Flame‐based synthesis and in situ functionalization of palladium alloy nanoparticles

Flame‐driven synthesis and functionalization of palladium‐containing nanoparticles is demonstrated using a high temperature reducing jet (HTRJ) process that decouples flame chemistry from particle formation chemistry and provides a reducing environment that enables synthesis of metal nanoparticles from low‐cost aqueous precursors. Nanoparticles with controlled palladium, copper, and silver content were synthesized and functionalized with amine‐containing ligands using both in situ and ex situ approaches. For in situ functionalization, octylamine was sprayed into the quench section of the HTRJ reactor to cap the nanoparticles in the gas phase. For the ex situ approach, the “bare” nanopowders were heated in various amines (hexylamine, octylamine, and oleylamine) to form stable dispersions. Use of oleylamine at high temperature allowed modification of the nanoparticle size and shape while maintaining the alloy composition. These in situ and ex situ functionalization methods provide flexibility to tailor particles for specific applications such as electrocatalysis or hydrogen purification. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3826–3834, 2018     

Synthesis and characterization of near monodisperse oligomeric polystyrenes

Oligomeric (<10³) polystyrenes have been synthesized on a practical scale by the use of secbutyllithium and triethylamine in cyclohexane. These samples were found to possess relatively narrow molecular weight distributions. The product analysis was accomplished by viscosity, vapour pressure osmometry, gel permeation chromatography and gas chromatography.     

Synthesis and characterization of star‐shaped PLLA with sorbitol as core and its microspheres application in controlled drug release

The purpose of this study was to investigate the suitability of a six‐arm star‐shaped poly(l ‐lactide)s (s‐PLLA) as controlled drug carriers for hydrophobic drug molecules. First, s‐PLLA was synthesized by ring‐opening polymerization of l ‐lactide using sorbitol as initiator and stannous octoate as catalyst. The structure and molecular weight (M_w) of s‐PLLA was characterized with ¹H NMR, ¹³C NMR, and GPC. Second, rifampicin (RIF) used as a model drug was encapsulated within the microspheres of s‐PLLA via oil‐in‐water emulsion/solvent evaporation technique. The morphology, drug encapsulation efficiency (EE), and in vitro release behavior of the prepared microspheres were studied in details. Results indicated that the average diameters of s‐PLLA microspheres can be controlled between 8 and 20 µm by varying the copolymer's concentration or M_w . The EE of RIF was mainly determined by the concentration of s‐PLLA. The in vitro study showed that the burst release behavior can be depressed by increasing the M_w of the s‐PLLA. Present work suggests that the synthesized s‐PLLA could be used as a new material for drug delivery. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42213.     

Remote actuation of hydrogel nanocomposites: Heating analysis,modeling, and simulations

Recently, there has been increasing interest in remote heating of polymer nanocomposites for applications such as actuators, microfluidic valves, drug delivery devices, and hyperthermia treatment of cancer. In this study, magnetic hydrogel nanocomposites of poly(ethylene glycol) (PEG) with varying amounts of iron oxide nanoparticle loadings were synthesized. The nanocomposites were remotely heated using an alternating magnetic field (AMF) at three different AMF amplitudes, and the resultant temperatures were recorded. The rate of the temperature rise and the steady state temperatures were analyzed with a heat transfer model, and a correlation of heat generation per unit mass with the nanoparticle loadings was established for different AMF amplitudes. The temperature rise data of a PEG system with different swelling properties were found to be accurately predicted by the model. Furthermore, the correlations were used to simulate the temperatures of the nanocomposite and the surrounding tissue for potential hyperthermia cancer treatment applications. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Dynamic population balance and flow models for granular solids in a linear vibrating screen

Vibrating screens are a widely applied form of particle separations. In spite of this significance, their understanding is still an obstacle. Three approaches were used to characterize the flow of granular material in a linear vibrating screen. The statistical model, mass action, and kinetic model based on conservation of momentum were derived. Experiments were then conducted on a multi‐sized prototype screen and glass beads of sizes 0.75, 1, 2, 3 mm. Deck inclinations were varied over 7.5,12.5, and 17.5°, and frequencies over 7, 15, and 20 Hz. A total of 72 feed batches and a constant power of 50 W was used. The experimental data was then used to validate the models. The three models provided accurate flow prediction over the screens. Additionally, the kinetic model also provided a basis for optimal design of the screening unit operation, by allowing manipulation of seven design variables to obtain a 95–100% efficient vibrating screen. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3889–3898, 2016     

Synthesis and characterization of monodisperse NiFe2O4 nanoparticles

Narrow size distribution nickel ferrite nanoparticles with average particle size of around 6 nm has been synthesized via rapid thermo-decomposition method in the presence of oleylamine in solution which acted as neutralizing, stabilizing and reducing agent OAm coated NiFe₂O₄ NPs. X-ray powder diffraction (XRD), Fourier Transform Infrared Spectra (FT-IR), Thermal Gravimetric Analysis (TGA), Scanning Electron Microscopy (SEM), Transmission electron microscopy (TEM), Vibrating Simple Magnetometer (VSM) and also Mössbauer Spectroscopy were used for structural, morphological, spectroscopic and magnetic characterization of the product. The XRD analysis revealed the formation of single phase nickel ferrite with Fd-3m space group. Both FT-IR and TGA analyses confirmed the formation of desired nanocomposite. FT-IR analysis also showed characteristic IR absorption bands of the spinel nickel ferrite phase and oleylamine. TEM and SEM analysis showed that product have almost spherical structural morphology. TEM images showed that NiFe₂O₄ nanoparticles have narrow size distribution and Energy Dispersive X-ray (EDX) analysis confirmed the presence of metal ions in the required stoichiometric ratio. Superparamagnetic property of the product was confirmed by VSM. From ⁵⁷Fe Mössbauer spectroscopy data, the variation in line width, isomer shift, quadrupole splitting and hyperfine magnetic field values have been determined. The Mössbauer spectra for OAm coated NiFe₂O₄ NPs. is consisting of one paramagnetic central doublets and one magnetic Zeeman sextet. Finally, the synthetic procedure can be extended to the preparation of high quality metal or alloy nanoparticles.     

Synthesis and characterization of colorless polyimide nanocomposite films

A poly(amic acid) was prepared through the reaction of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride and 2,2′‐bis(trifluoromethyl) benzidine in N,N‐dimethylacetamide. Hybrid films were obtained from blend solutions of the precursor polymer and the organoclay dodecyltriphenylphosphonium–mica, with the organoclay content varying from 0 to 1.0 wt %. The cast films of poly(amic acid) were heat‐treated at different temperatures to create polyimide (PI) hybrid films. These PI hybrid films showed excellent optical transparency and were almost colorless. The intercalation of PI chains in the organoclay was examined with wide‐angle X‐ray diffraction and electron microscopy. In addition, the thermomechanical properties were tested with differential scanning calorimetry and thermogravimetric analysis, and the gas permeability was determined. The addition of only a small amount of the organoclay was sufficient to improve the thermal and mechanical properties of the PI, with the maximum enhancement being observed with 0.5 wt % organoclay. However, the water vapor permeability decreased with the clay loading increasing from 0 to 0.5 wt %. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Preparation,characterization, and properties of modified barium sulfate nanoparticles/polyethylene nanocomposites as T‐shaped copper intrauterine devices

To improve the mechanical properties and shelf‐life of barium sulfate nanoparticles (BaSO₄‐NPs)/polyethylene (PE) composites, which are used as the scaffold of T‐shaped copper intrauterine devices (Cu‐IUDs) in the clinic, an Al coupling agent was used to modify BaSO₄‐NPs. The influence of the Al coupling agent on the microstructures, properties, and shelf‐life of the nanocomposites were investigated. The results showed that: (1) a chemical reaction occurred between the Al coupling agent and the hydroxyl groups adsorbed by BaSO₄‐NPs. (2) BaSO₄‐NPs modified by the Al coupling agent dispersed in the PE matrix were much better than unmodified NPs. The interface bonding between modified NPs and the PE matrix was better than unmodified NPs. (3) the maximum tensile strength of nanocomposites containing modified NPs was 11.87 MPa, flexural strength was 6.61 MPa, and the elongation rate was 66.78%. (4) After an accelerated aging experiment, the tensile strength of the nanocomposites only decreased 5–15%. All of these results indicate that m‐BaSO₄‐NPs/PE nanocomposites are more clinically useful than unmodified nanocomposites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40393.     

Flow-based reactor design for the continuous production of polymeric nanoparticles

Polymeric nanoparticles (NPs) are versatile and effective drug delivery systems (DDS) that can be produced via nanoprecipitation of block copolymers. Yet, translation into clinical products has been limited. Thus, methods for NP production that enable rapid formulation screening and continuous production are needed. Toward this end, we engineered a coaxial jet mixer (CJM) for controlled and continuous nanoprecipitation in flow. The CJM enabled continuous assembly of poly(ethylene glycol)-block-polylactide NPs with various co-solvents and was compared to batch nanoprecipitation. Other fabricated microfluidic devices were suitable for small scale formulation screening but more limited in scalable and continuous processes. In contrast, the CJM was tolerant to all water-miscible solvents tested, enabled formulation screening, and scalable production of NPs and DDS. In total, the CJM provides a complementary approach to the process engineering of polymeric NP formation that can be used broadly for formulation screening and production.     

Synthesis and characterization of urethane/acrylate composite latex

Polyurethane dispersion and urethane/acrylate composite latex were synthesized and characterized by using a particle size analyzer, gel permeation chromatograph (GPC), Fourier transform infrared spectroscopy coupled with attenuated total reflectance (FTIR‐ATR), dynamic mechanical analysis (DMA), and instron test machine. The amount of solvent and dimethylolpropionic acid (DMPA) used during synthesis of polyurethane resin straightway affected the average particle size and stability of aqueous polyurethane dispersion. The particle size of polyurethane dispersion had nothing to do with that of composite latex. FTIR‐ATR analyses displayed both air‐facing and substrate‐facing surfaces, containing more polyurethane component than the average composition. Some crosslinking reactions occurred in preparing urethane/acrylic composite latex, as indicated by FTIR analyses and solvent extraction. DMA demonstrated three glass transitions for the film from composite latex. Instron tests exhibited better film performance properties for the composite latex than for the corresponding blend latex. A possible particle growth mechanism for preparing urethane/acrylate composite latex was proposed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1620–1628, 2002; DOI 10.1002/app.10526     

On the use of process analytical technologies and population balance equations for the estimation of crystallization kinetics. A case study

The batch cooling solution crystallization of ammonium oxalate was performed in water at various constant cooling rates. Measurements of the solute concentration were obtained using in situ attenuated total reflectance fourier transform infrared (ATR‐FTIR) spectroscopy, and final estimates of the crystal size distribution (CSD) were computed; thanks to in situ image acquisition and off‐line image analysis. The crystallization process was then simulated using population balance equations (PBEs). Estimates of the nucleation and the growth parameters were computed through model/experiments fitting. According to the cooling rate, the PBE model allowed distinguishing between two distinct crystallization regimes, separated by an “intermediate regime.” The respective contributions and shortcomings of solute concentration measurements and granulometric data to the identification of nucleation and growth kinetic parameters are analyzed and discussed. It is shown in particular that no real separate estimation of nucleation and growth parameters can be obtained in the absence of CSD data. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

A qualitative study of atmospheric aerosols and particles deposited on flat membrane surfaces by microscopy and other techniques

Samples of atmospheric particulate matter placed on Nuclepore® filters were analyzed by microscopy and complementary techniques. Volcanic ash placed on glass surfaces and atmospheric material on Teflon® filters were also studied by microscopy. The analyzed samples are related to volcanic eruptions, urban environments, and mining activity. Nuclepore filters are thin sheets with smooth surfaces on which particles are fixed almost uniformly after filtration, which makes them especially adequate for study by microscopy. Here a selection of samples analyzed by microscopy is presented, along with information on the shape and size of particles and their distribution on the surface of the filter. Hypotheses are advanced on the origin of particles, their crystalline states, and the physical mechanisms to trap particles on the filter surface. A morphological classification of the particles was carried out according to their appearance in the several samples analyzed. Other complementary analyses performed by PIXE (particle induced X-ray emission), by electron microprobe, by X-ray diffraction and by granulometry, are commented. The implications of the particles studied to human health are also discussed.     

Synthesis and characterization of methyl methacrylate/styrene hyperbranched copolymers via living radical mechanism

Free‐radical copolymerizations of N,N‐diethylaminodithiocarbamoylmethylstyrene (inimer: DTCS) with a methyl methacrylate (MMA)/zinc chloride (ZnCl₂) complex were carried out under UV light irradiation. DTCS monomers play an important role in this copolymerization system as an inimer that is capable of initiating living radical polymerization of the vinyl group. The reactivity ratios (r₁ = 0.56 and r₂ = 0.52: DTCS [M₁]; MMA [M₂]) obtained for this copolymerization system were different from a corresponding model system (alternating copolymer) of a styrene and MMA/ZnCl₂ complex (r₁ = 0.25 and r₂ = 0.056). It was found that the hyperbranched copolymers produced exhibited a random branching structure. It was found that the Lewis acid ZnCl₂ formed the complex not only with MMA but also with the carbamate group of inimer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2490–2495, 2003     

具有b取向壳层MFI/MFI核壳分子筛的合成与表征

为了研究MFI/MFI核壳分子筛壳层b取向的形成机理,以圆柱形ZSM-5为核相,用碱性溶液对其表面预处理后,水热晶化合成具有高硅b取向壳层的MFI/MFI核壳分子筛,采用SEM、XRD、TEM、XPS和NMR等表征核相表面与晶化产物的结构。结果表明,核壳分子筛的（020）晶面衍射峰强度明显增强,壳层覆盖度为84％。核相碱处理是壳层形成的关键,未处理核相的表面上壳层不能生长,碱处理后在核相上形成的表面非骨架铝对高硅壳层颗粒的形貌和取向影响较大。在低铝含量条件下成核方式可能从非均相成核转变为均相成核,溶液中形成片状晶体,后经表面Si-OH强作用自组装得到二维紧密堆积的b取向壳层。     

Synthesis of nanosized poly(ethyl acrylate) particles via differential emulsion polymerization

Nanoparticles of poly(ethyl acrylate) were synthesized via a semibatch differential emulsion polymerization method with potassium persulfate as the initiator and sodium dodecyl sulfate as the surfactant. The effects of the reaction temperature, aging time, and surfactant/initiator/monomer ratios on the polymer particle sizes were investigated. Poly(ethyl acrylate) with particle sizes of less than 20 nm was synthesized under mild conditions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1609–1614, 2006     

单分散氢氧化钙/聚苯乙烯微球的制备与表征

以葡萄糖水溶液为反应介质,在氧化钙消化成氢氧化钙的过程中,加入苯乙烯单体和引发剂,采用原位悬浮聚合法成功制备了聚苯乙烯(PS)包覆氢氧化钙[Ca(OH)2]形成Ca(OH)2/PS微球.考察了葡萄糖水溶液、苯乙烯、稳定剂聚乙烯醇以及反应温度对单分散Ca(OH)2/PS微球的粒径及粒子分散系数的影响,得出较佳合成条件.在较佳条件下制备的Ca(OH)2/PS微球平均粒径为30～40 μm,粒子分散系数为0.08～0.10.扫描电镜照片表明,Ca(OH)2/PS具有良好的球形度,表面光滑、无破损.红外光谱表征显示,产物为Ca(OH)2/PS微球.     

纯相钼酸酐氮化合成技术及表征

以钼酸铵为原料,采用高温焙烧法制备颗粒状催化剂前驱体钼酸酐;以氮氢混合气为氮化剂合成氮化钼。考察空速、程序升温速率及氮化终温对氮化钼比表面积的影响,并通过SEM、XRD、BET对纯相氮化钼及前驱体钼酸酐表征。结果表明,一定条件下,当空速为42 000 h-1时,产物的比表面积最大,为129.2 m~2·g~(-1);当升温速率为1.0℃·min-1时,比表面积最大,为135.6 m~2·g~(-1);当氮化终温为750℃时,比表面积达到52.78 m~2·g~(-1)。纯相钼酸酐氮化条件温和、原料成本低。     

Pilot‐scale investigation and CFD modeling of particle deposition in low‐dust monolithic SCR DeNOx catalysts

Deposition of particles in selective catalytic reduction DeNO_x monolithic catalysts was studied by low‐dust pilot‐scale experiments. The experiments showed a total deposition efficiency of about 30%, and the deposition pattern was similar to that observed in full‐scale low‐dust applications. On extended exposure to the dust‐laden flue gas, complete blocking of channels was observed, showing that also in low‐dust applications soot blowing is necessary to keep the catalyst clean. A particle deposition model was developed in computational fluid dynamics, and simulations were carried out assuming either laminar or turbulent flow. Assuming laminar flow, the accumulated mass was underpredicted with a factor of about 17, whereas assuming turbulent flow overpredicted the experimental result with a factor of about 2. The simulations showed that turbulent diffusion in the monolith channels and inertial impaction and gravitational settling on the top of the monolith were the dominating mechanisms for particle deposition on the catalyst. © 2013 American Institute of Chemical Engineers AIChE J, 59: 1919–1933, 2013     

Synthesis and characterization of reactive copolymeric microgels

Hydrogels whose diameters range in the nanosize scale were synthesized by precipitation copolymerization of 4‐nitrophenol acrylate (NPA) with methacrylamide (MeAM) and N‐isopropylacrylamide (NIPAM). The polymerization reaction process was followed by attenuated total reflectance Fourier‐transform infrared spectrometry (ATR‐FTIR) and the conversion was studied by UV‐vis spectrometry. Poly(NPA‐co‐MeAM) and poly(NPA‐co‐NIPAM) microgels were characterized by proton nuclear magnetic resonance (¹H‐NMR) spectrometry. The thermal properties were studied by both thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) analysis. Transmission electron microscopy (TEM) of these microgels showed that the copolymer is located in spherical particles with a moderate polydispersity. The average particle diameter and the particle size distribution were measured in acetone by quasi‐elastic light scattering (QELS), which indicated a mean diameter close to 50 nm. Copyright © 2005 Society of Chemical Industry