Influence of fuels and combustion aids on solution combustion synthesis of bi-phasic calcium phosphates (BCP)

The possibility to obtain biphasic HA/TCP composite by solution combustion synthesis method using urea and glycine as fuels was investigated. Calcium nitrate was taken as a source of calcium, and diammonium hydrogen phosphate served as a source of phosphate ions. Nitric acid and nitrate ions were used as oxidizers. The effect of the nature of fuel (urea and glycine) and fuel to oxidizer ratio on the combustion behavior, as well as, chemical composition and morphology of as-formed powders was investigated. It was found that only monoclinic-TCP was formed in the combustion end-product when glycine was used. In contrast to this, the use of certain amount of urea led to the formation of rhombohedral-TCP. A series of combustion reactions were carried out to study the influence of fuel to oxidizer ratio on HA to TCP ratio in synthesized product.     

Effect of metal-ion-to-fuel ratio on the phase formation of bioceramic phosphates synthesized by self-propagating combustion

Synthetic calcium hydroxyapatite (HAP, Ca₁₀ (PO₄)₆ (OH)₂) is a well-known bioceramic material used in orthopedic and dental applications because of its excellent biocompatibility and bone-bonding ability due to its structural and compositional similarity to human bone. Here we report, for the first time, the synthesis of HAP by combustion employing tartaric acid as a fuel. Calcium nitrate is used as the source of calcium and diammonium hydrogen phosphate serves as the source of phosphate ions. Reaction processing parameters such as the pH, fuel-oxidant ratio and autoignition temperature are controlled and monitored. The products were characterized by powder x-ray diffraction, which revealed the formation of a hexagonal hydroxyapatite phase. Fourier transform infrared spectroscopy (FT-IR) spectra showed that the substitution of a carbonate ion occurs at the phosphate site. The morphology of the particles was imaged by scanning electron microscopy, which also revealed that the particles are of submicron size. Thermal analysis showed that the phase formation takes place at the time of combustion. Surface area and porosity analysis showed that the surface area is high and that the pores are of nanometer size. The mean grain size of the HAP powder, determined by the Debye–Scherrer formula, is in the range 20–30 nm. Chemical analyses to determine the Ca : P atomic ratio in synthesized ceramics were performed, and it was found to be 1 : 1.66.     

Effect of metal-ion-to-fuel ratio on the phase formation of bioceramic phosphates synthesized by self-propagating combustion

Abstract

Synthetic calcium hydroxyapatite (HAP, Ca₁₀ (PO₄)₆ (OH)₂) is a well-known bioceramic material used in orthopedic and dental applications because of its excellent biocompatibility and bone-bonding ability due to its structural and compositional similarity to human bone. Here we report, for the first time, the synthesis of HAP by combustion employing tartaric acid as a fuel. Calcium nitrate is used as the source of calcium and diammonium hydrogen phosphate serves as the source of phosphate ions. Reaction processing parameters such as the pH, fuel-oxidant ratio and autoignition temperature are controlled and monitored. The products were characterized by powder x-ray diffraction, which revealed the formation of a hexagonal hydroxyapatite phase. Fourier transform infrared spectroscopy (FT-IR) spectra showed that the substitution of a carbonate ion occurs at the phosphate site. The morphology of the particles was imaged by scanning electron microscopy, which also revealed that the particles are of submicron size. Thermal analysis showed that the phase formation takes place at the time of combustion. Surface area and porosity analysis showed that the surface area is high and that the pores are of nanometer size. The mean grain size of the HAP powder, determined by the Debye–Scherrer formula, is in the range 20–30 nm. Chemical analyses to determine the Ca : P atomic ratio in synthesized ceramics were performed, and it was found to be 1 : 1.66.     

丙酰胺为沉淀剂水热合成羟基磷灰石纤维

采用四水硝酸钙和磷酸氢二铵的混合物为前驱体, 以丙酰胺(PA)为沉淀剂来控制溶液的过饱和度, 经水热均相法处理成功制备了高结晶度、形貌均一、分散性良好的纤维状羟基磷灰石(HA)粉体。通过X射线衍射(XRD)、傅里叶红外光谱(FT-IR)、扫描电镜(SEM)和透射电镜(TEM)对所制备的HA进行了表征, 研究了初始pH值和前驱体浓度对HA形貌、组成、结晶度及生长习性的影响。结果表明: 初始pH值较低时有利于纤维状HA粉体的形成, 前驱体浓度较低时则能促进纤维的宽化; 但是初始pH值和前驱体浓度对产物的晶体结构、组成及结晶度影响不大。     

钛酸锶钡的自燃烧法合成、表征及电性能研究

以硝酸钡、硝酸锶、钛酸丁酯和柠檬酸为原料,采用自燃烧法合成了晶粒尺寸～20nm Ba0.5Sr0.5TiO3(BST)超细粉体。利用溶液中各种离子分布与溶液pH值的关系,研究了金属离子-柠檬酸水溶液体系中的络合pH条件,得到了自燃烧制备BST的最佳pH值范围。借助TG-DSC、IR、XRD和TEM研究了硝酸盐-柠檬酸盐干凝胶的自蔓延燃烧机理以及产物的物相结构和形貌特征。结果表明,自燃烧蔓延是在硝酸根离子和羧酸根离子之间进行的热诱导阴离子氧化还原反应,其中,硝酸根离子作氧化剂,羧酸根离子作还原剂。燃烧后得到了分散均匀,团聚少的BST纳米晶。将粉末压片在1100～1250℃烧结2h后,测试了烧结体样品的电容和介电损耗随频率变化的关系,并对变化的原因进行了详细分析。     

Synthesis of nano-sized hydroxyapatite powders through solution combustion route under different reaction conditions

Calcium hydroxyapatite, Ca₁₀(PO₄)₆(OH)₂ (HAp) was synthesized by combustion in the aqueous system containing calcium nitrate-diammonium hydrogen orthophosphate with urea and glycine as fuels. These ceramics are important materials for biomedical applications. Thermo-gravimetric and differential thermal analysis were employed to understand the nature of synthesis process during combustion. Effects of different process parameters namely, nature of fuel (urea and glycine), fuel to oxidizer ratio (0.6-4.0) and initial furnace temperature (300-700 °C) on the combustion behavior as well as physical properties of as-formed powders were investigated. A series of combustion reactions were carried out to optimize the reaction parameters for synthesis of nano-sized HAp powders. The combustion temperature (T_f) for the oxidant and fuels were calculated to be 896 °C and 1035 °C for the stoichiometric system of urea and glycine respectively. The stoichiometric glycine-calcium nitrate produced higher flame temperature (both calculated and measured) and powder with lower specific surface area (8.75 m²/g) compared to the stoichiometric urea-calcium nitrate system (10.50 m²/g). Fuel excess combustion in both glycine and urea produced powders with higher surface area. Nanocrystalline HAp powder could be synthesized in situ with a large span of fuel to oxidizer ratio (φ) in case of urea system (0.8 < φ < 4) and (0.6 < φ < 1.5) for the glycine system. Calcium hydroxyapatite particles having diameters ranging between 20 nm and 120 nm could be successfully synthesized through optimized process variable.     

柠檬酸钠调控水热合成羟基磷灰石微球

本研究采用四水硝酸钙(Ca(NO₃)₂·4H₂O)和磷酸氢二铵((NH₄)₂HPO₄)分别作为钙源和磷源, 以丙酰胺为pH调节剂调控溶液的过饱和度, 以柠檬酸钠为钙源缓释剂调控羟基磷灰石(Hydroxyapatite, HA)的形貌, 经水热法处理成功制备出高结晶度、形貌均一和分散性良好的HA微球。采用X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)和扫描电镜(SEM)对反应产物进行了表征, 研究了初始pH值、柠檬酸钠加入量和水热反应温度对HA结晶度、组成及形貌的影响。研究结果表明, 当初始pH值为3, 柠檬酸钠与钙源的摩尔比为1︰1.5, 反应温度为180℃时, 有利于HA微球的形成。     

Growth of calcium phosphate on ion-exchange resins pre-saturated with calcium or hydrogenphosphate ions: an SEM/EDX and XPS study

Calcium phosphate formed on the surfaces of ion-exchange resins pre-saturated with either Ca²⁺ or HPO₄ ^2- ions has been studied using a combination of scanning electron microscopy (SEM)/energy dispersive X-ray (EDX) analysis and X-ray photoelectron spectroscopy (XPS). Calcium phosphate was formed at a temperature of 36.5°C via two methods. On Ca²⁺ or HPO₄ ^2--saturated resins, 1.5xSBF (simulated body fluid) solution was used while on Ca²⁺-saturated resins only, a novel biomimetic growth medium using the alkaline phosphatase-catalysed hydrolysis reaction of disodium p-nitrophenylphosphate as a source of inorganic phosphate was employed. SEM micrographs showed that the use of 1.5xSBF growth medium solution led to extensive coverage of the resins with calcium phosphate. In contrast, calcium phosphate coatings formed via the alkaline phosphatase-catalysed reaction were of a more variable quality whose morphology could be influenced by adding albumin and collagen to the growth medium. Average Ca:P ratios determined by EDX for coatings formed from the 1.5xSBF growth medium were in the range 1.62–1.74 suggesting that hydroxyapatite had formed. In contrast, Ca:P ratios for the calcium phosphate compounds formed on resins from the alkaline phosphatase reaction were lower at 1.50 suggesting that calcium-deficient hydroxyapatite had formed which was confirmed by inductively coupled plasma (ICP) analysis and X-ray diffraction of isolated amorphous and crystallized powder samples, respectively. Evidence from X-ray photoelectron studies supports a mechanism of formation of the coatings which involves diffusion of the ion out of the interior of the resin to create a high local concentration at the surface thus stimulating precipitation of the coating material on the resin beads.     

In situ synthesis of calcium phosphates on chitosan macromolecules in the presence of glutamic and aspartic acids

Calcium hydrogen phosphate dihydrate and amorphous calcium phosphate have been synthesized in an aqueous suspension of medium molecular weight chitosan in the presence of glutamic or aspartic acid. X-ray diffraction and transmission and scanning electron microscopy characterization showed that the morphology of the phases present depended on the nature of the amino acid. The amino acids participate in the protonation of the amino groups of the chitosan and, probably, in the formation of chelate intermediate compounds with calcium ions, which act as calcium phosphate nucleation centers.     

Separation of americium from curium by oxidation and ion exchange

Nuclear energy has the potential to be a clean alternative to fossil fuels, but in order for it to play a major role in the US, many questions about the back end of the fuel cycle must be addressed. One of these questions is the difficult separation of americium from curium. Here, we report the oxidation of Am in two systems, perchloric acid and nitric acid and the affect of changing the acid has on the oxidation. K(d) values were observed and a direct separation factor was calculated and was seen to be as high as 20 for four metal(IV) pillared phosphate phosphonate inorganic organic hybrid ion exchange materials. These ion exchangers are characterized by very low selectivity for cations with low charge but extremely high uptake of ions of high charge.     

Synthesis and Ag Recovery of Nanosized ZnO Powder by Solution Combustion Process for Photocatalytic Applications

Nanometer-sized ZnO powders for photocatalytic applications were prepared by a solution combustion method with various starting materials and fuels. It was easy to obtain single-phase ZnO powders using the solution combustion method regardless of the starting materials and fuels. However, the particle size and shape of the synthesized ZnO powders were different than the used fuel. Using glycine as a fuel, the particle shape of ZnO powders was spherical with uniform nanosize. On the other hand, using carbohydrazide as a fuel, the particle shape was platelike. The ZnO powder synthesized using Zn(OH)₂ and glycine as starting material and fuel, respectively, showed good powder characteristics, such as average grain size of 75 nm and the specific surface area of 94 m²/g. The average particle size and specific surface area were greatly dependent on the types of oxidants and fuels. Removal of silver ions from a used photo-film developing solution was attempted to examine the photocatalytic activity of the prepared ZnO powders. It also showed excellent photocatalytic properties in that the silver ions were completely removed from the solution within 3 min.     

微波辅助溶胶凝胶自燃烧一步合成六角铁酸钡纳米晶及其磁性能

以乙二胺四乙酸柠檬酸+乙二醇为复合络合剂, 冷冻干燥去除溶胶中水分, 提高凝胶中金属离子与氧化剂的分布均匀性, 并利用微波辅助溶胶凝胶自燃烧一步合成了六角铁酸钡纳米晶. 所得纳米晶近于球形, 尺寸在50~100nm, 其饱和磁化强度为338.5kA/m, 矫顽场仅为20.7kA/m. 分析表明, 富氧条件有利于避免自燃烧过程中由于有机物还原引起的铁元素分布不均匀, 从而有利于铁酸钡的相形成.     

Synthesis of hollow structural hydroxyapatite with different morphologies using calcium carbonate as hard template

Hydroxyapatite (HAp) with hollow structure was successfully synthesized by hydrothermal process of as-prepared calcium carbonate used as a hard template and calcium sources in a diammonium phosphate solution. Calcium carbonate was fabricated by precipitation, which possessed different morphologies such as balls, rods and blocks through regulating the amount of citric acid. The synthesized powders were characterized by X-ray diffraction (XRD), Fourier transform infrared spectrograph (FT-IR), field-emission scanning electron microscope (FESEM) and high-resolution transmission electron microscopy (HRTEM) and nitrogen adsorption–desorption. Results indicated that different morphologies calcium carbonate could convert to hollow structural HAp with the higher BET surface area and the mesopores. Hydrothermal temperature and hydrothermal time play a slight role on transition percentage. As hydrothermal temperature and hydrothermal time increased, the conversion rate of calcium carbonate to hydroxyapatite increased. The possible formation mechanism of hydroxyapatite was preliminarily investigated. The resultants of HAp are interesting materials for drug delivery and sustained-release.     

Synthesis and sintering of nanocrystalline hydroxyapatite powders by citric acid sol-gel combustion method

The citric acid sol-gel combustion method has been used for the synthesis of nanocrystalline hydroxyapatite (HAP) powder from calcium nitrate, diammonium hydrogen phosphate and citric acid. The phase composition of HAP powder was characterized by X-ray powder diffraction analysis (XRD). The morphology of HAP powder was observed by transmission electron microscope (TEM). The HAP powder has been sintered into microporous ceramic in air at 1200 °C with 3 h soaking time. The microstructure and phase composition of the resulting HAP ceramic were characterized by scanning electron microscope (SEM) and XRD, respectively. The physical characterization of open porosity and flexural strength have also been carried out.     

Preconcentration of phosphate ion onto ion-imprinted polymer

In this study, selective separation and preconcentration of phosphate ions on the phosphate-imprinted chitosan-succinate beads have investigated. Chitosan-succinate, phosphate, epichlorohydrin were used as the complexing monomer, template and crosslinking agent, respectively. In the first step, chitosan was modified with succinic anhydrides and complex formation occurred between carboxylic acid functional groups and iron(III) ions. Secondly, Fe(III)-chitosan-succinate particles were reacted with phosphate ions. Afterwards, particles were crosslinked with epichlorohydrin and the template (phosphate ions) was removed using 1M KOH solution. Selective cavity for the phosphate ion was obtained in the phosphate-imprinted metal-chelate polymer. These phosphate-imprinted metal-chelate polymer was used in the adsorption-desorption process. The adsorption process was fast and equilibrium was reached around 30 min. The adsorption behaviour of this system was described approximately by the Langmuir equation. Percent extraction, distribution ratio and selectivity coefficients of phosphate and other ions using non-imprinted and phosphate-imprinted polymer were also determined and comparison of these data was reported.     

Synthesis of nanoporous calcium phosphate spheres using poly(acrylic acid) as a structuring unit

Calcium phosphate (CaP) spheres with nanopores were synthesized using poly(acrylic acid) (PAA) as the structuring unit. In this method, colloidal droplets of the PAA/Ca²⁺ complex were prepared by adding a Ca(NO₃)₂ solution to a PAA aqueous solution and then mixed with an (NH₄)₂HPO₄ solution, which allowed the nucleation and growth of CaP nanocrystals in the PAA matrix. Thereafter, the as-synthesized PAA/CaP spheres were heat-treated at 550 °C for 3 h to remove the PAA phase, followed by treatment in ammonium nitrate solution to remove the CaO phase formed as an impurity. The prepared CaP spheres showed a narrow size distribution with an average diameter of 146 ± 43 nm and nanopores formed via the removal of the CaO phase.     

Synthesis of castable sodium zirconium phosphate monoliths employing reactions between zirconyl nitrate hydrate and condensed phosphates

Reactions between zirconyl nitrate hydrate and condensed phosphates can be used to produce castable low CTE sodium zirconium phosphate (NZP) monoliths. Reaction between sodium nitrate, zirconyl nitrate hydrate and condensed phosphoric acid at room temperature (alkali nitrate method) produces monoliths having a heterogeneous microstructure, which are multiphasic in appearance. Except for the presence of crystalline sodium nitrate, they are X-ray amorphous. Differential thermal analysis revealed two distinct exothermic crystallization events when these materials are heated. The first event, with an onset temperature of 650°C, is the result of NZP and ZrO₂crystallization. The second is the result of ZrP₂O₇ crystallization. Reaction between zirconyl nitrate hydrate and condensed sodium phosphate (condensed alkali phosphate method) results in a more homogeneous microstructure in which crystalline zirconium hydrogen phosphate hydrate and sodium nitrate are present. Two exothermic peaks, with onset temperatures of approximately 570 and 860°C, are observed. The first exotherm is the result of NZP, ZrO₂ and ZrP₂O₇ crystallization; the second exotherm is the result of a further NZP formation. After heating materials made by these two methods at 940°C for 24 h, the condensed-alkali-phosphate-method-derived material converted to phase-pure NZP, while the alkali-nitrate-method-derived material contained ZrP₂O₇. The differences in phase evolution between the materials prepared by these two methods are attributable to the differences in chemical and microstructural homogeneity that result from the reactants used. This revised version was published online in September 2006 with corrections to the Cover Date.     

Synthesis of porous aluminum phosphate bulks by hydrothermal hot pressing process and their analytical characterizations

Aluminum phosphate was prepared from aluminum nitrate solution and phosphoric acid in the molar ratio of Al/P = 1/1 at pH 5, 7 and 9. Urea was added in phosphoric acid solution before mixing. These materials were used for aluminum phosphate bulks in hydrothermal hot pressing process. The chemical composition and thermal behavior of the precipitations was analyzed by inductivity coupled plasma, thermogravimetry—differential thermal analyses, X-ray diffraction, and Fourier transform infrared spectroscopy. Furthermore, materials before and after sintering by hydrothermal hot pressing process were estimated from specific surface area, pore size distribution, particle size distribution, and SEM images. The purpose of this work is to clarify the effect of pH, the addition of urea, and heating on hydrothermal hot pressing process of aluminum phosphate.     

Effect of preparation methods and optical band gap of ZnO nanomaterials on photodegradation studies

Improving of photo-oxidative efficiency of ZnO has become of importance to meet the requirements of environmental protection. In this research, ZnO nanomaterials prepared by three different methods (thermal decomposition, precipitation and sol-gel-combustion using metal nitrate and different fuels (urea, oxalic acid and citric acid)). Various molar ratios of citric acid to salt used as variable parameter (0.50, 0.75, 1.00, 1.25, and 1.50). These nanomaterials were characterized by studying their structural, morphological, surface and optical properties. The photocatalytic activity was evaluated by photocatalytic degradation of Remazol Red RB-133 (RR) under UV-light irradiation. The obtained results showed that the photocatalytic efficiency was affected by preparation method, type and ratio of fuel to salt. The optimum is a gel precursor containing zinc nitrate and citric acid prepared in the molar ratio of 1. The highly active nanomaterial was applied for photocatalytic degradation of mixtures of two dyes – (RR) and Methylene Blue (MB).     

纳米Co-Mn-Al-CO_3层状双金属氢氧化物的合成及表征

以过渡金属盐Co(NO3)2、Mn(NO3)2为钴源、锰源,Al(NO3)3为铝源,NaOH和Na2CO3混合溶液为碱性介质,利用共沉淀法分别制备了n(Co)∶n(Mn)∶n(Al)=4∶0∶2、4∶1∶1、4∶2∶0的CO32-离子插层纳米层状双金属氢氧化物(LDHs)。利用X射线衍射(XRD)、X射线荧光光谱分析(XRF)、N2吸附脱附、透射电镜(TEM)技术对样品进行了表征。结果表明,样品呈层状片状,随着LDHs样品中Mn、Al原子比的增加,结晶度变差,形貌变得无序,平均孔径减小,比表面积和孔道容量变大。