CN105477684A - Composite diamond-ene artificial joint and production method thereof - Google Patents

Composite diamond-ene artificial joint and production method thereof Download PDF

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CN105477684A
CN105477684A CN201510887162.6A CN201510887162A CN105477684A CN 105477684 A CN105477684 A CN 105477684A CN 201510887162 A CN201510887162 A CN 201510887162A CN 105477684 A CN105477684 A CN 105477684A
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diamond alkene
nanometer
nanometer diamond
alkene
layer
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郭留希
赵清国
杨晋中
刘永奇
薛胜辉
陈庆丰
尚跃增
项嘉义
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Zhengzhou Synthetic Diamond and Products Engineering Technology Research Center Co Ltd
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Zhengzhou Synthetic Diamond and Products Engineering Technology Research Center Co Ltd
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/303—Carbon
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/34—Macromolecular materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/02—Methods for coating medical devices
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/06—Coatings containing a mixture of two or more compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/24—Materials or treatment for tissue regeneration for joint reconstruction

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Abstract

The invention belongs to the technical field of artificial joints and particularly discloses a composite diamond-ene artificial joint. The composite diamond-ene artificial joint comprises an articular head and an articular fossa which are matched with each other. The articular head comprises a metal matrix, and a superfine diamond-ene layer formed by nano diamond-ene is arranged outside the metal matrix. The articular fossa comprises a polyethylene matrix, one side, matched with the articular head, of the polyethylene matrix is provided with a wear-resistant layer which is formed by nano diamond-ene and polyethylene, and the volume ratio of the nano diamond-ene to the polyethylene is 2:3 or 1:1. The composite diamond-ene artificial joint is high in hardness, good in wear resistance and long in service life.

Description

Compound diamond alkene artificial joint and preparation method
Technical field
The invention belongs to artificial joint technical field, relate to a kind of artificial joint, particularly one compound diamond alkene diamond alkene artificial joint and preparation method.
Background technology
In order to treat the diseases such as ankylosis, joint deformity and various destructive osteoarthrosis, within 1962, there is the artificial joint ultra-high molecular weight polyethylene and cochrome composition, and having fixed with bone cement (methacrylate), being applied to human body; Artificial joint replacement enters the new stage of practical application since then.In the history more than 50 years, arthroplasty has developed into a kind of method that current clinical treatment severe joint damages and joint failure curative effect is best.It is reported, what need to carry out prosthetic replacement in China about has 3,000 ten thousand people, because human synovial function is complicated, particularly has the mobility of multiple directions, and bear and certain to draw, press, roll over, the load such as to bend, so require very high to the selection of material property.For example: hip joint is made up of ball and socket joint and glenoid fossa, for connecting the glenoid fossa of femoral head and pelvis.Replacement of total hip comprises three parts: 1. with ultra-high molecular weight polyethylene glenoid fossa replacement hip joints nest; 2. replace cracked femoral head with metal joint head; 3. insert by metallic rod the stability that femoral shaft increases artificial joint.The metallic rod of usual connection femur is that cochrome or titanium alloy material are made, the sphere inserting the femur top of hip joint nest is then made up of cochrome or refining alumina ceramic material, hip joint nest itself is generally ultra-high molecular weight polyethylene hemisphere and forms, and directly can implant pelvis.Clinical research shows, the effective length of service based on the artificial joint implant into body of the materials such as ultra-high molecular weight polyethylene is 10 ~ 15 years.
Although arthroplasty is one of clinical operation the most effective and ripe at present, but the materials such as ultra-high molecular weight polyethylene have service life, the danger of inefficacy is faced equally after implant into body, in long-term use procedure, subject larger load and do relatively reciprocating motion with the hard material such as alloy, pottery, easily because wearing and tearing cause problems: hardness and the abrasion resistance properties of ultra-high molecular weight polyethylene are relatively low, in life-time service process, creep occur and make replacement joint produce comparatively galling; The abrasive dust that wearing and tearing produce is built up and is brought out soft tissue and produces a series of bad biologically, makes the Aseptic Loosening be fixed well, substantially reduces the service life of artificial joint implant.Clinical research shows, can lose efficacy gradually after artificial joint in implant into body uses 10 ~ 15 years because of wearing and tearing, and the patient of nearly 30% needed to carry out revision procedure in 10 years.Some patient another, in order to avoid second operation, bears by force time pain is waited until and failed to hold and treats.
Summary of the invention
The object of this invention is to provide that a kind of hardness is high, wearability good and the diamond alkene artificial joint of long service life and preparation method.
For achieving the above object, the present invention is by the following technical solutions: compound diamond alkene artificial joint, and comprise the ball and socket joint and glenoid fossa that cooperatively interact, ball and socket joint comprises metallic matrix, be provided with ultra-fine diamond alkene layer outside metallic matrix, ultra-fine diamond alkene layer is made up of nanometer diamond alkene; Glenoid fossa comprises base polyethylene, and the one side that base polyethylene matches with ball and socket joint is provided with wearing layer, and wearing layer is made up of nanometer diamond alkene and polyethylene, and wherein nanometer diamond alkene and poly volume ratio are 2:3 or 1:1; Glenoid surface roughness is less than 0.1 micron; Nanometer diamond alkene is lamellar mono-crystalline structures, in nanometer diamond alkene same lamella carbon atom between be same lamella carbon atom between for sp3 orbital hybridization carbon bond connect, between carbon atom between layers be sp2 hydridization carbon bond connection; The spacing of lattice of nanometer diamond alkene is 0.21nm; The mean diameter of nanometer diamond alkene is R, 20≤R≤500nm; The C content of nanometer diamond alkene is 99 ~ 100%.
Further, the thickness of ultra-fine diamond alkene layer is less than 3 microns.
Further, the mean diameter of the nanometer diamond alkene in ultra-fine diamond alkene layer is R, 20≤R≤50nm.
Further, the Thickness Ratio of base polyethylene and wearing layer is 3:2 or 7:3.
The preparation method of compound diamond alkene artificial joint,
One, the preparation method of ball and socket joint is as follows: first carry out surface cleaning process to the metallic matrix of ball and socket joint, then adopt chemical deposition or physical deposition methods, with nanometer diamond alkene for raw material, forms ultra-fine diamond alkene layer, obtain finished product at metal base surface;
They are two years old, glenoid preparation method is as follows: choose nanometer diamond alkene and polyethylene, wherein nanometer diamond alkene and poly volume ratio are 2:3 or 1:1, after being continuously stirring to mix homogeneously after adding binding agent, put into mould again and make wearing layer idiosome, after cooling by wearing layer and base polyethylene compressed together, obtain finished product.
Further, binding agent adopts modified epoxy.
The preparation technology of nanometer diamond alkene, comprises the following steps:
Pickling is purified: fine powder diamond raw material powder being broken into more than 8000 orders, adopts concentrated sulphuric acid and concentrated nitric acid mixed liquor, dilute hydrochloric acid, Fluohydric acid. to this fine powder pickling successively, then use washed with de-ionized water to cleanout fluid pH close to 7; Sorting: the material after cleaning is carried out centrifugalize, gets supernatant liquid and carries out the sorting of 1-5 days precipitations, remove the supernatant, by the nanometer diamond alkene that gets product after the drying of lower sediment thing.
Carry out ball milling shaping and airflow crash before acid pickling step, first the fines of more than 800 orders is sieved out in the ball milling shaping of diamond raw material; Again this fines is delivered in airflow crash machine and pulverizes and sieve out the fine powder of more than 8000 orders.
At ball milling shaping step, diamond sifts out the granule of more than 70 orders through the screen cloth of ball milling shaping barrel, and the broken time is 1-5h; This granule sieves out the fines of more than 800 orders through multistage vibrating sieving machine, and the sieve time of shaking is 30min-2h; At ball milling shaping step, fineves more than 800 orders sieved out repeats to sieve once; At ball milling shaping step, the coarse fodder below 70 orders returns ball milling shaping barrel and carries out again broken; Residue on sieve Returning flow disintegrating machine carries out again broken; In sorting step, centrifugation time is 30min-2h, and rotating speed is 8000rpm-15000rpm; Concentrated sulphuric acid and concentrated nitric acid mixed liquor are that 5:1 mixes by mass fraction to be 98% concentrated sulphuric acid and mass fraction be 10% concentrated nitric acid according to mass ratio; Adopting nanometer diamond alkene prepared by said method, is lamellar mono-crystalline structures, is that sp3 orbital hybridization carbon bond connects between the carbon atom of same lamella, is that sp2 hydridization carbon bond connects between carbon atom between layers; Granularity is 20-500nm, and C content is 99 ~ 100%, and spacing of lattice is 0.21nm.
Compared with prior art, beneficial effect of the present invention is as follows: ball and socket joint comprises metallic matrix, ultra-fine diamond alkene layer is provided with outside metallic matrix, ultra-fine diamond alkene layer is made up of nanometer diamond alkene, after metallic matrix covering ultra-fine diamond alkene layer, make ball and socket joint hardness high, wear-resisting and can long term shape retention; Glenoid fossa comprises base polyethylene, and the one side that base polyethylene matches with ball and socket joint is provided with wearing layer, and wearing layer is made up of nanometer diamond alkene and polyethylene, improves glenoid associativity, smooth abrasion-proof and good corrosion resistance; Wherein nanometer diamond alkene and poly volume ratio are 2:3 or 1:1, can either ensure the performance of original material, add again the new features of nanometer diamond alkene, improve biocompatibility, and can bear larger load, improve wear resistance; Glenoid surface roughness is less than 0.1 micron, ensures the smooth of surface, improves lubricity; The one side that base polyethylene matches with ball and socket joint is provided with wearing layer, and the Thickness Ratio of base polyethylene and wearing layer is 3:2 or 7:3, avoids the wearing and tearing of glenoid base polyethylene, increases the service life; Ball and socket joint after process and glenoid fossa coordinate, in the process of life-time service, abrasive dust can not be produced and build up the bad biologically of healthy hair soft tissue, artificial joint is avoided to occur to loosen, can be combined with surrounding soft tissue, there will not be the situation of getting rusty, after avoiding operation in patients, occur the malaise symptoms such as ache; Nanometer diamond alkene is lamellar mono-crystalline structures, be that sp3 orbital hybridization carbon bond connects between the carbon atom of same lamella, be that sp2 hydridization carbon bond connects between carbon atom between layers, nanometer diamond alkene pattern is multilayer chip structure, morphology controllable, good dispersion, without uniting, agglomeration occurs, and particle diameter and sheet is thick there is proportionate relationship; The spacing of lattice of nanometer diamond alkene is 0.21nm; The mean diameter of nanometer diamond alkene is R, 20≤R≤500nm, and nanometer diamond alkene particle diameter concentration degree is high, particle size range narrowly distributing, and particle diameter is 20-500nm, and size is controlled; The C content of nanometer diamond alkene is 99 ~ 100%, and crystallinity is very strong, to human non-toxic's side effect, can be used for preparation and its surface treatment of the bionic materials such as human teeth, bone, joint, can be used for the aspects such as preparation artificial teeth, artificial bone, artificial limb; The unsaturated nanometer diamond alkene of multilayer chip structure can by the between layers strong bonded of the particle absorption of other materials in itself, after adopting binding agent to be combined with nanometer diamond alkene, good consolidation effect can be reached, simultaneously nanometer diamond alkene multilayer chip structure makes obtained finished product smooth abrasion-proof, corrosion-resistant, hardness is high and not yielding.
Accompanying drawing explanation
Fig. 1 is the structural representation of the embodiment of the present invention 1;
Fig. 2 is the XRD spectra of nanometer diamond alkene;
Fig. 3 is the tem analysis figure of nanometer diamond alkene;
Fig. 4 is the MAS-NMR spectrogram of nanometer diamond alkene;
Fig. 5 is the atomic orbital schematic diagram of nanometer diamond alkene;
Fig. 6 is the Raman spectrum of nanometer diamond alkene.
Detailed description of the invention
Embodiment 1
Compound diamond alkene artificial joint, as shown in Figure 1, comprise the ball and socket joint and glenoid fossa that cooperatively interact, ball and socket joint comprises metallic matrix 1, is provided with ultra-fine diamond alkene layer 2 outside metallic matrix 1, and ultra-fine diamond alkene layer 2 is made up of nanometer diamond alkene; Glenoid fossa comprises base polyethylene 4, and the one side that base polyethylene 4 matches with ball and socket joint is provided with wearing layer 3, and wearing layer 3 is made up of nanometer diamond alkene and polyethylene, and wherein nanometer diamond alkene and poly volume ratio are 2:3 or 1:1; Glenoid surface roughness is 0.09 micron; Nanometer diamond alkene is lamellar mono-crystalline structures, in nanometer diamond alkene same lamella carbon atom between be same lamella carbon atom between for sp3 orbital hybridization carbon bond connect, between carbon atom between layers be sp2 hydridization carbon bond connection; The spacing of lattice of nanometer diamond alkene is 0.21nm; The mean diameter of nanometer diamond alkene is R, 20≤R≤500nm; The C content of nanometer diamond alkene is 99 ~ 100%.The thickness of ultra-fine diamond alkene layer 2 is 2.8 microns.The mean diameter of the nanometer diamond alkene in ultra-fine diamond alkene layer 2 is R, 20≤R≤50nm.Base polyethylene 4 is 3:2 with the Thickness Ratio of wearing layer 3.
The preparation method of compound diamond alkene artificial joint,
One, the preparation method of ball and socket joint is as follows: first adopt the metallic matrix 1 of supercritical ultrasonics technology to ball and socket joint to carry out surface cleaning process, then adopt chemical deposition or physical deposition methods, with nanometer diamond alkene for raw material, form ultra-fine diamond alkene layer 2 on metallic matrix 1 surface, obtain ball and socket joint finished product;
They are two years old, glenoid preparation method is as follows: first choose polythene material and make base polyethylene 4, choose nanometer diamond alkene and polyethylene, wherein nanometer diamond alkene and poly volume ratio are 2:3, after being continuously stirring to mix homogeneously after adding binding agent, put into mould again and make wearing layer idiosome, after cooling by wearing layer 3 and base polyethylene 4 compressed together, obtain glenoid fossa finished product.Binding agent adopts modified epoxy.
Embodiment 2
The difference of the present embodiment and embodiment 1 is: in glenoid fossa, nanometer diamond alkene and poly volume ratio are 2:3, and glenoid surface roughness is 0.08 micron, and the Thickness Ratio of base polyethylene and wearing layer is 3:2; In ball and socket joint, the thickness of ultra-fine diamond alkene layer is 2.5 microns, and the mean diameter R of the nanometer diamond alkene in ultra-fine diamond alkene layer is 40nm.
Embodiment 3
The difference of the present embodiment and embodiment 1 is: in glenoid fossa, nanometer diamond alkene and poly volume ratio are 1:1, and glenoid surface roughness is 0.06 micron, and the Thickness Ratio of base polyethylene and wearing layer is 7:3; In ball and socket joint, the thickness of ultra-fine diamond alkene layer is 2 microns, and the mean diameter R of the nanometer diamond alkene in ultra-fine diamond alkene layer is 30nm.
Embodiment 4
The difference of the present embodiment and embodiment 1 is: in glenoid fossa, nanometer diamond alkene and poly volume ratio are 1:1, and glenoid surface roughness is 0.04 micron, and the Thickness Ratio of base polyethylene and wearing layer is 7:3; In ball and socket joint, the thickness of ultra-fine diamond alkene layer is 1 micron, and the mean diameter R of the nanometer diamond alkene in ultra-fine diamond alkene layer is 20nm.
The performance test of nanometer diamond alkene is as follows:
(1) XRD analysis
Fig. 2 is a: explosion method Nano diamond; B: nanometer diamond alkene in the present invention; C: graphite; D: the XRD spectra of Graphene.
From the XRD spectra of Fig. 2, by x-ray powder diffraction instrument (CuK alpha ray, tube voltage 40Kv, tube current 40mA, λ=1.54056) test show, nanometer diamond alkene of the present invention in the angle of diffraction 2 θ=43.93 ° and 75.3 ° can see clearly diffraction maximum, with typical diamond phase diffraction maximum (111), (220) corresponding, can prove that novel nano diamond alkene of the present invention is the carbon nanosheet with diamond phase structure, the Nano diamond that the diffracted intensity of the diffracted primary peak (111) of novel nano diamond alkene of the present invention synthesizes much larger than explosion method can be found out XRD spectra simultaneously, illustrate that the Nano diamond that diamond alkene crystallinity of the present invention is synthesized more than explosion method is strong.Can find out that Graphene and graphite can see diffraction maximum significantly in the angle of diffraction 2 θ=26.3 ° simultaneously, corresponding with typical Graphene and graphite diffraction maximum (002), to go out peak position different from novel nano diamond alkene of the present invention, this illustrates that novel nano diamond alkene of the present invention is formed mutually from the thing of graphite, Graphene is different, the peak position that goes out of the main diffraction maximum of CNT is set to 26.4 °, corresponding crystal face is (002), and this is also different from diamond alkene of the present invention.According to Scherrer formula D=, K is constant, β is halfwidth, diamond alkene grain size of the present invention is about 5 times of the Nano diamond of explosion method synthesis, this means that diamond alkene of the present invention distorts on atomic structure of carbon very little, crystallinity is good, because crystal grain is more little more easily produce distortion of lattice, this is for expanding the range of application of Nano diamond advantageously.
(2) tem analysis
Fig. 3 is a: explosion method Nano diamond; B: novel nano diamond alkene of the present invention; C: graphite; D: the tem analysis figure of Graphene.Corresponding 1 is partial enlarged drawing, and 2 is corresponding HRTEM figure, and 1 figure upper left corner illustration is corresponding SAED figure.
Can find out that the pattern of nanometer diamond alkene of the present invention is different from other material with carbon element significantly by Fig. 3, and be a kind of multilayer chip structure, us are schemed as can be seen from the SAED in the 1 figure upper left corner, diamond alkene of the present invention is a kind of mono-crystalline structures, and Nano diamond prepared by explosion method is the granule composition of reuniting, and be polycrystalline structure, graphite and Graphene are laminated structure, this laminated structure is different from diamond alkene of the present invention, the length of a film of diamond alkene of the present invention is between 200-500nm, the length of a film of graphite and Graphene is more than 10 μm, and thickness is also than graphite, Graphene is thick.Us are schemed also as can be seen from SAED, although all present monocrystalline electronic diffraction, but the SAED figure of graphite and Graphene is the SAED figure of typical hexaplanar, and be different from diamond alkene prepared by the present invention, this illustrates that diamond alkene of the present invention has different crystal structures from graphite, Graphene.
Can find out that spacing of lattice is 0.21nm from HRTEM figure, close with diamond phase (111) face spacing of lattice 0.206nm, this illustrates that the product of this laminated structure is all along (111) face, from figure, we it can also be seen that the Nano diamond that nanometer diamond alkene dispersibility is prepared more than explosion method will be got well, and specific surface area is large, be more prone to adsorb other functional group from the teeth outwards, thus realize the functionalization to diamond surface, expand its range of application.
(3) MASNMR analyzes
Fig. 4 is a: nanometer diamond alkene of the present invention, b: the MASNMR of explosion method Nano diamond analyzes.
Nanometer diamond alkene of the present invention is layer structure as seen from Figure 4, the Nano diamond of explosion method synthesis is made up of two kinds of different carbon C1 and C2, wherein C1 carbon to go out peak position different from diamond alkene of the present invention, this illustrates that the carbon atom arrangement inside these two kinds of Nano diamonds also exists certain difference.Nanometer diamond alkene of the present invention has the sp3 orbital hybridization carbon carbon structure different with two kinds, sp2 orbital hybridization carbon, be that sp3 orbital hybridization carbon bond connects between the carbon atom of same lamella, be that sp2 hydridization carbon bond connects between carbon atom between layers, make there are many electron vacancys between layers, electron vacancy facilitates electronics freely to come in and go out, wherein, as shown in Figure 5, sp3 orbital hybridization carbon is the hydridization carbon of stereochemical structure, sp2 orbital hybridization carbon be planar structure hydridization carbon this be different from the carbon structure of the Nano diamond that explosion method is synthesized.And Graphene has a kind of two dimensional crystal structure, the hexagon that its lattice is made up of six carbon atom, combination between carbon atom is sp2 orbital hybridization, graphite is the hexagon of the six carbon atom composition of same layer, with layer carbon atom between combination be sp2 orbital hybridization formed chemical bond, and be connect by Van der Waals force between layers, carbon atom in nanotube is based on sp2 orbital hybridization, also there is certain bending simultaneously, certain sp3 hybrid bond can be formed, namely the chemical bond formed in same flexure plane has sp2 and sp3 mixed hybridization state simultaneously, the carbon atom arrangement of these material with carbon elements is all different from nanometer diamond alkene of the present invention.
(4) Raman spectrum analysis
Fig. 6 is the Raman spectrogram of nanometer diamond alkene, (a) particle diameter 250nm; (b) particle diameter 200nm; (c) particle diameter 100nm; (d) particle diameter 50nm.
As can be seen from Figure 6, the diamond alkene of layer structure of the different-grain diameter of synthesis has the similar Raman spectrogram of the Nano diamond of explosion method synthesis, but with its unlike, along with the change of sample particle diameter, also there is regular change in Raman spectrogram, the intensity at two main peak D peak and G peak is weakening gradually, this is mainly because the structure of sample itself there occurs change, sp2 carbon and sp3 carbon two kinds of carbon atoms constitute a kind of special dimeric structure, along with the change of sample particle diameter, this special dimeric structure content increases gradually and causes two main diffraction peak intensities to weaken gradually.

Claims (6)

1. compound diamond alkene artificial joint, comprises the ball and socket joint and glenoid fossa that cooperatively interact, it is characterized in that: described ball and socket joint comprises metallic matrix, is provided with ultra-fine diamond alkene layer outside metallic matrix, and ultra-fine diamond alkene layer is made up of nanometer diamond alkene; Described glenoid fossa comprises base polyethylene, and the one side that base polyethylene matches with ball and socket joint is provided with wearing layer, and wearing layer is made up of nanometer diamond alkene and polyethylene, and wherein nanometer diamond alkene and poly volume ratio are 2:3 or 1:1; Glenoid surface roughness is less than 0.1 micron; Described nanometer diamond alkene is lamellar mono-crystalline structures, in nanometer diamond alkene same lamella carbon atom between be same lamella carbon atom between for sp3 orbital hybridization carbon bond connect, between carbon atom between layers be sp2 hydridization carbon bond connection; The spacing of lattice of nanometer diamond alkene is 0.21nm; The mean diameter of nanometer diamond alkene is R, 20≤R≤500nm; The C content of nanometer diamond alkene is 99 ~ 100%.
2. compound diamond alkene artificial joint as claimed in claim 1, is characterized in that: the thickness of described ultra-fine diamond alkene layer is less than 3 microns.
3. compound diamond alkene artificial joint as claimed in claim 2, is characterized in that: the mean diameter of the nanometer diamond alkene in described ultra-fine diamond alkene layer is R, 20≤R≤50nm.
4. compound diamond alkene artificial joint as claimed in claim 3, is characterized in that: the Thickness Ratio of described base polyethylene and wearing layer is 3:2 or 7:3.
5. the preparation method of compound diamond alkene artificial joint as claimed in claim 4, is characterized in that:
One, the preparation method of ball and socket joint is as follows: first carry out surface cleaning process to the metallic matrix of ball and socket joint, then adopt chemical deposition or physical deposition methods, with nanometer diamond alkene for raw material, forms ultra-fine diamond alkene layer, obtain finished product at metal base surface;
They are two years old, glenoid preparation method is as follows: choose nanometer diamond alkene and polyethylene, wherein nanometer diamond alkene and poly volume ratio are 2:3 or 1:1, after being continuously stirring to mix homogeneously after adding binding agent, put into mould again and make wearing layer idiosome, after cooling by wearing layer and base polyethylene compressed together, obtain finished product.
6. the preparation method of compound diamond alkene artificial joint as claimed in claim 5, is characterized in that: binding agent adopts modified epoxy.
CN201510887162.6A 2015-12-07 2015-12-07 Composite diamond-ene artificial joint and production method thereof Pending CN105477684A (en)

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CN105860194A (en) * 2016-04-15 2016-08-17 郑州人造金刚石及制品工程技术研究中心有限公司 Thermoplastic polymer composite material containing nano diamond ene and preparation method of thermoplastic polymer composite material

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CN1416330A (en) * 2000-01-30 2003-05-07 岱密克龙有限公司 Component for prosthetic joint having diamond load bearing and articulation surface

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CN1416330A (en) * 2000-01-30 2003-05-07 岱密克龙有限公司 Component for prosthetic joint having diamond load bearing and articulation surface

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105860194A (en) * 2016-04-15 2016-08-17 郑州人造金刚石及制品工程技术研究中心有限公司 Thermoplastic polymer composite material containing nano diamond ene and preparation method of thermoplastic polymer composite material

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