CN114453593B - Preparation method of personalized custom titanium alloy implant stent with bioactivity - Google Patents
Preparation method of personalized custom titanium alloy implant stent with bioactivity Download PDFInfo
- Publication number
- CN114453593B CN114453593B CN202210126783.2A CN202210126783A CN114453593B CN 114453593 B CN114453593 B CN 114453593B CN 202210126783 A CN202210126783 A CN 202210126783A CN 114453593 B CN114453593 B CN 114453593B
- Authority
- CN
- China
- Prior art keywords
- titanium alloy
- bracket
- stent
- preparing
- bone
- 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.)
- Active
Links
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 95
- 239000007943 implant Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 49
- 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 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 238000002513 implantation Methods 0.000 claims abstract description 9
- 239000002086 nanomaterial Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 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
- 238000007639 printing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 34
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000010146 3D printing Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 11
- 230000008021 deposition Effects 0.000 claims description 10
- 230000004071 biological effect Effects 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 238000004544 sputter deposition Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 8
- 238000011282 treatment Methods 0.000 claims description 8
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 5
- 231100001240 inorganic pollutant Toxicity 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 230000003746 surface roughness Effects 0.000 claims description 3
- 230000008467 tissue growth Effects 0.000 claims description 3
- 238000004891 communication Methods 0.000 claims description 2
- 238000009304 pastoral farming Methods 0.000 claims description 2
- 239000013077 target material Substances 0.000 claims description 2
- 238000004381 surface treatment Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 11
- 238000010883 osseointegration Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 13
- 210000001519 tissue Anatomy 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000013532 laser treatment Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000012620 biological material Substances 0.000 description 3
- 230000010261 cell growth Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000021164 cell adhesion Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 230000000399 orthopedic effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035755 proliferation Effects 0.000 description 2
- 238000005488 sandblasting 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 208000027205 Congenital disease Diseases 0.000 description 1
- 208000037408 Device failure 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
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 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
- 230000006378 damage Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 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
- -1 firstly Chemical compound 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000000642 iatrogenic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000005542 laser surface treatment Methods 0.000 description 1
- 239000007791 liquid phase 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
- 150000002739 metals Chemical class 0.000 description 1
- 230000003278 mimic effect Effects 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
- 210000000963 osteoblast Anatomy 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000002271 resection Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
- 230000008733 trauma Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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)
- Prostheses (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention relates to a preparation method of a personalized custom titanium alloy implant stent with bioactivity, which comprises the following steps: s1, acquiring image data of damaged bone tissue of a 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 a titanium alloy artificial bone bracket by adopting a metal 3D laser or electron beam printing system according to the three-dimensional model of the implanted bracket; 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 utilizing laser, and regulating and controlling the surface energy and roughness of the surface; s6, plating a high-purity tantalum film with nanometer-level thickness on the surface of the titanium alloy artificial bone bracket. The invention has the advantages that: enhancing the bioactivity of the titanium alloy implant stent and improving the osseointegration effect.
Description
Technical Field
The invention relates to the technical field of medical titanium alloy stents implanted in vivo, in particular to a preparation method of a personalized titanium alloy implant stent with surface bioactivity.
Background
Bone defect treatment caused by trauma, infection, tumor resection or congenital diseases is extremely difficult, is a main cause of limb dysfunction, and causes great economic burden to families and society. Metal orthopedic implants are one of the main methods for treating large bone defects.
The medical titanium alloy has the advantages of low density, high specific strength, mechanical property close to human bone, fatigue resistance, excellent biocompatibility and the like, is widely applied to the aspects of bone joint replacement, tooth repair and the like, and the demand for the medical titanium alloy is rapidly increased.
The personalized customization of the bone implant realizes the minimization of iatrogenic damage and the maximization of patient benefit, embodies and implements the novel health medical service paradigm-accurate medical concept in clinical practice, and is the trend of medical development.
Insufficient osseointegration is an important factor in failure of titanium alloy implants. Personalized 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 osseointegration of the implant.
Improving the biocompatibility of the surface of the implant is beneficial to the attachment, proliferation and differentiation of osteoblasts, promotes osseointegration, is a long-term stable foundation of the implant, and is also a key to success or failure of implant operation. The surface modification is carried out on the personalized and customized titanium alloy stent, the beneficial tissue reaction can be promoted by adopting the surface components more suitable for tissue reconstruction and the multi-layer bionic structure surface, the tissue regeneration is induced, and the method is a very economical and effective method for improving the existing conventional biological materials to meet the clinical requirements of continuous development.
The personalized complex porous titanium alloy stent presents new challenges for changing the surface structure and composition. 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 the nanometer 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 traditional vapor phase and liquid phase deposition method to improve the interfacial adhesion of the film layer and the deposition quality of the porous inner film layer.
Disclosure of Invention
The technical problem to be solved by the invention is that the osseointegration of the medical titanium alloy implantation stent is insufficient, and the osseointegration effect of the titanium alloy implantation stent is improved by providing a preparation method of the personalized titanium alloy implantation stent with bioactivity.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a method for preparing a personalized custom titanium alloy implant stent with biological activity, as shown in fig. 1, comprising the following steps:
s1, obtaining damaged bone tissue image data;
s2, establishing a three-dimensional model of the implantation stent of the appointed part of the human body according to the image data of the damaged bone;
s3, manufacturing an 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;
s6, plating a tantalum film on the artificial bone scaffold.
Further, in the step S1, the bone tissue at the damaged portion or the symmetrical portion of the human body is scanned by using medical image acquisition devices such as medical CT, 3D-Micro CT, and bone magnetic resonance scanning (MRI) to obtain damaged bone tissue image data.
Further, in the step S2, the three-dimensional model of the titanium alloy implantation stent is a porous communication structure, and meets the elastic modulus and mechanical strength similar to those of the damaged part of the human body. The preferred pore type is dodecahedron, the porosity is 60% -90%, and the pore size is 300-900 μm, so as to be beneficial to bone tissue growth.
Further, 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 wire is used as a printing material. When titanium alloy powder is used, the powder particle size is preferably 10 to 50. Mu.m. When titanium alloy wires are used, the wire diameter is preferably 0.05-1mm.
Further, in the step S4, various organic and inorganic contaminants on the surface of the artificial stent are mainly cleaned. If the artificial stent is printed by using metal powder, the unmelted titanium alloy powder in the artificial stent also needs to be removed.
Further, in the step S5, a laser technology is used to process the surface of the titanium alloy artificial bone scaffold, and the scaffold is preferentially scanned by using a femtosecond laser. In order to enable the laser to process the inner surface of the bracket, the sample is subjected to multidimensional rotation according to the symmetry of the specific bracket, or the laser enters the porous bracket to process the surface by adopting grazing incidence.
Further, in the step S6, the preparation of the tantalum film is preferably performed by magnetron sputtering; the target material used for sputtering is a medical grade high-purity tantalum target; the support must be cleaned thoroughly before coating to remove organic or inorganic pollutants on the surface so as to realize good adhesion between the tantalum film and the support substrate titanium alloy; in order to realize the deposition of the tantalum film inside the porous bracket, the bracket is coated by different incidence angles in the sample preparation process or is rotated in multiple directions in the coating process, so that sputtering atoms can enter the inside of the porous bracket for deposition.
Further, in the step S5, the preferred 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 mu m, the scanning times are 1-10 times, and the scanning mode is line scanning. After the femtosecond laser scans the stent, the surface roughness is preferably 1-10 mu m, and the surface is in a super-hydrophilic state.
Further, in the step S6, a dc magnetron sputtering method is adopted, and 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.
The invention has the following advantages:
(1) The invention adopts tantalum with better biological performance than titanium alloy as a surface component, and combines the biological performance advantage of tantalum with the price advantage of titanium alloy. Tantalum is a novel metal biomaterial, called as a 'bio-philic' metal, has excellent biocompatibility and no irritation to body tissues, and is considered as an ideal orthopedic implant material. Tantalum has two fundamental distinct advantages over titanium alloys. Firstly, tantalum has more excellent chemical corrosion resistance, and at normal temperature, inorganic salts and the like cannot chemically or electrochemically corrode the tantalum simple substance; secondly, the reaction result of the body tissue cells and the inactive inorganic material of tantalum is better, and after the tantalum is implanted for a period of time, the cell tissue of the organism is adsorbed on the surface of the tantalum element and grows healthily, so the tantalum is called as 'biological metal'. However, the pure tantalum is adopted to prepare the prosthesis, the weight is four times that of the titanium alloy, and the price is high, so that the prosthesis is not beneficial to clinical popularization and medical use in future. The invention combines the advantages of titanium alloy and tantalum, namely: firstly, preparing personalized titanium alloy prosthesis, and then preparing a tantalum coating on the titanium-based surface, namely utilizing the advantages of light weight, low cost and the like of the titanium alloy, and 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 treatment of the surfaces of various materials including organic materials, and provides an implementation method for the surface personalized design. The laser textured samples showed better cell attachment and proliferation compared to the 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 area on 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 not only can effectively increase the adhesive force of the substrate material and the tantalum film, but also can increase the contact area with human body cell tissues, regulate the surface energy of the implant body, improve the cell adhesion and further increase the bioactivity of the titanium alloy. The control of the growth form and direction of the cells can be realized through the regulation and control of the micro-nano structure on the cells.
(3) The concepts, methods and techniques of the present invention for personalizing bone implant device systems and surface designs may be used not only with titanium alloys, but with 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 treatment of the surfaces of various materials including organic materials, and provides an implementation method for the surface personalized design; the magnetron sputtering can not only realize the preparation of the high-quality tantalum film, but also be used for the preparation of coatings of other materials. The method has strong universality, is easy to popularize in the preparation of other implanted medical instrument products, has representativeness and representativeness, and can forcefully promote the development of the surface of the medical implanted instrument.
Drawings
Fig. 1 is a flow chart of the present invention.
Fig. 2 is a scanning electron microscope contrast diagram of the titanium alloy 3D printing support before and after the femtosecond laser performs the line scanning treatment, wherein (a) diagram is an untreated titanium alloy surface, and (B) diagram is a titanium alloy surface after the femtosecond laser treatment.
FIG. 3 is a comparative image of a scanning electron microscope before and after deposition of a tantalum film on a titanium alloy 3D printing support according to the invention, wherein (A) is an untreated titanium alloy surface, and (B) is a titanium alloy surface after deposition of a tantalum film.
FIG. 4 is a graph of cell growth before and after femtosecond laser treatment of a titanium alloy 3D printing stent in the invention, (A) graph shows an untreated titanium alloy surface, cell shapes on the stent are star-shaped, and (B) graph shows a titanium alloy surface after femtosecond laser line scanning treatment, cell shapes on the stent are polarized and appear to stretch in a certain direction.
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 custom titanium alloy implant stent with biological activity comprises the following steps:
s1, scanning bone tissues at a damaged part or a symmetrical part of a human body by using medical image acquisition equipment such as medical CT, 3D-Micro CT, bone magnetic resonance scanning (MRI) and the like to acquire damaged bone tissue image data.
S2, importing the damaged bone image data obtained by the medical image acquisition equipment into software capable of performing bone tissue three-dimensional modeling, such as MIMIC software, and establishing a three-dimensional model of a damaged bone according to the damaged bone image data; repairing defects such as holes, burrs and the like in the defective bone three-dimensional model; designing a damaged bone porous structure bracket based on a CAD model, an implicit curved surface and other design methods; and (3) carrying out mechanical loading calculation and analysis on the designed porous scaffold structure by utilizing mechanical analysis software such as finite element analysis software of 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 defective bone scaffold. The preferred pore type is dodecahedron, the porosity is 60% -90%, and the pore size is 300-900 μm, so as to be beneficial to bone tissue growth.
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 defective bone porous structure scaffold. Medical grade high-purity titanium alloy powder or wires can be used as raw materials during 3D printing of metals. When titanium alloy powder is used, the powder particle size is preferably 10 to 50. Mu.m. When a titanium alloy wire is used, the wire diameter is preferably 0.05mm to 1mm. Taking a metal laser 3D printing device for preparing the titanium alloy artificial bracket as an example, the power of a laser can be 500W-1000W, the light spot size is 50-100 mu m, the slice layer thickness is 10-50 mu m, and the scanning speed is 100mm/s-1000mm/s.
S4, taking out the printed bracket, and removing the supporting substrate material by using a wire cutting machine. And (3) ultrasonically cleaning the artificial bone scaffold with the support removed in acetone and ethanol solution for 5-10min, ultrasonically cleaning with ultrapure water for 5-10min, and finally drying in a drying oven.
S5, performing microstructure manufacturing on the surface of the titanium alloy bracket by utilizing laser. Preferably, the roughness of the microstructure of the titanium alloy surface is the roughness required by the implantation part of the human body, and the microstructure processing treatment is carried out on the titanium alloy surface by selecting a skeleton-like pattern. The main control parameters of the femtosecond laser equipment are as follows: laser wavelength, laser power, scan speed, etc. The femtosecond laser preferably has the wavelength of 400-1500nm, the power of 1-200mW, the scanning speed of 1-100mm/s, the scanning interval of 10-100 mu m, the scanning times of 1-10 times, and the scanning mode is line scanning. The adjustment of the parameters can change the depth and the morphology of the surface microstructure, and the surface roughness is preferably 1-10 mu m and the surface is in a super-hydrophilic state after the femtosecond laser scans the stent. In the femtosecond laser treatment process, according to the characteristics of the bracket, the laser can be incident into the porous interior of the bracket in a rotary and translational mode, so as to treat the inner surface of the bracket. Fig. 2 is a scanning electron microscope contrast diagram of the titanium alloy 3D printing stent before and after the femtosecond laser performs the line scanning treatment, wherein (a) diagram is an untreated titanium alloy stent surface, and (B) diagram is a titanium alloy stent 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 diameter of 8mm, the pore size is 600 mu m, and the porosity is 65%. The wavelength of the femtosecond laser 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. The titanium alloy with the processed surface microstructure is cleaned by ultrasonic wave, so that the surface of the titanium alloy is clean enough to ensure the adhesion of the tantalum film and the titanium alloy substrate, and the preferable method is as follows: sequentially cleaning the titanium alloy by using ultrapure water, ethanol, acetone, ethanol and deionized water, carrying out ultrasonic vibration for at least 3 minutes for each cleaning, then carrying out the next cleaning, and drying the titanium alloy to remove water after the last cleaning is finished. And after the titanium alloy bracket is cleaned, plating a tantalum film on the surface. The magnetron sputtering coating equipment is preferably used for coating the tantalum film on the surface of the titanium alloy bracket, a direct current sputtering method is adopted, 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 graph showing a comparison of scanning electron microscope before and after deposition of a tantalum film on a titanium alloy 3D printing bracket in the invention, (A) a graph showing an untreated titanium alloy surface, and (B) a graph showing a titanium alloy surface after deposition of a tantalum film, wherein the thickness of the tantalum film is about 100nm, the preparation condition of the tantalum film is that the sputtering power is 250W, the argon pressure is 0.6Pa, the argon flow is 40msc, and the coating time is 30s.
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, and has good bonding strength, and meanwhile, the performance of the matrix is not affected. In addition, femtosecond laser changes the micro-nano structure of the surface of the material to regulate the surface of the bioactivity is an advanced technology which is verified. The surface of the titanium alloy is treated by laser, and the cell experimental result shows that compared with the untreated surface of the titanium alloy, the cell adhesion rate of the surface treated by the laser 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 of cell growth before and after femtosecond laser treatment of a titanium alloy 3D printing stent in the invention, wherein (A) the graph is an untreated titanium alloy surface, the shape of cells on the stent is star-shaped, and (B) the graph is the titanium alloy surface after femtosecond laser treatment, and the shape of the cells on the stent is polarized and shows that the cells stretch in a certain direction. It can be seen that the striped structure produced by the femtosecond laser directs the morphology of the cell growth. Finally, the magnetron sputtering is used as a technology of physical vapor deposition film, has the advantages of high purity, no pollution, strong film adhesion and the like, and is suitable for preparing a film layer of a medical implant material.
The invention and its embodiments have been described above without limitation, and the actual construction is not limited thereto. In summary, if one of ordinary skill in the art is informed by this disclosure, a structural manner and an embodiment similar to the technical solution should not be creatively devised without departing from the gist of the present invention.
Claims (7)
1. A method for preparing a personalized custom titanium alloy implant stent with biological activity, which is characterized in that:
the method comprises the following steps:
s1, obtaining damaged bone tissue image data;
s2, establishing a three-dimensional model of the implantation bracket of the appointed part of the human body according to the image data of the damaged bone;
s3, manufacturing an 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;
s6, plating a tantalum film on the artificial bone bracket,
in the step S5, the support is scanned by using a femtosecond laser, and the femtosecond laser parameters are as follows: the method comprises the following steps of (1) carrying out scanning treatment on a bracket by using femtosecond laser, wherein the wavelength 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 times are 1-10 times, the scanning mode is line scanning, the surface roughness is 1-10 mu m, and the surface is in a super-hydrophilic state, and in the step S6, a direct current magnetron sputtering method is adopted, and the parameters are as follows: the sputtering power is 100-300W, the argon pressure is 0.1-1Pa, the argon flow is 1-100sccm, the coating time is 10 s-30 min, and the thickness of the tantalum film on the surface of the titanium alloy is 10nm-1 mu m.
2. The method for preparing a personalized custom titanium alloy implant stent with biological activity according to claim 1, wherein the method comprises the following steps: in the step S1, a medical image acquisition device such as a medical CT, a 3D-Micro CT, a bone magnetic resonance scan (MRI) and the like is used to scan the bone tissue at the damaged portion or the symmetrical portion of the human body so as to obtain the damaged bone tissue image data.
3. The method for preparing a personalized custom titanium alloy implant stent with biological activity according to claim 1, wherein the method comprises the following steps: in the step S2, the three-dimensional model of the titanium alloy implantation bracket is of a porous communication structure, the elastic modulus and the mechanical strength similar to those of the damaged part of the human body are met, the hole pattern is a dodecahedron, the porosity is 60-90%, and the pore size is 300-900 mu m, so that the bone tissue growth is facilitated.
4. The method for preparing a personalized custom titanium alloy implant stent with biological activity according to claim 1, wherein the method comprises the following steps: in the step S3, the titanium alloy artificial bracket is realized by adopting a metal laser or electron beam 3D printing technology and equipment, and medical grade titanium alloy powder or silk thread is adopted as a printing material.
5. The method for preparing a personalized custom titanium alloy implant stent with biological activity according to claim 1, wherein the method comprises the following steps: in the step S4, various organic and inorganic pollutants on the surface of the artificial stent are mainly cleaned.
6. The method for preparing a personalized custom titanium alloy implant stent with biological activity according to claim 1, wherein the method comprises the following steps: in the step S5, in order to make the laser perform surface treatment on the inner surface of the stent, the sample is subjected to multidimensional rotation according to the symmetry of the specific stent, or the laser enters the porous stent to perform surface processing by adopting grazing incidence.
7. The method for preparing a personalized custom titanium alloy implant stent with biological activity according to claim 1, wherein the method comprises the following steps: in the step S6, the preparation of the tantalum film is realized by using magnetron sputtering; the target material used for sputtering is a medical grade high-purity tantalum target; the support must be cleaned thoroughly before coating to remove organic or inorganic pollutants on the surface so as to realize good adhesion between the tantalum film and the support substrate titanium alloy; in order to realize the deposition of the tantalum film inside the porous bracket, the bracket is coated by different incidence angles in the sample preparation process or is rotated in multiple directions in the coating process, so that sputtering atoms can enter the inside of the porous bracket for deposition.
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 CN114453593A (en) | 2022-05-10 |
| CN114453593B true 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) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115429940B (en) * | 2022-08-30 | 2024-01-26 | 电子科技大学 | Method for enhancing stability of bioactive coating |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10149921B2 (en) * | 2012-02-07 | 2018-12-11 | The Regents Of The University Of California | Implants having tantalum coated nanostructures |
| CN103977451B (en) * | 2014-05-19 | 2015-09-02 | 吉林大学 | The 3D of tantalum coating multi-stage porous polyether-ether-ketone artificial bone scaffold prints manufacture method |
| 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 |
| CN109261958B (en) * | 2018-11-15 | 2020-07-17 | 西北有色金属研究院 | Preparation method of medical porous titanium or titanium alloy material with tantalum coating coated on surface |
| CN110090072B (en) * | 2019-05-31 | 2020-07-28 | 赵德伟 | Personalized 3D printing porous titanium-based tantalum coating bone fracture plate 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 |
| CN113732307B (en) * | 2021-07-20 | 2023-03-24 | 暨南大学 | Method for manufacturing medical metal by mixing selective laser melting and laser surface texture |
-
2022
- 2022-02-11 CN CN202210126783.2A patent/CN114453593B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114453593A (en) | 2022-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shahali et al. | Recent advances in manufacturing and surface modification of titanium orthopaedic applications | |
| US5478237A (en) | Implant and method of making the same | |
| CN105903084B (en) | A kind of 3D printing porous support and preparation method thereof with antibacterial functions coating | |
| CN104127911B (en) | A kind of take titanium alloy as the Biocomposite material preparation method of implantation body | |
| EP1740128A1 (en) | Osseoinductive metal implants for a living body and producing method thereof | |
| EP2585516A2 (en) | Method for producing nanosurfaces with nano, micron, and/or submicron structures on a polymer | |
| CN212853732U (en) | Degradable magnesium net for reconstruction of personalized alveolar bone defect | |
| Pattanaik et al. | Biocompatible implant surface treatments | |
| KR101701264B1 (en) | Metal for transplantation, manufacturing method for metal, implant and stent using the same | |
| CN108478858A (en) | A kind of preparation method of titanium implant nanoscale ultra-hydrophilic surface | |
| CN114453593B (en) | Preparation method of personalized custom titanium alloy implant stent with bioactivity | |
| CN112402693A (en) | Orthopedic implant instrument with surface provided with bone promoting coating and preparation method | |
| CN109731135A (en) | A kind of hydrophilic treatment process of implant surface | |
| CN114099079A (en) | 3D prints individualized alveolar bone defect and rebuilds with degradable magnesium net | |
| CN104434539A (en) | method for the preparation of surfaces of devices implantable into human or animal body | |
| KR20070063114A (en) | Metal implants and manufacturing method thereof | |
| 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 | |
| JPH0731627A (en) | Implant and manufacture thereof | |
| CN105797208A (en) | Degradable metal implant for repairing skull and preparation method thereof | |
| CN108166044A (en) | A kind of method of the regulation and control medical TC4 titanium alloy surfaces tube diameters of 3D printing | |
| KR101822255B1 (en) | A method for preparation of a metallic implant comprising biocompatable fluoride ceramic coating | |
| CN112458514A (en) | Method for generating nanotube array oxide film on surface of medical porous titanium or titanium alloy | |
| Sun et al. | The influence of electrolytic concentration on the electrochemical deposition of calcium phosphate coating on a direct laser metal forming surface | |
| CN115090903B (en) | Medical implant based on molecular sieve functional element and preparation method thereof |
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 |