CN109529124A - A kind of preparation method of graphite alkenes material/hydroxyapatite crystal whisker composite material - Google Patents
A kind of preparation method of graphite alkenes material/hydroxyapatite crystal whisker composite material Download PDFInfo
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- CN109529124A CN109529124A CN201811375913.6A CN201811375913A CN109529124A CN 109529124 A CN109529124 A CN 109529124A CN 201811375913 A CN201811375913 A CN 201811375913A CN 109529124 A CN109529124 A CN 109529124A
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- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 38
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 38
- 239000013078 crystal Substances 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 21
- 239000010439 graphite Substances 0.000 title claims abstract description 21
- -1 graphite alkenes Chemical class 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 49
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims abstract description 7
- 235000019838 diammonium phosphate Nutrition 0.000 claims abstract description 7
- 239000011575 calcium Substances 0.000 claims abstract description 6
- 239000010452 phosphate Substances 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000012153 distilled water Substances 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000005253 cladding Methods 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 25
- 210000000988 bone and bone Anatomy 0.000 abstract description 16
- 230000007547 defect Effects 0.000 abstract description 8
- 241000446313 Lamella Species 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 239000011535 reaction buffer Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 206010048038 Wound infection Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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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
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/42—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
- A61L27/425—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix of phosphorus containing material, e.g. apatite
-
- 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
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/42—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
- A61L27/422—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix of carbon
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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
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Transplantation (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Dermatology (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- General Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
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- Materials For Medical Uses (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The present invention discloses a kind of preparation method of graphite alkenes material/hydroxyapatite crystal whisker composite material, belongs to biomedical materials field.Hydroxyapatite crystal whisker provides phosphate radical by calcium source, diammonium hydrogen phosphate of calcium nitrate in composite material of the present invention, urea makees reaction buffer, sorbierite is as template, nitric acid adjusts the pH value of initial reaction stage, makees additive with graphene oxide, graphene or one or more of two kinds of mixtures etc..Compound is prepared with water-bath homogenous synthesis, then by being aged, cleaning, being dried to obtain composite material；The structure of composite material are as follows: graphene oxide layer two-dimensional is about 80 μm, and hydroxyapatite crystal whisker is grown on above-mentioned lamella, and 15~100 μm of whisker length, averagely about 70 μm.The preparation of composite material of the present invention has process simply controllable, with short production cycle, stable yield；The compound being prepared not only has the Biological characteristics of hydroxyapatite crystal whisker, while having the advantages that the mechanical property for improving matrix of graphene oxide, grapheme material, there is potential application prospect in terms of Bone Defect Repari bone tissue engineer.
Description
Technical field
The present invention relates to a kind of preparation methods of graphite alkenes material/hydroxyapatite crystal whisker composite material, are mainly used for
The bone tissue engineers such as Bone Defect Repari, belong to biomedical materials field.
Background technique
Bone defect is clinical relatively conventional one of wound, and lesser bone defect patient can be fully recovered by self-regeneration,
And for large segmental bone defect, since self-regeneration is limited, and materials difficulty is faced by bone collection mode, wound infection, is immunized
The difficulties such as repel, therefore bone tissue engineer has unique advantage facing Bone Defect Repari problem.Bracket as bone tissue engineer application
Material is used to bone graft substitute, can satisfy biomechanics characteristic and structural repair function.Timbering material is implanted into human body
After defect, under the double action of body fluid and blood, reaches a bracket lip and dissolve the equilibrium process that new bone side generates.
Currently, the mechanical strength of the timbering material for bone tissue engineer is generally 0.5~1.5MPa, hydroxylapatite powder
The mechanical property intensity at end is poor, and hydroxyapatite crystal whisker plays the role of reinforcement, hydroxy-apatite when preparing compound rest
Each performance of stone crystal whisker is better than nanometer hydroxyapatite, selects hydroxyapatite crystal whisker to carry out with graphite alkenes material compound, mainly
It is the bioactivity for not only having retained hydroxyapatite, biocompatibility, but also utilizes the mechanical property of graphene oxide, graphene to multiple
The properties of condensation material are improved.And studies have shown that graphene nano sheet material etc. can with the compound of hydroxyapatite
Retain bioactivity, and there is certain anti-microbial property.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation sides of graphite alkenes material/hydroxyapatite crystal whisker composite material
Method prepares the compound that pine needle shape HA whisker is combined with the graphene oxide of big lamella, graphene, with hydrothermal synthesis legal system
Standby compound out enables to graphene oxide or graphene and HA whisker to attach growth together；Specifically include following step
It is rapid:
(1) calcium nitrate, urea, diammonium hydrogen phosphate, sorbierite, concentrated nitric acid are added in distilled water and sufficiently dissolution obtain solution A,
Ca in solution A2+Molar concentration be 0.167~0.334mol/L, PO4 3-Molar concentration be 0.100~0.200mol/L, calcium
The molar concentration rate of ion and phosphate radical is 1.67；0.749~1.000mol/L of urea molar concentration；Sorbierite molar concentration
0.011~0.022mol/L；0.167~0.334mol/L of concentrated nitric acid molar concentration.
(2) in graphite alkenes material and generation HA Theoretical Mass than the ratio for 1:17.7~26.5, by graphite alkenes material
Material is dissolved in distilled water, carries out ultrasonic vibration, obtains solution B, and the graphite alkenes material is graphene oxide, in graphene
One or two kinds of mixtures.
(3) it takes solution B made from step (2) to be added drop-wise in solution A, continues 1~2h of stirring, then carry out boiling water bath and add
Heat is aged 5~7 days, is adjusted pH with ammonium hydroxide in ageing process, is maintained the pH of solution between 10~11, is used after the completion of ageing
It is 7.0 that deionized water, which is cleaned to pH value, filters, is dry, graphene oxide or graphene/hydroxyapatite crystal whisker material is made
Expect compound.
Hydroxyapatite described in the composite material that the present invention is prepared be whisker-like material, whisker length be 15~
100 μm, average length is 70 μm, 30~100 μm of the lamella size of graphite alkenes material, about 80 μm of average platelet size, the two
Preferably attach growth together.
Preferably, step (2) solution of the present invention carries out ultrasonic vibration, 250~300w of ultrasonic power, and ultrasonic time is
1~2h carries out the layering of graphene oxide or grapheme material.
Preferably, rate of addition of the present invention is 5ml/min~10ml/min, and the volume ratio of solution A and solution B is 7:
1~10:1。
Preferably, step (3) of the present invention carries out the boiling water bath time after preparing mixed solution as 24~36h.
Beneficial effects of the present invention
(1) graphene oxide layer prepared by the present invention is larger, and the whisker length of growth is longer, can be subsequent timbering material
Intensity provides possibility.Graphene oxide layer is about 30~100 μm, and average length layer is about 80 μm, hydroxy-apatite
Stone crystal whisker is more equably grown on graphene oxide, graphene sheet layer, and the length of hydroxyapatite crystal whisker is 15 ~ 100 μm,
Average length is about 70 μm, and graphene oxide, graphene sheet layer are not destroyed because of the growth of hydroxyapatite crystal whisker, instead
It being capable of preferably toughening hydroxyapatite crystal whisker.
(2) in composite material prepared by the present invention, the combination of graphene oxide or graphene and hydroxyapatite crystal whisker makes
It obtains compound phase more evenly, avoids split-phase serious problems caused by mechanical mixture, so that mechanical strength is than single use one kind
Substance increases, and therefore, there is potential application prospect in Bone Defect Repari and bone tissue engineer.
(3) the advantages that the method for the invention is easy to operate, low manufacture cost, process is controllable, the compound tool prepared
Have that biocompatibility is good, the good characteristics such as bioactivity.
Detailed description of the invention
Fig. 1 is the XRD diagram for the compound that 1 water-bath of embodiment is prepared；
Fig. 2 is the FT-IR figure for the compound that 1 water-bath of embodiment is prepared；
Fig. 3 is the SEM figure for the compound that 1 water-bath of embodiment is prepared；
Fig. 4 is the TEM figure for the compound that 1 water-bath of embodiment is prepared.
Specific embodiment
Invention is further described in detail in the following with reference to the drawings and specific embodiments, but protection scope of the present invention is simultaneously
It is not limited to the content.
The embodiment of the present invention is raw materials used: calcium nitrate Ca (NO3)2·4H2O, urea (H2NCONH2), diammonium hydrogen phosphate
(NH4)HPO4, sorbierite C6H14O6, concentrated nitric acid HNO3, graphene oxide GO, ammonium hydroxide (NH3·H2It O), is that commercially available analysis is pure.
Embodiment 1
A kind of preparation method of graphite alkenes material/hydroxyapatite crystal whisker composite material, specifically includes the following steps:
(1) in the beaker equipped with 400ml distilled water, calcium nitrate 15.7748g, diammonium hydrogen phosphate 5.2824g are sequentially added, is urinated
Plain 18g, sorbierite 0.8036g, concentrated nitric acid 3ml make raw material be completely dissolved to obtain solution A, beaker be placed on magnetic stirring apparatus with
350 revs/min of rate stirs, and the calcium ion concentration in solution is 0.167mol/L, and the concentration of phosphate radical is 0.100 mol/
L adjusts the buffer of pH when urea is as subsequent water-bath, the pH value that nitric acid adjusts initial reaction stage is 4.5, and sorbierite is as template
Agent.
(2) 0.2532g graphene oxide is dissolved in the beaker for filling the distilled water of 40ml, is stirred well under room temperature molten
Solution, wherein the mass ratio of the quality of graphene oxide and HA whisker theory production quantity is 1:26.5, and wherein blender revolution is 250
Rev/min, mixing time 1h after the completion of stirring, places the beaker ultrasound 1h in the ultrasonic vibration instrument that power is 250w, is made
Solution B.
(3) solution B made from step (2) is taken to be added drop-wise in solution A with digital display constant flow pump with the speed of 5ml/min.
(4) after the completion of titrating, boiling water bath is carried out for 24 hours, after the completion of water-bath, adjusting pH value with ammonia spirit is 10, is carried out old
Change 5d.
(5) after the completion of being aged, constantly clean with deionized water until the pH value of solution is 7.0, then is filtered, dried,
It is put into the drying that the drying box that temperature is 37 ° carries out 48h when dry, the compound of graphene oxide/hydroxyapatite crystal whisker is made
Material.
The XRD of compound manufactured in the present embodiment is as shown in Figure 1, to occur peak type as seen from the figure, in compound sharp
Characteristic peak, these characteristic peaks be respectively belonging to (002), (210), (211), (112), (300), (222), (213), (321),
(410), peak type sharply illustrate, characteristic peak obviously illustrate crystallinity containing hydroxyapatite and hydroxyapatite in compound compared with
It is good.And there is characteristic peak in 2 θ=11.16 ° in graphene oxide, and the characteristic peak near 2 θ=26 ° of graphite disappears, and illustrates stone
Ink has been fully oxidized；In compound occur point and the characteristic peak of strong hydroxyapatite, illustrate that GO does not interfere with the generation of HA.
Compound FT-IR that the present embodiment is prepared is as shown in Fig. 2, the curve of compound is almost as seen from Figure 2
It is consistent with HA, illustrate to contain HA in compound.The compound sem analysis that the present embodiment is prepared is as shown in figure 3, the crystalline substance prepared
Must be evenly laid out on the lamella of graphene oxide, about 70 μm of whisker length.Fig. 4 is the transmission plot of compound, can be with from figure
Find out that whisker is tightly wrapped up in graphene oxide to be attached to together, can be obtained from the diffraction pattern typed it out, the addition of graphene oxide changes
The lattice fringe of hydroxyapatite, part striped broaden, and part striped narrows, illustrate graphene oxide and hydroxyapatite whisker
Chemical action must have occurred, the two has carried out compound.
Embodiment 2
A kind of preparation method of graphite alkenes material/hydroxyapatite crystal whisker composite material, specifically includes the following steps:
(1) it in the beaker equipped with 400ml distilled water, is placed on magnetic stirring apparatus and is stirred with 400 revs/min of rate, successively
Calcium nitrate 23.6632g, diammonium hydrogen phosphate 7.9236g, urea 20g is added, sorbierite 1.2055g, concentrated nitric acid 5ml keep raw material complete
Fully dissolved obtains solution A, and the calcium ion concentration in solution is 0.251mol/L, and the concentration of phosphate radical is 0.150 mol/L, urea
The buffer of pH is adjusted when as subsequent water-bath, the pH value that nitric acid adjusts initial reaction stage is 4, and sorbierite is as template.
(2) it by 0.5064g graphene, is dissolved in the beaker for containing the distilled water of 50ml, dissolution is stirred well under room temperature,
The quality of middle graphene and the mass ratio of HA whisker theory production quantity are 1:19.9, and wherein blender revolution is 300 revs/min,
Mixing time is 1.5h, after the completion of stirring, places the beaker ultrasound 1.5h in the ultrasonic vibration instrument that power is 300w, obtained solution
B。
(3) solution B made from step (2) is taken to be added drop-wise in solution A with digital display constant flow pump with the speed of 7ml/min.
(4) after the completion of titrating, boiling water bath is carried out for 24 hours, after the completion of water-bath, adjusting pH value with ammonia spirit is 10.5, is carried out
It is aged 6d.
(5) it after the completion of being aged, is constantly cleaned with deionized water until the pH value of solution is 7.0 neutral, then is filtered, done
It is dry, it is put into the drying that the drying box that temperature is 37 ° carries out 60h when dry, the composite wood of graphene/hydroxyapatite crystal whisker is made
Material.
After testing, the composite structure and performance that the present embodiment is prepared are similar to Example 1.
Embodiment 3
A kind of preparation method of graphite alkenes material/hydroxyapatite crystal whisker composite material, specifically includes the following steps:
(1) it in the beaker equipped with 400ml distilled water, is placed on magnetic stirring apparatus and is stirred with 500 revs/min of rate, successively
Calcium nitrate 31.5496g, diammonium hydrogen phosphate 10.5648g, urea 24g is added, sorbierite 1.6072g, concentrated nitric acid 6ml make raw material
It is completely dissolved to obtain solution A, the calcium ion concentration in solution is 0.334mol/L, and the concentration of phosphate radical is 0.200 mol/L, urine
The buffer of pH is adjusted when element is as subsequent water-bath, the pH value that nitric acid adjusts initial reaction stage is 3, and sorbierite is as template.
(2) by the mixture of 0.7596g graphene oxide and graphene, the wherein mass ratio of graphene oxide and graphene
It for 1:1, is dissolved in the beaker for containing the distilled water of 60ml, dissolution is stirred well under room temperature, wherein graphene oxide, graphene
The mass ratio of quality and generation HA whisker theoretical value is 1:17.7 after mixing, and wherein blender revolution is 350 revs/min, stirring
Time is 2h, after the completion of stirring, places the beaker ultrasound 2h, obtained solution B in the ultrasonic vibration instrument that power is 350w.
(3) solution B made from step (2) is taken to be added drop-wise in solution A with digital display constant flow pump with the speed of 10ml/min.
(4) after the completion of titrating, boiling water bath 36h is carried out, after the completion of water-bath, adjusting pH value with ammonia spirit is 11, is carried out old
Change 7d.
(5) after the completion of being aged, constantly clean with deionized water until the pH value of solution is 7.0, then is filtered, dried,
It is put into the drying that the drying box that temperature is 37 ° carries out 72h when dry, graphene oxide, graphene/hydroxyapatite crystal whisker is made
Composite material.
After testing, the composite structure and performance that the present embodiment is prepared are similar to Example 1.
Claims (4)
1. a kind of preparation method of graphite alkenes material/hydroxyapatite crystal whisker composite material, which is characterized in that specifically include with
Lower step:
(1) calcium nitrate, urea, diammonium hydrogen phosphate, sorbierite, concentrated nitric acid are added in distilled water and sufficiently dissolution obtain solution A,
Ca in solution A2+Molar concentration be 0.167~0.334mol/L, PO4 3-Molar concentration be 0.100~0.200mol/L, calcium
The molar concentration rate of ion and phosphate radical is 1.67；0.749~1.000mol/L of urea molar concentration；Sorbierite molar concentration
0.011~0.022mol/L；0.167~0.334mol/L of concentrated nitric acid molar concentration；
(2) in graphite alkenes material and generation HA Theoretical Mass than the ratio for 1:17.7~26.5, graphite alkenes material is molten
In distilled water, ultrasonic vibration is carried out, obtains solution B, the graphite alkenes material is one of graphene oxide, graphene
Or two kinds of mixture；
(3) it takes solution B made from step (2) to be added drop-wise in solution A, continues 1~2h of stirring, then carry out boiling water bath heating, it is old
Change 5~7 days, adjust pH with ammonium hydroxide in ageing process, maintain the pH of solution between 10~11, deionization is used after the completion of ageing
It is 7.0 that water, which is cleaned to pH value, filters, is dry, graphene oxide or graphene/hydroxyapatite crystal whisker Material cladding is made
Object.
2. graphite alkenes material/hydroxyapatite crystal whisker composite material preparation method, feature exist according to claim 1
Carry out ultrasonic vibration, 250~300w of ultrasonic power in: step (2) solution, ultrasonic time is 1~2h, carry out graphene oxide,
Or the layering of grapheme material.
3. graphite alkenes material/hydroxyapatite crystal whisker composite material preparation method, feature exist according to claim 1
It is 5ml/min~10ml/min in: rate of addition, the volume ratio of solution A and solution B is 7:1 ~ 10:1.
4. graphite alkenes material/hydroxyapatite crystal whisker composite material preparation method, feature exist according to claim 1
In: step (3) carries out the boiling water bath time after preparing mixed solution as 24~36h.
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| CN201811375913.6A CN109529124A (en) | 2018-11-19 | 2018-11-19 | A kind of preparation method of graphite alkenes material/hydroxyapatite crystal whisker composite material |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0416600A (en) * | 1990-05-09 | 1992-01-21 | Karushiide:Kk | Production of carbonate-containing hydroxyapatite whisker |
| KR101222019B1 (en) * | 2011-08-26 | 2013-01-14 | 한국과학기술원 | Graphene-biomineral hybrid films and preparing method thereof |
| US20140248319A1 (en) * | 2011-09-09 | 2014-09-04 | Board Of Trustees Of The University Of Arkansas | Multicomponent and biocompatible nanocomposite materials, methods of synthesizing same and applications of same |
| CN104415399A (en) * | 2013-09-10 | 2015-03-18 | 中国科学院宁波材料技术与工程研究所 | Hydroxyapatite/graphene nano-composite powder and preparation method thereof |
| CN106620871A (en) * | 2017-01-09 | 2017-05-10 | 中国人民解放军第二军医大学第二附属医院 | Bone repairing product taking degradable copolymer-calcium silicate composite bone repairing material enhanced by hydroxyapatite whisker as raw material |
| CN106986625A (en) * | 2017-03-17 | 2017-07-28 | 山东师范大学 | A kind of preparation method of graphene/hydroxyapatite composite ceramic material |
| CN107847640A (en) * | 2015-07-29 | 2018-03-27 | 卓英医疗有限责任公司 | The Biocomposite material of the graphene oxide of biomineralization and its purposes for bone tissue engineer |
-
2018
- 2018-11-19 CN CN201811375913.6A patent/CN109529124A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0416600A (en) * | 1990-05-09 | 1992-01-21 | Karushiide:Kk | Production of carbonate-containing hydroxyapatite whisker |
| KR101222019B1 (en) * | 2011-08-26 | 2013-01-14 | 한국과학기술원 | Graphene-biomineral hybrid films and preparing method thereof |
| US20140248319A1 (en) * | 2011-09-09 | 2014-09-04 | Board Of Trustees Of The University Of Arkansas | Multicomponent and biocompatible nanocomposite materials, methods of synthesizing same and applications of same |
| CN104415399A (en) * | 2013-09-10 | 2015-03-18 | 中国科学院宁波材料技术与工程研究所 | Hydroxyapatite/graphene nano-composite powder and preparation method thereof |
| CN107847640A (en) * | 2015-07-29 | 2018-03-27 | 卓英医疗有限责任公司 | The Biocomposite material of the graphene oxide of biomineralization and its purposes for bone tissue engineer |
| CN106620871A (en) * | 2017-01-09 | 2017-05-10 | 中国人民解放军第二军医大学第二附属医院 | Bone repairing product taking degradable copolymer-calcium silicate composite bone repairing material enhanced by hydroxyapatite whisker as raw material |
| CN106986625A (en) * | 2017-03-17 | 2017-07-28 | 山东师范大学 | A kind of preparation method of graphene/hydroxyapatite composite ceramic material |
Non-Patent Citations (2)
| Title |
|---|
| 何前军: "羟基磷灰石晶须的控制合成与机理探讨", 《武汉化工学院学报》 * |
| 潘炳力: "《先进高分子材料摩擦学》", 31 October 2016 * |
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