Enthalpy recovery and structural relaxation in layered glassy polymer films

Recent studies of physical aging in confined polymer glasses have revealed that aging behavior in confinement often differs from bulk behavior. This study used DSC to characterize physical aging and structural relaxation in bulk polysulfone (PSF) and co-extruded multilayered films of PSF and an olefin block copolymer (OBC) that have average PSF layer thicknesses of 640 nm, 260 nm, and 185 nm. The films were aged isothermally at 170 °C, and the recovered enthalpy upon reheating was measured over time. The films with 640 nm and 260 nm PSF layers had aging rates very similar to that of bulk PSF, while the film with 185 nm PSF layers had an aging rate slightly greater than the bulk value. The cooling rate dependence of the limiting fictive temperature (T_f′) in multilayered and bulk PSF samples was also characterized. Values of T_f′ were similar for all films at each cooling rate. The results of this work are in general agreement with our previous gas permeation aging study of multilayered PSF films aged at 35 °C, in which the effect of layer thickness on aging behavior was minimal. This stands in contrast to studies with thin, freestanding PSF films, which exhibit accelerated aging relative to bulk and have aging rates that depend strongly on film thickness.     

Physical aging of layered glassy polymer films via gas permeability tracking

The physical aging of polymers in confined environments has been an area of intensive study in recent times. The rate of physical aging in thin films of many polymers used in gas separation membranes is dependent on film thickness and accelerated relative to bulk. In this study, the physical aging of polymer films with alternating glassy polysulfone and rubbery polyolefin layers was monitored by measuring the gas permeability of O₂ and N₂ as a function of aging time at 35 °C. The alternating layer structures were formed by a melt co-extrusion process. The polysulfone layers have thicknesses ranging from 185 to 400 nm, and the overall thicknesses of the films are on the order of 80-120 μm. The aging of freestanding thin films of polysulfone is rapid and exhibits clear thickness dependence, whereas the aging of multilayered films was observed to be similar to bulk and showed no dependence on layer thickness. At 1000 h of aging time, a 400 nm freestanding PSF film decreased in O₂ permeability by 35%, whereas on average the bulk and multilayered films only experienced a decline of 10-15%. A slight increase in O₂/N₂ selectivity for the multilayered films was observed over the course of aging.     

Enthalpy relaxation of photopolymerized multilayered thiol‐ene films

Multilayered thiol‐ene network films with two and three different components were fabricated by spin coating and photopolymerization. The distinctive glass transition temperatures of each layer component were observed at corresponding glass transition regions of each bulk sample. Sub‐T_g aging of 10‐, 21‐, and 32‐layered thiol‐ene films was investigated in terms of enthalpy relaxation. Enthalpy relaxation of each layer component occurred independently and presented the characteristic time and temperature dependency. Overlapped unsymmetrical bell‐shaped enthalpy relaxation distribution having peak maximum at T_g‐10°C of each layer component was observed, resulting in broad distribution of enthalpy relaxation over wide temperature range. In addition, enthalpy relaxation of each layer component in the multilayered thiol‐ene films was significantly accelerated comparing to that of bulk thiol‐ene samples. Dynamic mechanical thermal properties of multilayered thiol‐ene films also showed two and three separated glass transition temperature. However, for 32‐layered thiol‐ene film consisting of three different layer components, glass transition and damping region are overlapped and the width is extended more than 100°C. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Study of the cooperativity at the glass transition temperature in PC/PMMA multilayered films: Influence of thickness reduction from macro- to nanoscale

In multilayered polymer films, the influence of thickness reduction on the glass transition temperature (T_g) and cooperatively rearranging region (CRR) size was investigated using temperature modulated differential scanning calorimetry (TMDSC). The materials used in this work are multilayered films comprising tens to thousands of alternating layers of two polymers, Bisphenol A Polycarbonate (PC) and polymethyl-methacrylate (PMMA) fabricated by layer multiplying coextrusion technique. The TMDSC measurements enable the calculation of the average values of CRR parameters at the dynamic glass transition temperature (T_g) using Donth’s method. The molecular mobility in each polymer is found to be altered in entirely different ways as the thickness of each component became thinner than 125 nm, whereby the polymers exist as two dimensional layers under those conditions. PC exhibits a drastic decrease in cooperativity volume at the glass transition while slight modifications are observed for PMMA. These observations are discussed in regard with the role of the large interface amount between the two different polymers and the evolution of the macromolecule conformations.     

Isothermal physical aging of thin PMMA films near the glass transition temperature

Isothermal physical aging and the glass transition temperature (T _g) of PMMA thin films were investigated by means of differential scanning calorimetry (DSC). Freestanding thin films of different molecular weights (M _w = 120,000, 350,000, 996,000 g/mol) and film thicknesses (40–667 nm) were obtained by spin coating onto a silicon wafer substrate and then releasing the coated film using a water floating technique. The thin films were stacked in a DSC pan and isothermally aged for different aging times (t _a = 1 and 12 h) and aging temperatures (T _a = 105, 110, and 115 °C) below but near T _g. Enthalpy relaxation (ΔH _Relax), resulting from the isothermal physical aging, initially increased with increasing ΔT (T _g − T _a, driving force of aging), reached a maximum value, and then decreased with further increase in ΔT. Below ~100 nm film thickness, ΔH _Relax of samples aged near their T _g (i.e., T _a = 110 and 115 °C) decreased with decreasing film thickness, indicating the suppression of physical aging. Up to 9.9 °C depression in T _g was observed for thinner films (~40 nm), when compared to the thicker films (~660 nm) in this study. The decrease in ΔH _Relax with decreasing film thickness at a given T _a appears to be associated with the reduction in T _g.     

Methacrylate-based polymer films useful in lithographic applications exhibit different glass transition temperature-confinement effects at high and low molecular weight

The effects of confinement on polymer films are important in applications related to photoresists. To optimize resolution, methacrylate polymers used in photoresists are often low molecular weight (MW). We use ellipsometry and fluorescence to study how the glass transition temperature (T_g) is affected by confinement in silica-supported films of low and high MW poly(1-ethylcyclopentyl methacrylate) (PECPMA) and poly(methyl methacrylate) (PMMA). With decreasing nanoscale thickness, T_g is nearly invariant for high MW (M_n = 22.5, 188 and 297 kg/mol) PECPMA but decreases for low MW PECPMA, with T_g – T_g,bulk = −7 to 8 °C in a 27-nm-thick film (M_n = 4.1 kg/mol) via ellipsometry and −15 °C in a 17-nm-thick film (M_n = 4.9 kg/mol) via fluorescence. Fluorescence studies using a 20-nm-thick dye-labeled layer in multilayer, bulk PECPMA films reveal a much greater perturbation to T_g in the free-surface layer for low MW PECPMA, which propagates tens of nanometers into the film. The effect of MW in single-layer monodisperse PMMA films is even more striking; T_g increases with confinement for high MW but decreases for low MW, with T_g – T_g,bulk = 9 °C in a 12-nm-thick film (nominal MW = 509 kg/mol) and −16 °C in a 17-nm-thick film (nominal MW = 3.3 kg/mol). The strong influence of MW on confinement effects in PECPMA and PMMA is in contrast to the previously reported invariance of the effect with MW in supported polystyrene films, reconfirmed here.     

Confined crystallization of nanolayered poly(ethylene terephthalate) using X-ray diffraction methods

The development of crystalline lamellae in ultra-thin layers of poly(ethylene terephthalate) PET confined between polycarbonate (PC) layers in an alternating assembly is investigated as a function of layer thickness by means of X-ray diffraction methods. Isothermal crystallization from the glassy state is in-situ followed by means of small-angle X-ray diffraction. It is found that the reduced size of the PET layers influences the lamellar nanostructure and induces a preferential lamellar orientation. Two lamellar populations, flat-on and edge-on, are found to coexist in a wide range of crystallization temperatures (T_c = 117–150 °C) and within layer thicknesses down to 35 nm. Flat-on lamellae appear at a reduced crystallization rate with respect to bulk PET giving rise to crystals of similar dimensions separated by larger amorphous regions. In addition, a narrower distribution of lamellar orientations develops when the layer thickness is reduced or the crystallization temperature is raised. In case of edge-on lamellae, crystallization conditions also influence the development of lamellar orientation; however, the latter is little affected by the reduced size of the layers. Results suggest that flat-on lamellae arise as a consequence of spatial confinement and edge-on lamellae could be generated due to the interactions with the PC interface.     

Glass Transition Behavior in Ultra-Thin Polystyrene Films

We have used ellipsometry to measure the glass transition temperature (T_g) of ultra-thin films of polystyrene (PS) (less than 20 nm thick) obtained by spin-casting from solution onto silicon substrates. We find that T_g in these ultra-thin films is depressed from the bulk value in qualitative accord with our earlier results on thicker films of PS. In films as thin as 8 nm, the depression from the bulk value of T_g is 35 K. We have also prepared ultra-thins by grafting PS-COOH on the native oxide of Si and by spin-casting PS-COOH onto Si. Here we have been able to measure the T_g of 5-nm films in which we find a T_g depression of 10 K. We tentatively ascribe the smaller value of T_g depression for these grafted chains to the constraining effect of the anchor.     

Observations of physical aging in a polycarbonate and acrylonitrile–butadiene–styrene blend

The effects of physical aging of a 75 : 25 PC/ABS blend have been studied using differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). From DSC, two distinct peak endotherms at about 90°C and 110°C, which are associated with the glass transition of ABS (T_g,ABS) and PC (T_g,PC) components, respectively, were observed. When progressive aging was monitored at 80°C for over 1000 h, the changes in enthalpic relaxation, glass and fictive temperatures for the blend followed similar trends to those already seen in the literature for PC aged between 125 and 130°C. The rate of enthalpy relaxation was also comparable. The plot of peak endotherm against logarithmic aging time for the PC blend constituent, however, behaved quite differently from the linear relationship known for highly aged PC. The ABS peak component also appeared to be insensitive to aging. Both observations were confirmed to be statistically significant using analysis of variance methods. Using temperature modulated‐DSC, there is evidence that aging increases the blend miscibility as the T_g,PC shifts toward the stationary T_g,ABS during aging. Parallel FTIR investigations found oxidation of butadiene during aging to be even at this relatively low temperature, forming hydroxyl and carbonyl degradation products. The presence of ABS in the blend also appeared to have prevented the shifting from the trans‐cis to trans‐trans arrangement of the carbonate linkage, which is a well‐known phenomenon during elevated temperature aging of PC alone. Moreover, the carbonate linkage appears to have been at the lower energy, trans‐trans, arrangement prior to the aging process. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Physical aging of thin glassy polymer films monitored by gas permeability

The physical aging at 35 °C of three glassy polymers, polysulfone, a polyimide and poly(2,6-dimethyl-1,4-phenylene oxide), has been tracked by measurement of the permeation of three gases, O₂, N₂, and CH₄, for over 200 days. Several techniques were used to accurately determine the thickness of films (∼400 nm-62 μm) in order to obtain absolute permeability coefficients and to study the effects of film thickness on the rate of physical aging. Each film was heated above the polymer T_g to set the aging clock to time zero; ellipsometry revealed that this procedure leads to isotropic films having initial characteristics independent of film thickness. A substantial pronounced aging response, attributed to a decrease in polymer free volume, was observed at temperatures more than 150 °C below T_g for thin films of each polymer compared to what is observed for the bulk polymers. The films with thicknesses of approximately 400 nm of the three polymers exhibit an oxygen permeability decrease by as much as two-fold or more and about 14-15% increase in O₂/N₂ selectivity at an aging time of 1000 h. The results obtained in this study were compared with prior work on thickness dependent aging. The effects of crystallinity on physical aging were examined briefly.     

Dynamics of the leveling process of nanoindentation induced defects on thin polystyrene films

Using Atomic Force Microscopy (AFM) we study the effect of nanoindentation induced defects on 50 and 120 nm thick unentangled polystyrene (PS) films, spin cast on silicon (Si) substrates. Indents with residual depths of penetration less than the film thickness level upon heating above the glass transition temperature (T_g) of bulk PS. The resulting leveling process is discussed in terms of a diffusion process driven by the curvature gradient. Calculated diffusivity values are close to the self-diffusivity of bulk PS.     

Physical aging of polystyrene films tracked by gas permeability

Most studies using gas permeation to characterize physical aging in thin polymer films have focused on polymers of interest as membrane materials, such as polysulfone (PSF) and Matrimid. Many other physical aging studies, using techniques other than gas permeation, focus on polystyrene (PS). In this work, physical aging in bulk PS films and PDMS-coated thin PS films was studied using well-established gas permeation techniques. The ～400 nm PS films aged slightly faster than bulk PS. However, the difference between rates of aging in thin and thick films was much less than that reported in PSF and Matrimid films of similar thicknesses. The ～800 nm films aged in a manner generally similar to bulk PS. Comparison of the normalized oxygen permeability of ～400 nm films of PS, PSF, and Matrimid revealed that a ～400 nm PS film experiences a slower decline in relative permeability than a PSF or Matrimid film does. Unlike what has been observed previously in studies of PSF and Matrimid films, PS films do not appear to show aging behavior that is strongly dependent on film thickness or highly accelerated relative to bulk. Because it would be difficult to use the results of PS aging studies to predict the aging behavior of typical gas separation polymers, we suggest that PS is not a good model for the aging behavior of commercially useful gas separation membrane materials.     

Erasure below glass‐transition temperature of effect of isothermal physical aging in fully cured epoxy/amine thermosetting system

The erasure below the glass‐transition temperature (T_g) of the effect of isothermal physical aging (at aging temperature T_a) in a fully cured epoxy/amine thermosetting system is investigated using the torsional braid analysis (TBA) dynamic mechanical analysis technique and the differential scanning calorimetry (DSC) technique. From the TBA temperature scans, the intensity of the localized perturbation of the moduli in the vicinity of the T_a (90°C), due to isothermal physical aging, is decreased by heating to below the T_g (T_g∞ = 177°C), indicating that the physical aging effect can be eliminated by heating to below the T_g. The isothermal aging effect in the vicinity of the T_a is almost completely eliminated by heating to 50°C above the T_a (i.e., 140°C); however, a competing aging effect occurs above T_a at higher temperatures during the heating. Erasure below T_g of the isothermal physical aging effect is inferred from DSC experiments from the diminished relaxation enthalpy in the vicinity of the T_g, which is measured from the difference in areas between the aged (T_a = 150°C) and deaged thermograms. A comparison of the TBA and DSC results is made. Implications on the heterogeneous nature of the amorphous glassy state of polymers are discussed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 396–404, 2001     

Aging and carbon dioxide plasticization of thin polyetherimide films

Industrial gas separation membranes have selective dense layers with thicknesses around 100 nm. It has long been assumed that these thin layers have the same properties as thick (bulk) films. However, recent research has shown that thin films with such thickness experience accelerated physical aging relative to bulk films and, thus, their permeation properties can differ significantly from the bulk. Thin films made from Extem^® XH 1015, a new commercial polyetherimide, have been investigated by monitoring their gas permeability. The permeability of the thin films is originally greater than the thick films but eventually decreases well below the permeability of the thick film. The CO₂ plasticization of Extem thin films is explored using a series of exposure protocols that indicate CO₂ plasticization is a function of film thickness, aging time, exposure time, pressure and prior history.     

Temperature- and thickness-dependent elastic moduli of polymer thin films

The mechanical properties of polymer ultrathin films are usually different from those of their counterparts in bulk. Understanding the effect of thickness on the mechanical properties of these films is crucial for their applications. However, it is a great challenge to measure their elastic modulus experimentally with in situ heating. In this study, a thermodynamic model for temperature- (T) and thickness (h)-dependent elastic moduli of polymer thin films E _f(T,h) is developed with verification by the reported experimental data on polystyrene (PS) thin films. For the PS thin films on a passivated substrate, E _f(T,h) decreases with the decreasing film thickness, when h is less than 60 nm at ambient temperature. However, the onset thickness (h*), at which thickness E _f(T,h) deviates from the bulk value, can be modulated by T. h* becomes larger at higher T because of the depression of the quenching depth, which determines the thickness of the surface layer δ.     

Physical aging in poly(methyl methacrylate)poly(styrene-co-acrylonitrile) blends. Part II: Enthalpy relaxation

An investigation of the effect of physical aging on excess enthalpy of compatible polymer blends was carried out. Poly(methyl methacrylate) (PMMA) and poly(styrene-co-acrylonitrile) (SAN) were chosen for this study. Blends of different ratios of PMMA and SAN were physically aged at different times and temperatures below their glass transition (T_g) and then subjected to enthalpy relaxation measurement in a differential scanning calorimeter (DSC). An improved procedure was developed and, employed to analyze the data. The error associated with the calculation of the normalized deviation in enthalpy, known as the “Φ” function, was below 4%. The relaxation was observed to proceed faster at higher aging temperature. It was also found that at higher aging temperatures of T_g – 20 and T_g– 35°C, enthalpy relaxation in SAN-rich blends proceeds faster than in PMMA rich blends, while at the low aging temperature of T_g– 50°C the rate of relaxation becomes independent of the composition.     

Physical aging of ultrathin glassy polymer films tracked by gas permeability

Membrane-based separations play a key role in energy conservation and reducing greenhouse gas emissions by providing low energy routes for a wide variety of industrially-important separations. For reasons not completely understood, membrane permeability changes with time, due to physical aging, and the rate of permeability change can become orders of magnitude faster in films thinner than one micron. The gas transport properties and physical aging behavior of free-standing glassy polysulfone and Matrimid^® films as thin as 18 nm are presented. Physical aging persists in glassy films approaching the length scale of individual polymer coils. The films studied ranged from 18–550 nm thick. They exhibited reductions in gas permeability, some more than 50%, after 1000 h of aging at 35 °C, and increases in selectivity. The properties of these ultrathin films deviate dramatically from bulk behavior, and the nature of these deviations is consistent with enhanced mobility and reduced T_g in ultrathin films. The Struik physical aging model was extended to account for the influence of film thickness on aging rate, and it was shown to adequately describe the aging data.     

Acid- and base-catalyzed epoxy-phenol thermosets from catechol,resorcinol and hydroquinone: A structure–property study

In order to better understand the design rules of epoxy–phenol thermosets we will report on the chemistry and (thermo)mechanical properties of cured epoxy–phenol thermoset films. Ortho-, meta- and para-isomers of dihydroxybenzene (DHB) were reacted with the diglycidyl ether of bisphenol A (DGEBA) in the presence of an acid catalyst or triphenylphosphine (PPh₃). The glass transition temperatures (T_g) of the cross-linked films decreases in the order of meta- (T_g = 115°C) > ortho- (T_g = 102°C) > para-DHB (T_g = 96°C) as measured by differential scanning calorimetry. Uniaxial tensile testing of cross-linked films showed excellent stress–strain behavior. The average ultimate strength values ranged from 65 to 82 MPa and the average values of the strain-at-break ranged from 4.8% to 6.9% at 25°C for all cross-linked films. When a PPh₃ was used, the network properties were profoundly different. The base catalyzed thermoset of DGEBA and meta-DHB shows a T_g of 85°C, which is 30°C lower than the T_g of the acid-catalyzed analog. Tensile films appear to be more ductile, as they exhibit a strain-at-break of 20%. The results of this study confirm that simple dihydroxybenzene hardeners can be used to prepare cross-linked films with excellent thermomechanical properties.     

Confinement, composition, and spin-coating effects on the glass transition and stress relaxation of thin films of polystyrene and styrene-containing random copolymers: Sensing by intrinsic fluorescence

The glass transition temperatures (T_gs) of polystyrene (PS) and styrene/methyl methacrylate (S/MMA) random copolymer films are characterized by intrinsic fluorescence, i.e., monomer fluorescence from an excited-state phenyl ring and excimer fluorescence from an excited-state dimer of two phenyl rings. The T_g is determined from the intersection of the rubbery- and glassy-state temperature dependences of the integrated fluorescence intensity measured upon cooling from an equilibrated state. With PS, the effects of nanoconfinement on T_g and the transition strength agree with results from studies using probe fluorescence and ellipsometry. The T_g-nanoconfinement effect is “tuned” by copolymer composition. As S-content is reduced from 100 mol% to 22 mol%, the confinement effect changes from a reduction to an enhancement of T_g relative to bulk T_g. Intrinsic fluorescence is also a powerful tool for characterizing relaxation of residual stresses. Stresses induced by spin coating affect local conformations, which in turn affect excimer and monomer fluorescence and thereby integrated intensity. The heating protocol needed to achieve apparently equilibrated local conformations is determined by equivalence in the integrated intensities obtained upon heating and subsequent cooling. While partial stress relaxation occurs upon heating in the glassy state, full relaxation of local conformations requires that a film be heated above T_g for times that are long relative to the average cooperative segmental relaxation time. For example, in thin and ultrathin films, equilibration is achieved by heating slowly (∼1 K/min) to 15-20 K above T_g. Dilute solution fluorescence of PS and S/MMA copolymers is also characterized and compared to reports in the literature.     

Dielectric and ferroelectric properties of multilayer BaTiO3/NiFe2O4 thin films prepared by solution deposition technique

In this work different lead-free multilayered structures, composed of perovskite BaTiO₃ and spinel NiFe₂O₄ thin layers, were obtained by solution deposition method. Structural characterization of the sintered thin films confirmed the well-defined layered structure with overall thickness from 160 to 600 nm, crystalline nature of perovskite BaTiO₃ and spinel NiFe₂O₄ phases without secondary phases (after sintering below 900 °C) and grains on nanometer scale. Dielectric properties of the multiferroic multilayer BaTiO₃/NiFe₂O₄ thin films were analyzed in temperature and frequency range from 30 °C to 200 °C and 100 Hz to 1 MHz, respectively. In comparison to the pure BaTiO₃ films, the introduction of ferrite layer reduces dielectric response and increases low frequency permittivity dispersion of the multilayer thin films. The multilayer samples have shown relatively low dielectric loss with stronger contribution of conductivity at higher temperatures, and characteristic broad peak representing “relaxation” of the interface charge accumulation.