Long-term corrosion studies in vitro of amalgams in contact

Three types of amalgams, one conventional and two with a high copper content, were stored in phosphate-buffered 0.9% NaCl solution, at pH 6, for 35 weeks. Every 7 weeks the solutions were changed and analyzed with regard to Cu, Zn, Sn, Hg, and Ag. In one of the amalgam combinations, the conventional amalgam and one of the copper-rich amalgams in an area ratio of 2:1, contact between the amalgams clearly increased the amounts of Cu, Hg, and Ag released the first 14 weeks compared with when immersed in separate solutions. With the reversed area relation, Cu, Hg, and Ag decreased when they were in contact. The conventional amalgam in contact with the other copper-rich amalgam, in an area ratio of 2:1, reduced the amount of Cu but increased the Zn released. Polishing initially decreased the amounts of Cu and Zn released compared with the unpolished amalgams.     

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.     

The microstructure of corroded amalgams

One conventional amalgam and two amalgams with a high copper content were stored in 0.9% NaCl solution buffered with phosphate to pH 6. In one experimental series the amalgams were placed in contact with a gold alloy. Every 7 weeks the solutions were changed and analyzed with regard to elements released from the amalgams. The microstructure of the specimens was studied in a scanning electron microscope before immersion and after 7 and 35 weeks in the solution. All the amalgams corroded along the grain boundaries in the gamma 1 phase. Corrosion was greatest in the gamma 2 phase of ANA 68, in the eta phase of ANA 2000 and in the reaction zone (eta + gamma 1) surrounding the Ag-Cu-eutectic particles of Dispersalloy. The microstructure of the corroded amalgams showed similarities to amalgams corroded in vivo. The change in microstructure observed in cross-sections of the corroded specimens was related to the amounts of corrosion products released into the saline solution.     

Corrosion of dental amalgams in solutions of organic acids

A conventional and two high copper amalgams were tested in 0.5% aqueous solutions of acetic, formic, lactic and succinic acid. The corrosion behavior of the amalgams in the different solutions was evaluated by analyzing the soluble corrosion products using an atomic absorption spectrophotomeler every month during a 6-month experimental period. The high copper amalgams showed a high dissolution rate in formic and lactic acid solutions from the initial stages of immersion when compared to the conventional. Later a marked decrease of the dissolution rate could be observed but it still remained at high levels. In acetic acid the amounts of elements dissolved from high copper amalgams were much less. Conventional amalgam released much smaller amounts of elements in almost all solutions tested except in the case of silver in lactic acid. Finally, in succinic acid solution, the amounts of elements dissolved were unexpectedly small considering the low pH of the solution and the dissolution rates of the amalgams in the other organic acid solutions.     

Corrosion of dental amalgams in solutions of organic acids

A conventional and two high copper amalgams were tested in 0.5% aqueous solutions of acetic, formic, lactic and succinic acid. The corrosion behavior of the amalgams in the different solutions was evaluated by analyzing the soluble corrosion products using an atomic absorption spectrophotometer every month during a 6-month experimental period. The high copper amalgams showed a high dissolution rate in formic and lactic acid solutions from the initial stages of immersion when compared to the conventional. Later a marked decrease of the dissolution rate could be observed but it still remained at high levels. In acetic acid the amounts of elements dissolved from high copper amalgams were much less. Conventional amalgam released much smaller amounts of elements in almost all solutions tested except in the case of silver in lactic acid. Finally, in succinic acid solution, the amounts of elements dissolved were unexpectedly small considering the low pH of the solution and the dissolution rates of the amalgams in the other organic acid solutions.     

Area ratio effects on metal ion release from amalgam in contact with gold

Abstract – The effect of area ratio, chloride concentration and brushing on amalgam in contact with gold was studied by measuring the amounts of elements released in the electrolyte. A type III gold alloy was stored for 4 months in contact with a conventional amalgam, area relations 6/1 and 6/3, in an electrolyte containing 85 mM NaCl with 10 mM phosphate buffer. A specimen with area relation 6/1 was also stored in a 10 mM NaCl solution with 10 mM phosphate buffer. The solutions were renewed each month and analyzed for Cu, Zn, Sn, Hg, and Ag in an atomic absorption spectrophotometer. Cross-sections of the amalgams were studied in a scanning electron microscope. The tendency for Sn and Cu to be released from the amalgam was greater than for the other elements. The Sn-release probably mainly originated from surface corrosion and Cu-release from subsurface corrosion. A stronger galvanic influence enhanced only the release of Cu, and to a less extent Zn. The subsurface corrosion of the amalgam and increasing release of Cu was, in contrast to the other elements, largely dependent on a high chloride concentration in the electrolyte. Light brushing of the specimens had no effect on the amounts of elements released.     

Area ratio effects on metal ion release from amalgam in contact with gold

The effect of area ratio, chloride concentration and brushing on amalgam in contact with gold was studied by measuring the amounts of elements released in the electrolyte. A type III gold alloy was stored for 4 months in contact with a conventional amalgam, area relations 6/1 and 6/3, in an electrolyte containing 85 mM NaCl with 10 mM phosphate buffer. A specimen with area relation 6/1 was also stored in a 10 mM NaCl solution with 10 mM phosphate buffer. The solutions were renewed each month and analyzed for Cu, Zn, Sn, Hg, and Ag in an atomic absorption spectrophotometer. Cross-sections of the amalgams were studied in a scanning electron microscope. The tendency for Sn and Cu to be released from the amalgam was greater than for the other elements. The Sn-release probably mainly originated from surface corrosion and Cu-release from subsurface corrosion. A stronger galvanic influence enhanced only the release of Cu, and to a less extent Zn. The subsurface corrosion of the amalgam and increasing release of Cu was, in contrast to the other elements, largely dependent on a high chloride concentration in the electrolyte. Light brushing of the specimens had no effect on the amounts of elements released.     

Corrosion of non –γ2– amalgams

Abstract – Abstract– Eight different dental amalgams were studied in an in vitro corrosion test. Cylindrical test specimens were stored in weak lactic acid solutions at different pH for 1 month. The concentrations of mercury and copper in the solutions were measured and corrosion depths estimated. The results indicated that more copper was released from non - γ₂ - amalgams compared with conventional ones. The amounts of copper from these amalgams were not directly correlated to the concentration in the alloys. Mercury was released in much lower amounts than copper for all amalgams and seemed to originate from the γ₁-phase. A low pH promoted the corrosion.     

Corrosion of non-gamma 2-amalgams

Eight different dental amalgams were studied in an in vitro corrosion test. Cylindrical test specimens were stored in weak lactic acid solutions at different pH for 1 month. The concentrations of mercury and copper in the solutions were measured and corrosion depths estimated. The results indicated that more copper was released from non-gamma 2-amalgams compared with conventional ones. The amounts of copper from these amalgams were not directly correlated to the concentration in the alloys. Mercury was released in much lower amounts than copper for all amalgams and seemed to originate from the gamma 1-phase. A low pH promoted the corrosion.     

Corrosion of amalgams

Abstract – The release of coppoer, mercury, silver, tin or zinc from conventional, dispersed phase and spherical high copper content amalgams immersed in artifucial saliva solutions for periods up to 30 d has been measured using nuclear tracer techniques. During initial corrosion, i.e. within a few hours, substaintial amounts of mercury were found to be present in particulate matter in the three type of amalgams. The release of particulate matter was pronounced for the dispersed phase type of amalgam. After about 30 d electrochemical corrosion was found to be the predominant process for release various corrosion products. Zinc was demonstrated to be the major corrosion product released to the artificial saliva solutions from conventional as well as dispresed phase amalgams. Due to low radioacivity levels silver and tin could not be quantitatively assayed. However, the upper limits of release of silver and tin in the artificial saliva solutions referring to exposure periods up to 30 d were estimated to 0.1 μg and 25 4mUg respectively. The chemical state of the various corrosion products has been evaluated. The deposition of CuCI₂ 3 Cu(OJ)₂ on the surfaces of copper rich amalgams was observed according to X-ray diffraction analysis.     

Electrochemical stability of dental materials. Part 4. Immersion test of amalgam

Specimens prepared with three commercial dental amalgams were immersed in three kinds of solutions: Ringer's, 1% lactic acid and 0.05% hydrochloric acid, at 37 degrees C, and subjected to a repeated corrosion test for fifteen weeks. Quantitative analysis was performed by inductively coupled plasma emission spectrometry for released metal elements to determine the composition of these amalgam alloy powders and immersed specimens. The immersion test for one week was not sufficient to prove the corrosion tendency of amalgam and a longer period of immersion was considered necessary. The kinds and amounts of released elements in each solution differed, and the corrosion tendency of high copper amalgam differed from that of conventional amalgam.     

Release of corrosion products from amalgam in phosphate containing solutions.

The effect of phosphate concentration on corrosion was compared for two types of amalgam: a conventional alloy (ANA 68) and a high-Cu admixed alloy (Dispersalloy). The test specimens were stored for 4 months in electrolytes containing 85 mM NaCl and 85 mM NaCl with 2.5, 10, or 100 mM phosphate buffer respectively. The solutions were renewed each month and analyzed for Cu, Zn, Sn, Hg, and Ag in an atomic absorption spectrophotometer. The surfaces and cross-sections of the specimens were studied in a scanning electron microscope (SEM) with an energy dispersive detector (EDAX). The corrosion products, mainly Sn-compounds, at the surface of the amalgams were less in the solutions containing high concentrations of phosphate. In cross-section subsurface corrosion of the high-Cu amalgam was observed especially in specimens immersed in the NaCl solution without phosphate. The conventional amalgam showed surface corrosion only. The decrease in release of elements with time from the conventional amalgam in all the experimental solutions might indicate passivation. For the high-Cu amalgam the release of elements increased with time, except for Cu and Sn in the solution with 100 mM phosphate, indicating that phosphate inhibits corrosion of the Cu-Sn-phases. Release of corrosion products from the high-Cu amalgam was more dependent on the presence of phosphate than the conventional amalgam.     

Release of corrosion products from amalgam in phosphate containing solutions

Abstract— The effect of phosphate concentration on corrosion was compared for two types of amalgam: a conventional alloy (ANA 68) and a high-Cu admixed alloy (Dispersalloy). The test specimens were stored for 4 months in electrolytes containing 85 mM NaCl and 85 mM NaCl with 2.5, 10, or 100 mM phosphate buffer respectively. The solutions were renewed each month and analyzed for Cu, Zn, Sn, Hg, and Ag in an atomic absorption spectrophotometer. The surfaces and cross-sections of the specimens were studied in a scanning electron microscope (SEM) with an energy dispersive detector (EDAX). The corrosion products, mainly Sn-compounds, at the surface of the amalgams were less in the solutions containing high concentrations of phosphate. In cross-section subsurface corrosion of the high-Cu amalgam was observed especially in specimens immersed in the NaCl solution without phosphate. The conventional amalgam showed surface corrosion only. The decrease in release of elements with time from the conventional amalgam in all the experimental solutions might indicate passivation. For the high-Cu amalgam the release of elements increased with time, except for Cu and Sn in the solution with 100 mM phosphate, indicating that phosphate inhibits corrosion of the Cu-Sn-phases. Release of corrosion products from the high-Cu amalgam was more dependent on the presence of phosphate than the conventional amalgam.     

Recent developments in alloys for dental amalgams: their properties and proper use.

Since the development more than ten years ago of a new type of amalgam alloy that will react with mercury without forming the unfavourable gamma2 (Sn7-8Hg) phase, several new alloy brands with a similar reaction pattern have been presented. This new generation of amalgam alloy is called non-gamma2 alloy as distinct from the conventional alloys. Three of the new alloys studied contain approximately three volume percent gamma2 and should be classified as modified concentional amalgams. The non-gamma2 amalgams may be characterized in the following way: (1) instead of gamma2 they contain a reaction product of copper and tin (Cu6Sn5), the so-called eta1 phase. (2) They are significantly more resistant to corrosion than the conventional amalgams but do in time produce sufficient solid corrosion products to seal the micro-fissures between filling and cavity walls. (3) When corroding, they do not release metallic mercury, and the solid corrosion products formed and precipitated on the free surface of the fillings seem relatively little resistant to the organic acids of the plaque. (4) Most of them have relatively low creep and tensile strength, but high compressive strength. (5) Clinically the non-gamma2 amalgams are remarkable for superior marginal integrity and, seemingly, also for improved persistence of surface lustre.     

Release of elements from some gold alloys and amalgams in corrosion

Abstract – The release of Au, Ag, Cu and Zn elements from six commercially available gold alloys and three amalgam alloys was studied. The polarizing electropotential system with modified Fusayama solution was used. The cycle process was repeated 500 times between ± 1000 mV during a period of 5 h 22 min. During the process samples of solution were analyzed in order to follow the release of elements. Results revealed rapid release of Zn from most alloys, release of Ag from most alloys and release of Au from two alloys. Also, rapid release of Gu was found from amalgams but not from gold alloys. Release of Ag from gold alloys showed very good passivation up to 3 h, after which it was released in varying amounts.     

Release of elements from some gold alloys and amalgams in corrosion

The release of Au, Ag, Cu and Zn elements from six commercially available gold alloys and three amalgam alloys was studied. The polarizing electropotential system with modified Fusayama solution was used. The cycle process was repeated 500 times between +/- 1000 mV during a period of 5 h 22 min. During the process samples of solution were analyzed in order to follow the release of elements. Results revealed rapid release of Zn from most alloys, release of Ag from most alloys and release of Au from two alloys. Also, rapid release of Cu was found from amalgams but not from gold alloys. Release of Ag from gold alloys showed very good passivation up to 3 h, after which it was released in varying amounts.     

Marginal microhardness of corroded amalgams: a comparative in vitro study

One conventional and two high-Cu amalgams were tested for marginal microhardness after 2 months' corrosion in an 85 mM NaCl solution. Amalgams immersed in 200 mM phosphate buffer solution were used as controls. The microhardness tests were conducted on cross-sections of the amalgams 50 microns from the surface edges. The microstructure of the amalgams was studied in SEM and the amounts of Sn, Cu, Zn, Ag, and Hg dissolved in the solutions were analyzed with an atomic absorption spectrophotometer. For the amalgams immersed in the NaCl solution the depth of corrosion after 2 months was between 50 and 400 microns. The specimens immersed in the phosphate solution showed no signs of subsurface corrosion. The marginal microhardness of all the amalgams was reduced after corrosion in the NaCl solution. The greatest microhardness in both the uncorroded and corroded states was shown in the two high-Cu amalgams. The reduction in marginal microhardness after corrosion can probably be attributed mainly to degradation of the gamma-2 phase for the conventional amalgam and to degradation of the eta' phase for the two high-Cu amalgams.     

Marginal microhardness of corroded amalgams: a comparative in vitro study

Abstract – One conventional and two high-Cu amalgams were tested for marginal microhardness after 2 months' corrosion in an 85 mM NaCl solution. Amalgams immersed in 200 mM phosphate buffer solution were used as controls. The microhardness tests were conducted on cross-sections of the amalgams 50μm from the surface edges. The microstructure of the amalgams was studied in SEM and the amounts of Sn, Cu, Zn, Ag, and Hg dissolved in the solutions were analyzed with an atomic absorption spectrophotometer. For the amalgams immersed in the NaCl solution the depth of corrosion after 2 months was between 50 and 400μm. The specimens immersed in the phosphate solution showed no signs of subsurface corrosion. The marginal microhardness of all the amalgams was reduced after corrosion in the NaCl solution. The greatest microhardness in both the uncorroded and corroded states was shown in the two high-Cu amalgams. The reduction in marginal microhardness after corrosion can probably be attributed mainly to degradation of the gamma-2 phase for the conventional amalgam and to degradation of the η' phase for the two high-Cu amalgams.     

Elemental release from dental casting alloys into biological media with and without protein.

OBJECTIVE: The objective of this study was to determine the role of proteins in affecting elemental release from a variety of clinically available dental casting alloys. An important role for proteins was suspected based on previous reports about the corrosion of stainless steel and the cytotoxicity of alloys after exposure to a saline-protein solution. METHODS: Clinically available alloys with compositions ranging from 0 to 94at.% noble elements were exposed for 1 week to either saline, saline with 3% bovine serum albumin (BSA), or complete cell-culture medium with 3% serum. Atomic absorption spectrophotometry was used to measure the release of elements from the alloys. Elemental release was normalized for the exposed surface area of the alloys. RESULTS: In general, more elemental release occurred into the saline-BSA solution compared to saline alone for all released elements (Ag, Cu, Pd, and Zn) except for Ni. Ni release from the NiCr alloy was lower in the presence of BSA. Each element responded somewhat differently with Pd being the least predictable in its behavior. Elemental release was less in the cell-culture medium than in the saline-BSA solution for most elements. For alloys which released multiple elements, all elements responded similarly but not identically to the presence of protein. A high elemental release during exposure to the saline-BSA solution correlated with a low alloy cytotoxicity post-exposure to the saline-BSA. SIGNIFICANCE: This study demonstrates the importance of defining exactly the composition of biological solutions used to assess in vitro corrosion and biocompatibility of dental casting alloys. Other molecules in addition to proteins appeared to be critical to the corrosion of these alloys in vitro.     

Ions released from dental amalgams in contact with titanium

The ions released from conventional and high-copper amalgams in contact with titanium were quantitatively analyzed in a 0.9% NaCl solution at 37 degrees C when the surface area ratio of titanium/amalgam was set up as 1/10, 1/1, or 10/1. The corrosion potentials of the amalgams and titanium were measured under the same conditions. Surface analyses on the amalgams were also employed using SEM with WDS. Though the potential of the conventional amalgam was always lower than that of titanium, that of the high-copper amalgam was reversed during the early stage of immersion and remained lower. When the surface area ratio of titanium grew at 10/1, tin and copper ions released from the conventional and high-copper amalgam, respectively, increased significantly compared with those of each amalgam that was not in contact with titanium. The galvanic corrosion in such a large surface area of titanium possibly led to the heavy corrosion of the amalgams.