Formation of thin calcium carbonate films with aragonite and vaterite forms coexisting with polyacrylic acids and chitosan membranes

CaCO3 crystallization on a chitosan membrane was studied using diffusion of (NH4)2CO3 vapors into a CaCl2 solution containing differing added amounts of two polyacrylic acids (PAAs) with molecular weights of ca. 2.0 x 10(3) and ca. 4.5 x 10(4). The coexistence of PAA and the chitosan membranes produced thin CaCO3 island crystals, which developed into a continuous CaCO3 film on the membranes. Continuous CaCO3 films consisting of only aragonite formed on the chitosan membranes at the optimum amount of PAA. When the amount of PAA is not optimum, the polymorph of CaCO3 switches from aragonite to vaterite, and the morphology has a tendency to become an isolated island structure. The formation of the aragonite and vaterite island crystals and the appearance of a range of added PAA suitable for their formation are explained by the action of two parallel phenomena: (a) the high concentration of Ca2+ ions in the chitosan membrane vicinity is achieved by the interaction between the -COO- groups of PAA adsorbed by the -NH3+ groups of the chitosan membrane through an electrostatic force and free Ca2+ ions in the CaCl2 solution, which produces the high supersaturation with CaCO3 in the membrane vicinity during CO2 diffusion; (b) PAA, remaining as mobile carboxylic anions in the CaCO3 solution, inhibits the growth of the CaCO3 island crystals by its adsorption. The CaCO3 supersaturation in the membrane vicinity is controlled by regulating the balance of these phenomena, which leads to the formation of the desired CaCO3 polymorph.     

Effects of calcium carbonate polymorph on the structure and properties of soy protein-based nanocomposites

Novel protein-based nanocomposites were well prepared by in vivo synthesis and co-precipitation of soy protein isolate (SPI) with calcium carbonate (CaCO3) in an aqueous solution. The resultant CaCO3 in the nanocomposites was identified as calcite- and aragonite-type, respectively. The morphology and structure of the CaCO3/SPI composites were investigated by means of wide-angle X-ray diffraction, Fourier transform infrared spectra, scanning electron microscopy, and high-resolution transmission electron microscopy. The results revealed that the polymorph and the size of CaCO3 in the nanocomposites were dependent on its content, pH, and the conformation of soy protein. At the content of more than 5%, CaCO3 was changed into calcite crystal with the preference of growing along (104) plane. However, at lower content of less than 5%, CaCO3 preferred to form aragonite in the composite as a result of the modulation by soy protein. The aragonite nanocrystals were arrayed in the direction of (111) plane and self-assembled along beta-sheet planes of soy protein polypeptides. The mechanical properties, thermal stability, and water resistance of the CaCO3/SPI nanocomposites were significantly improved as a result of the nanosized effects. Interestingly, the aragonite/SPI nanocomposite exhibited higher tensile strength (about 50 MPa) than that of calcite/SPI, owing to a good compatibility and strong interaction between aragonite and soy protein polypeptides. This work provided a simple pathway to develop the soy protein-based bio-hybrid materials with high mechanical strength and valuable information on their structure-properties relationship.     

Influence of sodium dodecyl sulfate and static magnetic field on the properties of freshly precipitated calcium carbonate

Properties of calcium carbonate precipitated from aqueous solutions of CaCl(2) and Na(2)CO(3) in the presence of sodium dodecyl sulfate (SDS) and S-S 0.1 T magnetic field (MF) were studied. The nucleation and precipitation processes of CaCO(3) were investigated by pH and zeta potential measurements at 20 +/- 1 degrees C up to 2 h after mixing the solutions. Also the amounts of calcium carbonate deposited on the glass surfaces and its structure were examined. It was found that SDS influences the kinetics of precipitation, crystallographic forms, and crystal size of CaCO(3). The SDS effects are more pronounced in MF presence. A small amount of SDS accelerates transformation of vaterite into calcite, whereas increasing surfactant concentration moderates such a transformation. On the other hand, in all the systems, MF in the presence of SDS causes a slower transformation of vaterite into calcite. These effects are reflected in pH and zeta potential changes, although there is no clear dependence between the SDS amount present during the precipitation and changes of the parameters investigated. It seems that MF effect is most significant at a defined optimal SDS concentration. The results, however, do not allow suggestion of any detailed mechanism of the field interaction.     

Calcium carbonate solubility: a reappraisal of scale formation and inhibition

Considerable disparity exists in the published thermodynamic data for selected species in the Ca(2+) /CO(2)/H(2)O system near 25 degrees C and 1 atm pressure. Some authors doubt the significance of CaCO(3)(0)aq) complexes although there is experimental evidence of their occurrence. Evaluation of all the published experimental and estimated data for aqueous calcium carbonate species confirms that the consistent set of constants given by Plummer and Busenberg in 1982 is the best available, and suggests a formation constant log beta = 3.22 for CaCO(3)(0)(aq). This value was confirmed by additional experimental data and calculations using a specially developed computer program. The solubility s and solubility product K(s) are critically evaluated for each solid polymorph (amorphous CaCO(3), ikaite, vaterite, aragonite and calcite) using a hydrated ion pair model and we give coherent explanations for the calcium carbonate precipitation/dissolution process and the existence of supersaturated waters. The practical cases of scale formation and its inhibition by phosphonate-type compounds are discussed and explained with the same model, taking into account the CaCO(3)(0)(aq) species.     

A novel morphology of aragonite and an abnormal polymorph transformation from calcite to aragonite with PAM and CTAB as additives

The abnormal structure conversion of CaCO3 from calcite to aragonite was investigated with a mixture of polyacrylamide (PAM) and cetyltrimethylammonium bromide (CTAB) as additives by a hydrothermal method. A novel morphology of aragonite, "magnified" cubic shape, was observed. In order to investigate the effects of PAM and experimental temperature on the morphology and phase of CaCO3, the samples were synthesized without any additives and with PAM as template at 90 and 120 degrees C, respectively. The results indicate that both the interaction between the mixed template and the CaCO3 and the elevated experiment temperature play important roles in the process of polymorph transformation.     

Divisive effect of alcohol-water mixed solvents on growth morphology of calcium carbonate crystals

Controlling the process of crystal growth is of importance to the biomineralization and materials science. In this work, some novel morphology of calcium carbonate (CaCO3) was precipitated in an ethanol-water binary solvent (EWBS) with a CaCl2/Na2CO3 reaction system. For the solutions of CaCl2/Na2CO3 in EWBS, the alcoholization and hydration of Ca2+ and CO3(2-) were discussed from the radial distribution functions by molecular dynamics simulations, and the number density profiles of water molecules around and approximately 15 A away from CO3(2-) were employed to reveal the distribution of water molecules. It is found that EWBS has a divisive effect on Ca2+ and CO3(2-), and the local inhomogeneity of EWBS would be enhanced by adding some Na2CO3 into it. This inhomogeneity results in an aqueous two-phase system as x E goes up to 0.7. In addition, the novel morphology of CaCO3 under different molar ratios of Ca2+/CO3(2-) and in different mixed solvents were confirmed by XRD and SEM, and the relationships between the morphology of CaCO 3 and the structural properties of mixed solvents were further explored.     

Controlling the polymorph and morphology of CaCO3 crystals using surfactant mixtures

Inspired by mineralization in biological organisms, fabrication of higher ordered CaCO(3) crystals modified by surfactants has received much attention. In our present work, mixed surfactants of hexadecyl(trimethyl)azanium bromide and sodium dodecyl sulfate were used to mediate the nucleation and growth of CaCO(3) crystals. When the concentration of sodium dodecyl sulfate in the solution is constant (0.1 mM), the polymorph of CaCO(3) crystals changed from pure vaterite to pure aragonite with increase of the ratio of hexadecyl(trimethyl)azanium bromide to sodium dodecyl sulfate. Various morphologies of vaterite and aragonite were obtained. Based on the time-resolved experiments, we suggest that the flower-like CaCO(3) formed via aggregation of hexagon-like vaterite induced by the surfactants. More importantly, we realized that a cluster-shaped morphology of aragonite was produced through the nucleation of aragonite at the surfaces of the hexagon-like vaterite.     

Oriented aggregation and novel phase transformation of vaterite controlled by the synergistic effect of calcium dodecyl sulfate and n-pentanol

Calcium dodecyl sulfate (CDS) was used for the first time both as an anionic surfactant and as the source of mineral ions in the precipitation process of calcium carbonate (CaCO3). The simple reaction of the enriched Ca2+ ions at the so-called organic-inorganic interfaces with the slowly bubbled CO2 gas resulted in the metastable vaterite polymorph with various structures. The single-crystalline vaterite of the hexagonal platelets, the lens-shaped structures with hexagonal symmetry, the olive-shaped superstructures and these with a concave at each top of olives, and another metastable polymorph of aragonite were obtained, respectively, depending upon the concentration ratio between CDS and n-pentanol. The synergistic effect of CDS and n-pentanol is believed to play a crucial role in driving the oriented aggregation of metastable nanoparticles. Simultaneously, the novel phase transformation of vaterite to aragonite was observed, implying the possible formation mechanism of aragonite at room temperature and in the absence of magnesium ions.     

Morphological control of CaCO3 films with large area: effect of additives and self-organization under atmospheric conditions

Hierarchically structured CaCO(3) films were synthesized at atmospheric conditions (room temperature and 1 atm) without the use of templates or amphiphilic molecules in this process. The resulting CaCO(3) film was formed by self-organization between Ca(OH)(2) and aqueous CO(2). The building blocks of the CaCO(3) film were thought to be CaCO(3) primary nanoparticles that aligned to build higher level structures with greater size, called mesocrystals, depending on the additives. The soluble additives played a key role in the control of the morphology, crystallinity, and polymorphism of the CaCO(3) film, and the effects strongly depended on the type of additive and their concentrations. The additives used in this study decreased the crystallinity of CaCO(3) (calcite) film in the order of glucose > aspartic acid > serine in a manner inversely proportional to the concentration of the additives. In addition, Mg(2+), K(+), and Na(+) ion additives led to the formation of an aragonite phase, the proportion of which increased with the concentration of ions. The threshold concentrations of these ions for the formation of the aragonite phase in CaCO(3) film were found to be in the order of Na(+) > K(+) > Mg(2+).     

用热重分析与X-射线衍射法探究中国花鲈耳石的微结构

为表征中国花鲈耳石的微结构,应用数码照相机、热重分析仪与X-射线衍射仪对中国花鲈耳石的外观形貌、化学组成与晶体结构进行记录及表征。结果显示:中国花鲈耳石为较厚的宽叶形,表面有不同大小的晶状突,边缘有叶形晶状突,内弯面有中央突,弯曲背面有嵴突及几乎贯穿整个耳石的主凹槽;TGA曲线分为晶体间隙水的挥发,有机质和无机盐的灰化与分解,碳酸钙热分解为氧化钙等三个平台,化学组成中碳酸钙含量为97.92%,水、有机质和其它无机盐含量为2.08%;XRD晶体结构属于稳定性较差的含很少量第二相的霰石。组成与结构的表征有助于鱼类耳石的化学生物学分类数据库的建立,也丰富了耳石的研究内涵。     

Crystal growth of aragonite and calcite in presence of citric acid, DTPA, EDTA and pyromellitic acid

The influence of four calcium complexing substances, i.e., citric acid (CIT), diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetraacetic acid (EDTA) and pyromellitic acid (PMA), on the crystal growth rate of the calcium carbonate polymorphs aragonite and calcite has been studied. Using a seeded constant supersaturation method supersaturation was maintained at 4 by keeping a constant pH of 8.5 through addition of sodium carbonate and calcium chloride solutions. The unique composition of each solution was calculated using chemical speciation. The growth rate was interpreted in terms of an overall growth rate. For both calcite and aragonite, the crystal growth rate is significantly reduced in the presence of the calcium complexing substances. The growth retarding effect depends on both the concentration and the polymorph. The relative crystal growth rate was correlated to the total complexing agent concentration using a Langmuir adsorption approach. Aragonite appeared fully covered for lower total concentrations than calcite. Furthermore, CIT very efficiently blocked aragonite growth contrary to what was observed for calcite. This is thought to be related to certain distinct features of the dominant aragonite crystal faces compared to the dominant calcite faces.     

一维多孔Fe-B合金纳米结构的制备及其磁性质

在十六烷基三甲基溴化铵(CTAB)的水溶液中,用NaBH₄还原FeCl₃,在反应过程中施加外部磁场,制得了一维多孔Fe-B合金纳米结构。研究表明,外部磁场对一维纳米结构的形成有重要影响,当不加外部磁场时得到的是离散的球形纳米粒子;外部磁场还影响Fe-B纳米粒子的晶体结构：外部磁场存在下得到的是无定形Fe-B合金,而不加外部磁场时则得到多晶Fe-B合金。CTAB对多孔的形成起到关键的作用,当不加CTAB时得到了实心球状纳米粒子。初步讨论了这种一维孔状Fe-B合金纳米结构的形成机理。用XRD、ICP-AES、TEM对样品进行了表征,测定了它们的磁性质。结果表明,在施加不同磁场强度条件下制得的样品具有不同的饱和磁化强度和矫顽力。     

Biosynthesis of CaCO3 crystals of complex morphology using a fungus and an actinomycete

The biosynthesis of CaCO3 by reaction of aqueous Ca2+ ions with a fungus, Fusarium sp., and an actinomycete, Rhodococcus sp. (both plant organisms), is described. In the case of the fungus, cruciform-shaped calcite crystals are obtained (SEM picture A) while the actinomycete yielded the unstable polymorph of CaCO3, vaterite (SEM picture B). Specific proteins secreted by the microorganisms are responsible for the morphology and crystallography control observed. A highlight of this approach is that the microorganisms also provide CO2 for reaction with the Ca2+ ions, making the crystals completely biogenic.     

无添加剂条件下文石型碳酸钙晶须制备及影响因素研究

在不加任何结晶控制剂或模板条件下,以CaCl2和Na2CO3为原料,利用复分解反应法制备了具有较好形貌和高长径比,且分布均一的文石型碳酸钙晶须,并利用扫描电镜(SEM)、X-射线粉末衍射(PXRD)和傅里叶转换红外光谱图(FT-IR)等手段对其进行了表征。研究了浓度、滴加速度、反应温度、搅拌速度以及滴加方式等因素对碳酸钙晶须的影响。结果表明最佳制备工艺为:CaC12溶液与Na2CO3溶液的浓度为0.05 mol.L-1,溶液滴加速度为1 mL.min-1,反应体系温度为80℃,搅拌速度为250 r.min-1。     

疏水球状碳酸钙的制备、表征及对聚丙烯力学性能的影响

以十二碳醇磷酸酯(DDP)为改性剂, 采用碳化法制备了分散性良好的球状碳酸钙粒子. 通过FESEM, XRD, FTIR及活化度和接触角测试对产物进行了表征. XRD分析结果表明, 随着DDP添加量的增加, 所得CaCO3由方解石型向文石型转变. FTIR结果表明, 改性剂与碳酸钙表面是以化学键合和物理吸附方式相结合. 当DDP含量达到2%时, 接触角为120.43°, 活化度达到99%, 碳酸钙粒子由亲水性转变为完全疏水性. 考察了反应温度和DDP含量对产物形貌与结晶行为的影响, 并对改性机理进行了初步探讨. 将产品填充到聚丙烯(PP)中, 测定了PP的力学性能.     

Zeta potential measurement of calcium carbonate

The problem of scaling, which one finds in industrial heat exchangers, particularly in atmospheric coolers in nuclear power stations, depends on calcium carbonate deposits from fresh water. To better understand this phenomenon, we have examined the eventual implication of superficial electric charge of precipitated crystal nuclei. After a bibliographical review showing a fundamental divergence from already published results, this paper describes an experimental plant to measure the zeta potential in controlled conditions of thermodynamic equilibrium, oversaturation, or undersaturation of a CaCO(3)-H(2)O-CO(2) system taking into account simultaneously the three phases: gas, liquid, and solid. The zeta potential is measured by a crystalline-plug method with calcite or aragonite crystals. The potential cancels at thermodynamic equilibrium and is always negative for other conditions, in particular for oversaturation where the possibility of scaling exists. The analysis of these results suggests that the potential determining ions of the system are Ca(2+) and HCO(-)(3).     

Influence of ozonized kraft lignin on the crystallization of CaCO3

Results are reviewed from a study examining how structural modifications introduced by ozonization enhance the influence of kraft lignin on the crystallization of CaCO(3). Ozone treatment of kraft lignin in an aqueous environment is shown to increase its carboxylic acid and overall oxygen content and reduce its molecular weight. Calcium concentration and temperature were monitored in heated supersaturated solutions containing ozonized kraft lignins to gauge their influence on CaCO(3) crystallization processes. The presence of kraft lignin raises the temperature necessary to induce crystallization. This effect is shown to level off at relatively low lignin concentrations and be dependent on the extent of ozone treatment the kraft lignin has undergone. A linear correlation is found between crystallization temperatures and the carboxylic acid content of ozonized lignin samples indicating the introduction of these functional groups plays an important role in enhancing its inhibitory effect. Scanning electron microscopy images of crystals grown in the presence of kraft lignins show significant morphological modifications. These are consistent with specific or pseudo specific interactions between the lignin and crystal faces of calcite to inhibit growth parallel to its c axis. The influence over crystal morphology demonstrated by modified kraft lignin increases with increasing ozonization. Also presented here are crystallization temperature data for a range of kraft lignin ultrafiltration fractions, which indicate that the optimal (nominal) molecular weight of kraft lignin for inhibiting the crystallization of CaCO(3) lies between 5000 and 10000.     

Thermal Stability of Haemoglobin Solutions Under DC and AC Magnetic Field and UV and IR Radiation

The influence of electromagnetic field in wide range of frequency (extra low frequency magnetic field, monochromatic laser light 840 nm, ultraviolet light) and static magnetic field on the stability of aqueous and NaCl 0.9% haemoglobin solutions was studied using differential scanning calorimetry (DSC) method. Three steps of denaturation process can be derived from experimental data. The shifts of transition temperatures are more marked for NaCl 0.9% than for aqueous solutions. The results suggest that static magnetic field is effective in protecting protein, while ultraviolet radiation destabilises haemoglobin. The laser light and alternating magnetic field have a little effect on the thermal stability of haemoglobin. This revised version was published online in July 2006 with corrections to the Cover Date.     

Morphology and Kinetics of Growth of CaCO<Subscript>3</Subscript> Precipitates Formed in Saline Water at 30°C

The crystallization kinetics and morphology of CaCO₃ crystals precipitated from the high salinity oilfield water were studied. The crystallization kinetics measurements show that nucleation and nuclei growth obey the first order reaction kinetics. The induction period of precipitation is extended in the high salinity solutions. Morphological studies show that impurity ions remain mostly in the solution phase instead of filling the CaCO₃ crystal lattice. The morphology of CaCO₃ precipitates can be changed from a smooth surface (calcite) to rough spheres (vaterite), and spindle rod bundles, or spherical, ellipsoid, flowers, plates and other shapes (aragonite).     

The Application of Ammonium Hydroxide and Sodium Hydroxide for Reagent Softening of Water

The calcium carbonate crystallization from aqueous solutions in the presence of alkali additives such as sodium hydroxide and ammonium hydroxide has been researched. It is found CaCO₃ crystallizes predominantly in the modification of aragonite in the presence of ammonium hydroxide. The calcium carbonate formation rate in an alkaline medium and the gaseous reaction products due to sorption of gas bubbles on crystal surfaces, affect the aragonite structure formation. It is shown use of ammonium hydroxide for water treatment can solve two urgent tasks such as water softening and exclusion sediment of deposits on the equipment surfaces by a calcium carbonate crystallization in the form of aragonite.