CN108310453A - Femur bulb, preparation method, the production method for including its artificial hip joint and artificial hip joint - Google Patents
Femur bulb, preparation method, the production method for including its artificial hip joint and artificial hip joint Download PDFInfo
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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Abstract
The present invention provides a kind of femur bulb, preparation method, the production methods for including its artificial hip joint and artificial hip joint.The femur bulb includes：Titanium alloy substrate；And wear-resistant coating, wear-resistant coating are differential arc oxidation zirconium coating.It is provided with the zirconium coating of differential arc oxidation containing Zr of high-wearing feature on titanium alloy substrate, realizes design of the titanium alloy as femur bulb, reduces the cost of femur bulb；After differential arc oxidation zirconium coating is set on titanium alloy substrate, the wetability of femur bulb is improved, effectively reduces joint to secondary abrasion；And since the differential arc oxidation zirconium coating is prepared for micro-arc oxidation process, the advantage high with bearing capacity, film layer coefficient is low can be preferably adapted with mortar cup liner.
Description
Technical field
The present invention relates to artificial joint prosthesis fields, in particular to a kind of femur bulb, preparation method, include
Its artificial hip joint and the production method of artificial hip joint.
Background technology
Titanium alloy is because with excellent comprehensive mechanical property, corrosion resistance and biocompatibility etc., being widely used as hip pass
Section implantation prosthese is applied to clinic.The joint product that Replacement of Hip Joint uses is mainly by metal acetabulum cup, macromolecule
Liner/ceramic-lined, metal femur bulb/ceramics femur bulb, metal femoral stem composition, wherein acetabular cup outer surface and femur
Situations such as abrasion of the fusion degree of handle and host bone, femur bulb and liner, directly affects the load and operation of hip prosthesis
Long-time stability in vivo afterwards, and then influence the service life of hip prosthesis.It in recent years, can be with by increases material manufacturing technology
Directly print the bone trabecula acetabular cup with three-dimensional porous structure.Three-dimensional porous structure makes moisture and nutriment in acetabular cup
Internal transmission promotes bone tissue in-growth to form biological fixation, reaches the function that acetabular cup prosthesis is merged with host bone tissue,
To enhance the interface stability between implantation hip joint and host bone tissue.
But titanium alloy acetabular cup and femoral stem and the binding ability of bone and soft tissue be not of great satisfaction at present, stock
Bone bulb and inner liner abrasive resistant performance also need to further increase, although ceramic-lined and ceramic femur bulb wearability is good, ceramics
Prosthese is more crisp and expensive.In addition, hip joint loosens one generated the reason is that leading to metal, pottery by being worn between interface
The clasts such as porcelain, macromolecule cause aseptic loosening so that femur bulb and the matching of mortar cup liner are deteriorated, and then cause artificial
The failure in joint, clast would generally cause the biological respinse in human body, such as inflammation or rejection, be damaged to human body.
Moreover, titanium alloy femoral stem used at present is mostly Ti6Al4V, the elasticity modulus of this titanium alloy material and people
Body bone photo ratio, it is still significantly higher, phenomena such as there is stress shielding after leading to Using prosthesis, easily cause fracture.
Invention content
The main purpose of the present invention is to provide a kind of femur bulb, preparation method, comprising its artificial hip joint and
The production method of artificial hip joint, the cost to solve the problems, such as femur bulb in the prior art are higher.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of femur bulb, including：Titanium alloy
Matrix；And wear-resistant coating, wear-resistant coating are differential arc oxidation zirconium coating.
Further, the thickness of above-mentioned differential arc oxidation zirconium coating is 13~58 μm.
Further, above-mentioned titanium alloy substrate is Ti-6Al-4V matrixes, Ti-6Al-17Nb matrixes, Ti-13Nb-13Zr bases
Any one in body or Ti-5Zr-3Mo-15Nb matrixes.
According to another aspect of the present invention, a kind of preparation method of femur bulb is provided, which includes：By titanium
Alloy substrate is placed in the first electrolyte, is outer surface of the cathode to titanium alloy substrate by anode, stainless steel of titanium alloy substrate
The first differential arc oxidation processing is carried out, differential arc oxidation zirconium coating is obtained, contains zirconium dioxide in the first electrolyte.
Further, the content of zirconium dioxide is 2.5~6.5g/L in above-mentioned first electrolyte, and preferably zirconium dioxide is grain
The powder that diameter is 0.5~10 μm.
Further, at least one auxiliary starting the arc agent is also contained in above-mentioned first electrolyte, auxiliary starting the arc agent is selected from lactic acid
The composition of calcium and calcium oxide, calcium acetate, calcium chloride, calcium dihydrogen phosphate, calcium glycerophosphate, calcium citrate, sodium glycero-phosphate, phosphorus
It is one or more in acid dihydride sodium, disodium hydrogen phosphate, calgon and polyphosphate sodium.
Further, the first power supply that above-mentioned first differential arc oxidation uses is alternating current, and the voltage of the first power supply is in 100
Between~900V, the output pulse frequency of the first power supply is 100~1000Hz, and the pulse width of the first power supply is 8~500 μ s,
The peak point current of first power supply is set as 50~400A, and the time of the first differential arc oxidation is 10~60min, preferably in first differential of the arc
Electrolyte temperature control is at 40 DEG C or less in oxidation process.
Further, above-mentioned preparation method further includes being polished to differential arc oxidation zirconium coating after the first differential arc oxidation
Obtain the differential arc oxidation zirconium coating that thickness is 13~58 μm.
According to another aspect of the present invention, a kind of artificial hip joint is provided, including contacts the femoral stem of setting, stock successively
Bone bulb, mortar cup liner and acetabular cup, the femur bulb are any of the above-described kind of femur bulb or any of the above-described kind of preparation side
The femur bulb that method obtains.
Further, above-mentioned mortar cup liner includes：Matrix, matrix have the surface contacted with femur bulb, preferred substrate
For ultra-high molecular weight polyethylene matrix or high crosslinked polyethylene matrix；Diamond-like carbon film-coating is arranged in matrix and femur bulb
On the surface of contact, preferably the thickness of diamond-like carbon film-coating is 500~3000nm, and preferably diamond-like carbon film-coating uses Nonequilibrium magnetic
Control sputtering technology is formed.
Further, above-mentioned femoral stem includes：Beta titanium alloy matrix；Growth in situ film layer is arranged in beta titanium alloy base
On the surface of body.
Further, above-mentioned growth in situ film layer includes Ca elements and P element, and the thickness of growth in situ film layer is 5~50 μ
The porosity of m, growth in situ film layer are 8~25%.
Further, above-mentioned growth in situ film layer is arranged far from femur bulb, and femoral stem further includes HA coatings, and HA coatings are set
It sets on the surface of beta titanium alloy matrix and close to femur bulb, preferably growth in situ film layer and the linking setting of HA coatings.
Further, the thickness of above-mentioned HA coatings is 50~120 μm, the pore-size rate in HA coatings is about 3%~
7%.
Further, above-mentioned beta titanium alloy matrix is Ti-Nb series titanium alloys matrix, Ti-Mo series titanium alloys matrix, Ti-Zr
Any one in series titanium alloy matrix, Ti-Nb-Hf series titanium alloys matrix and Ti-Nb-Zr series titanium alloy matrixes.
Further, above-mentioned acetabular cup is metal acetabulum cup, metal acetabulum cup for host bone tissue contact surface being
Porous structure titanium layer or titanium alloy layer, preferably porous structure titanium layer are 3D printing bone trabecula titanium structure, titanium pearl, titanium powder, titanium silk
In it is one or more, preferably titanium alloy layer be Ti-6Al-4V alloy-layers, Ti-6Al-17Nb alloy-layers, Ti-13Nb-13Zr close
Any one in layer gold or Ti-5Zr-3Mo-15Nb alloy-layers.
According to another aspect of the invention, a kind of production method of artificial hip joint is provided, the system of mortar cup liner is included
The preparation of the preparation of standby, femur bulb preparation and femoral stem, the femur bulb is implemented using any of the above-described kind of preparation method.
Further, the preparation of above-mentioned femoral stem includes：Second differential arc oxidation is carried out to beta titanium alloy, to be closed in beta titanium
Form growth in situ film layer on gold, in the second electrolyte used by the second differential arc oxidation, the concentration of calcium constituent is denoted as m mol/
The concentration of L, P elements are denoted as n mol/L, as 0.01≤m ＜ 0.2, (0.1m+0.025)≤n ＜ 0.05；When 0.2≤m≤
When 0.6, when 0.075≤n≤m/0.875, preferably 0.4 ＜ m≤0.6,0.25≤n≤m/0.875；It is preferred that calcium source is selected from acetic acid
The one or more of calcium, calcium chloride, calcium dihydrogen phosphate, calcium glycerophosphate, calcium citrate, calcium lactate and calcium oxide；More preferable phosphorus
Source is selected from one or more of sodium glycero-phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, calgon and polyphosphate sodium.
Further, above-mentioned second electrolyte further includes EDTA-2Na and sodium metasilicate, and sodium metasilicate contains in the second electrolyte
Amount is 0.01~0.04mol/L；The second electrolyte ph is adjusted between 11~14 preferably by sodium hydroxide or potassium hydroxide；
It is preferred that the second differential arc oxidation uses the voltage of second source for 50~500V, the output pulse frequency of second source is 100~
The pulse width of 1000Hz, second source are 8~500 μ s, and the peak point current of second source is 50~300A, the second differential arc oxidation
Time be 3~30min.
Further, the object of above-mentioned second differential arc oxidation is that the separate femur ball head of beta titanium alloy divides surface, femur
The preparation of handle further includes：To carrying out vacuum plasma spray coating after the cleaning of the second differential arc oxidation treated beta titanium alloy, drying,
With the close femur ball head in beta titanium alloy divide surface be arranged HA coatings, preferably the voltage of vacuum plasma spray coating be 40~
60V, electric current are 500~600A.
It applies the technical scheme of the present invention, the femur bulb of the application is provided with containing for high-wearing feature on titanium alloy substrate
Zr differential arc oxidation zirconium coatings realize design of the titanium alloy as femur bulb, reduce the cost of femur bulb；In titanium alloy
After differential arc oxidation zirconium coating is set on matrix, the wetability of femur bulb is improved, effectively reduces joint to secondary abrasion；And by
It is prepared for micro-arc oxidation process in the differential arc oxidation zirconium coating, therefore that it is high with bearing capacity, film layer coefficient is low is excellent
Gesture can be preferably adapted with mortar cup liner.
Description of the drawings
The accompanying drawings which form a part of this application are used to provide further understanding of the present invention, and of the invention shows
Meaning property embodiment and its explanation are not constituted improper limitations of the present invention for explaining the present invention.In the accompanying drawings：
Fig. 1 shows the part-structure schematic diagram for the femur bulb that a kind of preferred embodiment according to the present invention provides；
Fig. 2 shows a kind of part-structure schematic diagrams for the mortar cup liner that preferred embodiment provides according to the present invention；
Fig. 3 shows the stereo-resolution structural representation for the artificial hip joint that a kind of preferred embodiment according to the present invention provides
Figure.
Wherein, above-mentioned attached drawing includes the following drawings label：
10, femoral stem；11, beta titanium alloy matrix；12, growth in situ film layer；20, femur bulb；21, titanium alloy substrate；
22, wear-resistant coating；30, mortar cup liner；31, matrix；32, diamond-like carbon film-coating；40, acetabular cup.
Specific implementation mode
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.The present invention will be described in detail below with reference to the accompanying drawings and embodiments.
It is in the prior art in order to improve the matching of femur bulb and mortar cup liner as the application background technology is analyzed
Property, wearability between the two is improved using ceramic-lined and ceramic femur bulb, but ceramic material is more crisp and expensive,
In order to reduce the cost of femur bulb under the premise of ensureing the two wearability, this application provides a kind of femur bulb, its systems
Preparation Method, the production method for including its artificial hip joint and artificial hip joint.
In a kind of preferred embodiment of the application, above-mentioned a kind of femur bulb, as shown in Figure 1, above-mentioned femur bulb 20
Including titanium alloy substrate 21 and wear-resistant coating 22, wear-resistant coating 22 is differential arc oxidation zirconium coating.
Since the wearability of titanium alloy is poor, will not generally it use titanium alloy as femur bulb 20.The application's
Femur bulb 20 is provided with the zirconium coating of differential arc oxidation containing Zr of high-wearing feature on titanium alloy substrate 21, realizes titanium alloy conduct
The design of femur bulb 20 reduces the cost of femur bulb 20；After differential arc oxidation zirconium coating is set on titanium alloy substrate 21,
The wetability for improving femur bulb 20 effectively reduces joint to secondary abrasion；And since the differential arc oxidation zirconium coating is the differential of the arc
Oxidation technology is prepared, therefore the advantage that it is high with bearing capacity, film layer coefficient is low, can preferably with mortar cup liner phase
It adapts to.
In order to improve the wearability of differential arc oxidation zirconium coating, being polished after differential arc oxidation will be in differential arc oxidation zirconium coating
The thickness of loose part removal, preferably above-mentioned differential arc oxidation zirconium coating is 13~58 μm.
Above-mentioned titanium alloy substrate 21 can select common titanium alloy in current artificial prosthesis to prepare, preferably above-mentioned titanium alloy
Matrix 21 is in Ti-6Al-4V matrixes, Ti-6Al-17Nb matrixes, Ti-13Nb-13Zr matrixes or Ti-5Zr-3Mo-15Nb matrixes
Any one.
In another typical embodiment of the application, a kind of preparation method of femur bulb, the preparation side are provided
Method includes：Titanium alloy substrate is placed in the first electrolyte, is cathode to titanium alloy-based using titanium alloy substrate as anode, stainless steel
The outer surface of body carries out the first differential arc oxidation processing, obtains differential arc oxidation zirconium coating, contains zirconium dioxide in the first electrolyte.
The femur bulb of the application passes through differential of the arc oxygen on titanium alloy substrate using the first electrolyte containing zirconium dioxide
Chemical industry skill is provided with the zirconium coating of differential arc oxidation containing Zr of high-wearing feature, realizes design of the titanium alloy as femur bulb, reduces
The cost of femur bulb；After differential arc oxidation zirconium coating is set on titanium alloy substrate, the wetability of femur bulb is improved, is had
Effect reduces joint to secondary abrasion；And differential arc oxidation zirconium coating prepared by micro-arc oxidation process has fine and close smooth, bearing capacity
Advantage high, film layer coefficient is low can be preferably adapted with mortar cup liner.
Normally, be deionized water as the solvent of electrolyte, the solvent of the first electrolyte of the application also select to go from
Sub- water.In order to improve the efficiency of above-mentioned first differential arc oxidation, in preferably above-mentioned first electrolyte the content of zirconium dioxide be 2.5~
6.5g/L.In addition, in order to improve adhesive force and compactness of the zirconium on matrix, it is 0.5~10 μm that preferably zirconium dioxide, which is grain size,
Powder.
In addition, in order to reduce the arcing voltage of above-mentioned first differential arc oxidation, also contain extremely in preferably above-mentioned first electrolyte
Few a kind of auxiliary starting the arc agent, it is preferable that above-mentioned auxiliary starting the arc agent is selected from calcium lactate and the composition of calcium oxide, calcium acetate, chlorination
Calcium, calcium dihydrogen phosphate, calcium glycerophosphate, calcium citrate, sodium glycero-phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, calgon
With it is one or more in polyphosphate sodium.To increase the zwitterion of electrolyte, enhance the electric conductivity of electrolyte, to have assisted
Arc.
In a kind of preferred embodiment of the application, the voltage for the first power supply that above-mentioned first differential arc oxidation uses is in
Between 100~900V, the output pulse frequency of the first power supply is 100~1000Hz, and the pulse width of the first power supply is 8~
500 μ s, the peak point current of the first power supply are set as 50~400A, and the time of the first differential arc oxidation is 10~60min, preferably the
Electrolyte temperature control is at 40 DEG C or less in one micro-arc oxidation process.It within the above range by the control of above-mentioned power supply parameter, can
Metastable electric field is being formed in titanium alloy substrate, and then forms the differential arc oxidation that film layer is thicker and thickness is relatively uniform
Film layer.
Further, in order to improve the wearability of differential arc oxidation zirconium coating, preferably above-mentioned preparation method is in the first differential of the arc oxygen
Further include being polished to obtain the differential arc oxidation zirconium coating that thickness is 13~58 μm to differential arc oxidation zirconium coating after changing.Utilize throwing
The mode of light removes the of a relatively loose porous structure on about 2 μm of differential arc oxidation coating surface, and leaves more fine and close differential of the arc oxygen
Change zirconium coating.
In the application in another typical embodiment, a kind of artificial hip joint is provided, as shown in figure 3, this is artificial
Hip joint includes the femoral stem 10 for contacting setting successively, femur bulb 20, mortar cup liner 30 and acetabular cup 40, the femur bulb 20
The femur bulb obtained for any of the above-described kind of femur bulb or any of the above-described kind of preparation method.
Since the femur bulb 20 of the application is provided with the zirconium of differential arc oxidation containing Zr of high-wearing feature on titanium alloy substrate 21
Coating realizes design of the titanium alloy as femur bulb 20, reduces the cost of femur bulb 20；On titanium alloy substrate 21
After differential arc oxidation zirconium coating is set, the wetability of femur bulb 20 is improved, effectively reduces joint to secondary abrasion；And due to this
Differential arc oxidation zirconium coating is prepared for micro-arc oxidation process, therefore it is smooth with densification, bearing capacity is high, film layer coefficient is low
Advantage, can preferably with mortar cup liner 30 be adapted.The wearability of artificial hip joint with above-mentioned femur bulb 20 compared with
Height, cost are relatively low.
In addition, in order to further increase the wearability of mortar cup liner 30, preferably above-mentioned mortar cup liner 30 includes as shown in Figure 2
Matrix 31 and diamond-like carbon film-coating 32, it is supra polymer that matrix 31, which has the surface contacted with femur bulb 20, preferred substrate 31,
Weight northylen matrix or high crosslinked polyethylene matrix；Contacting with femur bulb 20 in matrix 31 is arranged in diamond-like carbon film-coating 32
On surface.The cost of above-mentioned ultra-high molecular weight polyethylene matrix or high crosslinked polyethylene matrix is big relative to the cost of ceramic matrix
It is big to reduce；And diamond-like carbon film-coating 32 is amorphous carbon-film coating, hardness is higher and excellent in abrasion resistance, therefore in matrix 31 and femur
The diamond-like carbon film-coating 32, which is arranged, on the surface that bulb 20 contacts can effectively reduce the generation of macromolecule clast, further drop
The low frictional behaviour of mortar cup liner 30 and femur bulb 20.Combination in order to ensure DLC film 32 and matrix 31 is strong
Degree reduces the internal stress of coating, and the preferably thickness of diamond-like carbon film-coating 32 is 500~3000nm, preferably diamond-like carbon film-coating 32
It is formed using non-balance magnetically controlled sputter technique.Non-balance magnetically controlled sputter technique is a kind of technique of relative maturity, can be avoided
Defect caused by diamond-like carbon film-coating 32 is made on high-molecular organic material using high temperature.
Existing femur handle structure may be used in the femoral stem 10 of the application, in order to improve femoral stem and human body bone structure
Chimeric degree, preferably above-mentioned femoral stem 10 include beta titanium alloy matrix 11 and growth in situ film layer 12, and growth in situ film layer 12 is arranged
On the surface of beta titanium alloy matrix 11.Matrix 31 of the beta titanium alloy as femoral stem 10, because its elasticity modulus is low, Ke Yiyou
Effect reduces stress shielding, can be realized with skeleton preferable chimeric；It is arranged simultaneously on 11 surface of beta titanium alloy matrix in situ
Film layer 12 is grown, which forms for micro-arc oxidation process, strong with 31 binding force of matrix, and growth in situ film
12 surface of layer have certain porosity, are conducive to Bone Ingrowth.
Further, it is preferable to which above-mentioned growth in situ film layer 12 includes Ca elements and P element, the biology of femoral stem 10 is improved
Activity.In order to further provide better condition for Bone Ingrowth and improve the bioactivity of femoral stem 10, preferably above-mentioned original position
The thickness for growing film layer 12 is 5~50 μm, and the porosity of growth in situ film layer 12 is 8~25%.
In addition, based on artificial hip joint in the installation position of human body, preferably above-mentioned growth in situ film layer 12 is far from femoral ball
First 20 setting, femoral stem 10 further include HA coatings, and HA coatings are arranged on the surface of beta titanium alloy matrix 11 and close to femoral ball
The Bone Ingrowth and Integrated implant of first 20, HA coatings being provided with conducive to operation initial stage improve the stabilization at artificial hip joint implantation initial stage
Property.At nearly femur end, spraying HA can make operation early stage realize the combination of bone and prosthese, the induction of especially new bone, and distal end
Growth in situ film layer 12 can be used as long-term fixation film layer and use.It is preferred that growth in situ film layer 12 and the linking setting of HA coatings.
Further, it is preferable to the thickness of above-mentioned HA coatings is 50~120 μm, the porosity in HA coatings is about 3%~
7%.So that Bone Ingrowth and Integrated implant preferably play.
The beta titanium alloy matrix 11 of the application may be used beta titanium alloy medical in the prior art and prepare, preferably above-mentioned
Beta titanium alloy matrix 11 is Ti-Nb series titanium alloys matrix, Ti-Mo series titanium alloys matrix, Ti-Zr series titanium alloys matrix, Ti-Nb-
Any one in Hf series titanium alloys matrix and Ti-Nb-Zr series titanium alloy matrixes.
In the application another kind preferred embodiment, above-mentioned acetabular cup 40 is metal acetabulum cup 40, metal acetabulum cup 40
For with host bone tissue contact surface be porous structure titanium layer or titanium alloy layer, preferably porous structure titanium layer be 3D printing bone it is small
One or more in beam titanium structure, titanium pearl, titanium powder, titanium silk, preferably titanium alloy layer is Ti-6Al-4V alloy-layers, Ti-6Al-
Any one in 17Nb alloy-layers, Ti-13Nb-13Zr alloy-layers or Ti-5Zr-3Mo-15Nb alloy-layers.
In the application in another typical embodiment, a kind of production method of artificial hip joint, including mortar are provided
The preparation of preparation, the preparation of femur bulb and the preparation of femoral stem of cup liner, femur bulb uses any of the above-described kind of side of preparation
Method is implemented.
The femur bulb of the application is provided with the micro- containing Zr of high-wearing feature on titanium alloy substrate by micro-arc oxidation process
Arc zirconia coating realizes design of the titanium alloy as femur bulb, reduces the cost of femur bulb；In titanium alloy substrate
After upper setting differential arc oxidation zirconium coating, the wetability of femur bulb is improved, effectively reduces joint to secondary abrasion；And differential of the arc oxygen
Differential arc oxidation zirconium coating prepared by chemical industry skill has fine and close advantage smooth, bearing capacity is high, film layer coefficient is low.It will utilize above-mentioned
The femur bulb that preparation method is prepared mutually is tied with the preparation of conventional mortar cup liner in the prior art with the preparation of femoral stem
It closes, the mortar cup liner that can not only be obtained with the prior art is adapted, and will not be impacted to other preparation process.
In a kind of preferred embodiment of the application, the preparation of above-mentioned femoral stem includes：It is micro- that second is carried out to beta titanium alloy
Arc aoxidizes, to form growth in situ film layer on beta titanium alloy, in the second electrolyte used by the second differential arc oxidation, and calcium member
The concentration of element is denoted as m mol/L, and the concentration of P elements is denoted as n mol/L, as 0.01≤m ＜ 0.2, (0.1m+0.025)≤n
＜ 0.05；As 0.2≤m≤0.6, when 0.075≤n≤m/0.875, preferably 0.4 ＜ m≤0.6,0.25≤n≤m/0.875；
It is preferred that calcium source is selected from one kind of calcium acetate, calcium chloride, calcium dihydrogen phosphate, calcium glycerophosphate, calcium citrate, calcium lactate and calcium oxide
Or it is several；More preferable phosphorus source is in sodium glycero-phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, calgon and polyphosphate sodium
One or more.Matrix using beta titanium alloy as femoral stem can effectively reduce stress screening because its elasticity modulus is low
Gear can be realized preferable chimeric with skeleton；It is arranged simultaneously in beta titanium alloy matrix surface using micro-arc oxidation process former
Position growth film layer, it is strong with basal body binding force, and growth in situ film surface has certain porosity, is conducive to Bone Ingrowth.
In the application another kind preferred embodiment, above-mentioned second electrolyte further includes EDTA-2Na and sodium metasilicate, on
It is complexing agent to state EDTA-2Na, is easy to ionize in the solution, generates free Na+And H2Y2-(wherein Y=[2
(OOCCH2)NCH2CH2N(CH2COO)2]4-), ionize the H of generation2Y2-Easily with the Ca in electrolyte2+Chelating generates CaY2-, to
Improve the conductivity of electrolyte.In order to reduce arcing voltage, sodium metasilicate (SiO is added in the electrolytic solution3 2-), and in order to ensure electricity
Pressure is stablized, and the content of sodium metasilicate is 0.01~0.04mol/L in the second electrolyte.Preferably by sodium hydroxide or potassium hydroxide tune
The second electrolyte ph is saved between 11~14, to form stable alkaline oxygenated environment.It is preferred that the second differential arc oxidation is using the
The voltage of two power supplys is 50~500V, and the output pulse frequency of second source is 100~1000Hz, the pulse width of second source
Peak point current for 8~500 μ s, second source is 50~300A, and the time of the second differential arc oxidation is 3~30min.By above-mentioned confession
Electrical parameter control within the above range, the metastable electric field that can be formed in beta titanium alloy, so formed film layer compared with
Thick and relatively uniform thickness growth in situ film layer.
In the application another preferred embodiment, the object of above-mentioned second differential arc oxidation is the separate of beta titanium alloy
Femur ball head divides the surface, the preparation of femoral stem to further include：To the cleaning of the second differential arc oxidation treated beta titanium alloy, drying
After carry out vacuum plasma spray coating, divide surface that HA coatings, preferably vacuum etc. are set with the close femur ball head in beta titanium alloy
Plasma spray, spray voltage are 40~60V, 500~600A of electric current.HA coatings be provided with conducive to operation initial stage Bone Ingrowth and
Integrated implant improves the stability at artificial hip joint implantation initial stage.
Below with reference to embodiment and comparative example, the advantageous effect of the application is further illustrated.
Embodiment 1
The preparation of femur bulb：
Ti-6Al-4V matrixes are placed in the first electrolyte, are cathode to above-mentioned using titanium alloy substrate as anode, stainless steel
The outer surface of matrix carries out the first differential arc oxidation processing, obtains differential arc oxidation zirconium coating, wherein the first electrolyte contains titanium dioxide
Zirconium and auxiliary starting the arc agent, zirconium dioxide is the powder that grain size is 0.5~10 μm and content is 5g/L, and the content of auxiliary starting the arc agent is
15g/L, and it is 1 to assist the group of starting the arc agent to become molar ratio:1:1 calcium acetate, calcium citrate and sodium dihydrogen phosphate.First differential of the arc
The voltage for aoxidizing the first power supply used is 500V, and the output pulse frequency of the first power supply is 500Hz, and the pulse of the first power supply is wide
Degree is 200 μ s, and the peak point current of the first power supply is set as 200A, and the time of the first differential arc oxidation is 30min, in the first differential of the arc oxygen
Electrolyte temperature control is at 40 DEG C or less during change.
After first differential arc oxidation, obtained differential arc oxidation zirconium coating is polished, is detected and is determined using scanning electron microscope
Obtain the differential arc oxidation zirconium coating that thickness is 45 μm.
Embodiment 2
The preparation of femur bulb：
Ti-6Al-4V matrixes are placed in the first electrolyte, are cathode to above-mentioned using titanium alloy substrate as anode, stainless steel
The outer surface of matrix carries out the first differential arc oxidation processing, obtains differential arc oxidation zirconium coating, wherein the first electrolyte contains titanium dioxide
Zirconium and auxiliary starting the arc agent, zirconium dioxide is the powder that grain size is 0.5~10 μm and content is 2.5g/L, assists the content of starting the arc agent
For 10g/L, and it is 1 to assist the group of starting the arc agent to become molar ratio:1:1 calcium acetate, calcium citrate and sodium dihydrogen phosphate.First is micro-
The voltage for the first power supply that arc oxidation uses is 500V, and the output pulse frequency of the first power supply is 500Hz, the pulse of the first power supply
Width is 200 μ s, and the peak point current of the first power supply is set as 200A, and the time of the first differential arc oxidation is 10min, in first differential of the arc
Electrolyte temperature control is at 40 DEG C or less in oxidation process.
After first differential arc oxidation, obtained differential arc oxidation zirconium coating is polished, is detected and is determined using scanning electron microscope
Obtain the differential arc oxidation zirconium coating that thickness is 15 μm.
Embodiment 3
The preparation of femur bulb：
Ti-6Al-4V matrixes are placed in the first electrolyte, are cathode to above-mentioned using titanium alloy substrate as anode, stainless steel
The outer surface of matrix carries out the first differential arc oxidation processing, obtains differential arc oxidation zirconium coating, wherein the first electrolyte contains titanium dioxide
Zirconium and auxiliary starting the arc agent, zirconium dioxide is the powder that grain size is 0.5~10 μm and content is 6.5g/L, assists the content of starting the arc agent
For 20g/L, and it is 1 to assist the group of starting the arc agent to become molar ratio:1:1 calcium acetate, calcium citrate and sodium dihydrogen phosphate.First is micro-
The first power supply that arc oxidation uses is alternating current, and the voltage of the first power supply is 500V, and the output pulse frequency of the first power supply is
500Hz, the pulse width of the first power supply are 200 μ s, and the peak point current of the first power supply is set as 200A, the first differential arc oxidation when
Between be 60min, in the first micro-arc oxidation process electrolyte temperature control at 40 DEG C or less.
After first differential arc oxidation, obtained differential arc oxidation zirconium coating is polished, is detected and is determined using scanning electron microscope
Obtain the differential arc oxidation zirconium coating that thickness is 56 μm.
Embodiment 4
The preparation of femur bulb：
Ti-6Al-4V matrixes are placed in the first electrolyte, are cathode to above-mentioned using titanium alloy substrate as anode, stainless steel
The outer surface of matrix carries out the first differential arc oxidation processing, obtains differential arc oxidation zirconium coating, wherein the first electrolyte contains titanium dioxide
Zirconium and auxiliary starting the arc agent, zirconium dioxide is the powder that grain size is 0.5~10 μm and content is 5g/L, and the content of auxiliary starting the arc agent is
13g/L, and it is 1 to assist the group of starting the arc agent to become molar ratio:1:1 calcium acetate, calcium citrate and calgon.First differential of the arc
It is alternating current to aoxidize the first power supply used, and the voltage of the first power supply is 100V, and the output pulse frequency of the first power supply is
1000Hz, the pulse width of the first power supply are 10 μ s, and the peak point current of the first power supply is set as 50A, the first differential arc oxidation when
Between be 90min, in the first micro-arc oxidation process electrolyte temperature control at 40 DEG C or less.
After first differential arc oxidation, obtained differential arc oxidation zirconium coating is polished, is detected and is determined using scanning electron microscope
Obtain the differential arc oxidation zirconium coating that thickness is 69 μm.
Embodiment 5
The preparation of femur bulb：
Ti-6Al-4V matrixes are placed in the first electrolyte, are cathode to above-mentioned using titanium alloy substrate as anode, stainless steel
The outer surface of matrix carries out the first differential arc oxidation processing, obtains differential arc oxidation zirconium coating, wherein the first electrolyte contains titanium dioxide
Zirconium and auxiliary starting the arc agent, zirconium dioxide is the powder that grain size is 0.5~10 μm and content is 5g/L, and the content of auxiliary starting the arc agent is
18g/L, and it is 1 to assist the group of starting the arc agent to become molar ratio:1:1 calcium chloride, calcium citrate and calgon.First differential of the arc
It is alternating current to aoxidize the first power supply used, and the voltage of the first power supply is 900V, and the output pulse frequency of the first power supply is
100Hz, the pulse width of the first power supply are 500 μ s, and the peak point current of the first power supply is set as 400A, the first differential arc oxidation when
Between be 5min, in the first micro-arc oxidation process electrolyte temperature control at 40 DEG C or less.
After first differential arc oxidation, obtained differential arc oxidation zirconium coating is polished, is detected and is determined using scanning electron microscope
Obtain the differential arc oxidation zirconium coating that thickness is 10 μm.
Embodiment 6
Difference lies in the content of zirconium dioxide is 2g/L in the first electrolyte with embodiment 1.First differential arc oxidation it
Afterwards, obtained differential arc oxidation zirconium coating is polished, scanning electron microscope detection determination is used to obtain thickness as 15 μm of differential of the arc oxygen
Change zirconium coating.
Embodiment 7
Difference lies in the content of zirconium dioxide is 7g/L in the first electrolyte with embodiment 1.First differential arc oxidation it
Afterwards, obtained differential arc oxidation zirconium coating is polished, scanning electron microscope detection determination is used to obtain thickness as 18 μm of differential of the arc oxygen
Change zirconium coating.
Comparative example 1
Compared with embodiment 1-7, femur bulb used is Ti-6Al-4V, does not use the differential arc oxidation skill described in this technology
Art processing.
The wearability of the femur bulb obtained to embodiment 1 to 7 is detected, and detection method is to be tried using ball disk-type friction
It tests on instrument and carries out the frictional wear experiment of film layer, to the silicon nitride bead that material is a diameter of 6mm that rubs, load 1N is relatively sliding
Dynamic speed is 0.1m/s, judges wear-resisting property by wear extent；Test the connecing using Germany Dataphysics productions of contact angle
Feeler tester, test equipment have the sample stage of liquid droplet system and loading by oneself, and test carries out at room temperature, by dropping in sample body
Product obtains for 4 microlitres of drop measurement.Each sample surfaces take 5 points to measure, and are averaged connecing as sample surfaces
Feeler size, testing result are shown in Table 1.
Table 1
It can be seen that according to above-mentioned data by the way that differential arc oxidation zirconium coating is arranged, can effectively improve the resistance to of femur bulb
Mill property and wettability.
In addition, after each embodiment femur bulb is matched with the mortar cup liner of each specification, in artificial hip joint wear Simulation
It is tested on testing machine, standard ISO14242-2 is pressed in experiment：2000《The abrasion of surgical implant full hip-joint prosthese the 2nd
Point：Measurement method》It carries out, test cycle number is 500000 times.Wear extent (10-6mm3/ Nr) test result is as shown in table 2.
Comparative example 1 is without diamond-like carbon film-coating.
Table 2
According to upper table as can be seen that the femur bulb of the application with the mortar cup liner of each specification in use, can also realize
Good adaptability.
Embodiment 8
The preparation of femoral stem：
Second differential arc oxidation is carried out to beta titanium alloy, to form growth in situ film layer, second differential of the arc on beta titanium alloy
In second electrolyte used by oxidation, a concentration of 0.01mol/L of calcium acetate, a concentration of 0.035mol/L of sodium dihydrogen phosphate,
A concentration of 0.02mol/L, Na of EDTA-2Na2SiO3A concentration of 0.04mol/L, add suitable KOH, adjust the pH of solution
Value is 11, and the second differential arc oxidation uses the voltage of second source for 200V, and the output pulse frequency of second source is 500Hz, the
The pulse width of two power supplys is 300 μ s, and the peak point current of second source is 150A, and the time of the second differential arc oxidation is 20min.It adopts
It is detected and is determined with the method in scanning electron microscopic observation oxidation film layer section, the thickness of growth in situ film layer is 14 μm, growth in situ film
The porosity of layer is 9%.
Embodiment 9
The preparation of femoral stem：
Second differential arc oxidation is carried out to the part surface of the separate femur bulb of beta titanium alloy, to form growth in situ film
Layer, in the second electrolyte used by the second differential arc oxidation, a concentration of 0.01mol/L of calcium acetate, sodium dihydrogen phosphate it is a concentration of
A concentration of 0.02mol/L, Na of 0.035mol/L, EDTA-2Na2SiO3A concentration of 0.04mol/L, add suitable KOH, adjust
The pH value for saving solution is 11, and the second differential arc oxidation uses the voltage of second source for 200V, the output pulse frequency of second source
Pulse width for 500Hz, second source is 300 μ s, and the peak point current of second source is 150A, the time of the second differential arc oxidation
For 20min.Use the thickness of scanning electron microscope detection growth in situ film layer for 11.4 μm, the porosity of growth in situ film layer is
10%.
To carrying out vacuum plasma spray coating after the cleaning of the second differential arc oxidation treated beta titanium alloy, drying, in β types
Titanium alloy divides surface that HA coatings are arranged close to the femur ball head, wherein the voltage of vacuum plasma spray coating is 50V, electricity
Stream is 550A.Growth in situ film layer and the linking of HA coatings.It is detected and is determined using scanning electron microscope, the thickness of HA coatings is 53 μm, HA
Porosity in coating is about 4.2%.
Embodiment 10
The preparation of femoral stem：
Second differential arc oxidation is carried out to the part surface of the separate femur bulb of beta titanium alloy, to form growth in situ film
Layer, in the second electrolyte used by the second differential arc oxidation, a concentration of 0.11mol/L of calcium acetate, sodium dihydrogen phosphate it is a concentration of
A concentration of 0.2mol/L, Na of 0.038mol/L, EDTA-2Na2SiO3A concentration of 0.04mol/L, add suitable KOH, adjust
The pH value for saving solution is 11, and the second differential arc oxidation uses the voltage of second source for 200V, the output pulse frequency of second source
Pulse width for 500Hz, second source is 300 μ s, and the peak point current of second source is 150A, the time of the second differential arc oxidation
For 20min.Using the method in scanning electron microscope detection oxidation film layer section, the thickness of growth in situ film layer is 14,5 μm, in situ raw
The porosity of long film layer is 12%.
To carrying out vacuum plasma spray coating after the cleaning of the second differential arc oxidation treated beta titanium alloy, drying, in β types
Titanium alloy divides surface that HA coatings are arranged close to the femur ball head, wherein the voltage of vacuum plasma spray coating is 50V, electricity
Stream is 550A.Growth in situ film layer and the linking of HA coatings.The method that oxidation film layer section is detected using scanning electron microscope, HA coatings
Thickness is 60 μm, and the porosity in HA coatings is about 5%.
Embodiment 11
The preparation of femoral stem：
Second differential arc oxidation is carried out to the part surface of the separate femur bulb of beta titanium alloy, to form growth in situ film
Layer, in the second electrolyte used by the second differential arc oxidation, a concentration of 0.18mol/L of calcium acetate, sodium dihydrogen phosphate it is a concentration of
A concentration of 0.38mol/L, Na of 0.045mol/L, EDTA-2Na2SiO3A concentration of 0.04mol/L, add suitable KOH, adjust
The pH value for saving solution is 11, and the second differential arc oxidation uses the voltage of second source for 200V, the output pulse frequency of second source
Pulse width for 500Hz, second source is 300 μ s, and the peak point current of second source is 150A, the time of the second differential arc oxidation
For 20min.Using the method in scanning electron microscope detection oxidation film layer section, the thickness of growth in situ film layer is 12 μm, growth in situ
The porosity of film layer is 11%.
To carrying out vacuum plasma spray coating after the cleaning of the second differential arc oxidation treated beta titanium alloy, drying, in β types
Titanium alloy divides surface that HA coatings are arranged close to the femur ball head, wherein the voltage of vacuum plasma spray coating is 50V, electricity
Stream is 550A.Growth in situ film layer and the linking of HA coatings.
Embodiment 12
The preparation of femoral stem：
Second differential arc oxidation is carried out to the part surface of the separate femur bulb of beta titanium alloy, to form growth in situ film
Layer, in the second electrolyte used by the second differential arc oxidation, a concentration of 0.2mol/L of calcium acetate, sodium dihydrogen phosphate it is a concentration of
A concentration of 1.04mol/L, Na of 0.21mol/L, EDTA-2Na2SiO3A concentration of 0.04mol/L, add suitable KOH, adjust
The pH value for saving solution is 11, and the second differential arc oxidation uses the voltage of second source for 200V, the output pulse frequency of second source
Pulse width for 500Hz, second source is 300 μ s, and the peak point current of second source is 150A, the time of the second differential arc oxidation
For 20min.Using the method in scanning electron microscope detection oxidation film layer section, the thickness of growth in situ film layer is 13 μm, growth in situ
The porosity of film layer is 12%.
To carrying out vacuum plasma spray coating after the cleaning of the second differential arc oxidation treated beta titanium alloy, drying, in β types
Titanium alloy divides surface that HA coatings are arranged close to the femur ball head, wherein the voltage of vacuum plasma spray coating is 50V, electricity
Stream is 550A.Growth in situ film layer and the linking of HA coatings.
Embodiment 13
The preparation of femoral stem：
Second differential arc oxidation is carried out to the part surface of the separate femur bulb of beta titanium alloy, to form growth in situ film
Layer, in the second electrolyte used by the second differential arc oxidation, a concentration of 0.58mol/L of calcium acetate, sodium dihydrogen phosphate it is a concentration of
A concentration of 3.8mol/L, Na of 0.65mol/L, EDTA-2Na2SiO3A concentration of 0.04mol/L, add suitable KOH, adjust
The pH value of solution is 11, and the second differential arc oxidation uses the voltage of second source for 200V, and the output pulse frequency of second source is
500Hz, the pulse width of second source are 300 μ s, and the peak point current of second source is 150A, and the time of the second differential arc oxidation is
20min.Using the method in scanning electron microscope detection oxidation film layer section, the thickness of growth in situ film layer is 12 μm, growth in situ film
The porosity of layer is 16%.
To carrying out vacuum plasma spray coating after the cleaning of the second differential arc oxidation treated beta titanium alloy, drying, in β types
Titanium alloy divides surface that HA coatings are arranged close to the femur ball head, wherein the voltage of vacuum plasma spray coating is 50V, electricity
Stream is 550A.Growth in situ film layer and the linking of HA coatings.
Embodiment 14
The preparation of femoral stem：
Second differential arc oxidation is carried out to the part surface of the separate femur bulb of beta titanium alloy, to form growth in situ film
Layer, in the second electrolyte used by the second differential arc oxidation, a concentration of 0.4mol/L of calcium acetate, sodium dihydrogen phosphate it is a concentration of
A concentration of 2.2mol/L, Na of 0.45mol/L, EDTA-2Na2SiO3A concentration of 0.04mol/L, add suitable KOH, adjust
The pH value of solution is 11, and the second differential arc oxidation uses the voltage of second source for 200V, and the output pulse frequency of second source is
500Hz, the pulse width of second source are 300 μ s, and the peak point current of second source is 150A, and the time of the second differential arc oxidation is
20min.Using the method in scanning electron microscope detection oxidation film layer section, the thickness of growth in situ film layer is 15 μm, growth in situ film
The porosity of layer is 18%.
To carrying out vacuum plasma spray coating after the cleaning of the second differential arc oxidation treated beta titanium alloy, drying, in β types
Titanium alloy divides surface that HA coatings are arranged close to the femur ball head, wherein the voltage of vacuum plasma spray coating is 50V, electricity
Stream is 550A.Growth in situ film layer and the linking of HA coatings.
Embodiment 15
The preparation of femoral stem：
Second differential arc oxidation is carried out to the part surface of the separate femur bulb of beta titanium alloy, to form growth in situ film
Layer, in the second electrolyte used by the second differential arc oxidation, a concentration of 0.38mol/L of calcium acetate, sodium dihydrogen phosphate it is a concentration of
A concentration of 2mol/L, Na of 0.42mol/L, EDTA-2Na2SiO3A concentration of 0.04mol/L, add suitable KOH, adjust molten
The pH value of liquid is 11, and the second differential arc oxidation uses the voltage of second source for 200V, and the output pulse frequency of second source is
500Hz, the pulse width of second source are 300 μ s, and the peak point current of second source is 150A, and the time of the second differential arc oxidation is
20min.Using the method in scanning electron microscope detection oxidation film layer section, the thickness of growth in situ film layer is 16 μm, growth in situ film
The porosity of layer is 14%.
To carrying out vacuum plasma spray coating after the cleaning of the second differential arc oxidation treated beta titanium alloy, drying, in β types
Titanium alloy divides surface that HA coatings are arranged close to the femur ball head, wherein the voltage of vacuum plasma spray coating is 50V, electricity
Stream is 550A.Growth in situ film layer and the linking of HA coatings.
Embodiment 16
The preparation of femoral stem：
Second differential arc oxidation is carried out to the part surface of the separate femur bulb of beta titanium alloy, to form growth in situ film
Layer, in the second electrolyte used by the second differential arc oxidation, a concentration of 0.015mol/L of calcium acetate, sodium dihydrogen phosphate it is a concentration of
A concentration of 0.032mol/L, Na of 0.02mol/L, EDTA-2Na2SiO3A concentration of 0.04mol/L, add suitable KOH, adjust
The pH value for saving solution is 11, and the second differential arc oxidation uses the voltage of second source for 200V, the output pulse frequency of second source
Pulse width for 500Hz, second source is 300 μ s, and the peak point current of second source is 150A, the time of the second differential arc oxidation
For 20min.Using the method in scanning electron microscope detection oxidation film layer section, the thickness of growth in situ film layer is 10 μm, growth in situ
The porosity of film layer is 19%.
To carrying out vacuum plasma spray coating after the cleaning of the second differential arc oxidation treated beta titanium alloy, drying, in β types
Titanium alloy divides surface that HA coatings are arranged close to the femur ball head, wherein the voltage of vacuum plasma spray coating is 50V, electricity
Stream is 550A.Growth in situ film layer and the linking of HA coatings.
Embodiment 17
The preparation of femoral stem：
Second differential arc oxidation is carried out to the part surface of the separate femur bulb of beta titanium alloy, to form growth in situ film
Layer, in the second electrolyte used by the second differential arc oxidation, a concentration of 0.01mol/L of calcium acetate, sodium dihydrogen phosphate it is a concentration of
A concentration of 0.02mol/L, Na of 0.035mol/L, EDTA-2Na2SiO3A concentration of 0.01mol/L, add suitable KOH, adjust
The pH value for saving solution is 14, and the second differential arc oxidation uses the voltage of second source for 200V, the output pulse frequency of second source
Pulse width for 500Hz, second source is 300 μ s, and the peak point current of second source is 150A, the time of the second differential arc oxidation
For 20min.Using the method in scanning electron microscope detection oxidation film layer section, the thickness of growth in situ film layer is 11 μm, growth in situ
The porosity of film layer is 19%.
To carrying out vacuum plasma spray coating after the cleaning of the second differential arc oxidation treated beta titanium alloy, drying, in β types
Titanium alloy divides surface that HA coatings are arranged close to the femur ball head, wherein the voltage of vacuum plasma spray coating is 50V, electricity
Stream is 550A.Growth in situ film layer and the linking of HA coatings.
Embodiment 18
Difference from Example 9 is that the second differential arc oxidation uses the voltage of second source for 500V, second source
Output pulse frequency is 100Hz, and the pulse width of second source is 10 μ s, and the peak point current of second source is 300A, and second is micro-
The time of arc oxidation is 3min.Using the method in scanning electron microscope detection oxidation film layer section, the thickness of growth in situ film layer is 17 μ
The porosity of m, growth in situ film layer are 13%.
Embodiment 19
Difference from Example 9 is that the second differential arc oxidation uses the voltage of second source for 50V, second source
Output pulse frequency is 1000Hz, and the pulse width of second source is 500 μ s, and the peak point current of second source is 50A, and second is micro-
The time of arc oxidation is 30min.Using the method in scanning electron microscope detection oxidation film layer section, the thickness of growth in situ film layer is 48
μm, the porosity of growth in situ film layer is 20%.
Embodiment 20
Difference from Example 9 is that the second differential arc oxidation uses the voltage of second source for 550V, second source
Output pulse frequency is 800Hz, and the pulse width of second source is 500 μ s, and the peak point current of second source is 30A, and second is micro-
The time of arc oxidation is 40min.Using the method in scanning electron microscope detection oxidation film layer section, the thickness of growth in situ film layer is 50
μm, the porosity of growth in situ film layer is 19%.
Embodiment 21
Difference from Example 9 is, to being carried out after treated beta titanium alloy cleaning, the drying of the second differential arc oxidation
Vacuum plasma spray coating, to divide surface that HA coatings are arranged close to the femur ball head in beta titanium alloy, wherein vacuum etc.
The voltage of plasma spray is 40V, electric current 600A.Using the method in scanning electron microscope detection oxidation film layer section, the thickness of HA coatings
Degree is 57 μm, the porosity 4% in HA coatings.
Embodiment 22
Difference from Example 9 is, to being carried out after treated beta titanium alloy cleaning, the drying of the second differential arc oxidation
Vacuum plasma spray coating, to divide surface that HA coatings are arranged close to the femur ball head in beta titanium alloy, wherein vacuum etc.
The voltage of plasma spray is 60V, electric current 500A.Using the method in scanning electron microscope detection oxidation film layer section, the thickness of HA coatings
Degree is 97 μm, the porosity about 6% in HA coatings.
Comparative example 2
Using the beta titanium alloy before the second differential arc oxidation of progress as the femoral stem of comparative example 2.
Using Human osteoblast-like cell system MG-63 osteoblasts model to the femoral stem of each embodiment 8 to 22 and comparative example 2 into
Row cytology biological activity test, the MG-63 osteoblasts sugared cell culture medium recovery of the height containing 10% fetal calf serum, is placed in 37
DEG C, humidity 95%, CO2Cultivated in the cell incubator of concentration 5%, the next day change liquid, the form of optical microphotograph microscopic observation cell,
MG-63 osteoblasts in exponential phase are prepared into cell suspension.
By the standard sample of experimental group and control group through gamma-ray irradiation sterilizing 2h, it is placed in 24 orifice plates.By what is prepared
MG-63 cell suspension inoculations terminate cell culture afterwards for 24 hours in each group specimen surface.It is detected using acridine orange flourescent staining thin
Born of the same parents adhere to and the quantity of proliferation.With PBS (phosphate buffer, 1L PBS formulas:8g sodium chloride, 0.2g potassium chloride, 1.44g phosphorus
Sour disodium hydrogen, 0.24g potassium dihydrogen phosphates) it rinses 3 times, a concentration of 95% ethyl alcohol fixes 5min, 0.05% Acridine orange 5min,
PBS is rinsed 3 times；Fluorescence microscopy under the microscope, counts, the cell quantity such as table 3 of material surface adherency and proliferation.
Table 2
The adherency that the product that the embodiment of the present application obtains is conducive to cell is can be seen that according to the data in table 3.
It can be seen from the above description that the above embodiments of the present invention realize following technique effect：Since titanium closes
The wearability of gold is poor, therefore will not generally use titanium alloy as femur bulb.The femur bulb of the application is titanium alloy-based
It is provided with the zirconium coating of differential arc oxidation containing Zr of high-wearing feature on body, realizes design of the titanium alloy as femur bulb, reduces
The cost of femur bulb；After differential arc oxidation zirconium coating is set on titanium alloy substrate, the wetability of femur bulb is improved, effectively
Joint is reduced to secondary abrasion；And since the differential arc oxidation zirconium coating is prepared for micro-arc oxidation process, has and hold
The advantage that loading capability is high, film layer coefficient is low can be preferably adapted with mortar cup liner.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, any made by repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (20)
1. a kind of femur bulb, which is characterized in that including：
Titanium alloy substrate (21)；And
Wear-resistant coating (22), the wear-resistant coating (22) are differential arc oxidation zirconium coating.
2. femur bulb according to claim 1, which is characterized in that the thickness of the differential arc oxidation zirconium coating is 13~58
μm。
3. femur bulb according to claim 1, which is characterized in that the titanium alloy substrate (21) is Ti-6Al-4V bases
Any one in body, Ti-6Al-17Nb matrixes, Ti-13Nb-13Zr matrixes or Ti-5Zr-3Mo-15Nb matrixes.
4. a kind of preparation method of femur bulb, which is characterized in that the preparation method includes：
Titanium alloy substrate is placed in the first electrolyte, is cathode to the titanium using the titanium alloy substrate as anode, stainless steel
The outer surface of alloy substrate carries out the first differential arc oxidation processing, obtains differential arc oxidation zirconium coating, contains in first electrolyte
Zirconium dioxide.
5. preparation method according to claim 4, which is characterized in that zirconium dioxide contains described in first electrolyte
Amount is 2.5~6.5g/L, and the preferably described zirconium dioxide is the powder that grain size is 0.5~10 μm.
6. preparation method according to claim 4, which is characterized in that also contain in first electrolyte at least one auxiliary
Help starting the arc agent, the auxiliary starting the arc agent is selected from the composition of calcium lactate and calcium oxide, calcium acetate, calcium chloride, calcium dihydrogen phosphate, sweet
One in oleophosphoric acid calcium, calcium citrate, sodium glycero-phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, calgon and polyphosphate sodium
Kind is a variety of.
7. preparation method according to claim 6, which is characterized in that the first power supply that first differential arc oxidation uses is
The voltage of alternating current, first power supply is between 100~900V, and the output pulse frequency of first power supply is 100~
The pulse width of 1000Hz, first power supply are 8~500 μ s, and the peak point current of first power supply is set as 50~400A,
The time of first differential arc oxidation is 10~60min, and electrolyte temperature controls preferably in first micro-arc oxidation process
At 40 DEG C or less.
8. preparation method according to claim 4, which is characterized in that the preparation method first differential arc oxidation it
Further include being polished to obtain the differential arc oxidation zirconium coating that thickness is 13~58 μm to the differential arc oxidation zirconium coating afterwards.
9. a kind of artificial hip joint, including contact successively the femoral stem (10) of setting, femur bulb (20), mortar cup liner (30) and
Acetabular cup (40), which is characterized in that the femur bulb is the femur bulb or right described in any one of claims 1 to 3
It is required that the femur bulb that the preparation method described in any one of 4 to 8 obtains.
10. artificial hip joint according to claim 9, which is characterized in that the mortar cup liner (30) includes：
Matrix (31), described matrix (31) are with the surface contacted with the femur bulb (20), preferably described matrix (31)
Ultra-high molecular weight polyethylene matrix or high crosslinked polyethylene matrix；
Diamond-like carbon film-coating (32) is arranged on the surface of described matrix (31) contacted with the femur bulb (20), preferably
The thickness of the diamond-like carbon film-coating (32) is 500~3000nm, and the preferably described diamond-like carbon film-coating (32) uses Nonequilibrium magnetic
Control sputtering technology is formed.
11. artificial hip joint according to claim 9, which is characterized in that the femoral stem (10) includes：
Beta titanium alloy matrix (11)；
Growth in situ film layer (12) is arranged on the surface of the beta titanium alloy matrix (11).
12. artificial hip joint according to claim 11, which is characterized in that the growth in situ film layer (12) includes Ca members
The thickness of element and P element, the growth in situ film layer (12) is 5~50 μm, and the porosity of the growth in situ film layer (12) is 8
~25%.
13. artificial hip joint according to claim 11, which is characterized in that the growth in situ film layer (12) is far from described
Femur bulb (20) is arranged, and the femoral stem (10) further includes HA coatings, and the HA coatings are arranged in the beta titanium alloy matrix
(11) it is set on surface and close to the femur bulb (20), the preferably described growth in situ film layer (12) and HA coatings linking
It sets.
14. artificial hip joint according to claim 13, which is characterized in that the thickness of the HA coatings is 50~120 μm,
Pore-size rate in the HA coatings is about 3%~7%.
15. artificial hip joint according to claim 11, which is characterized in that the beta titanium alloy matrix (11) is Ti-Nb
Series titanium alloy matrix, Ti-Mo series titanium alloys matrix, Ti-Zr series titanium alloys matrix, Ti-Nb-Hf series titanium alloys matrix and Ti-Nb-
Any one in Zr series titanium alloy matrixes.
16. artificial hip joint according to claim 11, which is characterized in that the acetabular cup (40) is metal acetabulum cup
(40), the metal acetabulum cup (40) for host bone tissue contact surface be porous structure titanium layer or titanium alloy layer, preferably
The porous structure titanium layer is 3D printing bone trabecula titanium structure, titanium pearl, titanium powder, one or more in titanium silk, preferably described
Titanium alloy layer is Ti-6Al-4V alloy-layers, Ti-6Al-17Nb alloy-layers, Ti-13Nb-13Zr alloy-layers or Ti-5Zr-3Mo-
Any one in 15Nb alloy-layers.
17. a kind of production method of artificial hip joint includes preparation, the preparation of femur bulb and the system of femoral stem of mortar cup liner
It is standby, which is characterized in that the preparation of the femur bulb is implemented using the preparation method described in any one of claim 4 to 8.
18. production method according to claim 17, which is characterized in that the preparation of the femoral stem includes：
To beta titanium alloy carry out the second differential arc oxidation, on the beta titanium alloy formed growth in situ film layer, described second
In second electrolyte used by differential arc oxidation, the concentration of calcium constituent is denoted as m mol/L, and the concentration of P elements is denoted as nmol/L,
As 0.01≤m ＜ 0.2, (0.1m+0.025)≤n ＜ 0.05；As 0.2≤m≤0.6,0.075≤n≤m/0.875, preferably
When 0.4 ＜ m≤0.6,0.25≤n≤m/0.875；It is preferred that calcium source is selected from calcium acetate, calcium chloride, calcium dihydrogen phosphate, phosphoglycerol
The one or more of calcium, calcium citrate, calcium lactate and calcium oxide；More preferable phosphorus source is selected from sodium glycero-phosphate, sodium dihydrogen phosphate, phosphorus
One or more of sour disodium hydrogen, calgon and polyphosphate sodium.
19. production method according to claim 18, which is characterized in that second electrolyte further include EDTA-2Na and
Sodium metasilicate, the content of sodium metasilicate described in second electrolyte are 0.01~0.04mol/L；Preferably by sodium hydroxide or hydrogen
Potassium oxide adjusts second electrolyte ph between 11~14；It is preferred that second differential arc oxidation uses the electricity of second source
Pressure is 50~500V, and the output pulse frequency of the second source is 100~1000Hz, and the pulse width of the second source is
The peak point current of 8~500 μ s, the second source are 50~300A, and the time of second differential arc oxidation is 3~30min.
20. production method according to claim 18, which is characterized in that the object of second differential arc oxidation is the β
Type Titanium Alloy divides the surface, the preparation of the femoral stem to further include far from the femur ball head：
To carrying out vacuum plasma spray coating after the cleaning of second differential arc oxidation treated beta titanium alloy, drying, with described
Beta titanium alloy divides surface that HA coatings are arranged close to the femur ball head, and the voltage of the preferably described vacuum plasma spray coating is
40~60V, electric current are 500~600A.
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