CN103705977A - Doped hydroxyapatite coating containing carbon/carbon composite material and preparation method thereof - Google Patents
Doped hydroxyapatite coating containing carbon/carbon composite material and preparation method thereof Download PDFInfo
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- CN103705977A CN103705977A CN201310753100.7A CN201310753100A CN103705977A CN 103705977 A CN103705977 A CN 103705977A CN 201310753100 A CN201310753100 A CN 201310753100A CN 103705977 A CN103705977 A CN 103705977A
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Abstract
The invention discloses a preparation method of a doped hydroxyapatite coating containing carbon/carbon composite material. The preparation method comprises the following steps: depositing a calcium hydrophosphate coating on the surface of the carbon/carbon composite material by an induction heating method; by means of potassium hydroxide hydro-thermal treatment, converting into a pure hydroxyapatite coating; and then, adding doping ion-containing bioglass in alkaline liquor for hydro-thermal treatment to obtain the doping ion-containing hydroxyapatite carbon/carbon composite material. According to the invention, bioglass is used to replace a chemical reagent to release ions required by osteolite under a hydro-thermal condition to dope the hydroxyapatite so as to obtain the high performance doped hydroxyapatite coating, thereby overcoming poor compatibility by directly using the chemical reagent to dope and multifarious metabolic problems.
Description
Technical field
The invention belongs to technical field of biological material, particularly a kind of containing doping type hydroxyapatite coating layer carbon/carbon compound material and preparation method thereof.
Background technology
Hydroxyapatite is that skeleton is organized main component, and after it implants, calcium and the phosphorus material surface that can dissociate is absorbed by bodily tissue, and the tissue that makes new advances of growth.And hydroxyapatite is compared with other bioactive materials, the inorganic salt in its composition, structure and skeleton is more approaching, has the regeneration function of guiding and induction skeleton and the synostosis ability that improves skeleton; In non-bone environment, hydroxyapatite still can be induced generation and the formation of bone in vivo, is one of main coating material of current biomaterial primary study and exploitation.Yet the fragility of hydroxyapatite has limited its application in bone reparation and alternate material.So when hydroxyapatite is applied to the field of artificial bone, being applied on high tough medical material is the main path of expanding its range of application; Wherein, hydroxyapatite is applied to the application potential on carbon/carbon compound material (C/C) surface larger.
C/C belongs to bio-inert material, its good biocompatibility, comprehensive mechanical property is excellent, especially its modulus and skeleton are suitable, can avoid stress shielding phenomenon, and reduce embedded material bone resorption around, avoid prosthetic loosening, extend the service life of embedded material, reduced the twice replaced misery of patient.Especially on surface, apply after hydroxyapatite, not only given the biological activity of C/C, and reduced because friction causes carbon granule the risk of polluting tissue, causing hepatocarcinoma.Therefore this novel composite has good potentiality in bone implant material application.
Yet the osteolith in human body is not pure hydroxyapatite.Osteolith is a class non-quantitation ratio, fault of construction type hydroxyapatite, its pattern is nano-sheet, in structure, along six square shafts, there is one " tunnel ", cause the hydroxyl ion in it easily by other ion, to be replaced, thereby in apatite, contain a small amount of Na, K, Mg, Si, F, CO
3 2-, citrate plasma.The existence of these ions not only makes the part calcium ion disappearance in osteolith composition, also affects the degree of crystallinity of apatite, and then affects metabolism, stability and the mechanical property of bone.In addition, the composition in osteolith, ratio, degree of crystallinity are with age, position difference and different, and these variations make skeleton have different functions and performance.Therefore containing the apatite of doping type ion, to using as bone reparation and alternate material be main attack goal in research in recent years in exploitation.
At present, the method of preparing doping type hydroxyapatite coating layer mainly contains three kinds, one, infusion method: prepare after hydroxyapatite coating layer by cathodic electrochemical deposition, hydroxyapatite coating layer is soaked in to a period of time in lanthanum nitrate hexahydrate, sample is taken out and is dried, obtain lanthanum doped hydroxyapatite composite coating; Two, coprecipitation: adopt NH
4h
2pO
4, Ca (NO
3)
2and NaNO
3for raw material, with the standby hydroxyapatite coating layer of mixing sodium type of electrochemical co-deposition legal system; Three, hydro-thermal method: adopt sodium silicate as raw material, carbon containing/carbonate hydroxyapatite coating is carried out to hydrothermal treatment consists, obtained hydroxyapatite siliceous, sodium ion.Yet above-mentioned three kinds of methods are all to using chemical reagent to obtain doped hydroxyapatite as doped raw material.In these reagent, part is poisonous to skeleton, or these reagent are except containing dopant ion, and subsidiary other ion has also increased subsequent treatment, even brought the serious problems of biocompatibility.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art, provide a kind of containing doping type hydroxyapatite coating layer carbon/carbon compound material preparation method, using and solve in prior art owing to adopting chemical reagent to cause the poor problem of process, biocompatibility poisonous, that the foreign ion that adulterated increases subsequent treatment as doped raw material.
Another object of the present invention is to provide a kind of non-toxic and safe, be easy to metabolism and biocompatibility good containing doping type hydroxyapatite coating layer carbon/carbon compound material.
Another object of the present invention is to provide a kind of and be used as bone repair and skeleton alternate material containing doping type hydroxyapatite coating layer carbon/carbon compound material.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A preparation method that contains the carbon/carbon compound material of doping type hydroxyapatite coating layer, comprises the steps:
Carbon/carbon compound material is placed in to salpeter solution and carries out room temperature processing, the time is 5～10 minutes, and wherein, described carbon/carbon compound material should be immersed in concentrated nitric acid;
Carbon/carbon compound material after above-mentioned hydrothermal treatment consists is placed in to the mobile mixed aqueous solution containing calcium salt and dihydric phosphate, and the flow velocity of described mixed aqueous solution is 200ml/min～2L/min, and sedimentation time is 15 minutes～2 hours, and temperature is 100～200 ℃; Eddy-current heating, described eddy-current heating is for passing through induction heating power pyrogenicity, the frequency of oscillation of described induction heating power is 1KHz～400KHz, output is 0.1KW～10KW, make its surface deposition go out calcium hydrogen phosphate coating, wherein, above-mentioned calcium salt is 0.5～1:0.3～0.6 with the mole ratio of dihydric phosphate;
The above-mentioned carbon/carbon compound material that deposits calcium hydrogen phosphate coating is placed in to the first alkaline solution and carries out hydrothermal treatment consists, the time is 24～96 hours, and temperature is 100～220 ℃, obtains the carbon/carbon compound material of hydroxyl apatite coating; Wherein, described in deposit calcium hydrogen phosphate coating carbon/carbon compound material should be immersed in completely in alkali liquor, its volume ratio is 50～10:1;
The carbon/carbon compound material of above-mentioned hydroxyl apatite coating is placed in to the second alkaline solution with the bio-vitric that contains dopant ion and carries out hydrothermal treatment consists, temperature is 100～220 ℃, time is 24～96 hours, described bio-vitric is at least one in silicate glass, phosphate glass, obtains above-mentioned containing doping type hydroxyapatite coating layer carbon/carbon compound material.
And, a kind of containing doping type hydroxyapatite coating layer carbon/carbon compound material, by the preparation method of above-mentioned doping type hydroxyapatite coating layer carbon/carbon compound material, prepared.
And the above-mentioned doping type hydroxyapatite coating layer carbon/carbon compound material that contains is applied to bone repair and skeleton alternate material field.
The present invention adopts induction heating to deposit calcium hydrogen phosphate coating at surface of carbon/carbon composite containing the preparation method of doping type hydroxyapatite coating layer carbon/carbon compound material, by alkaline solution hydrothermal treatment consists, change pure ha coating into, then add the bio-vitric containing dopant ion in alkaline solution, to carry out hydrothermal treatment consists, obtain containing dopant ion hydroxyapatite coating layer carbon/carbon compound material.The present invention discharges the required ion of osteolith so that hydroxyapatite is adulterated with bio-vitric instead of chemical reagent under hydrothermal condition, can obtain high performance dopant ion hydroxyapatite coating layer, overcome the adulterate bad compatibility that brings and because the foreign ion that adulterated increases the problem of subsequent treatment of direct use chemical reagent.
Of the present invention containing dopant ion hydroxyapatite coating layer carbon/carbon compound material non-toxic and safe, be easy to metabolism, with organism there is the good compatibility, can be applicable to the hard tissue Material Fields such as bone repair and skeleton alternate material.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is the process flow diagram that the embodiment of the present invention contains the preparation method of doping type hydroxyapatite coating layer carbon/carbon compound material;
Fig. 2 is the HA coating surface Calvarial osteoblast adhesion figure after Na, Si that adulterates in example 2 of the present invention.
The specific embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment and accompanying drawing, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the present invention provides a kind of non-toxic and safe, be easy to metabolism and the good condition of biocompatibility easily control containing doping type hydroxyapatite coating layer carbon/carbon compound material preparation method, comprise the steps:
S01: carbon/carbon compound material is immersed in salpeter solution and carries out room temperature processing, and the time is 5min-10min;
S02: the carbon/carbon compound material after hydrothermal treatment consists in step S01 is placed in to the mobile mixed aqueous solution containing calcium salt and dihydric phosphate, eddy-current heating, make its surface deposition go out calcium hydrogen phosphate coating, wherein calcium salt is 0.5～1:0.3～0.6 with the mole ratio of dihydric phosphate;
S03: the carbon/carbon compound material that deposits calcium hydrogen phosphate coating obtaining in step S02 is placed in to alkaline solution and carries out hydrothermal treatment consists, obtain the carbon/carbon compound material of hydroxyl apatite coating; Wherein, described in deposit calcium hydrogen phosphate coating carbon/carbon compound material should be immersed in completely in alkali liquor, its volume ratio is 50～10:1.
S04: the carbon/carbon compound material of the hydroxyl apatite coating obtaining in step S03 is placed in to alkaline solution with the bio-vitric material that contains dopant ion and carries out hydrothermal treatment consists, obtain above-mentioned containing dopant ion hydroxyapatite coating layer carbon/carbon compound material.
Particularly, in above-mentioned steps S01, carbon/carbon compound material is block, the carbon/carbon compound material that preferably diameter is 12*12mm.In this preferred carbon/carbon compound material, carbon element content is higher than 99%, and density is low, has extremely strong affinity, and wear resistance is good, and has excellent biocompatibility, and its biomechanical property is as very approaching with skeleton in elastic modelling quantity etc.Further, above-mentioned strong acid solution is concentrated nitric acid, all selects commercially available product.Adopt this preferred strong acid solution to carry out surface treatment to above-mentioned carbon/carbon compound material, make the c h bond of surface of carbon/carbon composite be oxidized to oxygen-containing functional group, contribute to make the calcium hydrogen phosphate of subsequent deposition to be evenly distributed, granule is more tiny.In a preferred embodiment, the volume of this carbon/carbon compound material and nitric acid is preferably 1:5.
In this step S01, before carrying out hydrothermal treatment consists, also comprise the step of a cleaning, drying: above-mentioned carbon/carbon compound material is placed in to deionized water, acetone or dehydrated alcohol ultrasonic cleaning, then dries.
In this step S01, the reaction of hydrothermal treatment consists can be carried out in water heating kettle, and the response time is 24～96 hours, and temperature is 100～220 ℃, preferably hydro-thermal reaction 24 hours at 140 ℃.
Particularly, in above-mentioned steps S02, the carbon/carbon compound material after first step S01 hydrothermal treatment consists is complete takes out and is placed in distilled water ultrasonic waves for cleaning, oven dry; Then being placed in flow velocity is the mixed aqueous solution eddy-current heating containing calcium salt and dihydric phosphate of 200ml/min～2L/min, deposits 15 minutes～2 hours at 100～200 ℃, deposits calcium hydrogen phosphate coating; Eddy-current heating in the above-mentioned mixed aqueous solution that to be preferably at flow velocity be 1ml/min deposits 15 minutes at 170 ℃.Further, the step of above-mentioned eddy-current heating is for passing through induction heating power pyrogenicity, and it is 1KHz～400KHz that frequency of oscillation is set, and output is 0.1KW～10KW; In a preferred embodiment, the frequency of oscillation that this eddy-current heating is set is 280KHz, and output is 0.7KW.This preferred eddy-current heating and deposition process parameters make that the efficiency of heating surface is high, speed is fast, and low consumption environment protection, make the calcium hydrogen phosphate coating conjugation of carbon/carbon compound material and surface deposition better.
In this step S02, above-mentioned calcium salt is at least one in calcium chloride, calcium acetate, lime nitrate, and above-mentioned dihydric phosphate is at least one in sodium dihydrogen phosphate, potassium dihydrogen phosphate, Ammonium biphosphate; This calcium salt is preferably calcium chloride, and dihydric phosphate is preferably Ammonium biphosphate.Further, the above-mentioned mixed aqueous solution containing calcium salt and dihydric phosphate can be uniformly mixed and obtain than the calcium salt, dihydric phosphate and the water that are 0.5～1:0.3～0.6 by mole, and the sodium dihydrogen phosphate that the calcium chloride solution that can be also 0.5～1M by molal weight and molal weight are 0.3～0.6M is mixed to get.The mixed aqueous solution of this calcium salt and dihydric phosphate reacts and generates calcium hydrogen phosphate in the condition of eddy-current heating, and at surface of carbon/carbon composite, deposits better under flow regime, further forms compact calcium hydrogen phosphate coating.
Particularly, in above-mentioned steps S03, the carbon/carbon compound material that deposits calcium hydrogen phosphate coating obtaining in step S02 is taken out, be placed in water heating kettle and be soaked in the first alkaline solution and carry out hydrothermal treatment consists, at 100～220 ℃, react 24～96 hours, be preferably and at 140 ℃, react 24 hours.Further, this first alkaline solution is any one in potassium hydroxide solution, sodium hydroxide solution, ammonia, and pH value is 10～12; Be preferably the potassium hydroxide solution of 0.01M.The calcium hydrogen phosphate of surface of carbon/carbon composite starts to occur dehydration at 140 ℃ and forms hydroxyapatite.In a preferred embodiment, when temperature is 140 ℃, pH value while being 10, the purity that calcium hydrogen phosphate changes into hydroxyapatite is the highest, obtains the carbon/carbon compound material of the best hydroxyl apatite coating of effect.This hydroxyapatite coating layer can be given surface of carbon/carbon composite biological activity, improves the bond strength of carbon/carbon compound material and surrounding tissue, reduces the generation of free carbon granules; Meanwhile, carbon/carbon compound material has good biocompatibility and biomechanical property, has improved the fragility of hydroxyapatite.
Particularly, in above-mentioned steps S04, bio-vitric containing the ion that adulterated is placed in to the bottom of another water heating kettle, then the carbon/carbon compound material of the hydroxyl apatite coating obtaining in step S03 is taken out and is placed on this bio-vitric, add the second alkaline solution, build kettle cover, carry out hydrothermal treatment consists.This second alkaline solution is any one in potassium hydroxide solution, sodium hydroxide solution, ammonia, and pH value is 10～12; Be preferably ammonia.The time of this hydrothermal treatment consists is 24～96 hours, and temperature is 100～220 ℃; Be preferably and at 140 ℃, react 24 hours.
In this step S04, above-mentioned bio-vitric is at least one in silicate glass, phosphate glass, is preferably the bio-vitric of silicate or phosphate material.The main component of this bio-vitric 45%Na that has an appointment
2o, 25%CaO, 25%SiO
2with 5%P
2o
5, this food ingredient is bionical, after combination reaction, can generate calcium hydroxy phosphate, can with the direct combination of body bone tissue, play that to repair osseous tissue, the effect of recovery, biocompatibility very good, and nontoxic, safety.By the various ions that adulterate as required in this bio-vitric, La, Sr, Na, K, Mg, Si, F, Ca, PO for example can adulterate
4 3-in at least one ion, then carry out hydro-thermal reaction with the carbon/carbon compound material of above-mentioned hydroxyl apatite coating, calcium hydroxy phosphate can be combined with the carbon/carbon compound material of hydroxyl apatite coating well, the carbon/carbon compound material combination to hydroxyl apatite coating by ion doping wherein simultaneously.
In this step S04, after hydro-thermal reaction, also comprise cooling and dry process: by containing after dopant ion hydroxyapatite coating layer carbon/carbon compound material natural cooling of obtaining, be placed in electric heating bellows, at 120 ℃, be dried 20 minutes.
The embodiment of the present invention is containing the preparation method of doping type hydroxyapatite coating layer carbon/carbon compound material, adopt induction heating to deposit calcium hydrogen phosphate coating at surface of carbon/carbon composite, by alkaline solution hydrothermal treatment consists, change pure ha coating into, then add the bio-vitric containing dopant ion in alkaline solution, to carry out hydrothermal treatment consists, obtain containing doping type hydroxyapatite coating layer carbon/carbon compound material.The present invention discharges the required ion of osteolith so that hydroxyapatite is adulterated with bio-vitric instead of chemical reagent under hydrothermal condition, can obtain high performance dopant ion hydroxyapatite coating layer, overcome the adulterate bad compatibility that brings and because the foreign ion that adulterated increases the problem of subsequent treatment of direct use chemical reagent.
The embodiment of the present invention containing doping type hydroxyapatite coating layer carbon/carbon compound material non-toxic and safe, be easy to metabolism, with organism there is the good compatibility, can be applicable to the hard tissue Material Fields such as bone repair and skeleton alternate material.
By a plurality of embodiment, illustrate below above-mentioned containing dopant ion hydroxyapatite coating layer carbon/carbon compound material preparation method.
Embodiment 1
Containing a doping type hydroxyapatite coating layer carbon/carbon compound material preparation method, comprise the steps:
S11: by diameter
carbon/carbon compound material be placed in water heating kettle, molal weight is that 0.1M salpeter solution carries out hydrothermal treatment consists, then takes out, clean and dry with distilled water ultrasonic cleaning;
S12: the carbon/carbon compound material after hydrothermal treatment consists in step S11 is placed in to the mixed aqueous solution that flow velocity is 500ml/min, it is the calcium chloride of 0.2M and the sodium dihydrogen phosphate of 0.15M that this mixed aqueous solution comprises molal weight, by induction heating power pyrogenicity carbon/carbon compound material, it is that 200KHz, output are 0.7KW that frequency of oscillation is set, make its surface deposition go out calcium hydrogen phosphate coating, sedimentation time is 30min;
S13: the carbon/carbon compound material that deposits calcium hydrogen phosphate coating obtaining in step S12 is placed in to the potassium hydroxide solution that concentration is 0.01M, carries out 24 hours hydrothermal treatment consists at 140 ℃, must deposit the carbon/carbon compound material that arrives of calcium hydrogen phosphate coating;
S14: the bio-vitric fragment containing treating dopant ion obtaining in step S13 is placed in to water heating kettle bottom, and this bio-vitric is the bio-vitric that comprises following formula: Na
2o24.5wt%, CaO24.5wt%, P
2o56.0wt%, SiO
245wt%; Then hydroxyapatite coating layer carbon/carbon compound material is placed on this bio-vitric fragment, pours ammonia into, regulates pH to 10, builds kettle cover, in temperature, is that 150 ℃, time are under the condition of 36 hours, carries out hydrothermal treatment consists; After natural cooling, in electric heating bellows dry 20min at 120 ℃, obtain mixing the carbon/carbon compound material of sodium, silicon type hydroxyapatite coating layer; After tested, this anchoring strength of coating reaches critical load 110N, and coating has the good Calvarial osteoblast compatibility, sees Fig. 2
Embodiment 2
Containing a dopant ion hydroxyapatite coating layer carbon/carbon compound material preparation method, comprise the steps:
S21: by diameter
carbon/carbon compound material be placed in water heating kettle, molal weight is that 0.1M salpeter solution carries out hydrothermal treatment consists, then takes out, clean and dry with distilled water ultrasonic cleaning;
S22: the carbon/carbon compound material after hydrothermal treatment consists in step S21 is placed in to the mixed aqueous solution that flow velocity is 500ml/min, it is the calcium chloride of 0.3M and the sodium dihydrogen phosphate of 0.25M that this mixed aqueous solution comprises molal weight, by induction heating power pyrogenicity carbon/carbon compound material, it is that 300KHz, output are 0.5KW that frequency of oscillation is set, make its surface deposition go out calcium hydrogen phosphate coating, sedimentation time is 40min;
S23: the carbon/carbon compound material that deposits calcium hydrogen phosphate coating obtaining in step S22 is placed in to the potassium hydroxide solution that concentration is 0.01M, carries out 24 hours hydrothermal treatment consists at 140 ℃, must deposit the carbon/carbon compound material that arrives of calcium hydrogen phosphate coating;
S24: the bio-vitric fragment containing treating dopant ion obtaining in step S23 is placed in to water heating kettle bottom, and this bio-vitric is the bio-vitric that comprises following formula: Na
2o4.8wt%, F1.0wt%, MgO2.9wt%, CaO33.4wt%, P
2o
5, 11.7%; Then hydroxyapatite coating layer carbon/carbon compound material is placed on this bio-vitric fragment, pours ammonia into, regulates pH to 10, builds kettle cover, in temperature, is that 200 ℃, time are under the condition of 36 hours, carries out hydrothermal treatment consists; After natural cooling, in electric heating bellows, at 120 ℃, be dried 28 hours, obtain mixing the carbon/carbon compound material of sodium, fluorine, silicon type hydroxyapatite coating layer; After tested, this anchoring strength of coating reaches critical load 105N.As shown in Figure 2, it is the HA coating surface Calvarial osteoblast adhesion figure having adulterated after Na, Si.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (6)
1. contain a preparation method for the carbon/carbon compound material of doping type hydroxyapatite coating layer, comprise the steps:
Carbon/carbon compound material is placed in to salpeter solution and carries out room temperature processing, the time is 5～10 minutes, and wherein, described carbon/carbon compound material should be immersed in concentrated nitric acid;
Carbon/carbon compound material after described hydrothermal treatment consists is placed in to the mobile mixed aqueous solution containing calcium salt and dihydric phosphate, and the flow velocity of described mixed aqueous solution is 200ml/min～2L/min, and sedimentation time is 15 minutes～2 hours, and temperature is 100～200 ℃; Eddy-current heating, described eddy-current heating is for passing through induction heating power pyrogenicity, the frequency of oscillation of described induction heating power is 1KHz～400KHz, output is 0.1KW～10KW, make its surface deposition go out calcium hydrogen phosphate coating, wherein, described calcium salt is 0.5～1:0.3～0.6 with the mole ratio of dihydric phosphate;
The described carbon/carbon compound material that deposits calcium hydrogen phosphate coating is placed in to the first alkaline solution and carries out hydrothermal treatment consists, the time is 24～96 hours, and temperature is 100～220 ℃, obtains the carbon/carbon compound material of hydroxyl apatite coating; Wherein, described in deposit calcium hydrogen phosphate coating carbon/carbon compound material should be immersed in completely in alkali liquor, its volume ratio is 50～10:1;
The carbon/carbon compound material of described hydroxyl apatite coating is placed in to the second alkaline solution with the bio-vitric that contains dopant ion and carries out hydrothermal treatment consists, temperature is 100～220 ℃, time is 24～96 hours, described bio-vitric is at least one in silicate glass, phosphate glass, obtain described containing dopant ion hydroxyapatite coating layer carbon/carbon compound material, wherein glass is the fragment of quenching, and volume accounts for 1/3～1/2 of final Treatment Solution.
2. the preparation method containing doping type hydroxyapatite coating layer carbon/carbon compound material according to claim 1, is characterized in that: described dopant ion is La, Sr, Na, K, Mg, Si, F, Ca, PO
4 3-in at least one.
3. the preparation method containing doping type hydroxyapatite coating layer carbon/carbon compound material according to claim 1, it is characterized in that: described the first aqueous slkali and/or the second aqueous slkali are any one in potassium hydroxide solution, sodium hydroxide solution, ammonia, and pH value is 10～12.
4. the preparation method containing doping type hydroxyapatite coating layer carbon/carbon compound material according to claim 1, is characterized in that: described calcium salt is at least one in calcium chloride, calcium acetate, lime nitrate; Described dihydric phosphate is at least one in sodium dihydrogen phosphate, potassium dihydrogen phosphate, Ammonium biphosphate.
5. containing a doping type hydroxyapatite coating layer carbon/carbon compound material, by the preparation method of dopant ion hydroxyapatite coating layer carbon/carbon compound material described in claim 1～4, prepared.
6. the application of the dopant ion hydroxyapatite coating layer carbon/carbon compound material being prepared by the preparation method that contains doping type hydroxyapatite coating layer carbon/carbon compound material described in claim 1～5 in bone repair and skeleton alternate material.
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| CN104746120A (en) * | 2015-03-06 | 2015-07-01 | 深圳大学 | Carbon/carbon composite material containing bioactive calcium phosphate coating on surface and preparation method for carbon/carbon composite material |
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| CN110713381A (en) * | 2019-10-08 | 2020-01-21 | 西北工业大学 | 1200-second-fire-resistant bio-based refractory paper and preparation method thereof |
| CN111017898A (en) * | 2019-12-26 | 2020-04-17 | 扬州大学 | Preparation method of iron-doped spherical calcium hydrophosphate |
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| RU2571080C1 (en) * | 2014-11-13 | 2015-12-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Саратовский государственный технический университет имени Гагарина Ю.А." (СГТУ имени Гагарина Ю.А.) | Method for bioceramic coating deposition on implants |
| CN104746120A (en) * | 2015-03-06 | 2015-07-01 | 深圳大学 | Carbon/carbon composite material containing bioactive calcium phosphate coating on surface and preparation method for carbon/carbon composite material |
| CN104701517A (en) * | 2015-03-27 | 2015-06-10 | 陕西科技大学 | Method for preparing NH4V3O8 anode material for lithium ion battery |
| CN110302424A (en) * | 2019-07-29 | 2019-10-08 | 西南交通大学 | A kind of preparation method of high throughput biomimetic mineralization multi-element doping calcium phosphor coating |
| CN110713381A (en) * | 2019-10-08 | 2020-01-21 | 西北工业大学 | 1200-second-fire-resistant bio-based refractory paper and preparation method thereof |
| CN110713381B (en) * | 2019-10-08 | 2022-03-15 | 西北工业大学 | 1200-second-fire-resistant bio-based refractory paper and preparation method thereof |
| CN111017898A (en) * | 2019-12-26 | 2020-04-17 | 扬州大学 | Preparation method of iron-doped spherical calcium hydrophosphate |
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