CN106756765B - A kind of fluorine-containing antimicrobial coating of metal material surface and preparation method thereof - Google Patents
A kind of fluorine-containing antimicrobial coating of metal material surface and preparation method thereof Download PDFInfo
- Publication number
- CN106756765B CN106756765B CN201611082593.6A CN201611082593A CN106756765B CN 106756765 B CN106756765 B CN 106756765B CN 201611082593 A CN201611082593 A CN 201611082593A CN 106756765 B CN106756765 B CN 106756765B
- Authority
- CN
- China
- Prior art keywords
- metal material
- fluorine
- plasma
- material surface
- antimicrobial coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
-
- 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
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/28—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases more than one element being applied in one step
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
- C23C8/38—Treatment of ferrous surfaces
-
- 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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
-
- 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
- A61L2420/02—Methods for coating medical devices
Abstract
A kind of fluorine-containing antimicrobial coating of metal material surface and preparation method thereof, belongs to antibacterial surface processing technology field；Coating composition includes oxygen element, fluorine element, R-F compound and R-O compound, and the coating has nanoscale hole hole structure and/or nanoscale bulge-structure；Wherein, R is one of titanium, titanium alloy, stainless steel, cobalt alloy, magnesium alloy or kirsite；Preparation method: 1) surface preparation；2) vacuum prepares；3) argon plasma cleans；4) fluorination treatment: while argon gas, oxygen and carbon tetrafluoride gas are passed through into plasma-reaction-chamber, fluorination treatment is carried out, plasma treatment metal material is made；The fluorine-containing antimicrobial coating of the present invention, can dissolve out fluorine ion when contacting with bacterium solution or other body fluid, have bactericidal effect, achieve the effect that antibacterial；The method of the present invention can get the medical use anti-infection metal material that will not generate cytotoxicity, solve the problems, such as bacterium infection relevant to metal implantation instrument in clinic.
Description
Technical field
The invention belongs to antibacterial surface processing technology fields, and in particular to a kind of fluorine-containing antimicrobial coating of metal material surface and
Preparation method.
Background technique
Conventional medical metal implant material (such as stainless steel, titanium and its alloy, cobalt alloy) have good biocompatibility,
Corrosion resistance under good comprehensive mechanical property and biotic environment, has been widely used in clinic, such as artificial root of the tooth, and tooth is rectified
Positive silk, molar crown bridge, metal gum, denture fixing device, jawbone, backbone and Bones and joints implantation material etc..But the gold for medical treatment
Belong to implantation material and find following point occur in use:
1) surgery artificial prosthesis, even if in strict implement operation sterile working and systemic prophylaxis anti-inflammatory treatment premise
Under, it is for a long time always puzzlement medical worker since the infection that metal implant causes still causes very high disease incidence
One thorny problem.Data shows: full marrow joint replacement postoperative infection rate is 0.1%-1%；Complete knee joint infection rate is 1%-
4%；And full elbow joint is 4%-47%；The infection rate of eyes bypass is up to 4%-30%.
2) with the treatment of metal implant infections relating: implantation material infections relating once occur, treat it is very intractable.It plants
Enter object surface bacterial adhesion, breeding occur and form biomembrane, may imply the generation of infection, local organization is caused to be destroyed,
The whole body of pathogen sends out the failure with implantation material, and it is even dead to even result in serious disease.In most cases, take out or
Replacing the implantation material of infection and combining systemic large dosage antibiotic and antifungal drug treatment is most effective treatment.And for
The implantation material infected patient of infeasible operative treatment, prolonged antibiotic suppression therapy are its unique selections.Thus make metal
The bacterium infection problem that there is implantation material itself antibiotic property can efficiently solve metal surface, raising is implanted to power, to changing
Kind patients ' life quality is of great significance.
Currently, antibacterial metallic materials include the modified antibacterial metallic materials in surface and two type of monolithic devices antibacterial metallic materials
Type.Monolithic devices antibacterial metallic materials often pass through the metals (or its ion) such as incorporation inorganic antiseptic silver, copper during the preparation process,
Lasting effective anti-microbial property can be played without being surface modified.The preparation major part base of market-oriented monolithic devices anti-biotic material
In processes such as smelting (such as anti-bacteria stainless steel, antibacterial titanium alloy), sintering (anti-bacteria ceramic, antibacterial titanium alloy), they require investment
Greatly, time-consuming, complex process etc..And material is surface-treated to reach the method for antibacterial requirement and there is simple process, behaviour
The characteristics of making convenience, being of relatively low cost.The modified antibacterial metallic materials in surface mainly pass through organic and inorganic antiseptic carry out table
Face modification assigns traditional metal materials different degrees of anti-microbial property.
The existing metal surface antimicrobial treatment technology for having disclosed report has: applying on metal implant electroplate, surface
Organic anti-bacterial coating containing antibiotic medicine, in TiO2In coating add Ag ion and Cu ion, in metal material table
Wheat flour injects copper or silver for argentum-carried hydroxylapatite layer, on surface to obtain antibiotic property.It is in the preparation of above-mentioned anti-biotic material
Reach ideal antibacterial effect, needs the antibiotic containing certain content, Ag or Cu element antimicrobial coating, but antibiotic antibacterial
That there are antimicrobial spectrums is limited for agent itself, high temperature resistance is poor, faces drug resistance risk, when coating fastness is difficult to ensure, coating is effective
Between be difficult to the defects of lasting, and the light sensitive effect of silver is very strong, easily changes colour when meeting illumination or long-term preservation, and higher cost,
These elements can generate dissolution metal ion in the subsequent use process simultaneously, be likely to result in biocompatibility issues.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of fluorine-containing antimicrobial coating of metal material surface and its preparation sides
Method, on existing medical metal material surface, progress plasma is fluorinated modified, to assign the metal material bacterial-infection resisting function；
The method of the present invention can be widely applied to all kinds of metal medical appliances used in the clinical medicines such as orthopaedics, department of stomatology field, solve
The bacterium infection caused in existing clinic by the implantation of medical metal medical instrument.
The fluorine-containing antimicrobial coating of metal material surface of the invention, the coating composition includes oxygen element, fluorine element, R-Fization
Object and R-O compound are closed, the coating has nanoscale hole hole structure and/or nanoscale bulge-structure；Wherein, R is titanium, titanium conjunction
The volume of one of gold, stainless steel, cobalt alloy, magnesium alloy or kirsite, nanoscale hole hole structure and/or nanoscale protrusion accounts for
The 30~70% of coating volume.
The fluorine-containing antimicrobial coating of the metal material surface, matrix in connection are metal material R, and R is titanium, titanium conjunction
One of gold, stainless steel, cobalt alloy, magnesium alloy or kirsite.
The fluorine-containing antimicrobial coating of the metal material surface, the ruler of nanoscale hole hole structure and/or nanoscale bulge-structure
Very little is 50~500nm.
The R-F compound is that oxygen and metal material matrix react the R-F compound to be formed.
The R-O compound is that oxygen and metal material matrix react the R-O compound to be formed.
The fluorine-containing antimicrobial coating of the metal material surface, it is equal to the antibiotic rate of staphylococcus aureus and Escherichia coli
Greater than 99%；
The fluorine-containing antimicrobial coating of the metal material surface, during antibacterial, R-F compound releases fluorine ion, from
And reach bactericidal effect.
The preparation method of the fluorine-containing antimicrobial coating of metal material surface of the invention, using controlled atmosphere plasma material table
Surface treatment device, preparation the following steps are included:
Step 1, surface preparation:
The greasy dirt and oxide layer for removing metal material, keep metal material surface smoothly clean；
Step 2, vacuum prepares:
Metal material is placed in the plasma-reaction-chamber of controlled atmosphere plasma material surface processing device,
It is vacuumized using vacuum pump plasma reaction chamber, until vacuum degree≤1 × 10-2Pa；
Step 3, argon plasma cleans:
(1) argon gas is passed through to plasma-reaction-chamber with 5~20sccm flow, adjusts vacuum pump, keeps plasma anti-
Answer the vacustat of room in 5~50Pa；
(2) radio frequency discharge and direct-current discharge are opened, at the same adjust vacuum pump make the vacuum degree 5 of plasma-reaction-chamber~
50Pa, when radio-frequency power, ionization voltage and stable vacuum degree, be denoted as argon plasma cleaning starting point, altogether clean 10~
Argon plasma cleaning is completed after 60min；Wherein, radio-frequency power is 100~200W, and ionization voltage is 400~1000V；
Step 4, fluorination treatment:
(1) it is passed through argon gas, oxygen and carbon tetrafluoride gas into plasma-reaction-chamber simultaneously, is adjusted by vacuum pump,
Make the vacustat of plasma-reaction-chamber in 5~50Pa；Wherein, argon flow is 5~20sccm, carbon tetrafluoride gas stream
Amount is 1~5.0sccm, the flow of oxygen: argon flow=0~2.5；
(2) radio frequency discharge and direct-current discharge are adjusted, 150~300W of radio-frequency power is made, ionization voltage is 400~1000V；
Vacuum pump is adjusted, 5~50Pa of vacuum degree of plasma-reaction-chamber is made；When radio-frequency power, ionization voltage and vacuum degree are steady
Periodically, it is denoted as the starting point of fluorination treatment, fluorination treatment is completed after 30~60min of coprocessing, and plasma treatment metal material is made.
In above-mentioned metal material surface antibacterial processing method:
In the step 1, the method for removing the oxide layer of metal material is the chemistry handled using mechanical grinding or soda acid
Method.
In the step 1, metal material is one of titanium, titanium alloy, stainless steel, cobalt alloy, magnesium alloy or kirsite.
In the metal material surface antibacterial processing method, plasma is realized by adjusting the angle valve of vacuum pump
The control of reaction chamber vacuum degree.
The concrete operations of the step 2 are as follows: by metal material in controlled atmosphere plasma material surface processing equipment
After plasma-reaction-chamber places, plasma-reaction-chamber hatch door and vent valve are closed；And successively open total power switch,
Mechanical pump control switch, valve, vacuum meter reading plotter switch, until opening molecule as vacuum chamber internal pressure≤10Pa
The power supply of pump simultaneously brings into operation, until vacuum degree≤1 × 10 of vacuum chamber-2Pa。
In the step 3, adjusting high-purity argon gas flow by mass flowmenter is 5~10sccm.
In the step 3, radio-frequency power supply is opened, adjusting radio-frequency power is 100~200W.
In the step 3, ionization power supply is opened, starts direct-current discharge, adjusting ionization voltage is 400~1000V.
In the step 3 and step 4, argon gas is the high-purity argon gas of purity >=99.9%.
In the step 4, oxygen is the high purity oxygen gas of purity >=99.9%.
In the step 4, carbon tetrafluoride gas is the high-pure carbon tetrafluoride gas of purity >=99.9%.
In the step 4, the flow of various gases is adjusted by mass flowmenter.
The preparation method of the fluorine-containing antimicrobial coating of metal material surface through the invention, metal surface antimicrobial treatment are to pass through
The method of plasma treatment forms one layer of fluorine-containing coat with antibacterial activity in metal surface, when what is be modified by this method
Metal material surface and bacterium solution or other body fluid will dissolve out fluorine ion when contacting, fluorine ion has strong bactericidal effect；
When bacterium and these fluorine ions contact, will be killed, to achieve the effect that metal material antibacterial.
The preparation method of the fluorine-containing antimicrobial coating of metal material surface of the invention is a kind of plasma surface antimicrobial treatment
Method adds Direct current plasma enhanced chemical vapour deposition equipment using using radio frequency, argon that vacuum glow discharge generates, oxygen and
Fluoro plasma bombards metal surface, obtains anti-microbial property.
The beneficial effect of the fluorine-containing antimicrobial coating of metal material surface of the invention and preparation method thereof is: utilizing fluorine plasma
The method that body handles metal material surface obtains the medical use anti-infection metal new material with broad spectrum antibiotic activity, and will not
Generate cytotoxicity；The invention discloses a kind of method of metal surface modification and obtained modified metal materials, solve existing
Bacterium infection problem relevant to metal implantation instrument in clinic.Method of the invention is generated using vacuum glow discharge
Argon, oxygen and fluoro plasma carry out fluorination treatment to metal surface, and treated metal material is to Escherichia coli and golden yellow Portugal
Grape coccus all has significant inhibitory effect.Suitable for all Treatment of Metal Surface including medical titanium alloy and stainless steel；It can
For medical domain or daily necessities field.
Detailed description of the invention
The structural schematic diagram of the P150B controlled atmosphere plasma material surface processing device of Fig. 1 embodiment of the present invention；Its
In, 1- vacuum pump, the first valve of 2-, 3- plasma-reaction-chamber, the second valve of 4-, 5- first flowmeter, 6- second flowmeter,
7- third flowmeter, the first gas cylinder of 8-, the second gas cylinder of 9-, 10- third gas cylinder, 11- vacuum meter reading plotter, 12- radio-frequency power supply
Operating device, 13- ionize power operation device；
The stereoscan photograph of the fluorine-containing antimicrobial coating of metal material surface prepared by Fig. 2 embodiment of the present invention 1；
The experiment knot of the anti-Staphylococcus aureus of the fluorine-containing antimicrobial coating of the metal material surface of Fig. 3 embodiment of the present invention 1
Fruit；Wherein, control sample is common glass sheet in figure；
The stereoscan photograph of the fluorine-containing antimicrobial coating of metal material surface prepared by Fig. 4 embodiment of the present invention 2；
The experiment knot of the anti-Staphylococcus aureus of the fluorine-containing antimicrobial coating of the metal material surface of Fig. 5 embodiment of the present invention 2
Fruit；Wherein, control sample is common glass sheet in figure；
The stereoscan photograph of the fluorine-containing antimicrobial coating of metal material surface prepared by Fig. 6 embodiment of the present invention 3；
The experiment knot of the anti-Staphylococcus aureus of the fluorine-containing antimicrobial coating of the metal material surface of Fig. 7 embodiment of the present invention 3
Fruit；Wherein, control sample is common glass sheet in figure；
The stereoscan photograph of the fluorine-containing antimicrobial coating of metal material surface prepared by Fig. 8 embodiment of the present invention 4；
The experiment knot of the anti-Staphylococcus aureus of the fluorine-containing antimicrobial coating of the metal material surface of Fig. 9 embodiment of the present invention 4
Fruit；Wherein, control sample is common glass sheet in figure；
Specific embodiment
Following embodiment, pure titanium refer to that the titanium of mass content >=99.9%, stainless steel refer to that 304 medical food grades are stainless
Steel.
Following embodiment, plasma enhanced chemical vapor deposition (PECVD) technique is in such a way that radio frequency adds direct current
Generate plasma.
Following embodiment, argon gas volumetric concentration >=99.999% of high-purity Ar, high-purity O2Oxygen volumetric concentration >=
99.999%；Carbon tetrafluoride gas volumetric concentration >=99.999% of high-pure carbon tetrafluoride gas.
Following embodiment, the device model of use are as follows: Branch Tech F-100/150 type turbomolecular pump；2.4L/S mechanical
Pump, Shanghai Foster；XG52-T type resistance vacuum gauge.
The controlled atmosphere plasma material surface processing equipment that following embodiment uses is P150B controlled atmosphere etc. from
Daughter material surface processing unit, structural schematic diagram are as shown in Figure 1；The composition of described device includes vacuum pump 1, the first valve
2, plasma-reaction-chamber 3, the second valve 4, first flowmeter 5, second flowmeter 6, third flowmeter 7, the first gas cylinder 8, the
Two gas cylinders 9, third gas cylinder 10, vacuum meter reading plotter 11, radio-frequency power supply operating device 12 and ionization power operation device 13；Institute
The vacuum pump 1 stated is connected by the first valve 2 with one end of plasma-reaction-chamber 3, the other end point of plasma-reaction-chamber 3
Not with the first gas cylinder 8, the second gas cylinder 9 is connected with third gas cylinder 10, is provided between plasma-reaction-chamber 3 and the first gas cylinder 8
First flowmeter 5, is provided with second flowmeter 6 between plasma-reaction-chamber 3 and the second gas cylinder 9, plasma-reaction-chamber 3 with
It is provided with third flowmeter 7 between third gas cylinder 10, first flowmeter 5, second flowmeter 6 and third flowmeter 7 are by the
Two valves 4 are connected with plasma-reaction-chamber 3, and vacuum meter reading plotter 11 is connected with plasma-reaction-chamber 3, radio-frequency power supply behaviour
Make device 12 to be connected with plasma-reaction-chamber 3, ionization power operation device is connected with plasma-reaction-chamber 3.
First valve 2 is the valve for connecting vacuum pump；Second valve 3 is the main valve for connecting three gas cylinders
Door.
First gas cylinder 8 is high-purity argon gas gas cylinder, and the second gas cylinder 9 is high purity oxygen gas gas cylinder, and third gas cylinder 10 is height
Pure carbon tetrafluoride gas gas cylinder.
The vacuum meter reading plotter 11 is XG52-T type resistance vacuum gauge.
The vacuum pump 1 is by Branch Tech F-100/150 type turbomolecular pump and 2.4L/S mechanical pump (Shanghai Fox
It is special) composition.
Embodiment 1
A kind of fluorine-containing antimicrobial coating of metal material surface, the coating composition includes fluorine element, R-F compound, the painting
Layer has nanoscale hole hole；Wherein, R is titanium, and the size of nanoscale hole hole is 50~200nm, and the volume of nanoscale hole hole accounts for painting
The 60% of layer volume.
The preparation method of above-mentioned metal material titanium fluorine-contained surface antimicrobial coating, using P150B controlled atmosphere plasma
Material surface processing unit, preparation the following steps are included:
Step 1, surface preparation:
The chemical method handled using mechanical grinding or soda acid, is removed the greasy dirt and oxide layer of metal material, makes metal material
Expect that smooth surface is clean；
Step 2, vacuum prepares:
Metal material is placed in the plasma-reaction-chamber of controlled atmosphere plasma material surface processing device,
It is vacuumized using vacuum pump plasma reaction chamber, its vacuum degree≤1 × 10 is controlled by the first valve regulated-2Pa；
Close plasma-reaction-chamber hatch door and the second valve；And successively open total power switch, mechanical pump control switch,
First valve, resistance vacuum gauge 11, when plasma-reaction-chamber internal pressure≤10Pa, open the power supply of molecular pump and open
Begin to run, until vacuum degree≤1 × 10 of plasma-reaction-chamber-2Pa；
Step 3, argon plasma cleans:
(1) high-purity argon gas gas cylinder is controlled by first flowmeter 5, argon is passed through to plasma-reaction-chamber with 20sccm flow
Gas adjusts vacuum pump, makes the vacustat of plasma-reaction-chamber in 20Pa；
(2) radio frequency discharge and direct-current discharge are opened, while adjusting vacuum pump to make the vacuum degree of plasma-reaction-chamber
20Pa is denoted as argon plasma cleaning starting point, cleans 30min altogether when radio-frequency power, ionization voltage and stable vacuum degree
Argon plasma cleaning afterwards is completed；Wherein, radio-frequency power 150W, ionization voltage 700V；
Step 4, fluorination treatment:
(1) high-purity argon gas gas cylinder is controlled by first flowmeter 5, high purity oxygen gas gas cylinder is controlled by second flowmeter 6, is led to
It crosses third flowmeter 7 and controls high-pure carbon tetrafluoride gas gas cylinder, while being passed through argon gas, oxygen and four into plasma-reaction-chamber
Carbon fluoride gas is adjusted by vacuum pump, makes the vacustat of plasma-reaction-chamber in 20Pa；Wherein, argon flow is
18sccm, carbon tetrafluoride gas flow are 2.0sccm, the flow of oxygen: argon flow=0；
(2) radio frequency discharge and direct-current discharge are adjusted, radio-frequency power 150W, ionization voltage 700V are made；Vacuum pump is adjusted,
Make the vacuum degree 20Pa of plasma-reaction-chamber；When radio-frequency power, ionization voltage and stable vacuum degree, it is denoted as at fluorination
The starting point of reason, fluorination treatment is completed after coprocessing 60min, and plasma treatment metal material is made.
The stereoscan photograph that the present embodiment prepares the fluorine-containing antimicrobial coating of metal material surface is as shown in Figure 2.
The fluorine-containing antimicrobial coating of metal material surface manufactured in the present embodiment, the anti-gold of the fluorine-containing antimicrobial coating of metal material surface
Staphylococcus aureus experimental result is shown in Fig. 3,99% is all larger than to the antibiotic rate of staphylococcus aureus and Escherichia coli.
The fluorine-containing antimicrobial coating of metal material surface manufactured in the present embodiment, during antibacterial, R-F compound releases fluorine
Ion, to reach bactericidal effect.
Embodiment 2
A kind of fluorine-containing antimicrobial coating of metal material surface, the coating composition includes oxygen element, fluorine element, R-F compound
With R-O compound, the coating has nanoscale bulge-structure；Wherein, R is titanium, the size of nanoscale bulge-structure is 100~
300nm, the volume of nanoscale hole hole account for the 50% of coating volume.
The preparation method of above-mentioned metal material titanium fluorine-contained surface antimicrobial coating, using device with embodiment 1, preparation method
Difference with embodiment 1 is to be passed through argon gas, oxygen and carbon tetrafluoride gas into plasma-reaction-chamber simultaneously in step 4
Body, wherein argon flow 20sccm, carbon tetrafluoride gas flow are 2.0sccm, the ratio of argon gas and oxygen are as follows: 1, other
Part is identical with embodiment 1.
The stereoscan photograph that the present embodiment prepares the fluorine-containing antimicrobial coating of metal material surface is as shown in Figure 4.
The fluorine-containing antimicrobial coating of metal material surface manufactured in the present embodiment, the anti-gold of the fluorine-containing antimicrobial coating of metal material surface
Staphylococcus aureus experimental result is shown in Fig. 5,99% is all larger than to the antibiotic rate of staphylococcus aureus and Escherichia coli.
The fluorine-containing antimicrobial coating of metal material surface manufactured in the present embodiment, during antibacterial, R-F compound releases fluorine
Ion, to reach bactericidal effect.
Embodiment 3
A kind of fluorine-containing antimicrobial coating of metal material surface, the coating composition includes oxygen element, fluorine element, R-F compound
With R-O compound, the coating has nanoscale hole hole and nanoscale protrusion composite construction；Wherein, R is titanium, nanoscale hole hole
Size be 50~100nm, the size of nanoscale protrusion is 50~100nm, nanoscale hole hole and nanoscale protrusion composite construction
Account for the 40% of coating volume.
The preparation method of above-mentioned metal material titanium fluorine-contained surface antimicrobial coating, using device with embodiment 1, preparation method
Difference with embodiment 1 is passed through argon gas, oxygen and carbon tetrafluoride gas into plasma-reaction-chamber while being in step 4
Body, wherein argon flow 5sccm, carbon tetrafluoride gas flow are 5.0sccm, the ratio of argon gas and oxygen are as follows: 1, other portions
Divide identical with embodiment 1.
The stereoscan photograph that the present embodiment prepares the fluorine-containing antimicrobial coating of metal material surface is as shown in Figure 6.
The fluorine-containing antimicrobial coating of metal material surface manufactured in the present embodiment, the anti-gold of the fluorine-containing antimicrobial coating of metal material surface
Staphylococcus aureus experimental result is shown in Fig. 7,99% is all larger than to the antibiotic rate of staphylococcus aureus and Escherichia coli.
The fluorine-containing antimicrobial coating of metal material surface manufactured in the present embodiment, during antibacterial, R-F compound releases fluorine
Ion, to reach bactericidal effect.
Embodiment 4
A kind of fluorine-containing antimicrobial coating of metal material surface, the coating composition includes oxygen element, fluorine element, R-F compound
With R-O compound, the coating has nanoscale bulge-structure；Wherein, R is titanium, the size of nanoscale protrusion is 50~
200nm, the volume of nanoscale hole hole account for the 55% of coating volume.
The preparation method of above-mentioned metal material titanium fluorine-contained surface antimicrobial coating, using device with embodiment 1, preparation method
Difference with embodiment 1 is passed through argon gas, oxygen and carbon tetrafluoride gas into plasma-reaction-chamber while being in step 4
Body, wherein argon flow 10sccm, carbon tetrafluoride gas flow are 1.0sccm, the ratio of argon gas and oxygen are as follows: 1, other
Part is identical with embodiment 1.
The stereoscan photograph that the present embodiment prepares the fluorine-containing antimicrobial coating of metal material surface is as shown in Figure 8.
The fluorine-containing antimicrobial coating of metal material surface manufactured in the present embodiment, the anti-gold of the fluorine-containing antimicrobial coating of metal material surface
Staphylococcus aureus experimental result is shown in Fig. 9,99% is all larger than to the antibiotic rate of staphylococcus aureus and Escherichia coli.
The fluorine-containing antimicrobial coating of metal material surface manufactured in the present embodiment, during antibacterial, R-F compound releases fluorine
Ion, to reach bactericidal effect.
Embodiment 5
A kind of fluorine-containing antimicrobial coating of metal material surface, the coating composition includes fluorine element, R-F compound, the painting
Layer has nanoscale hole hole；Wherein, R is titanium, and the size of nanoscale hole hole is 50~90nm, and the volume of nanoscale hole hole accounts for coating
The 45% of volume.
The preparation method of above-mentioned metal material titanium fluorine-contained surface antimicrobial coating, using device with embodiment 1, preparation method
Difference with embodiment 1 is that the radio-frequency power in step 4 is 150W, and other parts are identical with embodiment 1.
Embodiment 6
A kind of fluorine-containing antimicrobial coating of metal material surface, the coating composition includes fluorine element, R-F compound, the painting
Layer has nanoscale hole hole；Wherein, R is titanium, and the size of nanoscale hole hole is 100~250nm, and the volume of nanoscale hole hole accounts for painting
The 56% of layer volume.
The preparation method of above-mentioned metal material titanium fluorine-contained surface antimicrobial coating, using device with embodiment 1, preparation method
Difference with embodiment 1 is that the radio-frequency power in step 4 is 300W, and other parts are identical with embodiment 1.
Embodiment 7
A kind of fluorine-containing antimicrobial coating of metal material surface, the coating composition includes oxygen element, fluorine element, R-F compound
With R-O compound, the coating has nanoscale hole hole and nanoscale protrusion composite construction；Wherein, R is titanium, nanoscale hole hole
Size with protrusion is 100~200nm, and the volume of nanoscale hole hole accounts for the 48% of coating volume.
The preparation method of above-mentioned metal material titanium fluorine-contained surface antimicrobial coating, using device with embodiment 2, preparation method
Difference with embodiment 2 is that the ionization voltage in step 4 is 400V, and other parts are identical with embodiment 2.
Embodiment 8
A kind of fluorine-containing antimicrobial coating of metal material surface, the coating composition includes oxygen element, fluorine element, R-F compound
With R-O compound, the coating has nanoscale hole hole；Wherein, R is titanium, and the size of nanoscale hole hole is 300~500nm, is received
The volume of meter level hole accounts for the 57% of coating volume.
The preparation method of above-mentioned metal material titanium fluorine-contained surface antimicrobial coating, using device with embodiment 2, preparation method
Difference with embodiment 2 is that the ionization voltage in step 4 is 1000V, and other parts are identical with embodiment 2.
Embodiment 9
A kind of fluorine-containing antimicrobial coating of metal material surface, the coating composition includes fluorine element, R-F compound, the painting
Layer has nanoscale hole hole；Wherein, R is titanium, and the size of nanoscale hole hole is 50~150nm, and the volume of nanoscale hole hole accounts for painting
The 40% of layer volume.
The preparation method of above-mentioned metal material titanium fluorine-contained surface antimicrobial coating, using device with embodiment 1, preparation method
Difference with embodiment 1 is that the operating pressure in step 4 is 5Pa, and other parts are identical with embodiment 1.
Embodiment 10
A kind of fluorine-containing antimicrobial coating of metal material surface, the coating composition includes oxygen element, fluorine element, R-F compound
With R-O compound, the coating has nanoscale bulge-structure；Wherein, R is titanium, the size of nanoscale bulge-structure is 300~
450nm, the volume of nanoscale hole hole account for the 70% of coating volume.
The preparation method of above-mentioned metal material titanium fluorine-contained surface antimicrobial coating, using device with embodiment 2, preparation method
Difference with embodiment 2 is that the operating pressure in step 4 is 50Pa, and other parts are identical with embodiment 2.
Embodiment 11
A kind of fluorine-containing antimicrobial coating of metal material surface, the coating composition includes oxygen element, fluorine element, R-F compound
With R-O compound, the coating has nanoscale bulge-structure；Wherein, R is titanium, the size of nanoscale bulge-structure is 70~
The volume of 100nm, nanoscale protrusion account for the 60% of coating volume.
The preparation method of above-mentioned metal material titanium fluorine-contained surface antimicrobial coating, using device with embodiment 2, preparation method
Difference with embodiment 2 is the flow of the oxygen in step 4: argon flow=2.5, other parts and embodiment 2 are complete
It is identical.
Embodiment 12
A kind of fluorine-containing antimicrobial coating of metal material surface, the coating composition includes fluorine element and R-F compound, the painting
Layer has nanoscale hole hole structure；Wherein, R is titanium, and the size of nanoscale hole hole structure is 40~100nm, nanoscale protrusion
Volume accounts for the 30% of coating volume.
The preparation method of above-mentioned metal material titanium fluorine-contained surface antimicrobial coating, using device with embodiment 1, preparation method
It is 30min that difference with embodiment 2, which is the fluorination treatment time in step 4, and other parts are identical with embodiment 1.
Embodiment 13
A kind of fluorine-containing antimicrobial coating of metal material surface, the coating composition includes fluorine element, R-F compound, the painting
Layer has nanoscale hole hole；Wherein, R is stainless steel, and the size of nanoscale hole hole is 100~200nm, the volume of nanoscale hole hole
Account for the 52% of coating volume.
The preparation method of above-mentioned metal material titanium fluorine-contained surface antimicrobial coating, using device with embodiment 1, preparation method
Difference with embodiment 1 is the metal material that uses for stainless steel, and other parts are identical with embodiment 1.
The antibacterial of stainless steel after corona treatment manufactured in the present embodiment to the Escherichia coli of staphylococcus aureus
Rate is all larger than 99%.
Claims (4)
1. a kind of fluorine-containing antimicrobial coating of metal material surface, which is characterized in that the coating composition includes R-F compound and R-O
Compound, the coating have nanoscale hole hole structure and/or nanoscale bulge-structure；Wherein, R be titanium, it is titanium alloy, stainless
The volume of one of steel, cobalt alloy, magnesium alloy or kirsite, nanoscale hole hole structure and/or nanoscale protrusion accounts for coating body
Long-pending 30 ~ 70%；The fluorine-containing antimicrobial coating of the metal material surface, matrix in connection are metal material R, and R is titanium, titanium
One of alloy, stainless steel, cobalt alloy, magnesium alloy or kirsite；The fluorine-containing antimicrobial coating of the metal material surface, nanometer
Grade hole configurations and/or nanoscale bulge-structure are 50 ~ 500nm.
2. the fluorine-containing antimicrobial coating of metal material surface according to claim 1, which is characterized in that the metal material table
The fluorine-containing antimicrobial coating in face is all larger than 99% to the antibiotic rate of staphylococcus aureus and Escherichia coli.
3. the preparation method of the fluorine-containing antimicrobial coating of metal material surface described in claim 1, using controlled atmosphere plasma
Material surface processing unit, which comprises the following steps:
Step 1, surface preparation:
The greasy dirt and oxide layer for removing metal material, keep metal material surface smoothly clean；Wherein, the oxidation of metal material is removed
The method of layer is the chemical method handled using mechanical grinding or soda acid；Metal material be titanium, titanium alloy, stainless steel, cobalt alloy,
One of magnesium alloy or kirsite；
Step 2, vacuum prepares:
It is placed on metal material in the plasma-reaction-chamber of controlled atmosphere plasma material surface processing device, utilizes
Vacuum pump plasma reaction chamber vacuumizes, until vacuum degree≤1 × 10-2Pa；
Step 3, argon plasma cleans:
(1) argon gas is passed through to plasma-reaction-chamber with 5 ~ 20sccm flow, adjusts vacuum pump, makes plasma-reaction-chamber
Vacustat is in 5 ~ 50Pa；Wherein, adjusting argon flow by mass flowmenter is 5 ~ 10sccm；
(2) radio frequency discharge and direct-current discharge are opened, at the same adjust vacuum pump make the vacuum degree 5 of plasma-reaction-chamber ~
50Pa, when radio-frequency power, ionization voltage and stable vacuum degree, be denoted as argon plasma cleaning starting point, altogether clean 10 ~
Argon plasma cleaning is completed after 60min；Wherein, radio-frequency power is 100 ~ 200W, and ionization voltage is 400 ~ 1000V；Wherein,
Radio-frequency power supply is opened, adjusting radio-frequency power is 100 ~ 200W；Ionization power supply is opened, direct-current discharge is started, adjusting ionization voltage is
400~1000V；
Step 4, fluorination treatment:
(1) it is passed through argon gas, oxygen and carbon tetrafluoride gas into plasma-reaction-chamber simultaneously, is adjusted, is made by vacuum pump
The vacustat of gas ions reaction chamber is in 5 ~ 50Pa；Wherein, argon flow is 5 ~ 20sccm, and carbon tetrafluoride gas flow is
0.5 ~ 5.0sccm, the flow of oxygen: argon flow=0 ~ 2.5；
(2) radio frequency discharge and direct-current discharge are adjusted, 150 ~ 300W of radio-frequency power is made, ionization voltage is 400 ~ 1000V；It adjusts
Vacuum pump makes 5 ~ 50Pa of vacuum degree of plasma-reaction-chamber；When radio-frequency power, ionization voltage and stable vacuum degree,
It is denoted as the starting point of fluorination treatment, fluorination treatment is completed after cleaning 30 ~ 60min altogether, and plasma treatment metal material is made.
4. the preparation method of the fluorine-containing antimicrobial coating of metal material surface according to claim 3, which is characterized in that described
Argon gas is the high-purity argon gas of purity >=99.9%；The oxygen is the high purity oxygen gas of purity >=99.9%；The carbon tetrafluoride
Gas is the high-pure carbon tetrafluoride gas of purity >=99.9%；In the step 4, various gases are adjusted by mass flowmenter
Flow.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611082593.6A CN106756765B (en) | 2016-11-30 | 2016-11-30 | A kind of fluorine-containing antimicrobial coating of metal material surface and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611082593.6A CN106756765B (en) | 2016-11-30 | 2016-11-30 | A kind of fluorine-containing antimicrobial coating of metal material surface and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106756765A CN106756765A (en) | 2017-05-31 |
| CN106756765B true CN106756765B (en) | 2019-06-25 |
Family
ID=58901406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611082593.6A Active CN106756765B (en) | 2016-11-30 | 2016-11-30 | A kind of fluorine-containing antimicrobial coating of metal material surface and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106756765B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109366967A (en) * | 2018-11-13 | 2019-02-22 | 广州市安旭特电子有限公司 | A kind of method and segment encode liquid crystal device for reducing the fitting of waterproofing protection film and generating bubble |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115487353A (en) * | 2022-09-16 | 2022-12-20 | 华东交通大学 | Antibacterial osteogenesis-promoting fluorine-doped tantalum oxide coating and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105597159A (en) * | 2016-01-15 | 2016-05-25 | 国家纳米科学中心 | Gold nano-particle based antibacterial product and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6767836B2 (en) * | 2002-09-04 | 2004-07-27 | Asm Japan K.K. | Method of cleaning a CVD reaction chamber using an active oxygen species |
-
2016
- 2016-11-30 CN CN201611082593.6A patent/CN106756765B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105597159A (en) * | 2016-01-15 | 2016-05-25 | 国家纳米科学中心 | Gold nano-particle based antibacterial product and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| "氟离子注入钛表面对骨细胞相容性和抗菌性能的影响";刘慧颖;《中国博士学位论文全文数据库 医药卫生科技辑》;20080810(第8期);第18-63页 |
| "钛及钛合金表面离子注入改性的研究进展";方蛟等;《实用口腔医学杂志》;20140731;第4卷(第30期);第561页左栏第13-26行 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109366967A (en) * | 2018-11-13 | 2019-02-22 | 广州市安旭特电子有限公司 | A kind of method and segment encode liquid crystal device for reducing the fitting of waterproofing protection film and generating bubble |
| CN109366967B (en) * | 2018-11-13 | 2021-07-23 | 广州市安旭特电子有限公司 | Method for reducing bubbles generated by attaching waterproof protective film and segment code liquid crystal device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106756765A (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102146577B (en) | Pure-titanium metal surface micro-arc oxidation treatment electrolyte and antimicrobial bioactive coating preparation method thereof | |
| Mihailescu et al. | Structural, compositional, mechanical characterization and biological assessment of bovine-derived hydroxyapatite coatings reinforced with MgF2 or MgO for implants functionalization | |
| Esfandiari et al. | Size tuning of Ag‐decorated TiO2 nanotube arrays for improved bactericidal capacity of orthopedic implants | |
| CN106756765B (en) | A kind of fluorine-containing antimicrobial coating of metal material surface and preparation method thereof | |
| Lee et al. | ZrO2/ZnO/TiO2 nanocomposite coatings on stainless steel for improved corrosion resistance, biocompatibility, and antimicrobial activity | |
| CN102677125A (en) | Preparation method of active antibacterial composite coating on surface of titanium and titanium alloy medical instrument | |
| CN101869725B (en) | Antibacterial bioactivity composite coating comprising nano Ag particles and preparation method | |
| CN101073675A (en) | Antiseptic biological active titanium coating and its production | |
| CN102758202A (en) | Method for preparing biomedical titanium and titanium alloy surface antibacterial coatings | |
| EP2398517A2 (en) | Antibacterial surface and method of fabrication | |
| CN108904893A (en) | A kind of composite coating and its preparation method and application having both antibacterial and biocompatibility | |
| CN102912335A (en) | Surface modified medical metal material and preparation method thereof | |
| CN103834945A (en) | Titanium oxide composite coating and preparation method thereof | |
| Zhao et al. | Plasma-sprayed ZnO/TiO 2 coatings with enhanced biological performance | |
| Uhm et al. | Fabrication of bioactive, antibacterial TiO2 nanotube surfaces, coated with magnetron sputtered Ag nanostructures for dental applications | |
| CN107326336A (en) | Resistant amorphous carbon coating of antibacterial and preparation method thereof, antibacterial wear resistant appliance | |
| CN110144561A (en) | A kind of preparation method of hard coat of the durable with antibacterial functions | |
| Si et al. | A heterogeneous TiO2/SrTiO3 coating on titanium alloy with excellent photocatalytic antibacterial, osteogenesis and tribocorrosion properties | |
| Jeyachandran et al. | The effect of thickness of titanium nitride coatings on bacterial adhesion | |
| Yao et al. | Atomic layer deposition of zinc oxide on microrough zirconia to enhance osteogenesis and antibiosis | |
| KR20200097946A (en) | Antibacterial and corrosion-resistant MoS₂(WS₂, MoSe₂, WSe₂)/implant{omitted} | |
| Ferraris et al. | Antibacterial inorganic coatings on metallic surfaces for temporary fixation devices | |
| CN101033535A (en) | Medical titanium alloy hip joint bulb surface carburization process | |
| CN103911593B (en) | A kind of titanium alloy surface Ag doped Ti O 2the preparation method of film | |
| KR101822255B1 (en) | A method for preparation of a metallic implant comprising biocompatable fluoride ceramic coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |