Beneficial use of meat and bone meal combustion residue: "an efficient low cost material to remove lead from aqueous effluent"

Meat and bone meal (MBM) combustion residues, a natural apatite-rich substance, was evaluated as a low cost substitute for hydroxyapatite in lead sequestration from water effluents. The thermal behaviour of crude meat and bone meal was followed by TGA and 24% inorganic residue was collected. The resulting ashes were characterised by powder X-ray diffraction (XRD), particle size distribution, specific surface area (BET), and elemental analysis confirming apatite contents, with high level of phosphate (56.3%) and calcium (36.8%). Mechanism and kinetics of lead removal by this bioinorganic material were investigated and compared to mechanisms and kinetics involved with synthetic apatite. Batch metal removal experiments were carried out with 500 and 1500ppm (mg/kg) Pb(2+) solutions. Lead concentration, calcium and pH were monitored. We observed that the mechanism is similar to that occurring for pure apatite, and involved both surface complexation and calcium hydroyapatite (CaHA), Ca(10)(PO(4))(6)(OH)(2), dissolution followed by less soluble Pb(10)(PO(4))(6)(OH)(2) precipitation, as confirmed by XRD analysis of ashes after incubation with lead solution. Our results show that this natural apatite-rich material removes in a few minutes a large quantity of lead (275mg/g capacity) which remains however lower than the theoretical maximum capacity (if calcium were totally substituted by lead). Meat and bone meal combustion residues represent a valuable alternative apatite source for environmental application.     

Calcium Phosphate Phase Identification Using XPS and Time-of-Flight Cluster SIMS

Reproducible time-of-flight cluster static secondary ion mass spectra (ToF-SSIMS) were obtained for various standard calcium phosphate (CP) powders, which allowed for phase identification. X-ray diffraction was not able to detect signals from microscopic amounts of CP (～15 mmol m(-)(2)). The phases studied were α-tricalcium phosphate [α-Ca(3)(PO(4))(2)], β-tricalcium phosphate [β-Ca(3)(PO(4))(2)], amorphous calcium phosphate [Ca(3)(PO(4))(2)·xH(2)O], octacalcium phosphate [Ca(8)H(2)(PO(4))(6)·H(2)O], brushite (CaHPO(4)·2H(2)O), and hydroxyapatite [Ca(10)(PO(4))(6)(OH)(2)]. The SIMS spectra were obtained via bombardment with (CsI)Cs(+) projectiles. X-ray photoelectron spectroscopy (XPS) core levels of the P 2p, Ca 2p, and O 1s orbitals and the relative O 1s loss intensity were examined. The PO(3)(-)/PO(2)(-) ratios from ToF-SSIMS spectra in conjunction with XPS of the CP powders showed much promise in differentiating between these phases at microscopic CP coverages on the metal oxide surface.     

Non-aqueous synthesis of water-dispersible Fe3O4-Ca3(PO4)2 core-shell nanoparticles

The Fe(3)O(4)-Ca(3)(PO(4))(2) core-shell nanoparticles were prepared by one-pot non-aqueous nanoemulsion with the assistance of a biocompatible triblock copolymer, poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEO-PPO-PEO), integrating the magnetic properties of Fe(3)O(4) and the bioactive functions of Ca(3)(PO(4))(2) into single entities. The Fe(3)O(4) nanoparticles were pre-formed first by thermal reduction of Fe(acac)(3) and then the Ca(3)(PO(4))(2) layer was coated by simultaneous deposition of Ca(2+) and PO(4)(3-). The characterization shows that the combination of the two materials into a core-shell nanostructure retains the magnetic properties and the Ca(3)(PO(4))(2) shell forms an hcp phase (a = 7.490 ?, c = 9.534 ?) on the Fe(3)O(4) surface. The magnetic hysteresis curves of the nanoparticles were further elucidated by the Langevin equation, giving an estimation of the effective magnetic dimension of the nanoparticles and reflecting the enhanced susceptibility response as a result of the surface covering. Fourier transform infrared (FTIR) analysis provides the characteristic vibrations of Ca(3)(PO(4))(2) and the presence of the polymer surfactant on the nanoparticle surface. Moreover, the nanoparticles could be directly transferred to water and the aqueous dispersion-collection process of the nanoparticles was demonstrated for application readiness of such core-shell nanostructures in an aqueous medium. Thus, the construction of Fe(3)O(4) and Ca(3)(PO(4))(2) in the core-shell nanostructure has conspicuously led to enhanced performance and multi-functionalities, offering various possible applications of the nanoparticles.     

Development of bioactive PMMA-based cement by modification with alkoxysilane and calcium salt

Poly (methyl methacylate) (PMMA) bone cement is one of the popular bone-repairing materials for fixation of artificial hip joints. Significant problems on the PMMA bone cement are caused by loosening at the interface between bone and the cement, since the cement does not show bone-bonding, i.e. bioactivity. Development of PMMA bone cement capable of bone-bonding has been therefore long desired. The prerequisite for an artificial material to show bone-bonding is the formation of a biologically active bone-like apatite layer on its surface when implanted in the body. The same type of apatite formation can be observed on bioactive materials even in a simulated body fluid (Kokubo solution) with ion concentrations nearly equal to those of human blood plasma. Fundamental researches for bioactive glasses and glass-ceramics revealed that the apatite deposition is initiated by release of Ca2+ ions from the material into the body fluid, and by catalytic effect of Si-OH groups formed on the surface of the material. These findings lead an idea that novel bioactive cement can be designed by incorporation of Si-OH groups and Ca2+ ion into PMMA bone cement. In the present study, PMMA bone cement is modified with 20 mass % of various kinds of alkoxysilanes and calcium salts, and its apatite-forming ability was evaluated in Kokubo solution. The apatite formation was observed on the surface of the modified cements containing 20 mass % of CaCl2, irrespective of the kind of the examined alkoxysilane. On the other hand, the apatite formation was observed on the cement containing CaCl2, Ca(CH3COO)2 or Ca(OH)2, but not on the cement containing CaCO3 or beta-Ca3(PO4)2, even when the cement contains 3-methacryloxypropyltrimethoxysilane (MPS). The results indicate that modification with alkoxysilane and calcium salts showing high water-solubility is effective for providing PMMA bone cement with bioactivity.     

In Vivo Characteristics of Premixed Calcium Phosphate Cements When Implanted in Subcutaneous Tissues and Periodontal Bone Defects

Previous studies showed that water-free, premixed calcium phosphate cements (Pre-CPCs) exhibited longer hardening times and lower strengths than conventional CPCs, but were stable in the package. The materials hardened only after being delivered to a wet environment and formed hydroxyapatite as the only product. Pre-CPCs also demonstrated good washout resistance and excellent biocompatibility when implanted in subcutaneous tissues in rats. The present study evaluated characteristics of Pre-CPCs when implanted in subcutaneous tissues (Study I) and used for repairing surgically created two-wall periodontal defects (Study II). Pre-CPC pastes were prepared by combining CPC powders that consisted of CPC-1: Ca(4)(PO(4))(2)O and CaHPO(4), CPC-2: α-Ca(3)(PO(4))(2) and CaCO(3) or CPC-3: DCPA and Ca(OH)(2) with a glycerol at powder-to-liquid mass ratios of 3.5, 2.5, and 2.5, respectively. In each cement mixture, the Ca to P molar ratio was 1.67. The glycerol contained Na(2)HPO(4) (30 mass %) and hydroxypropyl methylcellulose (0.55 %) to accelerate cement hardening and improve washout resistance, respectively. In Study I, the test materials were implanted subcutaneously in rats. Four weeks after the operation, the animals were sacrificed and histopathological observations were performed. The results showed that all of the implanted materials exhibited very slight or negligible inflammatory reactions in tissues contacted with the implants. In Study II, the mandibular premolar teeth of mature beagle dogs were extracted. One month later, two-wall periodontal bone defects were surgically created adjacent to the teeth of the mandibular bone. The defects were filled with the Pre-CPC pastes and the flaps replaced in the preoperative position. The dogs were sacrificed at 1, 3 and 6 months after surgery and sections of filled defects resected. Results showed that one month after surgery, the implanted Pre-CPC-1 paste was partially replaced by bone and was converted to bone at 6 months. The pockets filled with Pre-CPC-2 were completely covered by newly formed bone in 1 month. The Pre-CPC-2 was partially replaced by trabecular bone in 1 month and was completely replaced by bone in 6 months. Examination of 1 month and 3 month samples indicated that Pre-CPC-2 resorbed and was replaced by bone more rapidly than Pre-CPC 1. Both Pre-CPC pastes were highly osteoconductive. When implanted in periodontal defects, Pre-CPC-2 was replaced by bone more rapidly than Pre-CPC-1.     

Chromium behavior during cement-production processes: a clinkerization, hydration, and leaching study

The behavior of chromium during the production of cement clinker, during the hydration of cement and during the leaching of cement mortars was investigated. The microstructures of clinker and mortar properties were investigated using free lime, XRD, SEM/EDS, and TG/DTA techniques. Chromium was found to be incorporated in the clinker phase. The formation of new chromium compounds such as Ca(6)Al(4)Cr(2)O(15), Ca(5)Cr(3)O(12), Ca(5)Cr(2)SiO(12), and CaCr(2)O(7), with chromium oxidation states of +3, +4.6, +5, and +6, respectively, was detected. After the hydration process, additional chromium compounds were identified in the mortar matrix, including Ca(5)(CrO(4))(3)OH, CaCrO(4)·2H(2)O, and Al(2)(OH)(4)CrO(4), with chromium oxidation states of +4.6, +6, and +6, respectively. Additionally, some species of chromium, such as Cr(3+) from Ca(6)Al(4)Cr(2)O(15) and Cr(6+) from CaCr(2)O(7), CaCrO(4)·2H(2)O, and Al(2)(OH)(4)CrO(4), were leached during leaching tests, whereas other species remained in the mortar. The concentrations of chromium that leached from the mortar following U.S. EPA Method 1311 and EA NEN 7375:2004 leaching tests were higher than limits set by the U.S. EPA and the Environment Agency of England and Wales related to hazardous waste disposal in landfills. Thus, waste containing chromium should not be allowed to mix with raw materials in the cement manufacturing process.     

Spectroscopic investigation in the mid- and far-infrared regions of phosphorus fertilizers derived from thermochemically treated sewage sludge ash

Inorganic phosphorus and nitrogen-phosphorus-potassium (NPK) fertilizers based on phosphates from thermochemically treated sewage sludge ash were analyzed using mid-infrared (mid-IR) and far-infrared (FIR) spectroscopy. The different compounds present in the fertilizers were qualitatively determined with the help of recorded reference spectra of pure substances. Differentiation between various phosphates and other compounds such as sulfates, nitrates, and oxides was possible using combined interpretation of the mid-IR and FIR spectra. The results are in agreement with previous X-ray diffraction (XRD) measurements of the same samples. The main phosphate phases detected were NH(4)H(2)PO(4), MgHPO(4)·3H(2)O, Mg(3)(PO(4))(2), Ca(5)(PO(4))(5)Cl, CaHPO(4)·2H(2)O, Ca(H(2-)PO(4))(2)·H(2)O, and AlPO(4). Furthermore, K(2)SO(4), NH(4)NO(3), Fe(2)O(3), and SiO(2) were identified in the IR spectra. However, ammonium and sulfate compounds were only identified in the mid-IR region but were not detectable in the FIR region.     

Characterization of aqueous lead removal by phosphatic clay: equilibrium and kinetic studies

Immobilization of heavy metals from contaminated environments is an emerging field of interest from both resource conservation and environmental remediation points of view. This study investigated the feasibility of using phosphatic clay, a waste by-product of the phosphate mining industry, as an effective sorbent for Pb from aqueous effluents. The major parameters controlling aqueous Pb removal, viz. initial metal ion concentrations, solution pH, sorbent amounts, ionic strength and presence of both inorganic and organic ligands were evaluated using batch experiments. Results demonstrated that aqueous Pb removal efficiency of phosphatic clay is controlled mainly by dissolution of phosphatic clay associated fluoroapatite [Ca(10)(PO(4))(5)CaCO(3)(F,Cl,OH)(2)], followed by subsequent precipitation of geochemically stable pyromorphite [Pb(10)(PO(4))(6)(F,Cl,OH)(2)], which was confirmed by both X-ray diffraction (XRD) and scanning electron microscopic (SEM) analysis. Lead removal efficiency of phosphatic clay increased with increasing pH, sorbent amount and decreasing ionic strength. It also depends on the nature of complexing ligands. Formation of insoluble calcium oxalate and lead oxalate in the presence of oxalic acid explained high uptake of Pb by phosphatic clay from aqueous solution. However, Pb sorption kinetics onto phosphatic clay were biphasic, with initially fast reactions followed by slow and continuous Pb removal reactions. The slow reactions may include surface sorption, co-precipitation and diffusion. The exceptional capability of phosphatic clay to remove aqueous Pb demonstrated its potential as a cost effective way to remediate Pb-contaminated water, soils and sediments.     

Boron removal and recovery from concentrated wastewater using a microwave hydrothermal method

Boron compounds are widely-used raw materials in industries. However, elevated boron concentrations in aqueous systems may be harmful to human and plants. In this study, calcium hydroxide (Ca(OH)(2)) alone and Ca(OH)(2) with phosphoric acid (H(3)PO(4)) addition (P-addition) were used to remove and recover boron from wastewater using hydrothermal methods. A microwave (MW) hydrothermal method was used and compared with the conventional heating (CH) method in batch experiments. Physicochemical properties of the precipitates obtained from both methods were analysed by XRD, SEM with EDX and BET. For the case of Ca(OH)(2) alone and the MW method, experimental results showed that boron recovery efficiency reached 90% within 10 min, and crystals of Ca(2)B(2)O(5)·H(2)O were found in the precipitates as indicated by the XRD analysis. For the case of P-addition and the MW method, boron recovery efficiency reached 99% within 10 min, and calcium phosphate species (CaHPO(4)·H(2)O, CaHPO(4) and Ca(10)(PO(4))(6)(OH)(2)) were formed. The experimental results of this study indicate that the required reaction time of the MW method was much less than that of the CH method, and the MW method is an effective and efficient method for boron removal and recovery from concentrated wastewater.     

Preparation of low-crystalline apatite nanoparticles and their coating onto quartz substrates

We prepared low-crystalline apatite nanoparticles and coated them onto a surface of a Au/Cr-plated quartz substrate by the electrophoretic deposition (EPD) method or by using a self-assembled monolayer of 11-mercaptoundecanoic acid (SAM method). Low-crystalline apatite nanoparticles around 10?nm in size with extremely low contents of undesirable residual products were obtained by adding (NH(4))(2)HPO(4) aqueous droplets into a modified synthetic body fluid solution that contained Ca(CH(3)COO)(2). The apatite nanoparticles were successfully coated by either the EPD method or the SAM method; the nanoparticle coating achieved by the SAM method was more uniform than that achieved by the EPD method. The present SAM method is expected to be a promising technique for obtaining a quartz substrate coated with apatite nanoparticles, which can be used as a quartz crystal microbalance device.     

In-vitro apatite formation on phosphorylated bamboo

Natural self-reinforced composite, bamboo, was surface modified by phosphorylation with urea–H3PO4 and NaOH–H3PO4 methods; then precalcification was performed by immersing samples in saturated Ca(OH)2 solution. After that, calcium phosphate can be formed on the surface of bamboo samples in calcification media: simulated body fluid (1.5 SBF) and accelerated calcification solution (ACS). Experimental results reveal that pre-calcification is an inevitable step for the formation of calcium phosphate. The calcium phosphate formed in 1.5 SBF was identified by thin-film X-ray diffraction as apatite which was not well crystallized. Compared with the urea–H3PO4 method, the NaOH–H3PO4 method has the advantages of quicker and continuous apatite formation and stronger adhesive between apatite and bamboo.     

Sorption of aqueous phosphorus onto bituminous and lignitous coal ashes

Aiming at the development of a phosphorus removal technology for waste water, phosphate (PO(4)(3-)) retention behavior of bituminous and lignitous coal ashes was investigated using a batch reactor. Ash samples, including fresh and weathered fly and bottom ashes, were studied for their sorption isotherms and reversibility. Fly ashes had a much higher phosphate retention capacity (4000-30,000mgP/kg) than bottom ashes (15-600mgP/kg). Lignitous coal ashes were more capable of retaining phosphate than bituminous coal ashes. The retention process was largely irreversible, and the irreversibility increased with the increase in the retention capacity. Weathering enlarged the retention capacity of the bituminous bottom ash, but substantially lowered that of the fly ash, likely due to the difference in the weather-induced changes between the fly and bottom ashes. Sorption isotherms of fly ashes were found to be adequately represented by the Langmuir model while those of bottom ashes fitted better to the Freundlich model. Concentrations of Ca(2+) and PO(4)(3-) in the aqueous phase were measured at the end of sorption and desorption experiments, and were compared with solubilities of three calcium phosphate minerals. The aqueous solutions were saturated or super-saturated with respect to tricalcium phosphate (Ca(3)(PO(4))(2)) and hydroxyapatite (Ca(5)(PO(4))(3)OH), and slightly under-saturated with respect to amorphous calcium phosphate. It is concluded that precipitation of calcium phosphate is the predominant mechanism for phosphate retention by coal ash under the conditions studied. There is a strong and positive correlation between alkalinity and phosphate sorption capacity. Consequently, acid neutralization capacity (ANC) can be used as an indicator of phosphate sorption capacity of coal ashes.     

Hydrothermal synthesis and electrochemical properties of Li₃V₂(PO₄)₃/C-based composites for lithium-ion batteries

To improve performance at higher rates, we developed a hydrothermal method to prepare carbon-coated monoclinic lithium vanadium phosphate (Li(3)V(2)(PO(4))(3)) powder to be used as a cathode material for Li-ion batteries. The structural, morphological and electrochemical properties were characterized by X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM and TEM), and galvanostatic charge-discharge cycling. A superior cycle and rate behavior are demonstrated for Li(3)V(1.85)Sc(0.15)(PO(4))(3)/C and Li(2.96)Ca(0.02)V(2)(PO(4))(3)/C electrodes at charge-discharge current rates above 5C.     

Cements from nanocrystalline hydroxyapatite

Calcium phosphate cements are used as bone substitute materials because they may be moulded to fill a void or defect in bone and are osteoconductive. Although apatite cements are stronger than brushite cements, they are potentially less resorbable in vivo. Brushite cements are three-component systems whereby phosphate ions and water react with a soluble calcium phosphate to form brushite (CaHPO4 x 2H2O). Previously reported brushite cement formulations set following the mixture of a calcium phosphate, such as beta-tricalcium phosphate (beta-TCP), with an acidic component such as H3PO4 or monocalcium phosphate monohydrate (MCPM). Due to its low solubility, hydroxyapatite (HA) is yet to be reported as a reactive component in calcium phosphate cement systems. Here we report a new cement system setting to form a matrix consisting predominantly of brushite following the mixture of phosphoric acid with nanocrystalline HA. As a result of the relative ease with which ionic substitutions may be made in apatite this route may offer a novel way to control cement composition or setting characteristics. Since kinetic solubility is dependent on particle size and precipitation temperature is known to affect precipitated HA crystal size, the phase composition and mechanical properties of cements made from HA precipitated at temperatures between 4 and 60 degrees C were investigated.     

Raman and infrared spectroscopic investigations on aqueous alkali metal phosphate solutions and density functional theory calculations of phosphate-water clusters

Phosphate (PO(4)(3-)) solutions in water and heavy water have been studied by Raman and infrared spectroscopy over a broad concentration range (0.0091-5.280 mol/L) including a hydrate melt at 23 degrees C. In the low wavenumber range, spectra in R-format have been constructed and the R normalization procedure has been briefly discussed. The vibrational modes of the tetrahedral PO(4)(3-)(aq) (T(d) symmetry) have been assigned and compared to the calculated values derived from the density functional theory (DFT) method for the unhydrated PO(4)(3-)(T(d)) and phosphate-water clusters: PO(4)(3-).H(2)O (C(2v)), PO(4)(3-).2H(2)O (D(2d)), PO(4)(3-).4H(2)O (D(2d)), PO(4)(3-).6H(2)O (T(d)), and PO(4)(3-).12H(2)O (T), a cluster with a complete first hydration sphere of water molecules. A cluster with a second hydration sphere of 12 water molecules and 6 in the first sphere, PO(4)(3-).18H(2)O (T), has also been calculated. Agreement between measured and calculated vibrational modes is best in the case of the PO(4)(3-).12H(2)O cluster and the PO(4)(3-).18H(2)O cluster but far less so in the case of the unhydrated PO(4)(3-) or phosphate-water cluster with a lower number of water molecules than 12. The asymmetric, broad band shape of v(1)(a(1)) PO(4)(3-) in aqueous solutions has been measured as a function of concentration and the asymmetric and broad band shape was explained. However, the same mode in heavy water has only half the full width at half-height compared to the mode in normal water. The PO(4)(3-) is strongly hydrated in aqueous solutions. This has been verified by Raman spectroscopy comparing v(2)(H(2)O), the deformation mode of water, and the stretching modes, the v(1)OH and v(3)OH of water, in K(3)PO(4) solutions as a function of concentration and comparison with the same modes in pure water. A mode at approximately 240 cm(-1) (isotropic R spectrum) has been detected and assigned to the restricted translational mode of the strong hydrogen bonds formed between phosphate and water, P-O...HOH. In very concentrated K(3)PO(4) solutions (C(0) > or = 3.70 mol/L) and in the hydrate melt, formation of contact ion pairs (CIPs) could be detected. The phosphate in the CIPs shows a symmetry lowering of the T(d) symmetry to C(3v). In the less concentrated solutions, PO(4)(3-)(aq) solvent separated ion pairs and doubly solvent separated ion pairs exist, while in very dilute solutions fully hydrated ions are present (C(0) < or = 0.005 mol/L). Quantitative Raman measurements have been carried out to follow the hydrolysis of PO(4)(3-)(aq) over a very broad concentration range. From the hydrolysis data, the pK(3) value for H(3)PO(4) has been determined to be 12.45 at 23 degrees C.     

A multi-scaled hybrid orthopedic implant: bone ECM-shaped Sr-HA nanofibers on the microporous walls of a macroporous titanium scaffold

We report here, for the first time, a novel multi-scaled hybrid orthopedic implant material consisting of a macroporous Ti scaffold, whose macropores' walls have a microporous titania layer which is fully covered with nanofibers of Sr-doped hydroxyapatite (Sr-HA). The microporous titania layer is formed on and within the Ti scaffold by micro-arc oxidation, which firmly binds to the Ti substrate and contains Ca2+, Sr2+ and PO4(3-) ions. It is then hydrothermally treated to form Sr-HA nanofibers. During the hydrothermal treatment, Sr-HA nanoprisms nucleate from Ca0.5Sr0.5TiO3 pre-formed on the TiO2 and grow in length to nanofibers at the expense of Ca2+, Sr2+ and PO4(3-) ions that migrate from the TiO2. These Sr-HA nanofibers construct a network structure similar to the hierarchical organization of bone extracellular matrix (ECM), and the resulting nanofibrous surface displays a firm adhesion to substrate, superhydrophilicity and apatite-inducing ability. The induced apatite prefers to nucleate on the basal-faceted surfaces of Sr-HA nanofibers. The nanofiber-walled scaffold has a great potential for load-bearing orthotopic use.     

Preparation, characterization and mechanical performance of dense β-TCP ceramics with/without magnesium substitution

Beta-tricalcium phosphate (beta-TCP) powder was prepared by a two-step process: wet precipitation of apatitic tricalcium phosphate [Ca(9)(HPO(4))(PO(4))(5)(OH)] (beta-TCP 'precursor') and calcination of the precursor at 800 degrees C for 3 h to produce beta-TCP. Magnesium-substituted tricalcium phosphate (beta-TCMP) was produced by adding Mg(NO(3))(2) . 6H(2)O into Ca(NO(3))(2) solution as Mg(2+) source before the precipitation step. The transition temperature from beta-TCP to alpha-TCP increases with the increase of Mg(2+) content in beta-TCMP. beta-TCMP with 3 mol.% Mg(2+) has beta-TCP to alpha-TCP transition temperature above 1,300 degrees C. Dense beta-TCMP (3 mol.% Mg(2+)) ceramics ( approximately 99.4% relative density) were produced by pressing the green bodies at 100 MPa and further sintering at 1,250 degrees C for 2 h. The average compressive strength of dense beta-TCP ceramics sintered at 1,100 degrees C is approximately 540 MPa, while that of beta-TCMP (3 mol.% Mg(2+)) ceramics is approximately 430 MPa.     

In situ study on the curing process of calcium phosphate bone cement

The aim of this study was to follow the entire curing process of modified alpha-TCP cement, and to explore how the liquid phase affects the curing reaction. Two calcium phosphate bone cements (CPCs) with a variety of aqueous solution were studied for comparison. In situ X-ray diffraction analysis and pH testing were employed to follow the chemical reaction, while quantitative ultrasonic measurement (QUS) was carried out to monitor the physical change. Results showed that CPC powders were completely consumed after 72 h. Two steps were presented in apatite formation. The first step was the precipitation of carbonated hydroxyapatite (CHA), and in the second step, conversion of calcium deficient hydroxyapatite (CDHA) was the dominant reaction. Finally, CPCs were fully converted to apatite except the cement with NaH2PO4 as liquid phase, because acidic environment inhibited the conversion of apatite. The pH increased linearly after mixing, when supersaturation was reached, it decreased to pH approximately 6.0 gradually. Ultrasound measurement indicated that the variation of speed of sound (SOS) was related to both apatite formation and microstructural evolution. Ultrasonic attenuation coefficient (UAC) was able to quantitatively describe the curing process from viscous paste to elastic solid as a function of curing time. Moreover, the curing reaction conformed to classical dissolution-precipitation mechanism.     

掺杂钠硅磷灰石水泥多孔支架用于骨缺损再生修复

采用磷酸四钙和磷酸氢钙为磷灰石水泥(AC)粉末, 5wt%硅酸钠水溶液为固化液, 氯化钠为致孔剂, 制备了掺杂钠元素的硅磷灰石水泥(s-AC)多孔支架用于骨缺损再生修复. 结果显示: s-AC多孔支架的成分为含钠硅元素的磷灰石, 支架大孔之间互相贯通, 孔径在200~600 μm, 孔隙率在58%~75%, 抗压强度在1.6~3.8MPa的范围内. 与AC相比, 掺杂一定量的钠硅元素提高了s-AC支架在Tris-HCl溶液中的降解性. 将s-AC多孔支架植入兔股骨缺损处, 组织学分析结果显示: 新生骨在支架材料的表面直接形成, 并长入其中, 相互贯通的多孔支架促进了新骨长入其内部. 结果表明: s-AC支架具有优良的生物相容性、降解性和成骨性, 将是一种优良的骨修复生物材料.     

Phosphate removal using sludge from fuller's earth production

This study assesses the phosphate removal capacity and mechanism of precipitation or adsorption from aqueous solutions in batch experiments by an industrial sludge containing gypsum (CaSO(4).2H(2)O) obtained as a by-product from a fuller's earth process. The potential capacity for phosphate removal was tested using various solution concentrations, pH values, reaction times, and amount of sludge. The maximum phosphate adsorption capacity calculated using the Langmuir equation was 2.0 g kg(-1). The pH for the maximum adsorption by the sludge was neutral to alkaline (pH 7-12). Over 99% of phosphate was removed from a phosphate solution of 30 mg L(-1) using 0.15 g of sludge in a 9-h reaction. Sulfate (SO(4)(2-)) concentration increased with increasing initial phosphate concentration, possibly because of dissolution of gypsum and adsorption of both sulfate and phosphate. At high phosphate concentration (>1000 mg L(-1)), relative constant concentration of Ca(2+) was not consistent with adsorption of the most important phosphate removal mechanism. Results suggest that precipitation of calcium phosphate is principally responsible for phosphate removal under its high concentration. Agglomerated precipitate in the reaction sludge was observed by SEM and identified as brushite (CaHPO(4).2H(2)O) by XRD, FT-IR, and DTA. Based on thermodynamic considerations, it is suggested that the brushite will readily transform to more stable phases, such as hydroxyapatite (Ca(5)(PO(4))(3).OH).