CN105435313A - Internal fixator and manufacturing method - Google Patents
Internal fixator and manufacturing method Download PDFInfo
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- CN105435313A CN105435313A CN201510887170.0A CN201510887170A CN105435313A CN 105435313 A CN105435313 A CN 105435313A CN 201510887170 A CN201510887170 A CN 201510887170A CN 105435313 A CN105435313 A CN 105435313A
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- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
- A61L31/082—Inorganic materials
- A61L31/084—Carbon; Graphite
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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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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- A—HUMAN NECESSITIES
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- 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
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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
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Abstract
The invention belongs to the technical field of fracture fixation materials, and particularly discloses an internal fixator. The internal fixator comprises a base body. A superfine diamond graphene layer is arranged on the base body and is composed of nanometer diamond graohene of a lamellar single-crystal structure, and titanium particles are arranged between layers of the nanometer diamond graphene. The thickness of the superfine diamond graphene layer is smaller than 3 microns. The internal fixator is good in performance, long in service life and high in safety.
Description
Technical field
The invention belongs to fracture fixation field of material technology, particularly a kind of inside-fixture and manufacture method.
Background technology
Patient is after fracturing, and for making bone reduction, Promotive union speed and healing quality, often adopt internal fixation treatment method.Internal fixtion is more direct and effective than simple extenal fixation, can keep the anatomical reduction of fracturing preferably, especially prevent in the scissors of fracture end or rotatory activity more effective; In addition, the supporting role of inside-fixture is good, can after surgery few with or without extenal fixation, effectively can reduce the scope and time of extenal fixation, internal fixtion is conducive to hindering the functional exercise of limb and gets up in early days, reduces the complication because of long-term bed initiation.But internal fixtion can adopt cobalt metal usually; the toxicity of cobalt metal pair cell is comparatively large, also may cause allergic reaction, even have carcinogenesis after implant into body; the inside-fixture taken out after second operation can get rusty, and patient may be caused to occur aching, the symptom such as sour swollen discomfort.
Summary of the invention
The object of this invention is to provide that a kind of performance is good, long service life and the high inside-fixture of safety.
For achieving the above object, the present invention is by the following technical solutions: a kind of inside-fixture, comprise matrix, matrix is provided with ultra-fine diamond alkene layer, the thickness of ultra-fine diamond alkene layer is less than 3 microns, inside-fixture covers ultra-fine diamond alkene layer, the bio-compatible performance of inside-fixture can be improved, can covalent in conjunction with the molecular interface layer of the tissue compatibility, can be good at being combined with surrounding tissue, can not damage surrounding soft tissue and skeleton, internal fixtion there will not be phenomenon of getting rusty, and does not have toxicity to human body cell; After being covered with ultra-fine diamond alkene layer, mechanical strength and the hardness of inside-fixture can being improved, improve anti-wear performance, shape can be kept lastingly for a long time, not easily loosen, extend the service life of inside-fixture; Ultra-fine diamond alkene layer is made up of the nanometer diamond alkene of lamellar mono-crystalline structures, nanometer diamond alkene have titanium particle between layers, ensure outside diamond alkene performance own, to add the new energy of conduction.
Ultra-fine diamond alkene layer is made up of the nanometer diamond alkene of 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, be the connection of sp3 orbital hybridization carbon bond between the carbon atom of simultaneously same lamella, be that sp2 hydridization carbon bond connects between carbon atom between layers, sp2 hybrid orbital carbon bond is unsaturated building, make there are many electron vacancys between layers, electron vacancy facilitates electronics freely to come in and go out, can better and titanium particle etc. combine, 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, effectively can improve the biocompatibility of inside-fixture in the present invention.
The manufacture method of inside-fixture, comprises the following steps: 1) adopt supercritical ultrasonics technology to carry out surface cleaning process to matrix; 2) adopt vacuum ionic plating method to nanometer diamond alkene plating titanium particle, obtain modified Nano diamond alkene; 3) adopt compound electric plating method, by the matrix surface of modification diamond alkene plating after step 1) process, form the inside-fixture with ultra-fine diamond alkene layer.
In step 1), the technological parameter of supercritical ultrasonics technology is: frequency of utilization is 40kHz-50kHz, and ambient temperature is 45 DEG C-60 DEG C, and the processing time is 1min-2min, and emulsifying agent adopts concentration to be the Na of 25g/L-30g/L
3pO
4be the polyoxyethylene nonylphenol ether of 5g/L-10g/L with concentration.
Step 2) in plating technic parameter be: substrate temperature 80 DEG C-100 DEG C, background vacuum (4-5) × 10-3Pa, reacting gas adopts concentration to be the N2 of 99.99%, substrate negative voltage 50V-200V, ionizing power sources electric current is 600mA-800mA, and Plating times is 5min-10min, and titanium particle is in the technical process of vacuum ion plating, because unsaturated diamond alkene material itself has absorption affinity, be platedly overlying on nanometer diamond alkene multilayer chip between layers.
In step 3), composite plating adopts thermostatic mode; Be adjusted to as 100r/min-1400r/min with speed governing motor stirrer by mixing speed, continuous stirring solution makes nanometer diamond alkene be suspended in electroplate liquid; Electroplating time is 40min-60min, and electroplating temperature is 50 DEG C-60 DEG C, and electric current density is 0.5A/dm
2-1A/dm
2, electroplate liquid pH value is 3.5-4, and after plating, form ultra-fine diamond alkene layer on the surface of inside-fixture matrix, the coating surface of formation is bright and clean, and hardness is high and wear-resisting, long service life.
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.
Accompanying drawing explanation
Fig. 1 is the structural representation of embodiment 1 in the present invention;
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
A kind of inside-fixture, as shown in Figure 1, comprise matrix 1, matrix 1 is provided with ultra-fine diamond alkene layer 2, and ultra-fine diamond alkene layer 2 comprises the nanometer diamond alkene of lamellar mono-crystalline structures, nanometer diamond alkene have titanium particle between layers; The thickness of ultra-fine diamond alkene layer 2 is 2.8 microns.Ultra-fine diamond alkene layer 2 comprises the nanometer diamond alkene composition of 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; The spacing of lattice of nanometer diamond alkene is 0.21nm; The mean diameter R of nanometer diamond alkene is 20nm; The C content of nanometer diamond alkene is 99 ~ 100%.
The manufacture method of inside-fixture, is characterized in that: comprise the following steps: 1) adopt supercritical ultrasonics technology to carry out surface cleaning process to matrix 1; 2) adopt vacuum ionic plating method to nanometer diamond alkene plating titanium particle, obtain modified Nano diamond alkene; 3) adopt compound electric plating method, by the matrix surface of modification diamond alkene plating after step 1) process, form the inside-fixture with ultra-fine diamond alkene layer 2.
In step 1), the technological parameter of supercritical ultrasonics technology is: frequency of utilization is 40kHz-50kHz, and ambient temperature is 45 DEG C-60 DEG C, and the processing time is 1min-2min, and emulsifying agent adopts concentration to be the Na of 25g/L-30g/L
3pO
4be the polyoxyethylene nonylphenol ether of 5g/L-10g/L with concentration.
Step 2) in plating technic parameter be: substrate temperature 80 DEG C-100 DEG C, background vacuum (4-5) × 10-3Pa, reacting gas adopts concentration to be the N2 of 99.99%, substrate negative voltage 50V-200V, ionizing power sources electric current is 600mA-800mA, and Plating times is 5min-10min, and titanium particle is in the technical process of vacuum ion plating, because unsaturated diamond alkene material itself has absorption affinity, be platedly overlying on nanometer diamond alkene multilayer chip between layers.
In step 3), composite plating adopts thermostatic mode; Be adjusted to as 100r/min-1400r/min with speed governing motor stirrer by mixing speed, continuous stirring solution makes nanometer diamond alkene be suspended in electroplate liquid; Electroplating time is 40min-60min, and electroplating temperature is 50 DEG C-60 DEG C, and electric current density is 0.5A/dm
2-1A/dm
2, electroplate liquid pH value is 3.5-4.
Embodiment 2
A kind of inside-fixture, its structure and embodiment one are consistent, and are with the difference of embodiment one: the thickness of ultra-fine diamond alkene layer 2 is 2.5 microns, and the mean diameter R of nanometer diamond alkene is 500nm.
Embodiment 3
A kind of inside-fixture, its structure and embodiment one are consistent, and are with the difference of embodiment one: the thickness of ultra-fine diamond alkene layer 2 is 2 microns, and the mean diameter R of nanometer diamond alkene is 300nm.
Embodiment 4
A kind of inside-fixture, its structure and embodiment one are consistent, and are with the difference of embodiment one: the thickness of ultra-fine diamond alkene layer 2 is 1.5 microns, and the mean diameter R of nanometer diamond alkene is 200nm.
Embodiment 5
A kind of inside-fixture, its structure and embodiment one are consistent, and are with the difference of embodiment one: the thickness of ultra-fine diamond alkene layer 2 is 0.8 micron, and the mean diameter R of nanometer diamond alkene is 100nm.
Embodiment 6
A kind of inside-fixture, its structure and embodiment one are consistent, and are with the difference of embodiment one: the thickness of ultra-fine diamond alkene layer 2 is 0.5 micron, and the mean diameter R of nanometer diamond alkene is 50nm.
Carry out performance test to the inside-fixture adopting said method to obtain, test case is as follows:
Test 1: by inside-fixture Implantation Test Mice, revive after white mice 2-3 hour, slowly come into play; Take out inside-fixture after 3 days, be as good as secretions around, the tissue such as muscle, without distortion necrosis phenomena, is formed without fibrous capsule; After 2 weeks, secretions without exception, has adhesion phenomenon with surrounding tissue, has fibrous connective tissue peplos to be formed; After 5 weeks, have no inflammatory reaction under mirror, the complete as seen and fibrous connective tissue peplos of densification is formed, chronic granulo hamartoplasia.This inside-fixture not only has and exceeds titanium alloy and poly biocompatibility, and can excite peripheral cell, diminishes inflammation, quickly-healing.
Test 2: by inside-fixture Implantation Test Mice, because its hardness is high, super lubrication, wear-resisting, corrosion-resistant, indeformable, excellent adsorption, excellent biocompatibility can excite peripheral cell to diminish inflammation, and quick and surrounding tissue bonds compatible.Respectively at implantation 2 weeks, after 4 weeks, 8 weeks by scanning electron microscope, be showed no the foreign bodies such as abrasive dust, thus judge that inside-fixture and surrounding soft tissue's compatibility are good, without wearing and tearing.So after implant into body, service life obviously extends.
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. an inside-fixture, is characterized in that: comprise matrix, and matrix is provided with ultra-fine diamond alkene layer, and ultra-fine diamond alkene layer is made up of the nanometer diamond alkene of lamellar mono-crystalline structures, nanometer diamond alkene have titanium particle between layers; The thickness of ultra-fine diamond alkene layer is less than 3 microns.
2. inside-fixture as claimed in claim 1, is characterized in that: for sp3 orbital hybridization carbon bond connects between the carbon atom of the same lamella of nanometer diamond alkene of described lamellar mono-crystalline structures, is that sp2 hydridization carbon bond connects between carbon atom between layers; 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%.
3. the manufacture method of inside-fixture described in claim 1 or 2, is characterized in that: comprise the following steps: 1) adopt supercritical ultrasonics technology to carry out surface cleaning process to matrix; 2) adopt vacuum ionic plating method to nanometer diamond alkene plating titanium particle, obtain modified Nano diamond alkene; 3) adopt compound electric plating method, by the matrix surface of modification diamond alkene plating after step 1) process, form the inside-fixture with ultra-fine diamond alkene layer.
4. the manufacture method of inside-fixture as claimed in claim 3, it is characterized in that: in described step 1), the technological parameter of supercritical ultrasonics technology is: frequency of utilization is 40kHz-50kHz, ambient temperature is 45 DEG C-60 DEG C, and the processing time is 1min-2min.
5. the manufacture method of inside-fixture as claimed in claim 4, is characterized in that: described step 2) in plating technic parameter be: substrate temperature 80 DEG C-100 DEG C, background vacuum (4-5) × 10
-3pa, reacting gas adopts concentration to be the N of 99.99%
2, substrate negative voltage 50V-200V, ionizing power sources electric current is 600mA-800mA, and Plating times is 5min-10min.
6. the manufacture method of inside-fixture as claimed in claim 5, is characterized in that: in described step 3), composite plating adopts thermostatic mode; Mixing speed is 100r/min-1400r/min; Electroplating time is 40min-60min; Electroplating temperature is 50 DEG C-60 DEG C.
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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 |
| CN106929703A (en) * | 2017-03-28 | 2017-07-07 | 河南省豫星华晶微钻有限公司 | A kind of new titanium matrix composite containing nanometer diamond alkene and preparation method thereof |
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