Time evolution of film formation from polystyrene particles: a percolation approach

This work reports the film formation process from surfactant-free polystyrene (PS) latex particles. Steady state fluorescence and photon transmission techniques were used to study the evolution of film formation. The films were prepared from fluorescein (F)-labeled PS latex particles at room temperature and annealed in 2.5-min-time intervals above the glass transition temperature (T _g) of PS. Fluorescence intensity (I _F) from F was measured after each annealing step to monitor the stages of film formation. Evolution of transparency of latex films was monitored by using the photon transmission intensity, I _tr. Drastic increase in I _tr and I _F above the critical annealing times, t _r and t _c, respectively, were attributed to the percolation behavior of the PS material. Critical exponents, β, of percolation clusters were measured and found to be around 0.31 and 0.37 for I _tr and I _F measurement, respectively, which were attributed to the site percolation model.     

Void closure and interdiffusion processes during latex film formation from surfactant-free polystyrene particles: a fluorescence study

This study reports a steady state fluorescence (SSF) technique for studying film formation from surfactant-free polystyrene (PS) latex particles. The latex films were prepared from pyrene (P)-labeled PS particles at room temperature and annealed at elevated temperatures for 5-, 10-, 20-, and 30-min time intervals above the glass transition (T(g)) temperature of polystyrene. During the annealing processes, the transparency of the film changed considerably. Scattered light (I(sc)) and fluorescence intensity (I(0P)) from P were measured after each annealing step to monitor the stages of film formation. Evolution of transparency of latex films were monitored using photon transmission intensity, I(tr). Scanning electron microscopy (SEM) was used to detect variation in the physical structure of annealed films. Onset temperature for film formation, T(0), void closure, T(v), and healing temperatures, T(h), were determined and corresponding activation energies were measured. Void closure and interdiffusion stages were modeled and related activation energies were determined.     

A photon transmission study for film formation from poly(vinyl acetate) latex particles with different molecular weights

The photon transmission technique was used to monitor the temperature evolution of film formation from poly(vinyl acetate) (PVAc) latex particles with two different molecular weights. Two sets of latex films were prepared below the glass transition temperature (T_g) of PVAc, which are named as low (LM) and high molecular weight (HM) films. These films were annealed at elevated temperatures above the T_g of PVAc for various time intervals. It is observed that transmitted photon intensity (I_tr) from these films increased as the annealing temperature was increased. Onset temperatures (T_H) at given times (τ_H) for starting the optical clarity of LM and HM films were measured and used to calculate the healing activation energies (ΔH) for the PVAc minor chains, and found to be as 28.1 kcal/mol and 27.7 kcal/mol, respectively. The increase in the transmitted photon intensity, I_tr above T_H was attributed to the increase in the number of disappeared interfaces between the deformed latex particles. Prager–Tirrell (PT) model was employed to interpret the increase in the crossing density of chains at the junction surfaces. The interdiffusion (backbone) activation energies (ΔE) were measured and found to be 177.5 kcal/mol and 210.7 kcal/mol for a diffusing PVAc chains across the junction surface of LM and HM latex films, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2918–2925, 2007     

Film formation stages for poly(vinyl acetate) latex particles: a photon transmission study

Photon transmission technique was used to monitor the evolution of transparency during film formation from poly(vinyl acetate) (PVAc) latex particles. The latex films were prepared below the glass transition temperature (T _g) of PVAc. These films were annealed at elevated temperatures in various time intervals above the T _g of PVAc. It is observed that transmitted photon intensity (I _tr) from these films increased as the annealing temperature is increased. It is seen from I _tr curves that there are two film formation stages. These successive stages are named void closure (viscous flow) and interdiffusion. The activation energies for viscous flow (ΔH) and backbone motion (ΔE _b) were obtained by using well-defined models. The averaged values of the backbone (ΔE _b) and the viscous flow activation energies (ΔH) were found to be 188.6 and 5.6 kcal/mol, respectively. The minimum film formation (τ _M,T _M) and healing points (τ _H,T _H) were determined. Minimum film formation (ΔE _M) and healing activation energies (ΔE _H) were measured using these time–temperature pairs. ΔE _M and ΔE _H were found to be 32.5 and 28.3 kcal/mol, respectively.     

Nanostructured latexes made by a sequential multistage emulsion polymerization

A series of linear and lightly crosslinked nanostructured latices was prepared by a sequential multistage semicontinuous emulsion polymerization process alternating styrene (S) and n‐butyl acrylate (BA) monomer feeds five times, that is ten stages, and vice versa, along with several control latices. Transmission electron micrographs of the RuO₄‐stained cross sections of nanostructured and copolymer latex particles and films showed that their particle morphologies were not very different from each other, but the nanostructured latex particles were transformed into a nanocomposite film containing both polystyrene (PS) and poly(n‐butyl acrylate) (PBA) nanodomains interconnected by their diffuse polymer mixtures (i.e. interlayers). The thermal mechanical behaviors of the nanostructured latex films showed broad but single T_gs slightly higher than those of their counterpart copolymer films. These single T_gs indicated that their major component phases were the diffuse interlayers and that they behaved like pseudopolymer alloys. The minimum film formation temperatures of nanostructured latices capped with PBA and PS, respectively, were 15 °C lower than and equal to those of their counterpart copolymer latices, but their T_gs were about 10 °C higher. Consequently, nanostructured latices enabled us to combine good film formation with high strengths for adhesives and coatings applications. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2826–2836, 2006     

Ceramic encapsulated latex composites

This work reports the encapsulation of latex particles in Al2O3-polystyrene (PS) composite films. These films were prepared from PS particles in Al2O3 dispersion at room temperature in various latex contents. Composite films were annealed at elevated temperatures in 10 min time interval above the glass transition temperature (Tg) of polystyrene. Transmitted photon intensities, I(tr) were monitored after each annealing step. AFM micrographs were also used to observe the physical changes of the composite films during annealing. It was observed that latex particles are encapsulated above a critical Al2O3 content of 33 wt% which corresponds to the critical occupation probability of p(c) = 0.33 at which the film obey the site-percolation model with a critical exponent of 0.45. Below p(c), it was seen that complete latex film formation process took place, where transparency of the film was increased by annealing.     

Film Formation from Nanosized Copolymeric Latex Particles: A Photon Transmission Study

The photon transmission technique was used to monitor the evolution of transparency during film formation from nanosized copolymeric latex particles. The latex films were prepared from poly(methyl methacrylate-co-butyl methacrylate) (P(MMA-co-BMA)) particles which were produced by microemulsion polymerization. These films were annealed at elevated temperatures in various time intervals above the glass transition temperature (T(g)) of P(MMA-co-BMA). It is observed that the transmitted photon intensity (I(tr)) from these films increased as the annealing temperature increased. There are three different film formation stages. These stages are explained by the void closure, healing, and interdiffusion processes, respectively. The activation energies for viscous flow (DeltaH approximately 16 kcal/mol), minor chains (DeltaE(H) approximately 27 kcal/mol), and backbone motion (Delta E(b) approximately 132 kcal/mol) were obtained using various models. Void closure (tau(v), T(v)) and healing points (tau(H), T(H)) were determined. Using the time-temperature pairs, void closure and healing activation energies were measured and found to be 21 and 30 kcal/mol, respectively. Copyright 2001 Academic Press.     

Reversible film formation from nano-sized PNIPAM particles below glass transition

Reversible film formation process from nano-sized Poly(N-isopropylacrylamide) (PNIPAM) microgel particles were studied during heating-cooling cycles at various rates. Photon transmission technique was used and transmitted photon intensity I _tr was monitored during heating–cooling cycles. The increase and decrease in I _tr during heating and cooling was explained with the void closure and void reconstruction processes, and the corresponding activation energies were measured. It was observed that PNIPAM microgels required less energy during reconstruction of voids than their closure.     

Effect of end group chemistry on surface molecular motion of monodisperse polystyrene films

The surface molecular motion of monodisperse polystyrene (PS) with various chain end groups was investigated on the basis of temperature‐dependent scanning viscoelasticity microscope (TDSVM). The surface glass transition temperatures, T_g^ss for the proton‐terminated PS (PS‐H) films with number‐average molecular weight, M_n of 4.9k–1,450k measured by TDSVM measurement were smaller than those for the bulk one, with corresponding M_ns, and the T_g^ss for M_n smaller than ca. 50k were lower than room temperature (293 K). In the case of M_n = ca. 50k, the T_g^ss for the α,ω‐diamino‐terminated PS (α,ω‐PS(NH₂)₂) and α,ω‐dicarboxy‐terminated PS (α,ω‐PS(COOH)₂) films were higher than that of the PS‐H film. On the other hand, the T_g^s for the α,ω‐perfluoroalkylsilyl‐terminated PS (α,ω‐PS(SiC₂C^F₆)₂) film with the same M_n was much lower than those for the PS films with all other chain ends. The change of T_g^s for the PS film with various chain end groups can be explained in terms of the depth distribution of chain end groups at the surface region.     

Effect of Molecular Weight on Packing during Latex Film Formation

A UV-visible technique is used to study the evolution of transparency during film formation from latex particles. Latex particles with high and low molecular weight (HM and LM) polymethyl methacrylate (PMMA) are used to prepare films. Two sets of films with different latex content were prepared from HM and LM particles separately, by annealing PMMA particles above the glass transition temperature. Transmitted photon intensity, I(tr), from HM and LM films increased as the annealing temperature was increased. The increase in the transmitted photon intensity is attributed to the latex content (film thickness) for the annealed film samples. It is suggested that as the latex particles are packed (film thickness is increased) fewer voids or cracks are formed in the films. Positive and negative absorption coefficients are measured below and above 210 and 180 degrees C annealing temperatures for the HM and LM films. Packing coefficients are obtained for films in various latex contents. It is observed that LM particles are packed much easier than HM particles. Copyright 2001 Academic Press.     

Effect of residual water and free volume on the glass‐transition temperature and heat capacity in polystyrene/poly(vinyl acetate‐co‐butyl acrylate) structured latex films

The dynamic heat capacity and glass‐transition temperature of polystyrene (PS)/poly(vinyl acetate‐co‐butyl acrylate) (VAc–BA) (50:50 w/w) structured latex films as a function of annealing time at 70, 77, and 85 °C were examined with modulated‐temperature differential scanning calorimetry. The PS and poly(vinyl acetate‐co‐n‐butyl acrylate) components were considered to be the cores and shells, respectively, in the structured latex. The dynamic heat capacity decreased with time. The glass‐transition temperatures of the PS and VAc–BA phases shifted to higher values after annealing. The results of thermogravimetry showed that there existed about 1.8% residual water in the films. The mean free volume and relative concentration of holes at room temperature (before and after annealing) and 85 °C, as a function of time, were obtained with positron annihilation lifetime spectroscopy (PALS). The PALS results indicated no significant change in free volume during annealing. It is believed that the loss, by diffusion, of residual water mainly caused a decrease in heat capacity and an increase in the glass‐transition temperatures. As little as 1.8% residual water in the structured latex films had a significant influence on the thermal properties. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1659–1664, 2001     

Interdiffusion of polymer chains during latex coating

The fluorescence method was used to study the interdiffusion of polymer chains during annealing of latex above its glass transition temperature (T_g). The latex film was prepared from mixture of naphthalene (N) (donor) and pyrene (P) (acceptor)-labeled poly(methyl methacrylate) (PMMA) latex particles. Heptane was used as the coalescent agent. A steady-state fluorescence technique was employed to measure the amount of direct nonradiative energy transfer from N to P during the interdiffusion of polymer chains across the particle–particle junction. Various latex films with different latex contents were used to measure the percentage critical occupation for the reliable steady-state fluorescence measurements. Diffusions 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.     

Effect of nanoscale confinement on the glass transition temperature of free-standing polymer films: Novel,self-referencing fluorescence method

The effect of nanoscale confinement on the glass transition temperature, T_g, of freely standing polystyrene (PS) films was determined using the temperature dependence of a fluorescence intensity ratio associated with pyrene dye labeled to the polymer. The ratio of the intensity of the third fluorescence peak to that of the first fluorescence peak in 1-pyrenylmethyl methacrylate-labeled PS (MApyrene-labeled PS) decreased with decreasing temperature, and the intersection of the linear temperature dependences in the rubbery and glassy states yielded the measurement of T_g. The sensitivity of this method to T_g was also shown in bulk, supported PS and poly(isobutyl methacrylate) films. With free-standing PS films, a strong effect of confinement on T_g was evident at thicknesses less than 80–90 nm. For MApyrene-labeled PS with M_n = 701 kg mol⁻¹, a 41-nm-thick film exhibited a 47 K reduction in T_g relative to bulk PS. A strong molecular weight dependence of the T_g-confinement effect was also observed, with a 65-nm-thick free-standing film exhibiting a reduction in T_g relative to bulk PS of 19 K with M_n = 701 kg mol⁻¹ and 31 K with M_n = 1460 kg mol⁻¹. The data are in reasonable agreement with results of Forrest, Dalnoki-Veress, and Dutcher who performed the seminal studies on T_g-confinement effects in free-standing PS films. The utility of self-referencing fluorescence for novel studies of confinement effects in free-standing films is discussed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2754–2764, 2008     

Effect of sample preparation on the glass‐transition of thin polystyrene films

We have investigated the effect of sample preparation on the glass‐transition temperature (T_g) of thin films of polystyrene (PS). By preparing and measuring the glass‐transition temperature T_g of multilayered polymer films, we are able to assess the contribution of the spincoating process to the reduced T_g values often reported for thin PS films. We find that it is possible to determine a T_g even on the first heating cycle, and that by the third heating cycle (a total annealing time of 15 min at T = 393 K) the T_g value has reached a steady state. By comparing multilayered versus single layered films we find that the whole T_g depends only on the total film thickness, and not on the thickness of the individual layers. These results strongly suggest that the spincasting process does not contribute significantly to T_g reductions in thin polymer films. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4503–4507, 2004     

Morphology and film formation of poly(butyl methacrylate)–polypyrrole core–shell latex particles

 Core–shell latex particles made of a poly(butyl methacrylate) (PBMA) core and a thin polypyrrole (PPy) shell were synthesized by two-stage polymerization. In the first stage, PBMA latex particles were synthesized in a semicontinuous process by free-radical polymerization. PBMA latex particles were labeled either with an energy donor or with an energy acceptor, in two different syntheses. These particles were used in a second stage as seeds for the synthesis of the core–shell particles. The PPy shell was polymerized around the PBMA core latex in an oxidative chemical in situ polymerization. Proofs for the success of the core–shell synthesis were obtained using nonradiative energy transfer (NRET) and atomic force microscopy (AFM). NRET gives access to the rate of polymer chain migration between adjacent particles in a film annealed at a temperature above the glass-transition temperature T _g of the particles. Slower chain migration of the PBMA polymer chains was obtained with the PBMA–PPy core–shell particles compared to rate of the PBMA polymer chain migration found with the pure, uncoated PBMA particles. This result is due to the coating of PBMA by PPy, which hinders the migration of the PBMA polymer chains between adjacent particles in the film. This observation has been confirmed by AFM measurements showing that the flattening of the latex film surface is much slower for the core–shell particles than for the pure PBMA particles. This result can again be explained by the presence of a rigid PPy shell around the PBMA core. Thus, these two complementary methods have given evidence that real core–shell particles were synthesized and that the shell seriously hinders film formation of the particles in spite of the fact that it is very thin (thickness close to 1 nm) compared to the size (750 and 780 nm in diameter) of the PBMA core. Transparency measurements confirm the results obtained by NRET and AFM. When the films are placed at a temperature higher than the T _g of PBMA, the increase in transparency is faster for films made with the uncoated PBMA particles than for films made with the coated PBMA particles. This result indicates again that the presence of the rigid PPy layer around the PBMA core reduces considerably the speed at which the structure of the film is modified when heated above the T _g of PBMA. Received: 02 September 1999 Accepted: 21 December 1999     

Interface characterization in latex blend films by fluorescence energy transfer

Immiscible polymer blend films were formed by air drying aqueous dispersions containing mixtures of a high-T_g latex, poly(methyl methacrylate), and a film-forming low-T_g latex, poly(butyl methacrylate-co-butyl acrylate). Fluorescence energy transfer experiments were used to characterize the interfaces in these films, in which one component was labeled with a donor dye and the other with an acceptor. The quantum efficiency of energy transfer (Φ_ET) between the donors and acceptors is influenced by the interfacial contact area between the two polymer phases. As the amount of soft component in the blend is increased, Φ_ET approaches an asymptotic value, consistent with complete coverage of the hard polymer surface with soft polymer. This limiting extent of energy transfer is very sensitive to the total surface area in the film, with correspondingly more energy transfer at constant volume fraction for small hard particles. Some of the details of the energy transfer are revealed through a fluorescence lifetime distribution analysis. The presence of ionic surfactant (sodium dodecyl sulfate) in the dispersion from which the latex blend film is prepared reduces the cross-boundary energy transfer by 30%, which implies that in these films the surfactant decreases the interfacial contact. After annealing the surfactant-free blends above 100°C, we observe an increase in energy transfer, consistent with a broader interface between the two polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1115–1128, 1998     

Glass transition of polymer/single-walled carbon nanotube composite films

The glass-transition temperatures (T_g's) of nanocomposites of polystyrene (PS) and single-walled carbon nanotubes were measured in the bulk and in thin films with differential scanning calorimetry and spectroscopic ellipsometry, respectively. The bulk T_g of the nanocomposites increased by approximately 3 °C and became much broader than that of PS. For the nanocomposite films thinner than 45 nm, T_g decreased with decreasing film thickness [i.e., ΔT_g(nano) < 0]. This phenomenon also occurred in thin PS films, the magnitude of the depression in PS [ΔT_g(PS)] being somewhat larger. The film thickness dependence and the differences in the magnitude of ΔT_g in the two systems were examined in light of current theory, and a quantitative comparison was made. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3339–3345, 2003     

A novel temperature‐step method to determine the glass transition temperature of ultrathin polymer films by liquid dewetting

A novel temperature‐step experimental method that extends the Bodiguel‐Fretigny liquid dewetting method of investigating polymer thin films is described and results presented from an investigation of thickness effects on the glass transition temperature (T_g) of ultrathin polystyrene (PS) films. Unlike most other methods of thin film investigation, this procedure promises a rapid screening tool to determine the overall profile of T_g versus film thickness for ultrathin polymer films using a limited number of samples. Similar to our prior observations and other literature data, with this new method obvious T_g depression was observed for PS thin films dewetting on both glycerol and an ionic liquid. The results for PS dewetting on the two different liquids are similar indicating only modest effects of the substrate on the T_g‐film thickness relationship. In both instances, the T_g depression is somewhat less than for similar PSs supported on silicon substrates reported in the literature. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1343–1349     

Chemical heterogeneity in emulsion copolymers of carboxylic monomers

Copolymer latices of butylacrylate (BA) with acrylic and methacrylic acid (AA and MAA) were prepared by batch type emulsion polymerization, and, for comparison, copolymers with identical monomer composition were prepared by batch type solution polymerization.The distribution of the carboxylic monomers in the latex particles and the serum was studied by density gradient and sedimentation experiments with the analytical ultracentrifuge. Dynamic mechanical measurements of films of these copolymers were used to determine the storage and loss moduli as a function of temperature. From these measurements the position and extension of the glass transition range on the temperature scale is obtained. For heterogeneous emulsion copolymers with two glass transition temperatures the distribution of the carboxylic monomer units in the different copolymer phases can be determined. Electron microscopy of ultra thin cross-sections of stained films gave further insight into the film morphology.The combination of the results obtained with the different methods gives rise to the following clues: In the BA/AA latices about 40% (by weight) of the total AA used in the recipe are found in the serum as a water soluble polymer, about 50% are found to increase the glass transition temperatureT _g of the bulk of the BA copolymer and, therefore, are thought to be incorporated into the interior of the latex particles, and the remaining 10% are, conclusively, located on the particle surface.In the BA/MAA latices no water soluble copolymer could be detected in the serum, about 90% of the MAA used is found in the bulk of the copolymer, and about 10% form a second hard phase on the surface of the latex particles.Dynamic mechanical measurements on the copolymer latex films show at least two phases with different glass transition temperatures: the bulk of the copolymer with a relatively low content of (M)AA units and a glass transition range at low temperatures, and a second (M)AA rich phase with a highT _g.The latter phase forms a honeycomb-like structure surrounding the packed latex particles. That results in a three-dimensional network of polymer with a highT _g extending throughout the latex film. In spite of the fact that this phase is built from a small fraction of the total copolymer only, it has a very pronounced influence on the performance behaviour of latex films.Dedicated to Professor Dr. R. Manecke on the occasion of his 70th birthday.     

Mechanical Properties and Orientation of Atactic Poly(methyl methacrylate): Sub‐Tg Annealing and Stereocomplex Formation

The mechanical properties and orientation behavior of atactic poly(methyl methacrylate) films cast from acetone (A‐aPMMA films) and chloroform (C‐aPMMA films), with subsequent sub‐T_g annealing, have been studied. The formation of a stereocomplex in sub‐T_g‐annealed A‐aPMMA films and C‐aPMMA films was demonstrated by means of differential scanning calorimetry. Stereocomplex in A‐aPMMA films is more pronounced than in C‐aPMMA films at each annealing temperature. It is proposed that stereocomplex formation can process at temperatures below T_g, leading to enhanced yield stress and higher orientation.