H. Dodiuk

The Relationship between Water Wetting and Ice Adhesion

Ice accretion on aircraft leads to difficulties in aircraft flight control due to weight increase and change in weight distribution. Conventionally these difficulties are overcome using anti-icing or de-icing products, such as freezing depressants and heating devices. A more cost effective way to solve these problems would be to use ice repellent surfaces (ice-phobic). As a first step in this direction the relationship between water wettability and ice adhesion was investigated. Using the appropriate chemistry and tailoring the surface roughness a variety of polycarbonate-coated surfaces were created: these included ultra-hydrophilic and ultra-hydrophobic surfaces and surfaces with surface properties in between the extreme ultra-surfaces. Ice adhesion tests and contact angle measurements indicated that the higher the contact angle the lower is the adhesion of ice. The best results were obtained in the case of ultra-hydrophobic surface treatment that led to an 18 fold decrease in ice adhesion compared to the untreated aluminum surface.

The effect of polymer surface on the wetting and adhesion of liquid systems

Youngs equation describes the wetting phenomenon in terms of the contact angle between a liquid and a solid surface. However, the contact angle is not the only parameter that defines liquid–solid interactions, an additional parameter related to the adhesion between the liquid drop and the solid surface is also of importance in cases where liquid sliding is involved. It is postulated that wetting which is related to the contact angle, and interfacial adhesion, which is related to the sliding angle, are interdependent phenomena and have to be considered simultaneously. A variety of models that relate the sliding angle to the forces developed along the contact periphery between a liquid drop and a solid surface have been proposed in the literature. Here, a modified model is proposed that quantifies the drop-sliding phenomenon, based also on the interfacial adhesion that develops across the contact area of the liquid/solid interface. Consequently, an interfacial adhesion strength parameter can be defined depending on the mass of the drop, the contact angle and the sliding angle. To verify the proposed approach the adhesion strength parameter has been calculated, based on experimental results, for a number of polymer surfaces and has been correlated with their composition and structure. The interaction strength parameter can be calculated for any smooth surface from measurements of the contact and the sliding angles.

The Effect of Tungsten Sulfide Fullerene-Like Nanoparticles on the Toughness of Epoxy Adhesives

In this work the effect of inorganic fullerene-like (closed cages) nanoparticles of tungsten disulfide (IF-WS2) on the mechanical properties and especially on the toughness of epoxy resins, was studied. The epoxy resin used was the well-known DGEBA (di-glycidyl ether of bis-phenol A) cured with polyamidoamine. The epoxy/IF-WS2 nanocomposites were prepared by applying a high shear mixing to obtain a uniform dispersion and homogeneous distribution of the IF nanoparticles in the epoxy matrix. Two mixing procedures were used — a low shear of short duration and high shear with a long mixing time. The resulting epoxy nanocomposites were first characterized for their shear and peel strength using appropriate bonded joints. The experimental results demonstrate that enhanced shear strengths and shear moduli were achieved, together with a significant increase in the peel strengths at low concentrations of the IF-WS2 nanoparticles (more than 100% increase at 0.5 wt% IF-WS2). Above the threshold value of 0.5% IF-WS2 the peel strength decreased sharply. The fractured surfaces of the bonded joints were examined by transmission and scanning electron microscopy in order to characterize the fracture mechanisms and analyze the dispersion level of the nanoparticles within the polymer. The electron micrographs indicated that the presence of the nanoparticles in the epoxy matrix induced fracture mechanisms which were different from those observed in the pristine epoxy phase. These mechanisms included: crack deflection; crack bowing; and crack pinning. Evidence for a chemical interaction between the nanoparticles and the epoxy were obtained by infrared measurements in the attenuated total transmittance mode. The data suggests the formation of new carbon–oxygen–sulfur bonds, which are most likely due to the reaction of the outermost sulfur layer of the IF nanoparticles with the reactive epoxy groups. The observed simultaneous increase in both shear and peel strengths at very low IF-WS2 concentrations, found in this work, could lead to the development of high performance adhesives and to new types of structural and ballistic fiber nanocomposites.

Room Temperature Curing Epoxy Adhesives for Elevated Temperature Service

Abstract Room Temperature curing compositions of epoxy resins with high temperature service capability (95–120°C) were formulated and evaluated. The compositions were based on selected high functionality atomatic epoxy polymers and multicomponent poly amine curing agent systems. Toughening was achieved by addition of a rubbery phase either by prereaction of the epoxy resin with carboxyl terminated (CTBN) or by amine terminated (ATBN) poly butadiene acrylonitrile. The latter elastomeric component served as a part of the poly amine curing agent. Best results were achieved with an adhesive formulation comprising tetra glycidyl-4-4′-diaminodiphenylmethane (TGDDM) and triglycidyl ether of p-aminophenol with triethylenetetramine and addition of ATBN with a felt carrier. Lap shear strengths of aluminum/aluminum specimens primed by silane coupling agent in the order of 22 MPa at 25°C and 11 MPa at 120°C with T-Peel strengths of 1.6N/mm at 25°C and 0.52 N/mm at 120°C, were obtained. The thermal behaviour and trans...

The Effect of WS2 Nanotubes on the Properties of Epoxy-Based Nanocomposites

In this paper we evaluated the effect of embedding inorganic nanotubes (INT) of tungsten disulfide (WS2) in an epoxy matrix, on the mechanical, thermal and adhesion properties of the resulting nanocomposites. The nanotube content spanned a range of values (0, 0.1, 0.3, 0.5 and 1.0 wt%), and the nanotube incorporation process consisted of a combination of both distributive (magnetic stirring) and dispersive (ultrasonic mixing) methods. The adhesion of the nanocomposites to an aluminum substrate was characterized by both a single lap shear and a T-peel test. The fracture toughness (K IC) of the nanocomposites was characterized by a standard compact tension (CT) plane-strain fracture test. The thermal properties of the nanocomposites were determined by dynamic mechanical thermal analysis (DMTA). Overall, the addition of INT-WS2 was found to improve the shear strength and peel properties of the nanocomposite, and to significantly improve its fracture toughness and glass transition temperature. The extent and character of the nanotube–epoxy interaction were examined by electron microscopy, as was the energy dissipation mechanisms during fracture.

Pre-bonding technology based on excimer laser surface treatment

Abstract The application of ArF excimer laser for surface pre-treatment of polycarbonate, polyetherimide, polyaryl ether–ether–ketone (PEEK) composite, fiberglass, aluminum, copper and fused silica was investigated. Various substrates were tested with excimer laser irradiation using various parameters, such as: intensity, repetition rate, and number of pulses. The optimal laser treatment parameters were found for each material needed for achieving maximum adhesional strength of the corresponding bonded joints. Experimental results indicated that UV laser surface treatment improved significantly the adhesion strength compared to conventional treated substrates for all the materials tested. The improved adhesion was correlated with the roughening of the irradiated surface, chemical modification and removal of contamination.

Polyurethane adhesives containing functionalized nanoclays

The development and commercialization of nanoclays (NCs) offers new possibilities to tailor adhesives on the nanoscale range. Three types of functionalized nanoclays were included in the current study, two novel ones and one commercial nanoclay. The novel ones were based on aminosilane and amidoamine hyperbranched polymer, and the commercial nanoclay possessed hydroxyl functionality. All the three functionalities were expected to react with the polyurethane (PU) based thermoset adhesive. Fourier transform infrared (FT-IR) spectroscopy was used to follow the disappearance of the isocyanate group of the polyurethane thermoset adhesive. Thermo-mechanical properties were studied using dynamic mechanical analysis (DMA). Shear and peel properties of adhesively-bonded joints were evaluated using the appropriate test standards. Atomic force microscopy (AFM) was used to analyze the nanoscale morphology of cryogenically fractured surfaces. DMA measurements indicated that the glass transition temperature (T g) of neat PU was 32°C. Incorporation of nanoclays in concentrations of 1, 3 and 5 wt% affected the glass transition temperature significantly. The functionalized nanoclays increased the T g gradually to the range of 60 to 62°C for 5 wt% loading. The incorporation of functionalized nanoclays into PU improved the shear strength by 170, 160 and 195% for the hydroxyl-, aminosilane- and hyperbranched-treated NCs, respectively. The functionalized nanoclays exhibited higher peel strength compared to the neat PU by 30% for the hydroxyl modified clay and by 40% for aminosilane-modified clay (at 1 wt% concentration) and almost no change for the hyperbranched modified one. AFM analysis indicated that different fracture mechanisms occurred with respect to the type and concentration of nanoclay used.

Nanotailoring of polyurethane adhesive by polyhedral oligomeric silsesquioxane (POSS)

The development and commercialization of nanoparticles such as nanoclays (NCs), carbon nanotubes (CNTs) and polyhedral oligomeric silsesquioxanes (POSS) offers new possibilities to tailor adhesives at the nanoscale. Four types of POSS, with reactive mono-functional groups of isocyanatopropyl, glycidoxypropyl, aminoethyl and non-reactive octaphenyl, were incorporated in concentrations of 1, 3 and 5 wt% into a polyurethane (PU)-based adhesive. Thermo-mechanical bulk properties were studied using dynamic mechanical analysis (DMA). Adhesive properties were characterized in shear and peel modes. Atomic force microscopy (AFM) was used to study the nanoscale morphology. DMA measurements indicated that the neat PU possessed a glass transition temperature (T g) of ≈ 30°C. The T g of PU/POSS-glycidoxypropyl nanocomposite adhesive increased gradually with POSS concentration to 50°C for 5 wt%. PU/POSS-octaphenyl nanocomposite adhesive exhibited an increased T g by 10°C for 5 wt%. The incorporation of POSS-isocyanatopropyl in the PU had no effect on the T g. With respect to shear properties of POSS-octaphenyl-, POSS-isocyanatopropyl- and POSS-glycidoxypropyl-based PU nanocomposite adhesives, shear strength improved by 230, 178 and 137%, respectively, compared to neat PU. POSS-aminoethyl exhibited lower shear and peel strengths, while POSS-isocyanatopropyl provided the best balance of both higher shear and peel strengths compared to neat PU. It was concluded that the grafted functional group on the POSS and its reactivity with the PU network components were the decisive factors with respect to the thermo-mechanical, morphological and adhesive properties of the resulting nanocomposite adhesives. Consequently, the POSS/polyurethane based nanocomposite adhesives could be tailored for a large range of applications.

The effects of nanostructure and composition on the hydrophobic properties of solid surfaces

The effects of nanoroughness and chemical composition on the contact and sliding angles on hydrophobic surfaces were studied theoretically and experimentally. A theoretical model based on forces developed at the contact area between a liquid drop and hydrophobic smooth or nanoroughened surface was developed and compared with the existing models, which are based on forces developed at the periphery between the drop and the solid surface. The contact area based model gives rise to an interfacial adhesion strength parameter that better describes the drop-sliding phenomenon. Consequently, relationships were derived describing the dependence between the interfacial adhesion strength of the liquid drop to the surface of a given composition, the mass of the drop, the measured contact angles and the sliding angle. For a given surface chemistry, the sliding angle on a nanometric roughened surface can be predicted based on measurements of contact angles and the sliding angle on the respective smooth surface. Various hydrophobic coatings having different surface nanoroughnesses were prepared and, subsequently, contact angles and sliding angles on them as a function of drop volume were measured. The validity of the proposed model was investigated and compared with the existing models and the proposed model demonstrated good agreement with experimental results.

Laser-induced adhesion enhancement of polymer composites and metal alloys

Proper surface treatment of an adherend is among the decisive factors concerning the final quality and durability of an adhesive joint. Various surface treatments are applied to plastic and metal adherends; among them are abrasive treatment, chemical treatment, and plasma etching. An alternative method is presented here which utilizes an excimer UV laser as a new technique for preadhesion surface treatment. Experimental results indicated that preadhesion laser surface treatment improved significantly the shear strength of adhesively bonded aluminum joints as compared with untreated or anodized substrates. Laser treatment also improved the adhesion strength of polycarbonate, polyetherimide, and composite adherends as compared with untreated or simply abraded substrates. Optimal laser treatment parameters (intensity, repetition rate, and number of pulses) depend on the substrate material and its chemical nature. As a result of laser treatment, the mode of failure changed from interfacial to cohesive as long...