CN110201222A - One kind facilitating bone titanium containing rubidium tantalum composite material and preparation method and application - Google Patents

One kind facilitating bone titanium containing rubidium tantalum composite material and preparation method and application Download PDF

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CN110201222A
CN110201222A CN201910603700.2A CN201910603700A CN110201222A CN 110201222 A CN110201222 A CN 110201222A CN 201910603700 A CN201910603700 A CN 201910603700A CN 110201222 A CN110201222 A CN 110201222A
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composite material
titanium
tantalum composite
rubidium
bone
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CN110201222B (en
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刘咏
陈曼可
谭彦妮
黄千里
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Central South University
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/04Metals or alloys
    • A61L27/047Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/045Alloys based on refractory metals
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C27/00Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/02Alloys based on vanadium, niobium, or tantalum
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2400/00Materials characterised by their function or physical properties
    • A61L2400/18Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/02Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

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Abstract

The invention discloses one kind to facilitate bone titanium containing rubidium tantalum composite material and preparation method and application, this method, which carries out sandblasting, acid processing and alkali heat-treatment to the titanium tantalum composite material synthesized through plasma activated sintering, keeps titanium tantalum composite material surface modified, and so that surface-modified titanium tantalum composite material surface is mixed rubidium salt by ion exchange, it is prepared finally by high-temperature calcination and facilitates the bone tantalum composite material of titanium containing rubidium.Material of the invention has good biocompatibility, does not have cytotoxicity, promotes cell Proliferation, has the function of good induction preosteoblast Osteoblast Differentiation.The material can effectively solve the problems such as bone renovating material is poor with human compatibility in clinical application, have wide application prospect in clinical Bone Defect Repari.

Description

One kind facilitating bone titanium containing rubidium tantalum composite material and preparation method and application
Technical field
The invention belongs to biomedical materials fields, and in particular to one kind facilitates bone titanium containing rubidium tantalum composite material and its preparation Methods and applications.
Background technique
Knee joint osseous arthritis, Hip Fracture, backbone degenerative disease are the higher orthopaedic disease of disease incidence, and with The aggravation of aging of population, cause disease incident in rise, rejuvenation trend.Titanium tantalum composite material is because of its good mechanics Performance, excellent biocompatibility and lower cost are widely used in clinical orthopaedics field, such as joint replacement, intraspinal solid The common fracture patient treatment method such as surely, is both needed to use titanium tantalum composite material as bone substitution material.But since titanium tantalum is compound Material is bio-inert material, and the combination after implanting with human body itself bone is mostly mechanically link, fail and human body into Row cell, tissue bonding, resistance to compression tensile capacity is poor, lower with human body combination degree, and tissue easily occurs and is implanted into the de- of material Falling leads to operative failure, and patient need to undertake larger pain, and greatly improve medical treatment cost.Therefore, titanium tantalum composite material is carried out Surface is modified, improves its biological activity, is the key that improve success rate of operation.
As China's rubidium mine is constantly exploited, rubidium extractive technique is constantly progressive, the development and utilization of rubidium resource constantly by The concern of people.Find in research in our prior: rubidium ion has certain promotion osteogenic action, and skeletonization is thin before capable of effectively inducing Born of the same parents improve the bioactivity of titanium tantalum composite material to osteoblast differentiation.It, can be by rubidium for the functional effect for improving bone renovating material Salt is added in titanium tantalum composite material, on the one hand can improve the mechanical property of titanium tantalum composite material, while making it have good Bioactivity, being formed, there is clinical value to facilitate bone titanium tantalum composite material.
However to being at present mesh, the report that rubidium doping is carried out to titanium tantalum composite material yet there are no.
Summary of the invention
For in the prior art, medical titanium tantalum composite material bioactivity is poor, easily causes to perform the operation in practical clinical The problem of failure, facilitates the bone tantalum of titanium containing rubidium with excellent mechanical performance, bioactivity the purpose of the present invention is to provide a kind of Composite material and preparation method and application.
In order to solve the above technical problems, the present invention adopts the following technical scheme:
One kind of the present invention facilitates the bone tantalum composite material of titanium containing rubidium, and the tantalum composite material of titanium containing rubidium is passed through by titanium tantalum composite material Rubidium acquisition is mixed on surface, and the titanium tantalum composite material is formed by discharge plasma sintering.
It is provided to facilitate the bone tantalum composite material of titanium containing rubidium in the present invention, it is the titanium tantalum composite wood as obtained by being sintered through SPS Material mixes rubidium acquisition, and inventor is found surprisingly that, through the titanium tantalum composite material of SPS sintering after mixing rubidium, has optimal facilitate On the one hand bone ability is derived from the performance of matrix, on the one hand derived from doping caused by substrate performance, such as burn relative to vacuum The obtained titanium tantalum composite material of knot, SPS sintering carries out mixing rubidium, and doping wants low, but this doping is for facilitating It is most suitable for bone, therefore optimal rush bone formation performance can be obtained.
Preferred scheme: in the titanium tantalum composite material, by atomic ratio measuring, titanium: tantalum=1:10-30.
As a further preference, in the titanium tantalum composite material, by atomic ratio measuring, titanium: tantalum=1:20-30.
In the present invention program, the atomic ratio of titanium tantalum composite material within the scope of the present invention, has optimal and human body bone The mechanical property and wear Characteristics that mechanical property matches.
A kind of preparation method for facilitating the bone tantalum composite material of titanium containing rubidium of the present invention, includes the following steps: titanium tantalum alloy powder It carries out discharge plasma sintering and obtains titanium tantalum composite material, titanium tantalum composite material successively carries out blasting treatment, acid is handled, at alkali heat Reason obtains the titanium tantalum composite material of surface treatment, is then soaked in surface treated titanium tantalum composite material in ribidium salt solution instead It answers, obtains the titanium tantalum composite material of rubidium salt treatment, it is compound that the titanium tantalum composite material calcining of rubidium salt treatment is obtained the tantalum of titanium containing rubidium Material.
In technical solution in the present invention, preferably promote bone formation performance in order to smoothly mix rubidium and obtain, Blasting treatment, acid processing, the multiple pretreatment of alkali heat-treatment are carried out before mixing rubidium, wherein sandblasting can make titanium tantalum composite material surface Form micron order rough surface.Acid processing can make titanium tantalum composite material surface form the hole of micro/nano level, can effectively expande thin The contact area of born of the same parents and titanium tantalum composite material, are conducive to cell adherence in implant surface, while enhancing soft tissue interface cohesion Intensity, can effectively improve the biology performance of titanium tantalum composite material, and expand subsequent alkali heat-treatment and ion exchange effecting reaction Area.Titanium tantalum composite material surface after alkali heat-treatment can further generate the compound hole of micron/nano similar with bone structure Hole, and be a kind of good surface modifying method, can prepare has high-compatibility and the higher biology work of adhesive force with bone Property coating, this is that other surfaces method of modifying cannot achieve.It can get using alkali heat-treatment titanium tantalum composite material best thick The titanate layer of degree, and mechanical and corrosion resistance change of gradient titanium tantalum composite material is obtained, and it is compound to optimize titanium tantalum The bioactivity of material.The present invention, can be effective by sandblasting, acid processing and the exchange of alkali heat-treatment coupled ion and high-temperature calcination Ground mixes rubidium to titanium tantalum composite material surface, obtains and facilitates the bone tantalum composite material of titanium containing rubidium with clinical value.
In the present invention, three kinds of pretreatment modes are mutually to cooperate with, all linked with one another, such as if without sandblasting, With regard to carrying out alkali process and mixing rubidium processing, surface can not form most beneficial for osteoblast attachment, can effectively lure for acid processing (acid etching) Leading osteoblast is to the surface topography of osteoblast differentiation, and by sandblasting, acid etching carries out alkali process again, and treated with rubidium is mixed Titanium tantalum surface is a kind of micro-nano compound hole configurations, is conducive to induce preosteoblast to osteoblast differentiation.Wherein sandblasting It is a kind of physical means, titanium tantalum composite material micron order hole can be assigned, acid etching is a kind of chemical means, the micron after sandblasting Grade surface forms nanoscale structures, Effective Regulation Osteoblast Differentiation.
Preferred scheme, the temperature of the discharge plasma sintering are 950-1400 DEG C, sintering time 3-7min, sintering Pressure is 10-60MPa, and heating rate is 50-400 DEG C/min.
As a further preference, the temperature of the discharge plasma sintering is 1000-1300 DEG C, sintering time 4- 6min, sintering pressure 30-60MPa, heating rate are 50-80 DEG C/min.
For the technique of sandblasting, using the technique in conventional prior, sandblasting raw material is preferably quartz sand.
The process of preferred scheme, the acid processing is that the titanium tantalum composite material through blasting treatment is soaked in acid solution In, in 60-85 DEG C of processing 20-30h.
As a further preference, the acid solution is that 7:7:7-8 is mixed by volume for hydrochloric acid solution, sulfuric acid solution, water The mixed solution of acquisition;In the hydrochloric acid solution, the mass fraction for dissolving HCl is 37-39%, in the sulfuric acid solution, sulfuric acid Mass fraction be 95-98%.
Inventors have found that when using hydrochloric acid solution, sulfuric acid solution, water three by volume ratio mixing of the invention, acid etching Effect is best.
The process of preferred scheme, the alkali heat-treatment is that the titanium tantalum composite material through acid processing is immersed in aqueous slkali, In 60-85 DEG C of processing 20-30h.
Preferred scheme, OH in the aqueous slkali-Concentration be 2-5mol/L.
As a further preference, OH in the aqueous slkali-Concentration be 4-5mol/L.
Preferred scheme, the aqueous slkali are selected from least one of sodium hydroxide, potassium hydroxide or strontium hydroxide solution.
Titanium tantalum composite material through alkali heat-treatment is using deionized water cleaning, drying;The titanium tantalum for obtaining surface treatment is compound Material.
Preferred scheme, the rubidium salt are selected from least one of rubidium chloride, rubidium nitrate, rubidium sulfate.
Preferred scheme, in the ribidium salt solution, the concentration of rubidium ion is 1~5mol/L.
As a further preference, in the ribidium salt solution, the concentration of rubidium ion is 2.5~5mol/L.
Preferred scheme, it is 60-85 that surface treated titanium tantalum composite material, which is soaked in the temperature reacted in ribidium salt solution, DEG C, time 20-30h.
Preferred scheme, the temperature of the calcining are 550-700 DEG C, time 1-4h.
A kind of application for facilitating the bone tantalum composite material of titanium containing rubidium of the present invention, facilitates the bone tantalum composite material of titanium containing rubidium to answer for described It is used as bone substitution material.
Beneficial effects of the present invention:
What the present invention initiated, which provide one kind, facilitates bone titanium containing rubidium tantalum composite material and preparation method and application, in this hair In bright, provided to facilitate the bone tantalum composite material of titanium containing rubidium be that the titanium tantalum composite material as obtained by being sintered through SPS is mixed rubidium and obtained, Inventor is found surprisingly that through the titanium tantalum composite material of SPS sintering after mixing rubidium, there is optimal rush osteogenic ability.
In the present invention, in order to obtain preferably promote bone formation performance and it is optimal mix rubidium amount, facilitating the bone tantalum of titanium containing rubidium In the preparation process of composite material, sandblasting, acid etching, the triple pretreatments of alkali heat-treatment first have been carried out to titanium tantalum composite material, wherein Sandblasting assigns titanium tantalum composite material micron order hole, and micro-scale surface of the acid etching after sandblasting forms nanoscale structures, effectively adjust Osteoblast Differentiation is controlled, and it is multiple so that titanium tantalum composite material surface is further generated micron/nano similar with bone structure after alkali heat-treatment The hole of conjunction, and the titanate layer of optimum thickness is formed, for carrying out ion exchange incorporation rubidium.Pass through three kinds of pretreated phases Mutually collaboration, it is final obtain have it is optimal at looks and mix rubidium amount, so that it is compound to obtain the excellent tantalum of titanium containing rubidium for promoting bone formation performance Material.
Facilitate the bone tantalum composite material of titanium containing rubidium that there is good biocompatibility obtained by through the invention, can effectively solve Certainly titanium tantalum composite material the problems such as biocompatibility is bad in clinical application, has in clinical Bone Defect Repari before being widely applied Scape.
Technical solution of the present invention is further elaborated in the following with reference to the drawings and specific embodiments.
Detailed description of the invention
The rubidium element XPS testing result figure of Fig. 1 embodiment sample.
Fig. 2 is the test result figure that MC3T3 cell second day, the 4th day CCK-8 are planted in different embodiment samples;Its In, A: gained sample in comparative example 1, B: gained sample in embodiment 1, C: gained sample, D: institute in comparative example 2 in embodiment 2 Sample is obtained, E: gained sample in comparative example 3, F: gained sample in comparative example 4.
Fig. 3 is the result figure of sirius red stains after planting MC3T3 cell 10 days in different embodiment samples;Wherein, A: gained sample in comparative example 1, B: gained sample in embodiment 1, C: gained sample in embodiment 2.
Specific embodiment
Embodiment 1
With titanium tantalum alloy powder is taken, wherein in titanium tantalum alloy powder, by atomic ratio measuring, titanium: tantalum=1:30;Then by titanium tantalum alloy Powder is placed in discharge plasma sintering furnace and is sintered, and sintering is completed to obtain titanium tantalum composite material, the program of sintering are as follows: heating Speed be 70 DEG C/min, 1000 DEG C of sintering temperature, sintering time 5min;Sintering pressure is 60MPa.
Titanium tantalum composite material is subjected to blasting treatment, is subsequently placed in acid solution in 70 DEG C of progress acid processing 28h, wherein acid By hydrochloric acid, (mass fraction: 38%), (mass fraction: 96%) water is that 7:7:8 mixing obtains to sulfuric acid to solution by volume.It will be through The titanium tantalum composite material of peracid treatment is placed in 4M potassium hydroxide solution, in 70 DEG C of progress alkali heat-treatment 28h;Then deionized water is clear The titanium tantalum composite material after alkali heat-treatment is washed, to remove the solution of titanium tantalum composite material surface, dry drying is obtained at surface The titanium tantalum composite material of reason, then the titanium tantalum composite material of surface treatment is immersed in 5M ribidium salt solution and is carried out at ion exchange Reason, treatment temperature are 70 DEG C, time 28h, and the titanium tantalum composite material of above-mentioned rubidium salt treatment is finally carried out high-temperature calcination, calcining Temperature is 600 DEG C, duration 4h, air-cooled to get the tantalum composite material of titanium containing rubidium with furnace.
To assess the ingredient for facilitating the bone tantalum composite material of titanium containing rubidium, using XPS to facilitating the bone tantalum composite material of titanium containing rubidium Elemental analysis is carried out, the XPS figure of the gained tantalum composite material of titanium containing rubidium in Fig. 1 embodiment 1, as can be seen from the figure oneself successfully mixes Rubidium element.
In order to assess the skeletonization situation of cell, the proliferative conditions detection (cck8 reagent closes characterization) of cell is carried out respectively, with And preosteoblast collagen secretion situation (sirius red dyeing), collagen secretion are important mark of the early metaphase to osteoblast differentiation Will, the two illustrate the skeletonization situation of cell jointly from different perspectives.
The proliferative conditions of CCK-8 detection cell
Facilitate bone titanium containing rubidium tantalum composite material to the toxicity of cell and the competence for added value of cell to assess this, by acquisition Facilitate the bone tantalum composite material of titanium containing rubidium to carry out cell Proliferation and toxicity (CCK-8) evaluation and cell is characterized by CCK-8 kit Proliferative conditions.Its experimentation is as follows:
(1) it will facilitate bone titanium containing rubidium tantalum composite material and mouse preosteoblast MC3T3 co-incubation after three days, suction has been abandoned Full culture medium;
(2) the CCK-8 solution and cell interaction that concentration is 10% is added in every hole, in 37 DEG C of incubation 1h;
(3) after being incubated for, 100 μ L solution to 96 orifice plates are transferred out of from every hole;
(4) absorbance of solution, Detection wavelength 450nm are detected by microplate reader.
As a result as shown in B in Fig. 2.It is shown in figure, skeletonization is thin before being inoculated in the mouse for facilitating the bone tantalum composite material of titanium containing rubidium The cell activity of born of the same parents MC3T3 is stronger.The result shows that originally facilitate the bone tantalum composite material of titanium containing rubidium that there is good biocompatibility, Without cytotoxicity, there is excellent ability of cell proliferation.
Sirius red stains detect preosteoblast collagen secretion situation
Facilitate bone titanium containing rubidium tantalum composite material to the induced osteogenesis differentiation capability of preosteoblast to assess this, by acquisition Facilitate the bone tantalum composite material of titanium containing rubidium to carry out the detection of collagen secretion situation, is evaluated using sirius red stains, collagen secretion The raising of amount is important symbol of the preosteoblast to osteocyte early differentiation, and experimentation is as follows:
MC3T3-E1 cell inoculation to material surface is contaminated after complete medium culture 10 days using Picro-Sirius red Color reagent box analyzes the collagen synthesized into the cell.Specific step is as follows:
(1) culture medium is discarded, is cleaned cell 2 times using PBS, each 5min.
(2) 4% paraformaldehyde, the fixed 15min of room temperature are added in every hole.
(3) fixer is discarded, is cleaned cell 3 times using PBS, each 5min.
(4) PBS is discarded, 200 μ L sirius red stains liquid are added in every hole, and room temperature dyes 18h.
(5) Picro-Sirius red dye liquor is discarded, cell is cleaned repeatedly using deionized water, until washing lotion does not redden.
(6) it observes and takes pictures using inverted microscope (DFC420C, German Lycra).
(7) every hole is added 200 μ L0.2M NaOH: methanol=1:1 mixed liquors and is eluted to sample and measure 520nm Absorbance value under wavelength.
As a result as shown by B in fig. 3.It is shown in figure, the type of being inoculated in facilitates skeletonization before the mouse of the bone tantalum composite material of titanium containing rubidium The collagen content of cell secretion is higher than control group.
The result shows that the bone tantalum composite material of titanium containing rubidium is originally facilitated to have good biocompatibility, do not have cytotoxicity, tool There is excellent cell Proliferation, has the function of good induction preosteoblast Osteoblast Differentiation, illustrate the present embodiment 1 facilitates bone Ability is excellent!
Embodiment 2
With titanium tantalum alloy powder is taken, wherein in titanium tantalum alloy powder, by atomic ratio measuring, titanium: tantalum=1:20;Then by titanium tantalum alloy Powder is placed in discharge plasma sintering furnace and is sintered, and sintering is completed to obtain titanium tantalum composite material, the program of sintering are as follows: heating Speed be 50 DEG C/min, 1300 DEG C of sintering temperature, sintering time 5min;Sintering pressure is 30MPa.
Titanium tantalum composite material is subjected to blasting treatment, is subsequently placed in acid solution in 65 DEG C of progress acid processing for 24 hours, wherein acid Solution is 7:7 by hydrochloric acid (mass fraction: 37% writes occurrence), sulfuric acid (mass fraction: 95% writes occurrence) water by volume: 8 mixing obtain.Titanium tantalum composite material through peracid treatment is placed in 5M sodium hydroxide solution, for 24 hours in 65 DEG C of progress alkali heat-treatments; Then deionized water cleans the titanium tantalum composite material after alkali heat-treatment, dry to remove the solution of titanium tantalum composite material surface Drying, obtains the titanium tantalum composite material of surface treatment, then the titanium tantalum composite material of surface treatment is immersed in 2.5M ribidium salt solution Middle carry out ion-exchange treatment, treatment temperature are 65 DEG C, and the time is for 24 hours, finally by the titanium tantalum composite material of above-mentioned rubidium salt treatment High-temperature calcination is carried out, calcination temperature is 650 DEG C, duration 2h, air-cooled to get the tantalum composite material of titanium containing rubidium with furnace.
Facilitate bone titanium containing rubidium tantalum composite material to the toxicity of cell to assess this, facilitates the bone tantalum of titanium containing rubidium compound acquisition Material carries out cell Proliferation and toxicity (CCK-8) evaluation characterizes the proliferative conditions of cell by CCK-8 kit.Its experimentation It is as follows:
(1) it will facilitate bone titanium containing rubidium tantalum composite material and mouse preosteoblast MC3T3 co-incubation after three days, suction has been abandoned Full culture medium;
(2) the CCK-8 solution and cell interaction that concentration is 10% is added in every hole, in 37 DEG C of incubation 1h;
(3) after being incubated for, 100 μ L solution to 96 orifice plates are transferred out of from every hole;
(4) absorbance of solution, Detection wavelength 450nm are detected by microplate reader.
As a result as shown in C in Fig. 2.It is shown in figure, skeletonization is thin before being inoculated in the mouse for facilitating the bone tantalum composite material of titanium containing rubidium The cell activity of born of the same parents MC3T3 is stronger.The result shows that originally facilitate the bone tantalum composite material of titanium containing rubidium that there is good biocompatibility, Without cytotoxicity, there is excellent ability of cell proliferation.
Facilitate bone titanium containing rubidium tantalum composite material to the induced osteogenesis differentiation capability of preosteoblast to assess this, by acquisition Facilitate the bone tantalum composite material of titanium containing rubidium to carry out the detection of collagen secretion situation, is evaluated using sirius red stains, collagen secretion The raising of amount is important symbol of the preosteoblast to osteocyte early differentiation, and experimentation is as follows:
MC3T3-E1 cell inoculation to material surface is contaminated after complete medium culture 10 days using Picro-Sirius red Color reagent box analyzes the collagen synthesized into the cell.Specific step is as follows:
(1) culture medium is discarded, is cleaned cell 2 times using PBS, each 5min.
(2) 4% paraformaldehyde, the fixed 15min of room temperature are added in every hole.
(3) fixer is discarded, is cleaned cell 3 times using PBS, each 5min.
(4) PBS is discarded, 200 μ L sirius red stains liquid are added in every hole, and room temperature dyes 18h.
(5) Picro-Sirius red dye liquor is discarded, cell is cleaned repeatedly using deionized water, until washing lotion does not redden.
(6) it observes and takes pictures using inverted microscope (DFC420C, German Lycra).
(7) every hole is added 200 μ L0.2M NaOH: methanol=1:1 mixed liquors and is eluted to sample and measure 520nm Absorbance value under wavelength.
As a result as shown in C in Fig. 3.It is shown in figure, skeletonization is thin before being inoculated in the mouse for facilitating the bone tantalum composite material of titanium containing rubidium The collagen content of intracrine is higher than control group.
The result shows that the bone tantalum composite material of titanium containing rubidium is originally facilitated to have good biocompatibility, do not have cytotoxicity, tool There is excellent cell Proliferation, has the function of good induction preosteoblast Osteoblast Differentiation, illustrate the present embodiment 2 facilitates bone Ability is excellent!
Comparative example 1
Its comparative example other conditions are same as Example 2, are only the acid solutions of the use in sour treatment process, by hydrochloric acid (mass fraction: 37% writes occurrence), sulfuric acid (mass fraction: 95% writes occurrence) water are that 1:1:8 mixing obtains by volume.
In order to assess the skeletonization situation of cell, the sample of comparative example 1 is carried out to the proliferative conditions detection (cck8 of cell respectively Reagent closes characterization) and preosteoblast collagen secretion situation (sirius red dyeing), test method is consistent with embodiment, As a result the proliferative conditions of cell are as shown in A in Fig. 2, and the secretion collagen ability of osteoblast is as shown in A in fig. 3, as the result is shown Both it is weaker than embodiment 1-2, can proves that the titanium tantalum composite material in embodiment has and more preferably promote osteogenic ability.
Comparative example 2
Other conditions and embodiment 2 are consistent, only without ion exchange, do not mix rubidium, i.e., gained is to be surface-treated Titanium tantalum composite material.
2 gained sample of comparative example carries out to the proliferative conditions detection (cck8 reagent close characterization) of cell, test method with Embodiment is consistent, and as a result as shown in D in Fig. 2, skeletonization before the mouse for the titanium tantalum composite material being inoculated in comparative example 2 is shown in figure The proliferative capacity of cell is significantly lower than embodiment 1-2, can prove that the titanium tantalum composite material in embodiment has and more preferably facilitate Bone ability.
Comparative example 3
Other conditions and embodiment 2 are consistent, only without blasting treatment with processing of turning sour, but by gained titanium tantalum composite wood The surface treatment of material directly carries out alkali heat-treatment.
3 gained sample of comparative example carries out to the proliferative conditions detection (cck8 reagent close characterization) of cell, test method with Embodiment is consistent,
As a result as shown in E in Fig. 2.Shown in figure, be inoculated in front of the mouse of the tantalum composite material of titanium containing rubidium in comparative example 3 at The proliferative capacity of osteocyte is significantly lower than embodiment 1-2, can prove that the titanium tantalum composite material in embodiment has and more preferably promote Osteogenic ability.
Comparative example 4
Other conditions and embodiment 2 are consistent, be only the preparation method of titanium tantalum composite material are vacuum-sintering, vacuum-sintering Specific step is as follows:
With titanium tantalum alloy powder is taken, wherein in titanium tantalum alloy powder, by atomic ratio measuring, titanium: tantalum=1:20;Then by titanium tantalum alloy Powder is placed in compression moulding in cold isostatic press, and the pressing pressure is 200MPa, then pressing time 4min will be pressed into The green compact of type, which are placed in vacuum-sintering, to be sintered, and control vacuum degree is 10-4Pa, the temperature of vacuum-sintering are 1200 DEG C, sintering time For 2h, heating rate is 45 DEG C/min.
4 gained sample of comparative example carries out to the proliferative conditions detection (cck8 reagent close characterization) of cell, test method with Embodiment is consistent,
As a result as shown in F in Fig. 2.Shown in figure, be inoculated in front of the mouse of the tantalum composite material of titanium containing rubidium in comparative example 4 at The proliferative capacity of osteocyte is significantly lower than embodiment 1-2, can prove that the titanium tantalum composite material in embodiment has and more preferably promote Osteogenic ability.

Claims (10)

1. one kind facilitates the bone tantalum composite material of titanium containing rubidium, it is characterised in that: the tantalum composite material of titanium containing rubidium is by titanium tantalum composite wood Material is mixed rubidium through surface and is obtained, and the titanium tantalum composite material is formed by discharge plasma sintering.
2. one kind according to claim 1 facilitates the bone tantalum composite material of titanium containing rubidium, it is characterised in that: the titanium tantalum composite wood In material, by atomic ratio measuring, titanium: tantalum=1:10-30.
3. a kind of preparation method for facilitating the bone tantalum composite material of titanium containing rubidium according to claim 1 or 2, which is characterized in that Include the following steps: that titanium tantalum alloy powder, which is carried out discharge plasma sintering, obtains titanium tantalum composite material, titanium tantalum composite material is successively Carry out blasting treatment, acid is handled, alkali heat-treatment obtains the titanium tantalum composite material of surface treatment, then by surface treated titanium tantalum Composite material, which is soaked in ribidium salt solution, to react, and obtains the titanium tantalum composite material of rubidium salt treatment, and the titanium tantalum of rubidium salt treatment is compound Calcined material obtains the tantalum of titanium containing rubidium composite material.
4. a kind of preparation method for facilitating the bone tantalum composite material of titanium containing rubidium according to claim 3, which is characterized in that described The temperature of discharge plasma sintering is 950-1400 DEG C, sintering time 3-7min, sintering pressure 10-60MPa, heating rate For 50-400 DEG C/min.
5. a kind of preparation method for facilitating the bone tantalum composite material of titanium containing rubidium according to claim 3, it is characterised in that: described The process of acid processing is that the titanium tantalum composite material through blasting treatment is soaked in acid solution, in 60-85 DEG C of processing 20-30h.
6. a kind of preparation method for facilitating the bone tantalum composite material of titanium containing rubidium according to claim 5, which is characterized in that described Acid solution is the mixed solution that the 7:7:7-8 mixing by volume of hydrochloric acid solution, sulfuric acid solution, water obtains;In the hydrochloric acid solution, The mass fraction of HCl is dissolved for 37-39%, and in the sulfuric acid solution, the mass fraction of sulfuric acid is 95-98%.
7. a kind of preparation method for facilitating the bone tantalum composite material of titanium containing rubidium according to claim 3, which is characterized in that described The process of alkali heat-treatment is that the titanium tantalum composite material through acid processing is immersed in aqueous slkali, in 60-85 DEG C of processing 20-30h, institute State OH in aqueous slkali-Concentration be 2-5mol/L, the aqueous slkali is in sodium hydroxide, potassium hydroxide or strontium hydroxide solution At least one.
8. a kind of preparation method for facilitating the bone tantalum composite material of titanium containing rubidium according to claim 3, which is characterized in that described Rubidium salt is selected from least one of rubidium chloride, rubidium nitrate, rubidium sulfate, and in the ribidium salt solution, the concentration of rubidium ion is 1~ 5mol/L。
9. a kind of preparation method for facilitating the bone tantalum composite material of titanium containing rubidium according to claim 3, which is characterized in that described The temperature of calcining is 550-700 DEG C, time 1-4h.
10. a kind of application for facilitating the bone tantalum composite material of titanium containing rubidium according to claim 1 or 2, is characterized in that: will be described The bone tantalum composite material of titanium containing rubidium is facilitated to apply as bone substitution material.
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