CN114453593A - Preparation method of personalized customized titanium alloy implant bracket with biological activity - Google Patents
Preparation method of personalized customized titanium alloy implant bracket with biological activity Download PDFInfo
- Publication number
- CN114453593A CN114453593A CN202210126783.2A CN202210126783A CN114453593A CN 114453593 A CN114453593 A CN 114453593A CN 202210126783 A CN202210126783 A CN 202210126783A CN 114453593 A CN114453593 A CN 114453593A
- Authority
- CN
- China
- Prior art keywords
- titanium alloy
- stent
- personalized
- preparing
- scaffold
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 100
- 239000007943 implant Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000004071 biological effect Effects 0.000 title description 3
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 50
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 41
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000002086 nanomaterial Substances 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 238000007639 printing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000007747 plating Methods 0.000 claims abstract description 5
- 238000010894 electron beam technology Methods 0.000 claims abstract description 4
- 238000002513 implantation Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 36
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 238000000151 deposition Methods 0.000 claims description 11
- 238000010146 3D printing Methods 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 7
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 238000004544 sputter deposition Methods 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 230000009286 beneficial effect Effects 0.000 claims description 5
- 230000012010 growth Effects 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 230000003746 surface roughness Effects 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims description 2
- 239000007888 film coating Substances 0.000 claims description 2
- 238000009501 film coating Methods 0.000 claims description 2
- 231100001240 inorganic pollutant Toxicity 0.000 claims description 2
- 238000009304 pastoral farming Methods 0.000 claims description 2
- 239000013077 target material Substances 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 11
- 238000010883 osseointegration Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 14
- 210000001519 tissue Anatomy 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- 238000013532 laser treatment Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000012620 biological material Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 208000014674 injury Diseases 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 230000010261 cell growth Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 230000000399 orthopedic effect Effects 0.000 description 2
- 230000035755 proliferation Effects 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 208000027205 Congenital disease Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000024245 cell differentiation Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000004064 dysfunction Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- -1 firstly Chemical compound 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 210000005260 human cell Anatomy 0.000 description 1
- 230000000642 iatrogenic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005542 laser surface treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 210000000963 osteoblast Anatomy 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002271 resection Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 230000008733 trauma Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/20—Direct sintering or melting
- B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium alloys
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/30—Process control
- B22F10/36—Process control of energy beam parameters
- B22F10/366—Scanning parameters, e.g. hatch distance or scanning strategy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/60—Treatment of workpieces or articles after build-up
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Public Health (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Inorganic Chemistry (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Dermatology (AREA)
- Veterinary Medicine (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plasma & Fusion (AREA)
- Physics & Mathematics (AREA)
- Automation & Control Theory (AREA)
- Materials For Medical Uses (AREA)
- Prostheses (AREA)
Abstract
The invention relates to a preparation method of a personalized customized titanium alloy implant bracket with bioactivity, which comprises the following steps: s1, acquiring image data of the damaged bone tissue of the human body; s2, establishing a three-dimensional porous model of the titanium alloy implantation bracket at the appointed part of the human body according to the image data of the damaged bone; s3, manufacturing the titanium alloy artificial bone scaffold by adopting a metal 3D laser or electron beam printing system according to the three-dimensional model of the implanted scaffold; s4, cleaning and drying the titanium alloy artificial bone scaffold; s5, preparing a micro-nano structure on the surface of the titanium alloy artificial bone scaffold by using laser, and regulating and controlling the surface energy and roughness of the micro-nano structure; s6, plating a high-purity tantalum film with nanometer-level thickness on the surface of the titanium alloy artificial bone scaffold. The invention has the advantages that: the bioactivity of the titanium alloy implant bracket is enhanced, and the osseointegration effect is improved.
Description
Technical Field
The invention relates to the technical field of medical titanium alloy stents implanted into a body, in particular to a preparation method of a personalized titanium alloy stent implanted into a body with surface bioactivity.
Background
Bone defects caused by trauma, infection, tumor resection or congenital diseases are extremely difficult to treat, are the main causes of limb dysfunction, and cause great economic burden to families and society. Metal orthopedic implants are one of the major methods of treating large bone defects.
The medical titanium alloy has the advantages of low density, high specific strength and mechanical property close to that of human bones, has the characteristics of fatigue resistance, excellent biocompatibility and the like, is widely applied to the aspects of bone joint replacement, tooth restoration and the like, and has rapidly increased demand.
The personalized customization of the bone implant realizes the minimization of iatrogenic damage and the maximization of patient benefit, embodies and implements a new health medical service paradigm-precise medical concept in clinical practice, and is a trend of medical development.
Inadequate osseointegration is an important factor in the failure of titanium alloy implants. Personalized custom titanium alloy stents are typically complex porous three-dimensional structures. The porous structure reduces the elastic modulus mismatch between the bone and the implant alloy, reduces the stress shielding effect and improves the morphology of the implant, provides a biomaterial anchoring effect for tissue ingrowth, and increases the osteointegration of the implant.
Improving the biocompatibility of the surface of the implant is beneficial to the attachment, proliferation and differentiation of osteoblasts and promoting osseointegration, is the basis for obtaining long-term stability of the implant and is also the key for success or failure of the implant operation. The surface modification is carried out on the titanium alloy stent customized individually, and the surface components more suitable for tissue reconstruction and the multi-layer bionic structure surface are adopted to promote beneficial tissue reaction and induce tissue regeneration, so that the method is a very economic and effective method for improving the conventional biomaterial to meet the continuously developed clinical requirements.
Personalized, customized complex porous titanium alloy scaffolds present new challenges to surface structure and composition changes. Mechanical methods such as sand blasting and chemical methods such as acid-base etching are the most commonly used preparation methods of surface micro-nano structures at present, but the controllability is poor, and gradient structures and complex patterns with good repeatability are difficult to generate on a nano scale. In addition, the deposition of a film layer with good adhesion on the inner and outer surfaces of a complex porous structure requires optimization and improvement of the conventional vapor and liquid deposition methods to improve the interfacial adhesion of the film layer and improve the deposition quality of the film layer in the porous structure.
Disclosure of Invention
The invention aims to solve the technical problem of insufficient osseointegration of a medical titanium alloy implanted bracket, and improves the osseointegration effect of the titanium alloy implanted bracket by providing a preparation method of a personalized titanium alloy implant with biological activity.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a method for preparing a personalized titanium alloy implant stent with bioactivity, as shown in fig. 1, comprising the following steps:
s1, acquiring damaged bone tissue image data;
s2, establishing a three-dimensional model of the implanted support of the designated part of the human body according to the image data of the damaged bone;
s3, manufacturing the artificial bone scaffold by adopting a metal 3D printing system according to the three-dimensional model of the implanted scaffold;
s4, cleaning and drying the titanium alloy artificial bone scaffold;
s5, preparing a micro-nano structure on the surface of the titanium alloy artificial bone scaffold;
and S6, plating a tantalum film on the artificial bone scaffold.
Further, in step S1, medical image collecting devices such as medical CT, 3D-Micro CT, and bone magnetic resonance scanning (MRI) are used to scan bone tissue of the damaged or symmetrical portion of the human body to obtain damaged bone tissue image data.
Further, in step S2, the three-dimensional model of the titanium alloy implant scaffold is a porous connected structure, and satisfies the elastic modulus and the mechanical strength similar to those of the damaged portion of the human body. The pore is preferably dodecahedron, the porosity is 60-90%, and the pore size is 300-900 μm, so as to be beneficial to the growth of bone tissues.
Further, in step S3, the titanium alloy artificial stent is implemented by using a metal laser or electron beam 3D printing technology and equipment, and medical grade titanium alloy powder or wire is used as a printing material. When titanium alloy powder is used, the particle size of the powder is preferably 10 to 50 μm. When a titanium alloy wire is used, the wire diameter is preferably 0.05-1 mm.
Further, in the step S4, various organic and inorganic contaminants on the surface of the artificial stent are mainly cleaned. If the metal powder is used for printing the artificial bracket, the titanium alloy powder which is not melted in the artificial bracket needs to be removed.
Further, in step S5, the surface of the titanium alloy artificial bone scaffold is processed by a laser technique, and the scaffold is preferentially scanned by a femtosecond laser. In order to enable the laser to process the inner surface of the support, the sample is subjected to multi-dimensional rotation according to the symmetry of the specific support, or the laser enters the interior of the porous support by adopting grazing incidence to carry out surface processing.
Further, in the step S6, the preparation of the tantalum film is preferentially achieved by using magnetron sputtering; the target material used for sputtering is a medical grade high-purity tantalum target; the stent must be fully cleaned before film coating, and organic or inorganic pollutants on the surface are removed, so as to realize good adhesion between the tantalum film and the titanium alloy of the stent substrate; in order to realize the deposition of the tantalum film in the porous support, the support is coated by different incidence angles in the preparation of a sample, or the support is rotated in multiple directions in the coating process, so that sputtered atoms can enter the porous support for deposition.
Further, in step S5, the femtosecond laser preferably has the parameters: the wavelength is 400-1500nm, the power is 1-200mW, the scanning speed is 1-100mm/s, the scanning interval is 10-100 μm, the scanning frequency is 1-10 times, and the scanning mode is line scanning. After the femtosecond laser scans the stent, the surface roughness is preferably 1-10 μm, and the surface is in a super-hydrophilic state.
Further, in step S6, a direct current magnetron sputtering method is adopted, and the preferable parameters are: the sputtering power is 100-300W, the argon pressure is 0.1-1Pa, the argon flow is 1-100msc, and the coating time is 10 s-30 min. The thickness of the tantalum film on the surface of the titanium alloy is preferably 10nm-1 μm.
The invention has the following advantages:
(1) the invention adopts tantalum with better biological performance than titanium alloy as surface component, and combines the biological performance advantage of tantalum and the price advantage of titanium alloy. Tantalum, as a novel metal biomaterial, is called as "biotophilic" metal, has excellent biocompatibility, has no stimulation to body tissues, and is considered as an ideal orthopedic implant material. Tantalum has two fundamental advantages over titanium alloys. Firstly, tantalum has more excellent chemical corrosion resistance, and substances such as inorganic salt and the like cannot generate chemical or electrochemical corrosion with a tantalum simple substance at normal temperature; secondly, the reaction result between the body tissue cells and the tantalum, namely the inactive inorganic material, is better, after the tantalum is implanted for a period of time, the biological cell tissue is normally adsorbed on the surface of the tantalum element and grows healthily, so the tantalum is called as 'parent biological metal'. However, the prosthesis prepared from pure tantalum is four times as heavy as titanium alloy, and is expensive, so that the prosthesis is not favorable for clinical popularization and medical use in the future. The invention combines the advantages of titanium alloy and tantalum, namely: firstly, preparing a personalized titanium alloy prosthesis, and then preparing a tantalum coating on the titanium-based surface, thereby utilizing the advantages of titanium alloy such as light weight, low price and the like and also exerting the characteristic of high biocompatibility of tantalum.
(2) The invention adopts laser as the preparation technology of the surface micro-nano structure, has the advantages of flexibility and no pollution, is suitable for the surface treatment of various materials including organic materials, and provides an implementation method for the personalized design of the surface. The laser texture samples showed better cell attachment and proliferation than surface micro/nanostructures produced by mechanical techniques such as sand blasting and chemical techniques such as acid-base etching. The high peak power of the femtosecond laser has small heat affected zone for material processing, and is the laser technology most suitable for surface micro-nano preparation at present. The micro-nano structure prepared on the surface of the implant material can effectively increase the adhesive force between the substrate material and the tantalum film, increase the contact area with human cell tissues, regulate and control the surface energy of the implant, improve the adhesion of cells and further increase the bioactivity of the titanium alloy. The control of the growth form and direction of the cells can be realized by regulating and controlling the cells by the micro-nano structure.
(3) The concepts, methods and techniques of the present invention for personalized bone implant device systems and surface designs can be applied not only to titanium alloys, but also to other medical implant materials and devices. The laser adopted in the invention, especially the femtosecond laser is a flexible and universal surface micro-nano preparation technology, is suitable for the surface treatment of various materials including organic materials, and provides a realization method for the surface personalized design; the magnetron sputtering can not only realize the preparation of high-quality tantalum films, but also be used for the preparation of coatings of other materials. The methods have strong universality, are easy to popularize for preparing other implanted medical equipment products, have typicality and representativeness, and can powerfully promote the development of the surface of the medical implanted equipment.
Drawings
FIG. 1 is a flow diagram of the present invention.
FIG. 2 is a comparative scanning electron microscope image of the titanium alloy 3D printing support before and after the femtosecond laser is used for line scanning treatment, wherein (A) is the untreated titanium alloy surface, and (B) is the titanium alloy surface after the femtosecond laser treatment.
FIG. 3 is a scanning electron microscope comparison of the titanium alloy 3D printing support of the present invention before and after the deposition of tantalum film, wherein (A) is the untreated titanium alloy surface, and (B) is the titanium alloy surface after the deposition of tantalum film.
FIG. 4 is a graph showing the cell growth of a titanium alloy 3D-printed stent before and after femtosecond laser treatment according to the present invention, wherein (A) is a graph showing an untreated titanium alloy surface, the shape of cells on the stent is star-shaped, and (B) is a graph showing a polarized shape of cells on the stent, which is elongated in a certain direction, on the titanium alloy surface after femtosecond laser line scanning treatment.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
With reference to all the drawings, the preparation method of the personalized titanium alloy implant stent with bioactivity comprises the following steps:
s1, scanning bone tissues of the human body injury part or the symmetrical part by medical image acquisition equipment such as medical CT, 3D-Micro CT, bone magnetic resonance scanning (MRI) and the like, and acquiring injury bone tissue image data.
S2, importing the damaged bone image data obtained by the medical image acquisition equipment into software capable of carrying out bone tissue three-dimensional modeling, such as mimics software, and establishing a three-dimensional model of the damaged bone according to the image data of the damaged bone; repairing defects such as holes, burrs and the like in the three-dimensional model of the defected bone; designing the porous structure scaffold of the damaged bone based on CAD models, implicit curved surfaces and other design methods; and (3) performing mechanical loading calculation and analysis on the designed porous scaffold structure by using mechanical analysis software, such as finite element analysis software such as ANSYS, ABAQUS and the like, optimizing key design parameters such as porosity, pore size and the like of the porous scaffold structure, and determining the porous structure of the defected bone scaffold. The pore is preferably dodecahedron, the porosity is 60-90%, and the pore size is 300-900 μm, so as to be beneficial to the growth of bone tissues.
S3, manufacturing the titanium alloy artificial bone scaffold by adopting a metal 3D laser or electron beam printing system according to the designed three-dimensional model of the defected bone porous structure scaffold. When the metal 3D is printed, medical grade high-purity titanium alloy powder or silk threads can be used as raw materials. When titanium alloy powder is used, the particle size of the powder is preferably 10 to 50 μm. When the titanium alloy wire is adopted, the wire diameter is preferably 0.05mm-1 mm. Taking the metal laser 3D printing equipment for preparing the titanium alloy artificial bracket as an example, the laser power can be 500W-1000W, the spot size is 50-100 μm, the slice thickness is 10-50 μm, and the scanning speed is 100mm/s-1000 mm/s.
And S4, taking out the printed bracket, and removing the supporting substrate material by using a wire cutting machine. Ultrasonic cleaning the artificial bone scaffold with the support removed in acetone and ethanol solution for 5-10min, ultrasonic cleaning with ultrapure water for 5-10min, and drying in a drying oven.
And S5, manufacturing a microstructure on the surface of the titanium alloy bracket by using laser. Preferably, the roughness of the microstructure on the surface of the titanium alloy is the roughness required by the implantation of the titanium alloy into a human body part, and the skeleton-like pattern is selected to carry out microstructure processing on the surface of the titanium alloy. The main control parameters of the femtosecond laser device are as follows: laser wavelength, laser power, scan speed, etc. The preferable wavelength of the femtosecond laser is 400-1500nm, the power is 1-200mW, the scanning speed is 1-100mm/s, the scanning interval is 10-100 mu m, the scanning frequency is 1-10 times, and the scanning mode is line scanning. The depth and the appearance of the surface microstructure can be changed by adjusting the parameters, the surface roughness is preferably 1-10 mu m after the support is scanned by femtosecond laser, and the surface is in a super-hydrophilic state. In the femtosecond laser processing process, according to the characteristics of the bracket, the laser can be emitted into the porous inner part of the bracket by adopting the modes of rotation, translation and the like, so as to realize the processing of the inner surface of the bracket. FIG. 2 is a comparative scanning electron microscope image of a titanium alloy 3D printing support before and after a femtosecond laser is used for carrying out a line scanning treatment, wherein (A) is the untreated titanium alloy support surface, and (B) is the titanium alloy support surface after the femtosecond laser treatment. The titanium alloy porous support is prepared by adopting metal laser 3D printing equipment, is a cube with the size of 8mm, and has the pore size of 600 mu m and the porosity of 65 percent. The femtosecond laser wavelength is 800nm, the pulse width is 104fs, the repetition frequency is 1kHz, the incident power is 100mW, the scanning speed is 3mm/s, the scanning interval is 30 mu m, and the line scanning is performed for 1 time.
S6, plating a tantalum film on the titanium alloy artificial bone scaffold. Cleaning the titanium alloy with ultrasonic waves after the surface microstructure processing to ensure that the surface of the titanium alloy is clean enough to ensure the adhesion between a tantalum film and a titanium alloy substrate, preferably: the titanium alloy is cleaned by ultrapure water, ethanol, acetone, ethanol and deionized water in sequence, ultrasonic oscillation is needed for at least 3 minutes for each cleaning, then the next cleaning is carried out, and the titanium alloy is dried to remove water after the last cleaning is finished. And after the titanium alloy bracket is cleaned, plating a tantalum film on the surface. Preferentially using magnetron sputtering coating equipment to coat a tantalum film on the surface of the titanium alloy bracket, and adopting a direct current sputtering method, wherein the preferred parameters are sputtering power of 100-300W, argon pressure of 0.1-1Pa, argon flow of 1-100msc and coating time of 10 s-30 min. The thickness of the tantalum film on the surface of the titanium alloy is preferably 10nm-1 μm. FIG. 3 is a scanning electron microscope comparison image of a titanium alloy 3D printing support before and after deposition of a tantalum film, wherein (A) is an untreated titanium alloy surface, and (B) is a titanium alloy surface after deposition of the tantalum film, wherein the thickness of the tantalum film is about 100nm, the preparation conditions of the tantalum film are sputtering power of 250W, argon pressure of 0.6Pa, argon flow of 40msc and coating time of 30 s.
The working principle of the invention is as follows: the laser surface treatment can increase the surface area of the titanium alloy bracket, increase the contact surface between the tantalum film and the titanium matrix, have good bonding strength and simultaneously can not influence the performance of the matrix. In addition, the femtosecond laser changes the micro-nano structure of the surface of the material to regulate and control the surface of the bioactivity is an advanced technology which is proved. The titanium alloy surface is treated by laser, and cell experiment results show that compared with the untreated titanium alloy surface, the cell attachment rate of the laser-treated surface is higher, the cell differentiation is facilitated, and the cell diffusion rate is higher than that of the untreated surface. FIG. 4 is a graph showing the cell growth of a titanium alloy 3D-printed stent before and after femtosecond laser treatment according to the present invention, wherein (A) is a graph showing an untreated titanium alloy surface and the shape of cells on the stent is star-shaped, and (B) is a graph showing a polarized shape of cells on the stent, which is expressed as being elongated in a certain direction, after the femtosecond laser treatment. As can be seen, the stripe structure prepared by the femtosecond laser guides the growth morphology of the cells. Finally, magnetron sputtering is used as a technology for physical vapor deposition of the film, has the advantages of high purity, no pollution, strong film adhesion and the like, and is suitable for film preparation of medical implant materials.
The present invention and its embodiments have been described above, but the description is not limitative, and the actual structure is not limited thereto. In summary, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A preparation method of a personalized customized titanium alloy implant bracket with bioactivity is characterized by comprising the following steps: the method comprises the following steps:
s1, acquiring damaged bone tissue image data;
s2, establishing a three-dimensional model of the human body appointed part implantation support according to the image data of the damaged bone;
s3, manufacturing the artificial bone scaffold by adopting a metal 3D printing system according to the three-dimensional model of the implanted scaffold;
s4, cleaning and drying the titanium alloy artificial bone scaffold;
s5, preparing a micro-nano structure on the surface of the titanium alloy artificial bone scaffold;
and S6, plating a tantalum film on the artificial bone scaffold.
2. The method for preparing a personalized titanium alloy implant stent with bioactivity according to claim 1, wherein the method comprises the following steps: in step S1, medical image acquisition devices such as medical CT, 3D-Micro CT, and bone magnetic resonance scanning (MRI) are used to scan bone tissue at the damaged or symmetrical part of the human body to obtain image data of the damaged bone tissue.
3. The method for preparing a personalized titanium alloy implant stent with bioactivity according to claim 1, wherein the method comprises the following steps: in the step S2, the three-dimensional model of the titanium alloy implant stent is a porous communicating structure, and meets the elastic modulus and mechanical strength similar to those of the injured part of the human body. The pore is preferably dodecahedron, the porosity is 60-90%, and the pore size is 300-900 μm, so as to be beneficial to the growth of bone tissues.
4. The method for preparing a personalized titanium alloy implant stent with bioactivity according to claim 1, wherein the method comprises the following steps: in the step S3, the titanium alloy artificial stent is implemented by using a metal laser or electron beam 3D printing technology and equipment, and medical-grade titanium alloy powder or wires are used as a printing material. When titanium alloy powder is used, the particle size of the powder is preferably 10 to 50 μm. When a titanium alloy wire is used, the wire diameter is preferably 0.05-1 mm.
5. The method for preparing a personalized titanium alloy implant stent with bioactivity according to claim 1, wherein the method comprises the following steps: in the step S4, various organic and inorganic contaminants on the surface of the artificial stent are mainly cleaned. If the metal powder is used for printing the artificial bracket, the titanium alloy powder which is not melted in the artificial bracket needs to be removed.
6. The method for preparing a personalized titanium alloy implant stent with bioactivity according to claim 1, wherein the method comprises the following steps: in step S5, the surface of the titanium alloy artificial bone scaffold is processed by a laser technique, and the scaffold is preferentially scanned by a femtosecond laser. In order to enable the laser to process the inner surface of the support, the sample is subjected to multi-dimensional rotation according to the symmetry of the specific support, or the laser enters the interior of the porous support by adopting grazing incidence to carry out surface processing.
7. The method for preparing a personalized titanium alloy implant stent with bioactivity according to claim 1, wherein the method comprises the following steps: in the step S6, the preparation of the tantalum film is preferably realized by magnetron sputtering; the target material used for sputtering is a medical grade high-purity tantalum target; the stent must be fully cleaned before film coating, and organic or inorganic pollutants on the surface are removed, so as to realize good adhesion between the tantalum film and the titanium alloy of the stent substrate; in order to realize the deposition of the tantalum film in the porous support, the support is coated by different incidence angles in the preparation of a sample, or the support is rotated in multiple directions in the coating process, so that sputtered atoms can enter the porous support for deposition.
8. The method for preparing the personalized titanium alloy implant stent with bioactivity according to claim 1, wherein the method comprises the following steps: in step S5, the preferable parameters of the femtosecond laser are: the wavelength is 400-1500nm, the power is 1-200mW, the scanning speed is 1-100mm/s, the scanning interval is 10-100 μm, the scanning frequency is 1-10 times, and the scanning mode is line scanning. After the femtosecond laser scans the stent, the surface roughness is preferably 1-10 μm, and the surface is in a super-hydrophilic state.
9. The method for preparing a personalized titanium alloy implant stent with bioactivity according to claim 1, wherein the method comprises the following steps: in the step S6, a direct current magnetron sputtering method is adopted, and the preferred parameters are as follows: the sputtering power is 100-300W, the argon pressure is 0.1-1Pa, the argon flow is 1-100msc, and the coating time is 10 s-30 min. The thickness of the tantalum film on the surface of the titanium alloy is preferably 10nm-1 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210126783.2A CN114453593B (en) | 2022-02-11 | 2022-02-11 | Preparation method of personalized custom titanium alloy implant stent with bioactivity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210126783.2A CN114453593B (en) | 2022-02-11 | 2022-02-11 | Preparation method of personalized custom titanium alloy implant stent with bioactivity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114453593A true CN114453593A (en) | 2022-05-10 |
| CN114453593B CN114453593B (en) | 2023-07-18 |
Family
ID=81412586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210126783.2A Active CN114453593B (en) | 2022-02-11 | 2022-02-11 | Preparation method of personalized custom titanium alloy implant stent with bioactivity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114453593B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115429940A (en) * | 2022-08-30 | 2022-12-06 | 电子科技大学 | Method for enhancing stability of bioactive coating |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140086962A1 (en) * | 2012-02-07 | 2014-03-27 | The Regents Of The University Of California | Products of manufacture having tantalum coated nanostructures, and methods of making and using them |
| CN103977451A (en) * | 2014-05-19 | 2014-08-13 | 吉林大学 | 3D printing manufacturing method for tantalum-coated hierarchical pore polyether-ether-ketone artificial bone scaffold |
| CN106421892A (en) * | 2016-09-30 | 2017-02-22 | 中国人民解放军总医院 | Titanium-based tantalum coating bio-scaffold material and preparation method thereof |
| CN109261958A (en) * | 2018-11-15 | 2019-01-25 | 西北有色金属研究院 | Surface coats the medical porous titanium of tantalum coating or the preparation method of titanium alloy material |
| CN110090072A (en) * | 2019-05-31 | 2019-08-06 | 赵德伟 | Personalized porous titanium-based tantalum coating bone plate of 3D printing and preparation method thereof |
| CN112057674A (en) * | 2020-08-19 | 2020-12-11 | 淮阴工学院 | Bone-luring medical titanium alloy with micro-nano structure on surface and preparation method thereof |
| CN113732307A (en) * | 2021-07-20 | 2021-12-03 | 暨南大学 | Method for manufacturing high-performance medical metal by mixing selective laser melting and laser surface texture |
-
2022
- 2022-02-11 CN CN202210126783.2A patent/CN114453593B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140086962A1 (en) * | 2012-02-07 | 2014-03-27 | The Regents Of The University Of California | Products of manufacture having tantalum coated nanostructures, and methods of making and using them |
| CN104203293A (en) * | 2012-02-07 | 2014-12-10 | 加利福尼亚大学董事会 | Products of manufacture having tantalum coated nanostructures, and methods of making and using them |
| CN103977451A (en) * | 2014-05-19 | 2014-08-13 | 吉林大学 | 3D printing manufacturing method for tantalum-coated hierarchical pore polyether-ether-ketone artificial bone scaffold |
| CN106421892A (en) * | 2016-09-30 | 2017-02-22 | 中国人民解放军总医院 | Titanium-based tantalum coating bio-scaffold material and preparation method thereof |
| CN109261958A (en) * | 2018-11-15 | 2019-01-25 | 西北有色金属研究院 | Surface coats the medical porous titanium of tantalum coating or the preparation method of titanium alloy material |
| CN110090072A (en) * | 2019-05-31 | 2019-08-06 | 赵德伟 | Personalized porous titanium-based tantalum coating bone plate of 3D printing and preparation method thereof |
| CN112057674A (en) * | 2020-08-19 | 2020-12-11 | 淮阴工学院 | Bone-luring medical titanium alloy with micro-nano structure on surface and preparation method thereof |
| CN113732307A (en) * | 2021-07-20 | 2021-12-03 | 暨南大学 | Method for manufacturing high-performance medical metal by mixing selective laser melting and laser surface texture |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115429940A (en) * | 2022-08-30 | 2022-12-06 | 电子科技大学 | Method for enhancing stability of bioactive coating |
| CN115429940B (en) * | 2022-08-30 | 2024-01-26 | 电子科技大学 | Method for enhancing stability of bioactive coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114453593B (en) | 2023-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shahali et al. | Recent advances in manufacturing and surface modification of titanium orthopaedic applications | |
| Muthaiah et al. | Surface engineering of additively manufactured titanium alloys for enhanced clinical performance of biomedical implants: A review of recent developments | |
| CN104127911B (en) | A kind of take titanium alloy as the Biocomposite material preparation method of implantation body | |
| US20090017087A1 (en) | Osseoinductive metal implants for a living body and producing method thereof | |
| CN102743789B (en) | Artificial tooth root with micro-nano hierarchical topologic surface structure and preparation method of artificial tooth root | |
| De Aza et al. | In vitro bioactivity of laser ablation pseudowollastonite coating | |
| CN108478858A (en) | A kind of preparation method of titanium implant nanoscale ultra-hydrophilic surface | |
| Pattanaik et al. | Biocompatible implant surface treatments | |
| JP2014534882A (en) | Metal material having calcium phosphate layer and method for producing the same | |
| CN113527749A (en) | Method for preparing multi-scale porous structure on surface of polyether-ether-ketone | |
| CN104434539B (en) | The preparation method on the surface layer of the device in implantable human or animal's body | |
| CN114453593B (en) | Preparation method of personalized custom titanium alloy implant stent with bioactivity | |
| CN109731135A (en) | A kind of hydrophilic treatment process of implant surface | |
| CN111921015A (en) | Plasma bionic implantation material and preparation method thereof | |
| CN114393312A (en) | Femtosecond laser preparation method of biomedical titanium and titanium alloy antibacterial activated surface periodic structure | |
| CN113174592B (en) | Preparation and application of coating for improving biocompatibility of medical zinc/zinc alloy surface | |
| CN108042847B (en) | Method for improving biomimetic mineralization capability of titanium alloy implant surface | |
| KR101822255B1 (en) | A method for preparation of a metallic implant comprising biocompatable fluoride ceramic coating | |
| CN1282489C (en) | Boneoid apatite bio-active gradient coated artificial joint material and preparing process thereof | |
| CN112458514A (en) | Method for generating nanotube array oxide film on surface of medical porous titanium or titanium alloy | |
| CN113304318B (en) | Amorphous-crystalline calcium phosphate composite material based on biomimetic mineralization and preparation method and application thereof | |
| CN110819865B (en) | Preparation method of Nb-Ta-Ti-Si biomedical composite material with surface activity | |
| CN112168431A (en) | Functional bionic porous titanium alloy femoral head support rod and preparation method thereof | |
| KR101092227B1 (en) | Metal surface treatment method and the metal treated thereby | |
| CN114392392A (en) | Preparation method of personalized and customized polyether-ether-ketone implanted prosthesis with high biological activity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| OL01 | Intention to license declared | ||
| OL01 | Intention to license declared |