Soft and Hard Adhesion

The force needed to pull a cylindrical stud from a soft elastomeric film depends on their elastic and geometric properties. For a rigid stud and a thick elastomeric film, the pull-off stress (σ) depends on the elastic modulus (E) of the film and the radius (a) of the stud as σ ∼ (E/a)^1/2 (soft adhesion). However, when the film is very thin, the pull-off stress is significantly higher than the case with thick films, and its value depends on the elastic modulus and the thickness (h) of the film as σ ∼ (E/h)^1/2 (hard adhesion). Here, we study the pull-off behavior of a soft cylindrical stud, one flat end of which is coated with a high modulus thin baseplate. As the flexural rigidity of this baseplate is varied, we observe the transition between the two types of adhesion. We present a simple physical interpretation of the problem, which could be of value in understanding various biofouling and adhesive situations.     

Thermoelectric characterization of NaxMx/2Ti1−x/2O2 (M=Co, Ni and Fe) polycrystalline materials

Layered -titanate materials, Na_xM_x/2Ti_1−x/2O₂ (M=Co, Ni and Fe, x=0.2–0.4), were synthesized by flux reactions, and electrical properties of polycrystalline products were measured at 300–800 °C. After sintering at 1250 °C in Ar, all products show n-type thermoelectric behavior. The values of both d.c. conductivity and Seebeck coefficient of polycrystalline Na_0.4Ni_0.2Ti_0.8O₂ were ca. 7×10³ S/m and ca. −193 μV/K around 700 °C, respectively. The measured thermal conductivity of layered -titanate materials has lower value than conductive oxide materials. It was ca. 1.5 Wm⁻¹ K⁻¹ at 800 °C. The estimated thermoelectric figure-of-merit, Z, of Na_0.4Ni_0.2Ti_0.8O₂ and Na_0.4Co_0.2Ti_0.8O₂ was about 1.9×10⁻⁴ and 1.2×10⁻⁴ K⁻¹ around 700 °C, respectively.     

Influence of long term oxidation on the microstructure, mechanical and electrical properties of pressureless sintered AlN–SiC–MoSi2 ceramic composites

The effects of long term oxidation on the microstructural modification and on the electrical resistivity and mechanical strength of an AlN–SiC–MoSi₂ electroconductive ceramic composite are presented. The microstructure of the pressureless sintered composite is described and the oxidation behaviour is discussed. The formation of protective mullite layer at temperatures above 1000 °C provides good oxidation resistance for use at higher temperatures. At temperatures below 1000 °C, the AlN/SiC matrix disables the “pesting” phenomena and strength degradation, despite the fact that at these temperatures MoSi₂ oxidizes rapidly. The surface modification induced by oxidation on AlN–SiC–MoSi₂ composites does not affect the mechanical strength, while the electrical conductivity strongly decreases.     

Comparative study of lithium ion conductors in the system Li1+xAlxA2−x (PO4)3 with A=Ti or Ge and 0≤x≤0·7 for use as Li sensitive membranes

Preparations and physico-chemical characterizations of NASICON-type compounds in the system Li_1+xAl_xA_2−x^IV(PO₄)₃ (A^IV=Ti or Ge) are described. Ceramics have been fabricated by sol-gel and co-grinding processes for use as ionosensitive membrane for Li⁺ selective electrodes. The structural and electrical characteristics of the pellets have been examined. Solid solutions are obtained with Al/Ti and Al/Ge substitutions in the range 0≤x≤0·6. A minimum of the rhombohedral c parameter appears for x about 0·1 for both solutions. The grain ionic conductivity has been characterized only in the case of Ge-based compounds. It is related to the carrier concentration and the structural properties of the NASICON covalent skeleton. The results confirm that the Ti-based framework is more calibrated to Li⁺ migration than the Ge-based one. A grain conductivity of 10⁻³ S cm⁻¹ is obtained at 25°C in the case of Li_1·3Al_0·3Ti_1·7(PO₄)₃. A total conductivity of about 6×10⁻⁵ S cm⁻¹ is measured on sintered pellets because of grain boundary effects. The use of such ceramics in ISE devices has shown that the most confined unit cell (i.e. in Ge-based materials) is more appropriate for selectivity effect, although it is less conductive.©     

Further studies on redoxokinetic titrations

The previously described “redoxokinetic effect” is used to indicate the end-points of titrations of Fe²⁺ with Cr₂O₇^2-, sulphuric acid with sodium hydroxide, AsO₂- with I₂ and Ag⁺ with Cl⁻. With the first three systems an accuracy of 0·1 per cent is possible. The method is not suited to the fourth system.

Abstract

Titrations of sulphuric acid vs. sodium hydroxide at 0·1 N concentration and ferrous ammonium sulphate vs. potassium dichromate at 0·05 N concentration can be carried out with an accuracy of ±0·1 per cent using the redoxokinetic technique. A very sharp end-point was obtained in the case of iodine vs. arsenite titration at 0·1 N concentration. Silver nitrate vs. chloride titrations cannot be carried out by the redoxokinetic technique.

Addition of MnSO₄ to the extent of 50 g/l. of the solution enhances the precision considerably in the titration of dilute solutions of ferrous ammonium sulphate with dichromate.     

Evaluation of Mass Transfer Resistances from Drying Experiments

A new approach to experimental evaluation of mass transfer resistances from drying experiments is proposed. A composite model of ginseng root mass transfer, based on one-dimensional treatment of diffusive and convective resistances as additive components of radial mass transfer, was developed. Mass transfer resistance was evaluated from a linear relationship between measured flux and thermodynamic driving force. Partitioning of mass transfer resistance into diffusive (core and skin) and convective (air boundary layer) resistances was done by modification of boundary conditions: (a) high (3 m/s) and low (1 m/s) air velocity; (b) skin removal. Total radial mass transfer resistance was evaluated as (146 ± 6) ∗ 10⁶ s/m at 38°C, significantly decreasing to (48 ± 1.5) ∗ 10⁶ s/m at 50°C. Boundary resistance was evaluated as (54 ± 5) ∗ 10⁶ s/m at 38°C and (26 ± 3) ∗ 10⁶ s/m at 50°C in the entire range of moisture contents. Core and skin resistances were both moisture dependent: core resistance increased from initial value of (6 ± 1) ∗ 10⁶ s/m to (61 ± 6) ∗ 10⁶ s/m toward the end of drying, whereas skin resistance decreased from initial value of (92 ± 5) ∗ 10⁶ s/m to (25 ± 5) ∗ 10⁶ s/m at the endpoint of drying. However, the sum of core and skin resistances, which represents composite diffusive resistance of intact ginseng root, was constant and independent of moisture content: (91 ± 4.6) ∗ 10⁶ s/m at 38°C and (22 ± 1.6) ∗ 10⁶ s/m at 50°C. The relationship between mass transfer resistance R and drying rate factor k = 1/RC was used for verification of the composite model.     

State of C-atoms on the modified nanodiamond surface

XPS, EEL, Auger and FTIR spectroscopies were used to testify the influence of chemical treatment upon the state of C-atoms in the core and on the surface of nanodiamond particles. The study was carried out with ND (JSC “Diamond Centre”). The different kinds of treatments were done ex-situ: with air (5 h) at 200 and 400 °C; with hydrogen (5 h) at 800, 850 and 900 °C; with fluorine (48 h) at 20 °C and 0.5 atm. Noticeable change was not found in the state of C-atoms both on the surface and up to 10 monolayers after these treatments. The concentration of F in the sample is equal to  9 at.%. The binding energy of the F 1s differs from the one in functional groups— –CF₂, –CF. Nevertheless FTIR spectra show bands that can be related to С–О, С–F bonds.     

Dilute solution properties of carboxymethylchitins in high ionic-strength solvent

The hydrodynamic characteristics in aqueous solution at ionic strength I=0.2  of carboxymethylchitins of different degrees of chemical substitution have been determined. Experimental values varied over the following ranges: the translational diffusion coefficient (at 25.0°C), 1.1<10⁷×D<2.9 cm² s⁻¹; the sedimentation coefficient, 2.4<s<5.0 S; the Gralen coefficient (sedimentation concentration-dependence parameter), 130<k_s<680 mL g⁻¹; the intrinsic viscosity, 130<[η]<550 mL g⁻¹. Combination of s with D using the Svedberg equation yielded ‘sedimentation–diffusion' molecular weights in the range 40 000<M<240 000 g mol⁻¹. The corresponding Mark–Houwink–Kuhn–Sakurada (MHKS) relationships between the molecular weight and s, D and [η] were: [η]=5.58×10⁻³ M^0.94; D=1.87×10⁻⁴ M^−0.60; s=4.10×10⁻¹⁵ M^0.39. The equilibrium rigidity and hydrodynamic diameter of the carboxymethylchitin polymer chain is also investigated on the basis of wormlike coil theory without excluded volume effects. The significance of the Gralen k_s values for these substances is discussed.     

GRAIN GROWTH AND DENSIFICATION IN PALLADIUM OXIDE PARTICLES DURING SPRAY PYROLYSIS

A model for aerosol-phase densification of particles during their synthesis by spray pyrolysis is presented. The model was used to describe the evolution of the specific surface area of PdO powders synthesized at temperatures between 400 to 800 °C (residence times 27.9 to 22.7 s). Surface areas and grain sizes ranged between 56 m²/g and 4 nm at 400 °C to 3.2 m²/g and 40 nm at 800 °C The characteristic coalescence lime was determined as: τ= 1.7 x 10¹³T d³ exp(1.3 x 10⁵/RT) [for lattice diffusion] and t = 2.7 x 10¹⁹Td⁴exp (1.6 x 10⁵/RT) [for grain boundary diffusion] (τ is in seconds, Tin degrees Kelvin, R is 8.314J/(mol.K)and d is in meters), but the data and model did not allow identification of the specific mechanism. The model provides a general approach for correlating changes in particle surface area with reactor operating conditions that is applicable to a wide variety of materials.     

Mass transfer by free convection at horizontal electrodes

Limiting currents were measured in an unstirred cell at horizontal cathodes facing upward. Electrolyte composition ranged from 0·01 to 0·7 M CuSO₄ in 1·5 M H₂SO₄. Cathode sizes varied from 0.1–30 by 10 cm, and the free height above the electrode from 1–16 cm. Limiting currents for deposition of copper ranged from 0·68–129 mA/cm². For electrode width larger than 20 mm the data is well represented by the general correlation

Nu′ = 0.19 (Sc. Gr) , where Nu′, Sc, and Gr are the Nusselt number for mass transfer, the Schmidt, and Grashof numbers, respectively. The experimental range used in the correlation included 10⁸ < (Sc. Gr) < 1·4 × 10¹² The results indicate that the boundary layer is turbulent, as it is in the case of the analogous heat-transfer model.     

Free convection mass transfer at horizontal electrodes

The free convection mass-transfer behaviour of upward-facing horizontal surfaces has been investigated experimentally using an electrochemical technique involving the measurement of limiting currents for the deposition of copper on copper electrodes from acidified cupric sulphate solutions. The data are well correlated by the equations

Sh = 0·64(Sc . Gr)^0·25 for 3 × 10⁴ < ScGr < 2·5 × 10⁷ and

Sh = 0·16(Sc . Gr)^0·33 for 2·5 × 10⁷ < ScGr < 10¹². Electrode diameters varied between 0·1 and 12 cm and cupric sulphate concentrations between 0·01 and 0·3 M.

The data compare favourably with previous experimental results for the corresponding heat-transfer case.     

Thermophysical and mechanical properties of novel polymers prepared by the cationic copolymerization of fish oils, styrene and divinylbenzene

New polymeric materials have been prepared from the cationic copolymerization of fish oil ethyl ester (NFO), conjugated fish oil ethyl ester (CFO) or triglyceride fish oil (TFO) with styrene and divinylbenzene initiated by boron trifluoride diethyl etherate (BF₃·OEt₂). These materials are typical thermosetting polymers with crosslink densities ranging from 1.1×10² to 2.5×10³ mol/m³. The thermogravimetric analysis of the new fish oil polymers exhibits three distinct decomposition stages at 200–340, 340–500 and >500°C, respectively, with the maximum weight loss rate at approximately 450°C. Single glass-transition temperatures of T_g=30–109°C have been obtained for the fish oil polymers. As expected, these new polymeric materials exhibit tensile stress–strain behavior ranging from soft rubbers through ductile to relatively brittle plastics. The Young's modulus (E) of these materials varies from 2 to 870 MPa, the ultimate tensile strength (σ_b) varies from 0.4 to 42.6 MPa, and the percent elongation at break (ε_b) varies from 2 to 160%. The failure topography indicates typical fracture mechanisms of rigid thermosets, and the unique fibrillation on the fracture surface gives rise to relatively high mechanical properties for the corresponding NFO polymer. The new fish oil polymers not only exhibit thermophysical and mechanical properties comparable to petroleum-based rubbery materials and conventional plastics, but also possess more valuable properties, such as good damping and shape memory behavior, which most petroleum-based polymers do not possess, suggesting numerous, more promising applications of these novel fish oil-based polymeric materials.     

Effect of Pulsed Electric Field and Osmotic Dehydration Pretreatment on the Convective Drying of Carrot Tissue

The influence of pulsed electric field (PEF) and subsequent centrifugal osmotic dehydration (OD) on the convective drying behavior of carrot is investigated. The PEF was carried out at an intensity of E = 0.60 kV/cm and a treatment duration of t_PEF = 50 ms. The following centrifugal OD was performed in a sucrose solution of 65% (w/w) at 40°C for 0, 1, 2, or 4 h under 2400 × g. The drying was performed after the centrifugal OD for temperatures 40-60°C and at constant air rate (6 m³/h).

With the increase of OD duration the air drying time is reduced spectacularly. The dimensionless moisture ratio Xr = 0.1 is reached for PEF-untreated carrots after 370 min of air drying at 60°C in absence of centrifugal OD against 90 min of air drying after the 240 min of centrifugal OD. The PEF treatment reduces additionally the air drying time. The total time of dehydration operations can be shortened when OD time is optimized. For instance, the minimal time required to dehydrate untreated carrots until Xr = 0.1 is 260 min (120 min of OD at 40°C and 140 min of drying at 60°C). It is reduced to 230 min with PEF-treated carrots.

The moisture effective diffusivity D_eff is calculated for the convective air drying based on Fick's law. The centrifugal OD pretreatment increases drastically the value of D_eff. For instance, 4 h of centrifugal OD permitted increasing the value of D_eff from 0.93 · 10^-9 to 3.85 · 10^-9 m²/s for untreated carrots and from 1.17 · 10^-9 to 5.10 · 10^-9 m²/s for PEF-treated carrots.     

Estimation of particle size distribution parameters in animal lungs

A constant of specific solubility of 2·5 × 10⁻⁸ g cm⁻²day⁻¹ was determined for fused aluminosilicate particles, by observing in vivo retention kinetics after intravenous injection into rats. Studies over the past years in this laboratory, in which dogs and rats have inhaled labeled aerosols of these particles, have shown retention half-lives in the lung of 460 and 285 days, respectively. By applying these values for solubility and half-life to Mercer's theory of dissolution from the deep lung, the initial distribution of particles deposited in the pulmonary regions of dogs and rats following inhalation was calculated. From an inhaled aerosol with a mass median diameter, D_m, of 1·0 μm and σ_o = 1·7, a distribution described by D_m = 0·51 μm and σ_o's ranging from 1·16–1·48 was estimated to have been deposited in the Beagle dog lung. and a D_m =< 0·32 μm and σ_o's ranging from 1·18–1·29 was similarly calculated for rats.     

Influence of Edible Films upon the Moisture Loss and Microstructure of Dietetic Sucrose-Free Sponge Cakes during Storage

The kinetics of changes in the bound water content in dietetic sucrose-free sponge cakes (DC) during storage was investigated. The effect of edible films of polymyxan, pectin, xanthan, and carboxymethylcellulose upon this kinetics was also investigated. The quantitative changes in both states of water (slightly bound water and strongly bound water) were registered by combined dynamic analysis (thermogravimetry analysis, TGA, and differential thermal analysis, DTA). The moisture changes in DC crumb were analyzed by drying out to constant mass. The rate constants were determined according the equation q = q_oe^-kt. The values of rate constants 'k', in day^-1, concerning the different edible films were as follows: for crumb moisture is (8.00 ≤ k ≤ 12.47) × 10^-3, for bound water is (3.07 ≤ k_w ≤ 6.26) × 10^-2, for slightly bound water is (4.22 ≤ k₁ ≤ 8.49) × 10^-2 and for strongly bound water is (2.02 ≤ k₂ ≤ 5.62) × 10^-2 as compared to 18.53 × 10^-3, 7.16 × 10^-2, 9.04 × 10^-2, and 5.36 × 10^-2 in the uncovered DC, respectively. The best water-retaining effect in respect to crumb moisture during storage was ascertained in the use of polymyxan and xanthan films. The lowest rate constant values for bound water and its two states were measured for DC covered with pectin. The relation between the kinetics of both bound water states during storage and ageing of the crumb of DC covered with different edible films and the crumb microstructure was represented. By means of scanning electron microscope was read the smallest change in crumb microstructure of pectin-covered DC on the sixth day of storage.     

EVALUATION OF UV DOSE IN FLOW-THROUGH REACTORS FOR FRESH APPLE JUICE AND CIDER

High absorptivity and turbidity interfere with the UV disinfection of apple cider. Three different configurations of flow-through UV reactors were evaluated to overcome this interference. Two approaches were employed: use of an extremely thin film UV reactor and increasing the turbulence within a UV reactor. Multiple-lamp UV reactors including the thin-film laminar flow “CiderSure” (8 lamps) and turbulent flow “Aquionics” (12 lamps) and annular single-lamp “UltraDynamics” reactor were studied. UV disinfection performance in laminar and turbulent flow reactors was compared by evaluation of UV dose delivery. UV fluence rate (irradiance) distribution was calculated using the multiple point source summation method. E. coli K12 was used as a target bacterium in a bioassay, and the log reduction per one pass was determined for each UV reactor. Finally, the UV decimal reduction dose (D₁₀) was calculated by dividing the average UV fluence by log bacterial reduction per pass. Variations of the UV decimal dose were observed with various designs of UV systems. The least inactivation of E. coli K12 but the highest UV decimal reduction dose, ranging from 90 to 150 mJ/cm², was observed in the Aquionics UV reactor in apple cider with apparent absorption coefficient (a) of 5.7 mm^-1. The lower value of UV decimal reduction dose of 7.3-7.8 mJ/cm² was required for inactivation of E. coli K12 in malate buffer and apple juice in the annular single-lamp UltraDynamics reactor. However, the decimal reduction dose for E. coli K12 in apple cider was significantly higher, about 20.4 mJ/cm². Similar UV decimal reduction doses from 25.1 to 18.8 mJ/cm² for inactivation of E. coli K12 were observed in the thin-film 'CiderSure' UV reactor in apple cider with identical absorption coefficient. Mathematical modeling of UV irradiance can improve the evaluation of UV dose delivery and distribution within the reactors.     

Electrical ageing of carbon nanotube composite cathode layers

Effect of electrical ageing (EA) on the field emission parameters of thin multiwall carbon nanotube composite (t-MWCNTs-composite) was studied. Initially, t-MWCNTs were mixed with -terpineol and ethyl cellulose and subjected to three roll milling process to obtain t-MWCNTs-composite. Following this, the composite was screen printed on a conducting substrate, annealed for 10 min and employed to the electrical ageing process for a period of 6 h. The ageing, on each cathode layer, was repeated for five times and J–E characteristics have been collected before and after each ageing attempt. The analysis revealed that, the magnitude of threshold turn-on-field gradually increased from its virgin value of 1.223 to 1.968 V µm^− 1 and corresponding mean field enhancement factor, γ_m, gradually decreased from 2700 ± 210 to 1940 ± 30 with a sequential increase in the ageing attempts. The degradation rate, δJ/δt, estimated for untreated and EA samples, indicated that the magnitude of δJ/δt reached to an equilibrium value of ~ 0.785 μA cm^− 2 min^− 1, which shows a stable emission state of the emitters. To investigate the effect of EA on the physical state of the emitters, a few virgin and all EA samples were subjected to scanning electron microscopy, micro Raman spectroscopy and X-ray photoelectron spectroscopy. The details of the analysis are presented.     

Critical crack-healing condition for SiC whisker reinforced alumina under stress

Alumina reinforced by SiC whisker, called here “alumina(w)” was developed with the objective of improving fracture toughness and crack-healing ability. The composites were crack-healed at 1200 °C for 8 h in air under elevated static and cyclic stresses. The bending strength at 1200 °C of the crack-healed composites were investigated. The threshold static stress during crack-healing of alumina(w) has been determined to be 250 MPa, and the threshold cyclic stress was found to be 300 MPa. Considering that the crack growth is time-dependent, the threshold stress of every condition during crack-healing of alumina(w) was found to be 250 MPa. The results showed that the threshold stress intensity factor during crack-healing was 3.8 MPa m^1/2. The same experiment conditions were applied to specimens cracked and annealed at 1300 °C for 1 h in Ar, to remove the tensile residual stress at a tip of the crack. Thus, the threshold stress intensity factor during crack-healing was found to be 3.2 MPa m^1/2 for the specimens crack-healed with annealing. The threshold stress intensity factor during crack-healing of alumina(w) was chosen to be 3.2 MPa m^1/2 to facilitate comparison with the values of the threshold stress intensity factor during crack-healing. The residual stress was slightly larger than the intrinsic value.     

Drying Kinetics of a Porous Spherical Particle and the Inversion Temperature

A model is presented for drying of a single porous particle with superheated steam and humid air. Experimental data for spherical porous ceramic particle reported in the literature were used for the validation of the model. An inversion temperature at which the evaporation rates within superheated steam and humid air are equal was predicted. The effect of thermophysical properties of the particle (permeability 10^-14 - 10^-17 m², diameter 3 × 10^-3 - 10 × 10^-3 m) and operating variables (gas mass flux 0.26 - 0.78 kg m^-2 s^-1, drying agent temperature 120-200°C) is tested. The inversion temperature is shown to be affected by the thermophysical properties of the porous particle and of the drying agent.     

Physico-Chemical Criteria for Maximum Adhesion. Part II: A New Comprehensive Thermodynamic Analysis

In this paper, two parameters defined as the relative work of adhesion [W_A/γ_L] and the relative interfacial energy [γ_SL/γ_L] have been examined for their assumed usefulness in correlating the thermodynamic properties of the components of the system substrate/ adhesive with its practical performance (strength). It is shown that the minimum value of [γ_SL/γ_L] relevant to conditions for the maximum adhesion becomes zero only for those systems (relatively rare) for which interaction factor Φ₀ is equal to 1.0.

Several transition points were identified for boundary conditions acquired at θ = 0° and θ = 90° which can be used to predict the properties and performance of an adhesive joint. These transition points are: a_MIN—energy modulus of the system (E. M. S.), relevant to the minimum interfacial energy; a_S—E. M. S. where self-spreading of adhesive occurs; a_CRIT—E. M. S. relevant to conditions under which the thermodynamic work of adhesion becomes negative and the system exhibits a tendency for self-delaminating or has “zero-strength”; a_CF—E. M. S. beyond which the geometry of the interface at any interfacial void or boundary of the joint may be regarded as a crack tip.

It is shown that only in those systems for which Φ₀ = 1.0 can a minimum contact angle of 0° indicate a condition for the maximum strength. If Φ₀ is known, the optimum contact angle can be estimated and hence the optimum surface energy of the substrate (adjusted by surface treatment, etc.) for the maximum adhesion.