A kind of manufacturing process of high antibiotic property titanium alloy artificial hip joint
Technical field
It is particularly a kind of to be based on laser 3D the present invention relates to a kind of manufacturing process of high antibiotic property titanium alloy artificial hip joint
The manufacturing process of the high antibiotic property Ti-Cu artificial hip joints of printing, belongs to medical bone implanting appliance manufacture field.
Background technology
In recent years, because of the continuous aggravation and the increase of unexpected injury of population in the world aging degree, the need of artificial hip joint
The amount of asking is increased sharply.Titanium and its alloy are because modulus of elasticity is low, specific strength is high, corrosion resistance and the excellent feature of biocompatibility and selected extensively
It is used as manufacturing artificial joint material, the pure titanium of such as Clinical practice, Ti6Al4V(TC4).At this stage, used on domestic market
Artificial hip joint implant majority is using casting and machining group technology processing and manufacturing.However, because of human hip macroscopic view
Structure is more complicated, and Conventional processing methods machining accuracy is low, easily cause that individual suitability is poor after implantation human body, postoperative event trace with
Stress is abnormal, the point-face way of contact abrasion of implant and the risk increase of Aseptic Loosening is ultimately resulted in, so as to cause postoperative
The increase of skeleton animation rate.
With developing rapidly for laser technology and intelligent Manufacturing Technology, the laser metal 3D printing based on increasing material manufacturing principle
It is many that technology is widely used in biologic medical, Aero-Space and automobile making etc. because of the advantages of forming speed is fast, precision is high
Field.Particularly can disposably formingspace is complicated, thin-wall member, manufacturing procedure is greatly decreased, shortens the process-cycle.
CN104498940A complies fully with the standard of medical titanium alloy joint prosthesis using increasing material manufacturing direct forming microstructure and property
The titanium alloy artificial joint of propertyization customization.
However, titanium alloy artificial joint is often more sensitive to bacterial adhesion, it is easier to trigger bacterium infection.In order to assign
Material surface anti-microbial property, needs the mechanism according to bacterium infection, targetedly carries out the structure of antimicrobial surface, assigns it
Anti-microbial property, to reduce the adhesion and breeding of bacterium, and then the generation avoided infection.Strengthen titanium alloy artificial joint antibacterial energy
Power, reduction surface bacteria infect the extensive concern by domestic and foreign scholars.CN103110981A is used to be induced by ultraviolet lighting
Doping deposition antibacterial silver particles, the oxygen of bioactivity is prepared on medical titanium alloy surface inside active oxidation titanium nano-tube array
Change titanium nano-tube array antimicrobial coating.CN101766840A is obtained using centrifugal load technology on titanium alloy artificial joint surface
The sodium titanate nanotube array layer of silver is mixed, to lift its anti-microbial property.CN102676985A is using glow ion percolation technology in doctor
Antibacterial, which is prepared, with titanium alloy surface oozes layers of copper.Wu Haibo etc. is thin in medical pure titanium surface sputtering Ti-Cu using magnetron sputtering technique
Film, with reference to differential arc oxidation and ion at high temperature Nitriding Technology, prepares Cu-TiO2With Ti-Cu-N antimicrobial coatings.But it is loaded with antimicrobial coating
Titanium alloy artificial joint implantation human body after, load with corrosion friction reciprocation under, antimicrobial coating and substrate combinating strength
It is low, be also easy to produce stress deformation and crackle, or even fracture failure, and then reduce its service life.What is more important, fracture it is anti-
Bacterium coating easy damaged implant surrounding tissue, increases patient suffering.Therefore, a kind of high antibiotic property, the titanium of service life length are developed
Alloy joint prosthesis is particularly important, and can significantly reduce the slight illness and second operation expense of patient, with good society's effect
Should be with economic benefit.
The content of the invention
Goal of the invention:To overcome the deficiencies in the prior art, the present invention provides a kind of high antibiotic property titanium alloy artificial
The manufacturing process of hip joint, this method is based on the excellent clinical anti-microbial property of copper, using advanced laser 3D printing technology
The baroque titanium alloy artificial hip joint of precision form is carried out, is modified by surfaces such as anodic oxidation and plasma high-temperature ammonolysis
The Ti-Cu-N surfaces of wiener yardstick loose structure are constructed in technology original position, finally obtain high antibiotic property titanium alloy artificial hip joint, with
Further lift its military service performance requirement under human body complex physiologic environment.
Technical scheme:To solve above-mentioned technical barrier, the present invention can be realized using following technical scheme:A kind of high antibacterial
The manufacturing process of property titanium alloy artificial hip joint, it is characterised in that:High antibacterial is shaped using laser 3D printing, surface modification technology
Property titanium alloy artificial hip joint, specifically includes following steps:
Step(1):Patient's hip joint is scanned by CT machines, 3D data models are obtained, and model is carried out at hierarchy slicing
Reason;
Step(2):After Titanium Powder, copper powder are weighed in proportion, Titanium Powder and copper powder are entered using high energy ball mill
Row ball milling mixing, obtains titanium-copper alloy powder;
Step(3):By step(1)The middle hip joint 3D data models through processing import laser 3D printing system, to step
(2)Described titanium-copper alloy powder carries out 3D printing precision form hip joint;
Step(4):By step(3)In titanium-copper alloy hip joint formed thereby carry out anodized in the electrolytic solution,
Construct the titanium alloy artificial hip joint on the loose structure surface with wiener yardstick;
Step(5):By step(4)Described in the hip joint on loose structure surface of wiener yardstick be placed in plasma high temperature
In nitriding furnace, high-temperature ammonolysis processing is carried out, the high antibacterial artificial hip joints of Ti-Cu-N are obtained;
Step(6):By step(5)Described in high antibacterial artificial hip joint cleaned, sterilized and done in clean room
After dry processing, it is packaged and saves backup.
Further, above-mentioned steps(1)In, the thickness that the model carries out hierarchy slicing processing is 30 μm.
Further, above-mentioned steps(2)In, the titanium alloy is medical pure titanium, Ti6Al4V, Ti6Al7Nb, Ti-Zr conjunction
One kind in gold, average grain diameter is 30 μm, and the copper powder average grain diameter is 50 nm.
Further, above-mentioned steps(2)In, the Titanium Powder, copper powder ratio are:Copper powder weight ratio is 1~5 %, titanium
Weight alloy ratio is 99~95 %.
Further, above-mentioned steps(2)In, the process conditions of the high energy ball mill are:Rotating speed is 400 rpm, ball milling
Time is 2 h, and the argon gas that purity is 99.99% is protective atmosphere.
Further, above-mentioned steps(3)In, the laser 3D printing forming parameters are set as:Laser power is 100
~250 W, sweep speed is 200~2000 mm/s, and sweep span is 60 μm, and laser facula is 70 μm.
Further, above-mentioned steps(4)In, the volume fraction composition of the electrolyte is:The % of hydrofluoric acid 5, ethylene glycol 92
%, the % of hydrogen peroxide 3.
Further, above-mentioned steps(4)In, the anode oxidation process condition is:Operating voltage 8V, the A of operating current 1,
Oxidization time is 5~20 min.
Further, above-mentioned steps(5)In, the high-temperature ammonolysis treatment process condition is:Nitrogen gas purity is 99.9 %, nitrogen
Throughput is 50 ml/min, and 550 °C of high-temperature ammonolysis temperature, the high-temperature ammonolysis time is 4 h.
At this stage, plurality titanium alloy artificial hip joint realizes that its manufacture shapes by traditional casting+machining.
Because of the special space structure of human hip, cause manufacturing process complex, the production cycle is higher with cost.However, traditional
Process does not account for the personalized difference of different patient's knee joint shapes and size, will directly contribute artificial hip joint with not
Best match can not be carried out with patient, causes its individual suitability poor, postoperative joint prosthesis event trace is abnormal with stress, finally
Cause the risk of implant corrosive wear, sterile loosening to increase severely, and then cause postoperative patient to bear painful ratio and revision rate
Increase.
Antimicrobial coating prepared by prior art mainly by numerous surface modifying methods, is loaded with titanium alloy surface deposition and contained
Cu the or Ag coatings of antibiotic property, improve the anti-microbial property of titanium alloy artificial hip joint.But above-mentioned antimicrobial coating exists with matrix
Composition, the difference of structure organization, bond strength are weak, load and corrode under friction reciprocal effect effect in human body, in antimicrobial coating
Portion is also easy to produce stress, causes its underbead crack to germinate, finally causes antimicrobial coating fracture failure, bring even more serious to patient
Pain and financial burden.In the manufacturing process of the present invention, based on the good antibacterial functions of copper, beaten by advanced laser 3D
Manufacturing technology is printed, the precision form of the Ti-Cu artificial hip joints of space three-dimensional structure complex is realized;Utilize anodic oxidation skill
Art constructs micro/nano-scale loose structure in above-mentioned titanium alloy artificial hip joint surface in situ, further promotes bone and its cells planting
Enter body surface face depends on growth, strengthens its bond strength, while the loose structure of growth in situ provides for the release of copper ion
Passage;In addition using plasma high-temperature ammonolysis technology, constructs above-mentioned micro/nano-scale loose structure through high-temperature ammonolysis and handles shape
Into Ti-Cu-N layers, its anti-microbial property is further lifted.The present invention is innovatively by advanced manufacturing technology, simple and feasible table
Surface modification process, and the excellent antibacterial functions of copper are merged, shape high anti-microbial property, the titanium alloy artificial hip of service life is closed
Section, not only shortens the production cycle, saves production cost, also improve the combination property of titanium alloy artificial hip joint, realize it
Customization of individual character, meets the use demand of different patients, is that patient brings Gospel.
In summary, compared with prior art, the present invention has advantages below and beneficial effect:
1st, the present invention is based on the excellent anti-microbial property of copper, using advanced laser 3D printing manufacturing technology formingspace
The complicated Ti-Cu alloy antibacterial artificial hip joints of three-dimensional structure, realize the integral forming of structure and function, with shaping essence
The characteristics such as height, efficiency height are spent, the hip joint performance requirement needed for different patient's displacements is met.
2nd, micro-nano is constructed in the titanium alloy artificial hip joint surface in situ of shaping using the anodizing technology of technical maturity
Yardstick loose structure, promotes body bone tissue cell in the growth of depending on of implant surfaces, promotes bone tissue and artificial hip joint
Embedded connection, its bond strength is significantly increased, while the loose structure of growth in situ carries for the release of antibiotic property copper ion
Passage is supplied.
3rd, the present invention utilizes using plasma high-temperature ammonolysis technology, will construct micro/nano-scale loose structure through high-temperature ammonolysis
Processing forms the Ti-Cu-N antibiotic layers with rock-steady structure tissue, further lifts its anti-microbial property and military service performance.
4th, antibiotic property copper is dispersed in titanium alloy artificial hip joint in the present invention, makes it that integrally there is antibacterial
Function, through going through abrasion after implantation human body, still with lasting antibacterial functions.
Brief description of the drawings
Fig. 1 is high antibiotic property Ti-Cu-N artificial hip joint surface topography maps made from embodiment 1;
Fig. 2 is high antibiotic property Ti-Cu-N artificial hip joint surface topography maps made from embodiment 3;
Fig. 3 is high antibiotic property Ti-Cu-N artificial hip joint surface topography maps made from embodiment 5.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples are only used for clearly illustrating
Technical scheme, and can not be limited the scope of the invention with this.
Embodiment 1
The present invention provides a kind of manufacturing process of high antibiotic property titanium alloy artificial hip joint, utilizes laser 3D printing, surface
Modified technique shapes high antibiotic property Ti-Cu-N artificial hip joints, specifically includes following steps:
Step(1):Patient's hip joint is scanned by CT machines, 3D data models are obtained, and model is carried out at hierarchy slicing
Reason, thickness is 30 μm;
Step(2):It is 50 nm copper powders by quality point by the % of medical pure titanium valve 99 that average grain diameter is 30 μm, average grain diameter
After number is weighed for 1 %, it is 99.99% for 400 rpm, in purity in rotating speed to Titanium Powder and copper powder to use high energy ball mill
The h of ball milling mixing 2 is carried out under argon gas protective condition, titanium-copper alloy powder is obtained;
Step(3):By step(1)Described in hip joint 3D data models through processing import laser 3D printing system, and
Select suitable laser forming technological parameter:Laser power is 100 W, and sweep speed is 200 mm/s, and sweep span is 60 μ
M, laser facula is 70 μm, to step(2)Described titanium-copper alloy powder carries out 3D printing precision form hip joint;
Step(4):By step(3)In titanium-copper alloy hip joint formed thereby in volume fraction be the % of hydrofluoric acid 5, second two
Anodized is carried out in the % of alcohol 92, the % of hydrogen peroxide 3 electrolyte, wherein, operating voltage 8V, the A of operating current 1, during oxidation
Between be 10 min, construct the titanium alloy artificial hip joint with micro/nano-scale loose structure surface;
Step(5):By step(4)Described in the hip joint on micro/nano-scale loose structure surface be placed in plasma high temperature nitrogen
Change in stove, adjust suitable technological parameter and carry out high-temperature ammonolysis processing, wherein, nitrogen gas purity is 99.9 %, and nitrogen flow is 50
Ml/min, 550 °C of high-temperature ammonolysis temperature, the high-temperature ammonolysis time is 4 h, obtains the high antibacterial artificial hip joints of Ti-Cu-N;
Step(6):By step(5)Described in high antibacterial artificial hip joint cleaned, sterilized and done in clean room
After dry processing, it is packaged and saves backup.
Anti-microbial Performance Tests are carried out to the high antibiotic property Ti-Cu-N artificial hip joints that the present embodiment shapes, selection is golden yellow
Staphylococcus is subjects, according to QB/T2591-2003《Antibiotic plastic-Anti-microbial Performance Tests method and antibacterial effect》Detection
The anti-microbial property of artificial hip joint, as a result shows, after testing one day, bacteriostasis rate of the titanium alloy hip joint to staphylococcus aureus
95 % are reached, bacteriostasis rate still reaches 94 % after testing 4 days, with good lasting bacteriostasis property.
Embodiment 2
Present embodiment is as different from Example 1 in step(2)Middle titanium alloy is set as Ti6Al4V powder, its quality point
Number is 97 %, and copper powder mass fraction is 3 %;In step(3)Middle is 175 W, other and the phase of embodiment 1 by laser power settings
Together.
Anti-microbial Performance Tests are carried out to the high antibiotic property Ti-Cu-N artificial hip joints that the present embodiment shapes, selection is golden yellow
Staphylococcus is subjects, according to QB/T2591-2003《Antibiotic plastic-Anti-microbial Performance Tests method and antibacterial effect》Detection
The anti-microbial property of artificial hip joint, as a result shows, after testing one day, bacteriostasis rate of the titanium alloy hip joint to staphylococcus aureus
97 % are reached, bacteriostasis rate still reaches 96 % after testing 4 days, with good lasting bacteriostasis property.
Embodiment 3
Present embodiment is as different from Example 2 in step(3)It is middle that laser scanning speed is set to 1100 mm/s;
In step(3)Middle that the anodized time is set into 12 min, other are same as Example 2.
Anti-microbial Performance Tests are carried out to the high antibiotic property Ti-Cu-N artificial hip joints that the present embodiment shapes, selection is golden yellow
Staphylococcus is subjects, according to QB/T2591-2003《Antibiotic plastic-Anti-microbial Performance Tests method and antibacterial effect》Detection
The anti-microbial property of artificial hip joint, as a result shows, after testing one day, bacteriostasis rate of the titanium alloy hip joint to staphylococcus aureus
96 % are reached, bacteriostasis rate still reaches 95 % after testing 4 days, with good lasting bacteriostasis property.
Embodiment 4
Present embodiment is as different from Example 3 in step(2)Middle titanium alloy is set as Ti6Al7Nb alloyed powders, its matter
Amount fraction is 95 %, and copper powder mass fraction is 5 %;In step(3)It is middle that laser scanning speed is set as 2000 mm/s, other
It is same as Example 3.
Anti-microbial Performance Tests are carried out to the high antibiotic property Ti-Cu-N artificial hip joints that the present embodiment shapes, selection is golden yellow
Staphylococcus is subjects, according to QB/T2591-2003《Antibiotic plastic-Anti-microbial Performance Tests method and antibacterial effect》Detection
The anti-microbial property of artificial hip joint, as a result shows, after testing one day, bacteriostasis rate of the titanium alloy hip joint to staphylococcus aureus
98 % are reached, bacteriostasis rate still reaches 97 % after testing 4 days, with good lasting bacteriostasis property.
Embodiment 5
Present embodiment is as different from Example 4 in step(3)Middle laser power settings are 250 W;In step(4)In
It is 20 min by anodized set of time, other are same as Example 4.
Anti-microbial Performance Tests are carried out to the high antibiotic property Ti-Cu-N artificial hip joints that the present embodiment shapes, selection is golden yellow
Staphylococcus is subjects, according to QB/T2591-2003《Antibiotic plastic-Anti-microbial Performance Tests method and antibacterial effect》Detection
The anti-microbial property of artificial hip joint, as a result shows, after testing one day, bacteriostasis rate of the titanium alloy hip joint to staphylococcus aureus
99 % are reached, bacteriostasis rate still reaches 98 % after testing 4 days, with good lasting bacteriostasis property.
The present invention is shaped high based on the good anti-microbial property of copper ion using laser 3D printing technology, surface modifying method
The Ti-Cu-N artificial hip joints of anti-microbial property, and its anti-microbial property is measured and evaluated, to prove that the technology of the present invention is excellent
Gesture.It can be found that the Ti-Cu-N artificial hip joints prepared under differing formed technique are respectively provided with higher antibacterial after experiment 1 day
Performance, meanwhile, after testing 4 days, good anti-microbial property is still kept, the Ti-Cu- for the anti-microbial property that the present invention shapes is further illustrated
N artificial hip joints have excellent durable antibiotic function.
Under the conditions of technological parameter after optimization, the excellent Ti-Cu-N artificial hip joints of antibiotic property can be obtained, it is improved
Antibacterial functions, meanwhile, the persistence of antibacterial functions is also enhanced, its performance requirement under the complicated physiological condition of human body is met,
Extend its service life.Process is simple, with low cost simultaneously, and this is domestic for high antibiotic property titanium alloy artificial hip joint
Solid foundation has been established in change.
Foregoing description is only embodiments of the invention, is easy to the understanding of the R&D personnel of the technical field and makes
With invention.Therefore, the present invention is not limited to above-described embodiment, and those skilled in the art do not depart from this according to the announcement of the present invention
Improvement, modification and the equivalent replacement that invention category is made should be all included within protection scope of the present invention.