CN106637121A - Medical titanium based metal material and manufacturing method thereof - Google Patents
Medical titanium based metal material and manufacturing method thereof Download PDFInfo
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- CN106637121A CN106637121A CN201610910508.4A CN201610910508A CN106637121A CN 106637121 A CN106637121 A CN 106637121A CN 201610910508 A CN201610910508 A CN 201610910508A CN 106637121 A CN106637121 A CN 106637121A
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Abstract
The invention relates to a medical titanium based metal material and a manufacturing method thereof. According to the method, manganese is directly injected into the surface and subsurface of the base of the titanium based metal material through a plasma immersion ion injection method. After manganese injection modification is conducted through the plasma immersion ion injection method, the medical titanium based metal material comprises a manganese doping modification layer. The material can continuously and slowly release manganese ions, has a certain inhibiting effect on growing of gram-negative escherichia coli and pseudomonas aeruginosa and can improve the osteogenic differentiation ability of mesenchymal stem cells among bone marrow, so that the problem that the antibacterial property and osteogenic property of an existing medical titanium material are poor is solved.
Description
Technical field
The invention belongs to medical metal material field, is related to one kind and mixes manganese medical titanium metal material and its manufacture method.
Background technology
Titanium and its alloy have become orthopedic first-selected 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 is sent out
It is existing, cause the principal element that the implant surgery of titanium material is failed to include following two aspects now：1. implant surfaces biologically active is not
Enough ideals, cause sclerous tissues's implant bone regeneration capability poor (or regeneration is slow), are combined with surrounding tissue not good；2. it is implanted into body surface
Face causes the infection of implant Related Bacteria to occur again and again without antibiotic property.In the reaction 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 trace element [Journal of trace with important function to bone uptake and development
elements in medicine and biology:organ of the Society for Minerals and Trace
Elements 2012,26:149-52.], be internal carbohydrate metabolism and bone in mucopolysaccharide building-up process in
Important co-factor [Biological trace element research 2008,124:28-34.], concern newly at some
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 Excessive Manganese element doping meeting trigger cell toxicity or to cell Osteoblast Differentiation
Have a negative impact [Applied Surface Science 2011,258:977-985；Journal of Materials
Chemistry B 2014,2:5397-5408.].On the other hand, there are some researches show, aoxidize manganese material or a kind of inorganic antibacterial
Agent, there is 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 intends seeking a kind of method to carry out manganese element on titanium surface trace doped and in addition smart to doping
Really control, to balancing Osteoblast Differentiation effect and the cytotoxicity that manganese element induction is produced, acquisition can be applicable to the titanium-based of clinic
Bone tissue reparation and alternate material.
The content of the invention
The present invention is not enough in order to solve the problems, such as existing medical titanium metal alkyl materials antibiotic property and skeletonization healing properties, there is provided
A kind of method of manufacture medical titanium metal alkyl materials, Clinical practice medical titanium metal alkyl materials are available for antibacterial and quick to meet
The demand of bone formation performance.
The present invention first aspect provide it is a kind of manufacture medical titanium metal alkyl materials method, methods described 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, described 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 medical titanium metal alkyl materials are mixed by obtained in the inventive method
Miscellaneous to have manganese element, without obvious boundary between modified layer and matrix, manganese ion is present in inside modified layer in metallic state form, with oxygen
Change state form and be 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 in the range of～20at%；In physiological saline is immersed in, manganese ion can be continuous slow from coating in a long time
Release.This effect causes modified layer compared with pure titanium, with good cell compatibility and anti-microbial property.Medulla mesenchyma is done
Cell can quickly be adhered to and bred and to the differentiation of Gegenbaur's cell direction on modified layer surface, to gram-negative Escherichia coli
And Pseudomonas aeruginosa has slight fungistatic effect, the rate of increase of above two bacterium can be reduced.It is modified what is obtained using the present invention
Titanium or titanium alloy, can be directly used as carrying bone tissue replacement and repair materials.
Compared with prior art, the present invention has advantage following prominent：
1st, the inventive method is to be modified to obtain additive Mn modified layer in titanium or titanium alloy-based basal surface direct in-situ, is being retained
On the premise of the original mechanics of titanium base material and biology performance, by the content for adjusting titanium surface manganese element, substrate material is improve
The antibacterial and bone formation performance of material；
2nd, stable preparation process of the present invention is controllable, simple to operate, comprehensive injection, is not limited by workpiece shapes；
3rd, without obvious boundary and gap between the additive Mn modified layer and metallic titanium matrix of Jing present invention preparation, with close
Physical and chemical performance, obvious internal stress will not be caused；
4th, additive Mn modified layer prepared by the present invention can slowly discharge manganese ion for a long time.
5th, additive Mn modified layer prepared by the present invention has certain resisting to gram-negative Escherichia coli and Pseudomonas aeruginosa
Bacterium effect, is expected to effectively prevent and treat implant POI.
6th, additive Mn modified layer prepared by the present invention has more excellent biocompatibility, and mesenchymal stem cells MSCs is in the painting
Layer has significantly more skeletonization to express, and can be used as the alternate material that femur, hip joint etc. bear big load position；
Description of the drawings
Fig. 1 is that additive Mn that the modification of Jing embodiments 1 is obtained is material modified to be compareed with pure titanium surface scan Electronic Speculum pattern
Figure.(a/c) it 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 that the modification of Jing embodiments 1 is obtained.
Fig. 3 is the manganese element XPS depth profiles of the additive Mn modified layer that the modification of Jing embodiments 2 is obtained.
Fig. 4 is the modified layer surface high-resolution XPS collection of illustrative plates of additive Mn that the modification of Jing embodiments 2 is obtained.
Fig. 5 is the additive Mn modified layer internal layer high-resolution XPS collection of illustrative plates that the modification of Jing embodiments 2 is obtained.
Fig. 6 is the manganese that the additive Mn modified layer that the modification of Jing embodiments 2 is obtained soaks different cycles in physiological saline
Plasma diffusing W,Mo rule.
Fig. 7 is the titanium metal material anti Bacillus pyocyaneu Flugge experimental result before and after the modification of Jing embodiments 5, (a) pure titanium；(b)
The modified additive Mn modified layer for obtaining.
Fig. 8 is the titanium metal material mesenchymal stem cells MSCs adhesion figure after before processing modified by this invention, (a/d) pure
Titanium；(b/e) the modified additive Mn modified layer for obtaining of embodiment 1；(c/f) the modified additive Mn modified layer for obtaining of embodiment 2.
Specific embodiment
As described above, the present invention provides a kind of method of manufacture 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 adopts titanium or titanium alloy as substrate,
Carried out using pure manganese as negative electrode.
Some preferred embodiment in, the plasma immersion and ion implantation method is entered using following technological parameter
OK：Background vacuum is 3 × 10-3～5 × 10-3Pa (such as 3,4 or 5 × 10-3Pa), injecting voltage be 10～40kV (for example
10th, 20,30 or 40kV), pulsewidth be 500～800 μ s (μ s of such as 500,600,700 or 800), frequency be 5～10Hz (such as 5,
6th, 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 hours).
In some preferred embodiments, the plasma immersion and ion implantation method is entered using following technological parameter
OK：Background vacuum is 5 × 10-3, injecting voltage is 30kV, and pulsewidth is 500～800 μ s (μ of such as 500,600,700 or 800
S), frequency is 5Hz, and injection length is 1～1.5h (for example, 0.5,1.0 or 1.5 hours).
Some preferred embodiment in, methods described is additionally included in be carried out being made before plasma immersion and ion implantation
The step of process being carried out with acid to substrate and is washed out.Preferably, the acid is nitric acid and the nitration mixture of hydrofluoric acid；In addition preferably
, the washing step is by being carried out with ultrasonic cleaning is carried out using acetone, ethanol and deionized water successively.
Some preferred embodiment in, manganese injection depth be 80nm to 120nm (such as 80,90,100,110 or
120nm), preferably 100nm.
The inventive method itself have stablize it is controllable, simple to operate, can comprehensive injection and do not limited by workpiece shapes
The advantages of.
The present invention provides a kind of medical titanium metal alkyl materials, described 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.
Some preferred embodiment in, the material releasable manganese ion in physiological saline.
Some preferred embodiment in, the material contain injection depth be 80nm to 120nm, preferably 100nm
Manganese.
Some preferred embodiment in, the medical titanium metal alkyl materials in the material contain with simple substance form presence
Manganese, and contain the manganese in the form of manganese oxide on the surface of material.
Some preferred embodiment in, the manganese the depth direction of the material distribution present Gaussian Profile.
Some preferred embodiment in, the manganese ion atomic percent on the surface of the material be more 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 be more than 0～
6.2at%, more than 0～10at%, 6.2at%～10at%, 6.2at%～13.4at% or 10at%～13.4at%.
Some preferred embodiment in, the peak value atomic percent of the manganese element of the material surface more 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 embodiments being more highly preferred to, method of the material by described in first aspect present invention is obtained.
Due to material of the present invention or the material by obtained in the inventive method 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, the material of the present invention causes such as rat marrow mesenchymal cell (rBMMSC) can be in the modified layer of material
Rapid adhesion propagation on surface, and accelerate to break up to skeletonization direction.
Embodiment
With reference to embodiment, the present invention is described in further detail and completely, but is not intended to limit present disclosure.
Embodiment 1
By the pure titanium sheet of 10mm × 10mm × 1mm through nitration mixture (hydrofluoric acid：Nitric acid：Deionized water=1：5：34) at ultrasound
After twice of reason (per all over 5 minutes), successively with each cleaning of acetone, ethanol and deionized water ultrasound twice, 5 minutes every time.Using etc.
Gas ions immersion ion injection technique, by manganese element Titanium base is injected, and its specific technological parameter is shown in Table 1：
The manganese ion injection parameter of table 1
| 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 that Jing the present embodiment modifications are obtained is compareed with the ESEM pattern on pure titanium surface
Figure, in figure：A/c be pure titanium, the titanium metal material that b/d is obtained for modification.As seen from Figure 1：Jing the present embodiment modifications,
Pure titanium surface disappears because of the nano particle that nitration mixture process is obtained, and coating becomes more smooth.
Fig. 2 is the manganese element XPS depth profiles of the additive Mn modified layer that Jing the present embodiment modifications are obtained.By Fig. 2
It can be seen that, the titanium material manganese ion injection depth about 100nm that Jing this embodiment modifications are obtained 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
By the pure titanium sheet of 10mm × 10mm × 1mm through nitration mixture (hydrofluoric acid：Nitric acid：Deionized water=1：5：34) at ultrasound
After twice of reason (per all over 5 minutes), successively with each cleaning of acetone, ethanol and deionized water ultrasound twice, 5 minutes every time.Using etc.
Gas ions immersion ion injection technique, by manganese element Titanium base is injected, and its specific technological parameter is shown in Table 2：
The manganese ion injection parameter of table 2
| 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 profiles of the additive Mn modified layer that Jing the present embodiment modifications are obtained.By Fig. 3
It can be seen that, the titanium material manganese ion injection depth about 100nm that Jing this embodiment modifications are obtained 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 collection of illustrative plates of additive Mn that Jing the present embodiment modifications are obtained.Fig. 5 is Jing sheets
The additive Mn modified layer internal layer high-resolution XPS collection of illustrative plates that embodiment modification is obtained.From Fig. 4 and Fig. 5：Manganese is in modification
With simple substance form presence in the titanium material matrix for obtaining, and in titanium material surface in the form of manganese oxide.
Fig. 6 is the manganese that the additive Mn modified layer that Jing the present embodiment modifications are obtained soaks 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
By the pure titanium sheet of 10mm × 10mm × 1mm through nitration mixture (hydrofluoric acid：Nitric acid：Deionized water=1：5：34) at ultrasound
After twice of reason (per all over 5 minutes), successively with each cleaning of acetone, ethanol and deionized water ultrasound twice, 5 minutes every time.Using etc.
Gas ions immersion ion injection technique, by manganese element Titanium base is injected, and its specific technological parameter is shown in Table 3：
The manganese ion injection parameter of table 3
| Injecting voltage (kV) | 30 | Pulsewidth (μ s) | 500 |
| Injection length (h) | 0.5h | Base vacuum (Pa) | 5×10-3 |
| Frequency (Hz) | 5 |
Embodiment 4
By the pure titanium sheet of 10mm × 10mm × 1mm through nitration mixture (hydrofluoric acid：Nitric acid：Deionized water=1：5：34) at ultrasound
After twice of reason (per all over 5 minutes), successively with each cleaning of acetone, ethanol and deionized water ultrasound twice, 5 minutes every time.Using etc.
Gas ions immersion ion injection technique, by manganese element Titanium base is injected, and its specific technological parameter is shown in Table 4：
The manganese ion injection parameter of table 4
| 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 that the modification of Jing above-described embodiments 2 is obtained：Using 75% ethanol by institute
There is sample to sterilize two hours, be 10 by concentration7The Pseudomonas aeruginosa bacterium solution of CFU/ml drops in the sample surfaces (0.06ml/ for sterilizing
cm2), then the sample that drop has bacterium solution is put into 37 DEG C of constant incubator culture 24h.The sample of 24h cultures is taken out, by bacterium solution times
Than being seeded on the agar plate containing culture medium after dilution.Postvaccinal agar plate is put into 37 DEG C of constant incubator culture 24h, Jing
Cross after the culture of 24h and take out the bacterial population that agar plate calculates work (with reference to standard GB/T/T 4789.2).The calculating root of antibiotic rate
According to below equation：
K:Sample antibiotic rate
A:Bacterium average on blank sample
B:Bacterium average in test sample
Fig. 7 is the experimental result of the titanium metal material anti Bacillus pyocyaneu Flugge that Jing above-described embodiment modifications are obtained.In figure：
A () is pure titanium；B () is the modified additive Mn modified layer for obtaining.As shown in Figure 7：The titanium that Jing above-described embodiment modifications are obtained
Material has obvious antibacterial ability, its antibiotic rate to 60%.
Embodiment 6
Cell adhesion experiments are carried out to the titanium metal material that Jing above-described embodiments 1 and the modification of embodiment 2 are obtained：Adopt
All samples are sterilized two hours with 75% ethanol, is 2 × 10 by concentration4The mesenchymal stem cells MSCs of cell/ml is planted in
Cultivate seven days on the sample for sterilizing, every three days nutrient solution was more renewed.Cell is fixed using 2.5% glutaraldehyde solution, and is adopted
Cell is dehydrated and is dried with the ethanol and HMDS of gradient concentration.Using SEM to cell in material surface
Adhesion situation observed.
Fig. 8 is the titanium metal material mesenchymal stem cells MSCs adhesion figure after before processing modified by this invention, (a/d) pure
Titanium；(b/e) the modified additive Mn modified layer for obtaining of embodiment 1；(c/f) the modified additive Mn modified layer for obtaining of embodiment 2.By scheming
8 is visible：Mesenchymal stem cells MSCs is good in the titanium metal material surface adhesion that Jing above-described embodiment modifications are obtained.
Claims (10)
1. it is a kind of manufacture medical titanium metal alkyl materials method, it is characterised in that methods described using plasma immersion ion
Injection method is directly by the surface of manganese Implanted Titanium metal alkyl materials substrate.
2. method according to claim 1, it is characterised in that：
The plasma immersion and ion implantation method, as substrate, is carried out using titanium or titanium alloy using pure manganese as negative electrode；
Preferably, the plasma immersion and ion implantation method is carried out using following technological parameter：Background vacuum is 3 × 10-3～5 × 10-3Pa, injecting voltage is 10～40kV, and pulsewidth is 500～800 μ s, and frequency is 5～10Hz, and injection length is 0.5
～3h；
It is further preferred that the plasma immersion and ion implantation method is carried out using following technological parameter：Background vacuum be 5 ×
10-3, injecting voltage is 30kV, and pulsewidth is 500～800 μ s, and frequency is 5Hz, and injection length is 1～1.5h.
3. method according to claim 1 and 2, it is characterised in that methods described is additionally included in carries out plasma immersion
The step of using acid process being carried out before ion implanting to substrate and is washed out；
Preferably, the acid is nitric acid and the nitration mixture of hydrofluoric acid；
Also it is preferred that the washing step by successively with using acetone, ethanol and deionized water carry out be cleaned by ultrasonic come
Carry out.
4. according to the method in any one of claims 1 to 3, it is characterised in that manganese injection depth is 80nm to 120nm,
Preferably 100nm.
5. a kind of medical titanium metal alkyl materials, it is characterised in that the medical titanium metal alkyl materials through plasma immersion from
Sub- injection method carry out manganese injection it is modified and including additive Mn modified layer.
6. material according to claim 5, it is characterised in that the material releasable manganese ion in physiological saline.
7. the material according to claim 5 or 6, it is characterised in that the material contain injection depth be 80nm extremely
The manganese of 120nm, preferably 100nm.
8. the material according to any one of claim 5 to 7, it is characterised in that：
The medical titanium metal alkyl materials in the material containing with simple substance form exist manganese, and the surface of material contain with
Manganese in the form of manganese oxide；Or
The manganese is presented Gaussian Profile in the distribution of the depth direction of the material.
9. the material according to any one of claim 5 to 8, it is characterised in that：
The manganese ion atomic percent on the surface of the material be more than 0～13.4at%, for example, more than 0～10at% or
6.2at%～13.4at%；And/or
The peak value atomic percent of the manganese element of the material surface be more than 0～17.5at%, preferably greater than 0～10at% or
Person 10at%～17.5at%.
10. the material according to any one of claim 5 to 9, it is characterised in that the material is by Claims 1-4
Method described in any one is obtained.
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