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1.
In laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS), the properties of laser-generated aerosols, such as size and composition, are crucial for matrix-independent quantification. In this study, the aerosol particle morphology and elemental composition generated by two state-of-the-art laser systems (ArF excimer nanosecond-UV laser and Ti:sapphire femtosecond-IR laser) were investigated by electron microscopic techniques. Electrostatic sampling of the aerosols directly onto transmission electron microscopy (TEM) grids allowed us to study the morphology and elemental composition of the aerosols using TEM and TEM–EDX (energy dispersive X-ray spectroscopy) analyses, respectively. The results of the electron microscopic studies were finally compared to the LA-ICPMS signals of the main matrix components. The investigations were carried out for non-conducting materials (glass and zircon), metallic samples (steel and brass) and semiconductors (sulfides). The studies confirm that ns-LA-generated aerosols dominantly consist of nanoparticle agglomerates while conducting samples additionally contain larger spherical particles (diameter typically 50 to 500 nm). In contrast to ns-laser ablation, fs-LA-generated aerosols consist of a mixture of spherical particles and nanoparticle agglomerates for all investigated samples. Surprisingly, the differences in elemental composition between nanoparticle agglomerates and spherical particles produced with fs-LA were much more pronounced than in the case of ns-LA, especially for zircon (Si/Zr fractionation) and brass (Cu/Zn fractionation). These observations indicate different ablation and particle formation mechanisms for ns- and fs-LA. The particle growth mechanism for ns-LA is most likely a gas-to-particle conversion followed by agglomeration and additional hydrodynamic sputtering for conducting samples. On the other hand, phase explosion is assumed to be responsible for the mixture of large spherical particles and nanoparticle agglomerates as found for fs-LA-generated aerosols. Based on these mechanisms, the overall temporal elemental fractionation effects in ns-LA-ICPMS seem to occur mainly during the ablation. This effect was not observed for fs-LA-ICPMS despite the element separation into different particle fractions, which, on the other hand, could induce severe ICP-induced fractionation.  相似文献   

2.
Ladder-like polymer poly(linear trans-quinacridine) (polyquin (2,3-b) acridine-7,14(5,12) dione, PTQA) was synthesized and identified. Anhydrous electrorheological fluid (ER fluid, ERF) with PTQA as dispersed particle and bromodiphenylmethane (BDPM) as dispersing medium were prepared; the electrorheological properties were studied. The temperature effect of PTQA suspensions was also discussed. The results showed that PTQA suspensions in BDPM performed excellent ER activity; at room temperature, the yield stress of the suspension with 30 wt.% of particles was up to 6.0 kPa (3.0 kV/mm). The shear stress increased with the rise in temperature, and the temperature effect was enhanced at higher temperature range. The differences of electrorheological properties between PTQA-based ERF and polyquin(2,3-b) acridine-12,14(5,7) dione-based ERF were attributed to the molecular structural regularity of the polymer.  相似文献   

3.
For high performance waterborne coatings usually polymer latexes with low emulsifier content are more preferred. Although polymer/clay nanocomposites offer improved properties, it is difficult to produce clay based nanocomposite latexes containing low emulsifier due to the stabilization problems especially caused by organoclays. Present study deals with the preparation of a tBA/BA/MAA ternary copolymer/clay nanocomposite containing 3 wt.% sodium montmorillonite (Na+-MMT) via seeded emulsion polymerization. Experimentally it was observed that even the usage of hydrophilic clay caused stabilization problem and a certain amount of emulsifier (>1 wt.%) was necessary to obtain stable latexes. In addition, the usage of a low molecular weight water soluble polymer as steric barrier was found to increase the stability of system. Obtained nanocomposite latex showed fine particle size diameter (127 nm) and very narrow size distribution (PDI = 0.06). The WAXD and TEM investigations indicated that a mostly exfoliated nanocomposite was obtained. Thermal analyses (DSC, DMTA and TGA) showed that there was no change at Tg of the copolymer while very high improvement was obtained for elastic modulus and a slight increase in thermal stability. According to the rheological measurements, the nanocomposite latex showed a higher low shear viscosity, a stronger shear thinning behavior and an improved physical stability in comparison to the reference latex.  相似文献   

4.
Aqueous crosslinked microparticle dispersions were prepared from a copolymer of d,l-lactic acid, 1,4-butanediol, and itaconic acid with a thermomechanical method. The copolymer was prepared in one step polycondensation reaction using Sn(Oct)2 as a catalyst. A polymer with Mn of 2800 g mol?1 and a molecular weight distribution of 1.41 was obtained (as determined by SEC), that contained double bonds introduced by the itaconic acid monomer units (6 mol-%, as determined by NMR). Crosslinking ability of the prepared copolymer was demonstrated in bulk by adding a thermal initiator and altering amounts of ethylene glycol dimethacrylate (EGDMA) crosslinking agent into molten polymer at 60–150 °C. A crosslinked gel was formed in less than 15 min at 80 °C when 10 wt.% of EGDMA was added and benzoyl peroxide (BPO) was used as the initiator. Aqueous dispersions were prepared of the non-crosslinked copolymer with a thermomechanical method that involved slow addition of aqueous polyvinyl alcohol (PVA) solution into molten copolymer at 60 °C under shear. Dispersions were prepared with 10 wt.% of EGDMA and 2 wt.% of BPO. Crosslinking of the dispersed microparticles was achieved by heating the dispersions at 80 °C for 30 or 60 min. The dispersions were characterized by SEM, DSC, TGA, FT-IR, solid state NMR, and gel content measurements. The effect of crosslinking was clearly seen in SEM images of films cast from the dispersions. The films cast from non-crosslinked dispersions had smooth morphology whereas in films cast from crosslinked dispersions separate spherical particles were observed. During the crosslinking reactions, glass transition temperatures increased (as determined by DSC), thermal stability of the samples increased (as determined by TGA), and the gel content of the samples increased.  相似文献   

5.
Electron beam (EB) crosslinked natural rubber (NR) gels were prepared by curing NR latex with EB irradiation over a range of doses from 2.5 to 20 kGy using butyl acrylate as sensitizer. The NR gels were systematically characterized by solvent swelling, dynamic light scattering, mechanical and dynamic mechanical properties. These gels were introduced in virgin NR and styrene butadiene rubber (SBR) matrices at 2, 4, 8 and 16 phr concentration. Addition of the gels improved the mechanical and dynamic mechanical properties of NR and SBR considerably. For example, 16 phr of 20 kGy EB-irradiated gel-filled NR showed a tensile strength of 3.53 MPa compared to 1.85 MPa of virgin NR. Introduction of gels in NR shifted the glass transition temperature to a higher temperature. A similar effect was observed in the case of NR gel-filled SBR systems. Morphology of the gel-filled systems was studied with atomic force microscopy. The NR gels also improved the processability of the virgin rubbers greatly. Both the shear viscosity and the die swell values of EB-irradiated gel-filled NR and SBR were lower than their virgin counterparts as investigated by capillary rheometer.  相似文献   

6.
The effect of sulfonated poly(ether ether ketone) (SPEEK) in membrane formation and separation properties has been investigated in polysulfone(PSU)/SPEEK/N-methyl-2-pyrrolidinone (NMP) systems. Charged ultrafiltration/nanofiltration membranes were obtained reliably in the range of 0.5–5 wt.% SPEEK in the polymer blend. All PSU/SPEEK blend membranes had substantially higher water flux, salt rejection, porosity and greatly reduced particle adhesion compared to the PSU base membrane. Further, all of these properties varied systematically with variation of SPEEK content. Reproducibility and stability of the membrane properties was excellent. Pore sizes determined from dextran retention data and AFM measurements showed reasonable agreement. Membranes with 5 wt.% SPEEK demonstrated excellent overall properties. Such membranes had very high permeability, 22.6±1.6×10−11 m3 s−1 N−1, 0.999 fractional rejection of 4000 Da dextran, 0.65 rejection of 0.001 M NaCl, and only 0.75 mN m−1 adhesion of a 4 μm silica particle. Such membranes are very promising for scale-up of production and testing on real process streams.  相似文献   

7.
Cellulose/polyethylene-co-acrylic acid blends (cellulose concentration 0–50 wt.%) was prepared via mixing their alkaline solutions. The formed suspension was precipitated and dried, where after the morphology as well the thermal and mechanical properties of the blends were characterized by Differential Scanning Calorimetry (DSC), Scanning Electron Microscopy (SEM), and Dynamic Mechanical Analyses (DMA). In addition, the melt properties of the blend were studied by rotational rheometer following some injection molding trials as well. The polymers were found to be dispersed homogenously in the blend and the crystallization temperature of the PE-co-AA phase was increased ~6 °C due to the nucleation ability of the cellulose phase. The size of the discontinuous cellulose phase was 5 μm at the most while at higher cellulose concentrations (30–50 wt.%) the polymers formed co-continuous morphology in the blend. This change in the morphology was observed also in their melt properties which showed that the blend reached so called percolation point at ~20 wt.% of cellulose. Finally, the blends were found to be injection moldable over the whole composition range, if only the injection molding became more challenging (i.e. higher mold temperatures and longer mold cooling times were required) after the percholation point.  相似文献   

8.
Organotriethoxysilanes (APS-PGE2) were synthesized by reacting 1 mol of 3-(aminopropyl)triethoxysilane with 2 mol of 1,2-epoxy-3-phenoxypropane (PGE). Polyhedral oligomeric silsesquioxanes functionalized with bulky amino groups (ASSQO) were prepared by hydrolytic condensation of APS-PGE2 catalyzed by formic acid. Methacrylate resins were activated for visible light polymerization by the addition of 1 wt.% CQ in combination with the synthesized ASSQO at loadings between 0 and 30 wt.%. The progress of monomer conversion versus irradiation time showed that the CQ/ASSQO pair is an efficient photoinitiator system because a fast reaction and high conversion result from 60 s irradiation at 600 mW/cm2. The lack of methacrylate groups in the ASSQO, able to polymerize with the methacrylate resin, results in the absence of chemical bond between the ASSQO cages and the matrix. Debonding of ASSQO cages from the polymer give rise to nanovoids; which allows the methacrylate matrix to yield and deform plastically. Consequently, the final effect is a decrease in the flexural modulus and compressive strength with increasing amounts of ASSQO. The present study highlights the surface effect on the overall properties in nanostructured materials.  相似文献   

9.
We have successfully developed a new process to prepare porous poly(methyl methacrylate-co-acrylonitrile) (P(MMA-AN)) copolymer based gel electrolyte. The porous structure in the polymer matrix is achieved by adding SnO2 nanoparticles which are mostly used as gas sensor materials. The quasi-aromatic solvent, NMP, has an electron-repulsion effect with the space charge layer on the surface of SnO2 nanoparticles and forms a special gas–liquid phase interface. Once the cast polymer solution is stored at an elevated temperature to evaporate the solvent, gas–liquid phase separation happens and spherical pores are obtained. The ionic conductivity at room temperature of the prepared gel polymer electrolyte based on the porous membrane is as high as 1.54 × 10−3 S cm−1 with the electrochemical stability up to 5.10 V (vs. Li/Li+). This method presents another promising way to prepare porous polymer electrolyte for practical use.  相似文献   

10.
Nanoparticles of Ag, Pt and Pt–Ag were synthesized using ultrasonic irradiation with no consecutive thermal treatment to catalyze the oxygen reduction reaction. Metal nanoparticles are supported on carbon substrate. The synthesized materials were characterized by XRD, TEM, and cyclic and lineal voltammetry techniques. The kinetic formation of the metallic nanoparticles in solution was followed using UV–vis spectroscopy. The metal particles have crystalline structure and particle size with < 10 nm in size and in the form of spherical agglomerates. Ag/C exhibits lower electrochemical activity and stability for the ORR compared to Pt/C and Pt–Ag/C in acid medium. The mass and specific activity results demonstrate that the synthesized bimetallic sample exhibits 1.5 and 5 times greater electrochemical activities for the ORR compared to the commercial sample.  相似文献   

11.
The characteristics of infra red femtosecond laser-induced aerosols are studied for monazite (LREE, Th(PO4)) ablation and correlations are established with inductively coupled plasma-mass spectrometry (ICP-MS) signals. Critical parameters are tested within wide ranges of values in order to cover the usual laser ablation -ICP-MS analysis conditions: pulse energy (0.15 < E0 < 1 mJ/pulse), pulse width (60 < τ < 3000 fs), ablation time (t  10 min) and transport length (l  6.3 m). Transmission electron microscopy reveals that aerosols are made of agglomerates of ~ 10 nm particles and 20–300 nm phosphorus depleted condensed spherical particles. These structures are not affected by any laser ablation parameter. Particle counting is performed using electronic low pressure impaction. Small changes on particle size distribution are noticed. They may be induced either by a peak of ablation rate in the first 15 s at high fluence (larger particles) or the loss of small particles during transport. We found a positive correlation between I (ICP-MS mean signal intensity in cps) and N (particle density in cm? 3) when varying E0 and t, suggesting that N is controlled by the irradiance (P0 in W·cm? 2). Elemental ratio measurements show a steady state signal after the initial high ablation rate (mass load effect in the plasma torch) and before a late chemical fractionation, induced by poor extraction of bigger, early condensed spherical particles from the deepening crater. Such chemical fractionation effects remain within uncertainties, however. These effects can be limited by monitoring E0 to shorten the initial transient state and delay the attainment of an unfavorable crater aspect ratio. Most adopted settings are for the first time deduced from aerosol characteristics, for infra red femtosecond laser ablation. A short transport (l < 4.0 m) limits the agglomeration of particles by collision process along the tube. Short τ is preferred because of higher P0, yet no benefit is found on ICP-MS signal intensity under 200 fs. Under such pulse widths the increased particle production induces more agglomeration during transport, thereby resulting in higher mass load effects that reduce the ionization efficiency of the plasma torch. Thus, pulse energy must be set to get an optimal balance between the need for a high signal/background ratio and limitation of mass load effects in the plasma torch.  相似文献   

12.
Submicro/micro-scaled spherical Sn–Ni–C alloy powders synthesized from oxides of Sn and Ni via carbothermal reduction at 900 °C were examined for use as anode materials in Li-ion battery. The synthesized spherical Sn–Ni–C particles show a loose micro-sized structure and a multi-phase composition. The reaction product carbon oxide gases yielded in the carbothermal reduction process should be responsible to the loose structure characteristics of Sn–Ni–C particles. The prepared Sn–Ni–C alloy composite electrode exhibits a stable reversible capacity of 310 mA h g−1 at constant current density of 100 mA g−1, and can be retained at 290 mA h g−1 after 25 cycles. The space existing in loose particle can accommodate the large volume changes during charge/discharge cycling. The ductile component Ni plays as a buffer to relieve the mechanical stress induced by the large volume changes upon cycling. The remained carbon can prevent the aggregation between small alloy particles. All these factors contribute greatly to the excellent cycling stability of Sn–Ni–C alloy electrode. This carbothermal reduction method is simple, cheap and mass-productive, thus suitable to large scale production of alloy anode powders used for lithium ion batteries.  相似文献   

13.
The radiopacity of alumina/yttrium stabilizer zirconia (Al2O3/Y-TSZ) particles with nitrile butadiene rubber (NBR) dispersed in PMMA denture base material has been investigated. PMMA matrix without filler was prepared from PMMA powder with 0.5% benzoyl peroxide (PBO) as the control material. The similar PMMA matrix was mixed with Al2O3/Y-TSZ (1:1) together with NBR particles as the reinforcement. The amount of NBR was fixed at 7.5 wt %, however, Al2O3/Y-TSZ varied from 1 to 10 wt %, respectively. Samples with 4 mm thickness for each composition were irradiated using 60 KV, 10 mA, 0.4 s to examine their radiopacity. This radiopacity was compared to radiopacity of aluminum plate which having the same thickness. The result shows that the radiopacity (i.e. the lower optical density the higher radiopacity) of reinforced PMMA matrix slightly increased from 1.40 to 1.05, respectively, with the increased of filler loading compared to unreinforced PMMA matrix.  相似文献   

14.
Solid polymer electrolyte (PEO:KI:I2) membranes doped with low viscosity (34 cP at 25 °C) ionic liquid EMImTFSI (1-ethyl 3-methylimidazolium bis(trifluoromethylsulfonyl)imide) showing plasticizing effect as well as improved dye sensitized solar cell efficiency have been reported first time. Apart from ionic conductivity enhancement due to large number of free charge carriers provided by ionic liquid (IL) it assist in reducing cystallinity of polymer electrolyte matrix which was confirmed by polarized optical microscopy (POM). Cyclic voltammetry was carried out to study the reactions of iodide, iodine and IL in polymer electrolyte matrix.  相似文献   

15.
Blends of polypropylene and ethylene–octene copolymers (EOC) were investigated by transmission electron microscopy, optical microscopy and differential scanning calorimetry (DSC). The main focus was on phase morphology and crystallization for blends containing EOC with different octene content (28, 37 and 52 wt.%). Also, for a given octene content (37 wt.%), the effect of molecular weight (115, 180, 229k) of EOC on morphology was observed. The largest particles were found in the blend with EOC-28 and the smallest with EOC-52. This blend with the smallest particles exhibits the fastest crystallization kinetics by two independent methods, optical microscopy and DSC. This behavior was explained by a model. Crystallizing polypropylene lamellae have to travel a longer distance going around large particles, which slows down overall crystallization growth rate. In the case of smaller particles, the obstacles are smaller and the crystallization is faster.  相似文献   

16.
Poly(butyl acrylate) was prepared by the free radical polymerization of butyl acrylate as an initiator in the presence of 2,2′-Azoisobu-tyronitrile (AIBN) and the average molecular weight, polydispersity and thermal stability were evaluated. PLA and PBA were melt blended using a Haake Rheometer, and the light transmission, thermal properties, dynamic rheological properties, mechanical properties, phase morphology of blends and toughening mechanism were investigated. Dynamic rheology, SEM and DSC results show that the PLA is partial miscible with PBA. The PBA component improved the crystallization ability of PLA and the crystallinity of PLA increased with content of PBA (<15 wt.%). With the increase of PBA, the tensile strength and modulus of the blend decreased slightly while the elongation at break and toughness were dramatically increased. With the addition of PBA, the failure mode changes from brittle fracture of neat PLA to ductile fracture of the blend. Rheological results revealed the complex viscosity and melt elasticity of the blends decreased with increasing content of PBA and phase segregation occurred at loading above 11 wt.% PBA. UV–vis light transmittance showed that PLA/PBA blends with a high transparency, and the transmittance decreased with the amount of PBA.  相似文献   

17.
Large number of papers has been published recently on the eleventh group metallic elements such as Ag, Au and Cu. Our study was focused on biosynthesis of silver nanoparticles, their morphology, reactivity and stability. We were interested to check these properties in two different samples, S1 and S2, respectively. The biosynthesis of silver nanoparticles was achieved by reacting the samples with 1 mM concentration of silver nitrate, one involves bacteria (S1) and the other involves the plant extract (S2). Spectrophotometric analysis revealed that the particles exhibited two peaks, one at 440 nm (for S1) and the other at 390 nm (for S2). It is well known that longer wavelength corresponds to increase in particle size. Since, S1 has got a longer wavelength; it is not known, whether it forms isolated particles or agglomerates? Morphological characterization has been done by adopting the procedures of Negative staining and Wedge smear preparation methods. This hybrid method may be of interest to study agglomerated particles. Microscopic examination of the smear S1 shows predominantly triangular or hexagonal shaped agglomerated particles which were not observed in S2. Hence further characterization was done using SEM, EDAX and XRD. The S2 particles were in the range of 45–70 nm and were stable for even four months. This study indicated that particle size can be controlled from micrometer to nanometer size by varying biological reductants.  相似文献   

18.
The solution rheology of poly(acrylonitrile-co-itaconic acid) (poly(AN-co-IA)) in 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) spanning dilute, semidilute unentangled and entangled regimes were investigated. The exponents in the specific viscosity ηsp  overlap parameter c[η] power law were 1, 2 and 4.7 for dilute, semidilute unentangled and entangled regimes, respectively, which were found to be consistent with the scaling prediction for neutral linear polymers in θ-solvent. For dilute solutions (lower than 0.9 wt.%), the linear viscoelastic responses were observed to be in good agreement with the Zimm model (Flory exponent ν = 0.5). While for semidilute unentangled solutions (between 0.9 and 8 wt.%), results obtained had been found to be consistent with Rouse model. Considering Flory exponent ν = 0.5 and the concentration dependences of the specific viscosity and relaxation time, it had been evaluated that poly(AN-co-IA) in [BMIM]Cl behaves as a neutral polymer in θ-solvent. It had also been suggested that according to the unusual deviation of Cox-Merz rule, poly(AN-co-IA)/[BMIM]Cl solutions are typical neutral polymeric liquids for the concentrated solutions but have shown a more complicated behavior at high deformation rates.  相似文献   

19.
We studied interaction of hydrophilic polymer chain and hydrophilic silica nanoparticles in a dilute aqueous system using an idealized model system comprised of a well characterized polyvinyl alcohol of 100 Å Rg and hard spherical LUDOX® silica of 80 Å radii. Interaction among the polymer chains forming polymer clusters with collective polymer structure factor induced by the polymer-mediated potentials of mean force between the nanoparticles, was observed. However, Gaussian nature of individual polymer chain remains unaltered. The dilute system of polymer with low silica volume fraction has the scattering form which was appropriately modeled as the sum of the individual profiles of spherical silica particles and polymer cluster of interchain packing. With increasing silica volume fraction in the dilute solution, the spatial range parameter between the particles is reduced; hence there is a net increase in the mean potential force and consequently to stronger interaction between the silica and polymer. In the dilute systems of high silica with low polymer volume fraction, the polymer chain apparently attracted closer to the silica and concurrently absorbed to the silica hard surface and their scattering data were excellently fit with a model form factor as comprising of one unit forming the core of the spherical silica particles and the interacting polymer as the corona. This result of severe change in polymer interchain conformation in a dilute system corroborated with reduced polymer viscosity observed.  相似文献   

20.
Density and viscosity were determined for binary mixtures of {hyperbranched polymer, a fatty acid modified dendritic polymer Boltorn U3000 (B-U3000) + 1-alcohol (1-butanol, 1-hexanol, and 1-octanol)} at T = (298.15, 308.15, 318.15, 328.15, and 338.15) K and of {B-U3000 + tert-butyl-methylether (MTBE)} at T = (298.15, 308.15, and 318.15) K and ambient pressure. The temperature dependence of density and viscosity for these systems can be described by linear regression and by the Vogel–Fucher–Tammann equation, respectively. Excess volumes were discussed in a function of mass fractions. Viscosity deviations were calculated and correlated by the Redlich–Kister polynomial expansions using also the mass fractions. The polynomial correlations describe the variation of viscosity with composition. A qualitative discussion on these quantities in terms of molecular interactions is reported.  相似文献   

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