CN104338182A - Method for coating titanium alloy surface and coating layer formed by using same - Google Patents
Method for coating titanium alloy surface and coating layer formed by using same Download PDFInfo
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- CN104338182A CN104338182A CN201310343129.8A CN201310343129A CN104338182A CN 104338182 A CN104338182 A CN 104338182A CN 201310343129 A CN201310343129 A CN 201310343129A CN 104338182 A CN104338182 A CN 104338182A
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Abstract
The invention relates to a coating for improving the biocompatibility of titanium alloy. The coating is characterized by comprising, from interior to exterior, i) an oxidation layer which is the innermost layer of the coating, is directly connected with titanium alloy and is used to activate titanium alloy; ii) a transition layer which is connected with the activated oxidation layer; and an optionally iii) bioactive protein layer which is connected with the transition layer and is used to improve the adhesion capability of cells. The coating is used to improve the biocompatibility of the titanium alloy and optionally improve the inflammatory reaction of a heat wound and/or improve the healing capability of cardiac muscle tissue. The invention also relates to a preparation method of the above coating.
Description
Technical field:
The present invention relates to a kind of appearance surface coatings of titanium alloy, belong to medical instruments field, be specially adapted to the modification of implanted human assistance heart material.The invention still further relates to the coating method of titanium alloy surface and described coating for improving the purposes of the biocompatibility of titanium alloy.
Background technology:
Heart transplantation is the most effective treatment means of heart disease at final stage.But it is due to the famine of heart donor, interior the waiting period of having a large amount of heart disease at final stage people to die from donor every year.The development of human assistance heart solves this difficult problem, can replace or auxiliary normal heart work, maintains human body Efficient Cycle, and therefore human assistance heart can as the important means of Patients with Cardiac Failure assist circulation or patients underwent heart transplantation bridging therapy.
Because human assistance heart belongs to external source implant, body can produce immune rejection, and cause inflammation reaction and thrombosis.In order to avoid body is to the rejection of human assistance heart, produce a large amount of inflammatory tissues, affect the normal work of human assistance heart pump, need to carry out respective handling to the material of human assistance heart.
Summary of the invention:
The present invention is for the biocompatibility improving human assistance heart and the one researched and developed has bioactive face coat.Meanwhile, coating of the present invention can also alleviate the inflammatory reaction that cardiac incision goes out, and promotes disappearing of inflammatory cell, improves the Adhering capacity of cell, improves the organization healing ability of heart wound.
An object of the present invention is to provide a kind of coating can improving titanium alloy histocompatibility; Preferably can also improve the inflammatory reaction of heart wound, improve the healing ability of cardiac muscular tissue.Be specially adapted to the material modification of implantable human assistance heart titanium alloy.
Another object of the present invention is to provide a kind of preparation method of above-mentioned coating.
Another object of the present invention is to provide a kind of above-mentioned coating for improving titanium alloy biocompatibility and optionally improving the inflammatory reaction of heart wound and/or improve the purposes of healing ability of cardiac muscular tissue.
Because human assistance heart is in operation process, can produce larger myocardium wound, healing rate is comparatively slow, and easily causes the immunoreation of body.Titanium alloy surface is comparatively stable, not portable electric charge, the absorbability of extracellular matrix albumen is lower, cause cell and titanium alloy to stick degree lower, the somatomedin of inducing macrophage and migration of fibroblast cells cannot be produced, cause a large amount of inflammatory cell to be gathered in wound, cause inflammation, reduce speed of wound healing.In order to improve the biocompatibility of human assistance heart, reducing body to the identification ability of foreign body, one can be prepared there is bioactive titanium alloy surface coating.
For reaching goal of the invention, on the one hand, present invention employs following coating:
1, for improving a coating for titanium alloy biocompatibility, it is characterized in that, it comprises from inside to outside successively:
I) oxide layer, is the innermost layer of coating, is directly connected with titanium alloy, for activating titanium alloy;
Ii) transition zone, it is connected with the oxide layer of activation.
Above-mentioned coating can improve titanium alloy histocompatibility, is mainly used in the surface modification of the titanium alloy material of the surfaces externally and internally of human assistance heart.Wherein said oxide layer is mainly titanium oxide (being called for short Ti-O) coating.
2, according to the coating described in project 1, wherein also comprise
Iii) biological activity protein layer, is connected with transition zone, for improving the Adhering capacity of cell.
Now transition zone is the intermediate layer of coating, fixing for protein.Biological activity protein layer is third layer or the outermost layer of coating, is connected with transition zone, for improving the Adhering capacity of cell.
With above-mentioned containing compared with two-layer coating, containing the coatings of three layers, there is better biocompatibility.
3, according to the coating described in project 1 or 2, the inner side of wherein said oxide layer is titanium alloy layer.
4, according to the coating described in project 1 or 2, wherein said transition zone is mainly phospholipid molecule, comprises phosphoglyceride and/or sphingomyelins.
5, according to the coating described in project 2, wherein said biological activity protein layer is mainly extracellular matrix protein, preferred collagen protein, elastin laminin, viscous protein and/or layer fibronectin, or its hydrolyzate such as gelatin.
6, according to the coating described in project 1 or 2, wherein said titanium alloy is whole or its outer metal for titanium alloy of metal solid, preferred titanium alloy artificial accessory heart.
On the other hand, present invention provides the method preparing above-mentioned coating:
First metal ester compounds and bronsted lowry acids and bases bronsted lowry organic solvent are mixed in proportion, form uniform High-pH solution, form gel at a certain temperature, oxide-film made by dried titanium alloy.Described alkali organic solvent is organic complex, dehydrated alcohol and water.Organic complex comprises such as diethanolamine, EDTA, acetylacetone,2,4-pentanedione etc.Oxide-film, through highly basic activation processing, makes oxide layer produce free free radical; By the interaction between the group on free radical and phospholipid molecule surface, phospholipid molecule is fixed on titanium alloy surface.Finally, extracellular matrix protein is fixed to the surface of phospholipid molecule by the method for covalence graft, is formed and be beneficial to sticking of cell.Specifically,
7, apply a method for titanium alloy surface, it is characterized in that, the method comprises step below:
I) metal ester compounds is mixed with bronsted lowry acids and bases bronsted lowry organic solvent, form uniform solution, form gel at a certain temperature, with described gel dip-coating titanium alloy surface, dried;
Ii) with highly basic activation process step i) titanium alloy, make its surface produce free free radical; Then the solution containing phospholipid molecule is immersed.
8, according to the method for project 7, wherein said method also comprises step below:
Iii) extracellular matrix protein solution is coated in through ii) titanium alloy that processes; Described extracellular matrix protein is preferably collagen protein, elastin laminin, viscous protein or layer fibronectin, or its hydrolyzate such as gelatin.
9, according to the method for project 7 or 8, wherein preferred at least one feature below:
(1), described metal ester compounds is titanate ester compound, preferred butyl titanate or butyl titanate;
(2), first preferred with the acidic organic solvent glacial acetic acid of described metal ester compounds mixes;
(3), the mixed proportion of metal ester compounds and acidic organic solvent is 1:1 ~ 20:1, preferred 10:1;
(4), step I) homogeneous solution that formed is for neutral or close to neutral;
(5), step I) described alkali organic solvent is organic complex such as diethanolamine, dehydrated alcohol and water, by 8:x:y(x=0.1-0.2, y=0.04-0.07) ratio mixing, preferably in 8:0.15:0.06 ratio;
(6), described phospholipid molecule is lecithin or cephalin;
(7), step I) described in temperature be about 60 DEG C of about 40-.
On the other hand, invention further provides a kind of above-mentioned coating for improving the purposes of titanium alloy biocompatibility, and optionally improve the purposes of the inflammatory reaction of heart wound and/or the healing ability of raising cardiac muscular tissue.
The biomimetic material that the present invention is designed by the characteristic of extracellular matrix protein, by microenvironment interconnective between analog cell, inducing heart histiocyte (as myocardial cell, smooth muscle cell, heart endothelial cell etc.) is attached on titanium alloy surface, secrete a large amount of cell growth factor, promote clearing up and discharging of inflammatory cell (as neutrophilic granulocyte, macrophage etc.); By heart tissue cells migration, propagation and differentiation, the tissue having function that final formation is new.
The present invention can improve the inflammatory reaction of body, promote the healing of impaired heart tissue, also can reduce the thrombosis of human assistance heart simultaneously, alleviate the problems such as the postoperative acute and chronic immunologic rejection brought by wound healing, improve the life quality of patient.
Accompanying drawing illustrates:
Fig. 1 is the cross-sectional view of the application's embodiment coating
1 is titanium alloy; 2 is oxide layer; 3 is phospholipid molecule layer; 4 is extracellular matrix protein layer.
Detailed description of the invention:
Below describe the specific embodiment of the present invention in detail, in any case but limitation of the present invention can not be interpreted as.
As shown in Figure 1, in a specific embodiment, described coating is made up of 4 parts, and arranges from inside to outside by the order of 1-4.Wherein the 1st layer is titanium alloy body, is also innermost one deck; 2nd layer is the oxide layer of titanium, is close to titanium alloy; 3rd layer is phospholipid molecule layer, adjacent with oxide layer; 4th layer of protein layer is outmost one deck.
Described coating can be prepared according to method below:
By butyl titanate, glacial acetic acid in the mixing of 10:1 ratio, 50 DEG C of heating mix homogeneously, are designated as solution A.Organic complex, dehydrated alcohol and water press 8:x:y(x=0.1-0.2, y=0.04-0.07) ratio mixing, stir, be designated as solution B.By solution A, B mix homogeneously, room temperature ageing 24-96h.Mixed liquor is coated in material surface uniformly, and 150-400 DEG C of heating 1-4h, obtains uniform Ti-O coating.
Material with Ti-O coating is put into NaOH, ambient temperature overnight, clean up after taking-up.Solution containing phospholipid molecule is added to material surface, makes liquid by material submergence, place more than 2h for 20-40 DEG C.Material surface is the colourless thin film of layer of transparent, therefore, and the basic and oxide layer solid colour of material color.But this coating is comparatively fragile, is easily destroyed.This thin film aseptically need carry out manipulation.
Take out the material scribbling phospholipid molecule, clean up, and dry.Material surface after drying drips the collagen solution that concentration is 1-10 μ g/mL, makes it cover this material surface, 20-40 DEG C of polymerization more than 1h.Taking-up cleans up post-drying.3rd coating is also the colourless thin film of layer of transparent, can be measured by contact angle detection.Therefore, after three layers of coating coating, material is still the color of oxide layer, and bright and clean degree slightly declines.Three layers of coating are more fragile, are easily destroyed.This thin film aseptically need carry out manipulation.
Therefore, the operations such as following process, preservation, transport want significant care, prevent coating to be destroyed.
Embodiment one:
By butyl titanate, glacial acetic acid in the mixing of 10:1 ratio, 50 DEG C of heating mix homogeneously, are designated as solution A.Diethanolamine, dehydrated alcohol and water, in the mixing of 8:0.15:0.06 ratio, stir, are designated as solution B.By solution A, B mix homogeneously, room temperature ageing 72h.Mixed liquor is coated in uniformly silvery white Titanium alloy Ti-6Al-4V material surface, 400 DEG C of heating 2h, obtain uniform titanium oxide azury (being abbreviated as Ti-O) coating.
Material with Ti-O coating is put into NaOH, ambient temperature overnight, clean by washed with de-ionized water after taking-up.Solution containing lecithin is added to material surface, makes liquid by material submergence, place 2h, obtain two layers of coatings for 20 DEG C.Material surface is the colourless thin film of layer of transparent, therefore, and the basic and oxide layer solid colour of material color.But this coating is comparatively fragile, is easily destroyed.This thin film aseptically need carry out manipulation.
Take out the material scribbling lecithin, clean by washed with de-ionized water, and dry.Material surface after drying drips the collagen solution that concentration is 5 μ g/mL, makes it cover this material surface, 20 DEG C of polymerization 1h.Taking-up cleans up post-drying, obtains three layers of coating.3rd coating is also the colourless thin film of layer of transparent, and therefore, after three layers of coatings coating, material is still the color of oxide layer, and bright and clean degree slightly declines.
Embodiment two:
By tetraethyl titanate, acetic acid in the mixing of 10:1 ratio, 40 DEG C of heating mix homogeneously, are designated as solution A.Diethanolamine, dehydrated alcohol and water, in the mixing of 8:0.10:0.04 ratio, stir, are designated as solution B.By solution A, B mix homogeneously, room temperature ageing 48h.Mixed liquor is coated in uniformly titanium alloy T i-6Al-7Nb material surface, 400 DEG C of heating 2h, obtain uniform Ti-O coating.
Material with Ti-O coating is put into NaOH, ambient temperature overnight, clean by washed with de-ionized water after taking-up.Solution containing DPPC is added to material surface, makes liquid by material submergence, place 5h for 20 DEG C.Material surface is the colourless thin film of layer of transparent, therefore, and the basic and oxide layer solid colour of material color.But this coating is comparatively fragile, is easily destroyed.This thin film aseptically need carry out manipulation.
Take out the material scribbling DPPC, clean by washed with de-ionized water, and dry.Material surface after drying drips the elastin laminin solution that concentration is 3 μ g/mL, makes it cover this material surface, 20 DEG C of polymerization 2h.Taking-up cleans up post-drying.3rd coating is also the colourless thin film of layer of transparent, and therefore, after three layers of coatings coating, material is still the color of oxide layer, and bright and clean degree slightly declines.
Embodiment three:
By butyl titanate, nitric acid in the mixing of 20:1 ratio, 55 DEG C of heating mix homogeneously, are designated as solution A.Acetylacetone,2,4-pentanedione, dehydrated alcohol and water, in the mixing of 8:0.20:0.06 ratio, stir, are designated as solution B.By solution A, B mix homogeneously, room temperature ageing 48h.Mixed liquor is coated in uniformly titanium alloy T i-5Al-2.5Fe material surface, 400 DEG C of heating 2h, obtain uniform Ti-O coating.
Material with Ti-O coating is put into NaOH, ambient temperature overnight, clean by washed with de-ionized water after taking-up.Solution containing choline glycerophosphatide is added to material surface, makes liquid by material submergence, room temperature places 5h.Material surface is the colourless thin film of layer of transparent, therefore, and the basic and oxide layer solid colour of material color.But this coating is comparatively fragile, is easily destroyed.This thin film aseptically need carry out manipulation.
Take out the material scribbling choline glycerophosphatide, clean by washed with de-ionized water, and dry.Material surface after drying drips the viscous protein solution that concentration is 4 μ g/mL, makes it cover this material surface, polymerized at room temperature 2h.Taking-up cleans up post-drying.3rd coating is also the colourless thin film of layer of transparent, and therefore, after three layers of coatings coating, material is still the color of oxide layer, and bright and clean degree slightly declines.
Test example
Adopt the method for the embodiment of the present invention 1 that implanted human assistance heart titanium alloy surface is coated coating of the present invention.6 sheep are divided into two groups, often organize 3.Compared with the titanium implanted human assistance heart not containing coating of the present invention, when other conditions are identical, titanium implanted human assistance heart containing coating of the present invention obtains successfully in animal experiment, make test group sheep Average Survival 106 days, and there is no obvious inflammatory reaction, time-to-live and quality of life are apparently higher than matched group test sheep (Average Survival 3 days) not applying coating of the present invention.
Find when dissect physiology, untreated experiment sheep wound produces pannus hard in a large number and fibrous tissue block, fits loosely, easily fall down with entrance outer wall.And the human assistance heart processed is contained in experiment sheep body, can improve the inflammatory reaction of wound, wound is firmly combined with entrance outer wall, can not produce pannus, and grows the new cardiac muscular tissue of one deck at entrance outer wall.
Above-mentioned specific embodiment is illustrative, can introduce multiple change based on these embodiments when not deviating from spirit or the claims scope of disclosure.
Claims (10)
1. for improving a coating for titanium alloy biocompatibility, it is characterized in that, it comprises from inside to outside successively:
I) oxide layer (2), is the innermost layer of coating, is directly connected with titanium alloy, for activating titanium alloy;
Ii) transition zone (3), it is connected with the oxide layer (2) of activation.
2., according to coating according to claim 1, wherein also comprise
Iii) biological activity protein layer (4), is connected with transition zone (3), for improving the Adhering capacity of cell.
3., according to the coating described in claim 1 or 2, the inner side of wherein said oxide layer (2) is titanium alloy layer (1).
4., according to the coating described in claim 1 or 2, wherein said transition zone (3) is mainly phospholipid molecule, comprises phosphoglyceride and/or sphingomyelins.
5., according to coating according to claim 2, wherein said biological activity protein layer (4) is mainly extracellular matrix protein, preferred collagen protein, elastin laminin, viscous protein and/or layer fibronectin, or its hydrolyzate such as gelatin.
6., according to the coating described in claim 1 or 2, wherein said titanium alloy is whole or its outer metal for titanium alloy of metal solid, preferred titanium alloy artificial accessory heart.
7. apply a method for titanium alloy surface, it is characterized in that, the method comprises step below:
I) metal ester compounds is mixed with bronsted lowry acids and bases bronsted lowry organic solvent, form uniform solution, form gel at a certain temperature, with described gel dip-coating titanium alloy surface, dried;
Ii) with highly basic activation process step i) titanium alloy, make its surface produce free free radical; Then the solution containing phospholipid molecule is immersed.
8., according to the method for claim 7, wherein said method also comprises step below:
Iii) extracellular matrix protein solution is coated in through ii) titanium alloy that processes; Described extracellular matrix protein is preferably collagen protein, elastin laminin, viscous protein or layer fibronectin, or its hydrolyzate such as gelatin.
9. according to the method for claim 7 or 8, wherein preferred at least one feature below:
(1), described metal ester compounds is titanate ester compound, preferred butyl titanate or butyl titanate;
(2), first preferred with the acidic organic solvent glacial acetic acid of described metal ester compounds mixes;
(3), the mixed proportion of metal ester compounds and acidic organic solvent is 1:1 ~ 20:1, preferred 10:1;
(4), step I) homogeneous solution that formed is for neutral or close to neutral;
(5), step I) described alkali organic solvent is organic complex such as diethanolamine, dehydrated alcohol and water, by 8:x:y(x=0.1-0.2, y=0.04-0.07) ratio mixing, preferably in 8:0.15:0.06 ratio;
(6), described phospholipid molecule is lecithin or cephalin;
(7), step I) described in temperature be about 60 DEG C of about 40-.
10. according to the coating described in any one of claim 1-6 for improving titanium alloy biocompatibility and optionally improving the inflammatory reaction of heart wound and/or improve the purposes of healing ability of cardiac muscular tissue.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107185055A (en) * | 2017-04-28 | 2017-09-22 | 淮阴工学院 | A kind of surface modifying method of medical magnesium alloy |
| CN110158075A (en) * | 2019-05-09 | 2019-08-23 | 中车青岛四方机车车辆股份有限公司 | A kind of patch and its application method for the processing of austenite stainless steel workpiece surface |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107185055A (en) * | 2017-04-28 | 2017-09-22 | 淮阴工学院 | A kind of surface modifying method of medical magnesium alloy |
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| CN110158075A (en) * | 2019-05-09 | 2019-08-23 | 中车青岛四方机车车辆股份有限公司 | A kind of patch and its application method for the processing of austenite stainless steel workpiece surface |
| CN110158075B (en) * | 2019-05-09 | 2021-02-09 | 中车青岛四方机车车辆股份有限公司 | Paster for surface treatment of austenitic stainless steel workpiece and use method thereof |
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