Solubility and diffusion in latex films formed from high glass transition temperature particles

In situ steady-state fluorescence measurements were used to study the dissolution of polymer films. These films were formed from pyrene labeled poly(methyl methacrylate) (PMMA) latex particles that were sterically stabilized by polyisobutylene. Annealing was performed above the glass transition temperature at 180°C at 1-h time intervals for film formation. Desorption of pyrene labeled PMMA chains was monitored in real time by the change of pyrene fluorescence intensity. Dissolution experiments were performed in various solvents with different solubility parameters, δ, at room temperature. Diffusion coefficients, D, in various solvents were measured and found to be around 10⁻¹⁰ cm²/s. A strong relation between D and δ was observed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1493–1502, 1998     

Real time monitoring of latex film dissolution by UVV technique

UV–visible (UVV) technique is used for monitoring of polymer film dissolution. These films are formed from pyrene (P)‐labeled poly(methyl methacrylate) (PMMA) latex particles, sterically stabilized by poly isobutylene (PIB, Annealing of films was performed above T_g at various temperatures for 30‐min time intervals. Diffusion of solvent molecules (chloroform) into the annealed latex film was followed by desorption of PMMA chains. Desorption of P‐labeled PMMA chains was monitored in real time by the absorbance change of P in the polymer–solvent mixture. A diffusion model with a moving boundary was used 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. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1075–1082, 2000     

Fluorescence technique to study thickness effect on dissolution of latex films

In situ steady‐state fluorescence (SSF) measurements were used for studying dissolution of Latex films in real time. Latex films with various thicknesses are formed from pyrene (P) labeled poly(methyl methacrylate) (PMMA) latex particles, sterically stabilized by polyisobutylene (PIB). Annealing of latex films were performed above T_g at 220°C temperature for 60 min. UV‐Visible (UVV) spectrometer was used to measure the transparency of latex films. It was observed that thicker films formed more opaque films than thinner films. Heptane (20%), chloroform (80%) mixture was used as a dissolution agent. Diffusion of pyrene labeled PMMA chains was monitored in real time by the change of pyrene fluorescence intensity, I_P in the polymer‐solvent mixture. Diffusion coefficients, D, and relaxation constants, k₀, of PMMA chains were measured and found to be strongly dependent on the latex films thicknesses. It is observed that thicker and opaque films dissolved much faster than the thinner and transparent films. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1087–1095, 2000     

The effect of solid content on latex coalescence and film formation: Steady-state energy transfer study with fluorescence labeled polymers

The steady-state fluorescence technique was used to examine the healing and interdiffusion of polymer molecules as a function of solid content during annealing of latex films above the glass transition (T_g). Films were prepared from a mixture of naphthalene (N)- and pyrene (P)-labeled poly(methy methacrylate) (PMMA) latex particles. Above T_g, interdiffusion of polymer chains was observed by detecting the steady-state energy transfer from excited naphthalene to pyrene molecules. Various latex films with different latex content were used to measure the critical occupation percent for the reliable steady-state fluorescence measurements. Diffusion activation energies in these latex films were measured and found to be around 30 kcal/mol, which was attributed to the backbone motion of PMMA chains. © 1996 John Wiley & Sons, Inc.     

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.     

Dissolution of latex films after γ‐ray treatment

Latex films were prepared by annealing pyrene (Py)‐labeled poly(methyl methacrylate) particles at glass‐transition temperature (100°C). These films were then irradiated by γ‐rays from ⁶⁰Co in a gamma cell at room temperature at the same dose rate (rad/h) for 30 min. Before dissolution films were annealed at elevated temperatures for a 30‐min time interval to complete the film formation process. Steady‐state fluorescence (SSF) technique were used to monitor the dissolution of these irradiated latex films. The dissolution of films in chloroform–heptane (80–20%) mixture was monitored in real time by the Py fluorescence intensity change. Relaxation constants k₀ and desorption coefficients D_d of polymer chains were measured. It was observed that both D_d and k₀ values first increased and then decreased by increasing the annealing temperature. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 129–137, 2002     

Percolation cluster on partially dissolving polymer film

Steady state fluorescence (SSF) technique was used for studying dissolution of UV-induced polymer films. These films are formed from poly(methyl methacrylate) (PMMA) chains labeled with pyrene (P) which was introduced as a fluorescence probe to monitor the dissolution processes. PMMA films in various ethylene glycol dimethacrylate (EGDM) content, cured by UV radiation, were dissolved in chlorofrom-heptane (20-80%) mixtures. Dissolution of the films were monitored in real-time by the P fluorescence intensity change in the solvent reservoir. It is observed that P intensity decreased dramatically above a critical EGDM content, which was atributed to the formation of a percolation cluster. The measured percolation threshold, (p_c=0.25) was found to be in accord with the bond percolation model. Desorption coefficients, D_d were measured for films prepared with various EGDM content and it was observed that D_d values are much lower above p_c than below p_c.     

Comparison of dissolution and mutual diffusion coefficients during dissolution of poly(methyl methacrylate) films

Steady state fluorescence measurements have been used for studying the dissolution of polymer films. These films are formed by free radical polymerization of methyl methacrylate (MMA) in which pyrene ( P_y ) was introduced as a fluorescence probe. Dissolution of poly(methyl methacrylate) (PMMA) films in chloroform–heptane mixtures were monitored in real-time by the P_y fluorescence intensity change. Dissolution coefficients D_d of P_y molecules were measured during dissolution of PMMA films, and found to be about 10⁻⁶ cm² s⁻¹. After dissolution, fluorescence quenching measurements were performed and the Stern–Volmer equation was employed to measure the mutual diffusion coefficients of heptane (D_h) and P_y (D_Py) molecules; these were found to be about 10⁻⁵ cm² s⁻¹. © 1999 Society of Chemical Industry     

Fluorescence and UV techniques for studying neck growth and equilibration processes during latex film formation

Steady state fluorescence (SSF) and UV–visible techniques have been used to study neck growth and equilibration processes during the coalescence of hard latex particles. Latex films were prepared separately by annealing pyrene (P_y) labelled and unlabelled poly(methyl methacrylate) (PMMA) particles above their glass transition temperature. During the annealing processes, the optical clarity of the films increased considerably. Direct fluorescence emission of excited pyrene from labelled latex films was monitored as a function of annealing temperature to detect this change. Void closure temperature (T_c) and time (t_c) were determined at the point where the fluorescence emission intensity became maximal. Below this point, the increase in fluorescence intensity (I_op) against temperature was used to determine the activation energy for viscous flow (ΔH≈47kcalmol⁻¹). The decrease in I_op above the void closure temperature was used to determine the backbone activation energy (ΔE≈44kcalmol⁻¹) for the interdiffusing chains. Unlabelled PMMA particles were used to prepare films for UV–vis measurements. The transmitted photon intensity (I_tr) from these films increased as the annealing temperature was increased. This behaviour was also used to determine the backbone activation energy (ΔE≈35kcalmol⁻¹) for the interdiffusing chains. © Society of Chemical Industry.     

Effect of molecular weight on the dissolution properties of polystyrene latex films

An in situ steady-state fluorescence (SSF) technique was applied in order to study the dissolution process of polystyrene (PS) latex films. The effect of the molecular weight M _w of the PS on the dissolution rate was investigated. The PS chains were copolymerized with (1-pyrene)methyl methacrylate in order to make use of pyrene (P) as a fluorescent probe to monitor the dissolution process. Seven different films were prepared from P-labeled PS latex dispersions with different molecular weights at room temperature. These films were then annealed at 200 °C for 15 min to complete the film formation process before dissolution. The dissolution of PS films in a toluene (70 %)–cyclohexane (30 %) mixture was monitored in real time by watching the change in the fluorescence intensity of P, I _P. We used a model that included both case I and case II diffusion kinetics to interpret the results of the dissolution experiments. The relaxation constants k ₀ and the dissolution coefficients D _d of the polymer chains were measured. Two different dissolution coefficients were obtained, which were attributed to the small and long polymer chains in the film, considering the high polydispersity of the polymer. It was also found that both of the D _d values scaled with M _w according to the law D _d ≈ M ^?n .     

Energy‐transfer method to study vapor‐induced latex film formation

Nonradiative energy transfer method was used to study latex film formation induced by organic solvent vapor. Seven different films with the same latex content were prepared separately from poly(methyl methacrylate) (PMMA) particles and exposed to ethyl benzene, toluene, chloroform, dichloromethane, tetrahydrofuran, and acetone vapor in seven different experiments. Energy‐transfer experiments were carried out between PMMA‐bound naphthalene (N) and pyrene (P) during vapor‐induced film formation. Latex films were prepared from equal amounts of N‐ and P‐labeled latex particles, and steady state spectra of N and P were monitored during film formation. It was observed that the P to N intensity ratio, I_P/I_N, increased as the vapor exposure time increased. The Prager–Tirrell (PT) model was employed to obtain back‐and‐forth frequencies, ν, of the reptating PMMA chains during latex film formation induced by solvent vapor. ν values were obtained and found to be correlated with the solubility parameter, δ. Polymer interdiffusion obeyed the t^1/2 law during film formation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 632–645, 2002; DOI 10.1002/app.10346     

Direct fluorescence technique to study evolution in transparency and crossing density at polymer–polymer interface during film formation from high-T latex particles

The Direct Fluorescence method was used to study the healing process during latex film formation above the glass transition temperature. The latex film was prepared from pyrene (P)-labeled poly(methyl methacrylate) (PMMA) particles. Heptane was used as a mixing agent. The steady-state fluorescence technique was employed to measure the density of polymer chains crossing the particle–particle interface. Various latex films with different latex content were used to study the transparency below and above the healing temperature. Crossing density was found to depend linearly on (time)^1/2, which was proposed by Prager and Tirrell. © 1996 John Wiley & Sons, Inc.     

Fast transient fluorescence technique (FTRT) for studying dissolution of polymer glasses

The fast transient fluorescence technique (FTRT) was used for studying the swelling and dissolution of a glassy polymer formed by free‐radical polymerization of methyl methacrylate (MMA). Anthracene (An) was introduced during polymerization as a fluorescence probe to monitor swelling and dissolution. Swelling and dissolution processes of disc‐shaped poly(methyl methacrylate) (PMMA) glasses in a chloroform–heptane mixture were monitored by measuring the fluorescence lifetimes of An from its decay traces. A method is developed for low quenching efficiencies for measuring lifetimes, τ, of An, and it was observed that τ values decreased as the dissolution process proceeded. Desorption, D, and mutual diffusion, D_m, coefficients of An molecules were measured during dissolution of PMMA and found to be around 5.4 × 10⁻⁶ (cm²/s) and 2.2 × 10⁻⁵ (cm²/s), respectively. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 948–957, 1999     

Molecular weight effect on polymer dissolution: a steady state fluorescence study

In situ steady state fluorescence (SSF) technique was used to study the dissolution of disc-shaped polymer glasses in various molecular weights, M_W. The glass discs were formed by free-radical polymerization of methyl methacrylate (MMA). Pyrene (P) was introduced during polymerization as a fluorescence probe to monitor the dissolution process in chloroform. Desorption of poly(methyl methacrylate) (PMMA) chains from discs were monitored simultaneously by observing the change of P fluorescence intensity, I. Diffusion model with a moving boundary was employed to quantify the fluorescence data observed from dissolving PMMA discs made at various molecular weights. It is observed that desorption coefficient, D decreased by increasing molecular weight, M_W by obeying D≈M⁻¹ law.     

Optical percolation and oxygen diffusion in poly(divinylbenzene) doped poly(methyl methacrylate) latex flms

A simple fluorescence technique is proposed for the measurement of the diffusion coefficient of oxygen into poly(methyl methacrylate) (PMMA) latex‐poly(divinylbenzene) (PDVB) composite films. Percolation model was used by using photon transmission (PT) technique to interpret the distribution of PDVB particles in PMMA lattice. Optical results were interpreted according to site percolation theory. The optical percolation threshold value and critical exponent were calculated as, R_c = 0.03 and, β = 0.34, respectively. PT measurements were performed for eight different PDVB content (0, 1.5, 3, 5, 10, 20, 40, and 60) wt%. Pyrene (P) functionalized PDVB cross‐linked spherical microspheres with diameters of 2.5 μm were synthesized by using precipitation polymerization technique followed by click coupling reaction. The diameter of the PMMA particles prepared by emulsion polymerization was in the range of 0.5–0.7 μm. PMMA/PDVB composite films were then prepared by physically blending of PMMA latex with PDVB microspheres at various compositions. The steady‐state fluorescence method was used to monitor oxygen diffusion into these (0, 5, 10, 20, and 40 wt%) latex films. Diffusion coefficients, D, of oxygen were determined by the fluorescence quenching method by assuming Fickian transport and were found to be increased from 1.8 × 10⁻¹¹ to 36.6 × 10⁻¹¹ cm² s⁻¹ with increasing PDVB content. This increase in D values was explained with formation of microvoids in the film by using PT technique. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers     

Film formation of poly (methyl methacrylate) latex with pyrene functional poly (divinylbenzene) microspheres prepared by click chemistry

This work reports on the application of steady state fluorescence (SSF) technique for studying film formation from poly(methyl methacrylate) (PMMA) latex and poly(divinylbenzene) (PDVB) microsphere composites. Pyrene (P) functionalized PDVB cross‐linked spherical microspheres with diameters of 2.5 μm were synthesized by using precipitation polymerization technique followed by click coupling reaction. The diameter of the PMMA particles prepared by emulsion polymerization were in the range of 0.5–0.7 μm. PMMA/PDVB composite films were then prepared by physically blending of PMMA latex with PDVB microspheres at various composition (0, 1, 3, 5, 10, 20, 40, and 60 wt%). After drying, films were annealed at elevated temperatures above T_g of PMMA ranging from 100 to 270°C for 10 min time intervals. Evolution of transparency of the composite films was monitored by using photon transmission intensity, I_tr. Monomer (I_P) and excimer (I_E) fluorescence intensities from P were measured after each annealing step. The possibility of using the excimer‐to‐monomer intensity ratio (I_E/I_P) from PDVB microparticles as a measure of PMMA latex coalescence was demonstrated. Diffusion of the PMMA chains across the particle–particle interfaces dilutes the dyes, increasing their separation. The film formation stages of PMMA latexes were modeled by monitoring the I_E/I_P ratios and related activation energies were determined. There was no observable change in activation energies confirming that film formation behavior is not affected by varying the PDVB composition in the studied range. SEM images of PMMA/PDVB composites confirmed that the PMMA particles undergo complete coalescence forming a continuous phase in where PDVB microspheres are dispersed. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Effects of annealing on morphology of polymer/polymer (PS/PMMA) blend; a fluorescence study

Steady state fluorescence (SSF) technique conjunction with optical microscopy were used to study the morphology of polystyrene (PS)/poly(methyl methacrylate) (PMMA) blend upon annealing above glass transition in elevated time intervals. The PS/PMMA blends were prepared from dissolution of pyrene (P) and naphthalene (N) labeled PS and PMMA particles, respectively. Monte Carlo simulations were performed to model the N and P fluorescence intensities (I_N and I_P), using photon diffusion theory. Number of N and P photons (N_N and N_P) emerging from the front surface of the blend are calculated when only N is excited, where N_P photons are combined of photons from radiative (N_PR) and nonradiative (N_PNR) energy transfer processes. Optical microscopy images were taken at each annealing step to support our findings from fluorescence measurements. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2104–2110, 2006     

Void closure by viscous flow during coalescence of hard latex particles

Steady state fluorescence (SSF) technique was used to study the void closure process during coalescence of hard latex particles. Latex films were prepared by annealing pyrene (P_y)-labelled poly(methyl methacrylate) particles above the glass transition temperature. During the annealing processes, the optical clarity of the film increased considerably. Direct fluorescence emission from excited pyrene was monitored as a function of annealing temperature to detect these changes. Scanning electron microscopy in conjunction with Monte Carlo simulations of photon diffusion in latex film were used to interpret the fluorescence results. Void Closure temperature (T_c) and time (t_c) were measured at the point at which the fluorescence emission intensity becomes maximum. This was associated with the longest optical path of a photon in latex film. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 651–659, 1997     

Solvent penetration and photoresist dissolution: A fluorescence quenching and interferometry study

A novel method, based upon fluorescence quenching measurements, is described for the study of the mechanistic details of solvent penetration into thin polymer films. Here poly(methyl methacrylate) (PMMA) labelled with phenanthrene (Phe) groups was coated as a film (0.8 μm thick) onto quartz disks. Diffusion of solvent (1 : 1 2-butanone/2-propanol) into the film was followed by a decrease in Phe fluorescence, while film dissolution was monitored simultaneously by laser interferometry. In the case of PMMA (M_w = 411,000, films annealed at 160°C) both processes occur at approximately the same rate and exhibit non-Fickian (relaxation-controlled) diffusion behavior. Correlating the results of these two experiments shows that, once the steady state is reached, the dissolution rate is controlled by the advance of the solvent front into the PMMA film. The “transition layer,” an important dissolution parameter, increases its thickness from 50 to 90 nm during the plasticization stage of solvent penetration and maintains its thickness until the solvent front reaches the quartz substrate.     

Fluorescence method of studying void closure kinetics during film formation from high-T latex particles

Void closure process due to viscous flow was studied during film formation from high-T latex particles. Steady-state fluorescence and photon transmission techniques were used to probe the evolution of optical clarity during film formation. The latex films were prepared from pyrene (P)-labeled poly(methyl methacrylate) particles and annealed in 10-min time intervals above glass transition temperature. Fluorescence intensity from P was measured after each annealing step. A relation for void closure time versus fluorescence intensity was derived, using the Vogel—Fulcher equation. Viscosity constant B was measured from the above relation and found to be as 11 × 10³ K. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 655–661, 1997