氟化羟基磷灰石的制备及氟的影响研究
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摘要
以Ca(CH_3COO)_2·H_2O、KH_2PO_4和KF·2H_2O为原料,室温下采用化学沉淀法在p H为7的条件下制备得到氟化羟基磷灰石(FHA)。通过对不同氟含量的FHA进行XRD、FTIR等手段分析,结果表明加入F不会改变FHA晶体结构,但晶格参数a减小;F取代HA中的OH,随着F加入量增大,F取代OH难度增加;在FHA中形成氢键OH…F,约束晶胞规则有序生长,使FHA的结晶性提高;HA中原有的长程有序排列…HOHOHO…逐渐转变为F和OH的间隔性排列…F(HO)_nF…;FHA晶体形态为短棒状,长度约为150 nm,直径约为20 nm,随F含量增加,FHA晶粒直径增大。
Fluoride-hydroxyapatite was synthesized by chemical precipitation method using Ca(CH_3COO)_2·H_2O、KH_2PO_4andKF·2H_2O as raw materials, controlling the p H value to 7. The structure and morphology of FHA containing different fluoride contents were analyzed by XRD, FTIR, etc.. Results showed that F wouldn't change the crystal structure of FHA but the lattice parameter a was decreased. OH was replaced by F, and OH was replaced difficultly with fluoride content increasing. OH…F bond was formed between crystalline, and the bond restrained the ordered growth of fluoride-hydroxyapatite crystal cells, which resulted in that the crystallinity increased as F content increased. The initial long-range order…HOHOHO…was transferred to intermittent arrangement of F and OH, …F(HO)_nF…. The morphology of fluoride-hydroxyapatite was rod-like shape with the length of about 150 nm, diameter of about 20 nm, and the width increased along with the increase of F content.
Fluoride-hydroxyapatite was synthesized by chemical precipitation method using Ca(CH_3COO)_2·H_2O、KH_2PO_4andKF·2H_2O as raw materials, controlling the p H value to 7. The structure and morphology of FHA containing different fluoride contents were analyzed by XRD, FTIR, etc.. Results showed that F wouldn't change the crystal structure of FHA but the lattice parameter a was decreased. OH was replaced by F, and OH was replaced difficultly with fluoride content increasing. OH…F bond was formed between crystalline, and the bond restrained the ordered growth of fluoride-hydroxyapatite crystal cells, which resulted in that the crystallinity increased as F content increased. The initial long-range order…HOHOHO…was transferred to intermittent arrangement of F and OH, …F(HO)_nF…. The morphology of fluoride-hydroxyapatite was rod-like shape with the length of about 150 nm, diameter of about 20 nm, and the width increased along with the increase of F content.
引文
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[2]Boanini E,Torricelli P,Gazzano M,et al.Combined effect of strontium and zoledronate on hydroxyapatite structure and bone cell responses[J].Biomaterials,2014,35(21):5619-5626.
[3]Hoepfner T P,Case E D.The influence of the microstructure on the hardness of sintered hydroxyapatite[J].Ceramics International,2003,29(6):699-706.
[4]Viswanath B,Shastry V V,Ramamurty U,et al.Effect of calcium deficiency on the mechanical properties of hydroxyapatite crystals[J].Acta materialia,2010,58(14):4841-4848.
[5]Gross K A,Rodrguez-Lorenzo L M.Sintered hydroxyfluorapatites.Part I:sintering ability of precipitated solid solution powders[J].Biomaterials,2004,25(7):1375-1384.
[6]Gross K A,Rodrguez-Lorenzo L M.Sintered hydroxyfluorapatites.PartⅡ:Mechanical properties of solid solutions determined by microindentation[J].Biomaterials,2004,25(7):1385-1394.
[7]Chen Y,Miao X.Thermal and chemical stability of fluorohydroxyapatite ceramics with different fluorine contents[J].Biomaterials,2005,26(11):1205-1210.
[8]Okazaki M,Tohda H,Yanagisawa T,et al.Differences in solubility of two types of heterogeneous fluoridated hydroxyapatites[J].Biomaterials,1998,19(7):611-616.
[9]Qu H,Wei M.The effect of fluoride contents in fluoridated hydroxyapatite on osteoblast behavior[J].Acta biomaterialia,2006,2(1):113-119.
[10]LeGeros R Z.Properties of osteoconductive biomaterials:calcium phosphates[J].Clinical orthopaedics and related research,2002,395:81-98.
[11]Qu H,Wei M.Effect of fluorine content on mechanical properties of sintered fluoridated hydroxyapatite[J].Materials Science and Engineering.C,2006,26(1):46-53.
[12]Harrison J,Melville A J,Forsythe J S,et al.Sintered hydroxyfluorapatitesⅣ:the effect of fluoride substitutions upon colonisation of hydroxyapatites by mouse embryonic stem cells[J].Biomaterials,2004,25(20):4977-4986.
[13]巩梦安,饶群力,王鸿烈.造孔剂和发泡剂结合法制备氟化羟基磷灰石多孔支架研究[J].无机材料学报,2014,29(3):289-293.
[14]Hughes J M,Cameron M,Crowley K D.Ordering of divalent cations in the apatite structure;crystal structure refinements of
[15]natural Mn-and Sr-bearing apatite[J].American Mineralogist,1991,76(11-12):1857-1862.
[16]Freund F,Knobel R M.Distribution of fluorine in hydroxyapatite studied by infrared spectroscopy[J].Journal of the Chemical Society,Dalton Transactions,1977(11):1136-1140.
[17]Wei M,Evans J H,Bostrom T,et al.Synthesis and characterization of hydroxyapatite,fluoride-substituted hydroxyapatite and fluorapatite[J].Journal of materials science:materials in medicine,2003,14(4):311-320.
[18]Zhai Y Q,Li K Z,Li H J,et al.Influence of NaF concentration on fluorine-containing hydroxyapatite coating on carbon/carbon composites[J].Materials Chemistry and Physics,2007,106(1):22-26.
[19]Kanchana P,Sekar C.Influence of sodium fluoride on the synthesis of hydroxyapatite by gel method[J].Journal of Crystal Growth,2010,312(6):808-816.