Investigation of scale inhibition mechanisms based on the effect of scale inhibitor on calcium carbonate crystal forms

To probe the scale inhibition mechanisms,calcium carbonate scale occurring before and after the ad- dition of scale inhibitors was collected.The results from scale SEM confirm that,without scale inhibitor, calcium carbonate scale shows rhombohedron and hexagon,which are the characteristic feathers of calcite.After addition of inhibitors,morphology of scale is changed,and the more efficient the scale inhibitor is,the more greatly the morphology is modified.To elucidate the scale constitute,they were further analyzed by FT-IR,XRD.Besides calcite,vaterite and aragonite occur in calcium carbonate scale after addition of inhibitors,and the higher scale inhibition efficiency is,the more vaterite presents in scale.It can be concluded that the alteration of morphology is ascribed to the change of crystal form. There are three stages in the crystallizing process including occurrence and disappearing of unstable phase,occurrence and disappearing of metastable phase,development of stable phase.Without scale inhibitors,metastable phases usually transform into stable phase,thus the main constitute of formed scale is calcite.When scale inhibitors are added,both formation and transformation of metastable phases are inhibited,which results in the occurrence of aragonite and vaterite.From the fact that more vaterite presents in scale with a more efficient scale inhibitor added,we can see that the function of scale inhibitor is realized mainly by controlling the crystallizing process at the second stage.     

STUDY ON THERMAL DENATURATION OF PROTEINS CONTAINING LOW WATER CONTENT BY DIFFERENTIAL SCANNING CALORIMETER——DEMONSTRATION OF PRE-THERMODENATURE NEW PEAK

Following the discovery that there is a low temperature endothermal peak for hydration bovine serum albumin, this work further measured DSC heating scanning curve for seven different kinds of hydration proteins with high purity from eleven sources. The measurements have shown that there is an obvious low temperature endothermal peak for all of the protein samples used. We term it "Pre-thermodenature New Peak". The appearance of pre-thermodenature new peak is the common property of proteins containing low water content. The studies of regularity and mechanism on new peak should help to understand the denaturation process of protein, protein folding, molecular association and/or molecular disassociation and solvent effect.     

Resolution method for overlapping peaks based on the fractional-order differential

Equations between the differential order and the maximum of the fractional-order differential for the specified peak signals are developed based on the variation of the maximum of the specified peak signals at different orders. Also, equations between the differential order and the zero-crossing of the fractional-order differential of the specified peak signals are proposed according to the variation of the zero-crossing of the specified peak signals at different orders. Characteristic paramters of the Gaus- sian peak, Lorentzian peak, and Tsallis peak can be estimated using estimator I and estimator II which are obtained by the equations above. As a result, a new method is presented to resolve the overlapped peaks signal. Firstly, a fractional-order differential of the specified peak signals is obtained with the fractional-order differentiation filter. Then, characteristic paramters of the specified peak signals can be extracted using estimator I and estimator II. Finally, the Tsallis peak is used as a model to assign the overlapping peak signals correctly. Experimental results show that the proposed method is efficient and effective for the simulated overlapping peaks and detected overlapping voltammetric peak signals.     

镁铁和镁铝双羟基复合金属氧化物的结构和性能差异

Layered Double Hydroxides MgFe-LDH and MgAl-LDH have been prepared by the method involving separate nucleation and ageing steps. The structure analyses for these two materials show that the values of the parameters both a and c of MgAl-LDH are smaller than that of MgFe-LDH though their structures are similar, and MgAl-LDH with higher crystallinity is more easily formed than MgFe-LDH in the same preparing conditions. The IR analyses manifest that the structures of layer sheets and the orderings of the anions in the interlayer regions of MgAl-LDH are more regular than that of MgFe-LDH. The temperature programmed XRD analyses reveal that the diffraction peak of 003 reflections for MgAl-LDH could be seen after calcining at 300℃, while this peak for MgFe-LDH disappears after calcining at 200℃. Together with the TG-DTA analysis it can be concluded that the thermal stability of MgAl-LDH is obviously higher than that of MgFe-LDH.     

Formation Process and Thermodynamic Poperties of Calcite

The fast mixing of aqueous solutions of calcium chloride and sodium carbonate resulted in crystalline forms of vaterite and calcite under vigorous stirring. Then, the vaterite was transformed to pure calcite within about 180 rain. The crystalline forms all grew with experimental time increase. Scanning electron microscopy （SEM）, Fourier transform infrared spectroscopy （FT-IR）, and X-ray diffraction spectroscopy （XRD） techniques were employed to characterize the as-prepared samples. The heat capacity of the stable as-synthesized calcite was determined by means of an adiabatic calorimeter from 80 to 390 K. The thermodynamic functions of the calcite were derived based on the relationships among the thermodynamic functions and the function of the measured heat capacity with respect to temperature.     

STUDY ON POLYMERIC CATALYST-PALLADIUM COMPLEX WITH RADIATION GRAFTING ACRYLONITRILE ON INORGANIC COMPOUND

Polymer bound palladium (Pd)complex catalysts with grafting acrylonitrile on inorganic compound(MgO,Y-molecular sieve and SiOz) by pre-radiation method were studied. The palladium - grafting polymers have been investigated by X-ray photoelectron spectrscopy(XPS). It is indicated that peak width of C1s and O1s spectra of MgO-g-PAN - Pd (radiation - induced graft) is wider than that of MgO -PAN - Pd(chemical method) and peak numbers of former are one more than later.According to the report in reference, this peak is attributed togroup. Thus, the graft acrylonitrile on MgO may complete through oxygen atoms in MgO and β-carbon atoms in acrylonitrile. The polymer catalyst obtained by radiation grafting is a higher active hydrogenation catalyst for olefines and better antitoxic than that of one obtained by chemical method, and it has selectivity for hydrogenation catalyst.     

Synthesis and Optical Properties of Ce-doped ZnO

ZnO nanorods were synthesized using the sol-gel method, and the effects of annealing temperature and Ce doping on the morphologies and optical properties of ZnO nanostructures were investigated in detail. The XRD measurements showed that the as-synthesized ZnO nanostructures had a hexagonal wurtzite structure. SEM images showed that uniform nanorods formed at 900 °C. Photoluminescence measurements showed an ultraviolet emission peak and a relatively broad visible light emission peak for the samples sintered at different temperatures. The UV emission peak bathochromically shifted when the annealing temperature rose from 850 to 1000 °C. Ce doping decreased the synthesized temperature of the ZnO nanorods to 500 °C, and the UV peaks hypsochromically shifted.     

^1H NMR Study of Polyvinylalcohol Irradiated by Ultra-violet

The effect of Ultra-violet light on the structure and motion of the polyvinyl alcohol (PVA) chains was studied by IH NMR, spin-lattice relaxation and IR spectroscopy. The results indicated that with the increase of irradiation time, the intensity of the polymer hydroxyl proton peaks decreased and finally vanished, which suggested the self-condensation between the hydroxyl groups proceeded. No methyl proton peaks appeared in the spectra after irradiation shows that there is no cleavage of polymer chain. The longer the irradiation time is, the wider the proton peak of the residual water of the solvent is and it shifted toward low field. This result implies that the hydrogen bonds formed between the polymer and the residual water. The absorption peak of hydroxyl group of the polymer moves toward the lower wave number in the IR spectrum that showed the existence of the hydrogen bonds between the PVA macromolecules.     

STUDY ON TPR OF NICKEL OXIDE CATALYSTS CALCINED AT HIGH TEMPERATURES

TPR technique has been used, to investigate the reducibilities of three types of nickel oxide catalysts calcined in air between 650℃and 1050℃: NiO/Al2O3, NiO/MgAl2O4and NiO/(CaO, MgO) · A12O3· xSiO2. The results indicate that the TPR peaks of all the catalysts were shifted toward high temperature and peak areas were gradually reduced with increasing calcination temperature. Particularly, the main TPR peaks almost disappeared at 1050℃-It was also observed that NiO/(CaO, MgO)· Al2O3 · xSiO2 catalyst was the easiest to be reduced of these catalysts, and there was a small shoulder peak before the main peak for each catalyst. Examination of these catalysts by XPS showed that there were two forms of nickel oxides on support surface .     

Synthesis of a New Cobalt （Ⅱ） Complex and its Interaction with DNA

A new complex of bis(N-benzyl benzotriazole-N^3) dichloro Co(Ⅱ) (Co(Ⅱ)L2Cl2) was synthesized and its crystal was characterized. The interaction of this new complex with fs-DNA was studied by electrochemical and UV spectrophotometric method. In 0.01 mol/L pH 4.2 Tris-HCl buffer solution Co(Ⅱ)L2Cl2 has two reductive peaks with peak potentials at 0.38 V and 0.27 V, respectively, and an oxidative peak at 1.05 V. After the addition of DNA, the peak currents decrease and the peak potential at 0.27 V shifts negatively. The UV spectrophotometric experiment indicates that the maximum absorbance of Co(Ⅱ)L2Cl2 at 204 nm decreases and exhibits bathochromic shift after the addition of DNA. All the results reveal that Co(Ⅱ)L2Cl2binds with DNA by intercalation as well as electrostatic interaction.     

利用室温固态反应制备球霰石型CaCO3粒子

合成形态、大小及结构可人为调控的无机材料是现代材料科学的重要研究方向[1]. 借助于各类有机添加剂及模板剂的调控作用, 可利用溶液合成方法制备出形貌与结构受到有效调控的无机粒子[2,3]. 室温固态化学反应已被成功地应用于多种无机纳米粒子[4]及纳米线[5]的合成, 并显示出高效、节能、无污染和操作简便等优点, 因而在材料合成领域具有应用前景[6].     

双亲水性嵌段共聚物对CaCO_3结晶的影响

以合成的带有磺酸基为端基的线型-超支化二嵌段共聚物PEG-b-PEI-SO3H为模板,探讨了其对CaCO3结晶的影响,并用FTIR、XRD、SEM、TEM等对产物进行了表征.结果表明,带有—SO3H端基的线型-超支化双亲水性嵌段共聚物PEG-b-PEI-SO3H对CaCO3晶体形貌和晶型表现出较强的调控能力.培养1天时得到空心环状方解石型CaCO3晶体,但当培养时间为3天和5天时,得到的CaCO3晶体形貌既有河蚌状也有类球状,同时其晶型既有方解石也有球霰石,而当培养时间达到7天后,得到的就只有球状球霰石CaCO3晶体.     

Evolution Mechanism of Calcium Carbonate in Solution

Calcium carbonate was synthesized in a CaCl₂/NaCO₃ mixed solution by using ethylenedi-aminetetraacetic acid (EDTA) as an additive. The thermodynamics and kinetics analyses indicate that although the driving force of amorphous calcium carbonate (ACC) precipi-tation is always less than that of calcite and vaterite precipitation, the nucleation rate of ACC is greater than that of calcite and vaterite at the initial stage of the precipitation reaction. With the increasing incubation time, vaterite and calcite particles nucleate het-erogeneously by using the as-formed particles as active sites. Scanning electron microscopyimages indicate that the transformation mechanism of ACC and vaterite to calcite is the dissolution-recrystallisation reaction. The presence of EDTA not only improves the stabil-ities of ACC and vaterite, but also leads to forming enlongated, connected rhombohedralcalcite crystals after incubation 7 days in solutions. The ACC and vaterite are stabler in air than in solutions at room temperature, although the dissolution-recrystallisation reaction occurs on the surface.     

Efficiently stabilized spherical vaterite CaCO3 crystals by carbon nanotubes in biomimetic mineralization

Carbon nanotubes were used to induce the formation of spherical vaterite crystals and stabilize the metastable crystals in the biomimetic mineralization of CaCO3 for the first time. It was found that carboxyl-functionalized multiwalled/single-walled carbon nanotubes (MWNT-COOH/SWNT-COOH) can favor the formation of spherical vaterite crystals and stabilize the crystals. In the presence of CNT-COOH, CaCO3 vaterite crystals with diameters of ca. 1-7 microm coated and embedded with the carbon nanotubes (CNTs) were obtained in 30 min by adding Na2CO3 aqueous solution to the aqueous solution of CaCl2. The spherical vaterite crystals covered by the carboxylic CNTs can exist stably in water for a week. Carboxylic-polymer-functionalized CNTs can also facilitate the formation of spherical vaterite crystals, whereas the formed crystals completely transformed into thermodynamically stable calcite crystals in water within 10 h. "Offline" TEM observations of the mineralization process of CaCO3 in the presence of CNT-COOH or pristine CNTs revealed the stability mechanism of vaterite crystals with carboxylic CNTs. The crystals nucleate at the carboxyl groups of CNT-COOH, grow around the CNTs, and finally form spherical vaterite crystals embedded and covered by the CNTs. The strong interaction between CNT-COOH and crystals together with the strong mechanical strength of CNTs stabilizes the formed vaterite crystals and makes them difficult to dissolve in water. These findings announce that nanomaterials could strongly influence the mineralization of biomineralization matters, which may help us prepare novel biomaterials and bionanomaterials.     

Bioinspired synthesis of calcium carbonate hollow spheres with a nacre-type laminated microstructure

In this Article, we combine the characters of hyperbranched polymers and the concept of double-hydrophilic block copolymer (DHBC) to design a 3D crystal growth modifier, HPG-COOH. The novel modifier can efficiently control the crystallization of CaCO(3) from amorphous nanoparticles to vaterite hollow spheres by a nonclassical crystallization process. The obtained vaterite hollow spheres have a special puffy dandelion-like appearance; that is, the shell of the hollow spheres is constructed by platelet-like vaterite mesocrystals, perpendicular to the globe surface. The cross-section of the wall of a vaterite hollow sphere is similar to that of nacres in microstructure, in which platelet-like calcium carbonate mesocrystals pile up with one another. These results reveal the topology effect of the crystal growth modifier on biomineralization and the essential role of the nonclassical crystallization for constructing hierarchical microstructures.     

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.     

Properties of amorphous calcium carbonate and the template action of vaterite spheres

The fast mixing of aqueous solutions of calcium chloride and sodium carbonate could immediately result in amorphous calcium carbonate (ACC). Under vigorous stirring, the formed ACC in the precipitation system will dissolve first and, then, transform within minutes to produce crystalline forms of vaterite and calcite. After that, the solution-mediated mechanism dominates the transformation of the thermodynamically unstable vaterite into the thermodynamically stable calcite. Although ACC is the least stable form of the six anhydrous phases of calcium carbonate (CaCO(3)), it could be, however, produced and stabilized by a variety of organisms. To better understand the formation-transformation mechanism of ACC and vaterite into calcite, ex-situ methods (i.e., scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction spectroscopy) were used to characterize the formation-transformation process of ACC and vaterite in aqueous systems without organic additives, showing that ACC sampled at different conditions has different properties (i.e., lifetime, morphology, and spectrum characterization). It is also very interesting to capture the obviously polycrystalline particles of CaCO(3) during the transformation process from vaterite to calcite, which suggests the formation mechanism for the calcite superstructure with multidimensional morphology.     

胆固醇/卵磷脂/壳聚糖体系中碳酸钙模拟生物矿化的研究

本文采用X射线衍射、红外光谱和扫描电子显微镜等方法研究了胆固醇／卵磷脂／壳聚糖体系中碳酸钙模拟生物矿化过程。通过改变有机基质的组成,使有机基质的模板作用 也发生改变,从而使生成方解在一重型里面在酸钙的模板可生成球霰石型的碳酸钙。文中还进一步探讨了体系中壳聚糖、卵磷脂、胆固醇三者的协同作用对生成碳酸钙晶型的影响。     

Crystallization of calcium carbonate controlled by Pluronic P123 in room-temperature ionic liquid

The crystallization of calcium carbonate (CaCO₃) controlled by Pluronic P123 in a room-temperature ionic liquid, ethylamine nitrate (EAN), was investigated. The CaCO₃ aggregates were obtained by rapid mixing of ammonium carbonate ((NH₄)₂CO₃) and calcium chloride (CaCl₂). Cubic calcite, spherical vaterite, and bagel-like vaterite were obtained easily by changing P123 concentration and reaction temperature. The morphologies of the as-prepared CaCO₃ aggregates were investigated by transmission electron microscopy and scanning electronic microscopy. The phase change of the obtained crystals was confirmed by X-ray diffraction and Fourier transform infrared spectroscopy. It was shown that higher P123 concentration and higher reaction temperature favor the formation of vaterite in EAN. Unusual bagel-like vaterite was first obtained at 60 °C in the presence of 5 g/L P123 in EAN. Mineralization of CaCO₃ regulated by P123 in EAN is a simple, novel, and environment-friendly strategy for vaterite synthesis.     

Formation of calcium carbonate films on chitosan substrates in the presence of polyacrylic acid

In this investigation, chitosan membranes with different surface average degrees of deacetylation (DA) are prepared and then are employed as the support matrix to culture calcium carbonate (CaCO₃). In the presence of high concentration of polyacrylic acid (PAA), the CaCO₃ films obtained on the surface of all chitosan films mainly consisted of vaterite, which suggests the presence of bulk PAA plays an overwhelming part in stabilizing the vaterite. As a comparison, the influences of active groups indicate that only in case of low concentration PAA the thin CaCO₃ films grown on chitosan with 8% DA mainly consisted of vaterite owing to the strong nucleation ability of -NH₂ group, whereas, for those grown on chitosan with 80% DA the CaCO₃ films mainly consisted of aragonite. A more complex scenario revealed that in the case of intermediate concentration of PAA the formed polymorphs behave as mixtures of vaterite and aragonite.