CN106637121B - A kind of medical titanium metal alkyl materials and its manufacturing method - Google Patents
A kind of medical titanium metal alkyl materials and its manufacturing method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/48—Ion implantation
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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
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium alloys
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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
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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
- A61L27/50—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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
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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
- 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
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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
- 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
- A61L2300/412—Tissue-regenerating or healing or proliferative agents
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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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
- A61L2300/602—Type of release, e.g. controlled, sustained, slow
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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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/24—Materials or treatment for tissue regeneration for joint reconstruction
Abstract
The present invention relates to a kind of medical titanium metal alkyl materials and its manufacturing methods.The method using plasma immersion ion injection method directly will be in the surface of manganese Implanted Titanium metal alkyl materials substrate and sub-surface.Medical titanium metal alkyl materials of the invention are by plasma immersion and ion implantation method progress manganese injection modification and including additive Mn modified layer.Material of the present invention can continue slow release manganese ion, there is certain inhibiting effect to the growth of Gram-E. coli and Pseudomonas aeruginosa, and the Osteoblast Differentiation ability of mesenchymal stem cell can be promoted, to solve the problems such as antibiotic property existing for existing medical titanium material and poor bone formation performance.
Description
Technical field
The invention belongs to medical metal material fields, are related to one kind and mix manganese medical titanium metal material and its manufacturing method.
Background technique
Titanium and its alloy have become orthopedic preferred hard because of its good mechanical property and biocompatibility
Tissue alternate material [Progress in Materials Science 2009,54:397-425.].But Long-term clinical research hair
Existing, the principal element for causing titanium material implant surgery to be failed now includes following two aspect: 1. implant surfaces bioactivity is not
Enough ideals cause sclerous tissues' implant bone regeneration capability poor (or regeneration is slow), bad in conjunction with surrounding tissue；2. being implanted into body surface
Face causes the infection of implant Related Bacteria to occur again and again without antibiotic property.In the reacting of biotic environment and implant material, material
Surface play very important effect.Therefore, by certain surface modification technology, control implant material surface structure and
Ingredient properties can be effectively improved implantation effect [the Materials Science&Engineering R-Reports of material
2004,47:49-121.]。
Manganese is a kind of pair of bone uptake and microelement [the Journal of trace that development plays a significant role
elements in medicine and biology:organ of the Society for Minerals and Trace
Elements 2012,26:149-52.], it is in the metabolism and bone of internal carbohydrate in the synthesis process of mucopolysaccharide
Important co-factor [Biological trace element research 2008,124:28-34.], certain concerning new
Play an important role [Trends in biotechnology in the signal path of old metabolism and the homeostasis of cell interior
2013,31:594-605.].But research shows that Excessive Manganese element doping can cause cytotoxicity or to cell Osteoblast Differentiation
Have an adverse effect [Applied Surface Science 2011,258:977-985；Journal of Materials
Chemistry B 2014,2:5397-5408.].On the other hand, some researches show that aoxidize manganese material or a kind of inorganic antibacterial
Agent has more significant restraining and sterilizing bacteria effect [Applied to various bacterias such as Escherichia coli and staphylococcus aureuses
microbiology and biotechnology 2012,95:213-22；Ceramics International 2013,39:
2239-46.].Therefore, the present invention is quasi- seeks a kind of method on titanium surface to carry out manganese element trace doped and be subject to essence to doping
Really control obtains to balance the Osteoblast Differentiation effect and cytotoxicity that manganese element induction generates and can be applied to clinical titanium-based
Bone tissue reparation and alternate material.
Summary of the invention
The present invention is insufficient in order to solve the problems, such as existing medical titanium metal alkyl materials antibiotic property and skeletonization healing properties, provides
A method of manufacture medical titanium metal alkyl materials, with meet for clinical use medical titanium metal alkyl materials to antibacterial and quickly
The demand of bone formation performance.
The present invention first aspect provide it is a kind of manufacture medical titanium metal alkyl materials method, the method using etc. from
Daughter immersion ion injection method is directly by the surface of manganese Implanted Titanium metal alkyl materials substrate.
The present invention provides a kind of medical titanium metal alkyl materials, the medical titanium metal alkyl materials process etc. in second aspect
Gas ions immersion ion injection method carry out manganese injection it is modified and including additive Mn modified layer.
Medical titanium metal alkyl materials of the present invention or the medical titanium metal alkyl materials as made from the method for the present invention are mixed
Miscellaneous to have manganese element, without obvious boundary between modified layer and matrix, manganese ion is present in inside modified layer in the form of metallic state, with oxygen
Change state form and is present in modified layer surface.Pulsewidth and injection length are injected by adjusting manganese ion, modified layer surface manganese element is 0
It is controllable within the scope of~20at%；In being immersed in physiological saline, manganese ion can be continuous slow from coating in a long time
Release.This effect makes modified layer compared with pure titanium, has good cell compatibility and anti-microbial property.Medulla mesenchyma is dry
Cell quickly can be adhered to and be proliferated and break up to osteoblast direction in modified layer surface, to gram-negative Escherichia coli
And Pseudomonas aeruginosa has slight fungistatic effect, can reduce the proliferation rate of above two bacterium.It is obtained using present invention modification
Titanium or titanium alloy can be directly used as the replacement of carrying bone tissue and repair materials.
Compared with prior art, the invention has the following outstanding advantages:
1, the method for the present invention is to obtain additive Mn modified layer in titanium or the modification of titanium alloy-based bottom surface direct in-situ, is being retained
Under the premise of the original mechanics of titanium base material and biology performance, by adjusting the content of titanium surface manganese element, substrate material is improved
The antibacterial and bone formation performance of material；
2, stable preparation process of the present invention is controllable, easy to operate, and comprehensive injection is not limited by workpiece shapes；
3, through, without obvious boundary and gap, having close between additive Mn modified layer prepared by the present invention and metallic titanium matrix
Physical and chemical performance, obvious internal stress will not be caused；
4, additive Mn modified layer prepared by the present invention can long-time slow release manganese ion.
5, additive Mn modified layer prepared by the present invention has certain resist to gram-negative Escherichia coli and Pseudomonas aeruginosa
Bacterium effect is expected to be effectively prevented and treated implant postoperative infection.
6, additive Mn modified layer prepared by the present invention has more excellent biocompatibility, and mesenchymal stem cell is in the painting
Layer has significantly more skeletonization to express, and can be used as the alternate material at the big load position of the receivings such as femur, hip joint；
Detailed description of the invention
Fig. 1 is that the additive Mn modified material obtained through 1 modification of embodiment is compareed with pure titanium surface scan Electronic Speculum pattern
Figure.It (a/c) is pure titanium, (b/d) is modification titanium material.
Fig. 2 is the manganese element depth XPS distribution map of the additive Mn modified layer obtained through 1 modification of embodiment.
Fig. 3 is the manganese element XPS depth profile of the additive Mn modified layer obtained through 2 modification of embodiment.
Fig. 4 is the modified layer surface high-resolution XPS map of additive Mn obtained through 2 modification of embodiment.
Fig. 5 is the additive Mn modified layer internal layer high-resolution XPS map obtained through 2 modification of embodiment.
Fig. 6 is that the additive Mn modified layer obtained through 2 modification of embodiment impregnates the manganese of different cycles in physiological saline
Plasma diffusing W,Mo rule.
Fig. 7 is through the titanium metal material anti Bacillus pyocyaneu Flugge experimental result before and after 5 modification of embodiment, (a) pure titanium；(b)
Modified obtained additive Mn modified layer.
Fig. 8 is titanium metal material mesenchymal stem cell adherency figure before and after the processing modified by this invention, and (a/d) is pure
Titanium；(b/e) the modified obtained additive Mn modified layer of embodiment 1；(c/f) the modified obtained additive Mn modified layer of embodiment 2.
Specific embodiment
As described above, the present invention provides a kind of method for manufacturing medical titanium metal alkyl materials, the side in first aspect
Method using plasma immersion ion injection method is directly by the surface of manganese Implanted Titanium metal alkyl materials substrate.
In some embodiments, the plasma immersion and ion implantation method using titanium or titanium alloy as substrate,
Pure manganese is used to carry out as cathode.
In some preferred embodiments, the plasma immersion and ion implantation method using following technological parameter into
Row: background vacuum is 3 × 10-3~5 × 10-3Pa (such as 3,4 or 5 × 10-3Pa), injecting voltage be 10~40kV (such as
10,20,30 or 40kV), pulsewidth be 500~800 μ s (such as 500,600,700 or 800 μ s), frequency be 5~10Hz (such as 5,
6,7,8,9 or 10Hz), injection length is 0.5~3 hour (for example, 0.5,1.0,1.5,2.0,2.5 or 3.0 hour).
In some preferred embodiments, the plasma immersion and ion implantation method using following technological parameter into
Row: background vacuum is 5 × 10-3, injecting voltage 30kV, pulsewidth is 500~800 μ s (such as 500,600,700 or 800 μ
S), frequency 5Hz, injection length are 1~1.5h (for example, 0.5,1.0 or 1.5 hour).
In some preferred embodiments, the method also includes making before carrying out plasma immersion and ion implantation
The step of processing is washed out is carried out to substrate with acid.Preferably, the acid is the nitration mixture of nitric acid and hydrofluoric acid；In addition preferably
, the washing step with being cleaned by ultrasonic using acetone, ethyl alcohol and deionized water by successively being carried out.
In some preferred embodiments, manganese injection depth be 80nm to 120nm (such as 80,90,100,110 or
120nm), preferably 100nm.
The method of the present invention itself have it is stably and controllable, easy to operate, can comprehensive injection without being limited by workpiece shapes
The advantages that.
The present invention provides a kind of medical titanium metal alkyl materials, the medical titanium metal alkyl materials process etc. in second aspect
Gas ions immersion ion injection method carry out manganese injection it is modified and including additive Mn modified layer.
In some preferred embodiments, the material releasable manganese ion in physiological saline.
In some preferred embodiments, it is 80nm to 120nm, preferably 100nm that the material, which contains injection depth,
Manganese.
In some preferred embodiments, the medical titanium metal alkyl materials contain in the material exists with simple substance form
Manganese, and manganese existing for containing in the form of manganese oxide on the surface of material.
In some preferred embodiments, Gaussian Profile is presented in the distribution of the depth direction of the material in the manganese.
In some preferred embodiments, the manganese ion atomic percent on the surface of the material be greater than 0~
13.4at% (for example, 1,2,3,5,6,6.2,7,8,9,10,11,12,13,13.4at%), for example, can for greater than 0~
6.2at%, it is greater than 0~10at%, 6.2at%~10at%, 6.2at%~13.4at% or 10at%~13.4at%.
In some preferred embodiments, the peak value atomic percent of the manganese element of the material surface be greater than 0~
17.5at% (for example, 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17 or 17.5at%), for example, greatly
In 0~10at% or 10at%~17.5at%.
In some more preferably embodiments, material method as described in first aspect present invention is made.
As material of the present invention or the material as made from the method for the present invention can continue slow release in physiological saline
Manganese ion, thus have certain fungistatic effect to Gram-E. coli and Pseudomonas aeruginosa etc., such as with 60% suppression
Bacterium effect.In addition, material of the invention makes such as rat marrow mesenchymal cell (rBMMSC) can be in the modified layer of material
Adherency is proliferated rapidly on surface, and accelerates to break up to skeletonization direction.
Embodiment
Below with reference to embodiment, the present invention is described in further detail and completely, but is not intended to limit the contents of the present invention.
Embodiment 1
The pure titanium sheet of 10mm × 10mm × 1mm is passed through at nitration mixture (hydrofluoric acid: nitric acid: deionized water=1:5:34) ultrasound
After twice of reason (every all over 5 minutes), successively twice with acetone, ethyl alcohol and each cleaning of deionized water ultrasound, 5 minutes every time.Using etc.
Manganese element is injected Titanium base by gas ions immersion ion injection technique, and specific technological parameter is shown in Table 1:
1 manganese ion injection parameter of table
| Injecting voltage (kV) | 30 | Pulsewidth (μ s) | 500 |
| Injection length (h) | 1h | Background vacuum (Pa) | 5×10-3 |
| Frequency (Hz) | 5 |
Fig. 1 is that the titanium metal material obtained through the present embodiment modification is compareed with the scanning electron microscope pattern on pure titanium surface
Scheme, in figure: a/c is pure titanium, and b/d is the titanium metal material that modification obtains.As seen from Figure 1: through the present embodiment modification,
Because the nano particle that nitration mixture is handled disappears, coating becomes more smooth on pure titanium surface.
Fig. 2 is the manganese element XPS depth profile of the additive Mn modified layer obtained through the present embodiment modification.By Fig. 2
As it can be seen that the titanium material manganese ion injection depth about 100nm obtained through this embodiment modification, is presented Gaussian Profile, surface
Manganese ion atomic percent is about 6.2at%, and peak value manganese ion atomic percent is about 10.0at%.
Embodiment 2
The pure titanium sheet of 10mm × 10mm × 1mm is passed through at nitration mixture (hydrofluoric acid: nitric acid: deionized water=1:5:34) ultrasound
After twice of reason (every all over 5 minutes), successively twice with acetone, ethyl alcohol and each cleaning of deionized water ultrasound, 5 minutes every time.Using etc.
Manganese element is injected Titanium base by gas ions immersion ion injection technique, and specific technological parameter is shown in Table 2:
2 manganese ion injection parameter of table
| Injecting voltage (kV) | 30 | Pulsewidth (μ s) | 800 |
| Injection length (h) | 1h | Base vacuum (Pa) | 5×10-3 |
| Frequency (Hz) | 5 |
Fig. 3 is the manganese element XPS depth profile of the additive Mn modified layer obtained through the present embodiment modification.By Fig. 3
As it can be seen that the titanium material manganese ion injection depth about 100nm obtained through this embodiment modification, is presented Gaussian Profile, surface
Manganese ion atomic percent is about 13.4at%, and peak value manganese ion atomic percent is about 17.5at%.
Fig. 4 is the modified layer surface high-resolution XPS map of additive Mn obtained through the present embodiment modification.Fig. 5 is through this
The additive Mn modified layer internal layer high-resolution XPS map that embodiment modification obtains.From Fig. 4 and Fig. 5: manganese is in modification
Exist in obtained titanium material matrix with simple substance form, and exists in the form of manganese oxide in titanium material surface.
Fig. 6 is that the additive Mn modified layer obtained through the present embodiment modification impregnates the manganese of different cycles in physiological saline
Plasma diffusing W,Mo rule.As seen from Figure 6, manganese ion can continue slow release in physiological saline.
Embodiment 3
The pure titanium sheet of 10mm × 10mm × 1mm is passed through at nitration mixture (hydrofluoric acid: nitric acid: deionized water=1:5:34) ultrasound
After twice of reason (every all over 5 minutes), successively twice with acetone, ethyl alcohol and each cleaning of deionized water ultrasound, 5 minutes every time.Using etc.
Manganese element is injected Titanium base by gas ions immersion ion injection technique, and specific technological parameter is shown in Table 3:
3 manganese ion injection parameter of table
| Injecting voltage (kV) | 30 | Pulsewidth (μ s) | 500 |
| Injection length (h) | 0.5h | Base vacuum (Pa) | 5×10-3 |
| Frequency (Hz) | 5 |
Embodiment 4
The pure titanium sheet of 10mm × 10mm × 1mm is passed through at nitration mixture (hydrofluoric acid: nitric acid: deionized water=1:5:34) ultrasound
After twice of reason (every all over 5 minutes), successively twice with acetone, ethyl alcohol and each cleaning of deionized water ultrasound, 5 minutes every time.Using etc.
Manganese element is injected Titanium base by gas ions immersion ion injection technique, and specific technological parameter is shown in Table 4:
4 manganese ion injection parameter of table
| Injecting voltage (kV) | 30 | Pulsewidth (μ s) | 500 |
| Injection length (h) | 1.5h | Base vacuum (Pa) | 5×10-3 |
| Frequency (Hz) | 5 |
Embodiment 5
Antibacterial experiment is carried out to the titanium metal material obtained through 2 modification of above-described embodiment: using 75% ethyl alcohol by institute
There is sample to sterilize two hours, is 10 by concentration7The Pseudomonas aeruginosa bacterium solution of CFU/ml is dripped in the sample surfaces (0.06ml/ to sterilize
cm2), the sample that drop has bacterium solution is then put into 37 DEG C of constant incubator cultures for 24 hours.The sample cultivated for 24 hours is taken out, by bacterium solution times
Than being seeded on the agar plate containing culture medium after dilution.Agar plate after inoculation is put into 37 DEG C of constant incubator cultures for 24 hours, warp
It takes out agar plate after culture for 24 hours and calculates bacterial population living (referring to standard GB/T/T 4789.2).The calculating root of antibiotic rate
According to following formula:
K: sample antibiotic rate
A: the bacterium average on blank sample
B: the bacterium average in test sample
Fig. 7 is the experimental result of the titanium metal material anti Bacillus pyocyaneu Flugge obtained through above-described embodiment modification.In figure:
It (a) is pure titanium；It (b) is modified obtained additive Mn modified layer.As shown in Figure 7: the titanium obtained through above-described embodiment modification
Material has obvious antibacterial ability, antibiotic rate to 60%.
Embodiment 6
Cell adhesion experiments are carried out to the titanium metal material obtained through above-described embodiment 1 and 2 modification of embodiment: being adopted
All samples are sterilized two hours with 75% ethyl alcohol, are 2 × 10 by concentration4Cell/ml mesenchymal stem cell is planted in
It is cultivated seven days on the sample to sterilize, more renewed culture solution every three days.Using the fixed cell of 2.5% glutaraldehyde solution, and adopt
Cell is dehydrated and is dried with the ethyl alcohol of gradient concentration and hexamethyldisilazane.Using SEM to cell on the surface of the material
Adherency situation observed.
Fig. 8 is titanium metal material mesenchymal stem cell adherency figure before and after the processing modified by this invention, and (a/d) is pure
Titanium；(b/e) the modified obtained additive Mn modified layer of embodiment 1；(c/f) the modified obtained additive Mn modified layer of embodiment 2.By scheming
8 is visible: mesenchymal stem cell is good in the titanium metal material surface adhesion obtained through above-described embodiment modification.
Claims (15)
1. a kind of medical titanium metal alkyl materials, which is characterized in that the medical titanium metal alkyl materials by plasma immersion from
Sub- injection method carries out manganese injection and is modified including additive Mn modified layer, and it is 80nm to 120nm's that the material, which contains injection depth,
Manganese；
The manganese ion atomic percent on the surface of the material is m1, 0 ﹤ m1≤ 13.4at%；And/or
The peak value atomic percent of the manganese element of the material surface is m2, 0 ﹤ m2≤ 17.5at%.
2. the material according to claim 1, which is characterized in that the material releasable manganese ion in physiological saline.
3. material according to claim 1, which is characterized in that the material contains the manganese that injection depth is 100nm.
4. material according to claim 1, it is characterised in that:
The medical titanium metal alkyl materials contain in the material with manganese existing for simple substance form, and the surface of material contain with
Manganese existing for the form of manganese oxide；Or
Gaussian Profile is presented in the distribution of the depth direction of the material in the manganese.
5. material according to claim 1, which is characterized in that the manganese ion atomic percent on the surface of the material is
m1', 0 ﹤ m1'≤10at%.
6. material according to claim 1, which is characterized in that the manganese ion atomic percent on the surface of the material is
6.2at%~13.4at%.
7. material according to claim 1, which is characterized in that the peak value atomic percent of the manganese element of the material surface
For m2', 0 ﹤ m2'≤10at%.
8. material according to claim 1, which is characterized in that the peak value atomic percent of the manganese element of the material surface
For 10at%~17.5at%.
9. material according to claim 1, which is characterized in that the material comprises the following steps: the method uses
Plasma immersion and ion implantation method is directly by the surface of manganese Implanted Titanium metal alkyl materials substrate；The plasma immersion ion
Injection method is using titanium or titanium alloy as substrate.
10. material according to claim 9, which is characterized in that the plasma immersion and ion implantation method uses pure manganese
It is carried out as cathode.
11. material according to claim 10, which is characterized in that the plasma immersion and ion implantation method is using as follows
Technological parameter carries out: background vacuum is 3 × 10-3~5 × 10-3Pa, injecting voltage are 10~40kV, and pulsewidth is 500~800 μ
S, frequency are 5~10Hz, and injection length is 0.5~3h.
12. material according to claim 11, which is characterized in that the plasma immersion and ion implantation method is using as follows
Technological parameter carries out: background vacuum is 5 × 10-3Pa, injecting voltage 30kV, pulsewidth be 500~800 μ s, frequency 5Hz,
Injection length is 1~1.5h.
13. according to the described in any item materials of claim 9 to 12, which is characterized in that the method also includes carry out etc. from
The step of processing is washed out is carried out to substrate using acid before the injection of daughter immersion ion.
14. material according to claim 13, which is characterized in that the acid is the nitration mixture of nitric acid and hydrofluoric acid.
15. material according to claim 13, which is characterized in that the washing step uses acetone, second by successively using
Pure and mild deionized water is cleaned by ultrasonic to carry out.
Priority Applications (1)
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| CN201610910508.4A CN106637121B (en) | 2016-10-19 | 2016-10-19 | A kind of medical titanium metal alkyl materials and its manufacturing method |
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| CN110559477A (en) * | 2018-11-01 | 2019-12-13 | 赵全明 | Medical titanium alloy surface manganese-containing hydroxyapatite/titanium dioxide biological ceramic coating and preparation method thereof |
| CN113827770B (en) * | 2020-06-23 | 2022-08-09 | 中国科学院上海硅酸盐研究所 | Manganese dioxide-poly (3, 4-ethylenedioxythiophene) biological coating capable of promoting bone activity and preparation method and application thereof |
| CN113073303B (en) * | 2021-03-26 | 2021-11-16 | 南京工程学院 | Biomedical pure magnesium surface functional structured ion implantation modified layer and preparation method and application thereof |
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| CN103014646A (en) * | 2012-12-12 | 2013-04-03 | 中国科学院上海硅酸盐研究所 | Modification method for titanium surface with osteogenic performance and antibacterial performance |
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