含量逐渐增加，而非金属元素氧(O)、碳(C)的含量则逐渐减少。由于钙(Ca)为介质中的元素，其含量也呈逐渐减少。结论 镍铬合金在人工唾液中，经过电化学极化曲线试验，会发生腐蚀反应，生成腐蚀产物附着于试样表面。