CN106139252A - A kind of hydroxyapatite of titania additive and preparation method thereof - Google Patents
A kind of hydroxyapatite of titania additive and preparation method thereof Download PDFInfo
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- CN106139252A CN106139252A CN201510177081.7A CN201510177081A CN106139252A CN 106139252 A CN106139252 A CN 106139252A CN 201510177081 A CN201510177081 A CN 201510177081A CN 106139252 A CN106139252 A CN 106139252A
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- hydroxyapatite
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Abstract
The present invention relates to hydroxyapatite of a kind of titania additive and preparation method thereof, its concrete solution is: (1) prepares hydroxyapatite: containing in certain density calcium salt and aqueous phosphatic, add precipitant generation homogeneous reaction, through filtering, wash, obtaining hydroxyapatite after drying.Wherein precipitant is carbamide or hexamethylenetetramine；(2) titania hydrosol is prepared: first titanium salt hydrolysis is obtained metatitanic acid precipitation, be subsequently adding hydrogen peroxide and carry out ultrasonic, then add stabilizer and carry out reflow treatment, obtain stable titania hydrosol；(3) titania additive: be soaked in titania hydrosol by hydroxyapatite, then by filtering, be dried, calcining, obtains the hydroxyapatite of titania additive.The hydroxyapatite particle diameter that the present invention obtains is at 76 ~ 150 microns, and distribution of sizes is narrower, and size is controlled.Technological process is simple, and low cost, the chemical substance related to is few, and the hydroxylapatite biology compatibility of gained is good, has significant bactericidal action.
Description
Technical field
The present invention relates to hydroxyapatite of a kind of titania additive and preparation method thereof.
Background technology
Hydroxyapatite is the main inorganic composition constituting human body hard tissue, accounts for the 77% of people's bone inorganic constituents, is more up to 97% in dentary.With other biomaterial significant difference, it is that it contains calcium necessary to tissue and P elements, and without other harmful element.After implanting, under the effect of body fluid, calcium and phosphorus can dissociate material surface, absorbed by body tissue, and can organize the formation of chemical bonds, the tissue that growth makes new advances with skeleton.Therefore, hydroxyapatite is the biomaterial generally acknowledged at present and have superperformance.Along with the development of modern medical techniques Yu material science, there is biocompatibility and bioactive artificial substituting material is widely used in the reparation of human body hard and soft tissue and organ.A lot of researchs in recent years show, in the infection caused by biomaterial, when the reason of 45% is due to biomaterial and human contact, one layer of albuminous coat is formed at material surface, and antibacterial is easy on this layer of albuminous coat adhere to, growth and breeding then, use traditional antibacterial therapy to eradicate.
Nano-TiO2Staphylococcus aureus, escherichia coli, Candida albicans etc. had the strongest bactericidal action.Its mechanism is TiO2Under illumination condition, the oxygen-derived free radicals of generation can destroy cell wall structure, makes cell wall fracture, breakage, and plasma membrane disintegrates.Subsequently into cell space internal sabotage inner membrance and cellular component, make cytoplasmic condensation, cause cellular content to overflow, may occur in which thalline cavitation phenomenon.The master thesis " titanium dioxide nano-particle impact on osteoblastic proliferation, differentiation and the mineralization function of original cuiture " of high Jinhua is thought, TiO2Nano-particle is while promoting Primary osteoblast cells propagation, it is suppressed that it then has promotion and inhibitory action concurrently to adipose cell transdifferentiationof and mineralization function thereof, the impact for alkaline phosphatase activities.The patent of invention (201410139015.6) of QiJian Wei reports a kind of for grade doping diamond-like rock layers and Ag, TiO2The preparation method of doped hydroxyapatite layer polynary nanometer composite coating, the method that wherein have employed magnetron sputtering.Yu Qifeng et al. is by anatase nano-TiO that particle mean size is 5 nm2Powder mixes hydroxylapatite powder, puts into dehydrated alcohol, through ultrasonic grinding and mixing, cold drying, by isostatic cool pressing base, sintering, prepare TiO2Hydroxyapatite composite ceramics, reaches the effect of automatically cleaning and sterilization, improves the materials microstructure compatibility and biological activity.Xu Kan et al. is in paper " titanium dioxide and Hydroxyapatite Nanocomposites preparation and sign ", use solution chemistry synthetic method, by Coated With Hydroxyapatite on the surface of nano titanium oxide, prepare titanium dioxide and Hydroxyapatite Nanocomposites, reach the purpose suppressing antibacterial to improve material safety.Zhang Hangzhou et al. is at paper " hydroxyapatite/TiO2The biocompatibility of nanotube complex " in, titania nanotube is combined with nanometer hydroxyapatite, shows good biocompatibility.
Summary of the invention
It is an object of the invention to overcome existing technical deficiency, it is provided that hydroxyapatite of a kind of titania additive and preparation method thereof.The method process equipment is simple, granule is uniform, size is controlled, with low cost, the chemical substance related to is few.For realizing the purpose of the present invention, adopt the following technical scheme that.
The preparation method of a kind of hydroxyapatite that can be used for the titania additive that biological tissue repairs, comprises the steps.
1, the preparation of hydroxyapatite
(1) compound concentration is 0.5-0.7
The calcium saline solution of mol/L, is the HNO of 32% by mass fraction3Solution drops to wherein, until the pH value of solution is 1.5 ~ 3.5；
Described calcium salt is Ca (NO3)2、CaCl2、CaCO3Or Ca (CH3COO)2；
(2) compound concentration is 0.1-0.2
The aqueous phosphatic of mol/L；
Described phosphate is KH2PO4、K2HPO4、(NH4)2HPO4Or Na2HPO4；
(3) aqueous phosphatic that step (2) is prepared is added dropwise in the calcium salt acid solution that step (1) obtains by limit mechanical agitation limit, is stirred vigorously so that it is mix homogeneously, then adds organic silicon surfactant after adding；
Described calcium salt and phosphatic mol ratio are 1.67, and described surfactant is for stepping figure CoatOSil 1211, CoatOSil
7602, CoatOSil 7604, CoatOSil 3573, CoatOSil
7500, CoatOSil 3509, CoatOSil 47, CoatOSil
77, CoatOSil 2400, CoatOSil 2812, CoatOSil
3500, or Silwet 408, HR-3408；
(4) a certain amount of precipitant is slowly added in the mixed solution that step (3) obtains, is warming up to 70 ~ 95 DEG C, ceaselessly mechanical agitation so that it is react 36-72 hour；
Described precipitant be the mol ratio of carbamide, hexamethylenetetramine or its mixture, calcium salt and precipitant be 1.1-1.5；
(5) reacting liquid filtering, the washing that step (4) are obtained are dried the most afterwards, i.e. available required hydroxyapatite.
2, the preparation of titania hydrosol
(1) a certain amount of titanium salt is dissolved in deionized water, by sufficient hydrolysis, obtains the metatitanic acid precipitation of yellow；
Described titanium salt is titanyl sulfate, titanium tetrachloride, tetraisopropyl titanate, metatitanic acid four n-propyl, tetraethyl titanate or butyl titanate；
(2) in above-mentioned metatitanic acid precipitates, add a certain amount of hydrogen peroxide again, then obtain faint yellow colloidal sol by ultrasonic；It is simultaneously introduced a small amount of isopropanol or acetylacetone,2,4-pentanedione, carries out reflow treatment, obtain the stable anatase titania hydrosol.
3, the preparation of the hydroxyapatite of titania additive
(1) being soaked in by hydroxyapatite in the titania hydrosol of above-mentioned preparation, the time is 4 ~ 8 hours；
(2) then obtained white product filtered, be dried, then 600 degree of calcinings 10 ~ 60 minutes.
The present invention, by changing the parameters such as reactant concentration, response time, temperature, system pH, mixing speed, doping content, can realize hydroapatite particles particle diameter, particle diameter distribution, doping content, the control of biocompatibility.The hydroxyapatite particle diameter obtained is at 76-150 micron, as shown in Figure 1.Hydroxyapatite even particle size distribution, has good biocompatibility and bactericidal action, may be used for the reparation of biological tissue.
Compared with prior art, being advantageous in that of the present invention:
1, using homogeneous precipitation method one-shot forming, can directly obtain product, preparation technology is simple, with low cost.Processing without carrying out the high-temperature calcination of secondary granulation and later stage, preparation process, without adding any chelating agent, oxidant, template and other metal ions that adulterate, advantageously ensures that purity and the performance of hydroxyapatite；
2, the technique preparing titanium dioxide is simple, and the chemical substance related to is less, can avoid the introducing of harmful substance.The technique of doping is simple, controlled, and prepared hydroxyapatite has good biocompatibility and bactericidal action.
Accompanying drawing explanation
Fig. 1 is the hydroxyapatite scanning electron microscope (SEM) photograph of the titania addition prepared by embodiment 1.
Specific implementation method
Below in conjunction with specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to following embodiment.
Embodiment
1
。
By HNO3Solution is slowly added into 99.8
The KH of ml 0.15 mol/L2PO4In solution, until the pH value of solution is 2.4, under mechanical agitation, by 50 ml 0.5 mol/L CaCl2Solution is added dropwise to KH2PO4In acid solution, it is stirred vigorously and makes its mix homogeneously, mixed solution adds 1.08 g carbamide, 10 Silwet 408, is warming up to 80 DEG C so that it is reaction 48h, reacting liquid filtering, washing are dried the most afterwards, i.e. available required hydroxyapatite.
2ml titanium tetrachloride is dissolved in 50ml deionized water, by sufficient hydrolysis, obtains the metatitanic acid precipitation of yellow.Adding the hydrogen peroxide of 5ml again in above-mentioned metatitanic acid precipitates, the concentration of hydrogen peroxide is 65%.Then it is that 50W ultrasound wave is carried out ultrasonic 30 minutes by power, obtains faint yellow colloidal sol.It is simultaneously introduced 1ml isopropanol, 70 degree of reflow treatment 50 minutes, obtains the stable anatase titania hydrosol.
Being soaked in by hydroxyapatite in the titania hydrosol of above-mentioned preparation, the time is 4 hours.Then obtained white product filtered, be dried, then 600 degree are calcined 40 minutes.
Embodiment
2
。
By HNO3Solution is slowly added into 50 ml
The KH of 0.3 mol/L2PO4In solution, until the pH value of solution is 2.4, under mechanical agitation, by 100 ml 0.25 mol/L CaCl2Solution is added dropwise to KH2PO4In acid solution, it is stirred vigorously and makes its mix homogeneously, mixed solution adds 1.2 g carbamide, 15 HR-3408, is warming up to 90 DEG C so that it is reaction 48h, reacting liquid filtering, washing are dried the most afterwards, i.e. available required hydroxyapatite.
2ml butyl titanate is dissolved in 50ml deionized water, by sufficient hydrolysis, obtains the metatitanic acid precipitation of yellow.Adding the hydrogen peroxide of 8ml again in above-mentioned metatitanic acid precipitates, the concentration of hydrogen peroxide is 65%.Then it is that 80W ultrasound wave is carried out ultrasonic 10 minutes by power, obtains faint yellow colloidal sol.It is simultaneously introduced 1ml acetylacetone,2,4-pentanedione, 90 degree of reflow treatment 20 minutes, obtains the stable anatase titania hydrosol.
Being soaked in by hydroxyapatite in the titania hydrosol of above-mentioned preparation, the time is 4 hours.Then obtained white product filtered, be dried, then 600 degree are calcined 40 minutes.
Embodiment
3
。
By HNO3Solution is slowly added into 50 ml
The NaH of 0.3mol/L2PO4In solution, until the pH value of solution is 2.6, under mechanical agitation, by 50 ml 0.5 mol/L Ca (CH3COO)2Solution is added dropwise to NaH2PO4In acid solution, it is stirred vigorously and makes its mix homogeneously, mixed solution adds 1.08 g carbamide, 10 CoatOSil 77, is warming up to 85 DEG C so that it is reaction 50h, reacting liquid filtering, washing are dried the most afterwards, i.e. available required hydroxyapatite.
1.5ml metatitanic acid four n-propyl is dissolved in 40ml deionized water, by sufficient hydrolysis, obtains the metatitanic acid precipitation of yellow.Adding the hydrogen peroxide of 4ml again in above-mentioned metatitanic acid precipitates, the concentration of hydrogen peroxide is 65%.Then it is that 90W ultrasound wave is carried out ultrasonic 30 minutes by power, obtains faint yellow colloidal sol.It is simultaneously introduced 1ml isopropanol, 70 degree of reflow treatment 50 minutes, obtains the stable anatase titania hydrosol.
Being soaked in by hydroxyapatite in the titania hydrosol of above-mentioned preparation, the time is 4 hours.Then obtained white product filtered, be dried, then 600 degree are calcined 40 minutes.
Embodiment
4
。
By HNO3Solution is slowly added into 99.8
(the NH of ml 0.15 mol/L4)2HPO4In solution, until the pH value of solution is 2.4, under mechanical agitation, by 50 ml 0.5 mol/L Ca (NO3)2Solution is added dropwise to (NH4)2HPO4In acid solution, it is stirred vigorously and makes its mix homogeneously, mixed solution adds 1.08 g carbamide, 10 Silwet 408, is warming up to 80 DEG C so that it is reaction 48h, reacting liquid filtering, washing are dried the most afterwards, i.e. available required hydroxyapatite.
2ml titanium tetrachloride is dissolved in 50ml deionized water, by sufficient hydrolysis, obtains the metatitanic acid precipitation of yellow.Adding the hydrogen peroxide of 5ml again in above-mentioned metatitanic acid precipitates, the concentration of hydrogen peroxide is 65%.Then it is that 30W ultrasound wave is carried out ultrasonic 100 minutes by power, obtains faint yellow colloidal sol.It is simultaneously introduced 1ml isopropanol, 70 degree of reflow treatment 50 minutes, obtains the stable anatase titania hydrosol.
Being soaked in by hydroxyapatite in the titania hydrosol of above-mentioned preparation, the time is 4 hours.Then obtained white product filtered, be dried, then 600 degree are calcined 40 minutes.
Claims (6)
1. hydroxyapatite of a titania additive and preparation method thereof, it is characterised in that specifically comprise the following steps that
(1) hydroxyapatite is prepared
Compound concentration is 0.1 ~ 0.8
The calcium saline solution of mol/L, by HNO3Solution drops to wherein, until the pH value of solution is 1.5 ~ 3.5；Compound concentration is the aqueous phosphatic of 0.1 ~ 0.5 mol/L；Then aqueous phosphatic is added dropwise in calcium salt acid solution, is stirred vigorously after adding so that it is mix homogeneously；Finally more a certain amount of precipitant is slowly added in this mixed solution, is warming up to 70 ~ 95 DEG C, carry out tool stirring simultaneously, control the response time at 24 ~ 72 hours；The white product obtained filtered after completion of the reaction, washing is dried the most afterwards, i.e. available required hydroxyapatite；
(2) titania hydrosol is prepared
A certain amount of titanium salt is dissolved in deionized water, by sufficient hydrolysis, obtains the metatitanic acid precipitation of yellow；
In above-mentioned metatitanic acid precipitates, add the hydrogen peroxide that a certain amount of concentration is 65% again, then obtain faint yellow colloidal sol by ultrasonic；It is simultaneously introduced a small amount of stabilizer, carries out reflow treatment, obtain the stable anatase titania hydrosol；
(3) titania additive hydroxyapatite is prepared
Being soaked in titania hydrosol prepared by step (2) by hydroxyapatite prepared by step (1), the time is 4 ~ 8 hours；Then carry out filtering, being dried, then 400 ~ 800 degree of calcinings 10 ~ 60 minutes.
The preparation method of hydroxyapatite the most according to claim 1, it is characterised in that: described calcium salt is Ca (NO3)2、CaCl2、CaCO3、Ca(CH3COO)2；Described phosphate is KH2PO4、K2HPO4、(NH4)2HPO4、Na2HPO4；Described calcium salt and phosphatic mol ratio are 1.67.
The preparation method of hydroxyapatite the most according to claim 1, it is characterised in that: described precipitant is carbamide, hexamethylenetetramine or its mixture；Described surfactant is for stepping figure CoatOSil 1211, CoatOSil 7602, CoatOSil 7604, CoatOSil 3573, CoatOSil 7500, CoatOSil 3509, CoatOSil 47, CoatOSil 77, CoatOSil 2400, CoatOSil 2812, CoatOSil 3500, one or more in Silwet 408 or HR-3408, addition is 0.01 ~ 0.5 weight %.
The preparation method of titania hydrosol the most according to claim 1, it is characterized in that the titanium salt described in step (2) is one or several in titanyl sulfate, titanium tetrachloride, tetraisopropyl titanate, metatitanic acid four n-propyl, tetraethyl titanate or butyl titanate, concentration is 0.01 ~ 1 mol/L；The addition of 65% described hydrogen peroxide is 1 ~ 25 weight %；Described stabilizer is one or more in isopropanol or acetylacetone,2,4-pentanedione, and addition is 0.01 ~ 0.5 weight %；Described ultrasonic power is 10 ~ 100W, and the time is 10 ~ 600 minutes, and the temperature of backflow is 40 ~ 90 degree, and the time is 4 ~ 8 hours.
The preparation method of titania additive hydroxyapatite the most according to claim 1, it is characterised in that the time that step (3) is soaked is 4 ~ 8 hours, the solid content of titania hydrosol used is 0.01 ~ 5 weight %.
The preparation method of titania additive hydroxyapatite the most according to claim 1, it is characterised in that the calcining heat that step (3) is used is 400 ~ 1000 degree, calcination time is 10 ~ 60 minutes.
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| CN108424138A (en) * | 2018-03-28 | 2018-08-21 | 华南理工大学 | Siliceous modified grain boundary phase hydroxylapatite ceramic, bone injury repair material and preparation method thereof |
| CN108456016A (en) * | 2018-04-13 | 2018-08-28 | 日正九安科技（北京）有限公司 | A kind of water solubility organic titanium fertilizer and preparation method thereof |
| CN109023366A (en) * | 2018-09-02 | 2018-12-18 | 张家港市六福新材料科技有限公司 | A kind of preparation method of hydroxyapatite-composite titania material |
| CN109701082A (en) * | 2019-02-22 | 2019-05-03 | 九江学院 | A kind of preparation method and application of hydroxyapatite-titanium hydroxide composite granule |
| CN115553302A (en) * | 2022-01-14 | 2023-01-03 | 华升科技集团有限公司 | Sterilizing composition containing nano-scale titanium dioxide and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108424138A (en) * | 2018-03-28 | 2018-08-21 | 华南理工大学 | Siliceous modified grain boundary phase hydroxylapatite ceramic, bone injury repair material and preparation method thereof |
| CN108456016A (en) * | 2018-04-13 | 2018-08-28 | 日正九安科技（北京）有限公司 | A kind of water solubility organic titanium fertilizer and preparation method thereof |
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| CN115553302A (en) * | 2022-01-14 | 2023-01-03 | 华升科技集团有限公司 | Sterilizing composition containing nano-scale titanium dioxide and preparation method thereof |
| CN115553302B (en) * | 2022-01-14 | 2023-11-03 | 华升科技集团有限公司 | Disinfecting composition containing nanoscale titanium dioxide and preparation method thereof |
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