Diffusion Kinetics of Carbonate Hydroxyapatite (CHAP) for Adsorbing F^- Dissolved in Water

A systematic research was performed about diffusion kinetics of adsorbing F^- dissolved in water for carbonate hydroxyapatite （CHAP） from the natural hydroxyapatite which was modified by adulterating with CO3^2-. The result shows that the speed of F^- adsorption is controlled by membrane diffusion when F^- concentration is relatively low, which is expressed by the kinetic equation of diffusion Q=0.0005（Ci-C）（t-ti）＋0.3967, or by vacancy diffusion when F^- concentration is relatively high, which is expressed by the kinetic equation of diffusion In[C（o, t）]=8.4718-0.5048Int. Based on the feature of CHAP for adsorbing F^- dissolved in water and its special channel of the structure of CO3^3- modified hydroxyapatite, models of vacancy diffusion and membrane diffusion were established.

Removal Mechanism of Aqueous Lead by a Novel Eco-material: Carbonate Hydroxyapatite

Kinetics and mechanisms on the removal of aqueous lead ion by carbonate hydroxyapatite （CHap） are investigated in the present work. Experimental results show that, in the whole pH range, the lead removal percentage increases with decreasing pH values and reaches a maximum at pH=2-3. Under some conditions, the lead residual concentration is below national integrated wastewater discharge standard, even drinking water standard. The removal behavior is a complicated non-homogeneous solid/liquid reaction, which can be described by two stages from kinetic point of view. At the earlier stage, reaction rate is so fast that its kinetic course is intricate, which requires further study. At the latter stage, the rate of reaction becomes slow and the process of reaction accords with one order reaction kinetic equation. Experimental results show that the relationship between reaction rate constant k1 and temperature T accords to Arrhenius Equation, and the activation energy of sorption （Ea） is 11.93 kJ/mol and frequency factor （A） is 2.51 s^-1. X-ray diffraction （XRD）, scanning electron microscopy with an energy dispersive X-ray fluoresence spectrometer （SEM-EDS） and toxicity characteristic leaching procedure （TCLP） test were conducted in this work. It is indicated that the main mechanism is dissolution-precipitation, accompanying with superficial sorption.

Statistical Studies of the Physicochemical Analytic Results of a Series of Synthetic Calcium Hydroxyapatite Containing Carbonate and Sodium

The objective of this study is to present a simple method of statistical calculation that allowed us to determine the relationship between the different data obtained from the characterization of the synthetic carbonated apatites containing sodium, in order to find the fundamental substitution mechanism(s) for incorporation of Na+ and?CO32- and to establish the general formula. For that, a series of hydroxyapatites containing carbonate and sodium (Na-CO3HAps) has been obtained by the precipitation method. All the compounds were characterized by infrared spectra (IR), powder X-ray diffraction (PXRD) and elemental analysis. The statistical treatment of the experiment result allows us to determine the relationship between one variable and the change in the other and to found the fundamental substitution mechanism(s) for incorporation of Na+ and?CO32- . Analysis of variance (ANOVA) allows us to test the models proposed.

Nanometre Carbonated Hydroxyapatite Powders Synthesis Controlled by Lecithin in Synthetic Body Fluids

Nanocrystal carbonated hydroxyapatite was prepared by lecithin-controlled chemical precipitation in synthetic body fluid （SBF）. The reactant was aged and heated at 850℃ for crystallization. The morphology and microstructure of the carbonated hydroxyapatite were investigated using transmission electron microscope （TEM）, X-ray diffraction （ XRD ） and FTIR. The experimental results demonstrate that the shapes of carbonated hydroxyapdtite particles display spheres with the average size of 20- 28 nm, and carbonated hydroxyapatite contained carbonate ions, similar to mineral of bone tissues.

Synthesis of Crystalline Hydroxyapatite from CaCO_3 and CaHPO_4·2H_2O by Mechanochemical Method

The mixture of CaHPO 4·2H 2O and CaCO 3 was ground in an aqueous system under appropriate conditions to investigate the mechanochemical reaction for the synthesis of crystalline hydroxyapatite (HA) powder. Hydroxyapatite of high crystallinity powder including trace Ca 10 (PO 4) 6CO 3(OH) and Ca 9HPO 4(PO 4) 6OH can be synthesized by mechanical activation without further thermal treatment at a high temperature. The synthesis reaction during the grinding process was almost completed within 1h. The as-ground powder exhibits a particle distribution of 20-100nm in size with a spherical or rodlike morphology. The composition and degree of crystallinity of the mechanochemical synthesized hydroxyapatite powders were coincident with the cement-type hydroxyapatite.

Engineering of Carbonate Apatite Bone Substitute Based on Composition-Transformation of Gypsum and Calcium Hydroxide

Even though a lot of research has been carried out concerning the preparation of carbonate apatite (CHA), they were related to CHA in the form of powder. In the present study, macroporous CHA bone substitutes were prepared through composition-transformation of gypsum and Ca-hydroxide. Here, we investigated the effect of added Ca-hydroxide to gypsum, carbonation periods, and hydrothermal temperatures for phosphatization to understand the basic principle of composition-transformation of gypsum added Ca-hydroxide to fabricate CHA bone substitutes. The specimens were characterized in terms of chemical and physical properties, such as extent of transformation of macroporous gypsum added Ca-hydroxide into CHA body, type and content of carbonate, and crystal morphology. It was observed that the transformation was faster with higher hydrothermal temperature. However, higher hydrothermal temperature caused de-carbonation phenomena which resulted in the lack of carbonate ions of the product. Moreover, the higher the percentage of Ca-hydroxide added to gypsum, caused the complete transformation of gypsum into CHA to be slower. These findings have been applied to the standard fabrication procedure of carbonate apatite, which in turn will allow scaling up process, and will be provided for biomedical purposes for the Indonesian community.

Bi-/multi-modal pore formation of PLGA/hydroxyapatite composite scaffolds by heterogeneous nucleation in supercritical CO_2 foaming

Scaffolds with multimodal pore structure are essential to cells differentiation and proliferation in bone tissue engineering. Bi-/multi-modal porous PLGA/hydroxyapatite composite scaffolds were prepared by supercritical C02 foaming in which hydroxyapatite acted as heterogeneous nucleation agent. Bimodal porous scaffolds were prepared under certain conditions, i.e. hydroxyapatite addition of 5%, depressurization rate of 0.3 MPa. min-1, soaking temperature of 55 ℃, and pressure of 9 MPa. And scaffolds presented specific structure of small pores （122 μM ± 66 μm） in the cellular walls of large pores （552 μm ±127 μm）. Furthermore, multimodal porous PLGA scaffolds with micro-pores （37 μM ± 11μM） were obtained at low soaking pressure of 7.5 MPa. The interconnected porosity of scaffolds ranged from （52.53 ± 2.69）% to （83.08±2.42）% by adjusting depressurization rate, while compression modulus satisfied the requirement of bone tissue engineering. Solvent-free CO2 foaming method is promising to fabricate bi-/multi-modal porous scaffolds in one step, and bioactive particles for osteogenesis could serve as nucleation agents.

Fabrication and Characterization of Hierarchically Nanostructured Porous Carbonated Hydroxyapatite Coatings

Hierarchically nanostructured porous carbonated hydroxyapatite coatings (HNPCs) on Ti6Al4V substrate were fabricated by a two-stage application route: fabrication of nacre coatings (NCs) on Ti6Al4V substrate by electrophoretic technique, and conversion of NCs to HNPCs in a phosphate buffer solution (PBS) by microwave irradiation method. Their samples were characterized by using XRD, FT-IR, SEM, TEM, and N2 adsorption-desorption isotherms. The results show that the microwave irradiation technique improves obviously the conversion rate of NCs to HNPCs as compared with conventional method. After soaking the NCs in the PBS, calcium ions are released from the nacre particles and react with phosphate ions to form carbonated hydroxyapatite nanoparticles. These nanoparticles aggregate to form the plate-like carbonated apatite. The mesopores with a size of about 3.9 nm and macropores with the diameters of 1~4μm exist within and among the carbonated apatite plates, respectively. Simulated body fluid immersion tests reveal that the HNPCs have a good in vitro bioactivity.

纳米CHAP的替换结构及其相变、吸F^-行为研究

用sol-gel法制备了不同CO32-掺量的碳羟磷灰石（CHAP）;采用FTIR、DTA、TG、XRD、TEM、晶粒密度测定、静态吸附等方法研究了CHAP的替换结构及其相变和吸F-行为.结果表明;CHAP属AB混合型替换结构;当WCO32-<3.34％时,随CO32-含量增加,RI增大,吸氟量减小,吸氟过程中有较强的优先吸附CO32-进入其晶格的能力,150～776℃脱CO32-相变为钙亏HAP,776℃时脱羟相变为TCP相;当WCO32-=3.34％时,RI达最大值,脱CO32-相变为正常配比HAP,在776℃时不发生脱羟相变;当3.34％<WCO32-≤7.52％时,随CO32-含量增加,RI减小,吸氟量增大,吸氟过程中有较强的优先吸附F-进入其晶格的能力而CO32-被交换出来,脱CO32-相变为钙盈HAP,在776℃时不发生脱羟相变;CHAP纳米晶有沿柱长方向的溶解行为,比纯HAP的吸氟量大2～3倍,表现出纳米尺度下的溶解-沉淀吸附效应.

微波等离子体烧结制备多孔纳米CHA/β-TCP双相生物陶瓷

为了提高钙磷陶瓷材料性能,以含碳酸化羟基磷灰石纳米粉体(CHA)为原料,采用含水蒸汽CO2微波等离子体快速烧结新技术阻止CHA分解和实现多孔CHA/β-TCP双相生物陶瓷的纳米化。在优化工艺条件下,制得平均晶粒尺寸为92 nm,气孔率为55.9%,CO32-含量约为4%,压缩强度为13.7 MPa的多孔纳米TCP/CHA双相生物陶瓷。与常规马弗炉烧结相比,微波等离子体烧结时间缩短,烧结温度降低,能有效阻止CHA分解,提高烧结效率。微波等离子体烧结是一种快速制备纳米生物陶瓷的有效方法。

n-CHA/HDPE和n-CHA/gHDPE生物复合材料的界面表征

采用常压共溶复合工艺,在溶液体系中合成了分散均匀的n-CHA/HDPE,n-CHA/gHDPE两种生物功能材料,利用各种检测手段分析复合材料的界面结合状态。结果表明:n-CHA/HDPE复合材料是简单物理共混;而n-CHA/gHDPE复合材料则具有稳定的界面结合,n-CHA与gHDPE两相界面间有化学键形成。

碳酸化羟基磷灰石/胶原(nCHAC)生物复合材料的室温制备及表征

通过仿生自组装法在室温下制备了纳米碳酸化羟基磷灰石/胶原(nCHAC)复合材料,并借助X射线衍射(XRD)分析、热分析(TGA)和透射电镜(TEM)的观察对其进行了表征,结果表明:(1)该材料具有与天然骨相同的纳米尺度和胶原蛋白无机相,含有2.8%～14.7%(wt)的碳酸成分;(2)显微结构是矿化的胶原纤维束,类似于天然骨的分级结构。揭示了碳酸和胶原含量不同的复合材料中具有微小差别的自组装单元。碳酸的百分含量影响矿物的晶体尺寸和胶原纤维的组装。因此,nCHAC复合材料是有前途的硬组织修复用材料,这要归功于生物仿生制备出的材料具有与天然骨类似的成分和类似的微观结构。

Hydroxyapatite composites with carbon allotropes:Preparation,properties,and applications

Hydroxyapatite(HA)and its composites with inorganic additives,dopants,and polymers is a rapidly developing branch in the materials chemistry.In particular,carbon allotropes are widely used in these composites being widely applied for medical purposes.Observing a gap of insufficient generalization of recent achievements in the field of the HA/Carbon composites,in this review we present the state of the art of the field of HA composites and hybrids with classic carbon allotropes and nanocarbons.These composites are known for carbon nanotubes,nanofibers,graphene and its oxidized forms,as well as,in a lesser grade,for graphite,fullerenes,nanodiamonds,carbon nanofoams,etc.These composites can be fabricated by a variety of classic and less-common methods,such as co-precipitation(with or without ultrasonic treatment),CVD,hot isostatic pressing,hydrothermal,spark plasma sintering,biomimetic mineralization,thermal and plasma spray,electrochemical and electrophoretic deposition,self-assembling,3D printing,electrospinning,and lyophilisation,among others.Combination of various synthesis techniques can be also carried out for composite preparation.Natural or synthetic HA can be used as it is for further interaction with carbon allotropes or it can be first prepared and then reacted with carbon counterpart;similarly,carbon allotropes can be introduced into the interaction with HA directly or they can be first synthesized,in particular from biomass.Resulting biocompatible composites can be produced in the form of coatings,powders,and scaffolds and can additionally contain quantitative amounts of third phases,frequently natural or synthetic polymers.In these composites,especially with O-containing functionalizing groups,HA disadvantages could be considerably decreased with simultaneous enhancement of mechanical properties,becoming similar to human bone,chemical stability and biocompatibility,as well as possessing antibacterial effect.GO→G reduction and higher HA decoration were observed in several experiments.The morphology of polymer-containing HA/GO composites can be tuned by variations of GO:polymer ratios.Predominant number of resulting applications of formed HA composites corresponds to the biomedical area,mainly for orthopedic applications/implants,osteoporosis treatment,myocardial,skin and dental regeneration,etc.Other important uses include applications as adsorbents for the elimination of impurities from wastewaters and/or removal/uptake of heavy metal cations,loading several medicines,and energy storage materials.Biocompatibility and hemocompatibility aspects of HA/Carbon composites are also discussed and future developments are proposed.

天然胶磷矿制备孔形CHAp及其表征

在研究宜昌磷矿矿物组成和化学组成的基础上,以宜昌磷矿中的胶磷矿为主要原料,采用模板诱导/均相沉淀法制备了孔型碳羟磷灰石,通过XRD、FT-IR、SEM对产物进行了表征分析.结果表明,所制得的产物为A型取代碳羟磷灰石.产物是由纳米薄片组装而成的多孔碳羟磷灰石球体,孔径约为1.5μm.

Effect of Synthesis Technique and Carbonate Content on the Crystallinity and Morphology of Carbonated Hydroxyapatite

The syntheses of nanosized carbonated hydroxyapatite （CHA） were performed by comparing dropwise and direct pouring of acetone solution of Ca（NO3）2·4H2O into mixture of （NH4）2HPO4 and NH4HCO3 at room temperature controlled at pH 11. Direct pouring method was later applied to study the increment of carbonate content in syntheses. The as-synthesized powders were characterized by various characterization techniques. The crystallographic results of the produced powders were obtained from X-ray diffraction analysis, whilst the carbonate content in the produced powders was determined by the CHNS/O elemental analyzer. Fourier transform infrared analysis confirmed that the CHA powders formed were B-type. Field emission scanning electron microscopy revealed that the powders were highly agglomerated in nanosized range and hence energy filtered transmission electron microscopy was employed to show elongated particles which decreased with increasing carbonate content.

Co-substitution of carbonate and fluoride in hydroxyapatite： Effect on substitution type and content

The nanosized hydroxyapatite substituted by fluoride and carbonate ions （CFHA） had been synthesized by aqueous precipitation method. CFHA had been considered as potential bone graft material for orthopedic and dental applications. The objective of this study was to determine the effects of simultaneously incorporated CO2/3- and F- on the substitution type and content. The morphologies of CFHAs were observed by TEM. The carbonate substitution type and content were characterized by FTIR. The fluoride contents were determined by F-selective electrode. The phase compositions and crystallinity of the samples were investigated by XRD. The fluoride and carbonate contents of CFHA increase with the dopant concentrations nonlinearly, The carbonate substitution has much more obvious effect on morphology compared with the fluoride substitution. The co-existence of CO2/3-and F- ions can influence the corresponding substitution fraction. The isomorphic substitution of sodium for calcium in the substitution process of CO2/3-can improve crystal degree and favor the B-type substitutions. Due to the closeness of the ion radii and equivalent substitution of F- and OH-, F- will occupy the OH- sites of HA crystals more easily, compelling most of the CO2/3- to be located in the B sites.

Facile Template-free Synthesis of Carbonated Hydroxyapatite Spheres in Aqueous Solution

Prickly carbonated hydroxyapatite（CHAp） spheres were obtained via a facile template-free self-assembly method with Na2HPO4 and self-made cubic CaCO3 as reactants. X-ray diffraction results of the product revealed CHAp with high crystallinity could be successfully prepared in a short reaction time. A nucleation mechanism was proposed according to the results of characterizing the resultant powders and analyzing the growth process. It shows that the self-made CaCO3 particles play an important role in the template-free synthesis of prickly spheres.

High-performance SSZ-13 membranes prepared using ball-milled nanosized seeds for carbon dioxide and nitrogen separations from methane

SSZ-13 membranes with high separation performances were prepared using ball-milled nanosized seeds by once hydrothermal synthesis.Separation performances of SSZ-13 membranes in CO2/CH4 and N2/CH4 mixtures were enhanced after synthesis modification.Single-gas permeances of CO2,N2 and CH4 and ideal selectivities were recorded through SSZ-13 membranes.The effects of temperature,pressure,feed flow rate and humidity on separation performance of the membranes were discussed.Three membranes prepared after synthesis modifications had an average CO2 permeance of 1.16×10-6 mol·(m2·s·Pa)-1(equal to 3554 GPU)with an average CO2/CH4 selectivity of 213 in a 50 vol%/50 vol%CO2/CH4 mixture.It suggests that membrane synthesis has a good reproducible.The membrane also displayed a N2 permeance of 1.07×10-7 mol·(m2·s·Pa)-1(equal to 320 GPU)with a N2/CH4 selectivity of 13 for a 50 vol%/50 vol%N2/CH4 mixture.SSZ-13 membrane displayed stable and good separation performance in the wet CO2/CH4 mixture for a long test period over 100 h at 348 K.The current SSZ-13 membranes show great potentials for the simultaneous removals of CO2 and N2 in natural gas purification as a facile process suitable for industrial application.