Microspheres and microcapsules, a survey of manufacturing techniques: Part III: Solvent evaporation

A methodological survey of microsphere formation and microencapsulation techniques based on solvent extraction/evaporation techniques is presented. Thus, basic features of solvent extraction and solvent evaporation processes, including droplet formation, droplet/particle stabilization, and solvent removal, are outlined. Preparation of a wide range of microspherical and microcapsular products based on biodegradable polyesters, polysaccharides, and nonbiodegradable polymers are discussed. Dependence of microcapsule characteristics on manufacturing parameters, as well as performance evaluation of microspherical and microcapsular products, are also briefly covered.

Synthesis and metallophilic properties of troponoid thiocrown ethers

A new class of ionophores with troponoid and thiocrown ether units was prepared. Cation-binding properties of troponoid dithiocrown ethers were characterized using UV and NMR spectroscopies. They have affinity with metal ions; in particular, they showed high affinity with Hg2+. Transport of Hg2+ through a CHCl3 liquid membrane with troponoid dithiocrown ethers was examined in a U-type cell. From an aqueous solution of HgCl2 and CuCl2, Hg2+ is transferred selectively and smoothly, while the Cu2+ remained quantitatively in the original solution. The cavity size of dithiocrown ethers is one of the requirements for effective extraction and transport of Hg2+. However, derivatives with a smaller cavity still extract and transport Hg2+. A polymer-supported troponoid dithiocrown ether was prepared to transport Hg2+ effectively and repeatedly. Comparing the troponoid dithiocrown ether with the benzenoid dithiocrown ether with a similar cavity size, the former was more effective for the transport of Hg2+. It is proposed that the tropone ring assisted the release of Hg2+ from the complex by Coulomb repulsion between the protonated tropone ring and Hg2+.

Effect of gamma-radiation on the thermal and mechanical properties of a commercial poly(butylene adipate-co-terephthalate)

BACKGROUND: Poly(butylene adipate-co-terephthalate) (PBAT) has attracted wide interest as a biodegradable polymer. However, its use is restricted in certain applications due to its low melting point.RESULTS: PBAT was treated using gamma-radiation. The radiation features were analyzed using Soxhlet extraction, and the ratio of chain scission and crosslinking and gelation dose were determined using the classical Charlesby-Pinner equation. The results showed that PBAT is a radiation-crosslinkable polymer. The degree of crosslinking increased with increasing radiation dose; the relation between sol fraction and dose followed the Charlesby-Pinner equation. Differential scanning calorimetry analyses showed that the melting temperature (T-m) and the heat of fusion (Delta H-m) of PBAT exhibited almost no change in the first scan. The second scan, however, showed a decrease in T-m and Delta H-m. The glass transition temperature of irradiated PBAT increased with increasing radiation dose.

Extraction kinetics of cerium(IV) from sulfuric acid medium by the primary amine N1923 using a constant interfacial area cell with laminar flow

BACKGROUND: Thermodynamic studies on Ce(IV) extraction with primary amine N1923 demonstrate that primary amine N1923 is an excellent extractant for separation of Ce(IV) from Re(III). In order to clarify the mechanism of extraction and to optimize the parameters in practical extraction systems used in the rare earth industry, the extraction kinetics was investigated using a constant interfacial area cell with laminar flow in the present work.RESULTS: The data indicate that the rate constant (k(ao).) becomes constant when stirring speed exceeds 250 rpm. The apparent forward extraction rate is calculated to be 10(-1.70). The activation energy (E.) was calculated to be 20.5 kJ/mol from the slope of log kao against 1000/T. The minimum bulk concentration of the extractant necessary to saturate the interface (C-min) is lower than 10(-5) mol L-1.CONCLUSION: Studies of interfacial tension and the effects of stirring rate and specific interfacial area on the extraction rate show that the extraction rate is kinetically controlled, and a mass transfer model has been proposed. The rate equation has been obtained as: -d[Ce(IV)]/dt = 10(-1.70)[Ce(IV)] [(RNH3)(2)SO4](1.376). The rate-controlling step has been evaluated from analysis of the experimental results.

Evaluation of a sequential extraction for the speciation of thorium in soils from Baotou area, Inner Mongolia

Sequential extraction procedures were widely applied for speciation of radioactive elements. In this study, the sequential extraction procedure developed by Martinez-Aguirre was employed for quantification of different chemical forms of thorium in the soil. The total amount of thorium in contaminated soil was much higher by four-fold than the local background value. The soil properties affect the amount of thoriurn and distribution of fractions in contaminated soil. Results showed that the proportion of thorium in soils from Baotou was found as the residual fraction (F5 + F6) > absorbed fraction (F3), coprecipitated fraction (F4) > carbonates fraction (172) and exchangeable fraction (F1) that could be available to plants. The recovery, calculated by ratio of the sum of the six fractions to the pseudo-total content of thorium, was in the range from 96% to 110%. A comparison was carried out between the sequential extraction and the single extraction to evaluate the selectivity of the extractants. It was found that the amount of thorium of absorbed fraction (H) was higher in the single extraction than that estimated in the sequential extraction, possibly duo to transform of the labile form. While for non-residual fraction analysis, the single extraction scheme was a desirable alternative to the sequential extraction procedure.

Liquid-liquid extraction of cerium(IV) from nitric acid media by di-(2-ethylhexyl) 2-ethylhexyl phosphonate (DEHEHP)

In this paper, the extraction of Ce(IV) from nitric acid solutions is investigated using di-(2-ethylhexyl) 2-ethylhexyl phosphonate (DEHEHP, B) in heptane as extractant. Ce(IV) can be extracted effectively from nitric acid solution, whereas it is poorly extracted from sulfuric acid solution. Compared with some other organophosphorus esters, DEHEHP has moderate extractablity for Ce(IV). The extraction efficiency varies with diluent in the order: aliphatic hydrocarbons > nitrobenzene > aromatic hydrocarbons > carbon tetrachloride > chloroform. Regeneration and loading capacities of DEHEHP have also been examined. Ce(IV) extraction in HNO3 solutions as well as extraction of HNO3 and H2O have been systematically studied. The Ce(IV) extraction increases with an increasing of HNO3 concentration and exhibits the maximum distribution ratio at 1-1.5 mol/L HNO3. Nitric acid, as a source of nitrate ion, enhances the extraction of metal ion. But it also competes with metal ions for extractant molecules by its own extraction under high acidities. The proposed extraction process is described by the following equilibrium equations

Kinetics of cerium(IV) extraction with DEHEHP from HNO3-HF medium using a constant interfacial cell with laminar flow

Studies of the extraction kinetics of cerium(IV) into n-heptane solutions of di(2-ethylhexyl)-2-ethylhexyl phosphonate DEHEHP from HNO3-HF solutions have been carried out using a constant interfacial cell with laminar flow. The experimental hydrodynamic conditions were chosen so that the contribution of diffusion to the measured rate of reaction was minimized. The data were analyzed in terms of pseudo-first order constants. The effects of the stirring rate, specific interfacial area, and temperature on the extraction rate showed that the most probable reaction zone is in the aqueous homogeneous phase. The results were compared with those of the system without HF. It was concluded that the presence of HF decreases the extraction rate of cerium. The addition of HF increases the activation energy for the forward reaction from 21.2 to 55.3 kJ/mol and for the reverse process from 57.9 to 79.0 kJ/mol. According to the experimental data correlated as a function of the concentration of the relevant species involved in the extraction reaction, the corresponding rate equation was deduced as follows:-d[Ce]/dt = k[Ce] center dot B-0.62 center dot HF-0.58 center dot [NO3-](0.57)

Three-phase extraction study in the Cyanex923-n-heptane/HNO3 system

The present paper reports a study of the extraction of HNO3 with Cyancx923 (C923)-n-heptane. A third phase appears at different aqueous HNO3 concentrations for various initial C923 concentrations. Data analysis indicates that almost all of HNO3 and H2O are extracted into the middle phase. More HNO3 and water at a fixed ratio are solubilized in the reverse micelles or microemulsion in the third phase, which leads to a sharp increase of their concentration. The effect of temperature on the phase behavior of the three-phase system has also been investigated.

Separation of heavy rare earth elements with extraction resin containing 1-hexyl-4-ethyloctyl isopropylphosphonic acid

This paper presents the results of the adsorption of heavy rare earth ions (Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III), Lu(III) and Y(III)) from hydrochloric acid solutions at 30 degreesC by the extraction resin containing 1-hexyl-4-ethyloctyl isopropylphosphonic acid (HEOPPA), which has higher steric hindrance, higher selectivities and lower extraction and stripping acidity than di(2-ethylhexyl)phosphoric acid (DERPA) or 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (HEH/EHP). The dependence of acid concentration, flow rate and amounts of rare earth ions sorbed on the separation of Er-Tm, Tm-Yb and Er-Tm-Yb mixtures has been studied. The baseline chromatographic separation of Er-Tm-Yb mixture has been observed. Satisfactory results with purity and yield of Tm2O3>99.71% and >71.25%, Er2O3>99-81% and >94.17%, and Yb2O3>99.74% and >89.83%, respectively, have been obtained. The parameters such,as resolution, separation factors and efficiencies have been determined as a function of acidity, loading of rare earth elements and flow rates. The stoichiometry of the extraction of rare earth ions has been suggested as well.

Three-phase extraction study of Cyanex 923-n-heptane/Ce4+-H2SO4 system

Phase behavior of the extraction system, Cyanex 923-heptane/Ce4+-H2SO4 has been studied and compared with Cyanex 923-heptane/H2SO4 System. Cerium(IV) is mainly extracted into the third phase, and its concentration in the third phase first increases with the increasing aqueous acid concentration, reaches maximum and then decreases. At higher acidity, cerium(IV) is hardly extracted in the third phase. The phase behavior and change of the contents of acid and water are similar to those in the acid system. The acid concentration increases with increase of the aqueous acid in the whole extraction region while the water content first decreases with it and then increases after the third phase formation. The third phase has a characteristic lamellar structure formed by the aggregates of Cyanex 923 (.) (H2SO4)(2) (.) H2O as those in the case of acid system. The third phase loaded Ce(IV) has been used to prepare ultrafine CeO2 powder conveniently by precipitation with oxalic acid, and powders with size mostly smaller than 100 nm can be obtained.

SOLVENT-EXTRACTION OF TERBIUM(III,IV) PERIODATE COMPLEXES WITH QUATERNARY AMINE

The differences between the solvent extraction of Tb(III) and Tb(IV) periodate complexes with quaternary amine were studied carefully for the first time. The effects of extractant concentration, phase ratio, the pH value of stock solution, salting-out agent, extractant form, diluent, and extraction time were comprehensively investigated. Under optimal conditions the separation factor between Tb(IV) and Tb(III) periodate complexes is over 5.5.

AN EXPERT SYSTEM FOR SOLVENT-EXTRACTION OF RARE-EARTHS

An expert system for solvent extraction of rare earths has been developed using LISP. The goal of this project was to mimic the chemists' inferential abilities to assist in the process of solvent extraction of rare earths. The system includes frequently used extractants, separation of specific rare earths, recommendation of procedures for the separation of mixtures of rare earths using (2-ethylhexyl)phosphonic acid 2-ethylhexyl monoester, selection of parameters for counter-current extraction and methods for evaluation of the technique, and the economics of the processing. The expert system runs on an IBM-PC/XT.

Sedimentation rates and provenance analysis in the Southwestern Okinawa Trough since the mid-Holocene

As a high-sedimentation rate depocenter along the path of the Kuroshio Current, the southwesternmost part of the Okinawa Trough is a key area to understand the Kuroshio history and sediments transportation. A 34.17-m-long sediment core was obtained by the advanced piston corer of Marco Polo/IMAGES XII MARION DUFRESNE during the May 2005 from the Southern Okinawa Trough at site MD05-2908. The recovered sediments were analyzed by AMS C-14 dating, coarse size fraction (> 63 mu m) extraction and moisture content determination in order to study its sedimentation flux and provenance. The depth-age relationship of core MD05-2908 was well constrained by 17 C-14 dating points. The sediments span across the mid-Holocene (6.8 ka B.P.) and have remarkablely high sedimentation rates between 1.8 and 21-2 m/ka, which is well consistent with the modern observations from sediment traps. We identified five 70-200 a periods of abnormally rapid sedimentation events at 6790-6600 a B.P., 5690-5600 a B.P., 4820-4720 a B.P., 1090-880 a B.P., and 260-190 a B.P., during which the highest sedimentation rate is up to 21-2 m/ka. In general, the lithology of the sediments were dominated by silt and clay, associated with less than 5% coarse size fraction (a parts per thousand << 63 mu m). As the most significant sediment source, the Lanyang River in northeastern Taiwan annually deliver about 10Mt materials to the coastal and offshore region of northeast Taiwan, a portion of which could be carried northward by currents toward the study area. Therefore, we concluded that the 5 abnormally rapid sedimentation events may be related to intensified rainfall in Taiwan and thus increased materials to our study area at that time. However, a few extreme-rapid sedimentation events cannot be explained by normal river runoff alone. The large earthquakes or typhoons induced hyperpycnal discharge of fluvial sediment to the ocean may also act as a potential source supply to the Okinawa Trough.

地球化学新方法在隐状矿床找矿预测中的应用研究

With the progress of prospecting, the need for the discovery of blind ore deposits become more and more urgent. To study and find out the method and technology for the discovery of blind and buried ores is now a priority task. New geochemical methods are key technology to discover blind ores. Information of mobile components related to blind ores were extracted using this new methods. These methods were tested and applied based on element' s mobile components migrating and enriched in geophysical-geochemical process. Several kinds of partial extraction techniques have tested based on element' s occurrence in hypergenic zone. Middle-large scale geochemical methods for exploration in forest and swamp have been tested. A serious of methods were tested and applied effetely about evaluation of regional geochemical anomaly, 1:25000 bedrock or soil geochemical methods sampling based on the net in dendritic water system instead of the normal net. 1. Element related with ores can be mobiled to migrate upwards and be absorpted by surface soil. These abnomal components can be concentrated by natural or artificial methods. These trace metalic ions partially exist in dissovlvable ion forms of active state, and partially have been absorbed by Fe-Mn oxide, soil and organic matter in the soil so that a series of reaction such as complex reaction have take place. Employing various partial extraction techniques, metallic ions related with the phase of the blind ores can be extracted, such as the technique of organic complex extraction, Fe-Mn oxide extraction and the extraction technique of metallic ions of various absorption phases. 2.1:200000 regional geochemical evaluation anomaly methods: Advantageous ore-forming areas were selected firstly. Center, concentration, morphological feature, belt of anomaly were choosed then. Geological and geochemical anomalies were combined. And geological and geochemical background information were restrained. Xilekuduke area in Fuyun sheet , Zhaheba area in Qiakuerte sheet, the west-north part in Ertai sheet and Hongshanzui anomaly in Daqiao sheet were selected as target areas, in Alertai, in the north of Xinjiang. in Xilekuduke area, 1:25000 soil geochemical methods sampling based on the net in dendritic water system was carried out. Cu anomaly and copper mineralization were determined in the center area. Au , Cu anomalies and high polarization anomaly were determined in the south part. Prospecting by primary halo and organic complex extraction were used to prognosis blind ore in widely rang outcrop of bedrock. 1:25000 bedrock or soil geochemical methods sampling based on the net in dendritic water system were used in transported overburden outside of mining area. Shallow seismic method and primary halo found a new blind orebody in mining area. A mineralization site was fou and outside of Puziwan gold mine, in the north of Shanxi province. Developing middle-large scale geochemical exploration method is a key technique based 1:200000 regional geochemical exploration. Some conditions were tested as Sampling density , distribution sites of sample, grain size of sample and occurrence of element for exploration. 1:50000 exploration method was advanced to sample clast sediment supplement clast sediment in valley. 1:25000 bedrock or soil geochemical methods sampling based on the net in dendritic water system was applied to sample residual material in A or C horizon. 1:2000 primary or soil halo methods used to check anomalies and determine mineralization. Daliang gold mineralization in the northern Moerdaoga was found appling these methods. Thermomagnetic method was tested in miniqi copper-polymetallic ore. Process methods such as grain size of sample, heated temperature, magnetic separating technique were tested. A suite of Thermomagnetic geochemical method was formed. This method was applied in Xiangshan Cu~Ni deposit which is cover by clast or Gobi in the eastern Xinjiang. Element's content and contrast of anomaly with Thermomagnetic geochemical method were higher than soil anomaly. Susceptibility after samples were heated could be as a assessment conference for anomaly. In some sectors thermo-magnetic Cu, Ni, Ti anomalious were found outside deposits area. There were strong anomal ies response up ore tested by several kind of partial extraction methods include Thermomagnetic, enzyme leach and other partial extractions in Kalatongke Cu-Ni deposit in hungriness area in the northern of Xinjiang. Element's anomalies of meobile were mainly in Fe-Mn oxide and salt. A Copper mineralization site in Xilekuduke anomaly area had been determined. A blind ore was foung by shallow seismic and geochemical method and a mineralization site was found outside this mining area in Puziwan gold deposit in shanxi province. A Gold mineralization site was found by 1:50000 geochemical exploration in Daliang, Inner Mongolia.

沙冬青抗冻组份的分离纯化和afp基因克隆的尝试

本文用三种方法分离纯化沙冬青（Ammopiptanthus mongolicus）叶片抗冻蛋白质。从70%硫酸铵沉淀后的上清液中得到了一种碱性的小分子物质，UiS，具有较高的溶解度( 260 mg/ml)和较强的降低溶液冰点的能力（200 mg/ml，冰点小于-20℃）：从10%硫酸铵和26%氯化铵共沉淀物中分离到一种抗冻蛋白-B3，B3分子量为39.8 kDa，热滞活性为0.45℃(10 mg/ml)：从沙冬青叶片热稳定蛋白质中用双向电泳一电泳回收法分离到afp,其分子量为40 kDa,pl为9.0。热滞活性为0.9℃(20 mg/ml)，和其他抗冻蛋白质进行比较，没有发现相同的类型。afp和uis在叶片含量都很高，可能是沙冬青抗冻生理过程中两种主要物质，它们对于沙冬青抵御-20℃左右的冷冻温度具有重要的意义。afp N端序列为SDDL SFTF NKFV PCQT DILF，据此合成了六段5’引物和一段3’引物，用RT - PCR方法从叶片中扩增出一段200 bp左右的片段。