ABSORPTION AND DESORPTION TO AND FROM LIQUID FILMS ON INCLINED PLANES

Two published theoretical models are examined and applied to experimental results for absorption and desorption. The system used was CO₂/H₂O and studies were made for liquid film flow down inclined planes. Experimental results give “Reduced” values of mass ransfer rates.

Interferometric studies give interfacial concentration, penetration and film depths, and take-up of carbon dioxide. In the case of desorption the interferograms are distorted by “deflections.”

All the experimental values for absorption and desorption differ from those calculated from theoretical models.

Desorption is not a mirror image of absorption, and it is approximately 75% of the transfer rate of absorption over a wide operating range.

A comparison is made of the behaviour of static pools and flowing liquid films.     

ESTIMATION OF FUNCTIONS IN DRYING EQUATIONS

In drying problem, particularly for drying foodstuff, modelling is very difficult. Many physical effects have to be taken into account for mass transfer ; then mass transfer coefficient varies

In different models unknown functions must be estimated. It is particularly the case in simple models of drying using average values of water content, where the mass transfer varies versus mean water content in falling rate period. On the other hand in the “diffusion model” we have the same problem concerning the diffusion coefficient which must be also estimated

The method we propose in this paper for these two models : simple and “diffusion model” of drying consists from measurements of temperature and water content of the product to search a numerical approach of the unknown function. This method uses optimization techniques on computer and least squares criterion between model values and experimental data

Results are given for the “diffusion model” applied to shelled corn drying to find the diffusion coefficient and for a simple 11107 del applied to plum drying to find the mass transfer coefficient.     

PHYSICAL ABSORPTION OF CARBON DIOXIDE IN WATER FLOWING IN AN INCLINED CELL

Studies of the mass transfer mechanisms which occur when CO₂ is absorbed into flowing water films in an inclined cell are described. The amount of gas absorbed is small and therefore a highly sensitive optical apparatus was used to obtain direct concentration readings. Gas bulk concentrations in the liquid were obtained by titration. The experimental work was mainly confined to angles of inclination less than 5^°.

Hydrodynamic studies showing increased flow rates at the sides of the inclined cell, due to meniscus effects, are presented. Hydrodynamic “end effects” at the liquid exit from the cell, which cause increases in the absorption, have been successfully minimised by the design of the apparatus and the experimental technique employed.

It is demonstrated, for angles of inclination less than 3^°, that convective disturbances (in the form of micioflows, eddies or perturbations) are present in the liquid. These perturbations are not visible or directly determinable. They produce an increased solute transport from the liquid surface over that which can occur by molecular diffusion alone. Beyond 3^° inclination the disturbances or perturbations persist and are reinforced by hydrodynamic instabilities eventually leading to observable wave formation.     

ISOTHERMAL AND NON-ISOTHERMAL MULTICOMPONENT ADSORPTION KINETICS

The model equations in the relaxation form for the multicomponent kinetics of isothermal and non-isothermal adsorption, taking into account all major distinctive features of the interphase heat and mass exchange inside porous grains and at their surface (see points 1 to 4 below) for P (“pore”) and S (“solid”) models of mass transfer within porous grains of the adsorbent, have been obtained.

First for isothermal and non-isothermal kinetics in the mixed kinetics region of mass and heat exchange in the absence natural mutual diffusion and natural thermal-diffusion the essential influence effective mutual diffusion and effective thermal-diffusion is shown.

Recommendations on the use of model equations of adsorption kinetics for describing isothermal and non-isothermal adsorption dynamics of multicomponent mixtures in the inner-diffusion and mixed (outer- and inner-diffusion) kinetic region of heat and mass exchange are made.     

ADDITION OF PORE DIFFUSION LIMITATION TO THE “UCKRON-I” KINETIC RATE OF METHANOL SYNTHESIS

Kinetic data with pore diffusion limitation on methanol synthesis were generated by extending the “UCKRON-I” kinetic rate expression. The best fit model and the extended “true” model were compared using their respective rates to simulate temperature profiles in a non-isothermal plug flow tubular reactor.

The objective of this work was to add pore diffusion resistance to the UCKRON-1 kinetic rate for methanol synthesis (Berty, et al. 1983). Kinetic modeling of the data with 5% experimental error added, showed the best model to be that developed from a previous kinetic model (Shalabi, et al. 1983) with apparent activation energy approximately one-half the activation energy at no pore diffusion.

Methods used in this work to determine and evaluate pore diffusion parameters can be utilized for other reaction systems where pore diffusion may play a role in reaction rate.

Temperature profiles estimated from reactor simulation studies showed good argeement between ideal and predicted models for temperature.     

Book Reviews

“lssledovaniya v oblasti poverkhnostnykh sil” (“Research on surface forces”) B. V. Deryagin, editor. Nauka Publ., Moscow 1967.544 pp. Rubles 3.00.

G. D. Andreevskaya, “Vysokoprochnye Orientirovannye Steklo-plastiki” (“High-strength Oriented Glass-Plastics”). Nauka Publ., Moscow 1966. 370 pp., Rubles 2.12.

A. D. Zimon, “Adgeziya pyli i poroshkov” (“Adhesion of dust and powders”) Khimiya Publ., Moscow 1967.372 pp. Rubles. 1.51.

J. J. Bikerman, “The Science of Adhesive Joints”. Academic Press, New York 1968.349 pages. $16.00.     

DEVELOPMENT OF RADIAL MODELS FOR FORMATION DAMAGE IN POROUS MEDIA

The continuously changing velocities in radial geometry have a significant effect on process characteristics, making it an intellectually challenging problem. In practical operations, fluid is generally pumped down injection wells from where it flows radially outward. Simulating this radial system with linear models is definitely restrictive. Consequently, the need for developing radial models for flow and particle entrapment in porous media is both fundamental and applied.

A radial network model, covering a 120° angle, has been developed to simulate formation damage due to deep bed filtration (DBF) of injected suspensions. The models draws upon our previously developed concepts of “wave-front movement” and “flow-biased probability” for linear systems. Systematic studies have been performed on formation damage using monodispersed and polydispersed suspensions. Case studies have been presented for constant flow rate and constant pressure injections, and comparisons are made between linear and radial systems.

Results show that the results obtained from linear models are conservative in comparison to those obtained from radial models. Furthermore, the use of monodispersed particles in mathematical models would show smaller differences between linear and radial predictions than would actually occur for polydispersed particles.     

TRANSPORT PROCESSES AND INTERFACIAL PHENOMENA IN AN EVAPORATING MENISCUS

The chemical potential of an extended meniscus on an inclined flat plate is a function of its temperature, curvature, film thickness and height above a reference level. The meniscus thickness profile, which is related to the stress field in the liquid, was used to measure the sensitivity of the meniscus to the non-equilibrium effects associated with evaporation/condensation. The thickness profiles of a completely wetting film of a 1,1,2-Trichlorotrifluoroethane were measured using microcomputer based image processing of interferometric images. The automated data acquisition procedures were used to achieve enhanced resolution and thereby a better understanding of the transport processes occurring in the contact line region.

The interfacial properties of the system were initially evaluated in situ and then used to describe the transport processes associated with a heated meniscus. Consistent with theoretical models, the curvature increased very rapidly from a value of zero in the adsorbed film at the leading edge of the intrinsic meniscus to a high value and then decreased rapidly until a thickness of about 1 μm. Flow results from a disjoining pressure gradient in the thinner region below the maximum curvature and from a curvature gradient in the thicker portion. At a higher power input, the meniscus was found to oscillate and the differences between the “advanced” and “receded” meniscus states were measured and analyzed. The curvature profiles in these two states are significantly different. The study showed that change of phase heat transfer and fluid flow in thin films are strongly coupled because of their common dependence on the intermolecular force field and gravity.     

ON CHARACTERIZATION AND MITIGATION O F COMBUSTION HAZARDS INVOLVED IN THE HANDLING OF PARTICULATE MATERIALS: A REVIEW OF THREE BOOKS

The three publications reviewed herein deal with the complex of hazards which may derive from the agricultural and commercial handling of combustible particulate and gaseous materials. The principal thrusts of each book differ substantially from those of the other two. This review first attempts to consider the essential combustion processes which underlie the hazards of common concern in all three works. Each of the three books is then considered on an individual basis. The three publications are designated Books (1)- (3) respectively and are listed below:

(1) “User Guide to Fire and Explosion Hazards in the Drying of Particulate Materials.” 1977. Institution of Chemical Engineers. Warwick Printing Company Limited, England.

(2) “Prevention of Grain Elevator and Mill Explosions.” 1982. NAS-NRC Publication NUB 367-2. National Academy Press, Washington, D. C.

(3) “Guidelines for the Investigation of Grain Dust Explosions.” 1983. NAS-NRC Publication NMAB 367-4, National Academy Press, Washington, D. C.     

New and Improved Tests for Adhesion

Three new methods are discussed for measuring the work G_a, required to detach unit area of an adhering material from a substrate. The first is a simple modification of the Outwater double-torsion test for long rectangular plates, bonded together. This method is suitable for evaluating aluminum-epoxy bonds, for example, or the transverse strength of fibrous composites. The second is a pull-off test for long strips adhering to a rigid surface. It seems suitable for adhesive tapes and laminates. The third is a reconsideration of the “blister” test for films and coatings, in which a circular debond at the interface is made to grow by internal pressure. The relation obtained between pull-off force F for a strip, or blow-off pressure P for a layer, takes the unusual form:

F⁴ (or P⁴) ∞ KG³_a

where K is the tensile stiffness of the detaching layer. This dependence arises from the non-linear (cubic) relation between load or pressure and deflection in these configurations. Nevertheless, the product Fθ, where θ is the angle of detachment of a strip, or Py, where y is the height of a “blister”, give direct measures of the strength of adhesion G_a, independent of the stiffness of the adhering material and of the extent of detachment.     

Aging Process of Metal/Epoxy Laminates Investigated with X-ray Photoelectron Microscopy and Spectroscopy

In this article we describe the application of X-ray photoelectron spectroscopy to epoxy/dicyandiamide laminates on zinc galvanized steel which were aged under different environmental conditions involving high humidity and temperatures.

X-ray photoelectron microscopy allows us to identify the distribution of chemical elements with a lateral resolution of 10μm. Areas selected in the microscopy mode were then analyzed in the spectroscopy mode in order to get information on the local chemical composition.

We compared the spectroscopic features of the aged but freshly delaminated surfaces of samples stored under ambient conditions at room temperature with samples exposed to the “Kataplasmann” and the “KWT” test, respectively. Furthermore, a comparison was made with a model sample which was prepared in vacuum and on which the curing process was investigated.

Though there is no substantial loss in the lap-shear strength of the samples, we find drastic spectroscopic changes in the Kataplasma and KWT treated samples compared with the sample kept at room temperature. We conclude that the chemical changes induced by these tests cause an internal interphase boundary between the epoxy/metal interface and the bulk adhesive along which delamination occurs. Comparison with the behavior of the water-vapor-treated model sample gives evidence that hydrolysis is the main reaction in these tests.

The results described here complement our former study.¹     

A STATISTICAL ANALYSIS OF A PACKED TOWER DEHUMIDIFIER

A dehumidifier is the heart of a liquid desiccant cooling system. In these systems, air is dehumidified using liquid desiccants and cooled with heat exchangers and/or evaporative coolers [I]. A Statistical Analysis Software (SAS) regression analysis was performed on experimental data from a packed tower desiccant dehumidifier tested at Texas Tech. The purpose of this analysis was to determine simple functional relationships for the liquid desiccant dehumidifier for use in computer models of liquid desiccant space cooling systems.

Six factors and four dependent variables were defined and four regression models were determined. These regression models were reduced to three factor models. The packed tower regression analysis showed Texas Tech's “Cost Effective Liquid Desiccant” (CELD) to be a well behaved stable desiccant solution.     

RIBBING INSTABILITY OF A TWO-ROLL COATER: NEWTONIAN FLUIDS

Data are presented for the critical conditions at which the ribbing instability appears on the surface of a Newtonian liquid film emerging from the nip between two rotating rolls. Data are obtained over two decades in Capillary number (Ca = μU/σ) for values of H₀/R in the range 3 × 10^-3 to 5 × 10^-2. The critical Capillary number is found to be given by the expression

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Data are compared to the predictions that follow from a theory due to Savage, and agreement is found to be poor.     

Adhesion of Plasticized Polyvinyl Butyral) to Glass

A study of safety glass provides a good example of the interplay among the many physical properties involved in “adhesion”, and the relationship between adhesion and performance. This work demonstrates the value of applying known fundamentals to practical problems.

An idealized model of a windshield fracture event is described in terms of interactions among mechanical responses of the interlayer, the fracture characteristics of the glass and the high speed, low angle peel behavior.

Data on the surface energies of glass, polyvinyl butyral) and water show that at thermodynamic equilibrium a stable system comprising glass, water and polyvinyl butyral) phases, an aqueous phase must lie between the glass and PVB.

The potassium salts are shown to be effective because they are deliquescent and give solutions at equilibrium with the water in the PVB at water contents of ∼0.40% or higher. The greater the amount of salt at the interface and the higher the water content of the sheeting during lamination, the thicker the interfacial layer and delamination occurs more readily. This relationship is quantified using a modified form of the Stefan equation.

Data on diffusion of water and salt are shown to be consistent with the amount of salt at the interface required for the observed performance (∼ 3 mg KAc/m²).

Data on electrical resistivity of the interface correlate with peel force and provide convincing support for the hypothesis.     

A GRAPHICAL DESIGN METHOD FOR A PARTIAL SOLAR DRYER FOR CORN

This paper presents the application of a design method for a partial solar heating system of polyvalent modular dryers called “GJ-ABAQUE” to the drying of thick layers of grains.

This method is based on the use of charts or polynomial correlations. In the actual case where the drying air is not recycled, we only need one chart which allows one to determine the fraction of the monthly heating load supply by solar energy as a function of two dimensionless parameters. The latter implies the use of monthly average radiation data, the collector surface and estimates of drying loads.

The “GJ-ABAQUE” method was applied for drying 777 kg of corn, corresponding to 1 m³ of fresh product, in a thick layer in each modular dryer.     

SUBLIMATION OF PURE SUBSTANCES IN GAS FLUIDIZED BEDS AT ATMOSHPERIC PRESSURE.

This paper deals with the sublimation of large bodies, or “objects”, made up from a pure substance in a bubbling gas fluidized bed of considerably smaller particles, or “fines”. The influence of such parameters as the gas velocity, the bed temperature, the size and the adsorption capacity of the fines has been investigated.

The results obtained clearly show that the rate of sublimation in fluidized beds is far higher than in air alone. It increases with increasing bed temperature, decreasing particle size, increasing powder mass capacity, and roughly varies as a parabolic function of time. It has also been observed that the temperature difference between the bed and the object surface, or “temperature depression”, depends on the fines characteristics as well as on bed temperature, but is independent of gas velocity when good solid mixing conditions are achieved.

Bed-to-object heat and mass transfer coefficients have been deduced from data points and attempts have been made to provide a reasonable theory to account for them. After a complete examination, the idea of interpreting transport phenomena based on a well-adapted “surface renewal model” has been proposed.     

INVESTIGATIONS ON TRANSITION TO TURBULENCE IN PIPE FLOW OF NEWTONIAN AND VISCOELASTIC FLUIDS

The linear stability analysis of fully developed pipe flow of a second order and a “contravariant” Maxwell-type fluid predicts stability against twodimensional infinitesimal disturbances of rotational symmetry.

A sinuous perturbation, superposed on the pipe flow of aqueous polymer solutions, produces distinct regions of instability, dependent on disturbance amplitude and frequency.

A broad region of Reynolds numbers is found for natural transition to turbulence with laminarization effect of polymer additions in two extremely different cases of inlet conditions.     

The Anisotropy of the Surface Tension of Polar Liquids: The Case of Liquid Crystals

The contact angle of the liquid crystal (LC) 4-phentyl, 4'-cyano biphenyl (5CB) on glass or polyethylene does not correspond to the value expected from its surface tension measured by the “du Nouy” method (29 × 10^-3 JM^-2). The value deduced from the Young-Dupre law is 40 × 10^-3 JM^-2.

Both these values have already been reported in the literature. Their apparent discrepancy is explained by the LC surface tension anisotropy. We show that 5CB as many other LCs orient perpendicular to the free surface but parallel to glass or polyethylene Thus both values of the surface tension correspond to two different molecular orientations.

The LC oriented perpendicularly has a surface tension of 29 × 10^-3 JM^-2 and 40 × 10^-3 JM when it lies parallel to the surface. We suggest that the anisotropy between the perpendicular and parallel state of LCs also exists between two perpendicular orientations. Furthermore, such anisotropy associated with any polar molecules explains the difference of the interfacial energy of similar polar or non polar (i.e., octanol-octane) compounds and water.     

Hydrogen Bonding and the Interfacial Component of Adhesion: Acid/Base Interactions of Corona-Treated Polypropylene

The effect of activation of the surface of polypropylene sheet, by a corona discharge, upon the contact angles of liquids and on the surface free energy parameters γ^LW, γ^⊕ and γ^⊖, was determined. Both advancing and retreating contact angles were measured. The “acid/base” theory of the components of surface free energy was employed.

The contact angles of water and glycerol were initially lower by as much as 30°, after treatment, and that of diiodomethane was lower by about 5°. With time, the advancing angles rose, and the γ^⊕ and γ^⊖ parameters fell, towards the values on the untreated solids, and attained more or less steady values after 5 to 10 days. The basic component, γ^⊖, was the most strongly affected by the corona treatment; it rose, typically, from 2.2 to as high as 25 mJ/m². The acidic component, γ^⊕, rose from zero to as high as 1.9 mJ/m². Its decay with time was only qualitatively the same as that of γ^⊖. The retreating angles, and the corresponding energy components, were changed in the same direction, and somewhat more strongly, than were the “advancing” data.

The well-known improvement in the property of forming strong joints or adherent coatings, after corona treatment, is no doubt due to the formation of sites or areas on the polymers where hydrogen bonds can be formed. The decay of the strength of adhesion with time is, no doubt, due to the decay of these sites or areas.     

Improvement of the Durability of Zinc-Coated Steel/Epoxy Bonded Joints

The durability properties of bonded lap shear joints made from an epoxy/dicyandiamide adhesive and hot-dipped galvanized (G2F) or electroplated-phosphated (EZ2) steel have been investigated. The degradation mechanisms have been studied after three accelerated ageing tests: the “cataplasme humide” (“C.H.T.”), immersion (“I.T.”), and salt spray (“S.S.T.”) tests. X-ray photoelectron spectroscopy (XPS) analysis of fracture surfaces after ageing have shown that anodic dissolution of the zinc-coating is responsible for debonding in all cases and that intergranular corrosion phenomena account for poorer performances of the hot-dipped galvanized substrate during “C.H.T.” and “I.T.” Silane coupling agents were successfully used as primers on both substrates to increase the hydrolytic stability of the metal/adhesive interface. XPS results indicate that both the interfacial dissolution of the phosphate coating of EZ2 and intergranular corrosion of G2F are delayed for silane-primed specimens. The observed improvements do not appear to depend on the nature of the silane coupling agents. Alkylsilanes have been found to perform as well as silanes having a group capable of reacting with the epoxy/dicyandiamide system.

Additional tests were carried out in view of the possible application of organosilane reagents as additives in corrosion-protective oils. Good durability properties have been obtained by priming the metal coupons with a standard oil/silane mixture prior to bonding.

When corrosion was the controlling degradation mechanism as is the case during the salt spray test, silane treated specimens did not generally perform better than control specimens.