CN110090072A - Personalized porous titanium-based tantalum coating bone plate of 3D printing and preparation method thereof - Google Patents
Personalized porous titanium-based tantalum coating bone plate of 3D printing and preparation method thereof Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/56—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor
- A61B17/58—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor for osteosynthesis, e.g. bone plates, screws, setting implements or the like
- A61B17/68—Internal fixation devices, including fasteners and spinal fixators, even if a part thereof projects from the skin
- A61B17/80—Cortical plates, i.e. bone plates; Instruments for holding or positioning cortical plates, or for compressing bones attached to cortical plates
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- A—HUMAN NECESSITIES
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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- A61L31/022—Metals or alloys
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- A—HUMAN NECESSITIES
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/146—Porous materials, e.g. foams or sponges
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Abstract
The present invention provides a kind of porous titanium-based tantalum metal coating bone plate of the personalized 3D printing with bone-inducting active, it is using titanium metal powder or titanium alloy metal powder as substrate, tantalum coating is formed by the surface of the porous titanium-based bone plate with gap structure of 3D printing processing and fabricating to be prepared, the porosity of the porous titanium-based tantalum metal coating bone plate is 50%~80%, bending strength is 50MPa~150MPa, elasticity modulus is 2GPa~30GPa, the diameter in the gap is 200 μm~800 μm, the tantalum coating with a thickness of 30~60 μm, has enough intensity, there is good osteoinductive energy simultaneously.Bone plate of the invention is implanted into bone plate with being consistent with fracture anatomical structure, and excellent Integrated implant can be formed with bone tissue, avoids after existing bone plate is chronically implanted in vivo and there is easy loosening and fracture, fixes in permanent biology to reach.
Description
Technical field
The present invention relates to a kind of medical internal fixation devices, in particular to a kind of for treating the medical fixation of acropathy long bone fractures
The porous titanium-based tantalum coating bone plate of the personalized 3D printing with bone-inducting active and preparation method thereof.
Background technique
For Long bone fracture, clinic mostly uses internal fixation, and traditional bone surgery bone plate is curved
During bent radian, screw placement, in order to ensure accuracy and the important features such as peripheral nerve, blood vessel, organ are avoided damage to,
Generally require to rely in the experience and art of patient and repeatedly have an X-rayed bone plate, screw position, cause operating time is long, bone plate with
The risk that bone cannot combine closely, screw loosening fails.The treatment common synthetism plate material of limbs fracture is titanium at present, though
Right titanium also has excellent obdurability, resistance to corrosion and an excellent fatigue behaviour, but since to belong to biology lazy for titanium
Property material, lack bioactivity, be easy to appear in clinical use low in bone tissue bond strength, wound, which is not easy to heal, etc. asks
Topic.This is because the elastic modulus difference of titanium and bone tissue is huge, it is existing that " stress shielding " is easy to appear in carrying
As so as to cause the failure of operative treatment.
Under the situation of metalworking technology fast development, in order to make up the defect of titanium alloy material, it is improved for bone
Repair of tissue defect reconstruction performance, some researchers propose the design concept of porous metal implants, to solve titanium implantation
The stress-shielding effect of object, and achieve preferable effect.
Although porous designs the generation that stress-shielding effect is alleviated or avoided, while porous structure is also freshman bone tissue
It grows into and brings space, facilitate implant and bone tissue forms stablizing for bioconjugation and fixes, eventually become an entirety.But simultaneously
Without fundamentally solving the property of titanium metal material, the Integrated implant ability that titanium implants how is improved, is materialogy
Family and clinician need to solve the problems, such as jointly.In history, there are two types of different mechanism be used to describe bone and planting body
In conjunction with: chemical bonding and bioconjugation.Bioconjugation mechanism is what the chemical composition based on bone matrix proposed.Bioconjugation is one
The process of a complexity is related to the mixing of collagen Yu the apatite containing carbonate, in addition, collagenous fibres can with free growth into
In the pore structure of rough surface, therefore, bioconjugation is influenced highly significant by implant surface pore structure.Especially bone is repaired
During multiple, osteoblast is very sensitive to stress and strain, and the stress condition of combination interface will directly affect the life of ossein
It is long.
Extracellular matrix environment can be changed after planting body implantation, the surface of planting body be earliest with contact biological tissue portion
Point.Therefore, the surface characteristics of planting body plays the role of the success or failure of implant surgery key.The surface to planting body material into
When row design, it is necessary to consider the change of extracellular matrix environment, should be design with the acknowledgement mechanism of cell and extracellular matrix
Foundation.
In recent years, metal tantalum has excellent a ductility and toughness and workability, and especially it is superpower corrosion-resistant
Property, good biocompatibility, the extensive concern by medical worker.But because tantalum density metal is high, molding not easy to be processed is faced
Bed application is restricted.With the development of science and technology and progress, Jie Mai company, the U.S. utilize chemical vapour deposition technique, preparation
Porous tantalum metal implant material and be applied to clinic, achieve preferable clinical effectiveness.But this method, the usage amount of tantalum
Bigger, high cost of material greatly limits its application.Therefore, metal tantalum coating is prepared on titanium alloy substrate,
Not only the excellent corrosion-resistant and biocompatibility of metal tantalum had been utilized but also has played the raw material relative moderate of titanium alloy itself and has easily added
The advantage of work, the application for metal tantalum in medical field provide new thinking.
Application No. is the Chinese invention patents of CN201510338752.3, disclose a kind of implantable medical devices, and tantalum applies
The preparation method of layer pedicle screw, the bone screw in the patent application can prepare metal coating with tantalum, be in reaction temperature
In the case of 950 DEG C, the coating layer thickness of preparation is only 2~4 microns, and most preferably 3 microns, the coating layer thickness of preparation is extremely weak, and
It can be seen that coating is uneven from attached drawing, there is partial exfoliation.In addition, the crystal grain for the porous tantalum metal coating prepared exists
40~50 microns are unfavorable for the adherency of cell and macromolecular substances.Therefore, it is necessary to a kind of new processes, improve tantalum
The roughness of metal surface reduces crystallite dimension, is more advantageous to the adherency of cell and macromolecular, increases the incipient stability of implant
Property.
Summary of the invention
The present invention has many drawbacks for above-mentioned conventional metals bone plate in material property, and toxic metal ions release is made
At the problem of infection and sterile loosening, stress shielding, secondary taking-up, shape mismatch etc., and a kind of use 3D of researching and designing is beaten
Print technology makes porous titanium-based bone plate and carries out tantalum coating, which Permanent implantation, avoids stress from hiding
Gear has high tissue compatibility and biomechanical property, and can induce bone tissue and generate.
The technical solution adopted by the invention is as follows:
The porous titanium-based tantalum metal coating bone plate of a kind of personalized 3D printing with bone-inducting active, with titanium powder
End or titanium alloy metal powder are substrate, pass through the table of the porous titanium-based bone plate with gap structure of 3D printing processing and fabricating
Face forms tantalum coating and is prepared, and the porosity of the porous titanium-based tantalum metal coating bone plate is 50%~80%, bending resistance
Intensity is 50MPa~150MPa, and elasticity modulus is 2GPa~30GPa, and the diameter in the gap is 200 μm~800 μm, the tantalum
Coating with a thickness of 30~60 μm.
In the above-mentioned technical solutions, the pore structure is interconnected porous structure.The porous structure is rule
Porous structure or by Micro-CT scanning obtain bone trabecula porous structure.
In the above-mentioned technical solutions, the porous titanium-based bone plate includes ontology, and the ontology includes being located at the ontology
The external reinforcing ribs of edge, interior reinforcing rib, gap structure and screw hole on the inside of the external reinforcing ribs.Preferably,
The external reinforcing ribs are in continuous structure, with a thickness of 1mm~2mm；The interior reinforcing rib is in reticular structure, is uniformly distributed in additional
In ontology on the inside of strengthening tendons.It can reinforce the power of the titanium-based bone plate as gap structure by setting external reinforcing ribs and interior reinforcing rib
Learn intensity.In preferred structure, in the titanium-based bone plate, the ratio of porous part and entity part is about 4~5:1,
More preferable 5:1.In preferred structure, the both ends of porous titanium-based bone plate are arc, and radian is 15 °~90 °, preferably 20 °
~45 °, the width of bone plate is 10mm~30mm, and length is 40~200mm, with a thickness of 2mm~5mm.In general, may be used
With, appropriate adjustment synthetism plate thickness and gap structure different to bone plate mechanical property requirements, root according to different implant sites
According to suitable width, length and radian can be used the characteristics of implant site.
In the above-mentioned technical solutions, the screw hole is type face counterbore, will not dashing forward due to screw after fixing convenient for screw
It rises, stimulation is generated to surrounding tissue, the screwhole diameter is 3mm~5mm.Screw hole is located at the center line of bone plate, the spiral shell at both ends
Pitch-row can be obtained according to bone plate length appropriate adjustment.
The present invention also provides a kind of preparation methods of the porous titanium-based tantalum metal coating bone plate of personalized 3D printing, including with
Lower step:
(1) based on the CT scan data at patients with fractures, the 3D several picture of fracture is obtained using three-dimensional imaging software；
(2) the 3D several picture of the fracture based on patient designs connecing for personalized customization using three-dimensional imaging software
The shape and gap structure of bone plate obtain the three-dimensional geometry image of target bone plate, by the three-dimensional geometry figure of the target bone plate
As file imported into 3D printer, using titanium metal powder or titanium alloy metal powder as raw material, carried out under argon atmosphere protection
Porous titanium-based bone plate is made in 3D printing；
(3) titanium-based bone plate obtained will be printed and is placed in blasting treatment in sand-blasting machine, remove the titanium powder of surfaces stick
End or titanium alloy metal powder are successively cleaned by ultrasonic 15~30 minutes using acetone, alcohol and distilled water, are dried at 40 DEG C；
(4) the porous titanium-based bone plate after drying is heat-treated, to eliminate residual stress, and keeps synthetism plate surface flat
Sliding, the heat treatment temperature is 1200~2000 DEG C, and heating rate is 5 DEG C/min, keeps the temperature 1 hour after reaching heat treatment temperature,
Furnace cooling；
(5) by the porous titanium-based bone plate soaked in absolute ethyl alcohol after heat treatment, after ultrasonic vibration cleans 30~60min,
With being dried with nitrogen, using chemical vapor deposition method in porous titanium-based bone plate surface deposition of tantalum metal, porous titanium-based tantalum is made
Metal coating bone plate.
Specifically, in the above preparation method, the 3D geometrical model (3D several picture) of the fracture based on patient uses
Auto CAD, Pro E, Magics software design obtain the 3D several picture of target bone plate and the .stl of the 3D several picture
Formatted file joins titanium metal powder or titanium alloy metal powder at the interface Building Processing in step (3)
Number packet merges with the .stl formatted file of above-mentioned target bone plate 3D several picture, obtains the target bone plate and sets in 3D printer
Identifiable .mtt formatted file in standby, is input to 3D printing equipment for the .mtt formatted file, closes in titanium metal powder or titanium
Golden metal powder is that raw material carries out 3D printing, and porous titanium-based bone plate is made.
In the above-mentioned technical solutions, in step (2), the 3D printing condition are as follows: powdering is with a thickness of 20~50 μm, laser
Power be 120~200w, 50~100 microns of laser point spacing, 60~100 microns of line spacing, 60~150 microsecond of time for exposure.
In the above-mentioned technical solutions, in step (5), using chemical vapor deposition method on porous titanium-based bone plate surface
Deposition of tantalum metal, the method that porous titanium-based tantalum metal coating bone plate is made include the following steps:
A) it will be placed in reaction chamber with the porous titanium-based bone plate after being dried with nitrogen, tantalum metal be placed in reaction chamber front end；
B) it is passed through inert gas in reaction chamber, purges 10~20min of reaction chamber, is evacuated under the conditions of 200~250Pa,
Reaction chamber is heated to 800 DEG C, is passed through chlorine and hydrogen, 7~10h of vapor deposition reaction is carried out, wherein the flow of the chlorine
For 80mL/min, the flow of the hydrogen is 100mL/min；
C) after reaction, hydrogen and chlorine are closed, cooling device is connected, is cooled to 200 DEG C under inert gas protection
Hereinafter, opening the titanium-based implantation material that reaction chamber takes out tantalum metal coating；
Wherein, the inert gas described in step b) and step c) is the mixed of one or both of argon gas or nitrogen
It closes.
In the above-mentioned technical solutions, in step (2), the titanium metal powder or titanium alloy metal powder are medical grade
Globular metallic powder, powder diameter are 15~45 μm, preferably 15~30 μm.
In the above-mentioned technical solutions, in step (3), abrasive material used in the blasting treatment is white fused alumina, institute
State white fused alumina partial size be 50 μm~150 μm, blasting treatment actuating pressure be 0.1~1.0MPa, the blasting treatment time 30~
120s.By blasting treatment, the roughness of titanium-based bone plate matrix surface is improved, improves the binding force of tantalum coating and matrix.
In the above-mentioned technical solutions, through the above steps a) in use the porous titanium-based bone plate for being dried with nitrogen processing and as
The metal tantalum of raw material is placed in phase depositing reaction chamber, is passed through chlorine and hydrogen carries out deposition reaction, wherein porous titanium-based synthetism
Plate is placed in the reaction pallet being arranged in reaction chamber, and metal tantalum is placed in reaction chamber front end, in this way, when being passed through chlorine and hydrogen
When, the tantalum metal of chlorine and gasification first chemically reacts, and generates tantalic chloride, and then tantalic chloride and hydrogen occur anti-
It answers, is reduced to gaseous state tantalum metal, permeate and deposit to porous support internal layer surface, superficies, form tantalum coating.The tantalum gold
Belong to preferably to use high-purity tantalum metal, purity is 99.99%~99.999%.
The binding force of tantalum coating and titanium-based bone plate that the method for the present invention is prepared reaches 43.2Mpa or more.
The present invention is based on 3D printing techniques, carry out preoperative CT scan, three-dimensional reconstruction to patient's art first, determine that bone plate is curved
Bent radian, matches with the anatomic landmark of bone, then prints the implantation bone plate being consistent with human anatomic structure.In turn,
Tantalum metal coating is carried out on bone plate, is improved the bioactivity of bone plate, is made the good mechanical property of titanium-based metal implant
It can be combined with the excellent bioactivity of tantalum metal, the two has complementary advantages, the clinical application effect being optimal.
The utility model has the advantages that
1. more meeting human anatomic structure, the plasticity of bone plate is good, can be according to plant using personalized 3D printing technique
The mechanical property for entering position bone tissue realizes personalized customization, avoids stress shielding, facilitates bone tissue healing.
2. in bone plate periphery and inside because of titanium or titanium alloy structure, to guarantee that bone plate is having osteoinductive energy
While porous structure, moreover it is possible to have enough intensity, realize that its mechanical support acts on.
3. bone plate has pore structure, suitable bone tissue is grown into, and helps to improve the bone of bone plate and bone tissue
Integration performance is realized and is fixed in permanent biology, and second operation taking-up is not required to.
4. self-bone grafting bone plate of the present invention, can be by adjusting the porosity of bone plate by 3D printing technique processing and fabricating
With the biomechanical property of pore-size optimization bone plate, bone plate is provided in biomethanics for implant site bone tissue and is fixed,
It can also guarantee that bone tissue by enough stress stimulations, excites the self-regeneration function of bone tissue simultaneously；Pass through implantation and bone
Anatomical structure is implanted into the bone inductive effect of bone plate and bone plate with being consistent at folding, realizes bone tissue and bone plate good
Integrated implant, avoid to exist after existing bone plate is chronically implanted in vivo and be easy to loosen, the problems such as needing second operation to take out, subtract
The light pain of patient.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of bone plate of the present invention.
Fig. 2 is the three-dimensional structure schematic diagram of bone plate of the present invention.
Fig. 3 is the porous titanium-based bone plate made by 3D printing, the bone plate actual size and calculate that 3D printing comes out
Machine design is almost the same.
Fig. 4 is connecing after preparing tantalum metal coating on the porous titanium-based bone plate of 3D printing by chemical vapour deposition technique
Bone plate photo.
Fig. 5 is the microstructure photo of porous titanium-based tantalum metal coating synthetism plate surface and the elemental analysis result of coating.
Fig. 6 is the SEM photograph for indicating the crystallite dimension of thickness and coating of coating.
Fig. 7 is with the shin bone x-ray photo for temporally observing union situation after plate fixation fracture site.
Symbol description: 1, ontology, 2, external reinforcing ribs, 3, interior reinforcing rib, 4, gap structure, 5, screw hole.
Specific embodiment
Present invention will be described in further detail below with reference to the accompanying drawings and specific embodiments, but the present invention does not limit to
In these embodiments.In following embodiments, unless otherwise specified, used experimental method is conventional method, material used
Material, reagent etc. can be bought from biological or chemical company.
Embodiment 1
The porous titanium-based tantalum metal coating bone plate of a kind of personalized 3D printing with bone-inducting active, with titanium powder
End is substrate, forms tantalum coating system by the surface of the porous titanium-based bone plate with gap structure of 3D printing processing and fabricating
It is standby to obtain.
As depicted in figs. 1 and 2, the porous titanium-based bone plate includes ontology, and the ontology includes being located at the ontology
The external reinforcing ribs of edge, interior reinforcing rib, gap structure and screw hole on the inside of the external reinforcing ribs.The outer reinforcement
Muscle is in continuous structure, constitutes the edge of ontology, the interior reinforcing rib is in reticular structure, to improve the mechanical strength of bone plate.
The gap structure is distributed between external reinforcing ribs, interior reinforcing rib and screw hole, is by the brilliant pore structure of inside connection
Composition, the voidage of the gap structure are 70%, and the diameter in gap is 500 μm.
Specifically, the length of the porous titanium-based bone plate is 72mm, and with a thickness of 3mm, 30 ° of the radian at both ends is axial wide
Degree is 12mm, and the width of external reinforcing ribs is 1.5mm, and the width of interior reinforcing rib is 1mm, and both ends respectively have 3 screw holes, screw hole it is straight
Diameter is 3.5mm, and screw hole is located at the center line of bone plate length direction, the screw hole at both ends away from be respectively respectively at a distance from end 6mm,
16mm,26mm.The screw hole is type face counterbore, after fixing convenient for screw, will not be generated due to the protrusion of screw to surrounding tissue
Stimulation.
Porous titanium-based tantalum metal coating bone plate shown in Fig. 1~2 generally comprises entity part and porous part, described
The outer portion in the hole in hole and screw hole in gap structure is entity part.
Embodiment 2
With high-purity titanium valve (spherical powder, 15 μm~30 μm of partial size) for raw material, the processing and fabricating by way of 3D printing, system
It is standby to obtain personalized 3D printing tantalum metal coating Porous titanium bone plate, specifically comprise the following steps:
(1) anatomical structure at patients with fractures is understood by CT scan, CT scan data is reconstructed into 3D model, and (i.e. 3D is several
What image)；
(2) go out shape and the gap of the bone plate of personalized customization using Auto CAD, Pro E, Magics software design
Structure obtains the 3-D geometric model (as shown in Figure 2) of porous target bone plate, further obtains the porous target bone plate
The .stl formatted file of 3-D geometric model；
(3) the 3D printing process of porous bone plate as shown in Figure 2 are as follows: at the interface Building Processing by titanium
Belong to parameter packet and .stl file mergences, bone plate identifiable .mtt formatted file in 3D printer equipment is obtained, by this
.mtt formatted file is input to 3D printing equipment, is printed under argon atmosphere protection；3D printing condition are as follows: powdering with a thickness of
30 μm, laser power 200W, 70 μ s of time for exposure, 60 μm of laser scanning point spacing, 60 μm of line spacing；In 3D printing process
In, the intracorporal oxygen content of working chamber is less than 1000ppm；
(4) printout is placed in blasting treatment in sand-blasting machine, removes the titanium metal powder of surfaces stick, successively use third
Ketone, alcohol, distilled water are cleaned by ultrasonic 15 minutes, 40 DEG C of drying；Wherein abrasive material used in sandblasting is white fused alumina, and white fused alumina partial size is 50
μm -70 μm, sandblasting processing active force is 0.3MPa, blast time 60s；
(5) printout after drying is eliminated into residual stress through Overheating Treatment, and makes bone plate smooth surface, heat treatment temperature
Degree is 1500 DEG C, is heated up with 5 DEG C/min of heating rate, keeps the temperature 1 hour after reaching heat treatment temperature, furnace cooling；
(6) the Porous titanium plate soaked in absolute ethyl alcohol of 3D printing is blown after ultrasonic vibration cleans 30min with nitrogen
It is dry, using chemical vapor deposition method in porous titanium-based bone plate surface deposition of tantalum metal, porous titanium-based tantalum metal coating is made
Bone plate specifically comprises the following steps:
A) it will be placed in reaction chamber with the porous titanium-based bone plate after being dried with nitrogen, tantalum metal be placed in reaction chamber front end；
B) inert protective gas argon gas is passed first into reaction chamber, is purged reaction chamber 10min, is evacuated to 240Pa condition
Under, reaction chamber is heated to 800 DEG C, is passed through chlorine and hydrogen, vapor deposition reaction 7h is carried out, wherein the flow of the chlorine is
80mL/min, the flow of the hydrogen are 100mL/min；
C) after reaction, close hydrogen and chlorine, connect cooling device, be cooled under protection of argon gas 200 DEG C hereinafter,
Obtain porous titanium-based tantalum metal coating bone plate.
In the porous titanium-based tantalum metal coating bone plate being prepared, tantalum coating with a thickness of 30 μm, porosity 70%,
Bending strength is about 110MPa, and elasticity modulus is about 25GPa, and the diameter in the gap is 500 μm.
Fig. 3 is the porous titanium-based bone plate made by 3D printing, the bone plate actual size and calculate that 3D printing comes out
Machine design is almost the same.Fig. 4 is to prepare the painting of tantalum metal on the porous titanium-based bone plate of 3D printing by chemical vapour deposition technique
The bone plate of layer.Significant change occurs for the color of bone plate before and after coating.Before coating, the original color of the titanium that bone plate shows
Pool, it is brighter；And after coating, what bone plate showed is the color of tantalum metal, and color is relatively dim.Can tentatively it judge,
Tantalum metal has been deposited into the pore surface coating uniform of porous titanium-based bone plate.
Fig. 5 A indicates the electron scanning micrograph of porous titanium-based tantalum metal coating synthetism plate surface microstructure, from figure
As can be seen that the pore structure before and after coating is similar to the three-dimensional structure of human body bone trabecula in 5A, tantalum metal coating deposits completely
To the surfaces externally and internally of titanium bone plate, exposed and coating breaks down, obscission are had no.In addition, the bone plate table after tantalum coating
Face relative coarseness.This microstructure characteristic is determined by rapid prototyping technology feature, because rapid prototyping technology is layering
Accumulation forming technology necessarily will form above-mentioned surface characteristics during Layered manufacturing.These rough rough surfaces have
Conducive to the adherency of cell and being fitted into for tissue, the bonding strength of bone plate and bone tissue can be enhanced.Fig. 5 B indicates porous titanium-based
The XRD composition analysis result of tantalum metal coating synthetism plate surface, as shown, main component are tantalum, are more further demonstrated
Surface covering is tantalum metal.Fig. 6 A can be seen that the thickness of tantalum metal coating is about 60 microns, and Fig. 6 B crystallite dimension is about 10 micro-
Rice, the tantalum Metal Surface Roughness that this crystallite dimension is formed is higher, is more advantageous to the adherency of cell and macromolecular substances, increases
The initial stability of implantation material.
Embodiment 3
Selection weight about 20kg male goat is experimental animal, and the anatomical structure of goat tibial is understood by CT scan, will
CT scan data is reconstructed into 3D model (i.e. several picture).Go out personalization using Auto CAD, Pro E, Magics software design
The shape and gap structure of the bone plate of customization obtain the 3-D geometric model of porous target bone plate, it is more further to obtain this
The .stl formatted file of the 3-D geometric model of hole target bone plate.Then at the interface Building Processing by titanium
Belong to parameter packet and .stl file mergences, bone plate identifiable .mtt formatted file in 3D printer equipment is obtained, by this
.mtt formatted file is input in 3D printing equipment and is printed, and synthetism board width is 1.2cm, length 10cm；Screw diameter
It is differed for 2.7mm, length 14mm.Then tantalum is being carried out with Porous titanium bone plate of the chemical vapour deposition technique to preparation
Metal deposit.3D printing condition and chemical vapour deposition reaction parameter are same as Example 2.
After goat is anaesthetized, routine disinfection, paving are single, successively cut skin, subcutaneous tissue and fascia；Exposure goat tibial,
Fracture modeling is carried out to shin bone, then in traction reduction, after reaching anatomical reduction, the firm fixation of reduction forceps selects suitable synthetism
After plate, periosteum is separated, with cortex bone at abrasive drilling polishing bone plate, groove identical with bone plate plate size is formed, then places
Bone plate, after screw is fixed, normal saline flushing successively sutures periosteum, fascia, subcutaneous tissue and skin.
4 weeks after surgery respectively, 8 weeks, 12 weeks progress shin bone x-ray positive side positions penetrate piece, observe union situation (Fig. 7), art
Visible union in 3 months is all right afterwards, has no the postoperative complications such as malunion, disunion, infection.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. the porous titanium-based tantalum metal coating bone plate of a kind of personalized 3D printing with bone-inducting active, with titanium metal powder
Or titanium alloy metal powder is substrate, passes through the surface of the porous titanium-based bone plate with gap structure of 3D printing processing and fabricating
It forms tantalum coating and is prepared, the porosity of the porous titanium-based tantalum metal coating bone plate is 50%~80%, and bending resistance is strong
Degree is 50MPa~150MPa, and elasticity modulus is 2GPa~30GPa, and the diameter in the gap is 200 μm~800 μm, and the tantalum applies
Layer with a thickness of 30~60 μm.
2. porous titanium-based tantalum metal coating bone plate according to claim 1, which is characterized in that the pore structure is phase
Intercommunicated porous structure.
3. porous titanium-based tantalum metal coating bone plate according to claim 2, which is characterized in that the porous structure is rule
Porous structure then or the bone trabecula porous structure by Micro-CT scanning acquisition.
4. porous titanium-based tantalum metal coating bone plate according to claim 1, which is characterized in that the porous titanium-based synthetism
Plate includes ontology, and the ontology includes positioned at the external reinforcing ribs of the edge of the ontology, on the inside of the external reinforcing ribs
Interior reinforcing rib, gap structure and screw hole.
5. porous titanium-based tantalum metal coating bone plate according to claim 4, which is characterized in that the external reinforcing ribs are in company
Continuous structure, the interior reinforcing rib are in reticular structure.
6. the preparation method of described in any item porous titanium-based tantalum metal coating bones plate of Claims 1 to 5, including walk as follows
It is rapid:
(1) based on the CT scan data at patients with fractures, the 3D several picture of fracture is obtained using three-dimensional imaging software；
(2) the 3D several picture of the fracture based on patient, the bone plate of personalized customization is designed using three-dimensional imaging software
Shape and gap structure, the three-dimensional geometry image of target bone plate is obtained, by the three-dimensional geometry image text of the target bone plate
Part imported into 3D printer, using titanium metal powder or titanium alloy metal powder as raw material, carries out 3D under argon atmosphere protection and beats
Print, is made porous titanium-based bone plate；
(3) air exercise print porous titanium-based bone plate obtained carries out blasting treatment, and the titanium metal powder or titanium for removing surfaces stick are closed
Golden metal powder is successively cleaned by ultrasonic 15~30 minutes using acetone, alcohol and distilled water, is dried at 40 DEG C；
(4) the porous titanium-based bone plate after drying is heat-treated, the heat treatment temperature is 1200~2000 DEG C, heating speed
Rate is 5 DEG C/min, keeps the temperature 1 hour after reaching heat treatment temperature, furnace cooling；
(5) the porous titanium-based bone plate soaked in absolute ethyl alcohol after heat treatment is used into nitrogen after ultrasonic vibration cleans 30~60min
Air-blowing is dry, and using chemical vapor deposition method in porous titanium-based bone plate surface deposition of tantalum metal, porous titanium-based tantalum metal is made
Coating bone plate.
7. preparation method according to claim 6, which is characterized in that in step (2), the 3D printing condition are as follows: paving
For powder with a thickness of 20~50 μm, laser power is 120~200w, 50~100 microns of laser point spacing, 60~100 microns of line spacing,
60~150 microsecond of time for exposure.
8. preparation method according to claim 6, which is characterized in that in step (5), utilize chemical vapor deposition method
In porous titanium-based bone plate surface deposition of tantalum metal, the method that porous titanium-based tantalum metal coating bone plate is made includes following step
It is rapid:
A) it will be placed in reaction chamber with the porous titanium-based bone plate after being dried with nitrogen, tantalum metal be placed in reaction chamber front end；
B) it is passed through inert gas in reaction chamber, purges 10~20min of reaction chamber, is evacuated under the conditions of 200~250Pa, it will be anti-
It answers room to be heated to 800 DEG C, is passed through chlorine and hydrogen, 7~10h of vapor deposition reaction is carried out, wherein the flow of the chlorine is
80mL/min, the flow of the hydrogen are 100mL/min；
C) after reaction, hydrogen and chlorine are closed, cooling device is connected, is cooled to 200 DEG C or less under inert gas protection；
The inert gas described in step b) and step c) is the mixing of one or both of argon gas or nitrogen.
9. preparation method according to claim 6, which is characterized in that in step (2), the titanium metal powder is doctor
With grade spherical shape titanium metal powder, powder diameter is 15~45 μm.
10. preparation method according to claim 6, which is characterized in that in step (3), institute in the blasting treatment
The abrasive material used is white fused alumina, and the partial size of the white fused alumina is 50~150 μm, and blasting treatment active force is 0.1~1.0MPa.
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| CN201910472013.1A CN110090072B (en) | 2019-05-31 | 2019-05-31 | Personalized 3D printing porous titanium-based tantalum coating bone fracture plate and preparation method thereof |
| PCT/CN2019/090047 WO2020237705A1 (en) | 2019-05-31 | 2019-06-05 | Personalized 3d-printed porous titanium-based tantalum-coated bone plate and preparation method therefor |
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| CN113210625A (en) * | 2021-05-08 | 2021-08-06 | 北京市春立正达医疗器械股份有限公司 | 3D porous titanium alloy material with tantalum coating deposited on surface and preparation method thereof |
| CN114453593A (en) * | 2022-02-11 | 2022-05-10 | 西南科技大学 | Preparation method of personalized customized titanium alloy implant bracket with biological activity |
| CN115591015A (en) * | 2022-10-25 | 2023-01-13 | 季华实验室（Cn） | Degradable metal/polymer composite bone fracture plate and preparation method thereof |
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| CN110090072B (en) | 2020-07-28 |
| WO2020237705A1 (en) | 2020-12-03 |
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