CN105689709B - A kind of construction method of SLM shapings titanium implant surface micro-nano hierarchy - Google Patents

A kind of construction method of SLM shapings titanium implant surface micro-nano hierarchy Download PDF

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CN105689709B
CN105689709B CN201610058471.7A CN201610058471A CN105689709B CN 105689709 B CN105689709 B CN 105689709B CN 201610058471 A CN201610058471 A CN 201610058471A CN 105689709 B CN105689709 B CN 105689709B
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slm
titanium
titanium implant
shapings
pickling
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CN105689709A (en
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欧阳江林
陈贤帅
罗坤连
黄佳明
管威
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Guangdong Zhongke Anchi Biotechnology Co ltd
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Foshan Angles Biotechnology Co Ltd
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    • 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
    • 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
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/60—Treatment of workpieces or articles after build-up
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    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/60—Treatment of workpieces or articles after build-up
    • B22F10/66—Treatment of workpieces or articles after build-up by mechanical means
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    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/60—Treatment of workpieces or articles after build-up
    • B22F10/68—Cleaning or washing
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/32—Alkaline compositions
    • C23F1/38—Alkaline compositions for etching refractory metals
    • 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
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
    • 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
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
    • 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
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses
    • 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
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/24—Materials or treatment for tissue regeneration for joint reconstruction
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/245—Making recesses, grooves etc on the surface by removing material
    • 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

Abstract

The invention discloses a kind of construction method of SLM shaping titanium implant surface micro-nano hierarchies, comprise the following steps：（1）Titanium implant SLM is molded：Using Titanium powder as raw material, printing surface using SLM shapings 3D printing method has the titanium implant of micron scale construction；（2）Blasting treatment：Titanium implant surface blasting treatment is molded to SLM using corundum or titanium dioxide；（3）Pickling impurity elimination：SLM shaping titanium implants after blasting treatment are inserted pickling processes are carried out in pickle；（4）Hydro-thermal process：SLM shaping titanium implants after pickling processes are inserted hydro-thermal process is carried out in alkali lye；All SLM shaping titanium implants are sequentially placed into acetone, 95% ethanol, deionized water after each step and are cleaned by ultrasonic respectively, are dried.Not only step is simple by the present invention, easily operated, and builds the SLM shaping titanium implant surfaces with micro-nano hierarchy, effectively improves roughness, microscopic pattern and the hydrophily of SLM shaping titanium implant surfaces.

Description

A kind of construction method of SLM shapings titanium implant surface micro-nano hierarchy
Technical field
The present invention relates to bio-medical metal implant material technical field of surface, more particularly to a kind of SLM shapings titanium The construction method of implant surface micro-nano hierarchy.
Background technology
With the development of medical science and 3D printing technique, titanium metal powder selective laser melting stereo shaping (SLM) is utilized Titanium artificial growth body be being increasingly used to treat bone tissue lesion and repair deficiency, such as tooth implant, artificial close Section, and bone inner fixing device etc..So that clinical treatment from primary simple " reparations " treat rise to it is higher level --- bone " substituted " treatment is organized, so as to be greatly enhanced the life quality of people.Preferable SLM laser fast shaping titanium-baseds bone implantation Body should exercise its corresponding physiological function in the form of (Integrated implant Osseointegration) to be combined closely with bone tissue, so And the titanium-based bone implant of considerable part SLM laser fast shapings can not reach the Integrated implant at initial stage with host, cause to be implanted into Body loosens, comes off and produced complication.In addition to the factors such as fine motion, stress masking and implant operation except early stage, bone-implant Bad interface cohesion is also key factor.Therefore, on the basis of titanium merit is ensured, how SLM titaniums " special " Micron order rough surface builds suitable Gegenbaur's cell microenvironment, so regulate and control Gegenbaur's cell SLM titaniums surface stick and Its physiological function is exercised, to promote the Integrated implant of bone-implantation body interface.
Research shows that titanium implant surface characteristic especially surface micro-structure affects the speed and quality of knitting.It is micro- Meter level surface topography augmenting bone bonded area and mechanical interlock power, stable fibers albumen blood clot and fixed fragile extracellular base Matter support, stable microenvironment is provided for Gegenbaur's cell；Urn Topography then simulates natural cellular environment, increases protein adsorption, Change cell behavior, promote adhesion, propagation and the differentiation of Gegenbaur's cell.Imitate bone in the surface for having micron-nanometer multi structure concurrently Institutional framework, be advantageous to bone cell function and give full play to, preferably induce new bone formation.In addition, the surface of Superhydrophilic can be with Further promote the Integrated implant effect of planting body, improve the implantation effect of planting body.
At present, the method for changing titanium implant surface roughness mainly utilizes surface oxidation, surface sand-blasting, chemical attack The means such as processing.Chinese patent CN102552044 and CN102912349 individually disclose a kind of tooth kind of multiple dimensioned labyrinth The titanium implant surface preparation method of the preparation method on implant surface and a kind of micro-nano compound structure, it is micro- to obtain more than ten by sandblasting Rice relief fabric, then handle to obtain the compound multiple dimensioned composite construction of micro-nano by multiple acid corrosion.Similar, Chinese patent A kind of disclosed titanium implant surface prepares the method and one of multi-level nano-structure to CN102921037 and CN102912357 respectively The method that kind titanium implant surface prepares micro-nano structure, the method for being similarly combined with sandblasting and acid treatment, however, these Micro-nano compound structure and its hydrophily are unsatisfactory.The titanium implant of existing business application lacks preferable micron-nanometer composite table Face micro-structural, the problems such as surface hydrophilicity, prolonged application interface stability effect is undesirable be present.
The content of the invention
It is an object of the invention to for above-mentioned the deficiencies in the prior art, there is provided a kind of SLM shapings titanium implant surface is micro- Receive the construction method of hierarchy.
The technical solution used in the present invention is：A kind of structure side of SLM shapings titanium implant surface micro-nano hierarchy Method, it comprises the following steps：
(1) titanium implant SLM is molded：Using Titanium powder as raw material, surface is printed using SLM shapings 3D printing method Titanium implant with micron scale construction, the surface roughness Ra of titanium implant is 7~9 μm after SLM shapings.
(2) blasting treatment：SLM is molded at titanium implant surface sandblasting using the corundum or titanium dioxide of 40~80 mesh Reason, compressed air pressure is 3~6bar, and jet length is 50~150mm, and injecting time is 2~20s；
(3) pickling impurity elimination：SLM shaping titanium implants after blasting treatment are inserted pickling processes are carried out in pickle；
(4) hydro-thermal process：SLM shaping titanium implants after pickling processes are inserted hydro-thermal process is carried out in alkali lye；
All SLM shaping titanium implants are sequentially placed into acetone, 95% ethanol, deionized water after each step and surpassed respectively Sound cleans, and dries.
As the further improvement of such scheme, alkali lye is 3~10M NaOH solution in step (3), the place of hydro-thermal process It is 150~200 DEG C to manage temperature, and processing time is 2~10h.
As the further improvement of such scheme, step (2) pickle by concentrated hydrochloric acid and deionized water by volume 1：2 compositions, pickling temperature are 50~90 DEG C, and pickling time is 5~15min.
As the further improvement of such scheme, the roughness Ra of the SLM shapings titanium implant surface is 2~5 μm.
As the further improvement of such scheme, the SLM shapings titanium implant surface is in the nanoscale structures of thick grass shape Form.
The beneficial effects of the invention are as follows：
(1) present invention passes through the blasting treatment of bulky grain on the basis of SLM is molded titanium implant micron order rough surface The titanium pearl of attachment in SLM forming processes or semi-molten shape is removed；A small amount of abrasive material that acid cleaning process introduces sandblasting procedures is broken Piece removes；Further handled by alkali liquor hydrothermal, nano level " thick grass shape " pattern formed in micron-sized titanium implant surface, Form " there is finesse in sb.'s roughness " preferably micro-nano hierarchy.Meanwhile after hydrothermal treatment titanium implant surface hydroxyl quantity increasing Capillarity caused by more and micro-structural, greatly enhances the hydrophily of titanium implant.
(2) present invention has by the combined use of physics and chemical method for treating surface and the optimization of specific process parameter SLM shaping titanium implant surface roughness is reduced to effect, further promotes the Integrated implant of SLM shaping titanium implants.
(3) present invention applies the surface treatment method that physical method is combined with chemical method in titanium implant field, if It is standby be simple and convenient to operate, production cost it is low, suitable for industrialized production.
Brief description of the drawings
Fig. 1 be SLM be molded titanium implant surface before processing SEM pictures (a, 35 ×, b, 400 ×)；
Fig. 2 is that SLM is molded SEM picture (400 ×) of the titanium implant after blasting treatment；
Fig. 3 be SLM be molded titanium implant after blasting treatment-pickling impurity elimination-hydro-thermal process SEM pictures (a, 4500 ×, b、20000×)。
Embodiment
In order to be better understood from the present invention, the present invention is done furtherly with reference to Figure of description and specific embodiment It is bright.The reagent used in the present invention is commercial reagent.Wherein the mass fraction of concentrated hydrochloric acid is 36~38%.Used in the present invention Assay method be mostly this area conventional method, this is no longer going to repeat them.
The hydrophily of titanium implant is represented by contact angle.The method of contact angle test is as follows：Sampling, with needle tubing in sample 10 μ L liquid drop is slowly added dropwise in top 2mm, and baseline is chosen after balancing 10s, using OCA20 contact angle measurements, describes drop Appearance profile, calculate contact angle with SCA softwares, afterwards every 5s measurements once, note down 10 time points, the measurement of each sample altogether The drop of 2 separation, the contact angle averaged as the sample, every kind of every group of sample of liquid measure 3.Calculate every group of sample Average value and standard deviation.
Embodiment 1
A kind of construction method of SLM shapings titanium implant surface micro-nano hierarchy, it comprises the following steps：
(1) titanium implant SLM is molded：Using Titanium powder as raw material, surface is printed using SLM shapings 3D printing method Titanium implant with micron scale construction, its surface topography are as shown in Figure 1；
(2) blasting treatment：SLM shaping titanium implants are carried out at surface sand-blasting using the corundum or titanium dioxide of 80 mesh Reason, the process conditions of blasting treatment：Compressed air pressure is 6bar, jet length 70mm, injecting time 10s；At sandblasting Reason removes the titanium pearl of titanium implant attachment or semi-molten shape after SLM shapings, and its surface topography is as shown in Figure 2；After blasting treatment SLM shaping titanium implants are sequentially placed into acetone, 95% ethanol, deionized water and are cleaned by ultrasonic 10min respectively, are dried；
(3) pickling impurity elimination：Pickle is volume ratio 1：2 concentrated hydrochloric acid and deionized water is formulated, pickling temperature 40 DEG C, pickling time 5min；Pickling processes remove the material spray fragment introduced in sandblasting procedures；SLM is molded titanium after pickling impurity elimination Planting body is sequentially placed into acetone, 95% ethanol, deionized water is cleaned by ultrasonic 10min respectively, dries；
(4) hydro-thermal process：SLM shaping titanium implants are placed in 5M NaOH solution, inserts in 160 DEG C of water heating kettle and locates Manage 3h；Hydro-thermal process makes the nanoscale structures of SLM shaping titanium implant multi level pit surface formation " thick grass shape ", i.e. SLM shapings Titanium implant surface forms the surface of micro-nano hierarchy, and its surface topography is as shown in Figure 3；SLM is molded titanium after hydro-thermal process Planting body is sequentially placed into acetone, 95% ethanol, deionized water is cleaned by ultrasonic 10min respectively, dries.
In order to be better understood by the physicochemical property of SLM shapings titanium implant surface after every step process, respectively to every step SLM shaping titanium implants after processing carry out contact angle and roughness value measure, and concrete outcome is shown in Table 1.
The contact angle and roughness of titanium implant surface after the different disposal technique of table 1
Handling process Untreated (SLM) Blasting treatment Sandblasting+pickling Sandblasting+pickling+hydro-thermal
Contact angle (°) 62.5±2.3 76.7±2.6 72.3±3.2 4.8±1.4
Ra(μm) 7.83±0.12 3.87±0.10 3.49±0.12 3.35±0.13
Rq(μm) 9.57±0.21 4.98±0.09 4.95±0.08 4.32±0.08
Rz(μm) 37.91±0.57 25.78±0.36 23.97±0.13 22.75±0.32
Embodiment 2
A kind of construction method of SLM shapings titanium implant surface micro-nano hierarchy, it comprises the following steps：
(1) titanium implant SLM is molded：Using Titanium powder as raw material, surface is printed using SLM shapings 3D printing method Titanium implant with micron scale construction；
(2) blasting treatment：SLM shaping titanium implants are carried out at surface sand-blasting using the corundum or titanium dioxide of 60 mesh Reason, the process conditions of blasting treatment：Compressed air pressure is 4bar, jet length 60mm, injecting time 20s；At sandblasting Reason removes the titanium pearl of SLM shaping titanium implant attachments or semi-molten shape；SLM shaping titanium implants are put successively after blasting treatment It is cleaned by ultrasonic 10min respectively in acetone, 95% ethanol, deionized water, dries；
(3) pickling impurity elimination：Pickle is volume ratio 1：2 concentrated hydrochloric acid and deionized water is formulated, pickling temperature 60 DEG C, pickling time 8min；Pickling processes remove the material spray fragment introduced in sandblasting procedures；SLM is molded titanium after pickling impurity elimination Planting body is sequentially placed into acetone, 95% ethanol, deionized water is cleaned by ultrasonic 10min respectively, dries；
(4) hydro-thermal process：SLM shaping titanium implants are placed in 6M NaOH solution, inserts in 180 DEG C of water heating kettle and locates Manage 3h；Hydro-thermal process makes the nanoscale structures of SLM shaping titanium implant multi level pit surface formation " thick grass shape ", i.e. SLM shapings Titanium implant surface forms the surface of micro-nano hierarchy；After hydro-thermal process by SLM shaping titanium implant be sequentially placed into acetone, It is cleaned by ultrasonic 10min in 95% ethanol, deionized water respectively, dries.
In order to be better understood by the physicochemical property of SLM shapings titanium implant surface after every step process, respectively to every step SLM shaping titanium implants after processing carry out contact angle and roughness value measure, and concrete outcome is shown in Table 2.
The contact angle and roughness of titanium implant surface after the different disposal technique of table 2
Handling process Untreated (SLM) Blasting treatment Sandblasting+pickling Sandblasting+pickling+hydro-thermal
Contact angle (°) 67.3±1.5 72.5±1.3 70.2±2.1 5.1±2.3
Ra(μm) 8.15±0.16 4.07±0.13 3.86±0.14 3.65±0.11
Rq(μm) 9.78±0.11 5.28±0.14 5.25±0.16 4.78±0.14
Rz(μm) 38.72±0.38 26.35±0.28 24.34±0.25 23.47±0.28
Embodiment 3
A kind of construction method of SLM shapings titanium implant surface micro-nano hierarchy, it comprises the following steps：
(1) titanium implant SLM is molded：Using Titanium powder as raw material, surface is printed using SLM shapings 3D printing method Titanium implant with micron scale construction；
(2) blasting treatment：SLM shaping titanium implants are carried out at surface sand-blasting using the corundum or titanium dioxide of 40 mesh Reason, the process conditions of blasting treatment：Compressed air pressure is 6bar, jet length 80mm, injecting time 15s；At sandblasting Reason removes the titanium pearl of SLM shaping titanium implant attachments or semi-molten shape；SLM shaping titanium implants are put successively after blasting treatment It is cleaned by ultrasonic 10min respectively in acetone, 95% ethanol, deionized water, dries；
(3) pickling impurity elimination：Pickle is volume ratio 1：2 concentrated hydrochloric acid and deionized water is formulated, pickling temperature 60 DEG C, pickling time 10min；Pickling processes remove the material spray fragment introduced in sandblasting procedures；SLM is molded titanium after pickling impurity elimination Planting body is sequentially placed into acetone, 95% ethanol, deionized water is cleaned by ultrasonic 10min respectively, dries；
(4) hydro-thermal process：SLM shaping titanium implants are placed in 4M NaOH solution, inserts in 180 DEG C of water heating kettle and locates Manage 6h；Hydro-thermal process makes the nanoscale structures of SLM shaping titanium implant multi level pit surface formation " thick grass shape ", i.e. SLM shapings Titanium implant surface forms the surface of micro-nano hierarchy；After hydro-thermal process by SLM shaping titanium implant be sequentially placed into acetone, It is cleaned by ultrasonic 10min in 95% ethanol, deionized water respectively, dries.
In order to be better understood by the physicochemical property of SLM shapings titanium implant surface after every step process, respectively to every step SLM shaping titanium implants after processing carry out contact angle and roughness value measure, and concrete outcome is shown in Table 3.
The contact angle and roughness of titanium implant surface after the different disposal technique of table 3
Handling process Untreated (SLM) Blasting treatment Sandblasting+pickling Sandblasting+pickling+hydro-thermal
Contact angle (°) 67.1±3.4 77.3±3.1 70.7±3.4 5.7±1.2
Ra(μm) 8.73±0.21 4.37±0.14 3.86±0.14 3.71±0.10
Rq(μm) 9.83±0.12 5.63±0.12 5.27±0.16 4.68±0.12
Rz(μm) 38.72±0.43 26.37±0.33 24.35±0.23 23.41±0.28
Embodiment 4
A kind of construction method of SLM shapings titanium implant surface micro-nano hierarchy, it comprises the following steps：
(1) titanium implant SLM is molded：Using Titanium powder as raw material, surface is printed using SLM shapings 3D printing method Titanium implant with micron scale construction；
(2) blasting treatment：SLM shaping titanium implants are carried out at surface sand-blasting using the corundum or titanium dioxide of 60 mesh Reason, the process conditions of blasting treatment：Compressed air pressure is 4bar, jet length 55mm, injecting time 20s；At sandblasting Reason removes the titanium pearl of SLM shaping titanium implant attachments or semi-molten shape；SLM shaping titanium implants are put successively after blasting treatment It is cleaned by ultrasonic 10min respectively in acetone, 95% ethanol, deionized water, dries；
(3) pickling impurity elimination：Pickle is volume ratio 1：2 concentrated hydrochloric acid and deionized water is formulated, pickling temperature 80 DEG C, pickling time 15min；Pickling processes remove the material spray fragment introduced in sandblasting procedures；SLM is molded titanium after pickling impurity elimination Planting body is sequentially placed into acetone, 95% ethanol, deionized water is cleaned by ultrasonic 10min respectively, dries；
(4) hydro-thermal process：SLM shaping titanium implants are placed in 6M NaOH solution, inserts in 180 DEG C of water heating kettle and locates Manage 4h；Hydro-thermal process makes the nanoscale structures of SLM shaping titanium implant multi level pit surface formation " thick grass shape ", i.e. SLM shapings Titanium implant surface forms the surface of micro-nano hierarchy；After hydro-thermal process by SLM shaping titanium implant be sequentially placed into acetone, It is cleaned by ultrasonic 10min in 95% ethanol, deionized water respectively, dries.
In order to be better understood by the physicochemical property of SLM shapings titanium implant surface after every step process, respectively to every step SLM shaping titanium implants after processing carry out contact angle and roughness value measure, and concrete outcome is shown in Table 4.
The contact angle and roughness of titanium implant surface after the different disposal technique of table 4
Handling process Untreated (SLM) Blasting treatment Sandblasting+pickling Sandblasting+pickling+hydro-thermal
Contact angle (°) 60.5±1.2 70.7±3.2 74.1±2.4 5.7±1.6
Ra(μm) 7.62±0.13 3.56±0.12 3.35±0.10 3.64±0.18
Rq(μm) 9.27±0.13 4.47±0.10 4.39±0.09 4.58±0.13
Rz(μm) 36.87±0.35 24.63±0.32 23.24±0.23 23.74±0.34
From the experimental result and accompanying drawing 1~3 of above-described embodiment 1~4, SLM is molded titanium implant through blasting treatment, spray Contact angle after sand processing+pickling impurity elimination increases successively, and hydrophily also reduces successively, but again after hydrothermal treatment, SLM shapings The contact angle of titanium implant falls sharply, and hydrophily greatly increases, and reaches Superhydrophilic.Simultaneously by surface treatment, it is effectively reduced The roughness Ra of SLM shaping titanium implant surfaces.
Above-described embodiment is only used for illustrating the present invention, rather than limits the invention, in the spirit and power of the present invention In the protection domain that profit requires, to any modifications and changes of the invention made, both fall within protection scope of the present invention.

Claims (3)

1. a kind of construction method of SLM shapings titanium implant surface micro-nano hierarchy, it is characterised in that comprise the following steps：
(1) titanium implant SLM is molded：Using Titanium powder as raw material, printing surface using SLM shapings 3D printing method has The titanium implant of micron scale construction, the surface roughness Ra of titanium implant is 7~9 μm after SLM shapings；
(2) blasting treatment：Titanium implant surface blasting treatment, pressure are molded to SLM using the corundum or titanium dioxide of 40~80 mesh Contracting air pressure is 3~6bar, and jet length is 50~150mm, and injecting time is 2~20s；
(3) pickling impurity elimination：SLM shaping titanium implants after blasting treatment are inserted pickling processes are carried out in pickle；
(4) hydro-thermal process：SLM shaping titanium implants after pickling processes are inserted hydro-thermal process is carried out in alkali lye；
It is clear that SLM shaping titanium implants are all sequentially placed into acetone, 95% ethanol, deionized water ultrasound respectively after each step Wash, dry；
The roughness Ra of the SLM shapings titanium implant surface micro-nano hierarchy is 2~5 μm；
The SLM shapings titanium implant surface is in the nanoscale structures form of thick grass shape.
2. a kind of construction method of SLM shapings titanium implant surface micro-nano hierarchy according to claim 1, its feature It is, alkali lye is 3~10M NaOH solution in step (4), and the treatment temperature of hydro-thermal process is 150~200 DEG C, processing time For 2~10h.
3. a kind of construction method of SLM shapings titanium implant surface micro-nano hierarchy according to claim 1, its feature It is, step (3) pickle is by concentrated hydrochloric acid and deionized water by volume 1：2 compositions, pickling temperature are 50~90 DEG C, acid It is 5~15min to wash the time.
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Denomination of invention: Construction method for micro-nano hierarchical structure on surface of SLM forming titanium implant

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