Adsorption of tetrachloroethylene (PCE) in gas phase on zeolites of faujasite type: Influence of water vapour and of Si/Al ratio

This study is focused on the adsorption of a chlorinated volatile organic compound, the tetrachloroethylene (PCE), on dealuminated faujasite type zeolites with framework Si/Al ratio between 5 and 100. PCE dynamic adsorption experiments with and without water vapour (relative humidity of, respectively, 50% and 0%) were carried out in a fixed bed reactor at 50 °C. Breakthrough curves were fitted by a model using the integral of a Gauss distribution. PCE adsorption capacities depend on the adsorbent microporous volume. However, in presence of water vapour, PCE adsorption is favoured on hydrophobic zeolites but also depends on the diffusional limitations inside the porous system. In order to have a better understanding of water molecules adsorption, isotherms were measured using thermogravimetric method at 25 °C. The presence of water vapour generally decreases PCE uptake but its influence decreases as the Si/Al ratio of the adsorbent increases. Experiments with various gases hourly space velocity (GHSV) and inlet PCE concentrations were also performed. PCE complete desorption was obtained on HFAU(Si/Al = 17) at 180 °C. This easy regeneration of the sample permitted adsorption/regeneration cycles maintaining good adsorption properties.     

Theoretical analysis of the decay of shear strength of adhesion in metal/epoxy/metal joints in an aqueous environment

A theory for the decay of shear adhesion strength has been applied to lead-alloy/ epoxy/lead-alloy joints in water at 65°C, 75°C and 85°C. Theoretical values for the retention of wet shear strength over time coincided with experimental data. From experiments on wet shear adhesion strength and water absorption, it has been clarified that the following two cases exist: (1) in adhesive system A, the diffusion coefficient of water is greater at the interface than in the adhesive; (2) in adhesive system B, the diffusion coefficient of water is lower at the interface than in the adhesive, and water at the interface does not immediately contribute to adhesion failure — ie, there is a time lag between contact with water and bond breakage.     

Influence of water vapour on high-temperature oxidation of Al2O3-MgO-doped hot-pressed silicon nitride

Silicon nitride is particularly sensitive to high-temperature oxidation. The intensity of oxidation is influenced by the chemical composition of the amorphous phases present at the grain boundaries and consequently by the sintering additives responsible for their formation. The presence of water vapour increases Si₃N₄ oxidation also in intermediate temperature conditions. In this study the influence of water vapour pressure at high temperature (1200°C) on the corrosion of hot-pressed silicon nitride (HPSN) doped with Al₂O₃-MgO was evaluated. The water vapour has a great influence on the devitrification of the amorphous oxide upper layer, due to the formation of crystalline oxides (primarily cristobalite and tridymite). This process increases the oxidation rate, consequently increasing the porosity of the exposed surface. The microstructural evolution of HPSN in the presence of water vapour at 1200°C was analysed by SEM and XRD.     

Gas and water vapour transport in a polyketone terpolymer

Gas and water vapour transport properties of a polyketone terpolymer (0.93/0.07/1 ethylene/propylene/carbon monoxide) have been investigated and related to the polymer structure. Permeability tests have been performed at several temperatures (from 25 to about 65°C) with five different gases (oxygen, nitrogen, methane, ethane and carbon dioxide), evaluating permeabilities, diffusivities and solubilities. Their dependence on temperature was interpreted on the basis of apparent activation energies of permeation and diffusion (E_P and E_D) and of heats of solution (ΔH_S). The investigated polymer was found to be rubbery at the test temperatures (glass transition temperature is about 17°C), but the detected permeabilities are comparable to those of the glassy polymers widely used for packaging applications. Data obtained in this investigation on samples exposed to moulding temperatures (240°C) for 3 min were compared to gas permeation data (presented in a previous paper) obtained for samples exposed at that temperature for 33 min in order to assess possible effects on gas transport properties. Water vapour transport was analysed by performing both sorption (35, 34, 55 and 65°C) and permeation (35°C) experiments at several activities. The analysis of sorption isotherms revealed the occurrence of water clustering, which was confirmed by a reduction of water diffusivity as a function of water concentration in the polymer.     

Pretreatment and physical activation of acetylene cokes

Pretreatment of acetylene cokes at 450 °C with a mixture of nitrogen, oxygen and water vapour creates a relatively large surface area and some initial microporosity, further developed by water activation at 800 °C. For the same degree of burn-off, but without pretreatment, large micropores (L > 2–3 nm) are obtained and the external surface area remains small.     

Water absorption by an epoxy resin and its effect on the mechanical properties and infra-red spectra

A filled epoxy resin used as a structural adhesive and based on the diglycidyl ether of bisphenol A cured with dicyandiamide has been subjected, in its bulk form, to ageing at 40, 55 and 70°C and ca. 100% relative humidity. Gravimetric, viscoelastometric and FTi.r. studies have been effected after various times of exposure. Water absorption in the polymer is essentially Fickian, although closer inspection reveals the finer behaviour to be sigmoidal. The activation energy for diffusion is of the order of 80 kJ mol⁻¹, but there appears to be no clear relationship between equilibrium absorption values and temperature. Viscoelastometry has shown that T_g diminishes from ca. 115°C before ageing to ca. 90°C at saturation, 1% of water uptake corresponding to ca. 8°C reduction in T_g. Reductions in Young's modulus were observed both in the glassy and rubbery states after ageing and the latter is associated with molecular chain scission. FTi.r. analysis has shown several modifications occurring due to water absorption, the main one being an increase in intensity of the band at 1740 cm⁻¹. It is concluded that water absorption leads both to plasticization effects and chemical modification of the epoxy resin.     

Inhibition of hydrogasification of brown coals by moisture: Influence of heating rate, temperature and pressure

Two types of Rheinische Braunkohle with different mineral matter contents, each with two different moisture contents plus a coke produced from the coal with the lower ash content, were gasified at total pressures between 0.2 and 5 MPa with pure or dry hydrogen, hydrogen/water vapour and argon/water vapour mixtures. In studies with controlled heating (4 K min⁻¹ up to 850 °C) it was found that: 1. methane formation rates and methane yields during gasification in dry hydrogen are drastically lowered with increased moisture of the coals but only at high pressures which reduce evaporation of water; 2. methane formation rates and methane yields during gasification with wet hydrogen (x_H2o = 0.02) are generally lowered with all materials; 3. increasing the water content does not further lower the yields or lead to water vapour gasification. Studies at constant temperature (after rapid heating, 100 K s⁻¹) confirmed these results. It was found that increasing the temperature to 950 °C does not eliminate the inhibiting effect of moisture (in hydrogen) if hydrogen pressure is low ≈ ≤ 1 MPa. It was also determined that raising the temperature above 850 °C with a simultaneous increase in pressure up to 5 MPa hydrogen effectively prevented the inhibition by moisture. It was concluded that extremely stable ether bridges are blocking the active sites at the carbon suface and are therefore responsible for the inhibitory effect of moisture in hydrogasification.     

Blistering as a Form of Degradation in Adhesive Joints

Water-filled blisters were observed to form during accelerated aging experiments with aluminum adherends and two structural epoxy adhesives. Both closed adhesive joints and open-face specimens were affected. The blisters grew with time, originated both in the adhesive and at the epoxy-aluminum interface, and were found only at 100% relative humidity at both 65°C and 85°C; blisters were never observed at 85% relative humidity or lower. The same water-soluble ionic species were found in the blister liquid, the two adhesives and water that had been in contact with adhesive samples for an extended period. It is proposed that the blisters grew under the influence of osmosis, originating in water clusters at microscopic voids. Contamination of the aluminum adherends by residual etching solution, although not a necessary precondition for blistering, could facilitate this process by lowering the partial pressure at which water condenses and by creating higher osmotic pressures.     

Diffusion of Moisture in Adhesively Bonded Joints

In this article, diffusion of moisture in adhesively bonded composite joints is discussed and analysed experimentally, analytically and numerically. The experimental studies concentrate on moisture diffusion in adhesive films and in unidirectional and multidirectional composite substrates exposed to two different conditioning environments, namely 45°C/85% RH and 90°C/97% RH for the absorption studies and 90°C/ambient for the desorption studies. The coefficients of diffusion are determined from the water uptake plots. The analytical solutions for diffusion in joints with impermeable adherends are based on the classical theory of diffusion and are used to derive equations in two-dimensions for different adhesive fillet shapes, namely radiused fillet, triangular fillet and rectangular fillet. In the finite element analysis, the diffusion of moisture from the composite substrates into lap-strap joints is also taken into account. Both unidirectional and multidirectional composites are considered, as well as two different fillet shapes, i.e., rectangular and triangular fillet. A comparison between the results obtained using FEA and those obtained using the analytical solution is made. Finally, fatigue test data for lap-strap joints aged and tested in different environments is presented and a tentative link between fatigue threshold and water concentration at the site of failure initiation is made, indicating a semi-empirical method of predicting the strength of joints subjected to moisture-induced degradation.     

Degradation of Interfacial Chemistry of Epoxy/Silane/Aluminium Interfaces as a Result of Aqueous Attack

The degradation of a thin layer of adhesive on a grit-blasted aluminium substrate, as a result of aqueous attack, was investigated and compared with the behavior of the adhesive on a grit-blasted aluminium substrate treated with γ-glycidoxypropyl trimethoxy silane (GPS). The degradation study was achieved by examining aluminium coupons treated with adhesive that had been immersed in water at 25°C and an elevated temperature (50°C) for various treatment times ranging between 10 min and 1 day. All samples were characterized using X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). XPS and ToF-SIMS data indicated that the adhesive layer on both types of substrate was readily displaced by water. This is shown to be a two-stage process with bond rupture being identified by ToF-SIMS analysis and the displacement of the organic phase occurring at a later stage, as indicated by the XPS analysis, which showed a reduction in surface carbon concentration. When the substrates were directly in contact with water, a hydration process occurred and hydrated oxide species were formed on the surfaces. The results indicated that the hydration process was a postfailure event.     

Catalytic combustion of methane on aluminate-supported copper oxide

Copper oxide has been deposited onto high surface area magnesium aluminate spinel prepared from alumina and magnesium nitrate. The catalytic properties of such a solid have been investigated in methane combustion. At the laboratory scale a very good activity is observed (light-off of 530°C) and no CO is detected. Aging at 1000°C under water vapour has no influence on activity. The previous catalyst has been washcoated on monolith and tested on a rig either with methane or synthetic natural gas at very high GHSV under conditions close to those of a gas turbine. In that case also, a good activity was observed.     

STUDIES ON FRYING KINETICS AND QUALITY OF FRENCH FRIES

Effects of temperature of oil (160, 170 and 180° C) and duration of pre-drying (0.00, 0.25, 0.50, 0.75 and 1.00 h) on the kinetics of moisture removal and oil uptake, and quality of French fries were studied. Frying times at each combination of temperature and pre-drying duration were standardized on the basis of sensory characteristics of the product in the preliminary trials. Results indicated that the rate of both moisture loss and oil uptake were higher in the beginning followed by a decrease in the later stages of frying. Mathematical models were developed to describe both the moisture removal and oil uptake by French fries. French fries prepared from potato fingers blanched in water for 4 min at 85° C and fried (without pre-drying) at 180° C were judged to be the most acceptable.     

Comparison of the Degradation Mechanisms of Zinc-Coated Steel, Cold-Rolled Steel, and Aluminium/Epoxy Bonded Joints

The durability properties of bonded lap shear joints made from an epoxy/dicyandiamide adhesive and zinc, zinc-coated steel, two different aluminium alloys or cold-rolled steel metal coupons have been investigated. The influence of the dicyandiamide content of the adhesive on the durability properties-has been assessed by salt spray testing or by storing the joints in water at 70°C or 90°C for periods of time up to five weeks. The degradation products formed during ageing of the epoxy adhesive in water have been investigated using high performance liquid chromatography (HPLC) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFT). The degradation mechanisms of aluminium/epoxy bonded joints have been thoroughly studied using X-ray photoelectron spectroscopy.

The performances of the bonded joints under a pure corrosive environment have been found to be little influenced by the quantity of dicyandiamide in the adhesive. When the bonded joints were aged in hot water, the stability of the interface toward an excess of dicyandiamide directly followed the sensitivity of the oxide layer at high pH values. Optimal durability properties without peel strength losses of the adhesive were aehieved both with zinc and aluminium-coated substrates by reducing the quantity of dicyandiamide in the epoxy adhesive by 20% (the initial dicyandiamide content in the commercial adhesive being ca. 9%, with respect to the epoxy resin).     

Surface acidic properties of alumina-supported niobia prepared by chemical vapour deposition and hydrolysis of niobium pentachloride

Niobia–aluminas were prepared by chemical vapour deposition at 150°C of niobium pentachloride on the surface of γ-aluminas calcined at different temperatures and with controlled degrees of hydration, followed by hydrolysis with water vapour at 150°C and a thermal treatment with steam at 440°C aimed at removing surface chloride contamination. The samples were characterised with respect to chemical composition, surface area, acidity by temperature-programmed desorption of ammonia, nature of acid sites by infrared spectroscopy of adsorbed pyridine and catalytic activity at 370°C in the dealkylation of cumene.

The results showed that, for each alumina calcination temperature, the catalysts with the lowest niobium content have a higher density of acid sites than the alumina support, but the acidity decreased, within each series with an increase in the niobium content. Comparatively to the TPD results, catalytic activity in cumene dealkylation was much more sensitive to the history and composition of the samples. The niobia-alumina samples were much less active than the alumina support, but this was most likely due to the severe hydrothermal treatment for chlorine removal, since their activity was close to that of an alumina submitted to the same treatment. A strong decrease in the acidic activity was observed with increase in the niobium content. A sample of pure niobium oxide had a much higher activity than the niobia-alumina samples. Brønsted acidic sites could only be observed by the IR spectra of adsorbed pyridine on the surface of the pure niobium oxide sample.     

PROTOTYPE HIGH TEMPERATURE/HIGH PRESSURE KILN FOR THE EVALUATION OF WOOD DRYING SCHEDULES

A new laboratory kiln was developed and built to perform over a very wide range of drying conditions. For example, the dry bulb temperature can vary from 30°C to 150°C and the dew point can be adjusted between 20°C and 130°C. Obviously, with such a high level of dew point, pressures over atmospheric pressure may be induced inside the chamber. For this reason, the kiln has been designed to withstand pressure of up to 3 bars. This kiln can also perform vacuum drying.

A programmable controller allows the temperature levels to be maintained within ± 0.2°C. Because the whole kiln can be heated only through the agitated water present at the bottom of the kiln, the load temperature can be increased up to 130°C in saturated conditions, without any change of moisture content.

The kiln has various sensors attached and is capable of withstanding severe conditions (high temperature, saturated vapour and elevated pressures). At present, air and water temperatures as well as temperature at different locations within the board can be collected during the drying process. A load cell and pressure gauges are also available. The first tests performed using this equipment are presented at the end of the paper.     

The Effect of Moisture on Polyurethane Adhesives

Polyurethane adhesives predominate for bonding shoe soles but the moisture resistance of the adhesive polymer has been questioned. A typical polymer was hydrolytically degraded at 120°C for up to 29 hours and at 20, 30 or 37°C for up to one year and changes in physical and bonding properties monitored. Considerable degradation was necessary before bonding was seriously impaired due to cohesive failure of the adhesive, although heat resistance declined more rapidly. Joints made with undegraded adhesive on exposure to moisture showed rapid loss of strength and cohesive failure at 60 or 70°C, but little loss of strength and failure at or near the interface at 30 or 40°C.     

F2, H2O, and O2 etching rates of diamond and the effects of F2, HF and H2O on the molecular O2 etching of (110) diamond

Oxidation kinetics of natural (110) diamond by oxygen and water were investigated using in situ Fizeau interferometry. Apparent activation energies of 53 and 26 kcal mol⁻¹ were obtained for the etching of (110) type Ia diamond by O₂ and H₂O respectively. The etch rate was found to follow second-order kinetics with respect to O₂ pressure in the pressure range 0.04–10 Torr. For water over the vapour pressure range 0.1–2 Torr, the reaction has a reaction order near unity. The diamond (110) surface was impervious to etching by molecular fluorine at all temperatures up to 1300 °C. Fluorine, hydrogen fluoride and water were found to inhibit the molecular oxygen etching of diamond. Below 900 °C, oxidation is inhibited by the addition of F₂ and HF presumably by blocking reactive sites on the diamond surface through formation of C---F bonds. Above 900 °C, the fluorine is thought to desorb from the diamond (110) surface, rendering the surface susceptible to further oxidation. Addition of water below 800 °C was found to retard etching by molecular oxygen. This is attributed to the formation of C---OH bonds, analogous to C---F.     

A Review of Certain Recent Work on the Durability of Aluminium Alloy Bonded with Epoxide and Phenolic Adhesives

Single lap joints of aluminium alloy, bonded with a number of structural adhesives, have been aged at 100% or 50% relative humidity (r.h.) at 50°C for up to 10000 hours. The adhesives used have included a simple epoxide and some modified phenolics and epoxides. Whilst joints are not significantly weakened on exposure at 50% r.h., significant weakening occurs at 100% rh. There is an initial fall in strength in the early stages of exposure, but after this period joints remain fairly stable, retaining approximately 40-60% of the strengths they had before exposure. Water diffusion coefficients in the adhesives have been obtained from experiments on the mass uptake of water by films of the adhesives. Water concentration profiles and overall levels of water in adhesive joints have been calculated from diffusion coefficients, and these show that the initial fall in strength is controlled by water diffusing through the adhesive layer. Joint strengths recover significantly when they are dried out. The behaviour of joints can be interpreted by there being ion-pairs at the interface. Water reduces the interionic force by raising the permittivity of the surroundings, and this is reversed when the water is removed.     

Polyetherimide Adhesive

High-temperature adhesives which can be adhered at adhesive temperatures lower than those of conventional polyimide adhesives were investigated. Polyetherimide (PEI), developed by General Electric Co., is one such promising low curing temperature adhesive because it melts at temperatures lower than those used for conventional polyimides. Lap shear adhesive strength was investigated in a 75 μm-thick PEI film using steel test pieces. 350 kgf/cm² was achieved after curing for 1 hour at 270°C and 150 kgf/cm² was achieved at the test temperature of 200°C. PEI adhesive dissolved by N, N-dimethylformamide exhibited a high adhesive strength of 240 kgf/cm² after curing for 2 hours at 200°C. In addition, it was found that PEI could be used at much lower adhesive pressures than those of conventional polyimide adhesives.     

Vapour pressure determinations of phthalic esters by analysis of a static aerosol with the aid of a flame ionization instrument

A new method for the determination of vapour pressures of high boiling substances has been developed. The substances, in this case phthalic esters, are dispersed at room temperature into a rotating chamber. With this method a small volume of the substance is distributed in a large number of aerosol particles with a corresponding large surface, which is vital for a rapid vapour pressure equilibrium. The concentration of the vapour phase is measured by an analyzing instrument with a flame ionization detector of a special design. Vapour pressure determinations are reported down to the region 10⁻⁵–10⁻⁶ mmHg and are carried out from 20°C to 70°C.