CN101862269A - Preparation of nano-coating micropore surface implant having regeneration activity and antibacterial property - Google Patents
Preparation of nano-coating micropore surface implant having regeneration activity and antibacterial property Download PDFInfo
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Abstract
The invention relates to the preparation of a nano-coating micropore surface implant having a regeneration activity and an antibacterial property. The preparation is characterized in that the implant is a dental implant taking pure titanium or titanium alloy as a matrix and an artificial joint medicinal hard tissue implant material; and the surface of a matrix material is subjected to micro-roughness treatment, improved biomimetic liquid treatment and nano silver grain coating technology treatment to form a nano biomimetic coating structure having the regeneration activity and the antibacterial property, wherein the nano silver grain is a metallic silver elementary substance which is attached to the surface of the implant and has the antibacterial property and a tissue repairing function, and has the grain diameter of 6 to 50nm; and a nano coating crystal grain formed on the surface of the implant through treatment and induction is a bone-like hydroxyapatite material rich in calcium and phosphor. The micro-nano biomimetic coating implant has a bone-promoting regeneration activity and a high affinity; compared with an un-coating material, the coating implant is improved in the bonding force with bones by several times so as to effectively avoid the phenomena of loosening and shedding and to be a novel medicinal implant material having both the antibacterial property and the regeneration activity.
Description
Technical field
The present invention relates to a kind of technology with preparation of active nano bionic coating micropore surface artificial growth body (as tooth implant, the joint prosthesis implantation body) medical material with antibiotic property of regeneration biological.
Background technology
Bio-medical material (Biomedical Materials) and apparatus (Biomedical Instruments) are class hi tech and new materials that grows up over nearly 20 years, be to be used for the implant into body replacement or to repair tissue, organ, promote the special artificial material and the biological apparatus of a class of its physiological function, and biomedical material and product fields such as health, treatment and prevention generally have been used for.
For a long time, be extensive use of various clinically with metal (as cobalt, rustless steel, pure titanium metal etc.), implantation body's substitute material that pottery or macromolecule are made, but because of these materials biological activity, biocompatibility, biological guided bone and with aspects such as the mechanics matching existence shortcoming separately of original bone alive, often cause implantation body to implant the later stage and occur from coming off and relaxation, now few with or be eliminated.In recent years, alternate material to bone (or tooth) artificial growth body sclerous tissues chronicity has proposed new requirement both at home and abroad: reliable (the NIP reaction of the necessary long-term safety of the biomaterial in the implant into body, not intoxicating, carcinogenic and teratogenesis), biological behavior and performance close with sclerous tissues or consistent (being complementary) with the constituent and the mechanical performance of bone tooth, biologically active and bone conduction performance (can urge osteanagenesis, healing and osteoblast expresses); Material settling out is (the material surface characteristic is not influenced easy operating by making and sterilization) or the like accurately.Therefore, current medical material science is changed and filling develops into permanent firm plantation from short-term latent, enters activated regrown material from abiotic material for repairing development.
Recently, scholars are devoted to study some bioactive materials always, be fixed on the pure titanium implant surface as protein, polypeptide, enzyme and cell growth factor etc., serve as the aglucon or the receptor that close on cell, mechanism, make the artificial growth surface form an energy and the transition zone that biological activity adapts, try hard to make implantation body's material to have bone conduction concurrently and bone is induced dual function.For developing novel bioactive materials, the surface treatment technology of material of variety of way arises at the historic moment.At orthopaedics and the present the most frequently used surface modifying material of the department of stomatology is with hydroxyapatite (Hydroxyapatite HA), by physical method coating (as titanium or titanium alloy) on the metal material of mechanics mechanical performance excellence, making not active inert metal material surface modifying is to have good biological activity.
The processing method of modern prosthetic face coat is a lot, the research of metal base surface coating biology pottery has been carried out more than 20 year, the method of approval commonly used is plasma spray (plasmaspray) at present, and this process for treating surface generally is used on artificial joint and the tooth root planting body.Wherein to prepare hydroxyapatite coating layer be modal a kind of to titanium-based surface, with inanimate matter structural similarity in tooth and the osseous tissue, can directly produce chemical action and cause synostosis with host tissue, and be a kind of good tooth and the damaged substitution material of bone.But separately as hard tissue material's implant into body, have the shortcoming of mechanical compatibility difference, titanium and alloy thereof are inert biologically, and intensity is good, but during as implantation body, and its surface can take place to corrode and cause implanting and loosen.The mid-80 is from utilize plasma spraying technology that hydroxyapatite is coated on the titanium surface relatively independently, make composite implant, it combines the advantage of two kinds of materials, not only possesses certain mechanical strength, and excellent biological compatibility arranged, plant behind people's human body in a short time can with the soft or hard tissue bond, be considered to a kind of implantation body in biomaterial field at that time with wide development prospect.Hydroxyapatite coating layer (HA-Coating) though function in a large amount of zooperies and clinical practice, obtained certainly, but, expose many problems in the prolonged application of this material gradually, increasing recently report is pointed out: along with the time lengthening of bearing a heavy burden in vivo, the HA coating can cause that separation is cracked on this titanium alloy surface, molecule comes off from metal, causes the loose of cell-mediated osteolysis and joint.Result of study shows, the formed coating of plasma spraying method is difficult to evenly, temperature requirement is too high in the preparation process, the biological activity HA of one deck thin layer easily undergoes phase transition embrittlement, in cooling procedure, also can there be higher residual stress between coating and the metal material, can in body fluid, produce certain dissolubility after in the implantation body, influence the stability and the life-span of coating.Therefore, the coating material for preparing with physical method is faced with the problem that is difficult to overcome, and is exactly sprayed on material and metal material, and the fused problem in the interface of the material between coating and the host tissue.Also have many problems to solve in the application of artificial joint and tooth root planting body, distinct issues are to solve long-term loosening, prolong the life-span of artificial prosthesis.
Summary of the invention
The objective of the invention is: propose a kind of preparation method, to avoid above-mentioned deficiency with compound implantation body (as tooth implant, joint prosthesis) medical material of the active nano bionic coating micropore surface with antibiotic property of regeneration biological.
For realizing the object of the invention, intend adopting following technology:
The present invention relates to a kind of preparation with micro-nano bionical coating micropore surface implant having of regeneration biological activity and antibiotic property, it is characterized in that: described implantation body is to be the tooth implant and the medical hard tissue implanting material of joint prosthesis of matrix with pure titanium or titanium alloy; Substrate material surface is handled through the bionical liquid processing of little roughening treatment, the improvement of series, the processing of nanometer silver granuel and induced protein self assembly, forms the nano bionic coating structure with regeneration activity and antibiotic property; Wherein the nanometer silver granuel is a kind of argent simple substance with broad-spectrum antimicrobial effect and histiocyte reparative regeneration function that is attached to implant surface, and its particle diameter is 6-50nm; The nano coating crystal grain of described implant surface (size＜100nm), be the class bone hydroxyapatite material that is rich in calcium, phosphorus; This micro-nano bionical coating implantation body possesses promoting bone regeneration activity and high-affinity, with no coating material ratio, itself and synosteosis power significantly increase, and effectively prevent the loosening and obscission of implantation body, are a kind of new medical embedded materials of not only having had antibiotic property but also a tool regeneration activity.
The preparation method of above-mentioned nano bionic coating micropore surface implant having, its concrete steps are as follows:
(1) matrix surface roughening treatment: pure titanium plate or the little roughening treatment of titanium alloy sheet surface finish, through acetone, dehydrated alcohol ultrasonic cleaning (about 20min), distilled water flushing, drying, standby;
(2) electrolyte/bionical liquid preparation: prepare alkaline calcium/phosphorus electrolyte, wherein electrolyte ph is 10～11, and the mol ratio of calcium/phosphonium ion is 3; Preparation lime nitrate and the bionical liquid of phosphorus pentoxide, according to Ca/P than for the arbitrary ratio between the 1.60-1.70 with the two mixing ageing 36-48h, standby;
(3) handle in the electrolyte that will prepare through the pure titanium or the titanium test specimen of above-mentioned (1) step process; In the processing procedure, can finish up to processing at the surface observation of test specimen to countless small, discharge arc lights bright, that move about, electrolyte temperature is in rising trend, uses washed with de-ionized water after pretreatment is finished;
(4) under the vacuum condition, to be added with immersion treatment in the bionical liquid of nanometer silver granuel (its content accounts for the 2-15% of bionical liquid total amount) in advance through the pure titanium after above-mentioned (3) step process or titanium test specimen, induce the self assembly of surface of metal titanium albumen to handle, make metal base surface form micro nano-coatings structure with regeneration activity and antibiotic property, take out metal specimen, adopt ultraviolet radiation that it is activated and stabilized treatment;
Handle through above-mentioned serial reaction: the little roughening treatment of matrix surface, alkali heat treatment, nanometer silver burl close dynamic bionical liquid processing, induced protein self assembly processing and steps such as ultraviolet radiation activation and stabilized treatment, the titanio surface can be induced the nano coating active substance that is rich in calcium phosphorus (Ga-P), promptly obtains the nano bionic coating micropore surface implant having of described tool regeneration activity and antibiotic property.
The present invention's characteristics compared with the prior art:
1. biological activity height, can with the combining closely of bone formation biological and chemical in the body, biological in vivo blending and good stability, with no coated titanium alloy phase ratio, this implantation body can promote osteanagenesis and the early stage bone interface that forms, increase several times with the adhesion of bone, on morphology and mechanics, all show its superiority;
2. because what adopt is that titanium or titanium alloy are matrix material, this inert material intensity of load height, anti-toughness, resistance to wear strong, good mechanical property;
4. compare with current metal material surface HA physics spraying technology, the work simplification environmental protection, can obtain biomimetic coating material at low temperatures, microstructure and coating thickness are easy to control, surface bioactive is more stable, can form special bone-GaP-material combination interface in the transplant, performance " bone conduction " effect, cost after this optimization of process conditions is than the bigger decline of like product, and price positioning is more reasonable;
5. owing to activate and stabilized treatment through ultraviolet irradiation, need not excessive temperature and rapid cooling procedure in the preparation process, there is not residual stress between coating and the material, do not influence the stability and the life-span of coating after in the implantation body, the phenomenon that no molecule comes off from the metal surface, overcome insoluble two kinds of material interface problems that plasma spraying method faces, lowered the complication after implanting greatly, the time and the life-span of bearing a heavy burden in the body are prolonged.
6. owing to metallic matrix of the present invention has added the nanometer silver granuel as effective antibacterial and promotion histiocyte reparative factor in the bionical liquid immersion treatment process of improvement, therefore the product of its preparation also has antibacterial effect and tissue repair function, the composite implant material for preparing under present widely used titanium and the hydroxyapatite sprayed technology is more excellent than its biological property, has avoided implanting the phenomenon that the back surrounding tissue is inflamed.
Description of drawings
Fig. 1 is the surface micropore structure sem photograph of little roughening treatment implantation body;
Fig. 2 is the implant surface bionic nano coating structure Electronic Speculum figure behind the adding nanometer silver granuel.
The specific embodiment
The present invention relates to a kind of preparation with nano bionic coating micropore surface implant having of regeneration activity and antibiotic property, it is characterized in that: described implantation body is to be the medical hard tissue implanting material of tooth implant, joint prosthesis of matrix with pure titanium or titanium alloy; Substrate material surface through little roughening treatment of series, improve that bionical liquid (in add 2-15% nanometer silver granuel) is handled, induced protein self assembly processing and ultraviolet radiation activation and stabilized treatment, form micro-nano bionical coating structure with regeneration activity and antibiotic property; Wherein the nanometer silver granuel is a kind of argent simple substance with broad-spectrum antimicrobial effect and histiocyte reparative regeneration function that is attached to implant surface, and its particle diameter is 6-25nm; The micro-nano bionical coating of described implant surface is the class bone hydroxyapatite material that is rich in calcium, phosphorus.Transition zone by surface coarsening combines titanio body and micro nano-coatings are effective, reach implantation body and perienchyma's tighter integration by the promoting bone regeneration activity of regeneration biological active micron/nanometer coating with the high-affinity of organizing, with no coating material ratio, itself and synosteosis power increase several times, prevent that effectively implantation body is loosening and come off; In addition, by the immersion treatment of nanometer silver granuel and bionical liquid, this implantation body also has antibacterial effect and histiocyte Regeneration and Repair function.
Coating processing procedure of the present invention activates and stabilized treatment the nano bionic crystal film through ultra-vioket radiation, owing to activate stabilized treatment through ultraviolet irradiation, need not excessive temperature and rapid cooling procedure in the preparation process, there is not residual stress between coating and the material, do not influence the stability and the life-span of coating after in the implantation body, the phenomenon that no molecule comes off from the metal surface does not have two kinds of material interface problems that are difficult to overcome that plasma spraying method faces yet.Lowering the complication after implanting greatly, is to prolong in the time and the life-span of bearing a heavy burden in the body.
Its concrete preparation process is as follows:
(1) matrix surface roughening treatment: after pure titanium plate or the roughening polishing of titanium alloy sheet surface, acetone, dehydrated alcohol ultrasonic cleaning (about 20min), distilled water flushing, drying, standby;
(2) electrolyte/bionical liquid preparation: prepare alkaline calcium/phosphorus electrolyte, wherein electrolyte ph is 10～11, and the mol ratio of calcium/phosphonium ion is 3; Compound concentration is lime nitrate and the bionical liquid of phosphorus pentoxide of 0.2mol/L, and implants antibacterial in bionical liquid, as the zirconium phosphate carrying silver antimicrobials, for the arbitrary ratio between the 1.60-1.70 the two is mixed according to the Ca/P ratio, and mixing ageing 36-48h, standby;
(3) differential arc oxidation is handled in the electrolyte that will prepare through the pure titanium or the titanium test specimen of above-mentioned (1) step process; In the processing procedure, can finish up to processing at the surface observation of test specimen to countless small, discharge arc lights bright, that move about, electrolyte temperature is in rising trend, uses washed with de-ionized water after pretreatment is finished;
Its technological requirement is as follows: with the titanium test specimen is anode, and stainless steel substrates is a negative electrode; Voltage is set at 400-500V, and frequency is 800-1000Hz, and the processing time is 5-10min;
(4) under the vacuum condition, will be through pure titanium after above-mentioned (3) step process or titanium test specimen immersion treatment in being added with the bionical liquid of nanometer silver granuel in advance, wherein nanometer silver granuel content accounts for the 2-15% (this embodiment gets 4%) of bionical liquid gross mass, can induce the self assembly of surface of metal titanium albumen to handle in the immersion process, form the micro-nano bionical coating of metal base surface, from solution, slowly pull out test specimen then, adopt the ultraviolet radiation irradiation to activate and stabilized treatment to micro-nano bionical crystal film coating, therefore need not through excessive temperature and rapid temperature-fall period.
Handle through above-mentioned serial reaction: the little alligatoring of matrix surface, alkali heat treatment, nanometer silver burl close dynamic bionical liquid processing, induced protein self assembly processing and steps such as ultraviolet irradiation activation and stabilized treatment, the micro-nano bionical coating active substance of the regeneration activity that is rich in calcium phosphorus (Ga-P) can be induced in the titanio surface, described nano bionic coating micropore surface implant having can be obtained with tool regeneration activity and antibiotic property.
Below the antibiotic property, tissue repair and the safety non-toxic that are embodied in the present invention by concrete elaboration nanometer silver granuel of the present invention.
(1) antibiotic property of nanometer silver granuel
Set up the HDPE culture plate of positive control sample (the HDPE culture plate of no nanometer silver granuel) and interpolation 4% nanometer silver granuel, respectively staphylococcus aureus and two kinds of tests of escherichia coli bacterium are cultivated test, cultivate and detect clump count after 24 hours, as shown in table 1.
Table 1: nanometer silver granuel antibacterial effect testing result
Do not add antibacterial normal growth and procreation fast on the culture medium of nanometer silver granuel as can be seen from Table 1, antibacterial significantly is suppressed or kills and wounds on the culture medium of nanometer silver granuel and be added with, and the antibiotic rate of staphylococcus aureus reaches 98.99%; Colibacillary antibiotic rate reaches 99.00%, and the nanometer silver granuel that visible this invention proposes not only has broad-spectrum antimicrobial effect, and shows extremely strong antibiotic rate.
(2) reparation of nanometer silver granuel
Nanometer silver can promote wound healing, promotes the reparation and the regeneration of damaged cell, and removing the necrotic tissue and promoting granulation, anti-inflammation improve the microcirculation of wound surrounding tissue, activates effectively and promotes histiocytic growth, and the healing of accelerated in wounds reduces the generation of cicatrix.
(3) toxicity of nanometer silver granuel
Silver material is put down in writing in Compendium of Material Medica: give birth to silver, and nontoxic; Explanation in U.S. public health bureau nineteen ninety " about the toxic investigation report of silver ": silver does not have obvious toxic-side effects to human body; Nanometer silver is a local application, and silver content is few, is safest application method.Investigate to find mice at oral maximum tolerated dose 925mg/kg through test, when promptly being equivalent to 4625 times of clinical using dosage, do not have any toxic reaction, in the skin irritation test of rabbit, also do not find any irritant reaction.Therefore, the nanometer silver granuel is the antimicrobial drug of safety non-toxic.
Further detect below, with the explanation biological superiority that product of the present invention was possessed by performance to the product (being nano-coating micropore surface implant having) of the present invention preparation.
Observe the surface topography of titanium metal implants coating with scanning electron microscope (SEM), with Rigaku D/max-3CX-x ray diffractometer x (X-ray diffraction, XRD) and the X-ray energy spectrum analyser (energydispersive X-rhy analysis, EDX) composition and the element of analyzing rete distributes.The automatic scratching instrument of WS-2002 coating adhesion is measured its adhesion, TR240 portable surface roughmeter measure surface roughness.
Testing result:
1, titanium metal implants coating surface pattern, energy spectrum analysis and coating substance facies analysis show, coating surface presents the structure (as shown in Figure 1) of rough porous, and the uniform distribution aperture is approximately 5 μ m micropores, and mutual traffic reticulates between the part micropore; Crystallite dimension in the nano coating is:＜100nm (as shown in Figure 2); Eddy current thickness meter shows: coating layer thickness is about 6 μ m, and coating surface is even.
2, coating surface is active observes: in bionical body fluid good response is arranged, the visible initial coating in micro nano-coatings surface is covered by the hydroxyapatite that one deck approaches, but this coating is thinner, and is not fine and close, the rough porous network structure of still visible bottom surface of metal titanium, the aperture is covered by HA and diminishes.
3, micro nano-coatings energy spectrum analysis found that the element kind does not change in the coating, but Ga, P element obviously rise, and the Ti constituent content obviously descends, and Ga/P element ratio is about 1.63.
4, coating's adhesion and roughness: testing result shows, the mechanical property of coating and people's bone photo symbol, its bond strength be applicable to the load-bearing of human body and load (＞20Mpa), coating surface roughness (Ra value) is 0.981, the adhesion of coating and matrix is (32 ± 2.5) N.
5, the present invention prepared implantation body after the nanometer silver granuel soaks not only has the tissue repair function, also has antibacterial effect, and its antibiotic rate reaches more than 99.00%.
Analyze and sum up:
The history in year surplus the titanium metal implants existing 50, pure titanium has excellent biological compatibility, and can form 5～10 μ m oxide-films naturally on its surface.But oxide-film of Xing Chenging and body binding ability are poor naturally, show as biologically inert.Therefore, the pure titanium implant surface modification becomes the focus of present embedded material research.Matrix material and coating that the present invention faces at present embedded material just, interface problem between coating and the tissue carries out research design, process conditions by improvement and optimization preparation implantation body, prepared the nano coating structure implantation body material of biologically active and bone biocompatibility, the adhesion of itself and bone increases several times, on morphology and mechanics, all show its superiority, and reduced the technical difficulty and the cost of preparation.Experiment in vivo and vitro proves, after the implantation body's product under the technology of preparing of the present invention implants, shows the good biological activity ability of facilitating osteocyte generation and osteanagenesis; And, owing to added the nanometer silver granuel in the metallic matrix immersion treatment process of the present invention as effective antibacterial and short histiocyte reparative factor, therefore the implantation body of its preparation also has antibacterial efficacy and tissue repair function, coated titanium implantation body under present widely used hydroxyapatite sprayed technology is more excellent, will be a kind of novel implantation body of micro-nano bionical coating material with antibacterial effect and regeneration activity.
Claims (4)
1. the preparation of the nano-coating micropore surface implant having of regeneration activity and antibiotic property is characterized in that: described implantation body is to be the tooth implant and the medical hard tissue implanting material of artificial joint of matrix with pure titanium or titanium alloy; Substrate material surface is handled through the bionical liquid processing of little roughening treatment, the improvement of series, nanometer silver granuel coating technology, forms the micro-nano bionical coating structure with regeneration activity and antibiotic property.
2. the nano-coating micropore surface implant having of regeneration activity according to claim 1 and antibiotic property, it is characterized in that: described nanometer silver granuel, be a kind of argent simple substance with broad-spectrum antimicrobial effect and histiocyte reparative regeneration function that is attached to implant surface, its particle diameter is 6-50nm.
3. the nano-coating micropore surface implant having of tool regeneration activity according to claim 1 and antibiotic property, it is characterized in that: the micro nano-coatings of described implant surface, it is one deck homogeneous film sample material that forms naturally in the metal implant surface after treatment, be rich in the class bone hydroxyapatite of calcium, phosphorus, constitute less than the crystal grain of 100nm by a plurality of needle point samples, size under the Electronic Speculum.
4. according to the preparation method of the nano-coating micropore surface implant having of claim 1 or 2 or 3 described tool regeneration activities and antibiotic property, it is characterized in that concrete steps are as follows:
(1) matrix surface roughening treatment: pure titanium plate or the little roughening treatment of titanium alloy sheet surface finish, through acetone, dehydrated alcohol ultrasonic cleaning, distilled water flushing, drying, standby;
(2) electrolyte and bionical liquid preparation: prepare alkaline calcium, phosphorus electrolyte, wherein electrolyte ph is 10～11, and the mol ratio of calcium/phosphonium ion is 3; Preparation lime nitrate and the bionical liquid of phosphorus pentoxide, according to Ca/P than for the arbitrary ratio between the 1.60-1.70 with the two mixing and ageing 36-48h, standby;
(3) handle in the electrolyte that will prepare through the pure titanium or the titanium test specimen of above-mentioned (1) step process; In the processing procedure,, finish up to processing to countless small, discharge arc lights bright, that move about at the surface observation of test specimen, electrolyte temperature is in rising trend, the back washed with de-ionized water of finishing dealing with;
(4) under the vacuum condition, will be through pure titanium after above-mentioned (3) step process or titanium test specimen immersion treatment in being added with the bionical liquid of nanometer silver granuel in advance, induce the self assembly of surface of metal titanium albumen to handle, make metal base surface form micro-nano bionical coating structure with regeneration activity and antibiotic property, take out metal specimen, adopt ultraviolet radiation that it is activated and stabilized treatment;
Handle through above-mentioned serial reaction: the little roughening treatment of matrix surface, alkali heat treatment, nanometer silver burl close dynamic bionical liquid processing, the induced protein self assembly is handled, and steps such as ultraviolet radiation activation and stabilized treatment, the titanio surface can be induced the micro nano-coatings active film that is rich in calcium, phosphorus, promptly obtains the nano-coating micropore surface implant having of described tool regeneration activity and antibiotic property.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102113919B (en) * | 2009-12-30 | 2013-07-03 | 财团法人金属工业研究发展中心 | Human body implant and manufacturing method thereof |
| CN104117093A (en) * | 2013-09-02 | 2014-10-29 | 靳潇潇 | Dental implant with biological coating and manufacturing method thereof |
| US9353453B2 (en) | 2012-07-19 | 2016-05-31 | Politecnico Di Milano | Metal substrate modified with silicon based biomimetic treatment having antibacterial property for the osteointegration thereof |
| CN106075593A (en) * | 2016-06-21 | 2016-11-09 | 林春梅 | A kind of preparation method of wear-resisting artificial joint coating material |
| CN107059006A (en) * | 2017-03-24 | 2017-08-18 | 纳狮新材料股份有限公司 | Composite coating skeletal support frame and preparation method thereof |
| CN108866601A (en) * | 2018-06-28 | 2018-11-23 | 内蒙古工业大学 | A kind of differential arc oxidation method of the Ti5111 alloy based on heat treatment |
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2010
- 2010-05-17 CN CN201010173655A patent/CN101862269A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102113919B (en) * | 2009-12-30 | 2013-07-03 | 财团法人金属工业研究发展中心 | Human body implant and manufacturing method thereof |
| US9353453B2 (en) | 2012-07-19 | 2016-05-31 | Politecnico Di Milano | Metal substrate modified with silicon based biomimetic treatment having antibacterial property for the osteointegration thereof |
| CN104117093A (en) * | 2013-09-02 | 2014-10-29 | 靳潇潇 | Dental implant with biological coating and manufacturing method thereof |
| CN104117093B (en) * | 2013-09-02 | 2015-12-09 | 靳潇潇 | A kind of mouth cavity planting body with biological coating and preparation method thereof |
| CN106075593A (en) * | 2016-06-21 | 2016-11-09 | 林春梅 | A kind of preparation method of wear-resisting artificial joint coating material |
| CN107059006A (en) * | 2017-03-24 | 2017-08-18 | 纳狮新材料股份有限公司 | Composite coating skeletal support frame and preparation method thereof |
| CN108866601A (en) * | 2018-06-28 | 2018-11-23 | 内蒙古工业大学 | A kind of differential arc oxidation method of the Ti5111 alloy based on heat treatment |
| CN108866601B (en) * | 2018-06-28 | 2019-06-21 | 内蒙古工业大学 | A kind of differential arc oxidation method of the Ti5111 alloy based on heat treatment |
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Application publication date: 20101020 |