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1.
Hardness of materials increases with decreasing indentation depth from macro-to nano-scales, which is known as the indentation size effect (ISE). This effect has been associated with indenter shape, frictional forces, dislocation models and other features. We show an anomalously high ISE for a 1-μm subsurface layer in the hybrid nanocomposites based on densely cross-linked Cyanate Ester Resins (CER) containing functionalized 3-D POSS or 2-D MMT nanoparticles (NP). This effect disappears after mechanical stripping of the surface layer. Energy dispersive X-ray (EDX) spectral analysis shows that this anomaly was caused by increased content of NP (Si and Al elements), by 2.5 times, in the 1-μm subsurface layer. The hardness of the 1-μm subsurface layer in these brittle nanocomposites is due to its peculiar composition, and must be taken into account when considering mechanical strength and frictional properties.  相似文献   

2.
The characterization of mass-transfer processes in a chromatographic column during a separation process is essential, since the influence of the mass-transfer kinetics on the shape of the chromatographic band profiles and on the efficiency of the separation is crucial. Several sources of mass transfer in a chromatographic bed have been identified and studied: the axial dispersion in the stream of mobile phase, the external mass-transfer resistance, intraparticle diffusion, and the kinetics of adsorption–desorption. We measured and compared the characteristics and performance of a new brand of shell particles and those of a conventional brand of totally porous silica particles. The shell stationary phase was made of 2.7-μm superficially porous particles (a 1.7-μm solid core is covered with a 0.5-μm-thick shell of porous silica). The other material consisted of totally porous particles of conventional 3.5-μm commercial silica. We measured the first and second central moments of the peaks of human insulin over a wide range of mobile phase velocities (from 0.02 to 1.3 mL/min) at 20°C. The plate height equations were constructed and the axial dispersion, external mass transfer, as well as the intraparticle diffusion coefficients were calculated for the two stationary phases.  相似文献   

3.
The effect of polishing time on measured oxidation thickness and elastic modulus of isothermally aged PMR-15 neat resin was investigated. A specimen aged 956 h in ambient air at 288 °C (550 °F) was selected for this study. Thermo-oxidation of the specimen results in a surface oxidation layer with different stiffness and polishing characteristics than the interior of the specimen. The specimen was repolished at consecutive time periods from a quick polishing time to extensive polishing time. A white light interferometer was used as a surface profiler to measure height variations from the specimen edges into the interior of the material. Subsequently, optical microscopy and nanoindentation experiments were conducted to correlate observations of oxidation thickness and elastic modulus measurements with polishing time. The modulus profiles obtained from nanoindentation experiments indicate formation of an outer brittle layer followed by a sharp drop in the transition region to the unoxidized interior. The oxidized material is polished at a greater rate than the unoxidized material. The maximum variation in the surface profile from polishing was limited to 5 μm across the oxidation layer (∼150 μm), which results in a slope of ∼2° over the oxidized region. Optical measurements of thickness of oxidized layer and transition region are in good agreement with the height and modulus profiles obtained using the interferometer and nanoindenter, respectively. Results from three techniques show that the measured oxidation thickness and elastic modulus are relatively independent of the polishing time.  相似文献   

4.
Carbon monoxide molecules generated in the channels of mesoporous MCM-41 silica sieve from a precursor (diphenyl cyclopropenone) by photodissociation with a nanosecond laser pulse were monitored by time-resolved Fourier transform infrared (FTIR) spectroscopy using the step-scan and rapid-scan methods. A very broad absorption of CO is observed in the region 2200-2080 cm(-1) at room temperature that decays in a biphasic mode. Two-thirds of the band intensity decays on the hundreds of microsecond scale (lifetime 344 +/- 70 micros). The process represents the escape of the molecules through the mesopores into the surrounding gas phase, and a diffusion constant of 1.5 x 10(-9) m(2)/s is derived (assuming control by intra-MCM-41 particle diffusion). The broad profile of the absorption is attributed to contact of the random hopping CO with siloxane and silanol groups of the pore surface. Measurements using MCM-41 with the silanols partially capped by trimethyl silyl groups gave further insight into the nature of the IR band profile. These are the first observations on the diffusion behavior of carbon monoxide in a mesoporous material at room temperature. The residual carbon monoxide remains much longer in the pores and features distinct peaks at 2167 and 2105 cm(-1) characteristic for CO adsorbed on SiOH groups C end on and O end on, respectively. The bands decrease with time constants of 113 +/- 3 ms (2167 cm(-1)) and 155 +/- 15 ms (2105 cm(-1)) suggesting that CO in these sites is additionally trapped by surrounding diphenyl acetylene coproduct and/or precursor molecules.  相似文献   

5.
Superficially porous particles are characterized by a non-porous particle core surrounded by a thin porous layer. Superficially porous particles have been shown to have chromatographic advantages over traditional totally porous particles by reducing the resistance to mass transfer and the eddy diffusion contributions to the theoretical plate height, particularly for biomolecule separations. Currently, 1.7 μm superficially porous particles are commercially available, but a further decrease in the particle diameter and reduction in the porous layer thickness has the potential to further improve the efficiency of the column packing material. In this study, the synthesis of smaller diameter superficially porous particles was investigated. As the particle diameter was decreased, however, synthesis parameters previously reported were rendered unsuitable due to particle agglomeration, non-uniform coating, and porous layer disintegration. Parameters such as colloidal silica size, drying process, and sintering temperature were investigated to improve the structural characteristics of smaller diameter superficially porous particles. Reported is a synthetic route for production of 1.1 μm superficially porous particles having a 0.1 μm porous layer. Based on the revised method, the particles produced have a surface area, pore diameter, and particle size distribution RSD of 52 m2/g, 71 Å, and 2.2%, respectively.  相似文献   

6.
Trejos T  Almirall JR 《Talanta》2005,67(2):388-395
The authors have previously reported the use of laser ablation ICP-MS as a powerful analytical tool for elemental analysis of glass. LA is a simpler, faster and less intrusive sample introduction method than the conventional solution ICP-MS. Due to the minute amount of material removed in LA (∼300 ng, 50 μm crater size), the analyst should be aware of special sampling considerations such as characterization of the glass fragments originating from the “known” source, fragment size and selection of the area and surface of ablation.The purpose of this work was to evaluate the micro-homogeneity of the elemental composition of glass samples commonly found in crime scenes like containers, architectural windows and windshields. The set of glasses under study was comprised of 56 fragments originated from glass containers, 28 fragments from automobile windshields and 20 fragments from architectural windowpanes. All fragments were selected with a size smaller than 2 mm2 in order to simulate the typical glass fragments transferred from the crime scenarios. A Nd:YAG laser, 266 nm, flat top beam profile was used in single point mode sampling 50 μm spot size for 50 s at 10 Hz (500 shots). In this study, 29Si was used as an internal standard and the standard reference material, SRM NIST 612, was used as a single point external calibrator. In addition, SRM 621 was used as another control standard for the containers set and SRM 1831 for the automobile and architectural window sets due to their very similar matrix with the samples of interest. For each set of glasses, the mean values and standard deviation of 10 replicates (n = 10) of a single fragment were compared with the values obtained from 10 (n = 10) different fragments of glass within the area of interest in order to evaluate whether or not the variation within a glass was bigger than the variation due to the method. In addition, a subset of tempered glasses was evaluated to perform an elemental composition profile within different depths of the fragments. Single shot (one laser pulse per analysis) was also evaluated and its limitations for the forensic analysis of glass are also presented. The results show that float glass is homogenous even at the micro-range level allowing LA-ICP-MS as an alternative technique to perform elemental analysis of glass. However, the variation of elemental composition of headlamps and containers is larger over the source than the instrumental variation due to inherent heterogeneity and therefore specific statistical methods are recommended to compare the glass samples.  相似文献   

7.
One of the most often used non-destructive methods for elemental analysis when performing field measurements on bronze sculptures is X-ray fluorescence (XRF) analysis based on portable instrumentation. However, when performing routine in-situ XRF analysis on corroded objects obtained results are sometimes considerably influenced by the corrosion surface products.In this work the suitability of portable XRF for bulk analysis of low corroded bronzes, which were initially precisely characterized using sophisticated and reliable laboratory methods, was investigated and some improvements in measuring technique and data processing were given. Artificially corroded bronze samples were analyzed by a portable XRF instrument using the same methodology and procedures as when performing in-situ analysis on real objects. The samples were first investigated using sophisticated complementary laboratory techniques: Scanning Electron Microscopy, Proton-Induced X-ray Emission Spectroscopy and Rutherford Backscattering Spectrometry, in order to gain precise information on the formation of the corrosion product layers and in-depth elemental profile of corrosion layers for different aging parameters. It has been shown that for corrosion layers of up to ca. 25 μm a portable XRF can yield very accurate quantification results.  相似文献   

8.
The aim of this work was to answer the question of whether the general amber force field (GAFF) is good enough to simulate fully hydrated POPC membrane bilayers. The test system contained 128 POPC and 2985 TIP3P water molecules. The equilibration was carried out in a nonarbitrary manner to reach the stable liquid-crystalline phase. The simulations were performed by using particle mesh Ewald electrostatics implemented in molecular dynamics packages Amber8 (NPT ensembles) and NAMD2 (NPgammaT ensembles). The computational results were assessed against the following experimental membrane properties: (i) area per lipid, (ii) area compressibility modulus, (iii) order parameter, (iv) gauche conformations per acyl chain, (v) lateral diffusion coefficients, (vi) electron density profile, and (vii) bound water at the lipid/water interface. The analyses revealed that the tested force field combination approximates the experimental values at an unexpectedly good level when the NPgammaT ensemble is applied with a surface tension of 60 mN m(-1) per bilayer. It is concluded that the GAFF/TIP3P combination can be utilized for aqueous membrane bilayer simulations, as it provides acceptable accuracy for biomolecular modeling.  相似文献   

9.
Voltammetric procedures for trace metals analysis in polluted natural waters using homemade bare gold-disk microelectrodes of 25- and 125-μm diameters have been determined. In filtered seawater samples, square wave anodic stripping voltammetry (SWASV) with a frequency of 25 Hz is applied for analysis, whereas in unfiltered contaminated river samples, differential pulse anodic stripping voltammetry (DPASV) gave more reliable results. The peak potentials of the determined trace metals are shifted to more positive values compared to mercury drop or mercury-coated electrodes, with Zn always displaying 2 peaks, and Pb and Cd inversing their positions. For a deposition step of 120 s at ?1.1 V, without stirring, the 25-μm gold-disk microelectrode has a linear response for Cd, Cu, Mn, Pb and Zn from 0.2 μg L?1 (1 μg L?1 for Mn) to 20 μg L?1 (30 μg L?1 for Zn, Pb and 80 μg L?1 for Mn). Under the same analytical conditions, the 125-μm gold-disk microelectrode shows linear behaviour for Cd, Cu, Pb and Zn from 1 μg L?1 (5 μg L?1 for Cd) to 100 μg L?1 (200 μg L?1 for Pb). The sensitivity of the 25-μm electrode varied for different analytes from 0.23 (±0.5%, Mn) to 4.83 (±0.9%, Pb) nA L μmol?1, and sensitivity of the 125-μm electrode varied from 1.48 (±0.7%, Zn) to 58.53 (±1.1%, Pb  nA L μmol?1. These microelectrodes have been validated for natural sample analysis by use in an on-site system to monitor Cu, Pb and Zn labile concentrations in the Deûle River (France), polluted by industrial activities. First results obtained on sediment core issued from the same location have shown the ability of this type of microelectrode for in situ measurements of Pb and Mn concentrations in anoxic sediments.   相似文献   

10.
The fluid transport produced by rectangular shaped, magnetically actuated artificial cilia of 70 μm length and 20 μm width was determined by means of phase-locked Micro Particle Image Velocimetry (μPIV) measurements in a closed microfluidic chamber. The phase-averaged flow produced by the artificial cilia reached up to 130 μm s(-1) with an actuation cycle frequency of 10 Hz. Analysis of the measured flow data indicate that the present system is capable of achieving volume flow rates of V[combining dot above](cilia) = 14 ± 4 μl min(-1) in a micro channel of 0.5 × 5 mm(2) cross-sectional area when no back pressure is built up. This corresponds to an effective pressure gradient of 6 ± 1 Pa m(-1), which equals a pressure difference of 0.6 ± 0.1 mPa over a distance of 100 μm between two rows of cilia. These results were derived analytically from the measured velocity profile by treating the cilia as a thin boundary layer. While the cilia produce phase-averaged velocities of the order of O(10(2)μm s(-1)), time-resolved measurements showed that the flow field reverses two times during one actuation cycle inducing instantaneous velocities of up to approximately 2 mm s(-1). This shows that the flow field is dominated by fluid oscillations and flow rates are expected to increase if the beating motion of the cilia is further improved.  相似文献   

11.
Nanometer depth resolution is investigated using an innovative pulsed-radiofrequency glow discharge time-of-flight mass spectrometer (pulsed-rf-GD-TOFMS). A series of ultra-thin (in nanometers approximately) Al/Nb bilayers, deposited on Si wafers by dc-magnetron sputtering, is analyzed. An Al layer is first deposited on the Si substrate with controlled and different values of the layer thickness, t Al. Samples with t Al = 50, 20, 5, 2, and 1 nm have been prepared. Then, a Nb layer is deposited on top of the Al one, with a thickness t Nb = 50 nm that is kept constant along the whole series. Qualitative depth profiles of those layered sandwich-type samples are determined using our pulsed-rf-GD-TOFMS set-up, which demonstrated to be able to detect and measure ultra-thin layers (even of 1 nm). Moreover, Gaussian fitting of the internal Al layer depth profile is used here to obtain a calibration curve, allowing thickness estimation of such nanometer layers. In addition, the useful yield (estimation of the number of detected ions per sputtered atom) of the employed pulsed-rf-GD-TOFMS system is evaluated for Al at the selected operating conditions, which are optimized for the in-depth profile analysis with high depth resolution.  相似文献   

12.
Doucet FJ  Maguire L  Lead JR 《Talanta》2005,67(1):144-154
This research has evaluated the ability of cross-flow filtration (CFF) to perform correct size fractionation of natural aquatic colloids (materials from 1 nm to 1 μm in size) and particles (>1 μm) using scanning electron microscopy (SEM) combined with atomic force microscopy (AFM). SEM provided very clear images at high lateral resolution (ca. 2-5 nm), whereas AFM offered extremely low resolution limits (sub-nanometer) and was consequently most useful for studying very small material. Both SEM and AFM were consistent in demonstrating the presence of colloids smaller than 50 nm in all fractions including the retentates (i.e. the fractions retained by the CFF membrane), showing that CFF fractionation is not fully quantitative and not based on size alone. This finding suggests that previous studies that investigated trace element partitioning between dissolved, colloidal and particulate fractions using CFF may need to be re-visited as the importance of particles and large colloids may have been over-estimated. The observation that ultra-fine colloidal material strongly interacted with and completely coated a mica substrate to form a thin film has important potential implications for our understanding of the behaviour of trace elements in aquatic systems. The results suggest that clean, ‘pure’ surfaces are unlikely to exist in the natural environment. As surface binding of trace elements is of great importance, the nature of this sorbed layer may dominate trace element partitioning, rather than the nature of the bulk particle.  相似文献   

13.
Lab-on-a-chip systems made of polymers are promising for the integration of active optical elements, enabling e.g. on-chip excitation of fluorescent markers or spectroscopy. In this work we present diffusion operation of tunable optofluidic dye lasers in a polymer foil. We demonstrate that these first order distributed feedback lasers can be operated for more than 90 min at a pulse repetition rate of 2 Hz without fluidic pumping. Ultra-high output pulse energies of more than 10 μJ and laser thresholds of 2 μJ are achieved for resonator lengths of 3 mm. By introducing comparatively large on-chip dye solution reservoirs, the required exchange of dye molecules is accomplished solely by diffusion. Polymer chips the size of a microscope cover slip (18 × 18 mm(2)) were fabricated in batches on a wafer using a commercially available polymer (TOPAS(?) Cyclic Olefin Copolymer). Thermal imprinting of micro- and nanoscale structures into 100 μm foils simultaneously defines photonic resonators, liquid-core waveguides, and fluidic reservoirs. Subsequently, the fluidic structures are sealed with another 220 μm foil by thermal bonding. Tunability of laser output wavelengths over a spectral range of 24 nm on a single chip is accomplished by varying the laser grating period in steps of 2 nm. Low-cost manufacturing suitable for mass production, wide laser tunability, ultra-high output pulse energies, and long operation times without external fluidic pumping make these on-chip lasers suitable for a wide range of lab-on-a-chip applications, e.g. on-chip spectroscopy, biosensing, excitation of fluorescent markers, or surface enhanced Raman spectroscopy (SERS).  相似文献   

14.
The development of highly ordered and self-assembled magnetic nanostructures such as arrays of Fe or Ni nanowires and their alloys is arousing increasing interest due to the peculiar magnetic properties of such materials at the nanoscale. These nanostructures can be fabricated using nanoporous anodic alumina membranes or self-assembled nanotubular titanium dioxide as templates. The chemical characterization of the nanostructured layers is of great importance to assist the optimization of the filling procedure or to determine their manufacturing quality. Radiofrequency glow discharge (RF-GD) coupled to optical emission spectrometry (OES) is a powerful tool for the direct analysis of either conducting or insulating materials and to carry out depth profile analysis of thin layers by multi-matrix calibration procedures. Thus, the capability of RF-GD-OES is investigated here for the in-depth quantitative analysis of self-aligned titania nanotubes and self-ordered nanoporous alumina filled with arrays of metallic and magnetic nanowires obtained using the template-assisted filling method. The samples analysed in this work consisted of arrays of Ni nanowires with different lengths (from 1.2 up to 5 μm) and multilayer nanowires of alternating layers with different thicknesses (of 1–2 μm) of Ni and Au, or Au and FeNi alloy, deposited inside the alumina and titania membranes. Results, compared with other techniques such as scanning electron microscopy and energy-dispersive X-ray spectroscopy, show that the RF-GD-OES surface analysis technique proves to be adequate and promising for this challenging application.  相似文献   

15.
A template-free seeded short-time in situ hydrothermal treatment was carried out in a brass autoclave to synthesize crystalline mordenite (MOR) membranes on alumina-silicate disk supports with micro-scale pores. According to XRD analysis, MOR was the only zeolitic material present in the membrane layers on the supports. SEM examination of the membranes showed three different layers of the membrane thickness: (i) support sub-layer, (ii) mix penetrated mid-layer, the MOR crystals filling the pores among the support (about 4–5 μm), and (iii) MOR top-layer (about 4–5 μm). The crystalline bonds between MOR crystals of the membrane top-layer and the crystals of the support were clearly observed within the mid-layer. The continuous top-layer of zeolitic membrane was formed by many large and well-shaped crystals. The seeding treatment significantly enhanced the formation of MOR crystals onto the surface of the supports. EDAX analysis showed a Si/Al ratio of 6.8 for the MOR layer of the membrane. Due to their hydrophilic natures, the polycrystalline MOR membranes were found to be selective for continuous dehydration of different EtOH–water mixtures through an adsorption–diffusion–desorption mechanism. Both total permeation flux and separation factor of the membrane were found to increase by increasing temperature and water concentration of feed. The continuity and high crystallinity of the membrane top-layer led to the fairly high dehydration of EtOH. It was found that there was no pinhole within the layer and the morphology of the membrane was almost defect-free.  相似文献   

16.
Copper contamination occurs frequently in silicon for photovoltaic applications due to its very fast diffusion coupled with a low solid solubility, especially at room temperature. The combination of these properties exerts a challenge on the direct analysis of Cu bulk concentration in Si by sputtering techniques like glow discharge mass spectrometry (GDMS). This work aims at addressing the challenges in quantitative analysis of fast diffusing elements in Si matrix by GDMS. N-type, monocrystalline (Czochralski) silicon samples were intentionally contaminated with Cu after solidification and consequently annealed at 900 °C to ensure a homogeneous distribution of Cu in the bulk. The samples were quenched after annealing to control the extent of the diffusion to the surface prior to the GDMS analyses, which were carried out at different time intervals from within few minutes after cooling onward. The Cu profiles were measured by high-resolution GDMS operating in a continuous direct current mode, where the integration step length was set to ~0.5 μm over a total sputtered depth of 8–30 μm. The temperature of the samples during the GDMS analyses was also measured in order to evaluate the diffusion. The Cu contamination of n-type Si samples was observed to be highly material dependent. The practical impact of Cu out-diffusion on the calculation of the relative sensitivity factor (RSF) of Cu in Si is discussed.  相似文献   

17.
Our recent investigations have indicated the potential of laser-induced breakdown spectroscopy (LIBS) for analysis of the co-deposited layers on the first wall in the Experimental Advanced Superconducting Tokamak (EAST) in the vacuum environment. Detailed information of compositions at the superficial and in-depth positions of the first wall of divertor tiles can be obtained by analyzing the spectra from 200 to 980 nm. The decrease in concentrations of the depositional elements (such as D, Li) was clearly observed in the depth from 0 to 100 μm, but the concentrations of the substrate elements were found to be relatively uniform in the depth after dozens of laser pulses. The linear correlation approach has been applied for improving the impurity depth profile accuracy and identifying the interface boundary between the deposition layer and the substrate for the first time. This would help us to develop LIBS technique to monitor the fuel retention and impurity deposition on the first wall of EAST.  相似文献   

18.
The exciton diffusion length in a nematically organized meso-tetra(4-n-butylphenyl)porphyrin (TnBuPP) layer was found to exceed 40 nm at a temperature of 90 K and to be equal to 22 +/- 3 nm at 300 K. The exciton diffusion coefficient decreases from > or = 3.1 x 10(-6) m(2)/s at 90 K to (2.5 +/- 0.5) x 10(-7) m(2)/s at 300 K. This thermal deactivation is attributed to exciton motion via a band mechanism. The motion of an exciton is not limited by polaronic effects; that is, the deformation of the atomic lattice around the exciton. The absence of polaronic self-trapping implies that the exciton diffusion coefficient can be enhanced by improvement of structural order and rigidity of the material.  相似文献   

19.
Refractory metals are primarily characterized by a high melting point combined with a rather poor corrosion resistance under oxidizing atmosphere and therefore are mainly used in high temperature processes under reducing atmosphere or in vacuum. Exposure to an atmosphere of high humidity can lead to oxidation of the material even at room temperature. Different methods of surface pre-treatment have been applied to investigate their influence on the oxidation behavior of high-purity molybdenum. Within the scope of this work molybdenum foils and molybdenum discs consisting of the same base material were investigated. Since lateral surface structure as well as the in-depth distribution of contaminants are expected to play an important role in the oxidation process, both the in-depth distribution of the constituents within the oxide layer and the lateral distribution at the surface level of the oxide have been analyzed. Scanning SIMS has been engaged to analyze the uppermost structures of the oxide layer. In order to achieve maximum detection power and to gain the in-depth information, stigmatic SIMS has been applied to investigate the in-depth distribution of the interesting specimen constituents.  相似文献   

20.
Advantages of application of UPLC in pharmaceutical analysis   总被引:1,自引:0,他引:1  
Ultra Performance Liquid Chromatography (UPLC) is a relatively new technique giving new possibilities in liquid chromatography, especially concerning decrease of time and solvent consumption. UPLC chromatographic system is designed in a special way to withstand high system back-pressures. Special analytical columns UPLC Acquity UPLC BEH C18 packed with 1.7 μm particles are used in connection with this system.The quality control analyses of four pharmaceutical formulations were transferred from HPLC to UPLC system. The results are compared for Triamcinolon cream containing trimacinolone acetonide, methylparaben, propylparaben and triamcinolone as degradation product, for Hydrocortison cream (hydrocortisone acetate, methylparaben, propylparaben and hydrocortisone degradation product), for Indomethacin gel (indomethacin and its degradation products 4-chlorobenzoic acid and 5-methoxy-2-methylindoleacetic acid) and for Estrogel gel (estradiol, methylparaben, propylparaben and estrone as degradation product).The UPLC system allows shortening analysis time up to nine times comparing to the conventional system using 5 μm particle packed analytical columns. In comparison with 3 μm particle packed analytical columns analysis should be shortened about three times. The negative effect of particle decrease is back-pressure increase about nine times (versus 5 μm) or three times (versus 3 μm), respectively. The separation on UPLC is performed under very high pressures (up to 100 MPa is possible in UPLC system), but it has no negative influence on analytical column or other components of chromatographic system. Separation efficiency remains maintained or is even improved. Differences and SST parameters, advantages and disadvantages of UPLC are discussed.  相似文献   

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