WO2016064296A1 - Method of producing the bioactive coating with antibacterial effect - Google Patents

Method of producing the bioactive coating with antibacterial effect Download PDF

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Publication number
WO2016064296A1
WO2016064296A1 PCT/RU2015/000055 RU2015000055W WO2016064296A1 WO 2016064296 A1 WO2016064296 A1 WO 2016064296A1 RU 2015000055 W RU2015000055 W RU 2015000055W WO 2016064296 A1 WO2016064296 A1 WO 2016064296A1
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Prior art keywords
additive
bioactive
implants
antibacterial effect
coatings
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PCT/RU2015/000055
Other languages
French (fr)
Inventor
Evgeny Aleksandrovich Levashov
Aleksander Evgen`evich KUDRYASHOV
Evgeniya Igorevna ZAMULAEVA
Dmitry Vladimirovich Shtansky
Yury Sergeevich POGOZHEV
Artem Yur`evich POTANIN
Nataliya Vladimirovna SHVYNDINA
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National University Of Science And Technology "Misis"
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Priority claimed from RU2014142170/15A external-priority patent/RU2580627C1/en
Priority claimed from RU2014142171/15A external-priority patent/RU2580628C1/en
Application filed by National University Of Science And Technology "Misis" filed Critical National University Of Science And Technology "Misis"
Priority to EA201700215A priority Critical patent/EA033318B1/en
Publication of WO2016064296A1 publication Critical patent/WO2016064296A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/32—Phosphorus-containing materials, e.g. apatite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • A61L2300/104—Silver, e.g. silver sulfadiazine
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/06—Coatings containing a mixture of two or more compounds

Definitions

  • This invention relates to surface engineering of medical purpose metals and their alloys and can be used for the production of implants for the replacement of damaged bone tissue fragments including, for example, orthopedic and dental implants, maxillofacial and spinal column surgery implants, artificial joints, clamps etc.
  • the coating on chromium-nickel stainless steel transosteal implants is deposited by oxidizing the implants for 0.3-1.0 h in air at 300-600°C and atmospheric pressure followed by gradual cooling of the as-treated implants in the furnace to the ambient temperature (20-30°C).
  • a disadvantage of said known method is the necessity of using furnaces for oxidation, long term process because of the requirement to have a slow furnace cooling with implants and low adhesion strength of coating to the substrate. Furthermore, said method does not provide antibacterial effect coatings.
  • a disadvantage of said known method is the necessity of using special chemicals, long term process that may reach 3 days and the relatively low adhesion strength of coating to the substrate. Furthermore, said method does not provide antibacterial effect coatings.
  • biocompatible coatings on titanium bone clamps are obtained by oxidizing titanium in an overheated steam atmosphere at 500-550°C for 1.5-2 h under 1.2-1.3 atm. Then the oxidized bone clamps are cooled first in the furnace in a steam atmosphere to 250-300°C and then in air down to 20-30°C.
  • a disadvantage of said known method is the necessity of using furnaces for oxidation, long term process because of requirement to have a slow furnace cooling with implants and low adhesion strength of coating to the substrate. Furthermore, said method does not provide antibacterial effect coatings.
  • the most closed counterpart of the method suggested herein is the method of applying corrosion resistant and biocompatible coatings on titanium alloys by electrospark alloying (A.M. Pavlenko, V.A. Vinokurov and E.V. Naidenkin, Application of Corrosion Resistant and Biocompatible Coatings on Titanium Alloys by Electric Spark Alloying, Modern Equipment and Technologies: Collection of Works of the 19 International Research and Practical Conference of Students, Post-Graduate Students and Young scientistss, Tomsk, April 15-19, 2013, TPU 2013, vol. 2, p. 120-121).
  • a disadvantage of the suggested method is that the coatings are not bioactive and have no antibacterial effect.
  • the technical task solved by this invention is the production of biocompatible bioactive coatings with antibacterial effect on medical purpose metals and alloys.
  • the technical result achieved by this method is the provision of implants made of special medical purpose alloys with continuous bioactive coatings and antibacterial effect and high adhesion strength (critical load more than 100 N), high wear resistance and controlled roughness.
  • the method of obtaining bioactive coatings with antibacterial effect comprises electrospark machining of the electrical conductive substrate with the processing electrode of the following compositions (wt. %):
  • biocompatible additive of metal or a refractory compound balance.
  • Electrospark machining is carried out under the following conditions:
  • the electrical conductive substrate is made of medical purpose alloys based on Ti, Ni, Fe, Zr, Nb, Ta.
  • the bioactive additive is hydroxylapatite and/or tricalciumphosphate and/or calcium oxide and/or titanium dioxide.
  • the antibacterial metallic additive is silver and/or copper.
  • the biocompatible additive of metal is titanium and/or zirconium and/or hafnium and/or tantalum.
  • the biocompatible additive of a refractory compound is carbide and/or carbonitnde and/or oxycarbonitride of titanium and/or zirconium and/or hafnium and/or tantalum.
  • Electrospark machining is carried out in an atmosphere of argon, helium or nitrogen.
  • Electrospark machining is carried out in a liquid selected from ethyl alcohol or distilled water or normal saline or Ringer solution.
  • Coatings are applied using electrospark machining equipment.
  • the implant acting as the electrical conductive substrate is placed in a special box so the implant and the working part of the processing electrode are in the protective atmosphere.
  • the tool with the processing electrode installed thereon which comprises the bioactive additive, the antibacterial metallic additive and the biocompatible additive of metal in the abovementioned ratios, as well as the implant, are connected to the plant power unit.
  • the processing electrode As the processing electrode approaches the implant an electric discharge occurs followed by electric erosion of the processing electrode material and polarized transfer of erosion products onto the implant surface.
  • the bioactive coating with antibacterial effect forms due to the processing electrode scans the implant surface at the preset rate, discharge power and frequency.
  • the coating roughness is controlled by the protective environment in which electrospark machining is carried out, e.g. gaseous or liquid.
  • Gaseous environment for electrospark machining can be argon, helium or nitrogen.
  • Liquid environment for electrospark machining can be ethyl alcohol or distilled water or H 2 0-NaCl normal saline or Ringer solution.
  • Bioactivity of the coating is achieved by inclusion into the electrode material of bioactive additives in the form of inorganic compounds or mixtures thereof, more specifically hydroxylapatite Cai 0 (PO 4 ) 6 (OH)2 and/or tricalciumphosphate Ca 3 (P0 4 ) 2 and/or calcium oxide CaO and/or titanium dioxide Ti0 2 in quantities of 5-40 wt.%.
  • the antibacterial effect of the coating is achieved by inclusion into the electrode material of an antibacterial metallic additive in a quantity of 0.5-5 wt.%, e.g. silver and/or copper.
  • the basis of the electrode material used for obtaining bioactive coatings with antibacterial effect is selected from biocompatible metals titanium Ti and/or zirconium Zr and or hafnium Hf and or tantalum Ta.
  • the basis of the electrode material used for obtaining bioactive coatings with antibacterial effect is selected from biocompatible refractory compounds carbide and/or carbonitride and/or oxycarbonitride of titanium and/or zirconium and/or hafnium and/or tantalum.
  • the range of electrospark machining parameters used for the implementation of the method was selected based on the following.
  • the electrode material heats excessively and as a result undergoes erosion in the form of large liquid drops and particles. Those particles cannot adhere sufficiently to the substrate surface.
  • the resultant coating has high roughness and insufficient density.
  • excessive electrode heating may reduce coating material hardness and increase its plasticity resulting in the loss of the electrode shape and preventing its further operation. And there is excessive consumption of the electrode material.
  • Electrospark machining at a pulse discharge frequency of less than 10 Hz reduces process output. In this case continuous and homogeneous coatings require greater processing time.
  • the coatings are incontinuous and contain an inhomogeneous distribution of bioactive and antibacterial additions on the implant surface.
  • the model system used for the biological studies was MC3T3-E1 line osteoblasts grown on the surface of the test materials.
  • Cell adhesion followed by spreading on the substrate surface is the first phase of cell interaction with the implant and therefore the quality of this phase is of a decisive importance for the biocompatibility of a material.
  • a quantitative colorimetric method with the use of alkaline phosphatase as a early cell differentiation marker was also used for assessing the ability of the coatings to affect MC3T3-E1 osteoblast differentiation for growth in a differentiating media.
  • the studies showed that osteoblasts growing on the coating surfaces are capable of differentiation.
  • After two-week growth of MC3T3-E1 osteoblasts their quantitative colorimetric analysis showed a higher level activity of alkaline phosphatase in cells growing on coatings surfaces compared with the reference (a specimen without a titanium alloy coating).
  • test bacterial cultures for studying the bactericide activity of the coatings were E. Coli coliform bacteria. We measured the quantity of bacteria surviving after 24 h (as the antibacterial activity parameter we accepted the percentage of surviving bacteria compared with the reference specimen (the one without the antibacterial addition)).
  • Electrospark machining at the abovementioned parameters ensures stable synthesis of bioactive coatings with antibacterial effect without defects in the form of closed pores or cracks with the preset roughness and chemical composition, high adhesion, continuity and wear resistance.
  • Tables 1 and 2 show embodiments of the method and the dependence of bioactive coating parameters on the preset range of electrospark machining parameters for a similar set of electrode materials.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • Dermatology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Veterinary Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Biomedical Technology (AREA)
  • Molecular Biology (AREA)
  • Materials For Medical Uses (AREA)
  • Dental Preparations (AREA)
  • Dental Prosthetics (AREA)

Abstract

Field of the Invention. This invention relates to surface machining of medical purpose metals and their alloys and can be used for the production of implants for the replacement of damaged bone tissue fragments including, for example, orthopedic and dental implants, maxillofacial and spinal column surgery implants, artificial joints, clamps etc. Disclosure of the Invention. The technical result achieved by this method is the provision of implants made from special medical purpose alloys with continuous bioactive coatings with antibacterial effect and high adhesion strength to substrate (critical load more than 100 N), high wear resistance and controlled roughness. The technical result is achieved as follows. The method of obtaining bioactive coatings with antibacterial effect comprises electrospark machining of the electrical conductive substrate surface with the processing electrode of the following compositions (wt. %): bioactive additive 5-40, antibacterial metallic additive 0.5-5 biocompatible additive of metal or a refractory compound: balance. Electrospark machining is carried out under the following conditions: 100≤Ni≤10 000 10≤f≤100 000 0,01≤v≤0.6, where Ni is the power of a unit pulse discharge, W; f is the frequency of pulse discharges, Hz; and v is the linear speed of the processing electrode, m/min.

Description

Method of Producing the Bioactive Coating with Antibacterial Effect
Field of the Invention. This invention relates to surface engineering of medical purpose metals and their alloys and can be used for the production of implants for the replacement of damaged bone tissue fragments including, for example, orthopedic and dental implants, maxillofacial and spinal column surgery implants, artificial joints, clamps etc.
Prior Art. Known is method of producing the biocompatible oxide coating on stainless steel transosteal implants (RU 2412723, published 27.02.201 1).
In said known method, the coating on chromium-nickel stainless steel transosteal implants is deposited by oxidizing the implants for 0.3-1.0 h in air at 300-600°C and atmospheric pressure followed by gradual cooling of the as-treated implants in the furnace to the ambient temperature (20-30°C).
A disadvantage of said known method is the necessity of using furnaces for oxidation, long term process because of the requirement to have a slow furnace cooling with implants and low adhesion strength of coating to the substrate. Furthermore, said method does not provide antibacterial effect coatings.
Known is a method of coatings deposition on titanium pieces (RU 2453630, published 20.06.2012) wherein calcite, apatite and composite coatings are formed on the surface of titanium implants by chemical methods.
A disadvantage of said known method is the necessity of using special chemicals, long term process that may reach 3 days and the relatively low adhesion strength of coating to the substrate. Furthermore, said method does not provide antibacterial effect coatings.
Known is a method of obtaining biocompatible coatings on titanium bone clamps (RU 2332239, published 27.08.2008).
For said known method biocompatible coatings on titanium bone clamps are obtained by oxidizing titanium in an overheated steam atmosphere at 500-550°C for 1.5-2 h under 1.2-1.3 atm. Then the oxidized bone clamps are cooled first in the furnace in a steam atmosphere to 250-300°C and then in air down to 20-30°C. A disadvantage of said known method is the necessity of using furnaces for oxidation, long term process because of requirement to have a slow furnace cooling with implants and low adhesion strength of coating to the substrate. Furthermore, said method does not provide antibacterial effect coatings.
The most closed counterpart of the method suggested herein is the method of applying corrosion resistant and biocompatible coatings on titanium alloys by electrospark alloying (A.M. Pavlenko, V.A. Vinokurov and E.V. Naidenkin, Application of Corrosion Resistant and Biocompatible Coatings on Titanium Alloys by Electric Spark Alloying, Modern Equipment and Technologies: Collection of Works of the 19 International Research and Practical Conference of Students, Post-Graduate Students and Young Scientists, Tomsk, April 15-19, 2013, TPU 2013, vol. 2, p. 120-121).
A disadvantage of the suggested method is that the coatings are not bioactive and have no antibacterial effect.
Disclosure of the Invention. The technical task solved by this invention is the production of biocompatible bioactive coatings with antibacterial effect on medical purpose metals and alloys.
The technical result achieved by this method is the provision of implants made of special medical purpose alloys with continuous bioactive coatings and antibacterial effect and high adhesion strength (critical load more than 100 N), high wear resistance and controlled roughness.
The technical result is achieved as follows.
The method of obtaining bioactive coatings with antibacterial effect comprises electrospark machining of the electrical conductive substrate with the processing electrode of the following compositions (wt. %):
bioactive additive 5-40,
antibacterial metallic additive 0.5-5
biocompatible additive of metal or a refractory compound: balance.
Electrospark machining is carried out under the following conditions:
100 < Ni < 10 000
Figure imgf000004_0001
where Nj is the power of a unit pulse discharge, W; f is the frequency of pulse discharges, Hz; v is the linear speed of the processing electrode, m/min.
The electrical conductive substrate is made of medical purpose alloys based on Ti, Ni, Fe, Zr, Nb, Ta.
The bioactive additive is hydroxylapatite and/or tricalciumphosphate and/or calcium oxide and/or titanium dioxide.
The antibacterial metallic additive is silver and/or copper.
The biocompatible additive of metal is titanium and/or zirconium and/or hafnium and/or tantalum.
The biocompatible additive of a refractory compound is carbide and/or carbonitnde and/or oxycarbonitride of titanium and/or zirconium and/or hafnium and/or tantalum.
Electrospark machining is carried out in an atmosphere of argon, helium or nitrogen.
Electrospark machining is carried out in a liquid selected from ethyl alcohol or distilled water or normal saline or Ringer solution.
Embodiments of the Invention. The invention implemented as follows.
Coatings are applied using electrospark machining equipment.
The implant acting as the electrical conductive substrate is placed in a special box so the implant and the working part of the processing electrode are in the protective atmosphere.
The tool with the processing electrode installed thereon, which comprises the bioactive additive, the antibacterial metallic additive and the biocompatible additive of metal in the abovementioned ratios, as well as the implant, are connected to the plant power unit.
As the processing electrode approaches the implant an electric discharge occurs followed by electric erosion of the processing electrode material and polarized transfer of erosion products onto the implant surface. The bioactive coating with antibacterial effect forms due to the processing electrode scans the implant surface at the preset rate, discharge power and frequency.
The coating roughness is controlled by the protective environment in which electrospark machining is carried out, e.g. gaseous or liquid.
Gaseous environment for electrospark machining can be argon, helium or nitrogen.
Liquid environment for electrospark machining can be ethyl alcohol or distilled water or H20-NaCl normal saline or Ringer solution.
Bioactivity of the coating is achieved by inclusion into the electrode material of bioactive additives in the form of inorganic compounds or mixtures thereof, more specifically hydroxylapatite Cai0(PO4)6(OH)2 and/or tricalciumphosphate Ca3(P04)2 and/or calcium oxide CaO and/or titanium dioxide Ti02 in quantities of 5-40 wt.%.
Introduction of a bioactive additive in a quantity of less than 5 wt.% does not increase the bioactivity of the resultant coating.
Introduction of a bioactive additive in a quantity of more than 40 wt.% causes a drastic increase in the inhomogeneity of the resultant coating, reduction of its continuity and a large scatter of roughness.
The antibacterial effect of the coating is achieved by inclusion into the electrode material of an antibacterial metallic additive in a quantity of 0.5-5 wt.%, e.g. silver and/or copper.
Introduction of an antibacterial additive in a quantity of less than 0.5 wt.% does not produce antibacterial effect of the resultant coating. Furthermore it is a complex technical task to provide for a homogeneous distribution of such a small quantity of an additive in the bulk of the electrode.
Introduction of an antibacterial additive in a quantity of more than 5 wt.% may produce toxic effects and even cause fatality.
The basis of the electrode material used for obtaining bioactive coatings with antibacterial effect is selected from biocompatible metals titanium Ti and/or zirconium Zr and or hafnium Hf and or tantalum Ta. The basis of the electrode material used for obtaining bioactive coatings with antibacterial effect is selected from biocompatible refractory compounds carbide and/or carbonitride and/or oxycarbonitride of titanium and/or zirconium and/or hafnium and/or tantalum.
The range of electrospark machining parameters used for the implementation of the method was selected based on the following.
If the power of unit pulse discharges is less than 100 W then electrospark machining is unstable. The resultant coatings have low density and minimum roughness. At these process parameters the distribution of bioactive and antibacterial additives in the surface layer can be inhomogeneous causing bioactivity and antibacterial effect.
If the power of unit pulse discharges used for electrospark machining is greater than 10 000 W the electrode material heats excessively and as a result undergoes erosion in the form of large liquid drops and particles. Those particles cannot adhere sufficiently to the substrate surface. The resultant coating has high roughness and insufficient density.
There is the possibility that poorly bound particles may break off the coating during the use of the implant into the patient's body.
Furthermore, excessive electrode heating may reduce coating material hardness and increase its plasticity resulting in the loss of the electrode shape and preventing its further operation. And there is excessive consumption of the electrode material.
Electrospark machining at a pulse discharge frequency of less than 10 Hz reduces process output. In this case continuous and homogeneous coatings require greater processing time.
However, increasing pulse discharge frequency to above 100,000 Hz forms coatings with minimum roughness and thickness of within 10 um. A coating with minimum roughness does not have a well-developed surface and does not improve the medico-biological characteristics of the product (bioactivity and antibacterial effect). Electrospark machining at a processing electrode linear speed of less than 0.01 m/min reduces the output of bioactive coating production.
However, if the linear speed of the processing electrode is greater than 0.6 m/min the coatings are incontinuous and contain an inhomogeneous distribution of bioactive and antibacterial additions on the implant surface.
The physical, mechanical and biological properties of bioactive coatings were studied using specialized precision tools.
The model system used for the biological studies was MC3T3-E1 line osteoblasts grown on the surface of the test materials.
Cell adhesion followed by spreading on the substrate surface is the first phase of cell interaction with the implant and therefore the quality of this phase is of a decisive importance for the biocompatibility of a material.
Morphological analysis of cell spreading area on the coating surface showed that the osteoblasts spread well on the surface of the test specimens. Immune and morphological study of the actin cytoskeleton showed no cytoskeleton destruction.
A quantitative colorimetric method with the use of alkaline phosphatase as a early cell differentiation marker was also used for assessing the ability of the coatings to affect MC3T3-E1 osteoblast differentiation for growth in a differentiating media. The studies showed that osteoblasts growing on the coating surfaces are capable of differentiation. After two-week growth of MC3T3-E1 osteoblasts their quantitative colorimetric analysis showed a higher level activity of alkaline phosphatase in cells growing on coatings surfaces compared with the reference (a specimen without a titanium alloy coating).
The test bacterial cultures for studying the bactericide activity of the coatings were E. Coli coliform bacteria. We measured the quantity of bacteria surviving after 24 h (as the antibacterial activity parameter we accepted the percentage of surviving bacteria compared with the reference specimen (the one without the antibacterial addition)).
Electrospark machining at the abovementioned parameters ensures stable synthesis of bioactive coatings with antibacterial effect without defects in the form of closed pores or cracks with the preset roughness and chemical composition, high adhesion, continuity and wear resistance.
Tables 1 and 2 show embodiments of the method and the dependence of bioactive coating parameters on the preset range of electrospark machining parameters for a similar set of electrode materials.
The tables suggest that the coatings have high adhesion (critical load) in excess of 100 N, high operation properties e.g. wear resistance, preset roughness R max 1.5-85.1 um and thicknesses of 15-90 um. The medical and biological properties of the coatings, i.e. bioactivity and antibacterial effect, are confirmed by:
- absence of damage to the actin cytoskeleton of cells on coating surfaces;
- higher activity of alkaline phosphatase;
- lower concentration of coli.
Figure imgf000009_0001
Figure imgf000010_0001
Figure imgf000011_0001

Claims

Claimed is a
1. Method of obtaining bioactive coatings with antibacterial effect comprises electrospark machining of the electrical conductive substrate with the processing electrode of the following compositions (wt. %):
bioactive additive 5-40,
antibacterial metallic additive 0.5-5,
biocompatible additive of metal or a refractory compound: balance, wherein electrospark machining is carried out under the following conditions:
Figure imgf000012_0001
where Nj is the power of a unit pulse discharge, W; f is the frequency of pulse discharges, Hz; and v is the linear speed of the processing electrode, m/min.
2. Method of Claim 1 wherein said electrical conductive substrate is made from medical purpose alloys based on Ti, Ni, Fe, Zr, Nb, Ta.
3. Method of Claim 1 wherein said bioactive additive is hydroxylapatite and/or tricalciumphosphate and/or calcium oxide and/or titanium dioxide.
4. Method of Claim 1 wherein said antibacterial metallic additive is silver and/or copper.
5. Method of Claim 1 wherein said biocompatible additive of metal is titanium and/or zirconium and/or hafnium and/or tantalum.
6. Method of Claim 1 wherein said biocompatible additive of a refractory compound is carbide and/or carbonitride and/or oxycarbonitride of titanium and/or zirconium and/or hafnium and/or tantalum.
7. Method of Claim 1 wherein electrospark machining is carried out in an atmosphere of argon, helium or nitrogen.
8. Method of Claim 1 wherein electrospark machining is carried out in a liquid selected from ethyl alcohol or distilled water or normal saline or Ringer solution.
PCT/RU2015/000055 2014-10-21 2015-01-30 Method of producing the bioactive coating with antibacterial effect WO2016064296A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115120783A (en) * 2022-06-29 2022-09-30 湖南华翔医疗科技有限公司 Porous titanium-based antibacterial active material, and preparation method and application thereof

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