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.     

Surface Mechanical Properties of the Spore Adhesive of the Green Alga Ulva

The mechanical properties of the adhesive produced by spores of the green, marine, fouling alga Ulva linza are reported. Atomic force microscopy studies were performed and nanoindentation data were analyzed using a model for an asymmetric indenter. Freshly secreted adhesive is characterized by multiple layers. We found that the modulus of the outer ∼600-nm thick layer was about 0.2 ± 0.1 MPa, whereas the modulus of the inner layer was about 3 ± 1 MPa. Older adhesive showed the formation of a “crust” of harder material with a yield strength of ∼20 MPa at a loading rate of 2.5 × 10^-6 N · s^-1. Mechanical properties under tension are also described, and extension profiles that showed either constant or nonlinear force changes with tip-sample separation were observed. Models for both kinds of behavior are described. The work of adhesion between poly-dimethylsiloxane (PDMS)-coated AFM tips and the adhesive was determined to be less than 1.5 mJ · m^-2.     

Electrosorption and inhibition properties of p-norborn2-yl phenolate ions at the mercury/solution interface

The electrosorption properties of p-norborn-2-yl phenolate ions in alkaline solutions were investigated by ac polarographic and electrocapillary measurements.

Two adsorption regions were found. At low bulk surfactant concentrations the adsorption at the positively charged electrode (−0.2 E −0.6 V) is predominant while at higher surfactant concentrations the adsorption at the negatively charged electrode (−0.6 E −1.0 V) is more pronounced. At E = −0.40 V the adsorption parameters were determined (a ≈ 2; ΔG°_A = −32.5 ± 1 kJ mol⁻¹. Between −0.6 E −1.0 V one potential of maximum adsorption for all concentrations does not exist and therefore the adsorption parameters could not be calculated.

At E = −0.40 V progressive two-dimensional nucleation with a nucleation order of 3 was observed which corresponds well with the high attraction constant.

The electrode reaction S₂O²⁻₈ + 2e⁻ → 2 SO²⁻₄ is inhibited by norborn-2-yl phenolate ions in the potential range −0.2 E −0.6 V. In the second potential range of capacity decrease the electrode process is much less retarded. At E = −0.40 V, in a similar manner as described for neutral molecules, a linear dependence of the log k_s (k_s apparent rate constant) on ln c_A and π (π = surface film pressure), respectively, has been found.     

Fracture Mechanics of aV-peel Adhesion Test - Transition from a Bending Plate to a Stretching Membrane

A linear elastic solution is proposed for a “V-peel” adhesion test for a thin film adhered to a rigid substrate. The mechanical responses of a stiff plate-like coating under pure bending, a semi-flexible film under mixed bending and stretching, and a flexible membrane-like film under pure stretching are discussed. For delamination to occur, the mechanical energy release rate is shown to be G = χ(Fw₀/2bl) with χ a numerical constant varying from 3/2 for a plate-like disc to 3/4 for a thin flexible membrane.     

Crystalline polythiophene film prepared by electrochemical polymerization of thiophene at a nickel electrode

Crystalline polythiophene (Pth) film was first electrochemically deposited onto a nickel substrate from freshly distilled BF₃-diethyl ether (BFEE) solution containing 15 mM thiophene. The crystalline film was studied by the X-ray diffraction technique and it was found to be a monoclinic unit cell with parameters a = 0.624 nm, b = 0.593 nm, c = 0.596 nm, and β = 103.6°. The film obtained from this medium has a compact morphology and great strength. © 1997 Elsevier Science Ltd.     

Fracture Mechanics of a Shaft-loaded Blister Test - Transition from a Bending Plate to a Stretching Membrane

A linear elastic solution is proposed for a circular disc in transition from a plate-like (pure bending) to a membrane-like behavior (pure stretching) under a central point load. The strain energy release rate for film delamination is found to be G = χ(Pw₀/πa²) with χ a numerical constant varying from 1/2 for a plate-like disc to 1/4 for a thin flexible membrane.     

Drying Kinetics and Color Retention of Dehydrated Rosehips

Freshly harvested rosehips (Rosa canina L.) were dehydrated in a parallel flow type air dryer at six air temperatures (30, 40, 50, 60, and 70°C) at air velocities of 0.5, 1.0, and 1.5 m/s. Drying air temperature and velocity significantly influenced drying time and energy requirement. Minimum and maximum energy requirement for drying of rosehips were determined as 6.69 kWh/kg for 70°C at 0.5 m/s, and 42.46 kWh/kg for 50°C, 1.5 m/s. In order to reduce drying energy consumption, it is recommended that the drying air velocity must not be more than 0.5 m/s and drying air temperature should be 70°C. In addition, the influence of drying air temperature and air velocity on the color of dried rosehip has been studied. Hunter L, a, b values were used to evaluate changes in the total color difference (ΔE) on dried rosehips. 70°C drying air temperature and 1 m/s air velocity were found to yield better quality product.     

Electric-Field Induced Morphological Transitions in Elastic Contact Instability of Soft Solid Films

A soft elastic film, when placed in adhesive proximity with a contactor in a crack-like geometry, spontaneously undergoes a surface instability to form finger patterns with a characteristic wavelength of approximately 4h, where h is the film thickness. We study the morphological evolution and control of this elastic contact instability under the influence of an external electric field. The distinct electric field induced morphological changes, leading to the formation of two-dimensional hexagonally arranged pillars, large-amplitude fingers, and straightening of contact edge, which are studied comprehensively. The conditions for the evolution of morphologically distinct patterns are governed by the film parameters, such as its shear modulus and thickness. A theoretical model and its stability analysis provide an approximate estimate of the critical voltage required for the onset of changes and its scaling with the film parameters (thickness and shear modulus). Further, three-dimensional simulations based on energy minimization are presented to provide important clues regarding the physics of pattern evolution on soft elastic interfaces.     

Kinetics of adherence of a rigid truncated cone on an elastic half-space (unfilled natural rubber)

The equilibrium contact of a rigid flat-ended cone, applied against the flat and smooth surface of a soft elastomer sample (unfilled natural rubber), is studied with the help of fracture mechanics concepts, which can be easily introduced in this class of problems by using Sneddon's solution (Int. J. Eng. Sci. 3 (1965) 47) of Boussinesq's problem extended to all axisymmetric adhesive punches with a convex profile. The kinetics of adherence is measured when an imposed tensile force is applied in order to disturb the size of the contact area. Variations of the strain energy release rate G and of the associated dissipation function Φ=(G−w)/w, where w is the Dupré energy of adhesion, are studied as a function of the crack propagation speed V at the interface between a truncated cone made of PMMA and the rubber sample (the limit of the contact is considered as a crack tip). As expected, a master curve Φ(V) is found, confirming the variation of Φ as the 0.55 power function of V, as recently established by Barquins et al. in adherence of a perfect cone and flat-ended spheres in pull-off/push-on tests, adherence and rolling of cylinders experiments and rebound of balls tests, with the same elastic rubber-like material.     

Deformation kinetics of ageing materials

A constitutive equation of time-dependent, chemically stable materials, which stems from the basic ideas of the irreversible thermodynamics of an internal variable and Eyring's absolute reaction rate theory, has been extended to chemically unstable materials. This formulation is quite general and, in principle, can be applied to many types of materials. In this paper, the ageing behaviour of time-dependent network polymers undergoing chain scission is considered. In the network scission process, we postulate that the energy barrier is affected by a changing of the chemical crosslink density. An explicit equation to account for the energy barrier change, which influences the relaxation process, is formulated. For the purpose of illustration, the effect of different chemical crosslink density, ν, on the relaxation rate has been considered, from which the following theoretical expression of relaxation modulus ΔE(t) is obtained:

ΔE = ΔE[t exp (γv/kT)]

It can be seen that a change in v leads to an effective change in the time scale, usually denoted by a_x. Here the analytical expression a_x = exp(γν/kT) correlates quite well with the experimental data.     

Surface Segmental Mobility and Adhesion—Effects of Filler and Molecular Mass

The adhesion of thin films of poly(methyl acrylate) (PMA) on glass slides in contact with tape has been measured as a function of thickness, molecular mass, and amount of silica-based filler. In all cases studied the polymer thin-film, tape-peel tests resulted in linear force-velocity plots. The best-fit lines were extrapolated to find the fracture energies at zero velocity. For thin layers of rubbery PMA on glass slides the PMA-tape fracture energies were found to decrease (from 55-20 J/m²) with increasing PMA thickness (50-1000 nm). Thin films made from glassy poly(methyl methacrylate) (PMMA) were found to have no thickness dependence and much higher fracture energies (∼ 140 J/m²). The effect of PMA molecular mass was found to be smaller than the effect of film thickness. Including silica in the films at low levels dramatically increased the fracture energies, with a maximum (182 J/m²) found with 5.2% silica. With larger amounts of silica, the fracture energy declined significantly.     

Thermodynamic Criteria for the Maximum and Minimum Strength of Fibre-Reinforced Composite Materials

The overall performance and reliability of composite materials are, in most cases, dependent upon the behaviour of the reinforcement-matrix interface, particularly upon its ability to transfer stress.

A theory for predicting thermodynamic conditions for the maximum and zero-adhesion at the reinforcement-matrix interface is tested in this paper, based on experimental data. Proposed is a model of the relationship between mechanical properties of composite materials (tensile strength, flexural strength, Young's modulus and impact resistance) and energetic properties of matrix and reinforcement expressed by the energy ratio a = γ_l/γ₂.     

Dewetting and Adsorption in Homopolymer Films Containing Triblock Copolymers: Role of Chain Architecture and Anchoring Block Molar Fraction

Triblock copolymer additives are found to stabilize thin-film dewetting of B-type homopolymers with degree of polymerization (DOP) P deposited on silicon oxide. The triblock copolymers' architectures are ABA and BAB, where A and B represent anchoring and nonadsorbing blocks with DOP's N_A and N_B, respectively. Upon adding 1 vol.% of the ABA additive, dewetting is only observed for anchoring block molar fractions, f_A, below 4%. Dewetting is arrested in films containing 1 vol.% ABA, BAB, or AB that have similar values of f_A ∼ 8%, showing that chain architecture is not the only indicator of a successful additive. Compared with films containing diblock copolymers, the interfacial excess, z*, of triblock copolymers at the melt/substrate interface is relatively small as measured by low-energy forward-recoil spectrometry. Because adsorbed copolymers can reduce the capillary driving force for dewetting and participate in entanglements with matrix chains, the higher coverage and grafting density observed for diblock copolymers suggests that diblocks are more effective than triblocks in improving thin-film stability.     

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.     

Influence of Kiln Venting on Brown Stain in Pinus Radiata Sapwood

This study assesses the influence of a closed drying environment on kiln brown stain in Pinus radiata sapwood. Three sets of matched timber samples (N = 50) were dried at low temperature (50°C), one without and two with kiln venting. Statistical analysis showed that the closed drying environment produced no significant change in the lightness (L*) of kiln brown stain. Relative to the samples dried in the vented process, there was a small but statistically significant increase in the green color (Δa* ≈ - 1.7) for both the stained area and the unstained early-wood of the samples dried in the non-vented kiln.     

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.     

Experimental study of falling film evaporation heat transfer outside horizontal tubes

The heat transfer process of falling film horizontal evaporation includes evaporation outside tubes and condensation inside tubes, the heat transfer coefficient of the former is about 50% of that of the latter. So the overall heat transfer coefficient is influenced mainly by the falling film evaporation outside tubes. An experimental study of falling film heat transfer outside horizontal tubes was carried out in order to show how the heat transfer coefficient is affected by different parameters such as flow density evaporation temperatures, temperature difference between wall and saturation water, and mass concentration of the seawater. Experiments were conducted using 14 mm outer diameter Al-brass tubes heated by internal electric heaters so that a uniform heat flux was generated on the outside surface of tubes. The results show that when flow density Γ varies between 0.013 kg/ms < Γ< 0.062 kg/ms, the heat stransfer coefficient of falling film evaporation outside horizontal tubes h increases with the increase in liquid feeding, evaporation boiling temperature and heat flux. h also increases with an increase in distributor height, however there is a maximum height in which any height above this. Besides, the amount of non-condensing gas has significant effect on h. The difference of heat transfer coefficient between freshwater and seawater is small. These results contribute to further improving the performance of heat transfer process and developing new evaporator.     

Adhesion of Patterned Reactive Interfaces

We demonstrate the role of chemical surface patterns on the adhesion of soft, elastomeric interfaces. The microscale patterns consist of periodic variation of two types of silane surface chemistries: a reactive silane that bonds covalently with the soft elastomer and a passive silane that is weakly adhered with the elastomer. Using an adhesion test based on 90° peel geometry, we demonstrate that the tuning of adhesion depends on the spatial distribution of the reactive silane groups. Given our material system and pattern symmetries, an enhancement in adhesion energy is observed in a majority of the patterns. The mechanism of enhancement is associated with the shape of the contact line. Specifically, the reactive silane interfaces play a significant role in defining the width of the contact line. In instances where enhancement is observed, the width of the contact line increases because of the “pinning” of the contact line by the reactive interfaces. These results emphasize the importance of contact line interaction with the pattern shapes and demonstrate opportunities for using well-defined two-dimensional patterns to actively tune polymer adhesion.     

Adhesion and Scratch Resistance of Polycarbonate Films on Ferroplate Substrates: Effect of γ-APS Primers

The influence of γ-aminopropyltriethoxysilane (γ-APS) primers on the adhesion and scratch resistance of polycarbonate (PC) films on ferroplate substrates was determined from the critical normal loads at which debonding of the films from the substrates occurred during scratch testing. The critical load was a strong function of the concentration of the aqueous solutions from which the γ-APS primers were adsorbed and of the thickness of the primer films. Thus, the critical normal load increased from 0.09 ± 0.02 N to 0.31 ± 0.07 N as the concentration of the γ-APS solutions increased from 0.05% to 0.2%, respectively. However, the critical load increased only slightly as the solution concentration increased beyond 0.2%. The increase in critical load as concentration of γ-APS solutions increased was related to the formation of an interphase involving chemical reaction and physical entanglement of PC and γ-APS molecules. The critical load for debonding of PC films from the substrates also depended strongly on the temperature at which the γ-APS films were dried before application of the PC films. Thus, the critical normal loads for debonding were 0.31 ± 0.07, 0.20 ± 0.02, and 0.05 ± 0.01 N for γ-APS films that were dried for 15 min at room temperature, 60°C, or 110°C, respectively. The decrease in critical load with increasing drying temperature was attributed to the greater cross-link density in γ-APS films that were dried at elevated temperatures, which limited interdiffusion and physical entanglement of PC and γ-APS molecules. High reaction temperature of γ-APS and PC induced a fragmentation of amine. However, it also increased the probability of amines to react with carbonate because of increasing mobility of PC chains. Optimization of these two factors was required to obtain the greatest adhesion and scratch resistance. Chemical reactions occurring between PC films and γ-APS primers were investigated by reflection-absorption infrared spectroscopy (RAIR) and X-ray photoelectron spectroscopy (XPS) using diphenyl carbonate (DPC) as a model compound. The carbonyl absorption band of neat DPC was observed at 1780 cm^-1. However, two carbonyl bands were observed at 1738 and 1652 cm^-1 in RAIR spectra of γ-APS films that were reacted with DPC and were assigned to urethane and urea groups, respectively. XPS results revealed that urethane was the main reaction product between DPC and γ-APS. It was concluded that urethane groups formed by the reaction of PC with γ-APS were responsible for adhesion and scratch resistance of PC to ferroplate substrates that were primed with γ-APS.     

Model Studies of the Effect of Surface Roughness and Mechanical Interlocking on Adhesion

The apparent strength of adhesion has been measured for a soft elastic layer adhering to model porous substrates, consisting of rigid plates containing regular arrays of cylindrical holes. Two contributions to the apparent strength have been identified and compared with the predictions of a simple theoretical treatment. The first is adhesion to the surface itself. Because “rough” surfaces have greater area for bonding, the strength of adhesion was increased by as much as twenty-fold. The second arises from the work of breaking deeply embedded or entangled strands in order to detach the overlayer. Contributions from this mechanism were as much as several hundred times the (low) intrinsic strength of adhesion. Satisfactory agreement was obtained with theory in both cases. Measurements were also made using cloth substrates, when the adhering layer penetrated the cloth completely. The work of detaching and breaking permeating strands was again much larger than the intrinsic strength of adhesion, in reasonable agreement with theoretical predictions.