CN104071764A - Preparation method of hydroxyapatite material doped with fluorine and potassium - Google Patents
Preparation method of hydroxyapatite material doped with fluorine and potassium Download PDFInfo
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- CN104071764A CN104071764A CN201410307955.1A CN201410307955A CN104071764A CN 104071764 A CN104071764 A CN 104071764A CN 201410307955 A CN201410307955 A CN 201410307955A CN 104071764 A CN104071764 A CN 104071764A
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- potassium
- fluorine
- preparation
- hydroxyapatite
- hydroxyapatite material
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Links
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 64
- 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 64
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 54
- 239000011737 fluorine Substances 0.000 title claims abstract description 54
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 48
- 239000011591 potassium Substances 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title claims abstract 18
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 37
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011259 mixed solution Substances 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 28
- 238000005406 washing Methods 0.000 claims abstract description 20
- 230000032683 aging Effects 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000011575 calcium Substances 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 18
- 238000000967 suction filtration Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 12
- 239000003637 basic solution Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 11
- 210000004268 dentin Anatomy 0.000 abstract description 7
- 239000013049 sediment Substances 0.000 abstract 6
- 206010020751 Hypersensitivity Diseases 0.000 abstract 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract 1
- 239000012670 alkaline solution Substances 0.000 abstract 1
- ICSSIKVYVJQJND-UHFFFAOYSA-N calcium nitrate tetrahydrate Chemical compound O.O.O.O.[Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ICSSIKVYVJQJND-UHFFFAOYSA-N 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- 239000002159 nanocrystal Substances 0.000 abstract 1
- 235000011007 phosphoric acid Nutrition 0.000 abstract 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 abstract 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 36
- 239000012153 distilled water Substances 0.000 description 21
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 20
- 239000002994 raw material Substances 0.000 description 19
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 13
- 229910001414 potassium ion Inorganic materials 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 235000011010 calcium phosphates Nutrition 0.000 description 11
- 229910052593 corundum Inorganic materials 0.000 description 7
- 239000010431 corundum Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 229940034610 toothpaste Drugs 0.000 description 7
- 239000000606 toothpaste Substances 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 6
- 229910001424 calcium ion Inorganic materials 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 210000005239 tubule Anatomy 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 5
- 238000000586 desensitisation Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000001103 potassium chloride Substances 0.000 description 5
- 235000011164 potassium chloride Nutrition 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 208000002925 dental caries Diseases 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- 238000000338 in vitro Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 210000000214 mouth Anatomy 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 229940044683 chemotherapy drug Drugs 0.000 description 2
- 238000005115 demineralization Methods 0.000 description 2
- 230000002328 demineralizing effect Effects 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 230000000857 drug effect Effects 0.000 description 2
- 230000001976 improved effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012567 medical material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 206010002198 Anaphylactic reaction Diseases 0.000 description 1
- 206010006956 Calcium deficiency Diseases 0.000 description 1
- 208000001132 Osteoporosis Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 1
- 229910001573 adamantine Inorganic materials 0.000 description 1
- 230000036783 anaphylactic response Effects 0.000 description 1
- 208000003455 anaphylaxis Diseases 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000008468 bone growth Effects 0.000 description 1
- 239000011797 cavity material Substances 0.000 description 1
- 230000004663 cell proliferation Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 201000002170 dentin sensitivity Diseases 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 210000004126 nerve fiber Anatomy 0.000 description 1
- 210000004409 osteocyte Anatomy 0.000 description 1
- 239000000902 placebo Substances 0.000 description 1
- 229940068196 placebo Drugs 0.000 description 1
- 210000003296 saliva Anatomy 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 235000020985 whole grains Nutrition 0.000 description 1
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention relates to a preparation method of a hydroxyapatite material doped with fluorine and potassium. The preparation method of the hydroxyapatite material doped with fluorine and potassium comprises the following steps: (1) uniformly mixing a Ca(NO3)2.4H2O aqueous solution with a H3PO4 aqueous solution to obtain a mixed solution, adjusting pH value of the mixed solution till sediment is generated, separating out the sediment and washing the sediment; (2) drying the sediment obtained by the step (1), calcining the sediment at the temperature of 1300-1500 DEG C, and then quickly cooling the sediment to prepare alpha-calcium phosphate powder; (3) dispersing the alpha-calcium phosphate powder prepared by the step (2) in an alkaline solution containing K<+> and F<->, standing and aging at 80-160 DEG C for more than 12 hours, separating out powder, and then washing and drying to prepare the hydroxyapatite material doped with fluorine and potassium. By virtue of the preparation method, the problems that potassium salt is easily dissolved in water and not easily doped in the hydroxyapatite are solved; nanocrystals of the prepared hydroxyapatite material doped with fluorine and potassium are small in grain size and high in crystal purity, so that the hydroxyapatite material doped with fluorine and potassium can be taken as a novel method with functions of treating hypersensitive dentin, desensitizing and repairing and is long-term and efficient in treatment on hypersensitive dentin.
Description
Technical field
The present invention relates to hydroxyapatite material preparation field, particularly a kind of preparation method who mixes fluorine, potassium hydroxyapatite material.
Background technology
Fluorochemical has been widely used in biomedical material, as treat osteoporosis or strengthen the acid attack resistivity of tooth, report, fluorion is by stimulating osteocyte propagation and differentiation, promote mineralising and bone forming, research shows that fluorine-containing hydroxyapatite has obvious high high-temp stability and biological activity, fluorion partly substitutes or the lattice energy of the hydroxyapatite material of replacing whole hydroxide ion promotes, the acid resistance of these hydroxyapatites is improved, in addition, the hydroxyapatite coating layer of fluoridizing can promote cell proliferation and bone growth, yet in practice, due to fluoridated hydroxyapatite having difficulties in industrial scale, and clinician lacks confidence to fluorine material.
Dental hypersensitiveness (Dentin Hypersensitivity, DH) is oral cavity common disease and frequently-occurring disease.Fluorochemical is filmed and is proved and can treats dentin hypersensitiveness in multinomial research, infers except the remineralization effect of fluorine, films and itself has effectively sealed the opening of dentinal tubule, and maintain fluorine concentration in facing and saliva, thereby promoted desensitization function.Containing the compound of potassium, be used in for a long time oral cavity partial desensitization, research shows, K～+ can stop the unpolarizing of Intradental nerve fiber.Therefore, in order to seek to have concurrently the type material of desensitization and repairing effect, treat for a long time, efficiently DH, need to prepare the hydroxyapatite material of mixing fluorine, potassium, but sylvite is soluble in water, be difficult for mixing hydroxyapatite.
At present, the synthetic method of hydroxyapatite material is mainly liquid-phase precipitation method and sol-gel method.Nano-grade hydroxy apatite has good adsorptivity and biocompatibility, can be widely used in the numerous areas such as biomedicine, environment protection, type material.In recent years, the existing remarkable progress of the research of nano-grade hydroxy apatite material and application, existing portioned product emerges at present.For example,
Opening the grade of respecting (opens and respects it, Lina WANG, Liu Qicheng.Dalian Medical Univ's journal, 2010,32,3,312～314), observation of curative effect containing potassium ion toothpaste treatment dentin hypersensitiveness, inquire into by use and contain potassium ion toothpaste treatment dentin hypersensitiveness, observe desensitization curative effect, draw by experiment, containing potassium ion toothpaste group air sensitive VAS value and tactile sensitivity VAS value, be all less than placebo toothpaste group air sensitive VAS value and tactile sensitivity VAS value, difference all has significant.Illustrate containing potassium ion toothpaste and can obviously alleviate dentin hypersensitiveness, improve the global comfort of patient's tooth, be worth of widely use.
(Gao Jing, the Wang Qin such as Gao Jing.Journal of Beijing Medical University, 1993,25,3,199～200), the adamantine early stage artificial caries of in vitro ox has been carried out to remineralization research; Normal baurodont glaze has been carried out to the experiment in vitro of anti-dental caries, and take microhardness, microradiograph and image analysis and experimental result is observed as index.Result shows: the toothpaste of fluorine-containing, calcium, phosphorus is best to the remineralization effect of enamel white spot; The fluorine-containing toothpaste without calcium, phosphorus is without remineralization effect; Both be improved effects of the anti-dental caries of normal glaze.(Ji Yingchen, Xia Lu, Chen Yaming, Xiong Zhenghui, the Sun Guifang such as Xia Lu.Oral cavity material apparatus, 2012,21,1,12～21), by experiment in vitro, study the effect of different condition to dentinal tubule sealing that imports fluorion.The most of open tubules of result demineralization group, visible significantly mineralizer deposition in remineralization group dentinal tubule, dentinal tubule area and the relative area of each group have significant difference (P0.05); And energy dispersion X-ray analysis demonstration demineralization group and remineralization are respectively organized surperficial ratio of calcium and phosphorus there was no significant difference (P0.05).The fluorion importing that conclusion NF-II type protects tooth instrument has certain sealing process for dentinal tubule.
Han Yaocong, α-TCP aquation legal system is for HA whisker and THERMAL STABILITY [D] thereof. and Guangxi University's 2009. experimental results show, utilize α-TCP aquation method can prepare length and reach 5um, the calcium deficiency type hydroxyapatite crystal whisker that length-to-diameter ratio is greater than 10.In affecting the various factors of α-TCP aquation, the impact of aquation initial pH value and hydration temperature is the most remarkable.Aquation initial pH value has a great impact the pattern of α-TCP hydrated product, and when aquation initial pH value is lower, hydrated product in the form of sheets and needle-like, and when aquation initial pH value is higher, is all needle-like.
20 middle of century epidemiological studies point out, fluorochemical has the effect of the carious tooth of preventing and treating.Study discovery in great detail: fluorion can react with dental surface generation mineralising, makes its surface firm, the acidic substance that are difficult for being produced by swill corrode, thereby have weakened anaphylaxis and reduced the probability of occurrence of carious tooth.
In sum, the hydroxyapatite of mixing fluorine, potassium is a kind of superior performance, widely used material.But up to the present, also do not have a kind of method to prepare purity high, output is large mixes fluorine, potassium hydroxyapatite.Bibliographical information mostly launches research around the hydroxyapatite of mixing fluorine at present, and the correlative study of mixing the hydroxyapatite of fluorine, potassium about preparation does not have report.In addition, above literature research discovery, the impurity in raw material is larger on prepared sample crystal property impact, and high-purity raw material is conducive to prepare the hydroxyapatite of mixing fluorine, potassium of superior performance.
Summary of the invention
The object of the present invention is to provide a kind of sylvite easily to mix hydroxyapatite and product purity is high, output the is large preparation method who mixes fluorine, potassium hydroxyapatite material.
For achieving the above object, the technical solution used in the present invention is:
Comprise the following steps:
1) by Ca (NO
3)
24H
2the O aqueous solution and H
3pO
4aqueous solution is even, obtains mixed solution, wherein Ca (NO
3)
24H
2o and H
3pO
4mol ratio be 3:2, regulate pH value to 8～14 of mixed solution to occur throw out, isolate throw out and wash;
2) by step 1) gained throw out is dried, and the quick cooling alpha-calcium phosphate powder that makes after calcining at 1300 ℃～1500 ℃;
3) by step 2) the alpha-calcium phosphate powder that makes is dispersed in and contains K
+and F
-basic solution in, under 80～160 ℃ of conditions more than still aging 12h, isolate powder after washing dry, prepare and mix fluorine, potassium hydroxyapatite material.
Described step 1) Ca (NO in
3)
24H
2the O aqueous solution is Ca (NO
3)
24H
2o and water is by 1:(10～20) quality than mixed preparing, form.
Described step 1) H in
3pO
4the aqueous solution is H
3pO
4with water by 1:(45～90) quality than mixed preparing, form.
Described step 1) in, use NaOH solution to regulate the pH value of mixed solution.
Described step 1) in, centrifugation goes out throw out, and continuous washing, suction filtration.
Described step 2), in, dry is to be incubated 1～2 hour under 100～200 ℃ of conditions.
Described step 2) in, after drying precipitate, grind and calcine, calcination time is 0.5～2 hour.
Described step 3) in, contain K
+and F
-basic solution be KOH and NH
4f is dissolved in water and forms, and alpha-calcium phosphate and KOH, NH
4the mol ratio of F is (1～2): (1～4): (1～2).
Described step 3) in, the still aging time is 12～72 hours.
Described step 3) chemical formula of mixing fluorine, potassium hydroxyapatite of preparing in is Ca
10-xk
x(PO
4)
6(OH)
2-yf
y0 < x≤2 wherein, 0 < y≤2.
Compared with prior art, the present invention has following useful technique effect:
The present invention is by Ca (NO
3)
24H
2o and H
3pO
4under alkaline environment, reaction generates throw out, thereby prepare calcium phosphate raw material, again by high-temperature calcination calcium phosphate raw material, high temperature is the cooling alpha-calcium phosphate powder that makes rapidly, avoided calcium phosphate inversion of phases in furnace cooling temperature-fall period to cause the impact of uneven components, prepared calcium phosphate purity is 99.9%; Alpha-calcium phosphate powder is carried out to the hydroxyapatite that aquation method prepares and there is good thermostability, by aquation method, fluorine, potassium are introduced in hydroxyapatite simultaneously, under 80～160 ℃ of conditions, ageing is more than 12 hours, because potassium ion and calcium ion belong to alkali metal, basic metal chemical property is all very active, the radius of potassium ion is greater than the radius of calcium ion simultaneously, so mode of replacing by ion, with potassium ion, replace calcium ion and form substitutional solid solution, potassium ion is fully introduced.It is soluble in water that preparation method of the present invention has overcome sylvite, is difficult for mixing the difficulty of hydroxyapatite; Meanwhile, adopt 80～160 ℃ of Aging Temperatures, be conducive to remove the impurity containing in precipitation, allow precipitation crystal grow, increase crystal particle diameter, and make its size distribution more even.According to preparation method of the present invention, make mix fluorine, potassium hydroxyapatite purity is high, dephasign is few, cost of material is cheap, source is abundant, preparation technology is simple, the high quality raw material of the high-quality hydroxylapatite biology medical material of preparation, combined chemotherapy drug use can strengthen drug effect and reduce toxic side effect, can be used as the type material that treatment dentin hypersensitiveness has desensitization function and repairing effect concurrently, for a long time, treat efficiently dental hypersensitiveness, so the invention provides a kind of prepare high-quality, the preparation method who mixes fluorine, potassium hydroxyapatite that output is large.
Further, the dry of raw material accelerated in the thermal treatment of 100～200 ℃.
Further, after drying precipitate, grind again and calcine, diameter of particle is more evenly distributed.
Accompanying drawing explanation
Fig. 1 is the diffraction photo that fluorine, potassium hydroxyapatite powder detect at X-ray diffractometer of mixing of the embodiment of the present invention 1 preparation, wherein X-coordinate be diffraction angle 2 θ/(°), ordinate zou is diffracted intensity.
Fig. 2 be the embodiment of the present invention 1 preparation mix fluorine, the image of potassium hydroxyapatite powder surface under scanning electronic microscope.
Fig. 3 be the embodiment of the present invention 2 preparation mix fluorine, the image of potassium hydroxyapatite powder surface under scanning electronic microscope.
Embodiment
The present invention includes following preparation process:
1) press Ca (NO
3)
24H
2o and H
3pO
4mol ratio be that 3:2 takes raw material; By Ca (NO
3)
24H
2o and distilled water are by 1:(10～20) mass ratio be hybridly prepared into Ca (NO
3)
24H
2o solution; By H
3pO
4with distilled water by 1:(45～90) mass ratio be hybridly prepared into H
3pO
4solution; By Ca (NO
3)
24H
2the O aqueous solution and H
3pO
4aqueous solution is even, obtains mixed solution, uses NaOH solution to regulate pH value to 8～14 of mixed solution to occur throw out, and centrifugation goes out throw out, and continuous washing, suction filtration.
2) by step 1) gained throw out puts into retort furnace, under 100～200 ℃ of conditions, being incubated 1～2 hour is dried, take out and grind, then put into corundum crucible and be warming up to 1300 ℃～1500 ℃ calcinings with 10 ℃/min, be incubated 0.5～2 hour, take out immediately, coolingly fast make white alpha-calcium phosphate powder.
3) by step 2) the alpha-calcium phosphate powder and KOH, the NH that make
4f is (1～2) in molar ratio: (1～4): (1～2), be dissolved in distilled water, still aging 12h～72 hour under 80～160 ℃ of conditions, washing suction filtration after taking out, then be dried, prepare and mix fluorine, potassium hydroxyapatite material, the chemical formula of wherein mixing fluorine, potassium hydroxyapatite is Ca
10-xk
x(PO
4)
6(OH)
2-yf
y0 < x≤2 wherein, 0 < y≤2.
Principal reaction process of the present invention and principle: step 1), under alkaline environment, principal reaction process is 3Ca (NO
3)
24H
2o+2H
3pO
4=Ca
3(PO4)
2↓+6HNO
3+ 4H
2o, thus prepare calcium phosphate raw material, raw material is in step 2) in through super-dry and after grinding size distribution even, again by high-temperature calcination calcium phosphate raw material, high temperature is the cooling alpha-calcium phosphate powder that makes rapidly, has avoided calcium phosphate inversion of phases in furnace cooling temperature-fall period to cause the impact of uneven components, and prepared calcium phosphate purity is high, step 3) in, alpha-calcium phosphate powder is carried out to the hydroxyapatite that aquation method prepares and there is good thermostability, pass through aquation method by fluorine simultaneously, potassium is introduced in hydroxyapatite, under 80～160 ℃ of conditions, ageing is more than 12 hours, because potassium ion and calcium ion belong to alkali metal, basic metal chemical property is all very active, the radius of potassium ion is greater than the radius of calcium ion simultaneously, so mode of replacing by ion, with potassium ion, replace calcium ion and form substitutional solid solution, potassium ion is fully introduced, overcome sylvite soluble in water, be difficult for mixing the difficulty of hydroxyapatite, meanwhile, adopt 80～160 ℃ of Aging Temperatures, be conducive to remove the impurity containing in precipitation, allow precipitation crystal grow, increase crystal particle diameter, and make its size distribution more even.
Below in conjunction with drawings and Examples, the present invention is described in further details.
Embodiment 1
Preparation method of the present invention comprises the following steps:
1) press Ca (NO
3)
24H
2o and H
3pO
4mol ratio be that 3:2 takes raw material, by Ca (NO
3)
24H
2o mixes by the mass ratio of 1:10 with distilled water, then by H
3pO
4the mass ratio of pressing 1:45 with distilled water mixes, then by H
3pO
4the aqueous solution joins Ca (NO
3)
2in solution, mix, obtain mixed solution, with NaOH solution, regulate the pH of mixed solution, make the pH value of mixture system maintain 8～10, then mixed solution is carried out centrifugal, continuous washing, suction filtration.
2) by step 1) gained throw out puts into retort furnace, and under 200 ℃ of conditions, heating and thermal insulation is 1 hour, takes out, grind, then put into corundum crucible and be warming up to 1300 ℃ with 10 ℃/min, be incubated after 2 hours, take out immediately, making white powder after cooling is alpha-calcium phosphate.
3) again by the alpha-calcium phosphate powder making and KOH, NH
4f is 2:2:1 in molar ratio, is dissolved in distilled water, and still aging 24h under 80 ℃ of conditions, after taking out, washing suction filtration, is then dried, and prepares and mixes fluorine, potassium hydroxyapatite material, and its chemical formula is Ca
9.5k
0.5(PO
4)
6(OH)
1.5f
0.5.
As shown in Figure 1, the hydroxy apatite powder grain-size of preparing after doping is larger, and crystallinity is better, and seldom, purity is higher for impurity.
Be illustrated in figure 2 the powder the prepared photo under scanning electronic microscope, crystal morphology is columnar structure as seen from the figure, and reason is that the basic crystal habit of hydroxyapatite belongs to hexagonal system, and crystal grain length is about 3-5um; There is new crystallization in part columnar grain, may be because mix K
+and F
-, due to K
+radius be greater than Ca
+so, after doping, form substitutional solid solution, crystalline structure is changed.
Embodiment 2
Preparation method of the present invention comprises the following steps:
1) press Ca (NO
3)
24H
2o and H
3pO
4mol ratio be that 3:2 takes raw material, by Ca (NO
3)
24H
2o mixes by the mass ratio of 1:12 with distilled water, then by H
3pO
4the mass ratio of pressing 1:90 with distilled water mixes, then by H
3pO
4the aqueous solution joins Ca (NO
3)
2in solution, mix, obtain mixed solution, with NaOH solution, regulate the pH of mixed solution, make the pH value of mixture system maintain 11～12, then mixed solution is carried out centrifugal, continuous washing, suction filtration.
2) by step 1) products therefrom puts into retort furnace, and under 150 ℃ of conditions, heating and thermal insulation is 1.5 hours, takes out, grind, then put into corundum crucible and be warming up to 1400 ℃ with 10 ℃/min, be incubated after 0.5 hour, take out immediately, making white powder after cooling is alpha-calcium phosphate.
3) again by the alpha-calcium phosphate powder making and KOH, NH
4f is 1:1:1 in molar ratio, is dissolved in distilled water, and still aging 48h under 120 ℃ of conditions, after taking out, washing suction filtration, is then dried, and can prepare and mix fluorine, potassium hydroxyapatite material, and its chemical formula is Ca
9.5k
0.5(PO
4)
6(OH) F.
Fig. 3 is prepared fluorine, the photo of potassium hydroxyapatite powder surface under scanning electronic microscope mixed.Whole grain formation comparison rule, is evenly distributed, and cluster appears in some areas.
Embodiment 3
Preparation method of the present invention comprises the following steps:
1) press Ca (NO
3)
24H
2o and H
3pO
4mol ratio be that 3:2 takes raw material, by Ca (NO
3)
24H
2o mixes by the mass ratio of 1:14 with distilled water, then by H
3pO
4the mass ratio of pressing 1:80 with distilled water mixes, then by H
3pO
4the aqueous solution joins Ca (NO
3)
2in solution, mix, obtain mixed solution, with NaOH solution, regulate the pH of mixed solution, make the pH value of mixture system maintain 13～14, then mixed solution is carried out centrifugal, continuous washing, suction filtration.
2) by step 1) gained throw out puts into retort furnace, and under 100 ℃ of conditions, heating and thermal insulation is 2 hours, takes out, grind, then put into corundum crucible and be warming up to 1350 ℃ with 10 ℃/min, be incubated after 1 hour, take out immediately, making white powder after cooling is alpha-calcium phosphate.
3) again by the alpha-calcium phosphate powder making and KOH, NH
4f is 1:2:1.5 in molar ratio, is dissolved in distilled water, and still aging 72h under 160 ℃ of conditions, after taking out, washing suction filtration, is then dried, and prepares and mixes fluorine, potassium hydroxyapatite material, and its chemical formula is Ca
9k (PO
4)
6(OH)
0.5f
1.5.
Embodiment 4
Preparation method of the present invention comprises the following steps:
1) press Ca (NO
3)
24H
2o and H
3pO
4mol ratio be that 3:2 takes raw material, by Ca (NO
3)
24H
2o mixes by the mass ratio of 1:16 with distilled water, then by H
3pO
4the mass ratio of pressing 1:50 with distilled water mixes, then by H
3pO
4the aqueous solution joins Ca (NO
3)
2in solution, mix, obtain mixed solution, with NaOH solution, regulate the pH of mixed solution, make the pH value of mixture system maintain 9～11, then mixed solution is carried out centrifugal, continuous washing, suction filtration.
2) by step 1) gained throw out puts into retort furnace, is incubated 1～2 hour and is dried under 100～200 ℃ of conditions, take out, grind, then put into corundum crucible and be warming up to 1450 ℃ with 10 ℃/min, be incubated after 1.5 hours, take out immediately, making white powder after cooling is alpha-calcium phosphate.
3) again by the alpha-calcium phosphate powder making and KOH, NH
4f is 1.5:4:1 in molar ratio, is dissolved in distilled water, and still aging 12h under 150 ℃ of conditions, after taking out, washing suction filtration, is then dried, and prepares and mixes fluorine, potassium hydroxyapatite material, and its chemical formula is Ca
8.5k
1.5(PO
4)
6(OH)
1.25f
0.75.
Embodiment 5
Preparation method of the present invention comprises the following steps:
1) press Ca (NO
3)
24H
2o and H
3pO
4mol ratio be that 3:2 takes raw material, by Ca (NO
3)
24H
2o mixes by the mass ratio of 1:18 with distilled water, then by H
3pO
4the mass ratio of pressing 1:60 with distilled water mixes, then by H
3pO
4the aqueous solution joins Ca (NO
3)
2in solution, mix, obtain mixed solution, with NaOH solution, regulate the pH of mixed solution, make the pH value of mixture system maintain 10～11, then mixed solution is carried out centrifugal, continuous washing, suction filtration.
2) by step 1) gained throw out puts into retort furnace, is incubated 1～2 hour and is dried under 100～200 ℃ of conditions, take out, grind, then put into corundum crucible and be warming up to 1500 ℃ with 10 ℃/min, be incubated after 1.5 hours, take out immediately, making white powder after cooling is alpha-calcium phosphate.
3) again by the alpha-calcium phosphate powder making and KOH, NH
4f is 1:3:1.75 in molar ratio, is dissolved in distilled water, and still aging 36h under 130 ℃ of conditions, after taking out, washing suction filtration, is then dried, and prepares and mixes fluorine, potassium hydroxyapatite material, and its chemical formula is Ca
8.75k
1.25(PO
4)
6(OH)
0.4f
1.6.
Embodiment 6
Preparation method of the present invention comprises the following steps:
1) press Ca (NO
3)
24H
2o and H
3pO
4mol ratio be that 3:2 takes raw material, by Ca (NO
3)
24H
2o mixes by the mass ratio of 1:20 with distilled water, then by H
3pO
4the mass ratio of pressing 1:70 with distilled water mixes, then by H
3pO
4the aqueous solution joins Ca (NO
3)
2in solution, mix, obtain mixed solution, with NaOH solution, regulate the pH of mixed solution, make the pH value of mixture system maintain 12～13, then mixed solution is carried out centrifugal, continuous washing, suction filtration.
2) by step 1) gained throw out puts into retort furnace, is incubated 1～2 hour and is dried under 100～200 ℃ of conditions, take out, grind, then put into corundum crucible and be warming up to 1420 ℃ with 10 ℃/min, be incubated after 2 hours, take out immediately, making white powder after cooling is alpha-calcium phosphate.
3) again by the alpha-calcium phosphate powder making and KOH, NH
4f is 1:4:2 in molar ratio, is dissolved in distilled water, and still aging 60h under 100 ℃ of conditions, after taking out, washing suction filtration, is then dried, and prepares and mixes fluorine, potassium hydroxyapatite material, and its chemical formula is Ca
8.2k
1.8(PO
4)
6(OH)
0.2f
1.8.
The prepared calcium phosphate purity of the present invention is 99.9%, by aquation method, fluorine, potassium are introduced in hydroxyapatite again, ageing for some time under 80～160 ℃ of conditions, potassium ion is fully introduced, by high-temperature calcination calcium phosphate raw material, high temperature is cooling rapidly, has avoided calcium phosphate inversion of phases in furnace cooling temperature-fall period to cause the impact of uneven components.The dry of raw material accelerated in thermal treatment; Meanwhile, adopt 80～160 ℃ of Aging Temperatures, be conducive to remove the impurity containing in precipitation, allow precipitation crystal grow, increase crystal particle diameter, and make its size distribution more even.It is soluble in water that this preparation process has overcome sylvite, is difficult for mixing the difficulty of hydroxyapatite, provide a kind of prepare high-quality, the preparation method who mixes fluorine, potassium hydroxyapatite that output is large.According to preparation method of the present invention, make mix fluorine, potassium hydroxyapatite purity is high, dephasign is few, cost of material is cheap, source is abundant, preparation technology is simple, be the high quality raw material of the high-quality hydroxylapatite biology medical material of preparation, combined chemotherapy drug use can strengthen drug effect and reduce toxic side effect.
Claims (10)
1. a preparation method who mixes fluorine, potassium hydroxyapatite material, is characterized in that: comprise the following steps:
1) by Ca (NO
3)
24H
2the O aqueous solution and H
3pO
4aqueous solution is even, obtains mixed solution, wherein Ca (NO
3)
24H
2o and H
3pO
4mol ratio be 3:2, regulate pH value to 8～14 of mixed solution to occur throw out, isolate throw out and wash;
2) by step 1) gained throw out is dried, and the quick cooling alpha-calcium phosphate powder that makes after calcining at 1300 ℃～1500 ℃;
3) by step 2) the alpha-calcium phosphate powder that makes is dispersed in and contains K
+and F
-basic solution in, under 80～160 ℃ of conditions more than still aging 12h, isolate powder after washing dry, prepare and mix fluorine, potassium hydroxyapatite material.
2. a kind of preparation method who mixes fluorine, potassium hydroxyapatite material according to claim 1, is characterized in that: Ca (NO described step 1)
3)
24H
2the O aqueous solution is Ca (NO
3)
24H
2o and water is by 1:(10～20) quality than mixed preparing, form.
3. a kind of preparation method who mixes fluorine, potassium hydroxyapatite material according to claim 1, is characterized in that: H described step 1)
3pO
4the aqueous solution is H
3pO
4with water by 1:(45～90) quality than mixed preparing, form.
4. according to a kind of preparation method who mixes fluorine, potassium hydroxyapatite material described in claim 2 or 3, it is characterized in that: described step 1), use NaOH solution to regulate the pH value of mixed solution.
5. a kind of preparation method who mixes fluorine, potassium hydroxyapatite material according to claim 4, is characterized in that: described step 1), centrifugation goes out throw out, and continuous washing, suction filtration.
6. a kind of preparation method who mixes fluorine, potassium hydroxyapatite material according to claim 1, is characterized in that: described step 2), dry is to be incubated 1～2 hour under 100～200 ℃ of conditions.
7. a kind of preparation method who mixes fluorine, potassium hydroxyapatite material according to claim 1, is characterized in that: described step 2), after drying precipitate, grind and calcine, calcination time is 0.5～2 hour.
8. a kind of preparation method who mixes fluorine, potassium hydroxyapatite material according to claim 1, is characterized in that: described step 3), contain K
+and F
-basic solution be KOH and NH
4f is dissolved in water and forms, and alpha-calcium phosphate and KOH, NH
4the mol ratio of F is (1～2): (1～4): (1～2).
9. a kind of preparation method who mixes fluorine, potassium hydroxyapatite material according to claim 1, is characterized in that: described step 3), the still aging time is 12～72 hours.
10. according to a kind of preparation method who mixes fluorine, potassium hydroxyapatite material described in claim 5-9 any one, it is characterized in that: the chemical formula of mixing fluorine, potassium hydroxyapatite of preparing described step 3) is Ca
10-xk
x(PO
4)
6(OH)
2-yf
y0 < x≤2 wherein, 0 < y≤2.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106691872A (en) * | 2016-11-24 | 2017-05-24 | 青岛大学 | Fluorine-doped tooth remediation material and preparation method thereof |
| GB2554484B (en) * | 2016-04-14 | 2021-07-07 | M B Lloyd Ltd | A dental formulation for the treatment of tooth sensitivity |
| CN114014288A (en) * | 2021-11-09 | 2022-02-08 | 中南大学 | Calcium fluoride modified hydroxyapatite powder and preparation method thereof |
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|---|---|---|---|---|
| CN1481343A (en) * | 2000-10-16 | 2004-03-10 | 南卡罗来纳州大学 | Biocompatible cement contg reactive calcium phosphate nanoparticles and methods for making and using such cement |
| EP1473273A1 (en) * | 2003-05-02 | 2004-11-03 | Biomet Deutschland GmbH | Method of preparing alpha-and beta-tricalcium phosphate powders |
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2014
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1481343A (en) * | 2000-10-16 | 2004-03-10 | 南卡罗来纳州大学 | Biocompatible cement contg reactive calcium phosphate nanoparticles and methods for making and using such cement |
| EP1473273A1 (en) * | 2003-05-02 | 2004-11-03 | Biomet Deutschland GmbH | Method of preparing alpha-and beta-tricalcium phosphate powders |
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| MONICA BEATRIZ THURMER ET AL.: "Synthesis of Alpha-tricalcium phosphate by wet reaction and evaluation of mechanical properties", 《MATERIALS SCIENCE FORUM》, vol. 727728, 31 December 2012 (2012-12-31), pages 1164 - 1169 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| GB2554484B (en) * | 2016-04-14 | 2021-07-07 | M B Lloyd Ltd | A dental formulation for the treatment of tooth sensitivity |
| CN106691872A (en) * | 2016-11-24 | 2017-05-24 | 青岛大学 | Fluorine-doped tooth remediation material and preparation method thereof |
| CN114014288A (en) * | 2021-11-09 | 2022-02-08 | 中南大学 | Calcium fluoride modified hydroxyapatite powder and preparation method thereof |
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