Zr-Laponite pillared clay-based nickel catalysts for methane reforming with carbon dioxide

Zr-Laponite pillared clays were prepared and used as supports of nickel catalysts for the methane reforming reaction with carbon dioxide to synthesis gas. The structural and textural characteristics of supports and catalysts were systematically examined by N-2 adsorption/desorption and X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron spectroscopy (TEM) techniques. The catalytic performance and carbon deposition were investigated. It is found that Zr-Laponite pillared clays are promising catalyst supports for carbon dioxide reforming of methane. The pore structure and surface properties of such supports greatly affect the catalytic behaviors of catalysts derived. Carbon deposition on catalysts was also affected by the property and structure of supports. The sintering of nickel metal and zirconia was another factor responsible for catalyst deactivation. This new-type nickel supported catalyst Ni/Zr-Laponite(8), with well-developed porosity, gave a higher initial conversion and a relatively long-term stability, and is therefore a promising catalyst for potential application to carbon dioxide reforming of methane to synthesis gas. (C) 2002 Elsevier Science B.V All rights reserved.

Immobilization of aluminum chloride on MCM-41 as a new catalyst system for liquid-phase isopropylation of naphthalene

A great deal of effort has been made at searching for alternative catalysts to replace conventional Lewis acid catalyst aluminum trichloride (AlCl3). In this paper, immobilization of AlCl3 on mesoporous MCM-41 silica with and without modification was carried out. The catalytic properties of the immobilized catalyst systems for liquid-phase isopropylation of naphthalene were studied and compared with those of H/MCM-41 and H/mordenite. The structures of the surface-immobilized aluminum chloride catalysts were studied and identified by using solid-state magic angle spinning nuclear magnetic resonance (MAS NMR), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), nitrogen adsorption, and X-ray diffraction (XRD) techniques. The catalytic activity of the immobilized catalysts was found to be similar to that of acidic mordenite zeolite. A significant enhancement in the selectivity of 2,6-diisopropylnaphthalene (2,6-DIPN) was observed over the immobilized aluminum chloride catalysts. Immobilization of aluminum chloride on mesoporous silica coupled with surface silylation is a promising way of developing alternative catalyst system for liquid-phase Friedel-Crafts alkylation reactions. (C) 2002 Elsevier Science B.V. All rights reserved.

Research on the BET surface area and packing of molecules on the activated carbon

Adsorption of different aromatic compounds (two of them are electrolytes) onto an untreated activated carbon (F100) is investigated. The experimental isotherms are fitted into Langmuir homogenous and heterogeneous Model. Theoretical maximum adsorption capacities that are based on the BET surface area of the adsorbent cannot be close to the real value. The affinity and the heterogeneity of the adsorption system observed to be related to the pK(a) of the solutes. The maximum adsorption capacity (Q(max)) of activated carbon for each solute dependent on the molecular area as well as the type of functional group attached on the aromatic compound and also pH of solution. The arrangement of the molecules on the carbon surface is not face down. Furthermore, it is illustrated that the packing arrangement is most likely edge to face (sorbate-sorbent) with various tilt angles. For characterization of the carbon, the N-2 and CO2 adsorption were used. X-ray Photoelectron Spectroscopy (XPS) measurement was used to surface elemental analysis of activated carbon.

Adsorption of p-nitrophenol in untreated and treated activated carbon

The adsorption of p-nitrophenol in one untreated activated carbon (F100) and three treated activated carbons (H-2, H2SO4 and Urea treated F100) was carried out at undissociated and dissociated conditions. To characterize the carbon, N-2 and CO2 adsorption were used. X-ray Photoelectron Spectroscopy (XPS) was used to analyze the surface of the activated carbon. The experimental isotherms are fitted via the Langmuir homogenous model and Langmuir binary model. Variation of the model parameters with the solution pH is studied. Both Q(max) and the adsorption affinity coefficient (K-1) were dependent on the PZC of the carbons and solution pH. The Effect of pH must be considered due to its combined effects on the carbon surface and on the solute molecules. Adsorption of p-nitrophenol at higher pH was found to be dependent on the concentration of the anionic form of the solute.

The physical and surface chemical characteristics of activated carbons and the adsorption of methylene blue from wastewater

Adsorption of a basic dye, methylene blue, from aqueous solutions onto as-received activated carbons and acid-treated carbons was investigated. The physical and surface chemical properties of the activated carbons were characterized using BET-N-2 adsorption, X-ray photoelectron spectroscopy (XPS), and mass titration. It was found that acid treatment had little effect on carbon textural characteristics but significantly changed the surface chemical properties, resulting in an adverse effect on dye adsorption. The physical properties of activated carbon, such as surface area and pore volume, have little effect on dye adsorption, while the pore size distribution and the surface chemical characteristics play important roles in dye adsorption. The pH value of the solution also influences the adsorption capacity significantly. For methylene blue, a higher pH of solution favors the adsorption capacity. The kinetic adsorption of methylene blue on all carbons follows a pseudo-second-order equation. (c) 2004 Elsevier Inc. All rights reserved.

Estimation of adsorption capacity for dissociating and non dissociating aromatic compounds on activated carbon with different models

The process of adsorption of two dissociating and two non-dissociating aromatic compounds from dilute aqueous solutions on an untreated commercially available activated carbon (B.D.H.) was investigated systematically. All adsorption experiments were carried out in pH controlled aqueous solutions. The experimental isotherms were fitted into four different models (Langmuir homogenous Models, Langmuir binary Model, Langmuir-Freundlich single model and Langmuir-Freundlich double model). Variation of the model parameters with the solution pH was studied and used to gain further insight into the adsorption process. The relationship between the model parameters and the solution pH and pK(a) was used to predict the adsorption capacity in molecular and ionic form of solutes in other solution. A relationship was sought to predict the effect of pH on the adsorption systems and for estimating the maximum adsorption capacity of carbon at any pH where the solute is ionized reasonably well. N-2 and CO2 adsorption were used to characterize the carbon. X-ray Photoelectron Spectroscopy (XPS) measurement was used for surface elemental analysis of the activated carbon.

Methacryloxyethyl phosphate-grafted expanded polytetrafluoroethylene membranes for biomedical applications

Expanded polytetrafluoroethylene (ePTFE) membranes were modified by graft copolymerization with methacryloxyethyl phosphate (MOEP) in methanol and 2-butanone (methyl ethyl ketone (MEK)) at ambient temperature using gamma irradiation. The effect of dose rate (0.46 and 4.6 kGyh(-1)), monomer concentration (1-40 %) and solvent were studied and the modified membranes were characterized by weight increase, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). XPS was used to determine the % degree of surface coverage using the C-F (ePTFE membrane) and the C-C (MOEP graft copolymer) peaks. Grafting yield, as well as surface coverage, were found to increase with increasing monomer concentration and were significantly higher for samples grafted in MEK than in methanol solution. SEM images showed distinctly different surface morphologies for the membranes grafted in methanol (smooth) and MEK (globular), hence indicating phase separation of the homopolymer in MEK. We propose that in our system, the non-solvent properties of MEK for the homopolymer play a more important role than solvent chain transfer reactions in determining grafting outcomes. (c) 2005 Society of Chemical Industry.

Electrochemical characteristics of ordered mesoporous carbon used as electrode material in Li-ion battery

Ordered mesoporous carbon CMK-5 was comprehensively tested for the first time as electrode materials in lithium ion battery. The surface morphology, pore structure and crystal structure were investigated by Scanning Electronic Microscopy (SEM), N-2 adsorption technique and X-ray diffraction (XRD) respectively. Electrochemical properties of CMK-5 were studied by galvanostatic cycling and cyclic voltammetry, and compared with conventional anode material graphite. Results showed that the reversible capacity of CMK-5 was 525 mAh/g at the third charge-discharge cycle and that CMK-5 was more compatible for quick charge-discharge cycling because of its special mesoporous structure. Of special interest was that the CMK-5 gave no peak on its positive sweep of the cyclic voltammetry, which was different from all the other known anode materials. Besides, X-ray photoelectron spectroscopy (XPS) and XRD were also applied to investigate the charge-discharge characteristics of CMK-5.

Synthesis of ordered nanoporous carbon and its application in Li-ion battery

Ordered nanoporous carbon (ONC) was comprehensively tested for the first time as electrode material in lithium-ion battery. Structure characterization shows the order nanoporous structure and tiny crystallite structure of as-synthesized ONC. The electrochemical properties of this carbon were studied by galvanostatic cycling and cyclic voltammetry. Of special interest is that ONC gave no peak on its positive sweep of the cyclic voltammetry, which was different from other known anode materials. Besides, X-ray photoelectron spectroscopy (XPS) and XRD were also used to investigate the electrochemical characteristics of ONC. (c) 2006 Elsevier Ltd. All rights reserved.

Introducing amine functionalities on a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) surface: Comparing the use of ammonia plasma treatment and ethylenediamine aminolysis

Amine functionalities were introduced onto the surface of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) films by applying radio frequency ammonia plasma treatment and wet ethylenediamine treatment. The modified surfaces were characterized by X-ray photoelectron spectroscopy (XPS) for chemical composition and Raman microspectroscopy for the spatial distribution of the chemical moieties. The relative amount of amine functionalities introduced onto the PHBV surface was determined by exposing the treated films to the vapor of trifluoromethylbenzaldehyde (TFBA) prior to XPS analysis. The highest amount of amino groups on the PHBV surface could be introduced by use of ammonia plasma at short treatment times of 5 and 10 s, but no effect of plasma power within the range of 2.5-20 W was observed. Ethylenediamine treatment yielded fewer surface amino groups, and in addition an increase in crystallinity as well as degradation of PHBV was evident from Fourier transform infrared spectroscopy. Raman maps showed that the coverage of amino groups on the PHBV surfaces was patchy with large areas having no amine functionalities.

The tribology of laminated magnetic recording heads

This thesis investigates the mechanisms that lead to pole tip recession (PTR) in laminated magnetic recording heads (also known as "sandwich heads"). These heads provide a platform for the utilisation of advanced soft magnetic thin films in practical recording heads suitable for high frequency helical scan tape recording systems. PTR results from a differential wear of the magnetic pole piece from the tape-bearing surface of the head. It results in a spacing loss of the playback or read signal of 54.6dB per recording wavelength separation of the poles from the tape. PTR depends on the material combination used in the head, on the tape type and the climate - temperature and relative humidity (r.h.). Five head materials were studied: two non-magnetic substrate materials- sintered multi granular CaTi03 and composite CaTi03/ZrTi04/Ti02 and three soft magnetic materials- amorphous CoNbZr, and nanocrystalline FeNbSiN and FeTaN. Single material dummy heads were constructed and their wear rates measured when cycling them in a Hi-8 camcorder against commercially available metal particulate (MP) and metal evaporated (ME) tapes in three different climates: 25°C/20%r.h., 25°C/80%r.h. and 40°C/80%r.h. X-ray photoelectron spectroscopy (XPS) was used to examine changes the head surface chemistry. Atomic force microscopy (AFM) was used to examine changes in head and tape surface topography. PTR versus cycling time of laminated heads of CaTi03/ZrTiO4/Ti02 and FeTaN construction was measured using AFM. The principal wear mechanism observed for all head materials was microabrasion caused by the mating body - the tape surface. The variation in wear rate with climate and tape type was due to a variation in severity in this mechanism, except for tape cycling at 40°C in which gross damage was observed to be occurring to the head surface. Two subsidiary wear mechanisms were found: third body scratching (all materials) and grain pullout (both ceramics and FeNbSiN). No chemical wear was observed, though tribochemical reactions were observed on the metal head surfaces. PTR was found to be caused by two mechanisms - the first differential microabrasion of the metal and substrate materials and which was characterised by a low (~10nm) equilibrium value. The second was by deep ploughing by third body debris particles, thought mainly to be grain pullout particles. This level of PTR caused by this mechanism was often more severe, and of a non-equilibrium nature. It was observed more for ME tape, especially at 40°C/80%r.h. and 25°c/20%r.h. Two other phenomena on the laminated head pole piece were observed and commented upon: staining and ripple texturing.

Modelling tribology of slider and disk in a computer hard drive system

Issues of wear and tribology are increasingly important in computer hard drives as slider flying heights are becoming lower and disk protective coatings thinner to minimise spacing loss and allow higher areal density. Friction, stiction and wear between the slider and disk in a hard drive were studied using Accelerated Friction Test (AFT) apparatus. Contact Start Stop (CSS) and constant speed drag tests were performed using commercial rigid disks and two different air bearing slider types. Friction and stiction were captured during testing by a set of strain gauges. System parameters were varied to investigate their effect on tribology at the head/disk interface. Chosen parameters were disk spinning velocity, slider fly height, temperature, humidity and intercycle pause. The effect of different disk texturing methods was also studied. Models were proposed to explain the influence of these parameters on tribology. Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM) were used to study head and disk topography at various test stages and to provide physical parameters to verify the models. X-ray Photoelectron Spectroscopy (XPS) was employed to identify surface composition and determine if any chemical changes had occurred as a result of testing. The parameters most likely to influence the interface were identified for both CSS and drag testing. Neural Network modelling was used to substantiate results. Topographical AFM scans of disk and slider were exported numerically to file and explored extensively. Techniques were developed which improved line and area analysis. A method for detecting surface contacts was also deduced, results supported and explained observed AFT behaviour. Finally surfaces were computer generated to simulate real disk scans, this allowed contact analysis of many types of surface to be performed. Conclusions were drawn about what disk characteristics most affected contacts and hence friction, stiction and wear.

Pole tip recession in linear tape systems

The tribology of linear tape storage system including Linear Tape Open (LTO) and Travan5 was investigated by combining X-ray Photoelectron Spectroscopy (XPS), Auger Electron Spectroscopy (AES), Optical Microscopy and Atomic Force Microscopy (AFM) technologies. The purpose of this study was to understand the tribology mechanism of linear tape systems then projected recording densities may be achieved in future systems. Water vapour pressure or Normalized Water Content (NWC) rather than the Relative Humidity (RH) values (as are used almost universally in this field) determined the extent of PTR and stain (if produced) in linear heads. Approximately linear dependencies were found for saturated PTR increasing with normalized water content increasing over the range studied using the same tape. Fe Stain (if produced) preferentially formed on the head surfaces at the lower water contents. The stain formation mechanism had been identified. Adhesive bond formation is a chemical process that is governed by temperature. Thus the higher the contact pressure, the higher the contact temperature in the interface of head and tape, was produced higher the probability of adhesive bond formation and the greater the amount of transferred material (stain). Water molecules at the interface saturate the surface bonds and makes adhesive junctions less likely. Tape polymeric binder formulation also has a significant role in stain formation, with the latest generation binders producing less transfer of material. This is almost certainly due to higher cohesive bonds within the body of the magnetic layer. TiC in the two-phase ceramic tape-bearing surface (AlTiC) was found to oxidise to form TiO2.The oxidation rate of TiC increased with water content increasing. The oxide was less dense than the underlying carbide; hence the interface between TiO2 oxide and TiC was stressed. Removals of the oxide phase results in the formation of three-body abrasive particles that were swept across the tape head, and gave rise to three-body abrasive wear, particularly in the pole regions. Hence, PTR and subsequent which signal loss and error growth. The lower contact pressure of the LTO system comparing with the Travan5 system ensures that fewer and smaller three-body abrasive particles were swept across the poles and insulator regions. Hence, lower contact pressure, as well as reducing stain in the same time significantly reduces PTR in the LTO system.

The boundary lubricated friction and wear of low alloy steel

Pin on disc wear machines were used to study the boundary lubricated friction and wear of AISI 52100 steel sliding partners. Boundary conditions were obtained by using speed and load combinations which resulted in friction coefficients in excess of 0.1. Lubrication was achieved using zero, 15 and 1000 ppm concentrations of an organic dimeric acid additive in a hydrocarbon base stock. Experiments were performed for sliding speeds of 0.2, 0.35 and 0.5 m/s for a range of loads up to 220 N. Wear rate, frictional force and pin temperature were continually monitored throughout tests and where possible complementary methods of measurement were used to improve accuracy. A number of analytical techniques were used to examine wear surfaces, debris and lubricants, namely: Scanning Electron Microscopy (SEM), Auger Electron Spectroscopy (AES), Powder X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), optical microscopy, Back scattered Electron Detection (BSED) and several metallographic techniques. Friction forces and wear rates were found to vary linearly with load for any given combination of speed and additive concentration. The additive itself was found to act as a surface oxidation inhibitor and as a lubricity enhancer, particularly in the case of the higher (1000 ppm) concentration. Wear was found to be due to a mild oxidational mechanism at low additive concentrations and a more severe metallic mechanism at higher concentrations with evidence of metallic delamination in the latter case. Scuffing loads were found to increase with increasing additive concentration and decrease with increasing speed as would be predicted by classical models of additive behaviour as an organo-metallic soap film. Heat flow considerations tended to suggest that surface temperature was not the overriding controlling factor in oxidational wear and a model is proposed which suggests oxygen concentration in the lubricant is the controlling factor in oxide growth and wear.

The mechanical and wear behaviour of B(SiC) fibre-reinforced composite materials

The mechanical properties and wear behaviour of B(SiC) fibre-reinforced metal matrix composites (MMCs) and aluminium alloy (2014) produced by metal infiltration technique were determined. Tensile tests were peliormed at different conditions on both the alloy matrix and its composite, and the tensile fracture surfaces were also examined by Scanning Electron Microscopy (SEM). Dry wear of the composite materials sliding on hardened steel was studied using a pin-on-disc type machine. The effect of fibre orientation on wear rate was studied to provide wear resistance engineering data on the MMCs. Tests were carried out with the wear surface sliding direction set normal, parallel and anti-parallel to the fibre axis. Experiments were perfonned for sliding speeds of 0.6, 1.0 and 1.6 m/s for a load range from 12 N to 60 N. A number of sensitive techniques were used to examine worn surface and debris, i.e: Scanning Electron Microscopy (SEM), Backscattered Electron Microscopy (BSEM) and X-ray Photoelectron Spectroscopy (XPS). Finally, the effect of fibre orientation on the wear rate of the Borsic-reinforced plastic matrix composites (PMCs) produced by hot pressing technique was also investigated under identical test conditions. It was found that the composite had a markedly increased tensile strength compared with the matrix. The wear results also showed that the composite exhibited extremely low wear rates compared to the matrix material and the wear rate increased with increasing sliding speed and normal load. The effect of fibre orientation was marked, the lowest wear rates were obtained by arranging the fibre perpendicular to the sliding surface, while the highest wear was obtained for the parallel orientation. The coefficient of friction was found to be lowest in the parallel orientation than the others. Wear of PMCs were influenced to the greatest extent by these test parameters although similar findings were obtained for both composites. Based on the results of analyses using SEM, BSED and XPS, possible wear mechanisms are suggested to explain the wear of these materials.