CN104985183B - A kind of low elastic modulus titanium-based jawbone implant and preparation method thereof - Google Patents

A kind of low elastic modulus titanium-based jawbone implant and preparation method thereof Download PDF

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CN104985183B
CN104985183B CN201510319631.4A CN201510319631A CN104985183B CN 104985183 B CN104985183 B CN 104985183B CN 201510319631 A CN201510319631 A CN 201510319631A CN 104985183 B CN104985183 B CN 104985183B
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jawbone
implant
titanium
preparation
model
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CN104985183A (en
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郑华德
朱祎纬
张明
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Dongguan Weixin Three Dimensional Technology Co ltd
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South China Institute of Collaborative Innovation
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Abstract

The invention discloses a kind of low elastic modulus titanium-based jawbone implant and preparation method thereof, preparation method mainly includes 6 steps, is respectively:The jawbone cross-section image data of CT scan are obtained, the jawbone three-dimensional digital model rebuild, the jawbone implant mathematical model for designing and obtaining loose structure is obtained, the processed file for obtaining slicing delamination cross-section data, jawbone implant is prepared using selective laser melting technology, implant is surface-treated.The present invention is used for the treatment of jaw defect patient, the design of the implant uses CAD digital design techniques, personalized designs and porous stent structure design are repaired with reference to jawbone, a kind of low elastic modulus titanium-based jawbone implant is prepared by selective laser melting technology.The implant can both meet the individual demand of patient, while modulus of elasticity can also be reduced, alleviate the stress concentration and stress shielding problem of traditional jawbone implant, shorten preparation time, reduce difficulty of processing and production cost.

Description

A kind of low elastic modulus titanium-based jawbone implant and preparation method thereof
Technical field
The present invention relates to artificial bone implant research field, more particularly to a kind of low elastic modulus titanium-based jawbone implant And preparation method thereof.
Background technology
Jawbone is the important component of stomatognathic system, and the bone for being not only Maxillary region is supported, or is chewed, swallowed and language The architecture basics of the functions such as speech.Once because inflammation, exterior trauma, tumour or developmental deformity etc. cause deformitas maxillaris, large area Defect, can not only cause patient's maxillofacial deformities, and severe patient can influence the chewing of patient, swallow and the basic training such as language Can, therefore the physiology and mental anguish of patient are added, cause the quality of life of patient to decline.But it is due to that jaw structure is answered It is miscellaneous, so the emphasis and difficult point of the reparation always surgical clinic work to jawbone large defect.
Traditional repair of jaw defect method common at present has autologous MSCs, vascularization autologous bone transplanting, allosome Bone- xenograft free grafting, bone distraction osteogenesis etc., these methods respectively have its advantage and disadvantage, and different degrees of presence bone amount is limited, for bone The problems such as operation wound is big, plasticity is difficult, it is difficult to fully meet the demand of surgical clinical.
The bone implant of titanium or titanium alloy material manufacture has good biocompatibility, nontoxicity, corrosion resistance, high machine Tool intensity and toughness, are widely used in the reparation and replacement of human body bearing position bone in decorative sursery and other orthopaedics.People The modulus of elasticity of body bone is 10~30GPa, and the titanium alloy material Ti-6Al- manufactured for bone implant wide at present 4V modulus of elasticity is 108GPa, still higher compared with skeleton.Modulus of elasticity between bone implant and host bone is not The bone implant that matching will cause stress concentration and stress shielding phenomenon, i.e. modulus of elasticity big bears the stress of the overwhelming majority, and Host bone is hardly undertaking stress with implant binding site so that the binding site between bone implant and host bone lacks Necessary stress stimulation, the bone information of host bone is more than ostosis, can delay the formation of poroma, and implant may be caused to produce A series of complication such as sterile loosening and fracture.ASSOCIATE STATISTICS shows that crash rate of the current implant in 15 years reaches 10%- 20%, wherein about 80% is due to that stress concentration and stress shielding are caused.Therefore, design and prepare and skeleton springform The jawbone implant matched is measured, ill effect caused by stress concentration and stress shielding is reduced, for promoting jaw defect to repair Multiple clinical practice, improves therapeutic effect, and reducing sufferer pain has important use value.
In order to reduce the modulus of elasticity of existing titanium or titanium alloy implant, it is matched as far as possible with host bone, make The microscopic feature of body bone tissue is simulated with porous technology of preparing and three-dimensional porous implant is prepared, and just becoming one is worth tasting The solution of examination.Correlative study person both domestic and external has begun to conduct a research in this regard, and Garrett E.Ryan etc. exist 《Biomaterial》" the Porous titanium delivered on (biomaterial, the 29th 3625-3635 pages of phase in 2008) scaffolds fabricated using a rapid prototyping and powder metallurgy In the texts of technique " one, describe and prepare the porous titanium alloy that height imitates bone tissue using multistage rapid shaping technique Material.Porous material structure design first is carried out with computer, a wax-pattern is produced by three-dimensional printer, then by titanium alloy Powder is made pulpous state and is filled into wax-pattern, then melts wax-pattern by 1000-1300 DEG C of high-temperature heating, forms cavernous titanium-based material Material.By changing the design of wax-pattern hole size, can by pore size control between 200-400 microns, porosity be 66.8 ± 3.6%.Through Mechanics Performance Testing, the axial compression strength of material is 104.4 ± 22.5MPa, and transverse compression intensity is then 23.5 ± 9.6MPa, shows anisotropic feature.But this manufacture craft is more complicated, it is impossible to disposable to complete to prepare.
The content of the invention
It is a primary object of the present invention to for existing traditional titanium-based jawbone implant in clinical practice it is not enough there is provided A kind of preparation method of low elastic modulus titanium-based jawbone implant, this method integrated application rapid shaping technique and selective laser Smelting technology, can both meet the individual demand of patient, while modulus of elasticity can also be reduced, alleviate traditional jawbone implant Stress concentration and stress shielding problem, shorten preparation time, reduce difficulty of processing and production cost.
Another object of the present invention is to provide a kind of low elastic modulus titanium-based jawbone prepared using above-mentioned preparation method Implant.
The purpose of the present invention is realized by following technical scheme:A kind of preparation of low elastic modulus titanium-based jawbone implant Method, including step:
(1) using CT examination device scan patient's jawbone position, obtain the cross-section image of relevant range bone and save as DICOM format file;
(2) DICOM format file is imported into image processing software, reconstructs the correct surface model of cooperation position, i.e. root Minute surface reconstruction is carried out to jawbone according to the concrete condition of patient, and saves as STL formatted files;
(3) STL formatted files are imported into CAD design software, according to the operation designing of patient, jawbone implant needed for choosing Magnitude range, interception needed for jawbone model;
(4) the jawbone model for generating step (3) is exported with STL formatted files, using corresponding software by the model layers Section, is converted into the sli file with machining informations such as cross section profile data;
(5) according to the sli file of step (4), using selective laser melting equipment, successively fabricate titanium-based jawbone and plant Enter body;
(6) surface acid etching is carried out to titanium-based jawbone implant, plant is remained in when removing and process using magnetic grinding equipment Enter the burr in body surface face, complete to prepare.
Specifically, in the step (1), during using CT examination device scan patient jawbone position, scanning area is eye socket Upper limb is to 2mm below angle of mandible, and scanning voltage is 120kV, and sweep current is 170-220mA, and Scan slice thickness is 1-1.5mm.
Specifically, in the step (2), the obtaining step of STL formatted files is:
The DICOM format file obtained in step (1) is imported image processing software Mimics by (2-1), checks CT tomographies Image whether there is apparent error or deformation, if being not present, and carry out step (2-2);
(2-2) defines a gray threshold, and area of bone tissue is regarded as in the region higher than the gray threshold, extracts bone tissue wheel Soft tissue and cancellous bone are regarded as in profile, the region less than the gray threshold, are removed as noise point;
(2-3) is according to the bone defects situation of patient, the automatic three-dimensional overlay computing of selection respective data area progress, software The three-dimensional reconstruction of jaw defect model is completed according to cloud data;
(2-4) completes the reconstruction of the jawbone of offside defect using mirror image systematic function according to the form for perfecting side jawbone;
The model finally obtained is saved as STL formatted files by (2-5).
Specifically, in the step (3), the step of obtaining mathematical model in CAD design software is:
The STL formatted files obtained in step (2) are imported CAD design software by (3-1), according to the operation designing of patient, The magnitude range of jawbone implant needed for choosing, using the interception function of software, the jaw needed for vertical jawbone central axis interception Bone model;
(3-2) sets a porous structural unit, and the porous structural unit is extended using mirror image instrument, obtains porous Structural model;
(3-3) by the Boolean calculation instrument of software, the loose structure model that step (3) is obtained with step (3-1) The jawbone model of interception is fitted, and obtains the jawbone implant mathematical model with porous structural unit;
(3-4) designs the connector of jawbone implant and jawbone, and connector is to be located at implant and jawbone connecting portion plane The rectangular parallelepiped structure of side, 1-3cm is extended to jawbone, and width is the 1/2 of the normal jawbone height of patient, and thickness is 0.8mm, and even The circular hole that standard bone titanium rebuilds screw (2.5x9mm) diameter is generated on junctor, the connector is fitted in step (3-3) and carried The jawbone implant mathematical model of porous structural unit, obtains final acquisition jawbone implant mathematical model.
Further, in the step (3-2), the structure of the porous structural unit is:Eight corners use eight points One of spheroid, cylinder is middle by a cube and a spheroid is overlapping forms as beam texture, is used as beam texture Coupling part.
Specifically, in the step (4), the obtaining step of sli file is:
The stl file of generation in step (3) is imported professional delamination software (such as RP-Tools) by (4-1);
(4-2) selects section/layer functions, obtains the hierarchy slicing data of stl file, checks data with the presence or absence of not complete The mistakes such as complete closure, unnecessary triangle, are replaced or removed using adjacent layer the functions such as triangle and change mistake;
(4-3) exports hierarchy slicing data, and saves as the sli file with cross section profile data mart modeling information.
Further, the hierarchy slicing thickness in the step (4-2) is 10 μm.
Specifically, in the step (5), according to the sli file of step (4), successively fabricating titanium-based jawbone implant The step of be:
The pure titanium or titanium alloy powder of 50 μm of average grain diameter are placed in raw cylinder by (5-1), and one piece of substrate is fixed on On shaped platform;
The powder being preset in raw cylinder is pushed and tiled to substrate by (5-2) powdering scraper;
(5-3) is swung according to cross section profile data, computer control scanning galvanometer, makes the fusing substrate of laser beam selectivity On powder;
(5-4) substrate declines the distance of a molding thickness with shaped platform, raw cylinder also rise accordingly it is certain away from From;
(5-5) repeating said steps (5-2) to (5-4), until titanium-based jawbone implant completion of processing.
Further, in the step (5-3), the laser power of the laser beam used is 50W-200W, laser scanning Speed is 200mm/s-1400mm/s.
Further, the molding thickness in the step (5-4) is the adjustable numerical value in 20-70 μ ms, and Keep fixing in whole process.
Further, the step (5-2) to (5-5) is carried out in ar gas environment.
Specifically, in the step (6), following handle is carried out to titanium-based jawbone implant:
(6-1) carries out acid treatment, nitric acid and hydrogen using nitric acid and hydrofluoric acid mixed solution to titanium-based jawbone implant surfaces The ratio of fluoric acid mixed solution is nitric acid:Hydrofluoric acid:Water=35:5:160;
(6-2) remains in the burr of implant surfaces when being removed and processed using magnetic grinding equipment.
The present invention compared with prior art, has the following advantages that and beneficial effect:
1st, deficiency of the present invention for traditional titanium-based jawbone implant in clinical practice, designs low elastic modulus titanium-based jaw Bone implant three-dimensional digital model, in combination with existing ripe rapid shaping technique-there is provided one for selective laser melting technology Plant the manufacture processing method of low elastic modulus titanium-based jawbone implant.By the CAD design to jawbone implant, tool can be met The individual demand of body patient, while porous stent structure also can be designed in relevant position as needed, reduces modulus of elasticity, from And effectively alleviate the stress concentration between jawbone implant and body bone tissue and stress shielding problem.Use selective laser melting Jawbone implant of the technology manufacture with loose structure, you can accurately to realize design effect, process the complexity of loose structure Internal morphology, while reaching good consistency, can reach the mechanics processing effect that foundry engieering can reach.
2nd, the titanium-based jawbone implant designed by the present invention employs loose structure, and is uniformly distributed, and framework is controllable.Compare With traditional entity titanium-based jawbone implant, loose structure, which is designed, causes the modulus of elasticity of implant to decline, closer to human body bone The modulus of elasticity of bone, can effectively alleviate the stress concentration and stress shielding between implant and body bone tissue.Loose structure Titanium-based jawbone implant reduces implant in deadweight and the consumption of titanium-base alloy on the basis of being consolidated after ensure that implantation, The burden for alleviating patient reduces material cost again.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of the inventive method.
Fig. 2 is a kind of structural representation of porous structural unit in the present embodiment.
The partial schematic diagram for the loose structure model that Fig. 3 constitutes for porous structural unit as shown in Figure 2.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited In this.
Embodiment 1
As shown in figure 1, a kind of preparation method of low elastic modulus titanium-based jawbone implant of the present embodiment, main to include 6 Step, be respectively:The jawbone cross-section image data of CT scan are obtained, the jawbone three-dimensional digital model rebuild is obtained, designs and obtain Obtain the jawbone implant mathematical model of loose structure, obtain the processed file of slicing delamination cross-section data, using selective laser Smelting technology prepares jawbone implant, implant is surface-treated, and above steps is specifically described below.
1st, the jawbone cross-section image data of CT scan are obtained
The present embodiment is that scanning area is under eye socket upper limb to angle of mandible using CT examination device scan patient's jawbone position Square 2mm, to ensure that data are complete.Scanning voltage is 120kV, and sweep current is 170-220mA, and Scan slice thickness is 1-1.5mm.Obtain Obtain the cross-section image of relevant range bone and save as DICOM format file.
2nd, the jawbone three-dimensional digital model rebuild is obtained
Image processing software Mimics is imported data to, the correct surface model of cooperation position is reconstructed, i.e., according to patient Concrete condition minute surface reconstruction is carried out to jawbone, and save as STL formatted files, comprise the concrete steps that:
The DICOM format file obtained in step (1) is imported image processing software Mimics by (2-1), checks CT tomographies Image whether there is apparent error or deformation, is modified if wrong, and step (2-2) is performed after qualified;
(2-2) defines a gray threshold, and area of bone tissue is regarded as in the region higher than the gray threshold, extracts bone tissue wheel Soft tissue and cancellous bone are regarded as in profile, the region less than the gray threshold, are removed as noise point;
(2-3) selects data area according to the bone defects situation of patient, carries out automatic three-dimensional overlay computing, software according to Cloud data completes the three-dimensional reconstruction of jaw defect model;
(2-4) completes the reconstruction of the jawbone of offside defect using mirror image systematic function according to the form for perfecting side jawbone;
The model finally obtained is saved as STL formatted files by (2-5).
3rd, design and obtain the jawbone implant mathematical model of loose structure
STL formatted files are imported into CAD design software (such as Pro-E, Geomagic), selection prepares jawbone implant Scope simultaneously carries out osteotomy.Loose structure is designed in CAD software simultaneously, the jaw of loose structure is carried by Boolean calculation tool design Bone implant mathematical model, is comprised the concrete steps that:
The STL formatted files obtained in step (2) are imported CAD software by (3-1), according to the operation designing of patient, are chosen The magnitude range of required jawbone implant, using the interception function of software, the jawbone mould needed for vertical jawbone central axis interception Type.
(3-2) sets a porous structural unit, and the porous structural unit is extended using mirror image instrument, obtains porous Structural model.
The present embodiment one species cancellous bone loose structure of design, even pore distribution, pore size is equal from the outside to the core, hole Footpath magnitude range is 100 μm of -1mm.Porous structural unit feature is as shown in Fig. 2 eight corners are using eighth spheroid (figure Example 2), as the coupling part with expanding element, cylinder (legend 1) is as beam texture, and centre is by a cube (legend 3) It is overlapping with a spheroid (legend 4) to form, it is used as the coupling part of beam texture.Mirror image is carried out to the unit using mirror image instrument Extension can obtain class cancellous bone porous stent structure model as shown in Figure 3.
(3-3) is fitted the jawbone model of interception in loose structure and step (3-1) by the Boolean calculation instrument of software, Obtain the jawbone implant mathematical model with designed loose structure.
(3-4) designs the connector of jawbone implant and jawbone, and connector is to be located at implant and jawbone connecting portion plane The rectangular parallelepiped structure of side, 1-3cm is extended to jawbone, and width is the 1/2 of the normal jawbone height of patient, and thickness is 0.8mm, and even The circular hole that standard bone titanium rebuilds screw (2.5x9mm) diameter is generated on junctor, jawbone implant mathematical model is obtained.
4th, the processed file of slicing delamination cross-section data is obtained
The jawbone model that step (3) is generated is exported with STL formatted files, is cut the model layers using corresponding software Piece, is converted into the sli file with machining informations such as cross section profile data.Comprise the concrete steps that:
The stl file of generation in step (3) is imported professional delamination software (such as RP-Tools) by (4-1);
(4-2) selects section/layer functions, and hierarchy slicing thickness is 10 μm, obtains the hierarchy slicing data of stl file, Check that the functions such as triangle are replaced or removed to data, with the presence or absence of mistakes such as not fully closed, unnecessary triangles, using adjacent layer Change mistake;
(4-3) exports hierarchy slicing data, and saves as SLI formatted files.
5th, jawbone implant is prepared using selective laser melting technology
According to the sli file of step (4), using selective laser melting equipment, low elastic modulus titanium is successively fabricated Base jawbone implant, processing thickness is 20-70 μm, and laser power is 50W-200W, and laser scanning speed is 200mm/s- 1400mm/s.Comprise the following steps that:
Pure titanium or titanium alloy powder (50 μm of average grain diameter) are placed in raw cylinder by (5-1), and one piece of substrate is fixed on On shaped platform;
The powder being preset in raw cylinder is pushed and tiled to substrate by (5-2) powdering scraper;
(5-3) is swung according to cross section profile data, computer control scanning galvanometer, makes the fusing substrate of laser beam selectivity On powder;
(5-4) substrate declines the distance of a molding thickness with shaped platform, raw cylinder also rise accordingly it is certain away from From;
(5-5) repeating said steps (5-2) to (5-4), until part completion of processing.
6th, implant is surface-treated
Use nitric acid and hydrofluoric acid mixed solution (nitric acid:Hydrofluoric acid:Water=35:5:160) to low elastic modulus titanium-based jaw Bone implant surface is handled.
The burr of implant surfaces is remained in when removing and process using magnetic grinding equipment.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (9)

1. a kind of preparation method of low elastic modulus titanium-based jawbone implant, it is characterised in that including step:
(1) using CT examination device scan patient's jawbone position, obtain the cross-section image of relevant range bone and save as DICOM Formatted file;
(2) DICOM format file is imported into image processing software, reconstructs the correct surface model of cooperation position, i.e., according to trouble The concrete condition of person carries out minute surface reconstruction to jawbone, and saves as STL formatted files;(3) STL formatted files importing CAD is set Software is counted, according to the operation designing of patient, the magnitude range of jawbone implant needed for choosing, the jawbone model needed for interception, step Suddenly it is:
The STL formatted files obtained in step (2) are imported CAD design software by (3-1), according to the operation designing of patient, are chosen The magnitude range of required jawbone implant, using the interception function of software, the jawbone mould needed for vertical jawbone central axis interception Type;
(3-2) sets a porous structural unit, and the porous structural unit is extended using mirror image instrument, loose structure is obtained Model;The structure of the porous structural unit is:Eight corners use eighth spheroid, cylinder as beam texture, It is middle by a cube and a spheroid is overlapping forms, be used as the coupling part of beam texture;
(3-3), by the Boolean calculation instrument of software, the loose structure model that step (3-2) is obtained in step (3-1) with cutting The jawbone model taken is fitted, and obtains the jawbone implant mathematical model with porous structural unit;
(3-4) designs the connector of jawbone implant and jawbone, and connector is positioned at implant and jawbone connecting portion surface side Rectangular parallelepiped structure, the connector is fitted to the jawbone implant mathematical model that porous structural unit is carried in step (3-3), obtained To final acquisition jawbone implant mathematical model;
(4) the jawbone model for generating step (3) is exported with STL formatted files, and the model layers are cut into slices using corresponding software, It is converted into the sli file of the machining information with cross section profile data;
(5) according to the sli file of step (4), using selective laser melting equipment, the implantation of titanium-based jawbone is successively fabricated Body;
(6) surface acid etching is carried out to titanium-based jawbone implant, implant is remained in when removing and process using magnetic grinding equipment The burr on surface, completes to prepare.
2. preparation method according to claim 1, it is characterised in that in the step (1), utilize CT examination device scan During patient jawbone position, scanning area is 2mm below eye socket upper limb to angle of mandible, and scanning voltage is 120kV, and sweep current is 170-220mA, Scan slice thickness is 1-1.5mm.
3. preparation method according to claim 1, it is characterised in that in the step (2), the acquisition of STL formatted files Step is:
The DICOM format file obtained in step (1) is imported image processing software Mimics by (2-1), checks CT faultage images With the presence or absence of apparent error or deformation, if being not present, step (2-2) is carried out;
(2-2) defines a gray threshold, and area of bone tissue is regarded as in the region higher than the gray threshold, extracts bone tissue profile Soft tissue and cancellous bone are regarded as in line, the region less than the gray threshold, are removed as noise point;
(2-3), according to the bone defects situation of patient, selection respective data area carries out automatic three-dimensional overlay computing, software according to Cloud data completes the three-dimensional reconstruction of jaw defect model;
(2-4) completes the reconstruction of the jawbone of offside defect using mirror image systematic function according to the form for perfecting side jawbone;
The model finally obtained is saved as STL formatted files by (2-5).
4. preparation method according to claim 1, it is characterised in that in the step (3-4), connector prolongs to jawbone 1-3cm is stretched, width is the 1/2 of the normal jawbone height of patient, and thickness is 0.8mm, and standard bone titanium is generated on connector and rebuild The circular hole of screw diameter.
5. preparation method according to claim 1, it is characterised in that in the step (4), the obtaining step of sli file It is:
The stl file of generation in step (3) is imported professional delamination software by (4-1);
(4-2) selects section/layer functions, obtains the hierarchy slicing data of stl file, checks that data whether there is and does not close completely Conjunction, the mistake of unnecessary triangle, the function of using adjacent layer to replace or remove triangle change mistake;
(4-3) exports hierarchy slicing data, and saves as the sli file with cross section profile data mart modeling information.
6. preparation method according to claim 1, it is characterised in that in the step (5), according to the SLI of step (4) texts Part, successively fabricate titanium-based jawbone implant the step of be:
The pure titanium or titanium alloy powder of 50 μm of average grain diameter are placed in raw cylinder by (5-1), and one piece of substrate is fixed on into shaping On platform;
The powder being preset in raw cylinder is pushed and tiled to substrate by (5-2) powdering scraper;
(5-3) swings, made on the fusing substrate of laser beam selectivity according to cross section profile data, computer control scanning galvanometer Powder;
(5-4) substrate declines the distance of a molding thickness with shaped platform, and raw cylinder also rises a certain distance accordingly;
(5-5) repeating said steps (5-2) to (5-4), until titanium-based jawbone implant completion of processing.
7. preparation method according to claim 6, it is characterised in that in the step (5-3), the laser beam of use swashs Luminous power is 50W-200W, and laser scan rate is 200mm/s-1400mm/s;
Molding thickness in the step (5-4) is the adjustable numerical value in 20-70 μ ms, and in whole process Keep fixing;
The step (5-2) to (5-5) is carried out in ar gas environment.
8. preparation method according to claim 1, it is characterised in that in the step (6), enter to titanium-based jawbone implant Row is following to be handled:
(6-1) carries out acid treatment, nitric acid and hydrofluoric acid using nitric acid and hydrofluoric acid mixed solution to titanium-based jawbone implant surfaces The ratio of mixed solution is nitric acid:Hydrofluoric acid:Water=35:5:160;
(6-2) remains in the burr of implant surfaces when being removed and processed using magnetic grinding equipment.
9. low elastic modulus titanium-based jawbone implant prepared by a kind of any one of use claim 1-8 preparation methods.
CN201510319631.4A 2015-06-12 2015-06-12 A kind of low elastic modulus titanium-based jawbone implant and preparation method thereof Expired - Fee Related CN104985183B (en)

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