CN108166044A - A kind of method of the regulation and control medical TC4 titanium alloy surfaces tube diameters of 3D printing - Google Patents
A kind of method of the regulation and control medical TC4 titanium alloy surfaces tube diameters of 3D printing Download PDFInfo
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- CN108166044A CN108166044A CN201810177224.8A CN201810177224A CN108166044A CN 108166044 A CN108166044 A CN 108166044A CN 201810177224 A CN201810177224 A CN 201810177224A CN 108166044 A CN108166044 A CN 108166044A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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Abstract
The invention discloses a kind of methods of the regulation and control medical TC4 titanium alloy surfaces tube diameters of 3D printing, the medical TC4 titanium alloy materials are prepared by the selective laser melting technology (SLM) in 3D printing technique, the TC4 titanium alloys mass percent is 5.5%≤Al≤6.7%, 3.5%≤V≤4.5%, the inevitable impurity such as 88.09%≤Ti, surplus Fe, O, H, C.Preparation method is as follows：The alloy is pre-processed first, then carries out anodic oxidation, is finally annealed in air.The present invention overcomes the larger macroscopic residual stress that current 3D printing finished product has, and the regulation and control to tube diameters are realized by voltage.The bigger serface of nanotube oxide layer provides space, conducive to drug bearing microsphere or Ag for bone growth+Wait the release of nano-particles；Hydrophily is increased, so as to promote the biocompatibility of material；And the crystal structure after annealing is conducive to the deposition of hydroxyapatite bioactive coating.Therefore, the present invention will have the utilization of current medical titanium alloy very big impetus.
Description
Technical field：
The present invention relates to a kind of surface modifying methods for 3D printing medical titanium alloy, and in particular to a kind of 3D printing doctor
With the preparation of titanium alloy surface nanotube oxide layer and the regulation and control of pipe diameter
Background technology：
Titanium alloy has that density is small, nonmagnetic, specific strength is high, corrosion-resistant, elasticity modulus is low and the property of good biocompatibility
Matter, it has also become one of most widely used metal material of material of clinical medicine implantation at present.But in practical applications, Integrated implant
The stress shielding that indifferent, implant is brought causes the phenomenon that osteoporosis or even secondary fracture also commonplace.Therefore, it is right
The surface modification of implant is extremely urgent.Titania nanotube oxide layer not only spatially has excellent property, i.e., greatly
Specific surface area be that growing into for bone tissue provides space, the deposition for Subsequent pharmacological microballoon or precious metal ion provides place, and
And oxide layer can alleviate the performance difference as caused by interface abruptness, improve the biocompatibility of material, Shaheer Maher etc.
People (S.Maher et al.Appllied Materials＆Interfaces 9 (2017):29562-29570) further confirm
The 3D printing titanium-based implant of micro-nano structure can enhance Integrated implant effect.
Since last century the eighties 3D printing technique comes out, due to its flexible design, rapid shaping, stock utilization
High advantage has obtained the extensive concern of scientific circles.In terms of biomedical material, Tideman et al. is early in 1992 to upper
Defect patient implements to be implanted into the rapid shaping casting titanium net customized and autologous ilium bone block in art i.e. after resection of jaw
Shi Xiufu has pulled open prelude of the 3D printing in biomedical sector from this.Selective laser melting technology (Selective
Laser Melting, SLM) represent the developing direction of quick manufacturing field, with the technology energy straight forming labyrinth,
The densified metal component of high dimensional accuracy, great surface quality, reduce manufacture metal parts technical process, be product design,
Production provides more efficiently approach, is the main 3D printing technique means of currently manufactured biomedical material.For titanium alloy
Powder, the relative density of molded part can reach 95%.
However having except many merits, since its moulding mechanism is the heat effect using pre-alloyed powder in laser beam
Under be completely melt, further according to laser scanning speed determine cooling velocity, layer by layer printing finally obtain finished product.Under this laser action
Fusing, phase transformation, the consecutive steps quickly solidified so that easily there is a situation where nodularization, warpage or crackles for molded part.Even if
Such situation does not occur, can generate larger macroscopic residual stress yet.Gu et al. (Gu.et
al.Internationalmaterialsreviews57.3(2012):133-164) point out that the remnants generated in cooling procedure should
Power is the principal element that material deformation is even finally layered.In addition, each position macro-stress type of molded part is different,
Mercelis et al. (Mercelis, Peter, and Jean-Pierre Kruth.Rapid Prototyping Journal
12.5(2006):It 254-265) is demonstrated in the molded part of SLM using Crack Compliance Method and XRD methods, is produced in top and bottom
Raw tensile stress generates compression in inside, and since material internal crystallization and overheat make the second class of grain deformation generation microcosmic
Stress.It is limited by 3D printing technique principle, even if by adjusting processing environment and technological parameter, it is smaller can not also to obtain stress
Molded part.
Cause TC4 titanium alloys molded part that there is larger residual stress just because of SLM technologies, lead to metal grain in alloy
Uncontrollable deformation occurs, stores larger elastic potential energy, lattice shape also changes, therefore in electrochemical anodic oxidation process
In, reactivity site is unevenly distributed, it is difficult to be formed nanotube pattern, and then be limited it in field of biomedical materials
Using.
Invention content：
The purpose of the present invention is to provide it is a kind of regulate and control the medical TC4 titanium alloy surfaces tube diameters of 3D printing method,
When applied to biomedical material, nanotube draw ratio is controllable, and then this elasticity modulus of materials is controllable for it, to be suitable for difference
The different demands at position.
For this purpose, the present invention uses following technical scheme：
A kind of method of the regulation and control medical TC4 titanium alloy surfaces tube diameters of 3D printing, it is characterised in that：Including at least with
Lower step：
(1) pretreatment of TC4 titanium alloys
3D printing TC4 titanium alloys in 100% acetone, 100% ethyl alcohol are respectively cleaned by ultrasonic 5 minutes successively, use level-one
Water rinses, then is impregnated 3-8 seconds in mixed acid and remove surface film oxide, and mixed acid volume ratio is the hydrogen that mass fraction is 40%
Fluoric acid：Mass fraction is 65% nitric acid：Level-one water=1:4:5；It reuses 3 points ultrasonic in level-one water after level-one water rinses
Clock is dried in air；
(2) preparation of electrolyte
Electrolyte by the ammonium fluoride of 0.1-0.7%w/v, the water of 1-20%v/v, 80-99%v/v 100% ethylene glycol group
Into；
(3) anodic oxidation
The 3D printing TC4 titanium alloy samples that step (1) obtains are positioned in two electrode anode oxidation units, 3D printing
TC4 titanium alloy samples are anode, and annular titanium sheet is cathode, and cathode is 3-5cm with anode spacing, adds in the electricity that step (2) obtains
Liquid is solved, constant voltage oxidation is carried out under the conditions of 25 DEG C of constant temperature, magnetic agitation, the anode oxidation process voltage is in 20-90V ranges
It is interior；
(4) it makes annealing treatment
The 3D printing TC4 titanium alloys that step (3) obtains are rinsed using level-one water, ultrasound 5-15 seconds in level-one water,
It anneals in air afterwards, the mean outside diameter of 3D printing TC4 titanium alloy surface nanotubes is directly proportional to applying voltage.
The oxidization time of step (3) the Anodic Oxidation process is 0.5-3 hours
Magnetic stirring apparatus rotating speed is 500-900rpm during step (3) Anodic Oxidation.
The annealing steps of the step (4) are：
1) from 2 DEG C to 450 DEG C of room temperature liter per minute
2) 450 DEG C of constant temperature 1 hour
3) from 450 DEG C of 2 DEG C of drops per minute to room temperature.
Beneficial effects of the present invention：
The present invention is directed to the characteristics of current 3D printing technique molded part, TC4 titanium alloys biomedical material is carried out adjustable
Control the surface modification of the nanotube pattern of elasticity modulus.Specifically using anodizing, controlled by regulating and controlling anode voltage
The pipe diameter of 3D printing TC4 titanium alloys, and then the elasticity modulus of controlled material make it be applied to the hard tissue substituting of different parts
Material, it is energy saving compared to micro-arc oxidation preparation oxide layer, it is easy compared to hydro-thermal method and controllable.It can with this caliber
The oxide nano of control has more wide application prospect in field of biomedical materials.
Description of the drawings：
Fig. 1 is the schematic device that anodic oxidation is carried out in embodiment 1,2,3, and wherein 1-3D prints TC4 titanium alloy samples
(anode), 2- annulars titanium sheet (cathode), 3- electrolytic cells；
Fig. 2 is the scanning electron microscope diagram piece of sample prepared by embodiment 1；
The scanning electron microscope diagram piece of sample prepared by Fig. 3 positions embodiment 2；
The scanning electron microscope diagram piece of sample prepared by Fig. 4 positions embodiment 3.
Specific embodiment：
With reference to embodiment, the present invention will be further described：
Embodiment 1：
The 3D printing TC4 titanium alloy samples of 1cm*1cm in acetone, ethyl alcohol are respectively cleaned by ultrasonic 5 minutes, use level-one water
It rinses, then in dense hydrofluoric acid：Concentrated nitric acid：Water=1:4:It is impregnated in 5 mixed acid and removes within 8 seconds oxidation film, after level-one water rinses
Ultrasound 3 minutes, are dried in air in level-one water；
0.3g ammonium fluorides are weighed, are dissolved in 10ml level-one water, add 90ml ethylene glycol, then ultrasonic mixing 3 minutes
It is configured to 100ml electrolyte；
Pretreated 3D printing TC4 titanium alloy samples are positioned over using electrode holder in circular anode oxidation unit, are adjusted
Whole 3D printing TC4 titanium alloy samples are 5cm (as shown in figure) with annular titanium sheet distance, add in the electrolyte of preparation, are adjusted permanent
Warm slot is 25 DEG C, and it is 773rpm to adjust magnetic stirring apparatus rotating speed, and wherein 3D printing TC4 titanium alloy samples are as anode, annular titanium
Piece makees cathode, and conducting wire and electrode are connected after-applied 60V constant voltages；
Above-mentioned anode oxidation process is made to continue 2h；
3D printing TC4 titanium alloy samples taking-up level-one water is rinsed, then be cleaned by ultrasonic 15 seconds immediately after oxidation, finally
It dries 10 minutes in an oven；
Dried sample is made annealing treatment in tube furnace, step is as follows：
1) from 2 DEG C to 450 DEG C of room temperature liter per minute
2) 450 DEG C of constant temperature 1 hour
3) from 450 DEG C of 2 DEG C of drops per minute to room temperature
Embodiment 2：
The 3D printing TC4 titanium alloy samples of 1cm*1cm in acetone, ethyl alcohol are respectively cleaned by ultrasonic 5 minutes, use level-one water
It rinses, then in dense hydrofluoric acid：Concentrated nitric acid：Water=1:4:It is impregnated in 5 mixed acid and removes within 8 seconds oxidation film, after level-one water rinses
Ultrasound 3 minutes, are dried in air in level-one water；
0.3g ammonium fluorides are weighed, are dissolved in 10ml level-one water, add 90ml ethylene glycol, then ultrasonic mixing 3 minutes
It is configured to 100ml electrolyte；
Pretreated 3D printing TC4 titanium alloy samples are positioned over using electrode holder in circular anode oxidation unit, are adjusted
Whole 3D printing TC4 titanium alloy samples are 5cm (as shown in figure) with annular titanium sheet distance, add in the electrolyte of preparation, are adjusted permanent
Warm slot is 25 DEG C, and it is 780rpm to adjust magnetic stirring apparatus rotating speed, and wherein 3D printing TC4 titanium alloy samples are as anode, annular titanium
Piece makees cathode, and conducting wire and electrode are connected after-applied 45V constant voltages；
Above-mentioned anode oxidation process is made to continue 2h；
3D printing TC4 titanium alloy samples taking-up level-one water is rinsed, then be cleaned by ultrasonic 15 seconds immediately after oxidation, finally
It dries 10 minutes in an oven；
Dried sample is made annealing treatment in tube furnace, step is as follows：
3) from 2 DEG C to 450 DEG C of room temperature liter per minute
4) 450 DEG C of constant temperature 1 hour
3) from 450 DEG C of 2 DEG C of drops per minute to room temperature
Embodiment 3：
The 3D printing TC4 titanium alloy samples of 1cm*1cm in acetone, ethyl alcohol are respectively cleaned by ultrasonic 5 minutes, use level-one water
It rinses, then in dense hydrofluoric acid：Concentrated nitric acid：Water=1:4:It is impregnated in 5 mixed acid and removes within 8 seconds oxidation film, after level-one water rinses
Ultrasound 3 minutes, are dried in air in level-one water；
0.3g ammonium fluorides are weighed, are dissolved in 10ml level-one water, add 90ml ethylene glycol, then ultrasonic mixing 3 minutes
It is configured to 100ml electrolyte；
Pretreated 3D printing TC4 titanium alloy samples are positioned over using electrode holder in circular anode oxidation unit, are adjusted
Whole 3D printing TC4 titanium alloy samples are 5cm (as shown in figure) with annular titanium sheet distance, add in the electrolyte of preparation, are adjusted permanent
Warm slot is 25 DEG C, and it is 784rpm to adjust magnetic stirring apparatus rotating speed, and wherein 3D printing TC4 titanium alloy samples are as anode, annular titanium
Piece makees cathode, and conducting wire and electrode are connected after-applied 30V constant voltages；
Above-mentioned anode oxidation process is made to continue 2h；
3D printing TC4 titanium alloy samples taking-up level-one water is rinsed, then be cleaned by ultrasonic 15 seconds immediately after oxidation, finally
It dries 10 minutes in an oven；
Dried sample is made annealing treatment in tube furnace, step is as follows：
1) from 2 DEG C to 450 DEG C of room temperature liter per minute
2) 450 DEG C of constant temperature 1 hour
3) from 450 DEG C of 2 DEG C of drops per minute to room temperature
The sample that embodiment 1,2,3 is obtained carries out SEM characterizations, successfully obtains the nanotube oxide layer by regulating and controlling voltage,
Mean outside diameter is respectively 170nm, 110nm and 80nm, and the mean outside diameter of pipe is directly proportional to applying voltage, such as the institute of Fig. 2,3,4
Show.
Finally it should be noted that：The foregoing is only a preferred embodiment of the present invention, is not limited to this hair
Bright, for those skilled in the art, the invention may be variously modified and varied.It is all in the spirit and principles in the present invention
Within, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (4)
- A kind of 1. method of the regulation and control medical TC4 titanium alloy surfaces tube diameters of 3D printing, it is characterised in that：Including at least following Step：(1) pretreatment of TC4 titanium alloys3D printing TC4 titanium alloys in 100% acetone, 100% ethyl alcohol are respectively cleaned by ultrasonic 5 minutes successively, are rushed using level-one water It washes, then is impregnated 3-8 seconds in mixed acid and remove surface film oxide, mixed acid volume ratio is the hydrogen fluorine that mass fraction is 40% Acid：Mass fraction is 65% nitric acid：Level-one water=1:4:5；Reuse level-one water rinse after in level-one water ultrasound 3 minutes, It dries in air；(2) preparation of electrolyteElectrolyte is made of 100% ethylene glycol of the ammonium fluoride of 0.1-0.7%w/v, the water of 1-20%v/v, 80-99%v/v；(3) anodic oxidationThe 3D printing TC4 titanium alloy samples that step (1) obtains are positioned in two electrode anode oxidation units, 3D printing TC4 titaniums Alloy sample is anode, and annular titanium sheet is cathode, and cathode is 3-5cm with anode spacing, adds in the electrolyte that step (2) obtains, Constant voltage oxidation is carried out under the conditions of 25 DEG C of constant temperature, magnetic agitation, the anode oxidation process voltage is in the range of 20-90V；(4) it makes annealing treatmentThe 3D printing TC4 titanium alloys that step (3) obtains are rinsed using level-one water, in level-one water ultrasound 5-15 seconds, after It anneals in air, the mean outside diameter of 3D printing TC4 titanium alloy surface nanotubes is directly proportional to applying voltage.
- It is 2. special according to the preparation method of the medical TC4 titanium alloy surfaces nanotube oxide layer of 3D printing described in claim 1 Sign is：The oxidization time of step (3) the Anodic Oxidation process is 0.5-3 hours.
- 3. according to the preparation method of the medical TC4 titanium alloy surfaces nanotube oxide layer of 3D printing described in claim 1, feature It is：Magnetic stirring apparatus rotating speed is 500-900rpm during step (3) Anodic Oxidation.
- It is 4. special according to the preparation method of the medical TC4 titanium alloy surfaces nanotube oxide layer of 3D printing described in claim 1 Sign is：The annealing steps of the step (4) are：1) from 2 DEG C to 450 DEG C of room temperature liter per minute2) 450 DEG C of constant temperature 1 hour3) from 450 DEG C of 2 DEG C of drops per minute to room temperature.
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Cited By (3)
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| CN109848546A (en) * | 2019-01-09 | 2019-06-07 | 北京科技大学 | A kind of titanium or titanium alloy surface micro-nano structure method of modifying |
| CN110528048A (en) * | 2019-08-30 | 2019-12-03 | 广东省新材料研究所 | A kind of titanium alloy implant Bio-surface active coating and preparation method thereof |
| CN112048749A (en) * | 2020-09-09 | 2020-12-08 | 西北有色金属研究院 | Method for preparing bioactive coating on surface of 3D printed titanium or titanium alloy |
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| CN109848546A (en) * | 2019-01-09 | 2019-06-07 | 北京科技大学 | A kind of titanium or titanium alloy surface micro-nano structure method of modifying |
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Application publication date: 20180615 |