CN101612418A - A kind of titanium-hydroxylapatite gradient coating and preparation method thereof and application - Google Patents
A kind of titanium-hydroxylapatite gradient coating and preparation method thereof and application Download PDFInfo
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- CN101612418A CN101612418A CN200910041438A CN200910041438A CN101612418A CN 101612418 A CN101612418 A CN 101612418A CN 200910041438 A CN200910041438 A CN 200910041438A CN 200910041438 A CN200910041438 A CN 200910041438A CN 101612418 A CN101612418 A CN 101612418A
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Abstract
The invention discloses a kind of titanium-hydroxylapatite gradient coating and preparation method thereof and application.Coating of the present invention is substrate with the matrix, and the composition of each layer is respectively from inside to outside: the titanium valve layer; Titanium valve and hydroxyapatite mixed layer, and the volume ratio of the two is 6: 4; Titanium valve and hydroxyapatite mixed layer, and the volume ratio of the two is 4: 6; Hydroxyapatite layer.Coating of the present invention all sprays with the low-voltage plasma spraying technology, can be used for handling the titanium alloy implant surface.Coating of the present invention has high stability, and it is good that its biological activity keeps, and is used to handle implant surface, can reduce thermal coefficient of expansion, elastic modelling quantity difference between coating material and the implantation body, thereby the residual stress of coating is reduced, with the bond strength rising of implantation body; Coating utilization low-voltage plasma technology of the present invention sprays, and can reduce the porosity of coating, can improve coating and implantation body's high base strength.
Description
Technical field
The present invention relates to the production of coatings field of bioactive implant, be specifically related to a kind of titanium-hydroxylapatite gradient coating and preparation method thereof and application.
Background technology
Hydroxyapatite (HA), chemical formula are Ca
10(PO
4)
6(OH)
2, have with human body bone and tooth in similar chemical composition and the crystal structure of main mine material apatite, be the main inanimate matter composition that constitutes body bone tissue.HA belongs to biological active ceramic material, has good biocompatibility and biological activity, can with body osseous tissue generation interfacial reaction, form chemical bonding, and promote the body osseous tissue in its superficial growth.Titanium alloy substrate surface deposition HA bioactivity coatings fully combines metal material and biological active ceramic material advantage separately, both had the high intensity of metal material, toughness, the good biological property and the biocompatibility of biologically active ceramic material again, and the metal ion that can stop or reduce implantation body's matrix discharges, be easy to form firm combining, improved the success rate after the plantation to a certain extent with osseous tissue.Scholars recognize that on the titanium or titanium alloy matrix single HA coating can't satisfy this requirement aspect two of the biological activity of coating and coating and high base strength simultaneously well.Therefore, domestic and international many researcheres all are devoted to the study on the modification to the HA coating.Mainly be that the coating after the spraying is heat-treated at present in the approach that improves aspect the strength of coating, and on matrix preparation gradient coating or composite coating, to improve the bond strength of coating interface.The main cause that lacks bond strength between matrix and the HA coating is the flip-flop that the difference of two kinds of material coefficient of thermal expansion coefficients causes the boundary zone physical property more greatly.Therefore carried out the research of gradient coating in order to reduce the coating failure phenomenon scholars that this discontinuity causes.The basic thought of gradient coating design be material with two kinds of different performances according to specific requirement, form by changing continuously, its internal interface is disappeared, to reduce or to overcome because of the do not match decline of the material property that caused of interface performance.Therefore have homogeneous material and the incomparable advantage of single coating material, overcome the bonded performance of the different materials factor that do not match, the advantage of two kinds of materials all is not fully exerted.Therefore, make up the HA gradient coating at titanium implant surface and become a research focus.Method mainly contains: 1. HA and other biological Ceramic Composite; 2. HA and inactive ceramic are compound; 3. HA and metal composite.Because titanium or titanium alloy is the main flow material of implantation body's matrix at present, chooses the compound preparation gradient coating of HA and titanium valve, then the transition zone of boundary zone is the fusion with metalloid, can effectively improve Bond Strength of Coating.
The method for preparing hydroxyapatite coating layer comprises the plated film sintering, immerses coating, high temperature insostatic pressing (HIP), ion plating, sputter, pulsed laser deposition and plasma spraying etc.Wherein plasma spraying is the domestic and international up to now preparation method of the HA coating of broad research the most, also is one of method of commercial implantation body employing.But because HA at high temperature easily goes hydroxyl and decomposition, cause the stability decreases of coating, thereby reduce Bond Strength of Coating, this will influence the secular firm and success of implantation body.And the active material titanium is not recommended to adopt conventional plasma spraying method yet, and is very strong because they react in high temperature, and absorbs gas, causes the performance of coating to descend.Low-voltage plasma spraying (LPPS) is from the flame-spraying technical development and a kind of novel spraying technology of coming, be widely used in industry and scientific research field owing to almost being sprayed at any material, this technology is one of developing state-of-the-art technology of plasma spray technology.LPPS works under the low-pressure argon inert gas shielding, and this technology has the particle rapidity height, and coating is characteristics such as vulnerable to pollution not, are particularly suitable for spray metal or metal alloy coating.Characteristics such as coatings prepared has the bond strength height, and porosity is low.According to the characteristics of LPPS, this technology can be used to prepare high dense oxide ceramic coating, easily causes the shortcoming of metal material oxidation under the mal-condition that conforms the demand of high-quality ceramic coating has been overcome it with respect to the plasma spraying under the atmospheric condition.The LPPS technology at first is applied on the aero-engine parts, because the coating densification that this technology is made, composition is even, and coating and matrix have good binding intensity, and deposition is higher.So now at a large amount of bottoms that adopt the LPPS technology on parts such as aeroturbine blade, guide vane, to make ORC and thermal barrier coating of countries such as America and Europe.According to NASA company, low-voltage plasma spraying 8%Y
2O
3-ZrO
2Coatings applications during some parts, can reach about 5 times of APS coated component its service life on shuttle motor.The LPPS technology has following characteristics: 1. under the low pressure condition, plasma flame flow has characteristics such as elongation, diffusion, diameter chap, and has improved the place soil and the powder particle speed of plasma flame flow; 2. under the low pressure condition, can obtain high-temperature plasma flame stream, controlled atmosphere is provided, and allows matrix surface that higher preheat temperature is arranged, and unlikelyly cause oxidation; 3. under the low pressure condition, can relax the excursion of spray distance, in the spraying process, crystallization and diffusing phenomenon be arranged on the interface of sprayed on material and matrix surface, improve coating and high base strength greatly.Therefore, other plasma spraying technologies utilize LPPS technology spraying titanium valve to have certain advantage relatively.
Summary of the invention
The objective of the invention is in the prior art, the defective tightness that combines of coating and implantation body, and the high temperature in the conventional spray paint process causes the stability of hydroxyapatite and the deficiency that biological activity all is damaged, a kind of titanium-hydroxylapatite gradient coating is provided, this coating is by the volume ratio of titanium valve and hydroxyapatite in the successive change coating, make coating form gradient, thereby the biological activity that has kept coating, reduce thermal coefficient of expansion and elastic modelling quantity difference between coating material and the implantation body, improved coating and implantation body's high base strength.
Another object of the present invention is to provide a kind of preparation method of titanium-hydroxylapatite gradient coating, promptly implantation body's matrix is sprayed with the low-voltage plasma spraying technology.This technology can overcome the shortcoming that the conventional spray paint technology causes the metal material oxidation easily, issue the characteristics such as elongation, diffusion and reducing of having waved plasma flame flow in the low pressure condition, make the titanium-hydroxylapatite gradient coating that obtains through this technology spraying be difficult for oxidation, also can reduce the porosity of coating, make coating tightr with combining of implantation body matrix.
The object of the invention is achieved by following scheme:
With the low-voltage plasma spraying technology matrix is sprayed, the titanium-hydroxylapatite gradient coating of formation is substrate with the matrix, and the composition of each layer is respectively from inside to outside: the titanium valve layer; Titanium valve and hydroxyapatite mixed layer, and the volume ratio of the two is 6: 4; Titanium valve and hydroxyapatite mixed layer, and the volume ratio of the two is 4: 6; Hydroxyapatite layer.
Titanium-hydroxylapatite gradient coating of the present invention is mainly used in and handles the titanium alloy implant surface.
Compared with prior art, the present invention has following beneficial effect:
Titanium-hydroxylapatite gradient coating of the present invention reduces or has eliminated titanium valve and hydroxyapatite performance decrease, has high stability, and it is good that biological activity keeps, be used to handle implantation body's matrix surface, can improve coating and implantation body's high base strength, reduce thermal stress, realize the graded of coating thermal coefficient of expansion, reduce the driving force that causes the material fracture, stop the crack to produce, improve the long-time stability of implantation body under physiological environment.
Description of drawings
Fig. 1 is a titanium alloy implantation body matrix sketch map.
Fig. 2 is a titanium-hydroxyapatite coating sketch map, and wherein, 1 is the titanium valve layer, and 2 and 3 is hydroxyapatite layer, and 4 is hydroxyapatite layer, and 5 is titanium alloy substrate.
Fig. 3 is a titanium-hydroxylapatite gradient coating implantation body.
The specific embodiment
The invention will be further described below in conjunction with embodiment, but specific embodiment is not done any qualification to the present invention.
Embodiment 1 implant surface morphology observation
Be machined into 100 pieces of solid column thread implant matrixes with titanium-6 aluminum-4 vanadium (Ti-6AL-4V) rod, material and processing provide by south, Guangzhou maple bio tech ltd.Specification is: total length 7.5mm, and the long 6.0mm of lower end threaded portion, diameter 3.0mm's is cylindric, flight pitch 1.0mm, depth of thread 0.3mm; The upper end unthreaded portion is the hexagon (Fig. 1) of long 1.5mm, diameter 2.38mm.Implantation body's matrix is carried out oil removing, cleaning step: place acetone, 75% ethanol, deionized water for ultrasonic to clean each 10min, 50 ℃ of dry 24h.Carry out different surface treatments and make up three groups of implantation bodys:
1. matched group I: (Machine Aided MA), inserts passivation 50min in 50% salpeter solution with 25 pieces of implantation body's matrixes in machine cuts implantation body.
2. control Group II: hydroxyapatite coating layer implantation body (Hydroxyapatite HA), with hydroxyapatite powder, adopts low-voltage plasma spraying equipment (DYDP-1), voltage 70V, and electric current 650A is at 25 pieces of implantation body's matrix surface spraying hydroxyapatite coatings.
3. the experimental group: (Titanium-Hydroxyapatite of titanium-hydroxylapatite gradient coating implantation body, Ti-HA), pure titanium and hydroxylapatite powder are mixedly configured into the mixed-powder of different volumes ratio, adopt low-voltage plasma equipment, voltage 70V, electric current 650A is at the 50 pieces of matrix surface spraying Ti-HA of implantation body gradient coatings.The sketch map of gradient coating such as Fig. 2, the sketch map of titanium-hydroxylapatite gradient coating implantation body such as Fig. 3.
The implant surface processing procedure is all finished at Guangzhou Research Institute of Nonferrous Metals surface treatment institute, more than three groups of implantation body's processed intact after, washed with de-ionized water for several times, 50 ℃ of dry 24h, after the packing, autoclaving 30min.
Titanium alloy implant surface after two kinds of different spray-on coatings are handled is made of the granule and the hole of numerous out-of-shapes, flat not of uniform size, is the rough porous form.The granule of flat interconnects, and constitutes continuous structure, and the part spheroidal particle is arranged or by the flat particle parcel or be attached on the flat particle surface, make rough surface form the shape characteristic in countless " secondary nest holes ".
Every group of implantation body's stochastic sampling is 1 piece from the above implantation body that handles, with scanning electron microscope (Scanning ElectronMicroscopic, SEM, JSM-5910) observation sample surface topography.Behind the scanning electron microscopic observation, each sample surfaces adopts X-ray diffraction (XRD, D/max-rc) analyze the XRD figure spectrum of implant surface chemical constitution by HA powder, HA coating and Ti-HA gradient coating, as seen the apatite crystal degree of coating is lower than the HA powder, in two kinds of coating XRD figure spectrum except the apatite peak shape of broadening and enhanced CaO mutually, also have TCP (tricalcium phosphate) phase, it produces the decomposition that reason may increase apatite for the high temperature in the spraying process.Generally the design of gradient coating does not obviously change the apatite crystalline phase.
The mensuration of embodiment 3 strength of coatings
With hot strength characterizing coating and high base strength.The method of testing of hot strength is carried out with reference to the ASTM-C633279 standard, utilizes the JDL-50KN cupping machine to test two kinds of Bond Strength of Coating respectively.Use two cylindric titanium alloy rods, diameter 25mm, wherein an end is Ti-HA gradient coating or HA coating, stick together by E7 resin glue and another barren titanium alloy rod, place 100 ℃/3h in the baking oven, utilize cupping machine to stretch then, until coating shedding to both sides.Every kind of coating tested 4 pairs of samples, gets the meansigma methods of test result and represents Bond Strength of Coating.
Found that gradient coating design raising to a certain degree the adhesion strength of coating and matrix.
All much larger than negative control group MA implantation body, its difference has statistical significance (P＜0.05) at the torque value of each time period in Ti-HA gradient coating implantation body; Its torque value also shows as with HA implantation body very nearly the same simultaneously.
Under optical microscope, observe the bone regeneration around implant tissue slice after HE dyeing, compare analysis.
2 weeks of postoperative: as seen respectively organize osteoblastic appearance in the bone regeneration around implant bone matrix, trabecular bone structure is tiny, part osteoid mineralising, the formation of visible a small amount of woven bone.MA bone regeneration around implant sclerotin is inmature relatively, and the existence of fibrous tissue is arranged between bone trabecula.
4 weeks of postoperative: the osteoblast of Ti-HA gradient coating implantation body and HA bone regeneration around implant is many slightly than MA implantation body, the formation of visible osteoid in subregion and lamellar bone.
6 weeks of postoperative: the more lamellar bone of Ti-HA gradient coating implantation body and HA bone regeneration around implant generates, and trabecular bone structure is comparatively thick, tight and seriality is good, and osteoblast quantity reduces to some extent.The osteoblast quantity of MA implantation body obviously reduces.
Claims (5)
1. a titanium-hydroxylapatite gradient coating is characterized in that this coating is substrate with the matrix, and ground floor from inside to outside is the titanium valve layer, and the second layer and the 3rd layer are titanium valve and hydroxyapatite mixed layer, and last one deck is a hydroxyapatite layer.
2. titanium-hydroxylapatite gradient coating according to claim 1 is characterized in that in this coating that the titanium valve in the second layer and the volume ratio of hydroxyapatite are 6: 4.
3 titanium-hydroxylapatite gradient coatings according to claim 1 is characterized in that in this coating, and the titanium valve in the 3rd layer and the volume ratio of hydroxyapatite are 4: 6.
4. the preparation method of the described titanium-hydroxylapatite gradient coating of claim 1 is characterized in that this method is to utilize the low-voltage plasma spraying technology, successively sprays titanium valve and hydroxyapatite.
5. the described titanium-hydroxylapatite gradient coating of claim 1 is in the application of titanium alloy implant surface processing.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104800887A (en) * | 2014-01-24 | 2015-07-29 | 苏州博恩瑞科生物材料有限公司 | Porous titanium coating, titanium-containing multi-coating, preparation method and application thereof |
| CN104841018A (en) * | 2015-04-21 | 2015-08-19 | 昆明理工大学 | Multilayered biological composite material and preparation method thereof |
| CN106215237A (en) * | 2016-08-23 | 2016-12-14 | 华南理工大学 | A kind of preparation method of the antibacterial tooth implant coating promoting the growth of gingiva neural blood vessel |
| CN108441805A (en) * | 2018-03-19 | 2018-08-24 | 浙江工业大学 | A method of titanium-based surface HA coatings are prepared using complex technique |
| CN108815581A (en) * | 2018-06-25 | 2018-11-16 | 新余学院 | A kind of preparation method of double nano hydroxyapatite/Ti complex gradient coating |
-
2009
- 2009-07-28 CN CN200910041438A patent/CN101612418A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104800887A (en) * | 2014-01-24 | 2015-07-29 | 苏州博恩瑞科生物材料有限公司 | Porous titanium coating, titanium-containing multi-coating, preparation method and application thereof |
| CN104841018A (en) * | 2015-04-21 | 2015-08-19 | 昆明理工大学 | Multilayered biological composite material and preparation method thereof |
| CN106215237A (en) * | 2016-08-23 | 2016-12-14 | 华南理工大学 | A kind of preparation method of the antibacterial tooth implant coating promoting the growth of gingiva neural blood vessel |
| CN108441805A (en) * | 2018-03-19 | 2018-08-24 | 浙江工业大学 | A method of titanium-based surface HA coatings are prepared using complex technique |
| CN108815581A (en) * | 2018-06-25 | 2018-11-16 | 新余学院 | A kind of preparation method of double nano hydroxyapatite/Ti complex gradient coating |
| CN108815581B (en) * | 2018-06-25 | 2021-01-08 | 新余学院 | Preparation method of double-nano hydroxyapatite/titanium composite gradient coating |
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Application publication date: 20091230 |