Thermal properties of barium-cadmium oxalate crystals

The kinetics and thermodynamics of the thermal dehydration of crystalline powders of BaC₂O₄·2H₂O, CdC₂O₄·3H₂O and Ba_1−x Cd _x C₂O₄·2·5H₂O have been studied by means of thermogravimetry, as a function of temperature. The dynamic dehydration kinetics are also examined using DTA, recorded simultaneously with TG as a function of temperature. The validity of the estimated mechanism and kinetic parameters is briefly discussed. From DTA study it is concluded that all dehydration peaks are endothermic and the decomposition peaks of barium oxalate to barium carbonate, cadmium oxalate to cadmium oxide and barium cadmium oxalate to barium carbonate and cadmium oxide are exothermic.     

Microhardness and acoustic behavior of calcium oxalate monohydrate urinary stone

Renal stone containing calcium oxalate monohydrate as a major component was subjected to microhardness and acoustic studies in order to understand its mechanical properties in vitro and use them to help in the treatment procedures for more effective stone fragmentation. The chemical composition and the crystalline nature of the stone were verified using Fourier Transform Infrared spectroscopy, X-ray diffraction and the stone was also analyzed using thermo gravimetric analysis and by differential thermal analysis. The microhardness values were almost constant around 1000 MNm^− 2 in the load range of 1.96 N-9.8 N. The values of fracture toughness and brittleness index for the stone in this load range was varying from 1.12 (0.307) MNm^− 3/2 to 1.48 (0.296) MNm^− 3/2 and 674.25 m^− 1/2 to 878.07 m^− 1/2 respectively. The density of the stone and the ultrasonic longitudinal wave velocity in the stone were found to be 1880 kgm^− 3 and 3399 ms^− 1 respectively indicating that the urinary stone under study was a compact one. The acoustic impedance and the dynamic modulus values were calculated as 6.39 × 10⁶ kgm^− 2 s^− 1and 21.72 GNm^− 2 respectively.     

The role of hyaluronic acid in biomineralization

Hyaluronic acid has been extensively investigated due to intrinsic properties of natural origin and strong ability to bind ions in water. Hyaluronic acid is an excellent crystal modifier because its abundant negatively charged carboxyl groups can bind the cations protruding from the crystal lattice. In this review, we mainly present the latest work focus on the role of hyaluronic acid in controlling the crystallization, breaking the symmetry of crystal, and the surface funtionalization of nanocrystals.     

Growth and study of barium oxalate single crystals in agar gel

Barium oxalate was grown in agar gel at ambient temperature. The effect of various parameters like gel concentration, gel setting time and concentration of the reactants on the growth of these crystals was studied. Prismatic platy shaped spherulites and dendrites were obtained. The grown crystals were characterized by X-ray powder diffractometry, infrared spectroscopy, thermogravimetric and differential thermal analysis. An attempt is made to explain the spherulitic growth mechanism.     

Control the polymorphism and morphology of calcium carbonate precipitation from a calcium acetate and urea solution

Two metastable calcium carbonate polymorphs, rod-like aragonite and spherical vaterite are selectively formed in this study. Aragonite rods were synthesized from a calcium acetate (Ca(AC)₂) and urea (CO(NH₂)₂) solution under a given condition. In contrast, the addition of polyacrylamide (PAM) and oleic acid results in the formation of spherical vaterite. The morphology, size and crystal structure were characterized by means of Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), and X-ray diffraction (XRD). The results show that PAM and oleic acid can be used as additives to select the polymorph from aragonite and vaterite. The contact angle of the modified products reached 112.49°. We have succeeded in surface modification of particles in situ at the same time.     

A methacrylic hyaluronic acid derivative for potential application in oral treatment of celiac disease

Objective: Aim of this work was the synthesis of a methacrylic hyaluronic acid (HA) derivative and the production, via photocrosslinking, of related hydrogels loaded with an endopeptidase intended for a potential oral treatment of celiac disease.

Methods: The methacrylic derivative of HA was prepared through a one-pot procedure involving the reaction with ethylenediamine (EDA) and methacrylic anhydride (MA). The obtained derivative, named HA-EDA-MA, was used to prepare photocrosslinked hydrogels loaded with a prolyl endopeptidase derived from Flavobacterium meningosepticum (PEP FM) able to detoxify gliadin. Obtained hydrogels were recovered as gels or freeze-dried powders.

Results: Hydrogels obtained as freeze-dried powders, are able to protect loaded enzyme from degradation due to freeze-drying process and from alteration during storage, overall in the presence of a cryoprotectant. All photocrosslinked HA-EDA-MA hydrogels (gels and powders) release PEP FM in simulated intestinal fluid in sustained manner and in active form. HA-EDA-MA hydrogels are nontoxic as demonstrated through in vitro studies on BALB 3T3 cells.

Conclusions: Prepared hydrogels show a potential application for oral treatment of celiac disease thanks to the possibility to release enzymes able to detoxify the gliadin peptide that induces the immunogenic response.     

Morphology control of amino acid particles in interfacial crystallization using inkjet nozzle

The aim of this study is to apply the inkjet technique to liquid–liquid interfacial crystallization. Instillation with an inkjet nozzle was compared with the batch process in order to evaluate the effectiveness of the inkjet technique for controlling particle morphology. The effects of amino acid solution concentration and organic solvent type on particle properties were investigated for instillation with an inkjet nozzle. The morphology of alanine and glycine particles was observed by scanning electron microscopy and X-ray powder diffraction. The inner structure of alanine and glycine particles was investigated by cutting particles with an ion milling machine. Controlling particle size by adjusting the droplet size in the instillation with an inkjet nozzle was found to be feasible. Most alanine and glycine particles produced by instillation were spherical, whereas most particles produced by the batch process were non-spherical. A higher concentration of amino acid in the solution may lead to the generation of solute particles at the spherical interface. It was found that the surface structure of alanine particles changed when using two kinds of organic solvents as anti-solvents. In addition, instillation allowed for β-glycine to be identified and the crystal polymorph of the particles to be controlled.     

Synthesizing a composite material of amorphous calcium carbonate and aspartic acid

A composite material of amorphous calcium carbonate and aspartic acid (Asp) was synthesized using a highly concentrated solution of calcium aspartate: a new approach. A transparent and amorphous solid with approximately 1 mm thickness was obtained. UV-vis transmittance spectrum of the composite shows no characteristic absorption in visible region. A Raman spectrum of the composite revealed a peak assigned to the symmetric stretching of carbonate ion. This study demonstrated that amorphous calcium carbonate could be stabilized using not only organic artificial macromolecules but also using Asp, a small biomolecule. This result is expected to engender development of new biomimetic materials.     

Growth and physico chemical characterization of lanthanum neodymium oxalate single crystals

Single crystals of lanthanum neodymium oxalate (LNO) are grown in sodium meta silicate gels, by the diffusion of a mixture of aqueous solutions of lanthanum nitrate and neodymium nitrate into the test tube having the set gel containing oxalic acid. The bluish pink coloured tabular crystals of LNO having well defined hexagonal basal planes appear either as ‘foggy’ or ‘clear’, the latter at the greater depths inside the gel. The colouration of LNO visually observed is evidenced in UV-visible spectrum, by the revelation of well pronounced characteristic peaks in the visible region (500–900 nm). X-ray diffraction (XRD) of powdered LNO is ordered, meaning crystalline in nature, besides its ‘isostructurality’ with similarly grown lanthanum samarium oxalate crystals. The single crystallinity of LNO is established by its oscillation XRD pattern. Thermogravimetric analysis (TGA) and differential scanning colorimetry (DSC) support that LNO loses water of crystallization around 120°C and CO and CO₂ around 350–450°C, while the infrared absorption (IR) spectrum of LNO establishes the presence of oxalate (C₂O₄)²⁻ ions. Energy dispersive X-ray analysis (EDAX) confirms the presence of La and Nd in the sample. X-ray photoelectron spectroscopic (XPS) studies of LNO establish the presence of La and Nd in their respective oxide states. An empirical structure for LNO has been proposed on the basis of these findings. The ‘smokiness’ in the foggy LNO crystal has been attributed due to the ‘gel inclusion’ during the growth process.     

溶胶稳定性对氧化锆超滤膜结构和性能的影响

针对锆溶胶的不稳定性,选取二氯氧锆作前驱体,考察了体系介质、高分子添加剂以及溶胶浓度对草酸氧锆溶胶稳定性的影响．结果表明,加入适量的有机溶剂ROH和MC可以提高草酸氧锆溶胶的稳定性,并采用了一种能较便捷地评价溶胶相对稳定性的方法．还进一步对比研究了不稳定溶胶和稳定溶胶对氧化锆超滤膜的孔结构及渗透性能的影响,发现使用稳定的草酸氧锆溶胶才能制备出孔径分布窄、截留率好的氧化锆超滤膜．     

The role of morphology and crystallographic structure of metal oxides in response of conductometric-type gas sensors

This review paper discusses the influence of morphology and crystallographic structure on gas-sensing characteristics of metal oxide conductometric-type sensors. The effects of parameters such as film thickness, grain size, agglomeration, porosity, faceting, grain network, surface geometry, and film texture on the main analytical characteristics (absolute magnitude and selectivity of sensor response (S), response time (τ_res), recovery time (τ_rec), and temporal stability) of the gas sensor have been analyzed. A comparison of standard polycrystalline sensors and sensors based on one-dimension structures was conducted. It was concluded that the structural parameters of metal oxides are important factors for controlling response parameters of resistive type gas sensors. For example, it was shown that the decrease of thickness, grain size and degree of texture is the best way to decrease time constants of metal oxide sensors. However, it was concluded that there is not universal decision for simultaneous optimization all gas-sensing characteristics. We have to search for a compromise between various engineering approaches because adjusting one design feature may improve one performance metric but considerably degrade another.     

Some structural aspects of neodymium praseodymium oxalate single crystals grown in hydro silica gels

The mixed crystals of neodymium praseodymium oxalate are grown by the diffusion of a mixture of aqueous solutions of neodymium nitrate and praseodymium nitrate (as an upper reactant) into the set gel embedded with oxalic acid. By varying the concentration (by volume) of rare earth nitrates in the upper reactant, the incorporation of Nd and Pr in the mixed crystals has been studied. Tabular crystals with the well defined hexagonal basal planes are observed in the mixed crystals of varying concentrations. X-ray diffraction patterns of these powdered samples reveal that these mixed crystals are ‘isostructural’, while IR and FTIR spectra establish the presence of oxalate groups. TGA and DSC analyses show the correctness of the chemical formula for the mixed crystals, by the release of water molecules (endothermic) and of CO and CO₂ (exothermic), with the rare earth oxides as the stable residue. X-ray fluorescence (XRF) and energy dispersive X-ray analyses (EDAX) establish the presence of heavy rare earth elements qualitatively and to a good extent quantitatively. X-ray photoelectron spectroscopic (XPS) studies confirm the presence of rare earth elements (Nd and Pr) as their respective oxides. The findings of these techniques of characterization are in excellent agreement with the proposed empirical structure for the mixed rare earth oxalates. The implications are discussed.     

Crystallization rules of calcium oxalate crystals in lithogenic urine and in healthy urine in vitro

Crystallization of calcium oxalate (CaOxa) was comparatively studied in vitro in diluted lithogenic urine and in diluted healthy urine by means of scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FT-IR) spectroscopy. In healthy urine, the crystallization was a growth-controlled process in the early stage of crystallization and a nucleation-controlled process in the middle and late stage. However, the crystallization of CaOxa was always a growth-controlled process in the lithogenic urine. That is, the size of CaOxa particles grow gradually and at last large size of CaOxa stones formed. Comparing the CaOxa crystals grown in lithogenic urine and in healthy urine, three differentiations were observed. First, the average particle size of CaOxa crystals precipitated in lithogenic urine is larger than that in healthy urine. Second, the morphology of calcium oxalate monohydrate (COM) crystals changes from sharp hexagonal in lithogenic urine to round and blunt in healthy urine. Third, calcium oxalate dihydrate (COD) crystals were induced in healthy urine. The results in this study may provide important clues to cure urinary stones.     

Simultaneous crystallization of calcium phosphate and calcium oxalate in the presence of ascorbic acid under physiological conditions

Ascorbic acid (AA—Vitamin C) plays a vital role in human body to preserve optimal health. However, high intake may cause the formation of pathological calcium oxalate stones. Calcium oxalate and calcium phosphates are the major crystalline constituents of the urinary calculi and commonly found together. The effect of AA on the crystallization of calcium phosphate was studied in gel matrix under physiological conditions. Calcium phosphates such as hydroxyapatite (HAp), brushite (DCPD) and calcium oxalate dihydrate (COD—Weddellite) were found to crystallize simultaneously in the gel matrix. The formation of HAp is accelerated by AA. A possible reaction scheme for the formation of COD by the metal induced conversion of AA is proposed.     

Effect of ethylenediaminetetraacetic acid (di sodium salt) and aquasoft 330 on crystal growth and morphology of calcium oxalate

Calcium oxalate was synthesized from calcium chloride solution using oxalic acid in the presence of di sodium salt of ethylenediaminetetraacetic acid (EDTA) and commercially available1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), aquasoft having chelating value 330 (AQ 330). The experiments were carried out at three different temperatures 60, 80 and 100 °C. The samples were characterized using scanning electron microscope (SEM), powder X-ray diffraction analysis (XRD) and Fourier transform infrared spectroscopy (FTIR) techniques. The morphological studies reveal that the tendency for agglomeration increases with increase in temperature. Interpretation of XRD pattern confirmed that whewellite with monoclinic structured is the most favored structure in the presence of EDTA where calcium oxalate hydrate having orthorhombic structure is most favored structure in the presence of AQ 330.     

Thermodynamics and kinetics of methane hydrate formation and dissociation in presence of calcium carbonate

Huge amount of gas hydrate deposits are identified in deep marine sediments, which may be considered as a future source of energy. Since carbonate is one of the major components of marine sediments, in the present study attention has been given to characterize methane hydrate formation and dissociation in presence of calcium carbonate. Experiments were performed with 0%, 2%, 4%, 6% and 10% by weight of calcium carbonate in distilled water. Extensive investigations have been done on pressure-temperature equilibrium behavior of hydrate formation and dissociation at varying concentrations of calcium carbonate. Hydrate formation rate was found to vary with concentration of calcium carbonate as the solubility of calcium carbonate in water is controlled by the presence of simultaneous chemical equilibria involving a high number of species like Ca²⁺, CO₃^2?, HCO₃^?, CO₂, etc. Induction time for hydrate formation has also been measured at different concentrations of carbonate. Nucleation point for the hydrate formation was observed to be slightly higher at higher concentration of calcium carbonate due to increased heat absorption. Dissociation enthalpy of hydrates was calculated by using Clausius-Clapeyron at different measured conditions. Moles consumption of methane gas during hydrate formation at different concentrations of carbonate was measured using real gas equation and found to be minimum at 10?wt%.     

催化剂结构与形态对碳纳米管生长的影响

采用溶胶-凝胶超临界流体干燥技术制备了含铁、钴的纳米SiO2复合气凝胶催化剂,用于碳纳米管和纳米碳包覆磁性纳米粒子的合成。利用N2物理吸附、XRD、TEM、HRTEM、EDS、SAED等手段对催化剂在不同温度下处理后晶型的转变、形态的变化进行了分析,并考察了催化剂对碳纳米管形貌、结构和碳增重率的变化。结果表明:随着处理温度从600℃升高到1000℃,催化剂比表面积从312.4m2 g降低到79.6m2 g,催化剂粒子从非晶态向晶态转变,粒径从5nm增大至60nm左右,碳的增重率从254.8%下降41.5%。采用低温处理的催化剂,碳产物中以碳纳米管为主,而采用较高温度处理后的催化剂,碳产物中则以碳包覆粒子为主,且随处理温度的升高碳包覆粒子的含量逐渐增加。     

Thermal properties and phase structure of PP + oligopinene blends

Blends of polypropylene (PP) and β-oligopinene, a synthetic low molar mass resin, were prepared by melt mixing in a Haake Rheocord at 473 K, 30 rpm during 600 s. The influence of the terpenic resin on the thermal properties, phase structure and crystallization of PP was evaluated. The DSC results indicated the presence of phase separation. The SEM analysis shows that the oligopinene was extracted along the whole surface and it was observed entities as cut cylinder atributted to low molar mass PP. The isothermal crystallization of blends was conducted at 396, 398 and 403 K. The mixtures did not show phase separation in molten, during crystallization and after solidification. The spherulite radial growth rate of PP decreased and was dependent on the temperature and composition. The results indicated that the system is an immiscible blend with at least three phases: a fine dispersion of the oligopinene in the amorphous PP, some boundary solubility of PP in oligopinene and a crystalline PP. Received: 13 November 2000 / Reviewed and accepted: 14 November 2000     

Effect of crystallization parameters and presence of aqueous extract of Nigella Sativa on growth inhibition of calcium oxalate monohydrate particles

For the first time, nucleation kinetics, crystal growth and agglomeration of calcium oxalate monohydrate (COM) are studied as a crystal growth inhibitor with and without Nigella Sativa(NS) extract. The induction period was determined under different supersaturation ratios ranging from 1.63 to 4.51 at 37°C using the conductivity method. Based on the classical homogeneous nucleation theory; the critical nucleation parameters were evaluated at higher supersaturation ratio. The calculated surface energy was increased from 7.97?mJ/m² without additive to 10.31?mJ/m² with NS extract. However, the nucleation rate at a supersaturation ratio of 3.26 corresponding to 5.44 with the NS extract was decreased from 3.9?×?10²⁹ nuclei/cm³.s (without additive) to 1.3?×?10²⁹ nuclei/cm³.s with NS extract addition. The number of molecules required for the formation of a stable nucleus was calculated with and without NS extract at different supersaturation ratios. The crystallite sizes of the formed crystals without and with the additive are 93 and 51?nm, respectively. Scanning electron microscopy (SEM) photomicrographs show the formation of small crystals and less aggregated with the NS inhibitor compared with the baseline (without the inhibitor). This study can help us with a clear understanding of the inhibition mechanism of an aqueous NS extract on COM crystals.     

Effect of supersaturation on the morphology of hydroxyapatite crystals deposited by electrochemical deposition on titanium

Cathodic deposition of calcium phosphate coating on titanium using electrochemical method was investigated in our study and well-defined hexagonal rod-like hydroxyapatite (HAp) crystals were synthesized. Scanning electron microscopic photographs of HAp coatings under different deposition durations revealed the morphology change of the HAp crystals in the coating film with the experimental process: from cone-like structure to hexagonal prism with sharp-angled tip, and finally turns to rod-like one with regular hexagonal cross section. It was suggested that both morphology and longitudinal length of the HAp crystals in the coating could be regulated by an accurate control of the degree of supersaturation of the aqueous system.