EP2878713A1 - Elektrolytzusammensetzung und Verfahren zur Elektropolierbehandlung von Nickel-Titan-Legierungen und/oder anderen Metallsubstraten mit Wolfram-, Niob- und Tantallegierungen - Google Patents

Elektrolytzusammensetzung und Verfahren zur Elektropolierbehandlung von Nickel-Titan-Legierungen und/oder anderen Metallsubstraten mit Wolfram-, Niob- und Tantallegierungen Download PDF

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EP2878713A1
EP2878713A1 EP13005538.7A EP13005538A EP2878713A1 EP 2878713 A1 EP2878713 A1 EP 2878713A1 EP 13005538 A EP13005538 A EP 13005538A EP 2878713 A1 EP2878713 A1 EP 2878713A1
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Prior art keywords
phosphonic acid
electrolyte composition
groups
substituted
electrolyte
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English (en)
French (fr)
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Ulf Fritz
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Abbott Laboratories Vascular Enterprises Ltd
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Abbott Laboratories Vascular Enterprises Ltd
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Priority to EP13005538.7A priority Critical patent/EP2878713A1/de
Priority to PCT/EP2014/075710 priority patent/WO2015078930A1/en
Priority to EP14803125.5A priority patent/EP3074553A1/de
Publication of EP2878713A1 publication Critical patent/EP2878713A1/de
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/16—Polishing
    • C25F3/22—Polishing of heavy metals
    • C25F3/26—Polishing of heavy metals of refractory metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/16—Polishing
    • C25F3/22—Polishing of heavy metals

Definitions

  • the present invention relates to an Electrolyte composition and to a method for electropolishing in the presence of said electrolyte composition, which is directed towards the surface treatment of medical devices.
  • the electrolyte composition comprises methanesulfonic acid and at least one phosphonic acid derivative.
  • the medical devices in question are formed from high-strength medical grade alloys, wherein the metals comprising said alloys are selected from a group of Nickel, Titanium, Cobalt, Chromium, Tantalum, Niobium, Tungsten, and whereas said alloys may contain one or more of said metals.
  • Nitinol a Nickel-Titanium alloy (often abreviated: NiTi) is used in a wide variety of medical device applications, because of a favourable combination of mechanical and surface properties, which include among others, shape memory capability, superelasticity and increased corrosion resistance.
  • Nitinol is available in different surface conditions, depending on the type of treatment employed. Typical commercially available surface conditions are Native, Sandblasted, Black Oxide, Air Aged, Heat Treated, Electropolished, and Surface Passivated.
  • NiTi implants can improve corrosion resistance (and thus the ability to decrease Nickel ion leaching from the surface) because it has been recognized that the corrosion resistance of NiTi is very dependent upon the quality and quantity of the passive oxide layer formed on its surface.
  • These surface treatment techniques also have a benign effect on the ability to 'heal' the Titanium oxide layer during deployment, as it is actually known that electropolished and passivated Nitinol exhibits at least an equivalent static corrosion behaviour and ability to resist and repassivate (repair) surface damage when compared with 316L stainless steel [Shabalovskaya, 2002].
  • the ability of the aforementioned surface treatment techniques to minimize the implant material's surface corrugation and roughness is a crucial factor for clinical device performance following implantation. Since electropolishing is capable of rendering the implant surface with a smooth surface finish as well as reducing the number and magnitude of potential surface defects, the implants flow characteristics and fatigue life performance will accordingly be improved.
  • the preferred surface treatments involve electropolishing and surface passivation of the NiTi implant, in an effort to achieve a smooth implant surface finish as well as building both a Nickel-depleted, passive Titanium oxide layer.
  • the surface treatments are intended to generate a titanium oxide layer which a) shares the same biocompatibility characteristics as a native Titanium oxide layer and b) renders the surface with an increased corrosion resistance and c) minders the surfaces' ability to leach out Nickel - ions [Shabalovskaya, 2002].
  • electrolyte compositions of the art allow formation of passive oxide layers with uneven thickness during the electropolishing process, thus reducing metal dissolution rates and therefore hindering formation of a desirable diffusion layer on the substrate.
  • the presence of the oxide layer thus hinders effective electropolishing, yielding inferior results (rough surfaces, uneven polishing effect etc.).
  • agents typically include, for example, hydrofluoric acid and organic or inorganic salts thereof.
  • Some electrolyte formulations have addressed the suppression of oxide layer formation via the incorporation of a methylating species as a surface masking agent, such as dimethyl sulphate, which is a known carcinogenic and mutagenic substance.
  • a methylating species such as dimethyl sulphate
  • Other formulations that have been known to produce good electropolished surfaces include very strong acids, such as perchloric acid in combination with organic solvents such as n-butanol, the particular combination requiring strict temperature control to prevent explosions.
  • These agents are of a rather hazardous, volatile or corrosive nature, which can represent itself as both an undesired health- as well as an environmental hazard.
  • an electrolyte composition capable of generating a smooth, even, protective film on the surface of the material to be electropolished during electropolishing methods, and which composition can suppress or reduce and thus control the formation of undesired oxide films during electropolishing.
  • Common surface masking agents in the art are typically a) rather unspecific as to the mechanism of action and binding mode incurred on the electrode or work piece surface(s), b) require a certain minimum concentration within the electrolyte composition in order to be effective, and are c) often quantitatively consumed/spent during electropolishing operations in relation to the amount of work piece material dissolved.
  • the surface masking agent should also have a protective effect on the electrode surfaces, in that sludge formation and dissolution of the electrode surfaces should be reduced, thus prolonging the work life of electrode materials in the process, and allowing cheaper electrode materials, such as stainless steel (as compared to inert, but very expensive materials such as gold or platinum) to be used for the electrodes and contacting circuits.
  • the invention refers to a electrolyte composition, comprising methane sulfonic acid; and at least one phosphonic acid derivative; wherein said phosphonic acid derivative contains at least three (n>2) phosphonic acid groups.
  • the at least one phosphonic acid derivative has the structure according to Formula I: wherein R 1 is a substituted C 1-3 alkyl group; wherein substituents are selected from -PO(OH) 2 or NR 4 R 5 , wherein R 4 and R 5 , independent from each other, can be H or a C 1-3 alkyl group, wherein the C 1-3 alkyl group is optionally substituted with -PO(OH) 2 ; wherein both the C 1-3 alkyl groups are substituted with a total of 0, 1 or 2 -PO(OH) 2 groups; R 2 is a substituted C 1-3 alkyl group; wherein substituents are selected from -PO(OH) 2 or NR 4 R 5 , wherein R 4 and
  • the at least one phosphonic acid derivative is selected from Amino-tris-(methylene phosphonic acid) (ATMP), Ethylenediamine tetra(methylene phosphonic acid) (EDTMP), Tetramethylenediamine tetra (methylene phosphonic acid) (TDTMP), Diethylenetriamine-penta(methylenephosphonic acid (DTPMP), Hexamethylenediamine tetra(methylene phosphonic acid) (HDTMP), and phytic acid (IP6) or respective salts thereof.
  • ATMP Amino-tris-(methylene phosphonic acid)
  • ETMP Ethylenediamine tetra(methylene phosphonic acid)
  • TTMP Tetramethylenediamine tetra (methylene phosphonic acid)
  • DTPMP Diethylenetriamine-penta(methylenephosphonic acid
  • HDTMP Hexamethylenediamine tetra(methylene phosphonic acid)
  • IP6 phytic acid
  • the concentration of methane sulfonic acid is between 20-98% (v/v).
  • the concentration of the at least one phosphonic acid derivative is between 0.1% and 10% (m/v).
  • the at least one phosphonic acid derivative is Ethylenediamine tetra(methylene phosphonic acid) (EDTMP).
  • composition further contains at least one additional additive selected from the group of viscosifying agents, chelating agents, stabilizer agents, buffering agents; and/or at least one other helping agents, selected from solvents and water.
  • composition contains polyethylene glycol as a viscosifying agent.
  • the composition is consisting of 20-40% (v/v) methane sulfonic acid, 0,1-5% (m/v) Ethylenediamine tetra(methylene phosphonic acid) (EDTMP), 1% (m/v) polyethylene glycol having a molecular weight of 1000g/mol (PEG-1000), an alcohol, selected from MeOH, EtOH, IprOH, and n-BuOH, and, preferably, H 2 O in an amount of between 0.1-10 % (v/v).
  • ETMP Ethylenediamine tetra(methylene phosphonic acid)
  • PEG-1000 polyethylene glycol having a molecular weight of 1000g/mol
  • an alcohol selected from MeOH, EtOH, IprOH, and n-BuOH, and, preferably, H 2 O in an amount of between 0.1-10 % (v/v).
  • the invention refers to a method of electropolishing comprising the steps of
  • the metal substrate is immersed in the electrolyte solution.
  • the metal is selected from Nickel Titanium, Cobalt, Chromium,Tantalum, Niobium, Tungsten,Vanadium, or alloys thereof, wherein said alloys can contain one or more of said metals.
  • the metal is a nickel, titanium or an alloy thereof, preferably a nickel-titanium alloy.
  • the nickel-titanium alloy is Nitinol.
  • the metal substrate is a medical device, preferably a stent.
  • the invention refers to an electrolyte composition, comprising methane sulfonic acid; and at least one phosphonic acid derivative; wherein said phosphonic acid derivative contains at least three (n>2) phosphonic acid groups.
  • Phosphonic acid derivatives which contain at least three (n>2) phosphonic acid groups possess a high binding affinity to metal surfaces, particularly those that form multivalent metal ions during anodic dissolution, such as Titanium, Chromium, Tungsten, and the like, with the phosphonic acids having the ability to form Mono- or Multilayers, and on the other hand, phosphonic acid derivatives which contain at least three (n>2) phosphonic acid groups also possess good complexation capability for Nickel or other multivalent ions.
  • any mentioning of phosphonic acid derivatives refers to phosphonic acid derivatives which contain at least three (n>2) phosphonic acid groups.
  • the electrolyte composition of the invention is unique in that the selected complexing agents are predominantly surface bound, i.e. selective to the anode respectively work piece or medical device surface.
  • phosphonic acid derivatives which contain at least three (n>2) phosphonic acid groups, serve as surface selective masking agents capable of rendering the medical device surface with a protective film to resist the formation of hardly soluble oxide films during electropolishing, while simultaneously being capable of complexing the metal ions released from the surface to allow for constant mass transfer into solution.
  • a distinctive feature of the masking agents of the invention is that, since the binding affinity of the masking agent can be qualitatively and quantitatively tailored towards the element composition of the medical device surface, a selective depletion of one or more elements of the elemental surface composition can be afforded during electropolishing. Also, the formation of hardly soluble oxide films, which can cause an inhomogeneous material dissolution from the anode (work piece, medical device surface) can be suppressed.
  • the proposed mechanism is provided in Figure 6 .
  • Tri- Example: ATMP, Figure 3
  • Tetra- Example: Ethylendiamine-tetra(methylenephosphonic acid, EDTMP, Figure 4
  • Penta- Example: Diethylenetriamine-penta(methylenephosphonic acid, DTPMP, Figure 5
  • other multivalent phosphonic acids and their derivatives possess a higher effectiveness to form stable passivation layers as compared to mono- or divalent phosphonic acids, such as for example 1-Hydroxyethane-(1,1-di-phosphonic acid (HEDP, Figure 2 ), because by multiplication of the number of possible phosphonic acid anchor groups of a given phosphonic acid or derivative thereof, the Nitinol surface is masked more efficiently - because such compounds have a higher binding capability to form mono- or multilayers on the Nickel-depleted, Titanium-enriched anode surface.
  • HEDP 1-Hydroxyethane-(1,1-di-phosphonic acid
  • multivalent alkyl-based phosphonic acids and / or derivatives (with n>2 acid groups) as surface selective masking agent, it is intended to facilitate a selective Nickel depletion of the anode surface while simultaneously masking the in-situ forming, Titanium-enrichened NiTi surface, so that in a subsequent passivation step, a well-defined, stable titanium oxide layer of decreased surface roughness can be formed on the electropolished NiTi implant surface.
  • Electrolyte composition refers to any liquid composition containing at least one electrolyte.
  • An electrolyte according to the invention is a compound that is capable of forming ionized species when subjected to an electric current. Therefore, most soluble salts, acids, and bases can function as electrolytes. Some gases, such as hydrogen chloride, under conditions of high temperature or low pressure can also function as electrolytes.
  • Electrolyte compositions can e.g. be formed when a salt is placed into a solvent such as water and the individual components dissociate due to the thermodynamic interactions between solvent and solute molecules, in a process called solvation. For example, when table salt, NaCl, is placed in water, the salt (a solid) dissolves into its component ions, according to the dissociation reaction NaCl(s) ⁇ Na+(aq) + Cl-(aq)
  • phosphonic acid derivatives which contain at least three (n>2) phosphonic acid groups can be used as surface passivation or masking agents in electrolyte compositions, which are capable of generating a protective film or passivation layer on the surface of the material or substrate during electropolishing.
  • phosphonic acid derivatives which contain at least three (n>2) phosphonic acid groups are capable of forming stable passivation layers on the anode surface, as well as to the ability to deplete surface-bound Nickel from the Nitinol (medical device) surface by complexation, when employed in electropolishing-methods of Nitinol-substrates,
  • employing the electrolyte compositions of the invention can protect the anode surface from formation of undesired oxide films during electropolishing - and avoid or reduce oxygen generation, gassing, in-situ oxide film formation and suppression of water at the anode interface
  • the surface masking agent competes with present oxygen on a molecular level for the anode surface, thus effectively reducing or suppressing said oxide layer formation tendency either in the absence or presence of water.
  • Water is the main source for gassing effects in the form of both hydrogen and oxygen generation during electropolishing operations at the electrode surfaces.
  • Hydrogen formation can cause so-called hydrogen embrittlement, which can negatively affect mechanoelastical properties and premature failure of either electrodes and/or work piece due to material fatigue, while oxygen formation increases the level of dissolved oxygen in the electrolyte, favoring oxide film formation at the electrode interfaces.
  • gas formation will physically prevent the contact of the electrolyte with the electrodes and /or work pieces by forming gas bubbles on their surfaces, thus leading to an uneven material dissolution or a generally less controlled material ablation process.
  • water-less electrolyte formulations are desirable on the basis of the given argumentation, water can and is not always excluded in electrolyte formulations, for the following reasons: Many electrolyte components are hygroscopic (Examples include sulfuric acid, methane sulfonic acid, ethylene glycol derivatives) and will attract water over prolonged exposure to ambient conditions. In some electrolyte formulations, water acts as solvent for electrolyte additives. It also represents a cheap and easily available solvent. While not wishing to be bound by theory, it may actually be needed to facilitate mass transport of watersoluble byproducts of the electropolishing process away from the electrode surfaces. Hence, the role of the surface masking agent is not to suppress the presence on water in the electrolyte formulation, but rather to suppress effects of gassing at the electrode interface, along with the dissolution and/or complexation of hardly soluble oxide species away from the surface.
  • Methods of the invention refers to a compound with the chemical formula CH 3 SO 3 H
  • phosphonic acid group refers to a chemical group having the following structure: -PO(OH) 2 .
  • phosphonic acid groups can be defined as -PO(OH 2 ) groups which, in a preferred embodiment of the invention, are covalently linked to a carbon atom, e.g. as they replace a hydrogen atom on a carbon atom, or in other words, the -PO(OH 2 ) groups are substituents of aliphatic radicals or groups, alkyl-, alkenyl-, alkynyl-, cycloalkyl- , heterocyclyl or aryl-groups, as defined herein.
  • Phosphonic acid derivative or “phosphonates”, according to the invention, refer to any organic compound containing at least three (n>2) -PO(OH) 2 groups or to any organic compound in which at least three (n>2) -PO(OH 2 ) groups are covalently linked to (a) carbon atom(s), e.g. as they replace a hydrogen atom on a carbon atom, or in other words, the -PO(OH 2 ) groups are substituents of aliphatic radicals or groups, alkyl-, alkenyl-, alkynyl-, cycloalkyl- , heterocyclyl or aryl-groups, as defined herein.
  • the at least one phosphonic acid derivative has the structure R-[PO(OH) 2 ] n with n>2, wherein R is an aliphatic group, a cycloalkyl group, a heterocyclic group, or an aryl group.
  • the phosphonic acid derivative or phosphonate may either be used in its protonated state or in form of a salt.
  • the respective counter ion may either be an inorganic or organic cation.
  • phosphonic acid group may interchangeably be applicable to phosphinic acid groups R-P(OH) 3 , therefore, any disclosure, aspect, embodiment or definition of the invention regarding phosphonic acid derivatives having phosphonic acid groups also applies to the respective compounds having phosphinic acid groups instead of phosphonic acid groups.
  • aliphatic group refers to alkyl-, alkenyl- or alkynyl-groups.
  • alkyl In the context of this invention, " alkyl ", " alkyl radical " or -group is understood as meaning saturated, linear or branched hydrocarbons, which can be unsubstituted or mono- or polysubstituted. Alkyl groups encompass e.g. -CH 3 and -CH 2 -CH 3 .
  • C 1-2 -alkyl represents C 1 - or C 2 -alkyl
  • C 1-3 -alkyl represents C 1 -, C 2 - or C 3 -alkyl
  • C 1-4 -alkyl represents C 1 -, C 2 -, C 3 - or C 4 -alkyl
  • C 1-5 -alkyl represents C 1 -, C 2 -, C 3 -, C 4 -, or C 5 -alkyl
  • C 1-6 -alkyl represents C 1 -, C 2 -, C 3 -, C 4 -, C 5 - or C 6 -alkyl
  • C 1-7 -alkyl represents C 1 -, C 2 -, C 3 -, C 4 -, C 5 -, C 6 - or C 7 -alkyl
  • C 1-8 -alkyl represents C 1 -, C 2 -, C 3 -, C 4 -, C 5 -, C 6 -, C
  • C 2-3 -alkenyl represents C 2 - or C 3 -alkenyl
  • C 2-4 -alkenyl represents C 2 -, C 3 - or C 4 -alkenyl
  • C 2-5 -alkenyl represents C 2 -, C 3 -, C 4 -, or C 5 -alkenyl
  • C 2-6 -alkenyl represents C 2 -, C 3 -, C 4 -, C 5 - or C 6 -alkenyl
  • C 2-7 -alkenyl represents C 2 -, C 3 -, C 4 -, C 5 -, C 6 - or C 7 -alkenyl
  • C 2-8 -alkenyl represents C 2 -, C 3 -, C 4 -, C 5 -, C 6 -, C 7 - or C 8 -alkenyl
  • C 2-9 -alkenyl represents C 2 -, C 3 -, C 4 -, C 5 -
  • alkynyl groups refers to, unsaturated, linear or branched, hydrocarbons, which can be unsubstituted or mono- or polysubstituted, like e.g. -C ⁇ C-CH 3 .
  • C 2-3 -alkynyl represents C 2 - or C 3 -alkynyl
  • C 2-4 -alkynyl represents C 2 -, C 3 - or C 4 -alkynyl
  • C 2-5 -alkynyl represents C 2 -, C 3 -, C 4 -, or C 5 -alkynyl
  • C 2-6 -alkynyl represents C 2 -, C 3 -, C 4 -, C 5 - or C 6 -alkynyl
  • C 2 - 7 -alkynyl represents C 2 -, C 3 -, C 4 -, C 5 -, C 6 - or C 7 -alkynyl
  • C 2-8 -alkynyl represents C 2 -, C 3 -, C 4 -, C 5 -, C 6 -, C 7 - or C 8 -alkynyl
  • C 2-9 -alkynyl represents C 2 -
  • aryl group is understood as meaning an aromatic ring.
  • Preferred aryl groups are phenyl, naphthyl, fluoranthenyl, fluorenyl, tetralinyl or indanyl, which can be unsubstituted or monosubstituted or polysubstituted.
  • heterocyclic group is understood as meaning a heterocyclic ring system which contain one or more heteroatoms from the group consisting of nitrogen, oxygen, phosphorus, and/or sulfur in the ring or ringsystem, and can also be mono- or polysubstituted.
  • Preferred heterocyclyl groups are furan, thiophene, pyrrole, pyridine, piperazine, pyrimidine, pyrazine morpholine,
  • cycloalkyl group or “radical” is understood as meaning saturated and unsaturated (but not aromatic) cyclic hydrocarbons (without a heteroatom in the ring), which can be unsubstituted or mono- or polysubstituted.
  • C 4-5 -cycloalkyl represents C 4 - or C 5 -cycloalkyl
  • C 4-6 -cycloalkyl represents C 4 -, C 5 - or C 6 -cycloalkyl
  • C 4-7 -cycloalkyl represents C 4 -, C 5 -, C 6 - or C 7 -cycloalkyl
  • C 4-8 -cycloalkyl represents C 4 -, C 5 -, C 6 -, C 7 - or C 8 -cycloalkyl
  • C 4-5 -cycloalkyl represents C 4 - or C 5 -cycloalkyl
  • C 4-6 -cycloalkyl represents C 4 -, C 5 - or C 6 -cycloalkyl
  • C 4-7 -cycloalkyl represents C 4 -, C 5 -, C 6 -or C 7 -cycloalkyl
  • C 4-8 -cycloalkyl represents C 4 -, C 5 -
  • cycloalkyl groups are cyclopropyl, 2-methylcyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, cycloheptyl, and cyclooctyl. Particularly preferred is cyclohexyl.
  • the at least one phosphonic acid derivative has the structure R-[PO(OH) 2 ] n with n>2, wherein R is selected from the group consisting of a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, wherein in R one or more "C-atoms" may be replaced by a nitrogen, and wherein R comprises n>0 primary, secondary or tertiary amino groups.
  • R wherein in R one or more " C-atoms " may be replaced by a nitrogen " refers to the possibility that in a given linear, branched or cyclic organic molecule, e.g. an aliphatic group, an alkyl group, an alkenyl group, an alkenyl group, a cycloalkyl group, a heterocyclic group, an aryl group etc. as defined herein, a carbon atom can be replaced by a nitrogen atom, such that, in relevant part, the hydrocarbon molecule is modified from CH 2 -CH 2 -CH 2 to CH 2 -NH-CH 2 , or to CH 2 -NHR-CH 2 , or the like, as will be readily understood by the skilled person.
  • the at least one phosphonic acid derivative has the structure R-[PO(OH) 2 ] n with n>2, wherein R is selected from the group consisting of an substituted or unsubstituted, linear or branched, alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted aryl group; wherein in R one or more "C-atoms" may be replaced by a nitrogen, and wherein R comprises n>0 primary, secondary or tertiary amino groups.
  • the at least one phosphonic acid derivative has the structure R-[PO(OH) 2]n with n>2, wherein R is selected from the group consisting of a substituted or unsubstituted, linear or branched, C 1-10 alkyl, C 2-10 alkenyl, C 2-10 alkynyl; wherein in R one or more "C-atoms" may be replaced by a nitrogen, and wherein R comprises n>0 primary, secondary or tertiary amino groups.
  • the at least one phosphonic acid derivative has the structure R-[PO(OH) 2 ] n with n>2, wherein R represents a substituted or unsubstituted, linear or branched, C 1-10 aminoalkyl, C 2-10 aminoalkenyl, C 2-10 aminoalkynyl; a substituted or unsubstituted, linear or branched, C 1-10 iminoalkyl, C 2-10 iminoalkenyl, C 2-10 iminoalkynyl, wherein in R one or more "C-atoms" may be replaced by a nitrogen, and wherein R comprises n>0 primary, secondary or tertiary amino groups.
  • the at least one phosphonic acid derivative has the structure R-[PO(OH) 2 ] n with n>2, wherein R is an aryl group selected from substituted or unsubstituted, cyclic C 4-12 aryl, or R is a substituted or unsubstituted C 4-8 cycloalkyl group, or a substituted or unsubstituted C 4-8 heterocyclyl group, wherein in R one or more "C-atoms" may be replaced by a nitrogen, and wherein R comprises n>0 primary, secondary or tertiary amino groups.
  • the at least one phosphonic acid derivative has the structure R-[PO(OH) 2 ] n with n>2, wherein R is an aliphatic group selected from a substituted or unsubstituted, linear or branched, C 1-10 aminoalkyl, C 2-10 aminoalkenyl, C 2-10 aminoalkynyl, wherein in R one or more "C-atoms" may be replaced by a nitrogen, and wherein R comprises at least one primary, secondary or tertiary amino groups.
  • the at least one phosphonic acid derivative has the structure R-[PO(OH) 2 ] n with n>2, wherein R is an aliphatic group selected from a substituted or unsubstituted, linear or branched, C 1-10 aminoalkyl, C 2-10 aminoalkenyl, C 2-10 aminoalkynyl, wherein in R one or more "C-atoms" may be replaced by a nitrogen, and wherein R comprises at least two primary, secondary or tertiary amino groups.
  • the at least one phosphonic acid derivative has the structure R-[PO(OH) 2 ] n with n>2, wherein R is an aliphatic group selected from a substituted or unsubstituted, linear or branched, C 1-10 aminoalkyl, C 2-10 aminoalkenyl, C 2-10 aminoalkynyl, wherein in R one or more "C-atoms" may be replaced by a nitrogen, and wherein R comprises at least three primary, secondary or tertiary amino groups.
  • the at least one phosphonic acid derivative has the structure R-[PO(OH) 2 ] n with n>2, wherein R is an aliphatic group selected from a substituted or unsubstituted, linear or branched, C 1-10 aminoalkyl, C 2-10 aminoalkenyl, C 2-10 aminoalkynyl, wherein in R one or more "C-atoms" may be replaced by a nitrogen, and wherein the number of primary, secondary or tertiary amino groups in R equals the number of phosphonic acid groups in the phosphonic acid derivative.
  • R is an aliphatic group selected from a substituted or unsubstituted, linear or branched, C 1-10 aminoalkyl, C 2-10 aminoalkenyl, C 2-10 aminoalkynyl, wherein in R one or more "C-atoms" may be replaced by a nitrogen, and wherein the number of primary, secondary or tertiary amino groups in R equals the number of phosphonic acid groups in the
  • the at least one phosphonic acid derivative has the structure R-[PO(OH) 2 ] n with n>2, wherein R is an aliphatic group selected from a substituted or unsubstituted, linear or branched, C 1-10 aminoalkyl, C 2-10 aminoalkenyl, C 2-10 aminoalkynyl, wherein in R one or more "C-atoms" may be replaced by a nitrogen, and wherein the number of primary, secondary or tertiary aminogroups in R equals the number of phosphonic acid groups in the phosphonic acid derivative, and wherein the phosphonic acid groups each bind covalently to an aminogroup.
  • R is an aliphatic group selected from a substituted or unsubstituted, linear or branched, C 1-10 aminoalkyl, C 2-10 aminoalkenyl, C 2-10 aminoalkynyl, wherein in R one or more "C-atoms" may be replaced by a nitrogen, and wherein the number of primary, secondary or
  • the at least one phosphonic acid derivative has the structure R-[PO(OH) 2 ] n with n>2, wherein R is an aliphatic group selected from a substituted or unsubstituted , branched, C 1-10 aminoalkyl, C 2-10 aminoalkenyl, C 2-10 aminoalkynyl, wherein in R one or more "C-atoms" may be replaced by a nitrogen, wherein the number of primary, secondary or tertiary aminogroups in R equals the number of phosphonic acid groups in the phosphonic acid derivative, and wherein the phosphonic acid groups each bind covalently to an aminogroup.
  • R is an aliphatic group selected from a substituted or unsubstituted , branched, C 1-10 aminoalkyl, C 2-10 aminoalkenyl, C 2-10 aminoalkynyl, wherein in R one or more "C-atoms" may be replaced by a nitrogen, wherein the number of primary, secondary or tertiary
  • the at least one phosphonic acid derivative has the structure R-[PO(OH) 2 ] n with n>2, wherein R is a substituted or unsubstituted mono-cyclic C 4-8 heterocyclyl group, wherein in R one or more "C-atoms" may be replaced by a nitrogen, and wherein R comprises n>0 primary, secondary or tertiary amino groups.
  • the at least one phosphonic acid derivative has the structure R-[PO(OH) 2 ] n with n>2, wherein R is a substituted or unsubstituted mono-cyclic C 4-12 aryl group, wherein in R one or more "C-atoms" may be replaced by a nitrogen, and wherein R comprises n>0 primary, secondary or tertiary amino groups.
  • the concept can be extended to include other possible anchor groups instead of the phosphonic acid component, such as, but not limiting to, phosphinic-, sulfamic-, and hydroxamic-, carboxylic acid based components, that can subsequently be derivatized with one ore more alkane-, amino-, hydroxyl-, or thiol- functional groups and /or combinations thereof.
  • phosphinic-, sulfamic-, and hydroxamic-, carboxylic acid based components that can subsequently be derivatized with one ore more alkane-, amino-, hydroxyl-, or thiol- functional groups and /or combinations thereof.
  • the at least one phosphonic acid derivative is Amino-tris-(methylene phosphonic acid) (ATMP) or a respective salt thereof.
  • the at least one phosphonic acid derivative is selected from Ethylenediamine tetra(methylene phosphonic acid) (EDTMP), Tetramethylenediamine tetra (methylene phosphonic acid) (TDTMP), Hexamethylenediamine tetra(methylene phosphonic acid) (HDTMP) or respective salts thereof.
  • ETMP Ethylenediamine tetra(methylene phosphonic acid)
  • TTMP Tetramethylenediamine tetra (methylene phosphonic acid)
  • HDTMP Hexamethylenediamine tetra(methylene phosphonic acid)
  • the at least one phosphonic acid derivative is Ethylenediamine tetra(methylene phosphonic acid) (EDTMP) or a respective salt thereof.
  • the at least one phosphonic acid derivative is Tetramethylenediamine tetra (methylene phosphonic acid) (TDTMP) or a respective salt thereof.
  • the at least one phosphonic acid derivative is Hexamethylenediamine tetra(methylene phosphonic acid) (HDTMP) or a respective salt thereof.
  • the at least one phosphonic acid derivative is Diethylenetriamine-penta(methylenephosphonic acid (DTPMP) or a respective salt thereof.
  • DTPMP Diethylenetriamine-penta(methylenephosphonic acid
  • the at least one phosphonic acid derivative is phytic acid (IP6) or a respective salt thereof.
  • the at least one phosphonic acid derivative is selected from Amino-tris-(methylene phosphonic acid) (ATMP), Ethylenediamine tetra(methylene phosphonic acid) (EDTMP), Tetramethylenediamine tetra (methylene phosphonic acid) (TDTMP), Diethylenetriamine-penta(methylenephosphonic acid (DTPMP), Hexamethylenediamine tetra(methylene phosphonic acid) (HDTMP), and phytic acid (IP6) or respective salts thereof.
  • ATMP Amino-tris-(methylene phosphonic acid)
  • ETMP Ethylenediamine tetra(methylene phosphonic acid)
  • TTMP Tetramethylenediamine tetra (methylene phosphonic acid)
  • DTPMP Diethylenetriamine-penta(methylenephosphonic acid
  • HDTMP Hexamethylenediamine tetra(methylene phosphonic acid)
  • IP6 phytic acid
  • the at least one phosphonic acid derivative has the structure according to Formula I: wherein R 1 is a substituted C 1-3 aliphatic group; wherein substituents are selected from -PO(OH) 2 or NR 4 R 5 , wherein R 4 and R 5 , independent from each other, can be H or a C 1-3 aliphatic group, wherein the C 1-3 aliphatic group is optionally substituted with -PO(OH) 2 ; wherein both the C 1-3 aliphatic groups are substituted with a total of 0, 1 or 2 -PO(OH) 2 groups; R 2 is a substituted C 1-3 aliphatic group; wherein substituents are selected from -PO(OH) 2 or NR 4 R 5 , wherein R 4 and R 5 , independent from each other, can be H or a C 1-3 aliphatic group, wherein the C 1-3 aliphatic group is optionally substituted with -PO(OH) 2 ; wherein R 1 is a substituted C 1-3 ali
  • aliphatic groups comprise alkyl-, alkenyl-, and aklynyl groups. Therefore, the above feature of an C 1-3 - aliphatic group reads on C 1-3 alkyl groups, C 2-3 alkenyl groups and C 2-3 alkynyl groups, as will be readily understood by the skilled person.
  • the at least one phosphonic acid derivative has the structure according to Formula I: wherein R 1 is a substituted C 1-3 alkyl group; wherein substituents are selected from -PO(OH) 2 or NR 4 R 5 , wherein R 4 and R 5 , independent from each other, can be H or a C 1-3 alkyl group, wherein the C 1-3 alkyl group is optionally substituted with -PO(OH) 2 ; wherein both the C 1-3 alkyl groups are substituted with a total of 0, 1 or 2 -PO(OH) 2 groups; R 2 is a substituted C 1-3 alkyl group; wherein substituents are selected from -PO(OH) 2 or NR 4 R 5 , wherein R 4 and R 5 , independent from each other, can be H or a C 1-3 alkyl group, wherein the C 1-3 alkyl group is optionally substituted with -PO(OH) 2 ; wherein both the C 1-3 al
  • the at least one phosphonic acid derivative is selected from Amino-tris-(methylene phosphonic acid) (ATMP), Ethylenediamine tetra(methylene phosphonic acid) (EDTMP), Tetramethylenediamine tetra (methylene phosphonic acid) (TDTMP), Diethylenetriamine-penta(methylenephosphonic acid (DTPMP), and Hexamethylenediamine tetra(methylene phosphonic acid) (HDTMP), or respective salts thereof.
  • ATMP Amino-tris-(methylene phosphonic acid)
  • ETMP Ethylenediamine tetra(methylene phosphonic acid)
  • TTMP Tetramethylenediamine tetra (methylene phosphonic acid)
  • DTPMP Diethylenetriamine-penta(methylenephosphonic acid
  • HDTMP Hexamethylenediamine tetra(methylene phosphonic acid)
  • the at least one phosphonic acid derivative has a structure according to formula (I) and contains three -PO(OH) 2 groups.
  • the at least one phosphonic acid derivative is Amino-tris-(methylene phosphonic acid) (ATMP) or a respective salt thereof.
  • the at least one phosphonic acid derivative has a structure according to formula (I) and contains at least four -PO(OH) 2 groups.
  • the at least one phosphonic acid derivative has a structure according to formula (I) and contains four -PO(OH) 2 groups.
  • the at least one phosphonic acid derivative is selected from Ethylenediamine tetra(methylene phosphonic acid) (EDTMP), Tetramethylenediamine tetra (methylene phosphonic acid) (TDTMP), Hexamethylenediamine tetra(methylene phosphonic acid) (HDTMP) or respective salts thereof.
  • ETMP Ethylenediamine tetra(methylene phosphonic acid)
  • TTMP Tetramethylenediamine tetra (methylene phosphonic acid)
  • HDTMP Hexamethylenediamine tetra(methylene phosphonic acid)
  • the at least one phosphonic acid derivative is Tetramethylenediamine tetra (methylene phosphonic acid) (TDTMP) or a respective salt thereof.
  • the at least one phosphonic acid derivative is Hexamethylenediamine tetra(methylene phosphonic acid) (HDTMP) or a respective salt thereof.
  • the at least one phosphonic acid derivative is Ethylenediamine tetra(methylene phosphonic acid) (EDTMP) or a respective salt thereof.
  • the at least one phosphonic acid derivative has a structure according to formula (I) and contains at least five -PO(OH) 2 groups.
  • the at least one phosphonic acid derivative has a structure according to formula (I) and contains five -PO(OH) 2 groups.
  • the at least one phosphonic acid derivative is Diethylenetriamine-penta(methylenephosphonic acid (DTPMP) or a respective salt thereof.
  • the at least one phosphonic acid derivative has a structure according to formula (I) and contains at least six -PO(OH) 2 groups.
  • the at least one phosphonic acid derivative has a structure according to formula (I) and contains six -PO(OH) 2 groups.
  • the at least one phosphonic acid derivative preferably according to the above structure R-[PO(OH) 2 ] n and/or according to formula (I), as defined herein, are two phosphonic acid derivatives.
  • the two phosphonic acid derivatives are Amino-tris-(methylene phosphonic acid) (ATMP) and Ethylenediamine tetra(methylene phosphonic acid) (EDTMP) or respective salts thereof.
  • the two phosphonic acid derivatives are Amino-tris-(methylene phosphonic acid) (ATMP) and Tetramethylenediamine tetra (methylene phosphonic acid) (TDTMP) or respective salts thereof.
  • the two phosphonic acid derivatives are Amino-tris-(methylene phosphonic acid) (ATMP) and Diethylenetriamine-penta(methylenephosphonic acid (DTPMP) or respective salts thereof.
  • the two phosphonic acid derivatives are Amino-tris-(methylene phosphonic acid) (ATMP) and (HDTMP) or respective salts thereof.
  • the two phosphonic acid derivatives are Amino-tris-(methylene phosphonic acid) (ATMP) and phytic acid (IP6) or respective salts thereof.
  • salts of the phosphonic acid derivatives as defined herein are inorganic salts.
  • inorganic salts are formed from alkali metal species, such as sodium or potassium.
  • salts of the phosphonic acid derivatives as defined herein are organic salts.
  • they can be formed via an organic cationic species (e.g. ionic liquids or complexing cationic counterions).
  • the concentration of the at least one phosphonic acid derivative is between 0.1 % and 10% (m/v).
  • the concentration of the at least one phosphonic acid derivative is between 0.1 % and 5% (m/v).
  • the concentration of methane sulfonic acid in the electrolyte composition is between 20-98% (v/v).
  • the concentration of methane sulfonic acid in the electrolyte composition is between 20-80% (v/v).
  • the concentration of methane sulfonic acid in the electrolyte composition is between 20-60% (v/v).
  • the concentration of methane sulfonic acid in the electrolyte composition is between 20-40% (v/v).
  • the electrolyte composition further contains at least one additional additive selected from the group of viscosifying agents, chelating agents, stabilizer agents, buffering agents; and/or at least one other helping agents, selected from solvents and water.
  • Solvents can be any organic solvent, or alcohol. Particularly preferred are alcohols selected from methanol (MeOH), ethanol (EtOH), isopropanol (IprOH); n-butanol (n-BuOH), propan-1,2-diol (pr-1,2-diOH), propan-1,3-diol (pr-1,3-diOH), 2-Methyl-1-butanol (2-Me-1-BuOH), 3-Methyl-2-butanol(3-Me-2-BuOH), 2-Methyl-1-pentanol (2-Me-PeOH), or tert-butyl (t-BuOH).
  • Alcohols selected from methanol (MeOH), ethanol (EtOH), isopropanol (IprOH); n-butanol (n-BuOH), propan-1,2-diol (pr-1,2-diOH), propan-1,3-diol (pr
  • Buffering agents are typically chosen for their ability to control the desired pH strength and buffering capacity of the electrolyte composition.
  • Typical pH buffering agents may include citrate, oxalate, borate compositions and the like.
  • the electrolyte composition itself or the electropolishing cell can contain buffering species bound to polymeric resins, i.e. in the form of anion or cation exchange resins that are capable of removing predominantly multivalent metal ions from the electrolyte solution, as well as replenishing or stabilizing the available proton concentration to a desired level.
  • the electrolyte cell may contain separate compartment(s) for either a cation- or anion exchange resin or both, which are immersed into the electrolyte, but placed outside of the electrode working space, i.e. the space between anode and cathode.
  • Complexing agents for use in electrolyte compositions are typically chosen for their ability to chelate metal ions in solution (and thus to prevent (re-) precipitation of hardly soluble residues that may form on the surface or in solution during electropolishing).
  • Such complexing agents are rather well known and documented and can include agents such as Oxychinolines, Catecholes, Quadrol, 1,2-Ethanediamine, Ethanolamines, Triisopropanolamines, N,N,N',N'-tetrakis(2-aminoethyl)-EDA, EDTA, NTA, N,N'-Bis(2-hydroxyethyl)ethylenediamines, N,N,N',N'-Tetrakis(2-hydroxyethyl)ethylenediamines, N,N,N',N'-Tetrakis(2-Hydroxypropyl)ethylenediamines and the like.
  • the electrolyte composition may include 0-5 % of a
  • Stabilizers and additional Helping Agents/Additives for use in electrolyte compositions according to the invention can include aliphatic, alicyclic or aromatic mono-, di-, tri- or multivalent alcohols, including, but not limited to compounds such as ethanediol, glycerine, sugars, dextrines, cyclohexanol, benzyl alcohol, aliphatic, alicyclic, or aromatic mono-, di-, tri- or multivalent amines, for example compounds such as ethylendiamine, ethanoldiamine, urea, tetramethyl urea, aliphatic, alicyclic or aromatic mono-, di-, tri- or multivalent thiol containing compounds, for example Thiourea, methylating agents, such as Dimethyl Sulfate, 1,3-Dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU), chelating acids, such as glycolic or
  • the electrolyte composition contains polyethylene glycol as a viscosifying agent.
  • the electrolyte composition contains polyethylene glycol 1000 (PEG-1000) or polyethylene glycol 1500 (PEG 1500), as a viscosifying agent.
  • the electrolyte composition contains polyethylene glycol 1000 (PEG-1000) or polyethylene glycol 1500 (PEG 1500) as a viscosifying agent, in a concentration between about 0,1-2,5% (m/v).
  • the electrolyte composition contains polyethylene glycol 1000 (PEG-1000) as a viscosifying agent, in a concentration between about 0,1-2,5% (m/v), preferably in a concentration between about 0,1-1% (m/v), more preferably in a concentration of about 1% (m/v).
  • PEG-1000 polyethylene glycol 1000
  • the electrolyte composition consists of 20-40% (v/v) methane sulfonic acid, 0,1-5% (m/v) Ethylenediamine tetra(methylene phosphonic acid) (EDTMP), 1% (m/v) polyethylene glycol having a molecular weight of 1000g/mol (PEG-1000), and an alcohol, selected from MeOH, EtOH, IprOH, and n-BuOH, and, preferably, H 2 O in an amount of between 0.1-10 % (v/v).
  • ETMP Ethylenediamine tetra(methylene phosphonic acid)
  • PEG-1000 polyethylene glycol having a molecular weight of 1000g/mol
  • an alcohol selected from MeOH, EtOH, IprOH, and n-BuOH, and, preferably, H 2 O in an amount of between 0.1-10 % (v/v).
  • the invention refers a method of electropolishing comprising the steps of
  • Electropolishing also known as electrochemical polishing or electrolytic polishing, according to the invention, refers to an electrochemical process that removes material from a metallic workpiece. It is used to polish, passivate, and deburr metal parts. It is often described as the reverse of electroplating. It may be used in lieu of abrasive fine polishing in microstructural preparation. Electropolishing streamlines the microscopic surface of a metal object by removing metal from the object's surface through an electrochemical process similar to, but the reverse of, electroplating. In electropolishing, the metal is removed ion by ion from the surface of the metal object in question. Electrochemistry and the fundamental principles of electrolysis replace traditional mechanical finishing techniques, including grinding, milling, blasting and buffing as the final finish.
  • the object to be electropolished is immersed in an electrolyte and subjected to a direct electrical current.
  • the object is maintained anodic, with the cathodic connection being made to a nearby metal conductor.
  • the polarized surface film is subjected to the effects of gassing (oxygen), which occurs with electrochemical metal removal, saturation of the surface with dissolved metal and the agitation and temperature of the electrolyte. Smoothness of the metal surface is a primary and very advantageous effect of electropolishing.
  • a film of varying thickness covers the surfaces of the metal. This film is thickest over microdepressions and thinnest over microprojections.
  • Electropolishing selectively removes microscopic high points or "peaks" much faster than the corresponding rate of attack on the corresponding micro-depressions or “valleys.”
  • the surface of the metal is microscopically featureless, with not even the smallest speck of a tom surface remaining.
  • the basic metal surface is subsequently revealedbright, clean and microscopically smooth.
  • even very fine mechanically finished surfaces will show smears and other directionally oriented patterns or effects.
  • the metal substrate is immersed in the electrolyte solution.
  • the metal is selected from Nickel Titanium, Cobalt, Chromium,Tantalum, Niobium, Tungsten,Vanadium, or alloys thereof, wherein said alloys can contain one or more of said metals.
  • the metal is a nickel, titanium or an alloy thereof.
  • the metal is a nickel-titanium alloy.
  • the nickel-titanium alloy is Nitinol.
  • the metal substrate is a medical device.
  • the medical device is a medical implant.
  • the medical implant is selected from the group consisting of vascular implants, preferably stents, filters, coils, closure devices, clips; orthopaedic implants or - prosthesis; or a mechanical heart valve.
  • the medical implant is an orthopaedic implant or -prosthesis, selected from the group consisting of Austin-Moore prosthesis for fracture of the neck of femur; Baksi's prosthesis for elbow replacement; Buttress plate for condylar fractures of tibia; Charnley prosthesis: for total hip replacement; Condylar blade plate for condylar fractures of femur;Dynamic compression plate; Ender's nail for fixing inter-trochanteric fracture; Grosse-Kempf (GK) nail for tibial or femoral staff fracture; Gamma nail for peri-trochanteric fractures; Harrington rod: for fixation of the spine; Hartshill rectangle for fixation of the spine; Insall Burstein prosthesis for total knee replacement; Interlocking nail for femoral or tibial shaft fractures; Kirschner wire for fixation of small bones; Kuntscher nail for fracture of the shaft of femur; Luque rod for fix
  • the medical implant is a mechanical heart valve.
  • the mechanical heart valve is a -disc heart valve or a bileaflet heart valve.
  • the.medical implant is a catheter.
  • the medical implant is a peripheral venous catheter.
  • the medical implant is a vascular implant.
  • the vascular implant is selected from the group consisting of stents, filters, coils, closure devices, clips.
  • the vascular implant is a stent.
  • a “stunt” is a mesh tube inserted into a natural passage/conduit in the body to prevent or counteract a disease-induced, localized flow constriction.
  • the term may also refer to a tube used to temporarily hold such a natural conduit open to allow access for surgery.
  • the medical implant is a stent, selected from the group consisting of bare-metal stent, a drug-eluting stent, a bio engineered stent, a BVS or a Dual Therapy Stent (Combination of both Drug and bioengineered stent) or a covered stent.
  • the medical implant is a bare-metal stent, comprising Nitinol.
  • the medical implant is a bare-metal stent, consisting of Nitinol.
  • the implant surface is subjected to a series of preconditioning steps prior to conducting electropolishing operations.
  • the implant surface is subjected to mechanical deburring, which is then followed by implant surface cleaning and etching.
  • implant surface cleaning and etching are carried out as wet chemical processes, whereas preferred cleaning and etching formulations, along with process time are provided below.
  • the implant surface is subjected to a series of preferred postconditioning steps, which comprise of surface passivation, rinsing and drying.
  • the first two two steps are carried out as wet chemical processes, whereas preferred surface passivation formulations, along with process time are provided below.
  • Electrode Temperature -10, 20, 50 °C Agitation [rpm]: Yes [100-400] /No [0]
  • Electropolishing Cell Configuration Electrode Material: Cathode: Stainless Steel Anode: Work piece, attached by Titanium rods
  • Dissolved Mass [%] Preferably less than 50%, more preferably 20-40%, most preferably 25-35%
  • Electrolyte Composition 125 ml MSA (25 %) 375 ml EtOH (75%) 5.0 g PEG 1000 ⁇ 2.1 g EDTMP (Saturation Limit)
  • Substrate NiTi based Stent
  • Electropolishing Time / cycle [min]: 60 s Number of Cycles [#]: 6 Current / Charge [A]: 7.0 V / variable current (Process Limit 1.5 A)
  • Electrolyte Temperature [°C]: 17 ⁇ 2 °C Stirring: 0 rpm
  • Substrate Weight after Etching and Cleaning 206.8 mg
  • Substrate Weigth after Electropolishing 145.8 mg Dissolved Mass: 30%
  • Electrolyte performed as intended, yielding a very smooth and shiny surface finish.
  • the results obtained are depicted in form of optical microscope images provided in Figures 7-11 .
  • Electrolyte Composition 250 ml MSA (25 %) 650 ml n-Butanol (65 %) 100 ml H 2 O 10.0 g PEG 1000 ⁇ 4.2 g EDTMP (Saturation Limit)
  • Example 2 The results obtained for Example 2 are depicted in .form of optical microscope images provided in Figure 13 . At 4% mass ablation, optical microscope images of the attained surface finish demonstrate a substantial improvement from the typical etched surface condition of the native substrate demonstrated in Fig.9 .
  • Electrolyte Composition 250 ml MSA (25 %) 650 ml n-Butanol (65 %) 100 ml H 2 O 10.0 g PEG 1000 ⁇ 4.2 g EDTMP (Saturation Limit)
  • Substrate(s) NiTi based Stents (NXP ⁇ 5 x 80 mm)
  • Example 3 The results obtained for Example 3 are depicted in form of optical microscope images provided in Figure 14 .
  • optical microscope images of the attained surface finish demonstrate a substantial improvement from the typical etched surface condition of the native substrate demonstrated in Fig.9 combined with desired edge rounding as compared to the mass ablation of 4% shown in Fig. 13 .
  • Electrolyte Composition 250 ml MSA (25 %) 650 ml n-Butanol (65 %) 100 ml H 2 O 10.0 g PEG 1000 ⁇ 4.2 g EDTMP (Saturation Limit)
  • Example 4 The results obtained for Example 4 are depicted in form of optical microscope images provided in Figure 15 .
  • optical microscope images of the attained surface finish demonstrate not only a substantial improvement from the typical etched surface condition of the native substrate shown in Fig.9 , but also desired edge rounding and additional removal of surface corrugation when compared to the mass ablation level of 10% shown in Fig. 13 .
  • Electrolyte Composition 250 ml MSA (25 %) 650 ml EtOH (65 %) 100 ml H 2 O 10.0 g PEG 1000 ⁇ 4.2 g EDTMP (Saturation Limit)
  • Example 5 The results obtained for Example 5 are depicted in form of optical microscope images provided in Figure 16 . At around 24% mass ablation, optical microscope images of the attained surface finish demonstrate a stark contrast to the previous example 4: Surface corrugation has significantly increased, showing a 'granular' surface with smooth valleys and pointed spikes.
  • Electrolyte Composition 250 ml MSA (25 %) 650 ml EtOH (65 %) 100 ml H 2 O 10.0 g PEG 1000 ⁇ 4.2 g EDTMP (Saturation Limit)
  • Substrate(s) Nickel foil, wall strength 0.127 cm
  • Example 6 The results obtained for Example 6 are provided in form of optical microscope images, whereas Figure 17 depicts the typical surface of the native Nickel foil prior to electropolishing and Figure 18 the Nickel foil surface after electropolishing. On Nickel substrates a perfect mirror like finish is obtained.

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EP13005538.7A 2013-11-28 2013-11-28 Elektrolytzusammensetzung und Verfahren zur Elektropolierbehandlung von Nickel-Titan-Legierungen und/oder anderen Metallsubstraten mit Wolfram-, Niob- und Tantallegierungen Withdrawn EP2878713A1 (de)

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EP13005538.7A EP2878713A1 (de) 2013-11-28 2013-11-28 Elektrolytzusammensetzung und Verfahren zur Elektropolierbehandlung von Nickel-Titan-Legierungen und/oder anderen Metallsubstraten mit Wolfram-, Niob- und Tantallegierungen
PCT/EP2014/075710 WO2015078930A1 (en) 2013-11-28 2014-11-26 Electrolyte composition and method for the electropolishing treatment of nickel-titanium alloys and/or other metal substrates including tungsten, niob and tantal alloys
EP14803125.5A EP3074553A1 (de) 2013-11-28 2014-11-26 Elektrolytzusammensetzung und verfahren zur elektropolierbehandlung von nickel-titan-legierungen und/oder anderen metallsubstraten einschliesslich wolfram-, niob- und tantallegierungen

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WO2018102845A1 (de) * 2016-12-09 2018-06-14 Hirtenberger Engineered Surfaces Gmbh Elektropolierverfahren und elektrolyt hierzu

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AT520365B1 (de) * 2017-08-29 2019-10-15 Hirtenberger Eng Surfaces Gmbh Elektrolyt zum elektropolieren von metalloberflächen
CN106567122B (zh) * 2017-02-17 2021-08-17 大博医疗科技股份有限公司 一种钛及钛合金的电化学抛光电解液及其抛光方法
CN117568878B (zh) * 2024-01-15 2024-05-03 甘肃海亮新能源材料有限公司 钛阳极和电解铜箔的生产设备

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WO2018102845A1 (de) * 2016-12-09 2018-06-14 Hirtenberger Engineered Surfaces Gmbh Elektropolierverfahren und elektrolyt hierzu
US11549194B2 (en) 2016-12-09 2023-01-10 Hirtenberger Engineered Surfaces Gmbh Electropolishing method and electrolyte for same

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