采用纳米Al203和碳纳米管颗粒强化CO2吸收的理论及实验研究（英文）

The influence of nano-particles on CO2 absorption was studied experimentally in a stirred thermostatic reactor. Nano-A1203 and carbon nanotube （CNT） particles which showed different hydrophobic properties were chosen for the investigation. The experimental results were compared with that of micron-size activated carbon （AC） and Al2O3 particles. From the results, no enhancement by micron-size A1203 was found, and with the increase of A1203 concentration, the enhancement factor decreased. However, nano-Al203 showed a weak enlaancement tor me COz absorption. AC and CNT particles all intensified the gas-liquid mass transfer effectively, yet the trend of the enhancement factor with stirring speed for the two particles was different. With increasing stirring speed, the enhancement factor of AC particles was decreased, wl＇iereas in CNT suspensions it was increased. The experimental phenomena demonstrated a difference in enhancement mechanism for different size particles. For nano-particles, besides the influence of adsorbability and hydrophobicity, the micro-convection caused by Brownian motion should be also taken into account. Considering the micro-convection effect, a theoretical model was developed to shed light on the absorption enhancement bv nano-oarticles.     

反应沉淀法制备超细硫酸沙丁胺醇颗粒及其粉雾剂的表征

The preparation of ultra-fine particles of salbutamol sulphate （SS） was accomplished with a reactive precipitation pathway, in which salbutamol and sulphuric acid were Used as reactants with the solvents of ethanol.The effects of sulphuric acid concentration, reaction temperature, stirring rate, and reaction time onthesize of the particle were investigated. A binary mixture composed of lactose and SS was prepared to evaluate SS. The results showed that ultra-fine SS particles with controlled diameters ranging between 3 μm and 0.8 μm and with a narrow distribution could be achieved. The morphology consisting of clubbed particles wassuccess.fully obtained. The purity of the particles reached above 98% with-UV detection. The dose- of dry powder inhalation was obtained by blending the particles with recrystallized lactose, which acted as a carrier. The deposition quantity of the drug in breathing tract was estimated using a twin imPinger apparatus. Compared with the Shapuer powder （purchased in the market）, the results showed that SS_particles had more quantifies.subsided in simulative lung.. _     

Effect of saline electrolyte on particle sizes in fat emulsions by electronic counting

The number of particles of specific diams in in the fat emulsions SR-151, Intralipid, and Lipofundin, by electronic counting, was critically dependent upon the elapsed time of contact of the emulsions with the diluting saline electrolyte. The most pronounced change in the number of particles as a function of time occurred with the particles of smallest diams, those less than 2μ. Increases in the number of particles by approx 100% occurred within 20 min of mixing the emulsions and electrolyte. Apparently coalescence or aggregation of smaller particles caused the increases in numbers. By extrapolation to zero time, accurate counts were obtained. Investigation supported by funds from the Office of the Surgeon General, U. S. Army, Washington, D. C. So. Utiliz. Res. & Dev. Div., ARS, USDA.     

载三氧化二砷的PEG—PLGA隐性纳米粒的制备及体外研究

The aim of this study was to prepare arsenic trioxide （ATO）-loaded stealth PEGylated PLGA nanoparticles （PEG-PLGA-NPs） and to assess the merits of PEG-PLGA-NPs as drug carriers for ATO delivery. PEG-PLGA copolymer was synthesized with methoxypolyethyleneglycol （Mw=5000）, D, L-lactide, and glycolide by the ring-opening polymerization method. Amorphous ATO was transformed into cubic crystal form to increase its solu-bility in the organic solvent. ATO-loaded PEG-PLGA-NPs were prepared by the modified spontaneous emulsification solvent diffusion （SESD） method, and the main experimental factors influencing the characteristics of nanopar- ticles were investigated, to optimize the preparation. To confirm the escape of PEG-PLGA-NPs from phagocytosis by phagocytes, PEG-PLGA-NPs labeled rhodamine B uptake by murine peritoneal macrophages （MPM） were analyzed by flow cytometry. The results showed that the physicochemical characteristics of PEG-PLGA-NPs were affected by the type and concentration of the emulsifiers, polymer concentration, and drug concentration. ATO-loaded PEG-PLGA-NPs, with particle size of 120.8nm, zeta potential of-10.73mV, encapsulation efficiency of 73.6%, and drug loading of 1.36%, were prepared under optimal conditions. The images of transmission electron micros-copy （TEM） indicated that the optimized nanoparticles were near spherical and without aggregation or adhesion. The release experiments in vitro showed the ATO release from PEG-PLGA-NPs exhibited consequently sustained release for more than 26d, which was in accordance with Higuchi equation. The uptake of PEG-PLGA-NPs by MPM was found to decrease markedly compared to PLGA-NPs. The experimental results showed that PEG-PLGA-NPs were potential nano drug delivery carriers for ATO.     

一种温敏性水凝胶复性体系：聚N-异丙基丙烯酰胺的制备及其在溶菌本科复性中的应用

Temperature-sensitive hydrogel-poly(N-isopropyl acrylamide) (PNIPA) was prepared and applied to protein refolding. PNIPA gel disks and gel particles were synthesized by the solution polymerization and inverse suspension polymerization respectively. The swelling kinetics of the gels was also studied. With these prepared PNIPA gels, the model protein lysozyme was renatured. Within 24h, PNIPA gel disks improved the yield of lysozyme activity by 49.3% from 3375.2U·mg-1 to 5038.8U·mg-1. With the addition of faster response PNIPA gel beads, the total lysozyme activity recovery was about 68.98% in 3h, as compared with 42.03% by simple batch dilution. The novel refolding system with PNIPA enables efficient refolding especially at high protein concentrations. Discussion about the mechanism revealed that when PNIPA gels were added into the refolding buffer, the hydrophobic interactions between denatured proteins and polymer gels could prevent the aggregation of refolding intermediates, thus enhanced the protein     

纳米金属钴粒子的制备及对高氯酸铵热分解的影响

The monodispersed Co nanoparticles were successfully prepared by means of hydrogen plasma method in inert atmosphere. The particle size, specific surface area, crystal structure and morphology of the samples were characterized by transmission electron microscopy （TEM）, BET equation, X-ray diffraction （XRD）, and the corresponding selected area electron diffraction （SAED）. The catalytic effect of Co nanoparticles on the decomposition of ammonium perchlorate （AP） was investigated by differential thermal analyzer （DTA）. Compared with the thermal decomposition of pure AP, the addition of Co nanoparticles （2%-10%, by mass） decreases the decomposition temperature of AP by 145.01-155.72℃. Compared with Co3O4 nano-particles and microsized Co particles, the catalytic effect of Co nanoparticles for AP is stronger. Such effect is attributed to the large specific surface area and its interaction of Co with decomposition intermediate gases. The present work provides useful information for the application of Co nanoparficles in the AP-based propellant.     

A comparison of soft magnetic composites designed from different ferromagnetic powders and phenolic resins☆

Soft magnetic composites (SMCs) were prepared from three different ferromagnetic powder particles:iron powder ASC 100.29, spherical FeSi particles and vitroperm (Fe73Cu1Nb3Si16B7) flakes. Two types of hybrid organic–inorganic phenolic resins modified with either silica nanoparticles or boron were used to design a thin insulating layer perfect-ly covering the ferromagnetic particles. Fourier transform infrared (FTIR) spectrometry confirmed an incorporation of silica or boron into the polymer matrix, which manifested itself through an improved thermal stability of the hybrid resins verified by thermogravimetric-differential scanning calorimetry (TG-DSC) analysis. The core-shell particles prepared from the ferromagnetic powder particles and the modified hybrid resins were further compacted to the cylindrical and toroidal shapes for the mechanical, electrical and magnetic testing. A uniform distribution of the resin between the ferromagnetic particles was evidenced by scanning electron microscope (SEM) analysis, which was also reflected in a rather high value of the electrical resistivity. A low porosity and extraordinary high values of mechanical hardness and flexural strength were found in SMC consisting of the iron powder and phenolic resin modified with boron. The coercive fields of the prepared samples were comparable with the commercial SMCs.     

酸白土催化体系开环八甲基环四硅氧烷的研究及机理探讨

Cationic ring opening polymerization of octamethylcyclotetrasiloxane （Da） initiated by acid treated bentonite was investigated. The experimental conditions were chosen on the basis of preliminary experiments.Higher temperature was found beneficial for the reaction process while stirring intensity beyond a certain level showed no obvious effect on the reaction rate. Polymers were characterized by Fourier transform infrared, proton nuclear magnetic resonance （IH-NMR） and gel perneation chromotography. The width of molecular mass distribution was found ranging between 1.2 and 1.4, which is extraordinarlly narrow compared with that of cationic polymerizations reported elsewhere （〉 1.9）. The results were believed due to the absence of free proton and counter ion which simplifies the polymerization process and the huge steric hindrance provided by bentonite particles which keeps the propagation of polysiloxane onto the surface of bentonite particles in a much more regular way. A feasible mechanism is proposed and seems to be supported well by experiments. Additionally, from the results of α, ω-dihydrogen terminated polysiloxanes prepared, the possibility of applying this potential environmentally friendly heterogeneous catalyst in industrial polymerization of cyclosiloxanes is anticipated.     

Removal of Cd（II） by Nanometer AIO（OH） Loaded on Fiberglass with Activated Carbon Fiber Felt as Carrier

A new nanometer material, nanometer AlO（OH） loaded on the fiberglass with activated carbon fibers felt（ACF） as the carrier, was prepared by hydrolytic reaction for the removal of Cd（II） from aqueous solution using column adsorption experiment. As was confirmed by XRD determination, the hydrolysis production loaded on fiberglass was similar to the orthorhombic phase AlO（OH）. SEM images showed that AlO（OH） particles were in the form of small aggregated clusters. The Thomas model was applied for estimating the kinetic parameters and the saturated adsorption ability of Cd（II） adsorption on the new adsorbent. The results showed that the maximum adsorption capacity of Cd（II） was 128.50 mg·g^-1 and 117.86 mg·g^-1 for the adsorbent mass of 0.3289 g and the adsorbent mass of 0.2867 g, respectively. The elution experiment result indicated that the adsorbed Cd ions was easily desorbed from the material with 0.1 mol·L^-1 HCl solution. Adsorption-desorption cycles showed the feasibility of repealed uses of the composited material. The adsorption capacities were influenced by pH and the initial Cd（II） concentration. The amount adsorbed was greatest at pH 6.5 and the initial Cd（II） concentration of 0.07 mg·L^-1, respectively. Nanometer AlO（OH） played a major role in the adsorption process, whereas the fiberglass and ACF were assistants in the process of removing Cd（II）. In addition, the adsorption capacities for Cd（II） were obviously reduced from 128.50 mg·L^-1 to 64.28 mg·L^-1 when Pb ions were present because Pb ions took up more adsorption sites.     

有机硅表面活性剂对水体中多环芳烃的浊点萃取研究

Cloud point extraction （CPE） processes with two silicone surfactants, Dow Coming DC-190 and DC-193, were studied as preconcentration and treatment for the water polluted by three trace polycyclic aromatic hydrocarbons （PAHs）： anthracene, phenanthrene and pyrene. For all cases, the volumes of surfactant-rich phase obtained by two silicone surfactants were very small, i.e. a lower water content in the surfactant-rich phase was obtained. For example, less than 3% of the initial solution was obtained in a 1% （by mass） surfactant solution, which was much smaller than that of TX-114 in the same surfactant concentration. And TX-114 is known as a high compact surfactant-rich phase among most nonionic surfactants, thus the comparison showed that an excellent enrichment was ensured in the analysis application by the CPE process with the silicone surfactants, and the lower water content obtained in the surfactant-rich phase is also important in the large scale water treatment. The influences of additives and phase separation methodology on the recovery of PAHs were discussed. Comparing with DC-193, DC-190 has a lower cloud point and a higher recovery （near 100%） of all the three PAHs in same surfactant concentration, which was required for application as a preconcentration process prior to HPLC system. However the DC-190 solution is hard to be phase separated only by heating, whereas DC-193 has a relative higher phase separating speed by heating, but a high cloud point （around 360K） limits its application. Due to the phase separation by heating is the only method of CPE suitable to the large scale water treatment, the mixtures of two silicone surfacrants solutions were investigated in this study. A solution containing 1% of mixed DC-190 and DC-193 （in the ratio of 90 ： 10） removed anthracene, phenanthrene and pyrene near 100% with a relative low cloud point and quick phase separating speed.     

化学共沉淀法制备纳米铋掺杂氧化锡

以SnCl4.5H2O和Bi(NO3)3.5H2O为原料,氨水为沉淀剂,采用化学共沉淀法制备了铋掺杂氧化锡(BTO)纳米粉体,考察了反应温度、滴定终点pH、铋掺杂量、煅烧温度和分散剂PEG-600对所得的纳米BTO粉体物相、晶粒度和形貌的影响,对粉末的前驱体进行综合热分析(TG-DTA),用X射线衍射(XRD)、扫描电镜(SEM)对产物的结构和形貌进行表征,得到共沉淀法制备纳米BTO粉体的最佳条件:反应温度60℃,滴定终点pH=3,煅烧温度600℃;该条件下制得BTO粉体的电阻率最小为3.48Ω.cm。     

Improved photoelectrocatalytic degradation of methylene blue by Ti3C2Tx/Bi12TiO20 composite anodes

In order to effectively reduce the high recombination rate of photogenerated carriers when Bi₁₂TiO₂₀ (BTO) was excited by visible light, Ti₃C₂T_x/BTO/fluorine-doped tin oxide photoanodes were conveniently prepared with the aid of mechanical coating by gentle ultrasonic mixing. Systematic characterization and the degradation of methylene blue in a photoelectrochemical cell were performed. The results showed that the Ti₃C₂T_x/BTO composite exhibited a strong light absorption ability and the effective separation of photogenerated carriers. The optimal anode (6 wt% Ti₃C₂T_x/BTO) degraded 85.4% of methylene blue within 120 min at an applied electric field of 1 V, with a reaction rate that was 3.5 times that of BTO. It was proved that Ti₃C₂T_x, as a useful co-catalyst, creates an internal electric field at the contact interface with BTO and an external electric field, which are responsible for the enhanced photoelectrocatalytic degradation capacity of the composite anode materials.     

Double Injection Synthesis and Dispersion of Submicrometer Barium Titanyl Oxalate Tetrahydrate

A modified Clabaugh method has been used to produce a well-dispersed barium titanyl oxalate tetrahydrate (BTO) powder with a particle size of less than 0.2 μm. Production of the BTO powder is based on a double injection system, with reactants rapidly mixed using pressurized gas. The mixture resulting from the double injection of the reactants was subsequently quenched into a solution containing polyethyleneimine as a dispersant. The resulting dispersed BTO powder forms a suspension that is stable against coarsening or aggregation for greater than 1400 h. The dispersed BTO powder was also shown to produce BaTiO₃ with a particle size of 0.25 μm or less after calcination.     

Control of tetragonality via dehydroxylation of BaTiO3 ultrafine powders

Nanosized barium titanate (BaTiO₃ (BTO)) powders with a pure perovskite phase and high c/a ratio were prepared using a two-step hydrothermal approach followed by removal of hydroxyl groups using organic solvents. No trace of carbonate was observed during the preparation process. The tetragonality of the BTO powder increased with an increase in the hydrothermal process duration on treating the powder at 240 °C with the two-step and one-step processes. The tetragonality increased with a decrease in the hydroxyl group content. The advantages of the two-step process can be ascribed to the two-step nucleation and growth process, and in the second step, BTO particles nucleate directly on the BTO crystallites, resulting in a higher crystallinity and tetragonality (c/a ratio). The new method has the potential to be scaled up for mass production of high-quality BTO nanopowder samples suitable for capacitor and sensor applications.     

Highly compressible ceramic/polymer aerogel-based piezoelectric nanogenerators with enhanced mechanical energy harvesting property

Ceramic piezoelectric materials have orders of magnitude higher piezoelectric coefficients compared to polymers. However, their brittleness precludes imposition of large strains in mechanical energy harvesting applications. We report here that ice templating affords low bulk modulus lead-free aerogel piezoelectric nanogenerators (PENG) with unprecedented combination of flexibility and high piezoelectric response (voltage and power density). A modified ice templating protocol was used to fabricate piezoelectric nanocomposites of surface modified BaTiO₃ (BTO) nanoparticles in crosslinked polyethylene imine. This protocol allowed incorporating a significantly high fraction of BTO particles (up to 83 wt %) in the aerogel, while retaining remarkably high compressibility and elastic recovery up to 80% strain. The output voltage, at an applied compressive force of 20 N (100 kPa), increased with BTO loading and a maximum output voltage of 11.6 V and power density of 7.22 μW/cm² (49.79 μW/cm³) was obtained for PENG aerogels containing 83 wt% BTO, which is orders of magnitude higher than previously reported values for foam-based piezoelectric energy harvesters. The BTO/PEI PENGs also showed cyclic stability over 900 cycles of deformation. PENGs with higher porosity showed better elastic recovery and piezoelectric properties than lower porosity and higher BTO content aerogels. To the best of our knowledge, this is the first report to demonstrate the piezoelectric properties of high ceramic content aerogels having very high compressibility and elastic recovery.     

The effect of barium titanate ceramic loading on the stress relaxation behavior of barium titanate-silicone elastomer composites

The stress relaxation behavior of barium titanate (BTO)-elastomer (Ecoflex) composites, as used in large strain sensors, is studied using the generalized Maxwell-Wiechert model. In this article, we examine the stress relaxation behavior of ceramic polymer composites by conducting stress relaxation tests on samples prepared with varying the particle loading by 0, 10, 20, 30, and 40 wt% of 100 and 200 nm BTO ceramic particles embedded in a Ecoflex silicone-based hyperelastic elastomer. The influence of BTO on the Maxwell-Wiechert model parameters was studied through the stress relaxation results. While a pristine Ecoflex silicone elastomer is predominantly a hyperelastic material, the addition of BTO made the composite behave as a visco-hyperelastic material. However, this behavior was shown to have a negligible effect on the electrical sensing performance of the large strain sensor.     

BaTiO3铁电薄膜在硅基片上的取向生长

采用脉冲激光沉积方法,在硅基片上先沉积MgO或CeO2缓冲层后再制备BaTiO3(BTO)铁电薄膜.通过原位反射高能电子衍射来监测MgO,CeO2缓冲层在硅基片上的生长行为.用X射线衍射测定BTO薄膜的结晶取向.并利用压电响应力显微镜观察了铁电薄膜的自发极化形成的铁电畴.结果表明:BTO薄膜在不同的缓冲层硅基片上以不同的取向生长,在织构的MgO/Si(001)基片上为(001)择优,择优程度与MgO织构品质有关,其中在双轴织构MgO缓冲层上为(001)单一取向;在CeO2(111)缓冲层上为(011)单一取向.(001)取向的BTO薄膜具有更大的面外极化,而(011)取向的BTO薄膜具有更大的面内极化.     

Formation of Sol–Gel In Situ Derived BTO/NZFO Composite Ceramics with Considerable Dielectric and Magnetic Properties

The BT/NZFO composite ceramics derived by sol–gel in situ process were successfully prepared. The phase composition, morphology, and microstructure of the composite ceramics were determined and observed by X‐ray diffractometer (XRD), SEM, and EDS. Results showed that the Ni–Zn ferrite (NZFO) phase started to grow initially and then the BaTiO₃ (BTO) phase grew among the interfaces of NZFO particles at high ferrite content. The observation of microstructure showed that the NZFO phase in large grain size is enwrapped by the BTO phase in small grain size, and the constituent phases existed in the form of solid solutions doped with Fe and Ti, respectively. The densification and microstructure depended on the volume fraction of ferrite (f_NZFO). The appropriate sintering temperature was 1280°C–1300°C at which stable phase structure could be obtained for the BTO/NZFO composite. The maximum permittivity could achieve 86 000, and the initial permeability was as high as 162 when the ceramics was loaded with 95% ferrite and sintered at 1300°C for 12 h. The BT/NZFO composite ceramics exhibited impressive dielectric and magnetic properties, making it a potential candidate for wide applications in the integration of electronic devices.     

Chemical Vapor Synthesis of FeOx–BaTiO3 Nanocomposites

Nanocomposite powders of FeO_x–BaTiO₃ (FO‐BTO) have been prepared by chemical vapor synthesis (CVS) in a single‐step process. The optimal parameters (reactor temperature, reactor length, precursor ratio) for the synthesis were investigated in an initial step for the individual systems, iron oxide (FO), and barium titanate (BTO); and in a second step optimized for the synthesis of the nanocomposites. The solid iron precursor was thermally evaporated, whereas the solid Ba‐ and Ti precursors were vaporized using laser flash evaporation to obtain ultrafine crystalline FO, BTO, and FO‐BTO nanoparticles. The possibility to influence the mass ratios of the two phases in FO‐BTO mixture by adjusting the ratio of the precursor in the two precursor delivery units has been investigated. The potential of CVS for the synthesis of nanocomposites containing iron oxide and barium titanate ultrafine crystalline nanopowders with particle size bellow 10 nm is demonstrated.     

Preparation of hydrophobic nanosilica-filled polyacrylate hard coatings on plastic substrates

Colloidal silica nanoparticles synthesized from tetraethoxysilane via a sol–gel process were surface-modified first by 3-(trimethoxysilyl)propyl methacrylate, and then by trimethylethoxysilane (TMES). The former agent acts both as a coupling agent and as a C=C provider, whereas the latter agent is used to prevent particle aggregation and to increase hydrophobicity of the coating. The modified silica particles were UV-cured together with the monomer, 2-hydroxyethyl methacrylate (2-HEMA), and the crosslinking agent, dipentaerythritol hexaacrylate (DPHA), to form highly transparent hard coatings on plastic (PMMA and PET) substrates. Both differential scanning calorimetric and thermal gravimetric analyses of the hybrid materials indicated enhanced thermal stability with respect to the neat HEMA–DPHA copolymer. Furthermore, due to the incorporation of TMES, hydrophobicity of the hybrid coating increased considerably with increasing modified silica content. In the extreme case, an antiabrasive hard coating (7H on PMMA) with a water contact angle of 99° was obtained at the silica content of 15 wt%.