Swelling activation energy of κ‐carrageenan in its gel state: A fluorescence study

A steady‐state fluorescence technique was employed to study the swelling of κ‐carrageenan gels at various temperatures. Pyranine was used as a fluorescence probe. The fluorescence intensity of pyranine was measured during the insitu swelling process of κ‐carrageenan gels. The fluorescence intensity increased exponentially as the swelling time increased. The increase in the fluorescence intensity was modeled with the Li–Tanaka equation, from which the swelling time constants and cooperative diffusion coefficients were determined. The swelling time constants decreased and the cooperative diffusion coefficients increased as the swelling temperature was increased. The swelling activation energies were measured to be 47.05 kJ/mol. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Films formed from polystyrene latex/clay composites: A fluorescence study

This study reports a steady-state fluorescence (SSF) technique for studying film formation from surfactant-free polystyrene (PS) latex and Na-montmorillonite (SNaM) composites. The composite films were prepared from pyrene (P)-labeled PS particles and SNaM clay at room temperature and annealed at elevated temperatures in 10-min intervals above glass transition temperature (t₃) of polystyrene. During the annealing processes, the transparency of the film improved considerably. Scattered light (I_s) and fluorescence intensity (I_p) from P were measured after each annealing step to monitor the stages of film formation. Evolution of transparency of composite films was monitored by using photon transmission intensity, I_tr. Scanning electron microscopy (SEM) was used to detect the variation in physical structure of annealed composite films. Minimum film formation temperature, T_q, and healing temperatures, T_h, were determined. Void closure and interdiffusion stages were modeled and related activation energies were determined. It was observed that both activation energies increased as the percent of SNaM was increased in composite films.     

UV-visible technique for studying powder coatings and their dissolution

UV-Visible (UVV) technique used to monitor powder coating and its dissolution processes from hard latex particles. Three sets of latex coatings were prepared from poly(methyl methacrylate) (PMMA) particles. The first set of coatings was annealed at elevated temperatures in various time intervals during which reflected photon intensity, I_rf, was measured. The second set of coatings was annealed at various temperatures in 10 min time intervals during which transmitted intensity, I_tr, was measured. I_rf first decreased and then increased as the annealing temperature was increased. Decrease in I_rf was explained with the void closure mechanism due to viscous flow. Increase in I_tr and I_rf against time and temperature were attributed to an increase in crossing density at the junction surface. The activation energy of viscous flow, ΔH, was measured and found to be around 8 kcal/mol and the back and forth activation energies (ΔE_rf and ΔE_tr) were measured and found to be around 49 and 53 kcal/mol for a reptating polymer chain across the junction surface. Diffusion of solvent molecules (chloroform) into the annealed latex coatings was followed by desorption of PMMA chains for the third set of films. Desorption of pyrene, P, labeled PMMA chains was monitored in real-time by the absorbance change of pyrene in the polymer-solvent mixture. A diffusion model with a moving boundary was employed to quantify real-time UVV data. Diffusion coefficients of desorbed PMMA chains were measured and found to be between 2 and 0.6 × 10⁻¹¹ cm² s⁻¹ in the 100 and 275°C temperature range. Presented at the 2000 Spring Meeting of the PMSE Div. of the American Chemical Society, March 26–30, 2000, San Francisco, CA. Dept. of Physics, Maslak 80626 Istanbul, Turkey. Dept. of Physics, 22030 Edirne, Turkey.     

Investigation of PSt-MWCNT concentration on epoxyacrylate photopolymerization and conductivity of polymer films

Photopolymerization kinetics and conductivity changes of epoxyacrylate composites for various loading modified PSt-MWCNT weight fractions changing from 0.0025 to 0.2 wt.% were evaluated by performing photo differential scanning calorimetry (photo-DSC) and four point conductivity measurements. 0.2% PSt-MWCNT additive polymeric films had their electrical conductivity boosted by 6% more than non-additive polymeric films.     

Photon transmission technique for monitoring drying processes in acrylamide gels formed with various crosslinker contents

In situ photon transmission experiments were performed using UV‐visible (UVV) spectrometer during the drying of polyacrylamide (PAAm) gels. These gels are formed from acrylamide (AAm) with various N,N′‐methylenebis(acrylamide) (Bis) contents by free radical crosslinking copolymerization (FCC) in water. The transmitted light intensity, I_tr increased continuously as PAAm gels are dried. Increase in I_tr was attributed to the decrease in the scattered light intensity, I_sc, which might be originated from the contrast between “frozen blob clusters” and holes in the drying gel. Decrease in I_sc was modeled using Rayleigh's equation, where drying times with various exponents were found to be proportional to the volume of frozen blob clusters. It was observed that the radius of frozen blob cluster (correlation length), ξ_c increased in various power of time, depending on Bis contents during drying of gels. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1898–1906, 2001     

ESR studies of molecular motions at the interphase region of a blendlike polymeric material

The molecular motions of spin probes at the interphase region of poly(methyl methacrylate) particles sterically stabilized by polyisobutylene (PIB) were studied by ESR spectroscopy. The correlation times (τ) were measured by using the methods of Freed and Kivelson. Activation energies for different modes of motion were calculated at wide temperature range between ?140 and 140°C. Viscosities were estimated in methanol saturated PIB channels in the polymer particles. © 1994 John Wiley & Sons, Inc.     

Drying process in vapor swollen heterogels

Disk-shaped heterogels were prepared by combining methyl methacrylate (MMA) and styrene (S) with ethylene glycol dimethacrylate (EGDM) as a crosslinker agent in the presence of 2,2′-azobisisobutyronitrile (AIBN). Swelling experiments were performed under chloroform vapor and the swollen gels are then allowed to dry under room temperature. Gravimetric technique was used to study drying processes. It is observed that two different regimes are present in the drying processes of these heterogels. Fickian diffusion model was used to determine desorption coefficients for each drying step in both regimes. Desorption coefficients, D _d, of heterogels were found to be strongly correlated with the mixture composition of polymeric materials in the heterogel system for both regimes. Heterogels with high S content dry much slower than the heterogels with low S content.     

Cation effect on gel – sol transition of kappa carrageenan

The steady state fluorescence (SSF) technique was employed to study gel – sol transitions of kappa carrageenan in NaCl, KCl and CaCl₂ solutions. Pyranine was used as a fluorescence probe for monitoring these transitions. Scattered light, I_sc and fluorescence intensity, I was monitored against temperature to determine the gel - sol (T_gs) transition temperatures and exponents. It was observed that T_gs values are strongly correlated to the NaCl, KCl and CaCl₂ contents. The weight average degree of polymerization, DP_w and gel fraction G, exponents (γ and β) were measured and found to be in accord with the classical Flory–Stockmayer Model.     

Studies on drying and swelling of PAAm‐NIPA composites in various compositions

The steady‐state fluorescence technique was introduced for studying the drying and swelling of disc‐shaped PAAm‐NIPA composites. Disc‐shaped gels were formed with various acrylamides (AAm) and N‐isopropylacrylamides (NIPA) by free radical crosslinking copolymerization in water. Composites were prepared with pyranine (Py) doped as a fluorescence probe. Scattered light, I_sc, and fluorescence intensities, I, were monitored during drying of these gels. The fluorescence intensity of pyranine increased and decreased as drying and swelling time increased respectively for all samples. The Stern‐Volmer equation combined with moving boundary and Li‐Tanaka models were used to explain the behavior of I during drying and swelling, respectively. It was found that the desorption coefficient, D, increased as NIPA contents were increased for a given temperature during drying. However, the cooperative diffusion coefficient, D₀, increased as NIPA contents were decreased during swelling at a given temperature. Supporting gravimetrical and volumetric experiments were also carried out during drying and swelling of PAAm‐NIPA composites. It was observed that NIPA contents affect the drying and swelling process. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Damage avoidance design of special truss moment frames with energy dissipating devices

An innovative concept using energy dissipating devices, such as buckling restrained braces (BRB), is proposed for special truss moment frames (STMF). The configuration of the proposed system consists of pins introduced at the ends of the top and bottom chord elements of the special segments. Subsequently, energy dissipating devices are used in the form of diagonal braces inside the special segments. An energy-based design methodology is adopted such that the BRBs are designed to provide sufficient energy dissipation capacity with respect to seismic input energy demand on the structure. This energy-based methodology is demonstrated to be accurate by means of a series of nonlinear time-history analyses. The overall seismic response of the proposed system is contrasted with the conventional STMF in terms of story displacements, interstory drifts, story shears and overturning moments, as well as observed damage to structural elements. The proposed system leads to more predictable seismic response and would potentially allow lighter construction and significant cost savings, due to significantly reduced member forces (up to 50% compared with conventional design). Furthermore, damage to structural elements is largely mitigated, hence allowing damage avoidance design of STMFs.