Ultrasonic Degradation of Poly(acrylic acid)

The ultrasonic degradation of poly(acrylic acid), a water-soluble polymer, was studied in the presence of persulfates at different temperatures in binary solvent Mixtures of methanol and water. The degraded samples were analyzed by gel permeation chromatography for the time evolution of the molecular weight distributions. A continuous distribution kinetics model based on midpoint chain scission was developed, and the degradation rate coefficients were determined. The decline in the rate of degradation of poly(acrylic acid) with increasing temperature and with an increment in the methanol content in the binary solvent mixture of methanol and water was attributed to the increased vapor pressure of the solutions. The experimental data showed an augmentation of the degradation rate of the polymer with increasing oxidizing agent (persulfate) concentrations. Different concentrations of three persulfates-potassium persulfate, ammonium persulfate, and sodium persulfate-were used. It was found that the ratio of the polymer degradation rate coefficient to the dissociation rate constant of the persulfate was constant. This implies that the ultrasonic degradation rate of poly(acrylic acid) can be determined a priori in the presence of any initiator.

Exceptional adhesive and gelling properties of fibrous nanoscopic tapes of self-assembled bipolar urethane amides of L-phenylalanine

Seven L-phenylalanine based alkyl (monopolar) and alkanediyl (bipolar) derivatives are synthesized; while the bipolar urethane amides form gels and show strong adhesive properties, the monopolar analogues form fibrous nanoscopic cloth-like tapes.

Oxidative and photooxidative degradation of poly(acrylic acid)

The oxidative degradation of poly(acrylic acid) (PAA), a water soluble polymer, was studied at various temperatures with different concentrations of persulfates, potassium persulfate (KPS), ammonium persulfate (APS) and sodium persulfate (SPS). The photodegradation of PAA was also examined with APS as oxidizer. The degraded samples were analyzed for the time evolution of molecular weight distribution by gel permeation chromatography. A theoretical model based on the continuous distribution kinetics was developed that accounted for the polymer degradation and the dissociation of persulfate. The rate coefficients for the oxidative and photooxidative degradation of PAA were determined from the parametric fit of the model with experimental data. The rate of degradation increased with increasing amount of persulfate in both oxidative and photooxidative degradation. The rate of degradation also increased with increasing temperature in the case of oxidative degradation.

Influence of adhesive non-linearities on the performance and optimal length of adhesive bonded joints

An analytical study for the static strength of adhesive lap joints is presented. The earlier solutions of Volkersen [i], DeBruyne[2] and others were limited to linear adhesives. The influence of adhesive non-linearity was first considered by Grimes' et al[3] and Dickson et al [4]. Recently Hart-Smith[5] successfully introduced elastic-plastic behaviour of the adhesive. In the present study the problem is formulated for general non-linear adhesive behaviour and an efficient numerical algorithm is written for the solution. Bilinear and trilinear models for the nonlinearity yield closed form analytical solutions.

Influence of Solvents on the MWCNT/Adhesive Grade Epoxy Nanocomposites Preparation

In this article, the effect of two solvents, namely dimethyl formamide (DMF) and N-methyl pyrrolidone (NMP), on the dispersion effectiveness and the resulting electrical and mechanical properties of multi-walled carbonanotubes (MNCNT) filled structural adhesive grade epoxy nanocomposites was studied. The solvents were used mainly to reduce the viscosity of the resin system to effectively disperse the nanofiller. The dispersion was carried out under vacuum using high energy sonic waves. SEM was undertaken to study the dispersion effectiveness. Electrical resistivity, tensile properties, and glass transition of the nanocomposites were studied. Between DMF and NMP, the former proved better in terms of dispersion effectiveness and the resulting electrical and mechanical properties of the nanocomposites. Addition of MWCNT into AV138M resulted in an increase in glass transition temperature irrespective of the solvent used and in both cases percolation threshold was found with respect to reduction in electrical resistivity of the nanocomposites. Less agglomeration and hence better interaction between CNT and epoxy was observed in the samples prepared using DMF compared with that using NMP.

Hidden order in crackling noise during peeling of an adhesive tape

We address the longstanding problem of recovering dynamical information from noisy acoustic emission signals arising from peeling of an adhesive tape subject to constant traction velocity. Using the phase space reconstruction procedure we demonstrate the deterministic chaotic dynamics by establishing the existence of correlation dimension as also a positive Lyapunov exponent in a midrange of traction velocities. The results are explained on the basis of the model that also emphasizes the deterministic origin of acoustic emission by clarifying its connection to stick-slip dynamics.

Lifting the singular nature of a model for peeling of an adhesive tape

We investigate the dynamics of peeling of an adhesive tape subjected to a constant pull speed. Due to the constraint between the pull force, peel angle and the peel force, the equations of motion derived earlier fall into the category of differential-algebraic equations (DAE) requiring an appropriate algorithm for its numerical solution. By including the kinetic energy arising from the stretched part of the tape in the Lagrangian, we derive equations of motion that support stick-slip jumps as a natural consequence of the inherent dynamics itself, thus circumventing the need to use any special algorithm. In the low mass limit, these equations reproduce solutions obtained using a differential-algebraic algorithm introduced for the earlier singular equations. We find that mass has a strong influence on the dynamics of the model rendering periodic solutions to chaotic and vice versa. Apart from the rich dynamics, the model reproduces several qualitative features of the different waveforms of the peel force function as also the decreasing nature of force drop magnitudes.

Behaviour of Bi-adhesive Joints

The use of relatively low modulus adhesive at the ends of overlap in a bi-adhesive bondline of a bonded joint can reduce the stress concentration significantly and, therefore, potentially lead to higher strength of the joint. This study presents the two-dimensional and three-dimensional nonlinear (geometric and material) finite element analyses of adhesively bonded single lap joints having modulus-graded bondline under monotonic loading conditions. The adhesives were modelled as an elasto-plastic multi-linear material, while the substrates were regarded as both linear elastic and bi-linear elasto-plastic material. The computational simulations have been performed to investigate the bondline behaviour by studying the stress and strain distributions both at the mid-plane as well as at the interface of the bondline. It has been observed that the static strength is higher for joints with bi-adhesive bondlines compared to those with single adhesives in bondline. Higher joint strength has also been observed for optimum bi-adhesive bondline ratio through parametric studies. Effects of load level, and bondline thickness on stress distribution in the bi-adhesive bondline have also been studied. 3D analysis results reveal the existence of complex multi-axial stress/strain state at the ends of the overlap in the bondline which cannot be observed in 2D plane strain analysis. About 1/3rd of the width of the joint from the free edge in the width direction has 3D stress state, especially in the compliant adhesive of the bondline. Magnitudes of longitudinal and lateral stress/strain components are comparable to peel stress/strain components. It has also been analytically shown that the in-plane global stiffness of the joint remains unaffected by modulus gradation of the bondline adhesive. (C) Koninklijke Brill NV, Leiden, 2010.

Influence of viscoelastic nature on the intermittent peel-front dynamics of adhesive tape

We investigate the influence of viscoelastic nature of the adhesive on the intermittent peel front dynamics by extending a recently introduced model for peeling of an adhesive tape. As time and rate-dependent deformation of the adhesives are measured in stationary conditions, a crucial step in incorporating the viscoelastic effects applicable to unstable intermittent peel dynamics is the introduction of a dynamization scheme that eliminates the explicit time dependence in terms of dynamical variables. We find contrasting influences of viscoelastic contribution in different regions of tape mass, roller inertia, and pull velocity. As the model acoustic energy dissipated depends on the nature of the peel front and its dynamical evolution, the combined effect of the roller inertia and pull velocity makes the acoustic energy noisier for small tape mass and low-pull velocity while it is burstlike for low-tape mass, intermediate values of the roller inertia and high-pull velocity. The changes are quantified by calculating the largest Lyapunov exponent and analyzing the statistical distributions of the amplitudes and durations of the model acoustic energy signals. Both single and two stage power-law distributions are observed. Scaling relations between the exponents are derived which show that the exponents corresponding to large values of event sizes and durations are completely determined by those for small values. Th scaling relations are found to be satisfied in all cases studied. Interestingly, we find only five types of model acoustic emission signals among multitude of possibilities of the peel front configurations.

Surface chemical studies on the competitive adsorption of poly(acrylic acid) and poly(vinyl alcohol) onto alumina

The adsorption of poly(acrylic acid) (PAA) and poly(vinyl alcohol) (PVA) onto alumina has been studied as a function of pH, both individually and in the presence of each other. The adsorption density of PAA is found to decrease with an increase of pH while that of PVA shows the opposite trend. In a binary system containing PAA and PVA, the presence of PVA does not affect the adsorption of PAA onto alumina, but the addition of PAA diminishes the adsorption of PVA in the pH range investigated. The adsorption isotherm of PAA at acidic pH exhibits high-affinity Langmuirian behavior. The isotherms for PVA appear rounded and are of the low-affinity type, Once again the adsorption isotherms of PAA remain unaltered in the presence of PVA whereas those of PVA are significantly affected resulting in a lowering of the adsorption density consequent to PAA addition. A variation in the sequence of addition of PAA and PVA does not affect the adsorption behavior of either of the polymers, The electrokinetic behavior of alumina with PAA is hardly influenced by the addition of PVA, On the other hand, the electrophoretic mobility of alumina in the presence of PVA is significantly altered in the presence of PAA and closely resembles the trend observed with PAA alone. Desorption studies reveal that over 80% of PVA could be desorbed in the pH range 3-9 whereas in the case of PAA, the percent desorption increases from 20 to about 70% as the pH is increased from about 3 to 8. Solution conductivity tests confirm interaction of aluminum species and PAA in the bulk solution. FTIR spectroscopic data provide evidence in support of hydrogen bonding and chemical interaction in the case of the PAA-alumina system and hydrogen bonding with respect to the PVA-alumina interaction. (C) 1999 Academic Press.

Reversible Swelling/Deswelling Characteristics of Ethylene Glycol Dimethacrylate Cross-Linked Poly(acrylic acid-co-sodium acrylate-co-acrylamide) Superabsorbents

Poly(acrylic acid-co-sodium acrylate-co-acrylamide) superabsorbent polymers (SAPs) cross-linked with ethylene glycol dimethacrylate (EGDMA) were synthesized by inverse suspension polymerization. The SAPs were swollen in DI water, and it was found that the equilibrium swelling capacities varied with the acrylamide content. The SAPs were subjected to reversible swelling/deswelling cycles in DI water and aqueous NaCl solution, respectively. The effect of the addition of an electrolyte on the swelling of the SAP was explored. The equilibrium swelling capacity of the SAPs was found to decrease with increasing concentration of added electrolyte in the swelling medium. The effect of the particle size of the dry SAPs on the swelling properties was also investigated. A first order model was used to describe the kinetics of swelling/deswelling, and the equilibrium swelling capacity, limiting swelling capacity, and swelling/deswelling rate coefficients were determined.

Adsorption of cationic dyes on poly(acrylic acid-co-sodium acrylate-co-acrylamide) superabsorbents

Inverse suspension polymerization was carried out to synthesize poly(acrylic acid-co-sodium acrylate-co-acrylamide) superabsorbent polymers (SAPs) crosslinked with ethylene glycol dimethacrylate (EGDMA). The equilibrium swelling capacities of the SAPs, determined by swelling them in DI water, were found to vary with the acrylamide (AM) content. The SAPs were used to adsorb four cationic dyes (Acriflavine, Auramine-O, Azure-I and Pyronin-Y). The effect of AM content in the SAPs on the adsorption of the cationic dyes was investigated. Different initial concentrations of Azure-I were used with the same amount of the SAP to explore the effect of initial dye concentration on the adsorption. The effect of the adsorbent amount was investigated by taking different amounts of SAP with a fixed initial concentration of Acriflavine. The kinetics of the dye adsorption was modeled by a first order model and the equilibrium amount of the dye adsorbed, adsorption rate coefficients, removal efficiency and partition coefficients were determined. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Photo, thermal, and ultrasonic degradation of EGDMA-crosslinked poly(acrylic acid-co-sodium acrylate-co-acrylamide) superabsorbents

Superabsorbent polymers (SAPs) based on acrylic acid (AA), sodium acrylate (SA), and acrylamide (AM) were synthesized by inverse suspension polymerization using ethylene glycol dimethacrylate as the crosslinking agent. The equilibrium swelling capacities and the rates of swelling of SAPs varied with the AM content and followed first-order kinetics. The photodegradation of SAPs in their equilibrium swollen state was carried out by monitoring their swelling capacity and the residual weight fraction. The SAPs degraded in two stages, wherein the swelling capacity increased to a maximum and then subsequently decreased. Thermogravimetric analysis of the SAPs indicated that the copolymeric superabsorbents had intermediate thermal stability between the homopolymeric superabsorbents. The activation energies of SAPs with 0, 20, and 100 mol % AM content were determined by Kissinger method and were found to be 299, 248, and 147 kJ mol-1, respectively. The ultrasonic degradation of the superabsorbents was carried out in their equilibrium swollen state, and the change in the viscosity with ultrasonication time was used to quantify the degradation. The ultrasonic degradation of AA/SA superabsorbent was also investigated at various ultrasound intensities. The degradation rate coefficients were found to increase with the intensity of ultrasound. The ultrasonic degradation of AA/SA/AM (20% AM) was also carried out, and degradation rate was found to be more than that of the AA/SA superabsorbent. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012