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WO2017058670A1 - Procédé de traitement de surface pour verres métalliques à base de nickel visant à réduire la libération de nickel - Google Patents

Procédé de traitement de surface pour verres métalliques à base de nickel visant à réduire la libération de nickel Download PDF

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Publication number
WO2017058670A1
WO2017058670A1 PCT/US2016/053550 US2016053550W WO2017058670A1 WO 2017058670 A1 WO2017058670 A1 WO 2017058670A1 US 2016053550 W US2016053550 W US 2016053550W WO 2017058670 A1 WO2017058670 A1 WO 2017058670A1
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Prior art keywords
solution
metallic glass
based metallic
concentration
sample
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PCT/US2016/053550
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English (en)
Inventor
Maximilien LAUNEY
Marios D. Demetriou
Glenn GARRETT
Jong Hyun NA
William L. Johnson
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Glassimetal Technology Inc
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Glassimetal Technology Inc
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Publication of WO2017058670A1 publication Critical patent/WO2017058670A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/18—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions
    • C23C10/26—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions more than one element being diffused
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/04—Amorphous alloys with nickel or cobalt as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/58—Treatment of other metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/20—Other heavy metals

Definitions

  • the disclosure is directed to Ni-based metallic glasses having passive layers that limit Ni leaching when the metallic glasses are exposed to a saline containing environment, and surface treatment methods for Ni-based metallic glasses to promote formation of such passive layers.
  • the disclosure is directed to surface treatment methods for Ni-based metallic glasses to reduce the amount of Ni released when the Ni-based metallic glass is exposed to a saline containing environment.
  • the disclosure is directed to a surface treatment method for a Ni- based metallic glass. At least a portion of a sample of a Ni-based metallic glass is immersed in a chemical treatment solution to produce a surface treated portion. The surface treated portion is removed from the chemical treatment solution to terminate the chemical surface treatment.
  • the chemical treatment solution comprises at least one of an acid solution, a chromate solution, and a molybdate solution.
  • the Ni ion release rate from the surface treated portion of the sample when immersed in a saline solution for one day is less than 80% of the Ni ion release rate from an as-cast Ni-based metallic glass sample having the same composition immersed in the same saline solution for the same period.
  • the surface treatment method comprises at least two immersion steps.
  • the surface treatment method comprises at least two immersion steps, wherein at least one step comprises immersion in a first chemical treatment solution comprising an acid and at least one other step comprising immersion in a second chemical treatment solution comprising a chromate solution.
  • each immersion step comprises immersing at least a portion of the Ni-based metallic glass in a chemical treatment solution to produce a surface treated portion. The surface treated portion then is removed from the chemical treatment solution.
  • the first chemical treatment solution is an acid solution while the second chemical treatment solution is a chromate solution.
  • the second chemical treatment solution is a sodium dichromate solution.
  • the sodium dichromate concentration in the sodium dichromate solution is between 5 and 200 g/L.
  • the surface treatment method comprises at least two immersion steps, wherein at least one step comprises immersion in a first chemical treatment solution comprising an acid and at least one other step comprising immersion in a second chemical treatment solution comprising a molybdate solution.
  • each immersion step comprises immersing at least a portion of the Ni-based metallic glass in a chemical treatment solution to produce a surface treated portion. The surface treated portion is then removed from the chemical treatment solution.
  • the first chemical treatment solution is an acid solution while the second chemical treatment solution is a molybdate solution.
  • the second chemical treatment solution is a disodium molybdate.
  • the disodium molybdate concentration in the disodium molybdate solution is between 10 and 100 g/L.
  • the duration of immersion is at least 1 minute.
  • the duration of immersion is at least 10 minutes. [0015] In another embodiment, the duration of immersion is at least 20 minutes.
  • the duration of immersion is at least 30 minutes.
  • the duration of immersion is at least 60 minutes.
  • the temperature of the chemical treatment solution ranges between 10 and 80°C.
  • the temperature of the chemical treatment solution ranges between 20 and 60°C.
  • the temperature of the chemical treatment solution is in the range of 20 to 30°C.
  • the temperature of the chemical treatment solution is in the range of 40 to 60°C.
  • the first chemical treatment solution comprises a nitric acid solution.
  • the nitric acid concentration in the nitric acid solution is between 5 and 60 vol.%.
  • the nitric acid concentration in the nitric acid solution is between 20 and 45 vol.%.
  • the nitric acid concentration in the nitric acid solution is between 15 and 30 vol.%.
  • the nitric acid concentration in the nitric acid solution is between 20 and 25 vol.%.
  • the disclosure is directed to a surface treatment method for a Ni-based metallic glass. At least a portion of a sample of a Ni-based metallic glass is immersed in an acid solution to promote chemical surface treatment. The sample is removed from the acid solution to terminate the chemical surface treatment. Afterwards, the Ni ion release rate from the treated portion of the sample when immersed in a saline solution for one day is less than 80% of the Ni ion release rate from an as-cast Ni-based metallic glass sample having the same composition immersed in the saline solution for one day.
  • the Ni ion release rate from the treated portion of the sample when immersed in a saline solution for one day is less than 60% of the Ni ion release rate from an as-cast Ni-based metallic glass sample having the same composition immersed in the saline solution for the one day.
  • the Ni ion release rate from the treated portion of the sample when immersed in a saline solution for one day is less than 50% of the Ni ion release rate from an as-cast Ni-based metallic glass sample having the same composition when immersed in the saline solution for the one day.
  • the Ni ion release rate from the treated portion of the sample when immersed in a saline solution for one day is less than 40% of the Ni ion release rate from an as-cast Ni-based metallic glass sample having the same composition immersed in the saline solution for the one day.
  • the Ni ion release rate from the treated portion of the sample when immersed in a saline solution for one day is less than 20% of the Ni ion release rate from an as-cast Ni-based metallic glass sample having the same composition immersed in the saline solution for the one day.
  • the Ni ion release rate from the treated portion of the sample when immersed in a saline solution for 4 days reaches a steady state.
  • the Ni ion release rate from the treated portion of the sample when immersed in a saline solution for 2 days reaches a steady state.
  • the Ni ion release rate from the treated portion of the sample when immersed in a saline solution for one day reaches a steady state.
  • the Ni ion release rate from the treated portion of the sample when immersed in a saline solution for 12 hours reaches a steady state.
  • the Ni ion release rate from the treated portion of the sample when immersed in a perspiration solution is less than 0.88 ⁇ g/cm 2 /week.
  • the Ni ion release rate from the treated portion of the sample when immersed in artificial perspiration is less than 0.88 ⁇ g/cm 2 /week.
  • the Ni ion release rate from the treated portion of the sample when immersed in a perspiration solution is less than 0.5 ⁇ g/cm 2 /week.
  • the Ni ion release rate from the treated portion of the sample when immersed in a perspiration solution is less than 0.1 ⁇ g/cm 2 /week.
  • the Ni ion release rate from the treated portion of the sample when immersed in a perspiration solution is less than 0.05 ⁇ g/cm 2 /week.
  • the Ni ion release rate from the treated portion of the sample when immersed in a perspiration solution is less than 0.01 ⁇ g/cm 2 /week.
  • the mass of Ni ion released from the treated portion of the sample when immersed in a saline solution for one day is less than 35 ⁇ g.
  • the mass of Ni ion released from the treated portion of the sample when immersed in a biological solution for one day is less than 35 ⁇ g.
  • the mass of Ni ion released from the treated portion of the sample when immersed in blood or saliva for one day is less than 35 ⁇ g.
  • the mass of Ni ion released from the treated portion of the sample when immersed in artificial blood or artificial saliva for one day is less than 35 ⁇ g.
  • the duration of immersion in the chemical treatment solution is at least 1 minute.
  • the duration of immersion in the chemical treatment solution is at least 10 minutes.
  • the duration of immersion in the chemical treatment solution is at least 20 minutes.
  • the duration of immersion in the chemical treatment solution is at least 30 minutes.
  • the duration of immersion in the chemical treatment solution is at least 60 minutes.
  • the temperature of the chemical treatment solution ranges between 10 and 80°C.
  • the temperature of the chemical treatment solution ranges between 20 and 60°C.
  • the temperature of the chemical treatment solution is in the range of 20 to 30°C.
  • the temperature of the chemical treatment solution is in the range of 40 to 60°C.
  • the duration of immersion in the acid solution is at least 1 minute.
  • the duration of immersion in the acid solution is at least 10 minutes.
  • the duration of immersion in the acid solution is at least 20 minutes.
  • the duration of immersion in the acid solution is at least 30 minutes. [0059] In another embodiment, the duration of immersion in the acid solution is at least 60 minutes.
  • the temperature of the acid solution ranges between 10 and 80°C.
  • the temperature of the acid solution ranges between 20 and 60°C.
  • the temperature of the acid solution is in the range of 20 to 30°C.
  • the temperature of the acid solution is in the range of 40 to 60°C.
  • the acid solution comprises nitric acid.
  • the acid solution comprises nitric acid, where the nitric acid concentration is between 5 and 60 vol.%.
  • the acid solution comprises nitric acid, where the nitric acid concentration is between 20 and 45 vol.%.
  • the acid solution comprises nitric acid, where the nitric acid concentration is between 15 and 30 vol.%.
  • the acid solution comprises nitric acid, where the nitric acid concentration is between 20 and 25 vol.%.
  • the chemical treatment solution comprises a chromate solution.
  • the chemical treatment solution comprises sodium dichromate.
  • the chemical treatment solution comprises sodium dichromate, where the sodium dichromate concentration is between 5 and 200 g/L.
  • the chemical treatment solution comprises sodium dichromate, where the sodium dichromate concentration is between 10 and 100 g/L.
  • the chemical treatment solution comprises a molybdate solution.
  • the chemical treatment solution comprises disodium molybdate.
  • the chemical treatment solution comprises disodium molybdate, where the disodium molybdate concentration is between 5 and 200 g/L. [0076] In another embodiment, the chemical treatment solution comprises disodium molybdate, where the disodium molybdate concentration is between 10 and 100 g/L.
  • the saline solution has a pH of at least 2.
  • the saline solution has a pH of at least 4.
  • the saline solution has a pH of at least 6.
  • the saline solution has a concentration of NaCl of at least 0.1 g/L.
  • the saline solution has a concentration of NaCl of at least 0.25 g/L.
  • the saline solution has a concentration of NaCl of at least 1 g/L.
  • the saline solution has a concentration of NaCl of at least 2 g/L.
  • the saline solution has a concentration of NaCl of at least 5 g/L.
  • the saline solution is a biological solution.
  • the saline solution is saliva.
  • the saline solution is perspiration.
  • the saline solution is blood.
  • the saline solution is a simulated body fluid.
  • the saline solution is artificial saliva.
  • the saline solution is artificial perspiration.
  • the saline solution is artificial blood.
  • the saline solution is sea water.
  • the saline solution is simulated sea water.
  • the metal moiety of the Ni-based metallic glass comprises at least one of Cr, Mo, Mn, Nb, Ta, Fe, Co, and Cu in its metal moiety.
  • the metal moiety of the Ni-based metallic glass comprises at least Cr.
  • the metal moiety of the Ni-based metallic glass comprises at least Mo.
  • the metalloid moiety of the Ni-based metallic glass comprises at least one of P, B, and Si. [0099] In another embodiment, the metalloid moiety of the Ni-based metallic glass comprises P and B.
  • the metalloid moiety of the Ni-based metallic glass comprises P and Si.
  • the metalloid moiety of the Ni-based metallic glass comprises Si and B.
  • the Ni-based metallic glass comprises Cr and P.
  • the Ni-based metallic glass is free of Ti.
  • the passivated Ni-based metallic glass has a composition according to the following formula (subscripts denote atomic percent):
  • X is Cr, Mo, Mn, Nb, Ta, Fe, Co, Cu or combinations thereof;
  • Z is P, B, Si, or combinations thereof
  • a is between 5 and 25;
  • b is between 15 and 25.
  • X is Cr and at least one of Nb and Ta, and Z is P and B.
  • X is Cr and Nb
  • Z is P and Si.
  • X is Mo and at least one of Nb and Mn, and Z is P and B.
  • X is Mo and at least one of Nb and Mn, and Z is P and Si.
  • the passive layer has an amorphous structure.
  • the passive layer of a surface-treated sample is thicker compared to the passive layer of an untreated sample.
  • Ni-based metallic glass and/or passivated Ni-based metallic glass comprises Cr and P
  • the passive layer of the surface-treated sample comprises O, P, and Cr
  • Ni-based metallic glass and/or passivated Ni-based metallic glass comprises Mo and P
  • the passive layer of the surface-treated sample comprises O, P, and Mo
  • the passive layer of the surface-treated sample is poor in Ni.
  • the average concentration of O within the passive layer of the surface-treated sample of a Ni-based metallic glass is higher than the concentration of O in an untreated sample.
  • the average concentration of Ni within the passive layer of the surface treated sample of a Ni-based metallic glass and/or passivated Ni-based metallic glass is lower than the concentration of Ni in an untreated sample.
  • the average concentration of P within the passive layer of the surface-treated sample of a Ni-based metallic glass and/or passivated Ni-based metallic glass comprising P is higher than the concentration of P in an untreated sample.
  • the average concentration of Cr within the passive layer of the surface-treated sample of a Ni-based metallic glass and/or passivated Ni-based metallic glass comprising Cr is higher than the concentration of Cr in an untreated sample.
  • the average concentration of O within the passive layer of the surface-treated sample of a Ni-based metallic glass and/or passivated Ni-based metallic glass comprising Cr and P is at least 5% higher than the concentration of O in an untreated sample.
  • the average concentration of O within the passive layer of the surface-treated sample of a Ni-based metallic glass and/or passivated Ni-based metallic glass comprising Cr and P is at least 10% higher than the concentration of O in an untreated sample.
  • the average concentration of O within the passive layer of the surface-treated sample of a Ni-based metallic glass and/or passivated Ni-based metallic glass comprising Cr and P is at least 20% higher than the concentration of O in an untreated sample.
  • the average concentration of P within the passive layer of the surface-treated sample of a passivated Ni-based metallic glass comprising Cr and P is at least 5% higher than the concentration of P in an untreated sample.
  • the average concentration of P within the passive layer of the surface-treated sample of a passivated Ni-based metallic glass comprising Cr and P is at least 10% higher than the concentration of P in an untreated sample.
  • the average concentration of P within the passive layer of the surface-treated sample of a passivated Ni-based metallic glass comprising Cr and P is at least 20% higher than the concentration of P in an untreated sample.
  • the average concentration of Cr within the passive layer of the surface-treated sample of a Ni-based metallic glass and/or passivated Ni-based metallic glass comprising Cr and P is at least 5% higher than the concentration of Cr in an untreated sample.
  • the average concentration of Cr within the passive layer of the surface-treated sample of a Ni-based metallic glass and/or passivated Ni-based metallic glass comprising Cr and P is at least 10% higher than the concentration of Cr in an untreated sample.
  • the average concentration of Cr within the passive layer of the surface-treated sample of a Ni-based metallic glass and/or passivated Ni-based metallic glass comprising Cr and P is at least 20% higher than the concentration of Cr in an untreated sample.
  • the average concentration of Ni within the passive layer of the surface-treated sample of a Ni-based metallic glass and/or passivated Ni-based metallic glass comprising Cr and P is at least 5% lower than the concentration of Ni in an untreated sample.
  • the average concentration of Ni within the passive layer of the surface-treated sample of a Ni-based metallic glass and/or passivated Ni-based metallic glass comprising Cr and P is at least 10% lower than the concentration of Ni in an untreated sample.
  • the average concentration of Ni within the passive layer of the surface-treated sample of a Ni-based metallic glass and/or passivated Ni-based metallic glass comprising Cr and P is at least 20% lower than the concentration of Ni in an untreated sample.
  • the passive layer of the surface-treated sample of a Ni- based metallic glass and/or passivated Ni-based metallic glass comprising Cr and P is thicker than the passive layer of an untreated sample.
  • the passive layer of the surface-treated sample of a Ni- based metallic glass and/or passivated Ni-based metallic glass comprising Cr and P is at least 5% thicker than the passive layer of an untreated sample.
  • the average concentration of Ni within the passive layer of the surface-treated sample of a Ni-based metallic glass and/or passivated Ni-based metallic glass comprising Cr and P is at least 10% lower than the concentration of Ni in an untreated sample.
  • the average concentration of Ni within the passive layer of the surface-treated sample of a Ni-based metallic glass and/or passivated Ni-based metallic glass comprising Cr and P is at least 20% lower than the concentration of Ni in an untreated sample.
  • the average concentration of O within the passive layer of the surface-treated sample of a Ni-based metallic glass and/or passivated Ni-based metallic glass comprising Cr and P that has been surface treated in a nitric acid solution of concentration of at least 15 vol.% for at least 30 minutes is at least 5% higher than the concentration of O in an untreated sample.
  • the average concentration of O within the passive layer of the surface-treated sample of a Ni-based metallic glass and/or passivated Ni-based metallic glass comprising Cr and P that has been surface treated in a nitric acid solution of concentration of at least 15 vol.% for at least 30 minutes is at least 50% higher than the concentration of O in an untreated sample.
  • the average concentration of P within the passive layer of the surface-treated sample of a passivated Ni-based metallic glass comprising Cr and P that has been surface treated in a nitric acid solution of concentration of at least 15 vol.% for at least 30 minutes is at least 10% higher than the concentration of P in an untreated sample.
  • the average concentration of P within the passive layer of the surface-treated sample of a passivated Ni-based metallic glass comprising Cr and P that has been surface treated in a nitric acid solution of concentration of at least 15 vol.% for at least 30 minutes is at least 20% higher than the concentration of P in an untreated sample.
  • the average concentration of Cr within the passive layer of the surface-treated sample of a Ni-based metallic glass and/or passivated Ni-based metallic glass comprising Cr and P that has been surface treated in a nitric acid solution of concentration of at least 15 vol.% for at least 30 minutes is at least 15% higher than the concentration of Cr in an untreated sample.
  • the average concentration of Cr within the passive layer of the surface-treated sample of a Ni-based metallic glass and/or passivated Ni-based metallic glass comprising Cr and P that has been surface treated in a nitric acid solution of concentration of at least 15 vol.% for at least 30 minutes is at least 15% higher than the concentration of Cr in an untreated sample.
  • the average concentration of Ni within the passive layer of the surface-treated sample of a Ni-based metallic glass and/or passivated Ni-based metallic glass comprising Cr and P that has been surface treated in a nitric acid solution of concentration of at least 15 vol.% for at least 30 minutes is at least 5% lower than the concentration of Ni in an untreated sample.
  • the average concentration of Ni within the passive layer of the surface-treated sample of a Ni-based metallic glass and/or passivated Ni-based metallic glass comprising Cr and P that has been surface treated in a nitric acid solution of concentration of at least 15 vol.% for at least 30 minutes is at least 10% lower than the concentration of Ni in an untreated sample.
  • the passive layer of the surface-treated sample of a Ni- based metallic glass and/or passivated Ni-based metallic glass comprising Cr and P that has been surface treated in a nitric acid solution of concentration of at least 15 vol.% for at least 30 minutes is thicker than the passive layer of an untreated sample.
  • the passive layer of the surface-treated sample of a Ni- based metallic glass and/or passivated Ni-based metallic glass comprising Cr and P that has been surface treated in a nitric acid solution of concentration of at least 15 vol.% for at least 30 minutes is at least 5% thicker than the passive layer of an untreated sample.
  • the passive layer of the surface-treated sample of a Ni- based metallic glass and/or passivated Ni-based metallic glass comprising Cr and P that has been surface treated in a nitric acid solution of concentration of at least 15 vol.% for at least 30 minutes is at least 10% thicker than the passive layer of an untreated sample.
  • the passive layer of the surface-treated sample of a Ni- based metallic glass and/or passivated Ni-based metallic glass comprising Cr and P that has been surface treated in a nitric acid solution of concentration of at least 15 vol.% for at least 30 minutes is at least 25% thicker than the passive layer of an untreated sample.
  • the disclosure is also directed to a Ni-based metallic glass and/or passivated Ni-based metallic glass comprising an inner bulk material portion, and an outer passive layer portion.
  • the Ni-based metallic glass and/or passivated Ni-based metallic glass comprise at least one of Cr and Mo.
  • the average atomic concentration of Cr and/or Mo within the passive layer portion is higher than the respective concentrations in the inner bulk material portion.
  • the average atomic concentration of Cr and/or Mo within the passive layer is at least 2% higher than the respective concentrations in the inner bulk material portion.
  • the average atomic concentration of Cr and/or Mo within the passive layer is at least 5 % higher than the respective concentrations in the inner bulk material portion.
  • the average atomic concentration of Cr and/or Mo within the passive layer is at least 10% higher than the respective concentrations in the inner bulk material portion.
  • the average atomic concentration of Cr and/or Mo within the passive layer is at least 20% higher than the respective concentrations in the inner bulk material portion.
  • the disclosure is also directed to a Ni-based metallic glass and/or passivated Ni-based metallic glass comprising an inner bulk material portion, and an outer passive layer portion.
  • the Ni-based metallic glass and/or passivated Ni-based metallic glass comprise P.
  • the average atomic concentration of P within the passive layer portion is higher than the P concentration in the inner bulk material portion.
  • the inner bulk material portion that comprises Cr and P and an outer passive layer portion that comprises Cr, P, and O.
  • the inner bulk material portion comprises Mo and P and the outer passive layer comprises Mo, P, and O.
  • the average atomic concentration of Cr and Mo in the outer passive layer is at least 2% higher than the average atomic concentration of Cr and Mo in the inner bulk material portion.
  • the average atomic concentration of P in the outer passive layer is at least 5 % higher than the average atomic concentration of P in the inner bulk material portion.
  • the average atomic concentration of P within the passive layer is at least 5% higher than the P concentration in the inner bulk material portion.
  • the average atomic concentration of P within the passive layer is at least 10% higher than the P concentration in the inner bulk material portion.
  • the average atomic concentration of P within the passive layer is at least 20% higher than the respective concentration in the inner bulk material portion. [00155] In another embodiment, the average atomic concentration of P within the passive layer is at least 30% higher than the respective concentration in the inner bulk material portion.
  • the disclosure is also directed to an article of a passivated Ni-based metallic glass.
  • FIG. 1 provides a plot showing the effect of surface treatment in a Nitric acid solution on the Nickel-ion release rate of Ni71.4Cr5.52Nb 3 . 38 Pi 6 . 6 7B 3 .03 metallic glass in a PBS (Phosphate Buffered Solution) solution in accordance with embodiments.
  • PBS Phosphate Buffered Solution
  • FIG. 2 provides a plot showing the effect of surface treatment in a Citric acid solution on the Nickel-ion release rate of Ni71.4Cr5.52Nb3.38Pi6.67B3.03 metallic glass in a PBS (Phosphate Buffered Solution) solution in accordance with embodiments.
  • PBS Phosphate Buffered Solution
  • FIG. 3 provides a plot showing the effect of surface treatment in a Nitric acid solution on the Nickel- ion release rate of Ni68.nCr8.65Nb2.98Pi6.42B3.28Sio.5 metallic glass in a PBS (Phosphate Buffered Solution) solution in accordance with embodiments.
  • PBS Phosphate Buffered Solution
  • FIG. 4 provides a plot showing the effect of surface treatment on the weekly Nickel-ion release rate of Ni68.nCr8.65Nb2.98Pi6.42B3.28Sio.5 metallic glass in an artificial perspiration solution.
  • FIG. 5 provides a plot of depth profile up to 200 angstrom for the concentration of Oxygen on the surfaces of an as-polished sample and samples surface treated in nitric acid solutions at various acid concentrations, as detected by XPS in accordance with embodiments.
  • FIG. 6 provides a plot of depth profile up to 200 angstrom for the concentration of Phosphorus/Boron on the surfaces of an as-polished and samples surface treated in nitric acid solutions at various acid concentrations, as detected by XPS in accordance with embodiments.
  • FIG. 7 provides a plot of depth profile up to 200 angstrom for the concentration of Chromium on the surfaces of an as-polished sample and samples surface treated in nitric acid solutions at various acid concentrations, as detected by XPS in accordance with embodiments.
  • FIG. 8 provides a plot of depth profile up to 200 angstrom for the concentration of Niobium on the surfaces of an as-polished sample and samples surface treated in nitric acid solutions at various acid concentrations, as detected by XPS in accordance with embodiments.
  • FIG. 9 provides a plot of depth profile up to 200 angstrom for the concentration of Nickel on the surfaces of an as-polished sample and samples surface treated in nitric acid solutions at various acid concentrations, as detected by XPS in accordance with embodiments.
  • FIG. 10 provides a plot of depth profile up to 200 angstrom for the concentration of Oxygen on the surfaces of an as-polished sample and a sample surface treated in a 20 vol.% nitric acid solution, as detected by SIMS in accordance with embodiments.
  • the insets provide plots of depth profile up to 60 angstrom for the detected Oxygen, and the regions for the "organic layer,” “passive layer,” and “bulk material” are designated by arrows.
  • the “bulk material” designation in the figures refers to the inner bulk material portion.
  • FIG. 11 provides a plot of depth profile up to 200 angstrom for the concentration of Phosphorus on the surfaces of an as-polished sample and a sample surface treated in a 20 vol.% nitric acid solution, as detected by SIMS in accordance with embodiments.
  • the insets provide plots of depth profile up to 60 angstrom for the detected Phosphorus, and the regions for the "organic layer,” “passive layer,” and “bulk material” are designated by arrows.
  • FIG. 12 provides a plot of depth profile up to 200 angstrom for the concentration of Chromium on the surfaces of an as-polished sample and a sample surface treated in a 20 vol.% nitric acid solution, as detected by SIMS in accordance with embodiments.
  • the insets provide plots of depth profile up to 60 angstrom for the detected Chromium, and the regions for the "organic layer,” “passive layer,” and “bulk material” are designated by arrows.
  • FIG. 13 provides a plot of depth profile up to 200 angstrom for the concentration of Niobium on the surfaces of an as-polished sample and a sample surface treated in a 20 vol.% nitric acid solution, as detected by SIMS in accordance with embodiments.
  • the insets provide plots of depth profile up to 60 angstrom for the detected Niobium, and the regions for the "organic layer,” “passive layer,” and “bulk material” are designated by arrows.
  • FIG. 14 provides a plot of depth profile up to 200 angstrom for the concentration of Boron on the surfaces of an as-polished sample and a sample surface treated in a 20 vol.% nitric acid solution, as detected by SIMS in accordance with embodiments.
  • the insets provide plots of depth profile up to 60 angstrom for the detected Boron, and the regions for the "organic layer,” “passive layer,” and “bulk material” are designated by arrows.
  • FIG. 15 provides a plot of depth profile up to 200 angstrom for the concentration of Silicon on the surfaces of an as-polished sample and a sample surface treated in a 20 vol.% nitric acid solution, as detected by SIMS in accordance with embodiments.
  • the insets provide plots of depth profile up to 60 angstrom for the detected Silicon, and the regions for the "organic layer,” “passive layer,” and “bulk material” are designated by arrows.
  • FIG. 16 provides a plot of depth profile up to 200 angstrom for the concentration of Nickel on the surfaces of an as-polished sample and a sample surface treated in a 20 vol.% nitric acid solution, as detected by SIMS in accordance with embodiments.
  • the insets provide plots of depth profile up to 60 angstrom for the detected Nickel, and the regions for the "organic layer,” “passive layer,” and “bulk material” are designated by arrows.
  • FIG. 17 provides a plot of depth profile up to 350 angstrom for the concentration of Oxygen on the surfaces of an as-polished sample and a sample surface treated in a 50 g/L sodium dichromate solution, as detected by SIMS in accordance with embodiments.
  • the insets provide plots of depth profile up to 100 angstrom for the detected Oxygen, and the "passive layer” region for each sample is designated by an arrow (solid arrow designates the "passive layer” region of the as-polished sample, while broken arrow designates the "passive layer” region of the surface treated sample).
  • FIG. 18 provides a plot of depth profile up to 350 angstrom for the concentration of Phosphorus on the surfaces of an as-polished sample and a sample surface treated in a 50 g/L sodium dichromate solution, as detected by SIMS in accordance with embodiments.
  • the insets provide plots of depth profile up to 100 angstrom for the detected Phosphorus, and the "passive layer” region for each sample is designated by an arrow (solid arrow designates the "passive layer” region of the as-polished sample, while broken arrow designates the "passive layer” region of the surface treated sample).
  • FIG. 19 provides a plot of depth profile up to 350 angstrom for the concentration of Chromium on the surfaces of an as-polished sample and a sample surface treated in a 50 g/L sodium dichromate solution, as detected by SIMS in accordance with embodiments.
  • the insets provide plots of depth profile up to 100 angstrom for the detected Chromium, and the "passive layer” region for each sample is designated by an arrow (solid arrow designates the "passive layer” region of the as-polished sample, while broken arrow designates the "passive layer” region of the surface treated sample).
  • FIG. 20 provides a plot of depth profile up to 350 angstrom for the concentration of Niobium on the surfaces of an as-polished sample and a sample surface treated in a 50 g/L sodium dichromate solution, as detected by SIMS in accordance with embodiments.
  • the insets provide plots of depth profile up to 100 angstrom for the detected Niobium, and the "passive layer” region for each sample is designated by an arrow (solid arrow designates the "passive layer” region of the as-polished sample, while broken arrow designates the "passive layer” region of the surface treated sample).
  • FIG. 21 provides a plot of depth profile up to 350 angstrom for the concentration of Boron on the surfaces of an as-polished sample and a sample surface treated in a 50 g/L sodium dichromate solution, as detected by SIMS in accordance with embodiments.
  • the insets provide plots of depth profile up to 100 angstrom for the detected Boron, and the "passive layer” region for each sample is designated by an arrow (solid arrow designates the "passive layer” region of the as-polished sample, while broken arrow designates the "passive layer” region of the surface treated sample).
  • FIG. 22 provides a plot of depth profile up to 350 angstrom for the concentration of Silicon on the surfaces of an as-polished sample and a sample surface treated in a 50 g/L sodium dichromate solution, as detected by SIMS in accordance with embodiments.
  • the insets provide plots of depth profile up to 100 angstrom for the detected Silicon, and the "passive layer” region for each sample is designated by an arrow (solid arrow designates the "passive layer” region of the as-polished sample, while broken arrow designates the "passive layer” region of the surface treated sample).
  • FIG. 23 provides a plot of depth profile up to 350 angstrom for the concentration of Nickel on the surfaces of an as-polished sample and a sample surface treated in a 50 g/L sodium dichromate solution, as detected by SIMS in accordance with embodiments.
  • the insets provide plots of depth profile up to 100 angstrom for the detected Nickel, and the "passive layer” region for each sample is designated by an arrow (solid arrow designates the "passive layer” region of the as-polished sample, while broken arrow designates the "passive layer” region of the surface treated sample).
  • FIG. 24 provides a plot of depth profile up to 200 angstrom for the concentration of Oxygen on the surfaces of an as-polished sample and a sample surface treated by a two-step chemical solution treatment (the first solution comprises 20 volume% nitric acid combined with 25 g/L sodium dichromate, and the second solution comprises 50 g/L sodium dichromate), as detected by SIMS in accordance with embodiments.
  • the insets provide plots of depth profile up to 60 angstrom for the detected Oxygen, and the "passive layer” region for each sample is designated by an arrow (solid arrow designates the "passive layer” region of the as-polished sample, while broken arrow designates the "passive layer” region of the surface treated sample).
  • FIG. 25 provides a plot of depth profile up to 200 angstrom for the concentration of Phosphorus on the surfaces of an as-polished sample and a sample surface treated by a two-step chemical solution treatment (the first solution comprises 20 volume% nitric acid combined with 25 g/L sodium dichromate, and the second solution comprises 50 g/L sodium dichromate), as detected by SIMS in accordance with embodiments.
  • the insets provide plots of depth profile up to 60 angstrom for the detected Phosphorus, and the "passive layer” region for each sample is designated by an arrow (solid arrow designates the "passive layer” region of the as-polished sample, while broken arrow designates the "passive layer” region of the surface treated sample).
  • FIG. 26 provides a plot of depth profile up to 200 angstrom for the concentration of Chromium on the surfaces of an as-polished sample and a sample surface treated by a two-step chemical solution treatment (the first solution comprises 20 volume% nitric acid combined with 25 g/L sodium dichromate, and the second solution comprises 50 g/L sodium dichromate), as detected by SIMS in accordance with embodiments.
  • the insets provide plots of depth profile up to 60 angstrom for the detected Chromium, and the "passive layer” region for each sample is designated by an arrow (solid arrow designates the "passive layer” region of the as-polished sample, while broken arrow designates the "passive layer” region of the surface treated sample).
  • FIG. 27 provides a plot of depth profile up to 200 angstrom for the concentration of Niobium on the surfaces of an as-polished sample and a sample surface treated by a two-step chemical solution treatment (the first solution comprises 20 volume% nitric acid combined with 25 g/L sodium dichromate, and the second solution comprises 50 g/L sodium dichromate), as detected by SIMS in accordance with embodiments.
  • the insets provide plots of depth profile up to 60 angstrom for the detected Niobium, and the "passive layer” region for each sample is designated by an arrow (solid arrow designates the "passive layer” region of the as-polished sample, while broken arrow designates the "passive layer” region of the surface treated sample).
  • FIG. 28 provides a plot of depth profile up to 200 angstrom for the concentration of Boron on the surfaces of an as-polished sample and a sample surface treated by a two-step chemical solution treatment (the first solution comprises 20 volume% nitric acid combined with 25 g/L sodium dichromate, and the second solution comprises 50 g/L sodium dichromate), as detected by SIMS in accordance with embodiments.
  • the insets provide plots of depth profile up to 60 angstrom for the detected Boron, and the "passive layer” region for each sample is designated by an arrow (solid arrow designates the "passive layer” region of the as-polished sample, while broken arrow designates the "passive layer” region of the surface treated sample).
  • FIG. 29 provides a plot of depth profile up to 200 angstrom for the concentration of Silicon on the surfaces of an as-polished sample and a sample surface treated by a two-step chemical solution treatment (the first solution comprises 20 volume% nitric acid combined with 25 g/L sodium dichromate, and the second solution comprises 50 g/L sodium dichromate), as detected by SIMS in accordance with embodiments.
  • the insets provide plots of depth profile up to 60 angstrom for the detected Silicon, and the "passive layer” region for each sample is designated by an arrow (solid arrow designates the "passive layer” region of the as-polished sample, while broken arrow designates the "passive layer” region of the surface treated sample).
  • FIG. 30 provides a plot of depth profile up to 200 angstrom for the concentration of Nickel on the surfaces of an as-polished sample and a sample surface treated by a two-step chemical solution treatment (the first solution comprises 20 volume% nitric acid combined with 25 g/L sodium dichromate, and the second solution comprises 50 g/L sodium dichromate), as detected by SIMS in accordance with embodiments.
  • the insets provide plots of depth profile up to 60 angstrom for the detected Nickel, and the "passive layer” region for each sample is designated by an arrow (solid arrow designates the "passive layer” region of the as-polished sample, while broken arrow designates the "passive layer” region of the surface treated sample).
  • FIG. 31 presents a plot of the logarithm of the Ni ion release rate in units of ⁇ g/cm 2 /week against the average atomic concentration of Cr in the passive layer in units of atomic percent.
  • the line is a power- law fit through the data.
  • the disclosure is directed to methods of chemical surface treatment for Ni- based metallic glasses to reduce the amount of Ni release when the metallic glass is exposed to a saline containing environment.
  • Embodiments of the chemical surface treatment methods improve the corrosion resistance of Ni-based metallic glasses in biological, physiological, and other saline-containing environments by protecting the material with a stable passive layer that acts as a barrier coating against Ni ion release.
  • Chemical surface treatments are generally applied in order to encourage passivation of a material by promoting surface oxidation and by dissolving foreign materials that might be present on the surface of the material from previous operations. Rapid passivation of the material will provide corrosion resistance when exposed to a corrosive environment, and prevent leaching of the various elemental constituents of the material into the corrosive environment.
  • the surface oxide layer increases the stability of the surface layers by protecting the bulk material from corrosion, and creates a physical and chemical barrier against Ni oxidation by modifying the oxidation pathways of Ni.
  • the applicability of the surface treatment also depends on the atomic structure of the material, as well as that of the surface oxide layer.
  • the type of chemical treatment that promotes passivation changes depending on the crystal structure of the stainless steel.
  • stainless steels with austenitic, ferritic, or martensitic crystal structures require very specific chemical treatment processes (e.g. solution chemistry, additives, solution temperature, etc.) to successfully promote passivation.
  • certain chemical treatments that work for some crystal structures don't work for others (e.g.
  • citric acid works for ferritic type Chrome Core 18FM but not nitric acid; by contrast, nitric acid works for ferritic types 430F and 430FR but not citric acid) (DeBold, Terry A. & Martin, James W. "How To Passivate Stainless Steel Parts" Modern Machine Shop, 10/1/2003).
  • inappropriate chemical treatment of stainless steels may cause "flash attacks", where instead of passivating the material by obtaining the desired oxide film, which typically appears as a shiny and clean surface layer, a heavily etched or darkened surface layer is produced. This causes degradation of the surface rather than passivation, and generally leads to higher corrosion rates.
  • Ni-based alloys i.e. to alloys that comprise Ni at an atomic fraction of at least 50%, in order to reduce the amount of Ni ion release when the alloy is exposed to a corrosive environment.
  • metallic materials that have an amorphous structure, i.e. to Ni-based metallic glasses.
  • the metal moiety of the Ni-based metallic glass comprises at least one of Cr, Mo, Mn, Nb, Ta, Fe, Co, and Cu.
  • the metal moiety of the Ni-based metallic glass comprises at least Cr.
  • the metal moiety of the Ni-based metallic glass comprises at least Mo. In another embodiment, the metalloid moiety of the Ni-based metallic glass comprises at least one of P, B, and Si. In another embodiment, the metalloid moiety of the Ni-based metallic glass comprises P and B. In another embodiment, the metalloid moiety of the Ni-based metallic glass comprises P and Si. In another embodiment, the metalloid moiety of the Ni-based metallic glass comprises Si and B. In another embodiment, the Ni-based metallic glass is free of Ti.
  • the Ni-based metallic glass and/or passivated Ni- based metallic glass has a composition according to the following formula (subscripts denote atomic percent):
  • X is Cr, Mo, Mn, Nb, Ta, Fe, Co, Cu or combinations thereof;
  • Z is P, B, Si, or combinations thereof
  • a is between 5 and 25;
  • b is between 15 and 25.
  • X is Cr and at least one of Nb and Ta, and Z is P and B. In another embodiment, X is Cr and Nb, and Z is P and Si. In another embodiment, X is Mo and at least one of Nb and Mn, and Z is P and B. In another embodiment, X is Mo and at least one of Nb and Mn, and Z is P and Si.
  • Example Ni-based metallic glass alloy systems include, but are not limited to, Ni-Cr-Nb-P-B, Ni-Co-Cr-Nb-P-B, Ni-Fe-Cr-Nb-P-B, Ni-Cu- Cr-Nb-P-B, Ni-Cr-Nb-P-Si, Ni-Cr-Ta-P-B, Ni-Cr-Mn-P-B, Ni-Mo-Nb-Mn-P-B, Ni-Mo-Nb-Mn-P-B, Ni-Mo-Nb- Mn-P-Si, Ni-Mn-Nb-P-B, Ni-Mn-Nb-P-Si, Ni-Cr-Mn-Nb-P-B, Ni-Cr-Mn-Mo-P-B, Ni-Mn- Ta-P-B, Ni-Cr-Si-B-P, Ni-Cr-Mo-Si-B-P, and Ni-Fe-Si
  • the Ni-based metallic glass and/or passivated Ni- based metallic glass has a chemical composition represented by the following formula (subscripts denote atomic percent):
  • a is greater than 3 and less than 15 ;
  • b is greater than 1.5 and less than 4.5 ;
  • c is greater than 14.5 and less than 18.5;
  • the Ni-based metallic glass and/or passivated Ni- based metallic glass has a chemical composition represented by the following formula (subscripts denote atomic percent): Ni(69-w- j c-y-z ) Cr 8 .5 +M ;Nb 3+ : Pi6.5+yB3 +z
  • the Ni-based metallic glass and/or passivated Ni- based metallic glass has a composition according to the following formula (subscripts denote atomic percent):
  • b is determined by x - y*a, where x ranges from 3.8 to 4.2 and y ranges from 0.11 to 0.14; c ranges from 16.25 to 17;
  • d ranges from 2.75 to 3.5
  • the Ni-based metallic glass and/or passivated Ni-based metallic glass has a chemical composition represented by the passivated Ni-based metallic glass has a composition according to the following formula (subscripts denote atomic percent):
  • b ranges from 1 to 3.25;
  • d ranges from 3 to 6.5
  • Ni-based metallic glass and/or passivated Ni- based metallic glass has a chemical composition according to the following formula (subscripts denote atomic percent):
  • b ranges from 4.5 to 5.5;
  • d ranges from 4.5 to 5.5
  • the Ni-based metallic glass and/or passivated Ni- based metallic glass has a chemical composition according to the following formula (subscripts denote atomic percent):
  • a ranges from 0.5 to 30;
  • b ranges from 2 to 15 ;
  • c ranges from 1 to 5 ;
  • d ranges from 14 to 19;
  • e ranges from 1 to 5 ;
  • X can be at least one of Co, Fe, and Cu
  • the Ni-based metallic glass and/or passivated Ni- based metallic glass has a chemical composition according to the following formula
  • c is between 14 and 17.5 ;
  • d is between 2.5 and 5
  • the Ni-based metallic glass and/or passivated Ni- based metallic glass has a chemical composition according to the following formula (subscripts denote atomic percent):
  • a ranges from 0.5 to 40;
  • b ranges from 3 to 11 ;
  • c ranges from 1.5 to 4.
  • d ranges from 14 to 17.5;
  • e ranges from 2 to 5 ;
  • X can be at least one of Co, Fe, and Cu
  • the Ni-based metallic glass and/or passivated Ni- based metallic glass has a chemical composition according to the following formula
  • a is between 2 and 18;
  • b is between 1 and 6;
  • c is between 16 and 20;
  • d is up to 4,
  • Ni-based metallic glass and/or passivated Ni- based metallic glass has a chemical composition according to the following formula (subscripts denote atomic percent): where:
  • a is between 0.25 and 12;
  • b is up to 15;
  • c is between 14 and 22;
  • d is between 0.25 and 5;
  • X can be at least one of Cr and Mo
  • the Ni-based metallic glass and/or passivated Ni- based metallic glass has a composition according to the following formula (subscripts denote atomic percent):
  • a is between 0.5 and 10;
  • b is up to 15;
  • c is between 14 and 24;
  • d is between 1 and 8;
  • X can be at least one of Cr and Mo
  • the Ni-based metallic glass and/or passivated Ni- based metallic glass has a chemical composition according to the following formula (subscripts denote atomic percent):
  • a is between 2 and 12;
  • b is up to 8.
  • c is between 14 and 19; and d is between 1 and 4,
  • the Ni-based metallic glass and/or passivated Ni- based metallic glass has a chemical composition according to the following formula
  • a is between 1 and 5;
  • b is between 3 and 5 ;
  • c is up to 2;
  • d is between 16 and 17;
  • e is between 2.75 and 3.75
  • the Ni-based metallic glass and/or passivated Ni- based metallic glass has a chemical composition according to the following formula
  • a is between 3.5 and 6
  • c is between 4.5 and 7
  • ⁇ i is between 10.5 and 13
  • e is between 4 and 6
  • the passive layer of the treated sample comprises oxygen, P, and Cr.
  • the passive layer of the treated sample comprises oxides and phosphides of Cr.
  • the passive layer of the treated sample comprises oxygen, P and/or B, and Cr.
  • the passive layer of the treated sample comprises oxides and phosphides and/or borides of Cr.
  • the passive layer of the treated sample comprises oxygen, P, and Mo. In another embodiment, where the Ni-based metallic glass comprises Mo and P, the passive layer of the treated sample comprises oxides and phosphides of Mo. In another embodiment, where the Ni-based metallic glass comprises Mo, P and B, the passive layer of the treated sample comprises oxygen, P and/or B, and Mo. In another embodiment, where the Ni-based metallic glass comprises Mo and P and B, the passive layer of the treated sample comprises oxides and phosphides and/or borides of Mo. In another embodiment, where the Ni-based metallic glass comprises Cr and Si, the passive layer of the treated sample comprises oxygen, Si, and Cr.
  • the passive layer of the treated sample comprises oxides and silicides of Cr.
  • the passive layer of the treated sample comprises oxygen, Si and/or B, and Cr.
  • the passive layer of the treated sample comprises oxides and silicides and/or borides of Cr.
  • the passive layer of the treated sample comprises oxygen, Si, and Mo.
  • the passive layer of the treated sample comprises oxides and silicides of Mo.
  • the passive layer of the treated sample comprises oxygen, Si and/or B, and Mo. In another embodiment, where the Ni-based metallic glass comprises Mo, Si and B, the passive layer of the treated sample comprises oxides and silicides and/or borides of Mo. In another embodiment, the passive layer of the treated sample is poor in Ni.
  • the surface oxide layer has an amorphous structure.
  • the disclosure is directed to a chemical treatment solution that may be an acid solution, a chromate solution, a molybdate solution, or combinations thereof.
  • the chemical treatment solution comprises an acid solution.
  • the chemical treatment solution comprises nitric acid.
  • the chemical treatment solution comprises nitric acid, where the nitric acid concentration is between 5 and 60 vol.%.
  • the chemical treatment solution comprises nitric acid, where the nitric acid concentration is between 20 and 45 vol.%.
  • the chemical treatment solution comprises nitric acid, where the nitric acid concentration is between 15 and 30 vol.%.
  • the chemical treatment solution comprises nitric acid, where the nitric acid concentration is between 20 and 25 vol.%.
  • the chemical treatment solution comprises a chromate solution.
  • the chemical treatment solution comprises sodium dichromate.
  • the chemical treatment solution comprises sodium dichromate, where the sodium dichromate concentration is between 5 and 200 g/L.
  • the chemical treatment solution comprises sodium dichromate, where the sodium dichromate concentration is between 10 and 100 g/L.
  • the chemical treatment solution comprises a molybdate solution. In another embodiment, the chemical treatment solution comprises disodium molybdate. In another embodiment, the chemical treatment solution comprises disodium molybdate, where the disodium molybdate concentration is between 5 and 200 g/L. In another embodiment, the chemical treatment solution comprises disodium molybdate, where the disodium molybdate concentration is between 10 and 100 g/L.
  • the saline solution has a pH of at least 2. In yet another embodiment, the saline solution has a pH of at least 4. In another embodiment, the saline solution has a pH of at least 6. In one embodiment, the saline solution has a concentration of NaCl of at least 0.1 g/L. In another embodiment, the saline solution has a concentration of NaCl of at least 0.25 g/L. In yet another embodiment, the saline solution has a concentration of NaCl of at least 1 g/L. In yet another embodiment, the saline solution has a concentration of NaCl of at least 2 g/L. In another embodiment, the saline solution has a concentration of NaCl of at least 5 g/L.
  • the disclosure is directed to a surface treatment method for a Ni-based metallic glass comprising immersing at least a portion of a sample of a Ni-based metallic glass in a chemical treatment solution to produce a surface treated portion and removing the surface treated portion from the chemical treatment solution to terminate the chemical surface treatment.
  • the chemical treatment solution comprises at least one of an acid solution, a chromate solution, and a molybdate solution.
  • the Ni ion release rate from the surface treated portion of the sample when immersed in a saline solution for one day is less than 80% of the Ni ion release rate from an as-cast Ni-based metallic glass sample having the same composition similarly immersed in the saline solution for one day.
  • the first chemical treatment solution comprises a nitric acid solution.
  • the nitric acid concentration in the nitric acid solution is between 5 and 60 volume %.
  • the nitric acid concentration in the nitric acid solution is between 20 and 45 volume %.
  • the surface treatment method comprises at least two immersion steps.
  • the method includes (1) immersing at least a portion of the Ni-based metallic glass in a first chemical treatment solution comprising an acid to produce a surface treated portion, and (2) removing the surface treated portion from the first chemical treatment solution.
  • the method may further include immersing the surface treated portion in a second chemical treatment solution.
  • the second chemical solution comprises at least one of a chromate solution and a molybdenum solution.
  • the surface treated portion is also removed from the second chemical treatment solution.
  • the Ni ion release rate from the surface treated portion when immersed in a saline solution for one day is less than 80% of the Ni ion release rate from an as-cast Ni-based metallic glass sample having the same composition immersed in the saline solution for one day.
  • the second chemical treatment solution comprises a sodium dichromate solution.
  • the sodium dichromate concentration in the sodium dichromate solution is between 5 and 200 g/L.
  • the sodium dichromate concentration in the sodium dichromate solution is between 10 and 100 g/L.
  • the second chemical treatment solution comprises a disodium molybdate solution.
  • the disodium molybdate concentration in the disodium molybdate solution is between 5 and 200 g/L.
  • the disodium molybdate concentration in the disodium molybdate solution is between 10 and 100 g/L.
  • the saline solution is a biological solution.
  • the saline solution is saliva.
  • the saline solution is perspiration.
  • the saline solution is blood.
  • the saline solution is simulated body fluid.
  • the saline solution is artificial saliva.
  • the saline solution is artificial perspiration.
  • the saline solution is artificial blood.
  • the saline solution is sea water.
  • the saline solution is simulated sea water.
  • Ni ion release refers to the mass of extracted Ni ions from a sample exposed to a corrosive environment per surface area of the sample, measured in units of ⁇ g/cm 2 .
  • the Ni ion release rate means the mass of extracted Ni ions from a sample exposed to a corrosive environment per surface area of the sample per day, measured in units of ⁇ g/cm 2 /day.
  • a steady-state Ni ion release rate means the Ni ion released rate varies by less than 40% as a function of time in the extraction solution. In other embodiments, a steady-state Ni ion release rate means the Ni ion released rate varies by less than 20% as a function of time in the extraction solution, while in yet other embodiments by less than 10% as a function of time in the extraction solution.
  • a steady-state Ni ion release rate means the Ni ion released rate varies by less than 0.1 ⁇ g/cm 2 /day as a function of time in the extraction solution, while in other embodiments by less than 0.06 ⁇ g/cm 2 /day as a function of time in the extraction solution, while in yet other embodiments by less than 0.03 ⁇ g/cm 2 /day as a function of time in the extraction solution.
  • as-cast metallic glass refers to a metallic glass in its as-formed or as-quenched state that has not undergone any chemical surface treatment.
  • Ni-based metallic glass refers to a metallic glass that comprises Ni at an atomic fraction of at least 50%.
  • the "organic layer” refers to an outermost layer (i.e. the most exterior layer) of the material comprising organic compounds that include elements such as O, C, H and N. The organic layer extends from the outermost surface of the material to a depth into the material where the concentration of Cr peaks. In embodiments of the disclosure, the "organic layer” is not regarded to be an integral part of the "passivated Ni- based metallic glass.”
  • passivated Ni-based metallic glass refers to a Ni-based metallic glass that comprises an inner “bulk material” portion and an outer “passive layer” portion.
  • the passive layer refers to the outer portion of a Ni-based metallic glass (with the organic layer disregarded) that may comprise oxygen in which the atomic concentration of oxygen changes by more than 1% per nanometer of depth into the material (or equivalently, by more than 0.1 % per angstrom of depth into the material).
  • the passive layer may be amorphous (i.e. at least 90% amorphous by volume, or in other embodiments at least 95% amorphous by volume, or in other embodiments at least 98% amorphous by volume).
  • the passive layer may be crystalline (i.e. more 10% crystalline by volume, or in other embodiments more than 30% crystalline by volume, or in other embodiments more than 50% crystalline by volume).
  • the "bulk material” refers to the inner portion (the inner bulk material portion) of a Ni-based metallic glass that may comprise oxygen in which the atomic concentration of oxygen changes by less than 1 % per nanometer of depth into the material.
  • the inner bulk material portion is substantially amorphous (i.e. at least 90% amorphous by volume, or in other embodiments at least 95% amorphous by volume, or in other embodiments at least 98% amorphous by volume).
  • the metal moiety of the Ni-based metallic glass refers to the composition of transition metals included in the alloy other than Ni.
  • the metalloid moiety of the Ni-based metallic glass refers to the composition of metalloids, semimetals, or non-metals included in the alloy.
  • a Ni-based metallic glass free of Ti refers to a Ni-based metallic glass that contains Ti in an atomic fraction that is equal to or less than the atomic fraction consistent with an incidental impurity.
  • a Ni-based metallic glass free of Ti refers to a Ni-based metallic glass that contains Ti in an atomic fraction that is equal to or less than 1 %.
  • a Ni-based metallic glass free of Ti refers to a Ni-based metallic glass that contains Ti in an atomic fraction that is equal to or less than 0.5%.
  • a Ni-based metallic glass free of Ti refers to a Ni-based metallic glass that contains Ti in an atomic fraction that is equal to or less than 0.1%.
  • a saline solution refers to an aqueous solution that comprises at least sodium chloride.
  • the saline solution is a biological solution, including without limitation saliva, perspiration, and blood plasma.
  • the saline solution is a physiological solution, including without limitation artificial saliva, artificial perspiration, and artificial blood plasma.
  • the saline solution is sea water.
  • the saline solution is simulated sea water.
  • the passive layer of the surface treated sample being poor in Ni refers to a passive layer comprising Ni at a concentration of less than 60 percent of the nominal concentration of Ni in the inner bulk material portion, and in some embodiments less than 40 percent, in other embodiments less than 20 percent, in other embodiments less than 10 percent, while in other embodiments less than 5 percent.
  • Many embodiments are directed to a method of chemically surface treating a Ni-based metallic glass comprising at least one immersion step that comprises:
  • the surface-treated metallic glass may be rinsed and dried.
  • the chemical treatment solution comprises an acid solution, a chromate solution, a molybdate solution, or a combination thereof.
  • the method of chemically surface treating a Ni-based metallic glass involves at least two immersion steps.
  • at least one step comprises immersion in an acid solution and at least one other step comprises immersion in a chromate solution.
  • at least one step comprises immersion in an acid solution and at least one other step comprises immersion in a molybdate solution.
  • immersing the Ni-based metallic glass sample in a chemical treatment solution may comprise exposing one or more portions of the metallic glass sample to the chemical treatment solution under the chemical treatment conditions in order to chemically surface-treat the metallic glass sample.
  • chemical treatment conditions may include any combination of acid solution a chromate solution, a molybdate solution, or a combination thereof, and also any combination of temperature and immersion time suitable to produce a surface treated metallic glass.
  • the Ni-ion release rate of the surface treated metallic glass when exposed to a saline containing environment is lower compared to the Ni ion release rate from an as-cast Ni-based metallic glass sample having the same composition exposed to the same saline environment for the same period.
  • the decrease in the Ni ion release rate for the chemically surface treated Ni-based metallic glass sample when exposed to a saline- containing environment for one day is less than 80% of the Ni ion release rate from an as-cast Ni-based metallic glass sample having the same composition immersed in the same saline solution for the same period.
  • any chemical treatment conditions including immersion time and chemical treatment solution temperature, suitable to produce a surface-treated Ni-based metallic glass sample may be used.
  • the immersion time is at least 1 min. In one embodiment, the immersion time is at least 10 minutes. In another embodiment, the immersion time is at least 30 minutes. In another embodiment, the immersion time is at least 60 minutes. In yet another embodiment, the immersion time is at least 180 minutes. In yet another embodiment, the immersion time is at least 360 minutes.
  • the temperature of the chemical treatment solution is at least as high as room temperature. In one embodiment, the temperature of the chemical treatment solution is at least 40°C. In another embodiment, the temperature of the chemical treatment solution is at least 50°C.
  • the temperature of the chemical treatment solution is at least 60°C. In some embodiments, the temperature of the chemical treatment solution is below 100°C. In one embodiment, the temperature of the chemical treatment solution is below 80°C. In another embodiment, the temperature of the chemical treatment solution is below 70°C. In yet another embodiment, the temperature of the chemical treatment solution is below 60°C.
  • the time required for passivation may be temperature dependent with passivation occurring more quickly at higher temperatures. Accordingly, in other embodiments the acid solution temperature may be less than 80°C, and the immersion time may be at least 1 minute.
  • any suitable method of rinsing and drying the sample as may be known in the art suitable to remove any unwanted residues from the sample prior to working may be utilized.
  • Ni-ion release rate data are provided in Tables 1 and 2.
  • the daily Ni-ion release rates are provided in Table 1, while the weekly Ni- ion release rates are provided in Table 2.
  • the first column in Table 1 lists the total period (in days) that a sample is immersed in solution.
  • the second column lists the period of extraction, that is, the immersion period in a new solution.
  • the third, fourth, and fifth columns list the average daily Ni ion release rate (averaged over the period of extraction) recorded for the as- cast sample, the sample that has undergone surface treatment in nitric acid solution, and the sample that has undergone surface treatment in citric acid solution, respectively.
  • Table 2 provides the weekly Ni-ion release rates observed during the first and second week of immersion.
  • Table 1 Effect of surface treatments in a 20 volume % nitric acid solution and a 10 weight % citric acid solution on the average daily Ni-ion release rate of Ni71.4Cr5.52Nb3.38Pi6.67B3.03 metallic glass in a Phosphate Buffered Saline solution.
  • Table 2 Effect of surface treatments in a 20 volume % nitric acid solution and a 10 weight % citric acid solution on the weekly Ni-ion release rate of Ni71.4Cr5.52Nb 3 . 38 Pi 6 . 6 7B 3 .03 metallic glass in a Phosphate Buffered Saline solution.
  • the third and fourth columns list the average daily Ni ion release rate (averaged over the period of extraction) recorded for the untreated as-cast sample, and the sample that has undergone surface treatment in nitric acid solution, respectively.
  • Table 4 provides the weekly Ni-ion release rates observed during the first and second week of immersion.
  • Table 3 Effect of surface treatments in 20 volume % nitric acid solution on the average daily Ni-ion release rate of Ni68.i7Cr8.65Nb2.98Pi6.42B3.28Sio.5 metallic glass in a Fusayama/ Mayer artificial saliva solution.
  • Ni-ion Release Rate (m*/cm 2 /week) Ni-ion Release Rate (m*/cm 2 /week)
  • Ni71.4Cr5.52Nb3.38Pi6.67B3.03 metallic glass in PBS extraction solution and Ni6 8 .i 7 Cr 8 .65Nb 2 .9 8 Pi6. 42 B3. 28 Sio.5 in the FAS extraction solution.
  • the Ni-ion release rates in Ni71.4Cr5.52Nb3.38Pi6.67B3.03 that underwent surface-treatment in nitric acid are 0.260 ⁇ g/cm 2 /day on day 1 in simulated body fluid (PBS solution).
  • Ni release rate in the as-cast untreated material is 1.000 ⁇ g/cm 2 /day, which corresponds to a -74% higher Ni release rate (Table 1).
  • the Ni-ion release rates in Ni6 8 .i 7 Cr 8 .6 5 Nb 2 .9 8 Pi6. 42 B3. 28 Sio.5 that underwent surface-treatment in nitric acid is 0.082 ⁇ g/cm 2 /day on day 1 in artificial saliva.
  • the Ni release rate in the untreated material is 0.650 ⁇ g/cm 2 /day, which corresponds to a -87% higher Ni release rate (Table 3).
  • the nitric acid surface treatment is very effective at creating a stable passive oxide layer and in limiting the bulk of Ni extraction within day 1 , thereby enabling the Ni-release process to reach a near steady state in roughly one day.
  • the Ni release process in the untreated as-cast Ni alloys takes roughly 7 days to reach a near steady-state.
  • the surface treatment in nitric acid solution decreased the weekly Ni release rates of both Ni71.4Cr5.52Nb 3 . 38 Pi 6 . 6 7B 3 .03 and Ni6 8 .i 7 Cr 8 .6 5 Nb 2 .9 8 Pi6. 42 B3.
  • 28 Sio. 5 are significantly lower than in Ni71.4Cr5.52Nb 3 . 3 sPi 6 . 6 7B 3 .03 in both the samples that have undergone surface-treatment in nitric acid and the untreated as-cast samples throughout the entire immersion period. The difference may be due to the difference in extraction solution - PBS vs FAS media. Another factor may be the difference in the Cr content of the alloys.
  • 28 Sio.5 has a higher Cr content than Ni71.4Cr5.52Nb3.38Pi6.67B3.03.
  • metallic glass samples that have undergone a surface treatment according to the methods disclosed herein and have a surface area such that the total Ni ion release rate would not exceed 35 g/day would not give rise to Ni toxicity.
  • such samples can be used as biomedical components, implants, or devices, including without limitation dental, orthodontic, endodontic, orthopedic, masculofascial, cardiovascular components, implants, or devices.
  • Ni was extracted from the four surface treated samples as well as from an untreated as-polished sample by immersing the samples in an artificial perspiration solution prepared according to standard BS EN1811 :2011, which is a simulated perspiration solution whose osmolarity and ion concentrations of the solutions match those of the human skin.
  • Step 1 20 vol.% HN0 3 , 22 g/L Na 2 Cr 2 0 7
  • Step 2 50 g/L Na 2 Cr 2 0 7
  • the most effective surface treatment process in reducing Ni leaching is the a two-step chemical solution treatment with the first solution comprising 20 volume% nitric acid combined with 25 g/L sodium dichromate and the second solution comprises 50 g/L sodium dichromate, as the weekly Ni leach from the treated sample was just 0.032 ⁇ g/cm 2 /week, i.e. about 98% decrease compared to the Ni leach form an untreated sample of 1.7 ⁇ g/cm 2 /week.
  • the second most effective surface treatment process in reducing Ni leaching is treatment in a solution comprising 20 volume% nitric acid combined with 44 g/L sodium dichromate, as the weekly Ni leach from the treated sample was 0.066 ⁇ g/cm 2 /week, i.e. about 96% decrease compared to the Ni leach form an untreated sample of 1.7 ⁇ g/cm 2 /week.
  • the third most effective surface treatment process in reducing Ni leaching is treatment in a solution comprising 40 volume% nitric acid combined with 22 g/L sodium dichromate, as the weekly Ni leach from the treated sample was 0.083 ⁇ g/cm 2 /week, i.e.
  • the fourth most effective surface treatment process in reducing Ni leaching is treatment in a solution comprising 50 g/L sodium dichromate, as the weekly Ni leach from the treated sample was 0.62 ⁇ g/cm 2 /week, i.e. about 64% decrease compared to the Ni leach form an untreated sample of 1.7 ⁇ g/cm 2 /week.
  • Ni was extracted from the treated sample as well as from an untreated as-polished sample by immersing the samples in an artificial perspiration solution prepared according to standard BS EN1811 :2011 , which is a simulated perspiration solution whose osmolarity and ion concentrations of the solutions match those of the human skin.
  • metallic glass samples that have undergone a surface treatment according to the methods disclosed herein can be used as products or articles that are in contact with the skin over extended periods of time, including without limitation ornamental products (e.g. necklaces or rings), watches, or electronic phones.
  • organic layer comprising organic compounds that include elements such as O, C, H and N was detected in samples analyzed, having a thickness of less than about 5 angstrom.
  • Table 6 contains XPS sputter depth profile data obtained for an untreated as- polished Ni6 8 .i 7 Cr 8 .6 5 Nb 2 .9 8 Pi6. 42 B3. 28 Sio.5 metallic glass rod. Data for the composition of the organic layer are not included. The data shows that the surface layer of the untreated as- polished sample comprises O, P/B, Cr, Nb and Ni (a negligible concentration of Ca was also detected). The thickness of the passive layer (with the organic layer disregarded) is approximately 30 angstrom. The average atomic concentration of O within the passive layer thickness is about 7.2%, that of P/B about 13.1%, that of Cr about 5.5%, that of Nb about 3.0%, and that of Ni about 55.6%.
  • the concentration of P/B is higher in the passive layer than in the inner bulk material portion; the concentration of Cr is approximately the same in the passive layer and inner bulk material portion; while the concentrations of Nb and Ni are lower in the passive layer than in the inner bulk material portion. This suggests that Ni and possibly Nb leach out of the surface into the solution as P/B diffuses from the bulk material to the surface to form the passive layer by combining with O and possibly Cr.
  • Table 7 contains XPS sputter depth profile data obtained for Ni6 8 . i 7 Cr 8 .65Nb 2 .9 8 Pi6. 42 B3. 28 Sio.5 metallic glass rods surface treated in a 20 vol.% nitric acid solution for 60 minutes. Data for the composition of the organic layer are not included. The data shows that the passive layers of the surface treated samples comprise O, P/B, Cr, Nb, and Ni (along with a small concentration of Ca). The thickness of the passive layer (with the organic layer disregarded) is approximately 45 angstrom, i.e. about 50% thicker compared to the as-polished sample.
  • the average atomic concentration of O within the passive layer thickness is about 14%, that of P/B about 17.3%, that of Cr about 7.0%, that of Nb about 3.8%, and that of Ni about 55.6%.
  • the concentration of P/B is higher in the passive layer than in the inner bulk material portion; the concentration of Cr is slightly higher in the passive layer than in the inner bulk material portion; while the concentrations of Nb and Ni are lower in the passive layer than in the inner bulk material portion. This suggests that Ni and possibly Nb leaches out of the surface into the solution as P/B and Cr diffuse from the bulk material to the surface to form the passive layer by combining with O.
  • the average concentration of O in the passive layer of the treated sample is about 97% higher, the average concentration of P/B in the passive layer of the treated sample is about 33% higher, the average concentration of Cr in the passive layer of the treated sample is about 27% higher, the average concentration of Nb in the passive layer of the treated sample is about 28% higher, while the average concentration of Ni in the passive layer of the treated sample is about 17% lower.
  • the average concentration of O within the passive layer thickness of a sample of a Ni-based metallic glass comprising Cr and P/B that has been surface treated in a nitric acid solution of concentration of at least 15 vol.% for at least 30 minutes is at least 50% higher when compared to an untreated sample.
  • the average concentration of P/B within the passive layer thickness of a sample of a Ni-based metallic glass comprising Cr and P/B that has been surface treated in a nitric acid solution of concentration of at least 15 vol.% for at least 30 minutes is at least 20% higher when compared to an untreated sample.
  • the average concentration of Cr within the passive layer thickness of a sample of a Ni-based metallic glass comprising Cr and P/B that has been surface treated in a nitric acid solution of concentration of at least 15 vol.% for at least 30 minutes is at least 15% higher when compared to an untreated sample.
  • the average concentration of Ni within the passive layer thickness of a sample of a Ni-based metallic glass comprising Cr and P/B that has been surface treated in a nitric acid solution of concentration of at least 15 vol.% for at least 30 minutes is at least 10% lower when compared to an untreated sample.
  • the passive layer of a sample of a Ni-based metallic glass comprising Cr and P/B that has been surface treated in a nitric acid solution of concentration of at least 15 vol.% for at least 30 minutes is at least 25 % thicker when compared to an untreated sample.
  • Table 8 contains XPS sputter depth profile data obtained for Ni6 8 .i 7 Cr 8 .6 5 Nb 2 .9 8 Pi6. 42 B3. 28 Sio.5 metallic glass rods surface treated in a 30 vol.% nitric acid solution for 60 minutes. Data for the composition of the organic layer are not included. The data shows that the passive layers of the surface treated samples comprise O, P/B, Cr, Nb, and Ni (along with a small concentration of Ca). The thickness of the passive layer (with the organic layer disregarded) is approximately 60 angstrom, i.e. about 100% thicker compared to the as-polished sample.
  • the average atomic concentration of O within the passive layer thickness is about 18%, that of P/B about 16.8%, that of Cr about 7.5%, that of Nb about 4.1%, and that of Ni about 50.8%.
  • the concentration of P/B is higher in the passive layer than in the inner bulk material portion; the concentration of Cr is slightly higher in the passive layer than in the inner bulk material portion; while the concentrations of Nb and Ni are lower in the passive layer than in the inner bulk material portion. This suggests that Ni and possibly Nb leach out of the surface into the solution as P/B and Cr diffuse from the bulk material to the surface to form the passive layer by combining with O.
  • the average concentration of O in the passive layer of the treated sample is about 150% higher, the average concentration of P/B in the passive layer of the treated sample is about 28% higher, the average concentration of Cr in the passive layer of the treated sample is about 37% higher, the average concentration of Nb in the passive layer of the treated sample is about 39% higher, while the average concentration of Ni in the passive layer of the treated sample is about 24% lower.
  • the average concentration of O within the passive layer thickness of a sample of a Ni-based metallic glass comprising Cr and P/B that has been surface treated in a nitric acid solution of concentration of at least 25 vol.% for at least 30 minutes is at least 75% higher when compared to an untreated sample.
  • the average concentration of P/B within the passive layer thickness of a sample of a Ni-based metallic glass comprising Cr and P/B that has been surface treated in a nitric acid solution of concentration of at least 25 vol.% for at least 30 minutes is at least 20% higher when compared to an untreated sample.
  • the average concentration of Cr within the passive layer thickness of a sample of a Ni-based metallic glass comprising Cr and P/B that has been surface treated in a nitric acid solution of concentration of at least 25 vol.% for at least 30 minutes is at least 20% higher when compared to an untreated sample.
  • the average concentration of Ni within the passive layer thickness of a sample of a Ni-based metallic glass comprising Cr and P/B that has been surface treated in a nitric acid solution of concentration of at least 25 vol.% for at least 30 minutes is at least 15% lower when compared to an untreated sample.
  • the passive layer of a sample of a Ni-based metallic glass comprising Cr and P/B that has been surface treated in a nitric acid solution of concentration of at least 25 vol.% for 60 minutes is at least 50% thicker when compared to an untreated sample.
  • Table 8 Atomic concentrations of elements detected by XPS analysis as a function of depth on the surface of polished Ni 8 .i 7 Cr 8 .65Nb 2 .9 8 Pi6. 42 B3. 28 Sio. 5 metallic glass sample after surface treatment in a 30 vol.% Nitric solution.
  • Table 9 contains XPS sputter depth profile data obtained for Ni6 8 .i 7 Cr 8 .65Nb 2 .9 8 Pi6. 42 B3. 28 Sio.5 metallic glass rods surface treated in a 40 vol.% nitric acid solution for 60 minutes. Data for the composition of the organic layer are not included. The data shows that the passive layers of the surface treated samples comprise O, P/B, Cr, Nb, and Ni (along with a small concentration of Ca). The thickness of the passive layer (with the organic layer disregarded) is approximately 90 angstrom, i.e. about 200% thicker compared to the as-polished sample.
  • the average atomic concentration of O within the passive layer thickness is about 29.6%, that of P/B about 16.3%, that of Cr about 8.1%, that of Nb about 4.8%, and that of Ni about 38.1%.
  • the concentration of P/B is higher in the passive layer than in the inner bulk material portion; the concentration of Cr is slightly higher in the passive layer than in the inner bulk material portion; while the concentrations of Nb and Ni are lower in the passive layer than in the inner bulk material portion. This suggests that Ni and possibly Nb leach out of the surface into the solution as P/B and Cr diffuse from the inner bulk material portion to the surface to form the passive layer by combining with O.
  • the average concentration of O in the passive layer of the treated sample is about 310% higher, the average concentration of P/B in the passive layer of the treated sample is about 24% higher, the average concentration of Cr in the passive layer of the treated sample is about 47% higher, the average concentration of Nb in the passive layer of the treated sample is about 61% higher, while the average concentration of Ni in the passive layer of the treated sample is about 43% lower.
  • the average concentration of O within the passive layer thickness of a sample of a Ni-based metallic glass comprising Cr and P/B that has been surface treated in a nitric acid solution of concentration of at least 35 vol.% for at least 30 minutes is at least 100% higher when compared to an untreated sample.
  • the average concentration of P/B within the passive layer thickness of a sample of a Ni-based metallic glass comprising Cr and P/B that has been surface treated in a nitric acid solution of concentration of at least 35 vol.% for at least 30 minutes is at least 20% higher when compared to an untreated sample.
  • the average concentration of Cr within the passive layer thickness of a sample of a Ni-based metallic glass comprising Cr and P/B that has been surface treated in a nitric acid solution of concentration of at least 35 vol.% for at least 30 minutes is at least 30% higher when compared to an untreated sample.
  • the average concentration of Ni within the passive layer thickness of a sample of a Ni-based metallic glass comprising Cr and P/B that has been surface treated in a nitric acid solution of concentration of at least 35 vol.% for at least 30 minutes is at least 25% lower when compared to an untreated sample.
  • the passive layer of a sample of a Ni-based metallic glass comprising Cr and P/B that has been surface treated in nitric acid solution of concentration of at least 35 vol.% for 60 minutes is at least 100% thicker when compared to an untreated sample.
  • FIGS. 5-9 provide plots of depth profile up to 200 angstrom for the detected elements by XPS on the surfaces of the as-polished and surface treated samples, including O (FIG. 5), P/B (FIG. 6), Cr (FIG. 7), Nb (FIG. 8), and Ni (FIG. 9), respectively. Data for the composition of the organic layer are not included in the plots.
  • Table 10 contains SIMS sputter depth profile data up to 60 angstrom in depth obtained for an untreated as-polished Ni6 8 .i 7 Cr 8 .65Nb 2 .9 8 Pi6. 42 B3. 28 Sio.5 metallic glass rod. Data for the composition of the organic layer are included, but the concentrations of the elements that contribute to the formation of the organic compounds, such as C, H, and N, are not included. The data shows that the organic layer has a thickness of about 4 angstrom (or less than 5 angstrom), and in addition to C, H, and N, the organic layer also comprises primarily O and Si, and is depleted in P, Cr, Nb, B, and Ni.
  • the average atomic concentration of O within the organic layer (within the first 4 angstrom) is about 39.9%, that of Si about 10.7%, that of P about 17.4%, that of Cr about 2.9%, that of Nb about 0.5%, that of B about 0.7%, and that of Ni about 30.2%.
  • the concentration of P is significantly higher in the passive layer than in the inner bulk material portion; the concentrations of Cr, Ni, and Si are approximately the same in the passive layer and inner bulk material portion; while the concentrations of Nb and B are significantly lower in the passive layer than in the inner bulk material portion. This suggests that Nb and B leach out of the surface into the solution as P diffuses from the bulk material to the surface to form the passive layer by combining with O and possibly Cr.
  • Table 11 contains SIMS sputter depth profile data obtained for Ni6 8 . i 7 Cr 8 .65Nb 2 .9 8 Pi6. 42 B3. 28 Sio.5 metallic glass rods surface treated in a 20 vol.% nitric acid solution for 60 minutes. Data for the composition of the organic layer are included, but the 5 concentrations of the elements that contribute to the formation of the organic compounds, such as C, H, and N, are not included. The data shows that the organic layer has a thickness of about 4 angstrom (or less than 5 angstrom), and in addition to C, H, and N, the organic layer is rich in O, Si, and P, and is depleted in Cr, Nb, B, and Ni.
  • the average atomic concentration of O within the organic layer thickness is about 10 49.1%, that of Si about 7.1%, that of P about 24.8%, that of Cr about 3.3%, that of Nb about 0.15%, that of B about 0.5%, and that of Ni about 16.3%.
  • Data for the composition of the passive layer is presented in Table 10. The composition data suggest that the thickness of the passive layer (excluding the organic layer) is approximately 14 angstrom, and is enriched in O and P and poor in Nb and B.
  • the average atomic concentration of O within the passive layer thickness is about 4.6%, that of P about 35.3%, that of Cr about 5.8%, that of Nb about 0.3%, that of B about 0.94%, that of Si about 0.54%, and that of Ni about 52.8%.
  • the concentration of P is significantly higher in the passive layer than in the inner bulk material portion; the concentration of Si is approximately the same in the passive layer as in the inner bulk material portion; the concentrations of Cr and Ni are slightly lower in the passive layer than in the inner bulk material portion; while the concentrations of B and Nb are significantly lower in the passive layer than in the inner bulk material portion.
  • Nb and B and possibly Ni and Cr leach out of the surface into the solution as P diffuses from the bulk material to the surface to form the passive layer by combining with O and possibly Cr.
  • the average concentration of O in the passive layer of the treated sample is about 19% higher, the average concentration of P in the passive layer of the treated sample is about 21 % higher, the average concentration of Cr in the passive layer of the treated sample is about 25% higher, the average concentration of Nb in the passive layer of the treated sample is about 30% higher, the average concentration of B in the passive layer of the treated sample is about 3% lower, the average concentration of Si in the passive layer of the treated sample is about 30% lower, while the average concentration of Ni in the passive layer of the treated sample is about 12% lower.
  • the average concentration of O within the passive layer thickness of a sample of a Ni-based metallic glass comprising Cr and P that has been surface treated in a nitric acid solution of concentration of at least 15 vol.% for at least 30 minutes is at least 5% higher when compared to an untreated sample.
  • the average concentration of P within the passive layer thickness of a sample of a Ni-based metallic glass comprising Cr and P that has been surface treated in a nitric acid solution of concentration of at least 15 vol.% for at least 30 minutes is at least 10% higher when compared to an untreated sample.
  • the average concentration of Cr within the passive layer thickness of a sample of a Ni-based metallic glass comprising Cr and P that has been surface treated in a nitric acid solution of concentration of at least 15 vol.% for at least 30 minutes is at least 15% higher when compared to an untreated sample.
  • the average concentration of Ni within the passive layer thickness of a sample of a Ni-based metallic glass comprising Cr and P that has been surface treated in a nitric acid solution of concentration of at least 15 vol.% for at least 30 minutes is at least 5% 5 lower when compared to an untreated sample.
  • FIGS. 10-16 provide plots of depth profile up to 200 angstrom for the detected elements by SIMS on the surfaces of the as-polished and surface treated samples, including O (FIG. 10), P (FIG. 11), Cr (FIG. 12), Nb (FIG. 13), B (FIG. 14), Si (FIG. 15), and Ni (FIG.
  • the insets provide plots of depth profile up to 60 angstrom for the detected
  • the depth profiles indicate the samples have a general profile comprising a passive layer that has thickness in the range of 10 to 100 angstrom, with the thickness
  • the inner bulk material portion of the metallic glass alloy is located underneath the passive layer.
  • Table 12 contains SIMS sputter depth profile data obtained for Ni6 8 . i 7 Cr 8 .65Nb 2 .9 8 Pi6. 42 B3. 28 Sio.5 metallic glass rods surface treated in 50 g/L sodium dichromate at 60°C for 30 minutes. Data for the composition of the organic outermost layer
  • the concentrations of the elements that contribute to the formation of the organic compounds, such as C, H, and N, are not included.
  • the data shows that the organic layer has a thickness of about 8 angstrom (or less than 9 angstrom), and in addition to C, H, and N, the organic layer is also rich in O and Si and is depleted in Cr, Nb, B, and Ni.
  • the average atomic concentration of O within the passive layer thickness is about 8.5%, that of P about 22.6%, that of Cr about 4.8%, that of Nb about 0.45%, that of B about 1.6%, that of Si about 0.72%, and that of Ni about 61.4%.
  • the passive layer thickness of the treated sample is about 385% thicker.
  • the passive layer of a sample that has been surface treated in a sodium dichromate solution having concentration of at least 25 g/L at temperature of at least 45°C for at least 15 minutes is at least 50% thicker than the passive layer of an untreated sample.
  • the passive layer of a sample that has been surface treated in a sodium dichromate solution having concentration of at least 25 g/L at temperature of at least 45 °C for at least 15 minutes is at least 200% thicker than the passive layer of an untreated sample.
  • the passive layer of a sample that has been surface treated in a sodium dichromate solution having concentration of at least 25 g/L at temperature of at least 45 °C for at least 15 minutes is at least 200% thicker than the passive layer of an untreated sample.
  • the passive layer of a sample that has been surface treated in a sodium dichromate solution having concentration of at least 25 g/L at temperature of at least 45 °C for at least 15 minutes is at least 200% thicker than the passive layer of an untreated sample.
  • the passive layer of a sample that has been surface treated in a sodium dichromate solution having concentration of at least 25 g/L at temperature of at least 45 °C for at least 15 minutes is at least 200% thicker than the passive layer of an untreated sample.
  • FIGS. 17-23 provide plots of depth profiles up to 350 angstrom for the detected elements by SIMS on the surfaces of the as-polished sample and the sample surface treated in a 50 g/L sodium dichromate solution, including O (FIG. 17), P (FIG. 18), Cr (FIG. 19), Nb (FIG. 20), B (FIG. 21), Si (FIG. 22), and Ni (FIG. 23), respectively.
  • the insets provide plots of depth profiles up to 100 angstrom for the detected elements, and the regions for the "organic layer,” "passive layer,” and “bulk material” are designated by arrows.
  • Table 13 contains SIMS sputter depth profile data obtained for Ni6 8 . i 7 Cr 8 .6 5 Nb 2 .9 8 Pi6. 42 B3. 28 Sio.5 metallic glass rods surface treated by a two-step chemical solution treatment (the first solution comprises 20 volume% nitric acid combined with 25 g/L sodium dichromate, and the second solution comprises 50 g/L sodium dichromate) at 60°C for 30 minutes in each step. Data for the composition of the organic outermost layer are included, but the concentrations of the elements that contribute to the formation of the organic compounds, such as C, H, and N, are not included.
  • the organic layer has a thickness of about 8 angstrom (or less than 9 angstrom), and in addition to C, H, and N, the organic layer is also rich in O and Si and is depleted in Cr, Nb, B, and Ni.
  • the average atomic concentration of O within the organic layer thickness (within the first 8 angstrom) is about 54.8%, that of Si about 10.6%, that of P about 16.2%, that of Cr about 5.6%, that of Nb about 0.21 %, that of B about 0.63%, and that of Ni about 15.1 %.
  • the concentration of P is significantly higher in the passive layer than in the inner bulk material portion; the concentration of Si is approximately the same in the passive layer as in the inner bulk material portion; the concentration of Cr is slightly lower in the passive layer than in the inner bulk material portion; while the concentrations of Ni, B and Nb are significantly lower in the passive layer than in the inner bulk material portion. This suggests that Nb and B and possibly Ni and Cr leach out of the surface into the solution as P diffuses from the bulk material to the surface to form the passive layer by combining with O and possibly Cr.
  • the average concentration of O in the passive layer of the treated sample is about 63 % lower, the average concentration of P in the passive layer of the treated sample is about 9% higher, the average concentration of Cr in the passive layer of the treated sample is about 34% higher, the average concentration of Nb in the passive layer of the treated sample is about 36% lower, the average concentration of B in the passive layer of the treated sample is about 23% lower, the average concentration of Si in the passive layer of the treated sample is about 34% lower, while the average concentration of Ni in the passive layer of the treated sample is about 5% lower.
  • the average concentration of P within the passive layer thickness of a sample of a Ni-based metallic glass comprising Cr and P that has been surface treated by a two-step chemical solution treatment, where the first solution comprises nitric acid combined with odium dichromate, and the second solution comprises sodium dichromate, for at least 15 minutes is at least 5% higher when compared to an untreated sample.
  • the average concentration of Cr within the passive layer thickness of a sample of a Ni-based metallic glass comprising Cr and P that has been surface treated by a two-step chemical solution treatment, where the first solution comprises nitric acid combined with odium dichromate, and the second solution comprises sodium dichromate, for at least 15 minutes is at least 25% higher when compared to an untreated sample.
  • the average concentration of Ni within the passive layer thickness of a sample of a Ni-based metallic glass comprising Cr and P that has been surface treated by a two-step chemical solution treatment, where the first solution comprises nitric acid combined with odium dichromate, and the second solution comprises sodium dichromate, for at least 15 minutes is at least 2% lower when compared to an untreated sample.
  • FIGS. 24-30 provide plots of depth profiles up to 200 angstrom for the detected elements by SIMS on the surfaces of the as-polished sample and the sample surface treated by a two-step chemical solution treatment (where the first solution comprises 20 5 volume% nitric acid combined with 25 g/L sodium dichromate, and the second solution comprises 50 g/L sodium dichromate), including O (FIG. 24), P (FIG. 25), Cr (FIG. 26), Nb (FIG. 27), B (FIG. 28), Si (FIG. 29), and Ni (FIG. 30), respectively.
  • the insets provide plots of depth profile up to 60 angstrom for the detected elements, and the regions for the "organic layer" of each sample are designated by arrows.
  • 28 Sio.5 metallic glass rods surface treated in a sodium dichromate solution is 4.8% (analysis of Table 12), while the Ni-ion release rate during exposure of those rods to an artificial perspiration solution is 0.62 ⁇ g/cm 2 /week (Table 5).
  • 28 Sio.5 metallic glass rods surface treated by a two-step chemical solution treatment is 6.2% (analysis of Table 13), while the Ni-ion release rate during exposure of those rods to an artificial perspiration solution is 0.032 ⁇ g/cm 2 /week (Table 5).
  • Ni ion release rate in units of ⁇ g/cm 2 /week can be denoted as y, while the average atomic concentration of Cr in the passive layer in units of atomic percent can be denoted as x.
  • FIG. 31 presents a plot of the logarithm of the Ni ion release rate (log(y), on the vertical axis) against the average atomic concentration of Cr in the passive layer in units of atomic percent, denoted as x (on the horizontal axis).
  • the three data points discussed above are presented by round symbols.
  • the Ni ion release rate in a saline solution from a Ni- based metallic glass that has been surface treated according to embodiments of the disclosure in a given solution is related to the average atomic concentration of Cr in the passive layer by a power-law according to EQ. (1), where the Ni ion release rate is in units of ⁇ g/cm 2 /week and the average atomic concentration of Cr is in units of atomic percent, and where a is between -0.5 and -5 and b is between 1 and 10. In other embodiments, a is between -0.25 and -2.5 and b is between 2 and 8. In yet other embodiments, a is between -0.5 and -1.5 and b is between 3 and 7.
  • the passivation of the Ni-based metallic glasses may not rely on the formation of a stable metal oxide such as ⁇ 3 ⁇ 4 ⁇ 3, T1O2, or ⁇ Os for example. Instead, a different mechanism involving formation of a combination of oxides and phosphides of Cr and/or Mo is present in the current alloys. Such compounds are likely to form on the surface of the Ni-based metallic glasses, which would act as Ni leach barriers.
  • Ni68.i7Cr 8 .65Nb 2 .98Pi6.42B3.28Sio.5 and Ni71.4Cr5.52Nb3.38Pi6.67B3.03 metallic glasses formation of a passive Ni-depleted and Cr-rich and P-rich layer occurs as a consequence of the chemical surface treatment. Having higher Cr content, Ni71.4Cr5.52Nb 3 . 38 Pi 6 . 6 7B 3 .03 likely forms a more stable chromium oxide/phosphide layer and therefore demonstrates a lower Ni-ion release rate in both treated and untreated states.
  • Ni and P bearing Cr-free Ni-based metallic glass such as Ni7 3 .oMo2.5Nb 3 .5Mni.5Pi 8 .oSii.5 metallic glass
  • formation of a passive Ni-depleted and Mo-rich and P-rich layer may occur as a consequence of the chemical surface treatment.
  • the import of Cr from the chromate solution is also likely to promote the formation a chromium oxide/phosphide layer, which has been demonstrated here to mitigate Ni leaching.
  • the passive layer of a sample of a Ni-based metallic glass that has been surface treated is thicker compared to the passive layer of an untreated sample.
  • the average concentration of O within the passive layer of a sample of a Ni-based metallic glass that has been surface treated according to the disclosure is higher compared to an untreated sample.
  • the average concentration of Ni within the passive layer of a sample of a Ni-based metallic glass that has been surface treated according to the disclosure is lower compared to an untreated sample.
  • the average concentration of P within the passive layer of a sample of a Ni-based metallic glass comprising P that has been surface treated according to the disclosure is higher compared to an untreated sample.
  • the average concentration of Cr within the passive layer of a sample of a Ni-based metallic glass comprising Cr that has been surface treated according to the disclosure is higher compared to an untreated sample.
  • a Ni-based metallic glass that comprises at least one of Cr and Mo, the average atomic concentration of Cr and/or Mo within the passive layer is higher than the respective concentrations in the inner bulk material portion.
  • the average atomic concentration of Cr and/or Mo within the passive layer is at least 2% higher than the respective concentrations in the inner bulk material portion.
  • the average atomic concentration of Cr and/or Mo within the passive layer is at least 5% higher than the respective concentrations in the inner bulk material portion.
  • the average atomic concentration of Cr and/or Mo within the passive layer is at least 10% higher than the respective concentrations in the inner bulk material portion.
  • the average atomic concentration of Cr and/or Mo within the passive layer is at least 20% higher than the respective concentrations in the inner bulk material portion.
  • a Ni-based metallic glass that comprises P the average atomic concentration of P within the passive layer is higher than the P concentration in the inner bulk material portion. In another embodiment, the average atomic concentration of P within the passive layer is at least 5% higher than the P concentration in the inner bulk material portion. In another embodiment, the average atomic concentration of P within the passive layer is at least 10% higher than the P concentration in the inner bulk material portion. In another embodiment, the average atomic concentration of P within the passive layer is at least 20% higher than the P concentration in the inner bulk material portion. In another embodiment, the average atomic concentration of P within the passive layer is at least 30% higher than the P concentration in the inner bulk material portion.
  • the specific method used to produce the example alloy ingots involves inductive melting of the appropriate amounts of elemental constituents in a fused silica crucible under inert atmosphere.
  • the specific purity levels of the constituent elements used to create the example alloys were as follows: Ni 99.995%, Cr 99.996%, Mo 99.95%, Mn 99.98%, Nb 99.95%, B 99.5%, P 99.9999%, and Si 99.9999%.
  • Metallic glass rods of Ni68.i7Cr 8 .65Nb 2 . 9 8Pi6.42B3.28Sio.5 and Ni71.4Cr5.52Nb3.38Pi6.67B3.03 5 mm in diameter were produced from the alloy ingots using counter-gravity casting.
  • molten liquid contained in fused silica is injected upwards (against gravity) into a mold using gas pressure.
  • An inert atmosphere was created in the melt chamber by first applying vacuum at mbar and subsequently following several purges with argon, an argon atmosphere was 5xl0 ⁇ 2 mbar established having a pressure of -20 in-Hg.
  • the feedstock was heated inductively first to 1350°C and back to 1250°C to create a homogeneous high temperature melt, and subsequently urged upwards using an argon pressure of 10 psi through a fused silica tube of 4 mm inner diameter into an HI 3 tool steel mold fill a rod-shaped cavity with a diameter of 5 mm and length of 100 mm.
  • the melt was rapidly cooled in the mold to produce an amorphous rod.
  • the amorphicity of the rods was verified by x-ray diffraction.
  • the cast amorphous rods were sectioned into 10 mm-long segments. Both ends of the sectioned rods were polished with a 1200-grit sandpaper.
  • Metallic glass rods of Ni 7 3.oMo 2 .5Nb3.5Mni.5Pi 8 .oSii.5 3 mm in diameter were produced from the alloy ingots by quartz tube casting.
  • the method for producing metallic glass rods from the alloy ingots involves re-melting the alloy ingots in quartz tubes having 0.5-mm thick walls in a furnace at 1350°C, under high purity argon and rapidly quenching in a room-temperature water bath.
  • the cast amorphous rods were sectioned into 10 mm-long segments. Both ends of the sectioned rods were polished with a 1200-grit sandpaper.
  • Ni-based amorphous rods were subjected to the following chemical surface treatments:
  • Ni was extracted from rods of Ni71.4Cr5.52Nb3.38Pi6.67B3.03 with a surface area of ⁇ 1.6 cm 2 (4.5 mm-diameter and 10 mm-long) in a lx PBS (Phosphate Buffered Solution) solution - a simulated body fluid solution - for 24 hours (one day), 144 hours (6 days), and 192 hours (8 days), at 37 ⁇ 1°C under static condition, respectively. The solution was replaced with fresh solution for each extraction. The same sample was used for each time point.
  • PBS Phosphate Buffered Solution
  • the PBS solution with a pH of 7.4 had a concentration of 8.0 g/L NaCl, 0.2 g/L KCl, 1.44 g/L Na 2 HP0 4 , and 0.24 g/L KH 2 P0 4 .
  • Ni extraction was performed in 1.6 ⁇ 0.1 mL of working solutions for a total of one day, 7 days, and 15 days, at 37 ⁇ 1°C under static condition.
  • the solution volume to sample surface area ratio is ⁇ 1 mL/cm 2 as recommended by ISO standards 10993 and BS EN1811 :2011.
  • Ni was extracted from rods of Ni6 8 .i 7 Cr 8 .6 5 Nb 2 . 98 Pi6. 42 B3. 28 Sio.5 with a surface area of ⁇ 1.6 cm 2 (4.5 mm-diameter and 10 mm-long) in a Fusayama/Mayer Artificial Saliva solution for 24 hours (one day), 144 hours (6 days), and 192 hours (8 days), at 37 ⁇ 1°C under static condition, respectively. The solution was replaced with fresh solution for each extraction. The same sample was used for each time point.
  • the Fusayama/Mayer Artificial Saliva solution with a pH of 4.9 had a concentration of 0.4 g/L NaCl, 0.4 g/L KCl, 0.795 g/L CaCi 2 -2H 2 0, 0.690 g/L NaH 2 P0 4 -H 2 0, 0.005 g/L Na 2 S-9H 2 0, and 1 g/L Urea.
  • Ni extraction was performed in 1.6 ⁇ 0.1 mL of working solutions for a total of one day, 7 days, and 15 days, at 37 ⁇ 1°C under static condition.
  • the solution volume to sample surface area ratio is ⁇ 1 mL/cm 2 as recommended by ISO standards 10993 and BS EN1811 :2011.
  • Ni was extracted from rods of Ni6 8 .i 7 Cr 8 .65Nb 2 .9 8 Pi6. 42 B3. 28 Sio.5 with a surface area of ⁇ 1.6 cm 2 (4.5 mm-diameter and 10 mm-long) in an artificial perspiration solution.
  • the pH of the solution was adjusted to 6.5 + 0.05 prior to sample immersion.
  • the artificial perspiration solution was prepared according to guidelines from BS EN1811 :2011, and has a concentration of 0.5% sodium chloride, 0.1% lactic acid, and 0.1 % urea.
  • Sodium hydroxide was added to adjust the pH, according to guidelines from BS EN1811 :2011.
  • Ni extraction was performed in 1.6 ⁇ 0.1 mL of working solutions for a total of 7 days at 30 ⁇ 2°C under static condition.
  • the solution volume to sample surface area ratio is ⁇ 1 mL/cm 2 as recommended by ISO standards 10993 and BS EN1811 :2011.
  • Ni was extracted from rods of Ni 7 3 . oMo 2 .5Nb3.5Mni .5 Pi 8. oSii.5 with a surface area of ⁇ 1.0 cm 2 (2.8 mm-diameter and 10 mm-long) in an artificial perspiration solution.
  • the pH of the solution was adjusted to 6.5 + 0.05 prior to sample immersion.
  • the artificial perspiration solution was prepared according to guidelines from BS EN1811 :2011, and has a concentration of 0.5% sodium chloride, 0.1% lactic acid, and 0.1 % urea.
  • Sodium hydroxide was added to adjust the pH, according to guidelines from BS EN1811 :2011.
  • Ni extraction was performed in 1.0 ⁇ 0.1 mL of working solutions for a total of 7 days at 30 ⁇ 2°C under static condition.
  • the solution volume to sample surface area ratio is ⁇ 1 mL/cm 2 as recommended by ISO standards 10993 and BS EN1811 :2011.
  • the Ni concentration in the PBS and Fusayama/Mayer Artificial Saliva extraction solutions was analyzed by ICP-MS/AES for 24 hours (one day), 144 hours (6 days), and 192 hours (8 days) of immersion.
  • the Ni in the artificial perspiration solution was analyzed by ICP-MS/AES for 7 days of immersion.
  • the ICP-MS/AES instruments were calibrated with NIST traceable calibration standards. To provide a baseline, blank samples containing only PBS, only Fusayama/Mayer Artificial Saliva, and only artificial perspiration solutions were also extracted.
  • Ni concentration (in ppb) (C s - Ct > ) x (Wf/Wi), where C s is the measured concentration (ppb) in the prepared sample solution, C b is the measured concentration (ppb) in the prepared blank solution, W f is the final weight of the prepared sample (g), and Wi is the initial weight of the prepared sample (g).
  • the Ni release in ng /cm 2 was then calculated by multiplying the Ni concentration (in ppb) by the solution volume (in mL) and dividing by the surface area of the sample (in cm 2 ), as follows: Ni concentration (in ppb) x solution volume (in mL)
  • Ni release (m ng/cm 2 ) , c : - -.
  • the average daily Ni release rate over each extraction period was then calculated by dividing the Ni release recorded over the extraction period by the number of days of extraction, and is listed in Tables 1 and 3.
  • the first extraction period was one day, which represents a total immersion period of one day.
  • the Ni release recorded at the end of the first extraction period was divided by the extraction period of one day to give the average daily Ni release rate over the immersion period of one day, which is listed in Tables 1 and 3.
  • the second extraction period was 6 days, which represents a total immersion period of 7 days.
  • the Ni release recorded at the end of the second extraction period was divided by the extraction period of 6 days to give the average daily Ni release rate over the immersion period of 2-7 days, which is listed in Tables 1 and 3.
  • the third extraction period was 8 days, which represents a total immersion period of 15 days.
  • the Ni release recorded at the end of the third extraction period was divided by the extraction period of 8 days to give the average daily Ni release rate over the immersion period of 8-15 days, which is listed in Tables 1 and 3.
  • XPS X- ray photoelectron spectroscopy
  • ESA electron spectroscopy for chemical analysis
  • XPS data is quantified using relative sensitivity factors and a model that assumes a homogeneous layer.
  • the analysis volume is the product of the analysis area (spot size or aperture size) and the depth of information. Photoelectrons are generated within the X-ray penetration depth (typically many microns), but only the photoelectrons within the top three photoelectron escape depths are detected.
  • Escape depths are on the order of 15-35 A, which leads to an analysis depth of -50-100 A. Typically, 95% of the signal originates from within this depth.
  • Depth profiles were obtained by alternating an acquisition cycle with a sputter cycle during which material was removed from the sample using an Ar + source. The sputter rate was 50 A/min relative to the S1O 2 standard. The analysis area was 1400 ⁇ x 300 ⁇ .
  • the concentrations of the elements detected by XPS are provided in atomic %. Concentration values provided are normalized to 100% using the elements detected. The atomic concentrations provided can be reproduced for major constituents of sample surfaces to better than ⁇ 10%.
  • SIMS Secondary Ion Mass Spectrometry
  • SIMS provides ultra-high depth resolution profiling with detection limit and depth resolution better than 10 10 -10 16 at/cm 3 and 5 A, respectively. Chemical composition analysis of the samples was performed every 1-1.5 A in depth. SIMS allows detection of all elements and isotopes, including B and Si. The lateral resolution/probe size is ⁇ or better.
  • the concentrations of the elements detected by SIMS are provided in atomic %. SIMS is element specific, and in the context of the present disclosure it was performed for detection of O, P, Cr, Nb, B, Si, and Ni, while elements that contribute to the organic layer, such as C, N, and H, were not detected. Because the detected concentrations are element specific, i.e., not normalized to 100% using the elements detected, summation of the concentrations does not necessarily add up to 100%. The atomic concentrations provided can be reproduced for major constituents of sample surfaces.

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Abstract

L'invention concerne des procédés de traitement de surface pour verres métalliques à base de Ni qui favorisent la passivation et diminuent la quantité de Ni libérée lorsque le verre métallique à base de Ni est exposé à un environnement contenant une solution saline.
PCT/US2016/053550 2015-09-28 2016-09-23 Procédé de traitement de surface pour verres métalliques à base de nickel visant à réduire la libération de nickel Ceased WO2017058670A1 (fr)

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