Soft and Hard Adhesion

The force needed to pull a cylindrical stud from a soft elastomeric film depends on their elastic and geometric properties. For a rigid stud and a thick elastomeric film, the pull-off stress (σ) depends on the elastic modulus (E) of the film and the radius (a) of the stud as σ ～ (E/a)^1/2 (soft adhesion). However, when the film is very thin, the pull-off stress is significantly higher than the case with thick films, and its value depends on the elastic modulus and the thickness (h) of the film as σ ～ (E/h)^1/2 (hard adhesion). Here, we study the pull-off behavior of a soft cylindrical stud, one flat end of which is coated with a high modulus thin baseplate. As the flexural rigidity of this baseplate is varied, we observe the transition between the two types of adhesion. We present a simple physical interpretation of the problem, which could be of value in understanding various biofouling and adhesive situations.     

Heat sealing of semicrystalline polymer films. II. Effect of melting distribution on heat-sealing behavior of polyolefins

Heat sealing of films, i. e., formation of a joint between two films by placing them fleetingly between heated platens, was experimentally investigated for a variety of semicrystalline polyolefins, especially various polyethlenes, to determine how sealing temperature affected seal strength measured at room temperature. Seal strength as a function of sealing temperature, SS(T), is closely related to the melting distribution of the polymer determined by DSC measurements, i. e., to the fraction of amorphous phase as a function of temperature, f_a(T). Seal initiation temperature, the temperature at which a specific, low level of seal strength of polyethylene films is achieved, corresponds to the temperature at which the fraction of amorphous phase equals 77±3%. At higher temperatures, SS(T) increases approximately as f_a(T) increases. At the final melting point of the polymer, i.e., when f_a(T) =1, seal strength reaches an approximately constant value termed the plateau seal strength. The magnitude of the plateau seal strength is determined by the yield stress of the polymer film. Thus, the heat-sealing curve, SS(T), for a polyethylene can be semiquantitatively predicted from the melting distribution and yield stress of the polymer. © 1994 John Wiley & Sons, Inc.     

Multiwavelength interferometry and competing optical methods for the thermal probing of thin polymeric films

Multiple‐wavelength interferometry (MWI), a new optical method for the thermal probing of thin polymer films, is introduced and explored. MWI is compared with two standard optical methods, single‐wavelength interferometry and spectroscopic ellipsometry, with regard to the detection of the glass transition temperature (T_g) of thin supported polymer films. Poly(methyl methacrylate) films are deposited by spin coating on Si and SiO₂ substrates. MWI is also applied to the study of the effect of film thickness (25–600 nm) and polymer molecular weight (1.5 × 10⁴ to 10⁶) on T_g, the effect of film thickness on the coefficients of thermal expansion both below and above T_g, and the effect of deep UV exposure time on the thermal properties (glass transition and degradation temperatures) of the films. This further exploration of the MWI method provides substantial insights about intricate issues pertinent to the thermal behavior of thin polymer films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4764–4774, 2006     

In situ AFM study of near‐surface crystallization in PET and PEN

The surface crystallization behavior of poly(ethylene terephthalate) (PET) and poly(ethylene 2,6‐naphthalate) (PEN) spin‐coated thin films was compared by means of atomic force microscopy (AFM) with an in situ heating stage. As the films were heated up stepwise, characteristic surface crystals appeared at a crystallization temperature (T_c) in the near‐surface region which is about 15 °C under the bulk T_c, and were replaced by bulk crystals when the temperature was increased to the bulk T_c. In the case of films whose thickness is less than 70 nm (PET) and 60 nm (PEN), significant increases in the bulk T_c were observed. Scanning force microscopy (SFM) force‐distance curve measurements showed that the glass transition temperature (T_g) of the near‐surface region of PET and PEN were 22.0 and 26.6 °C below their bulk T_g (obtained by DSC). After the onset of surface crystallization, edge‐on and flat‐on crystals appeared at the free surface of PET and PEN thin films, whose morphologies are very different to those of the bulk crystals. Although the same general behavior was observed for both polyesters, there are significant differences both the influence of the surface and substrate on the transition temperatures, and in morphology of the surface crystals. These phenomena are discussed in terms of the differences in the mobility of polymer chains near the surface. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44269.     

Free volume of liquids and polymers from internal pressure studies

The free volume, v_f, of liquids is defined in many ways. Comparison of solid and liquid behavior indicates that the definition for free volume in terms of the internal pressure of the liquid (?E/?V)_T, is physically reasonable. Application of the definition of free volume, v_f = RT/(?E/?V)_T, to polymethylenes, coupled with surface energy values, leads to an evaluation of both polymer segmental volume, ?_s, and free volume per segment, (v_f)_s, as a function of temperature. These equilibrium thermodynamic measurements of ?_s and (v_f)_s lead to an energy of activation for viscous flow in good agreement with viscosity studies. Information of this type could be of great use in considering many current problems in polymer flow such as the effect of pressure on viscosity.     

Influence of symmetry/asymmetry of the nanoparticles structure on the thermal stability of polyhedral oligomeric silsesquioxane/polystyrene nanocomposites

The thermal degradation of two polyhedral oligomeric silsesquioxane/polystyrene (POSS/PS) nanocomposites of formula R₈(SiO_1.5)₈ POSS/PS and R′₁R₇(SiO_1.5)₈ POSS/PS (where R′ = Phenyl and R = Cyclopentyl), at 5% of POSS concentration, was studied in both inert (flowing nitrogen) and oxidative (static air) atmospheres. Compounds were prepared by the polymerization of styrene in the presence of POSS. Degradations were carried out into a thermobalance, in the scanning mode, at various heating rates, and the obtained thermogravimetric (TG) curves were discussed and interpreted. The initial decomposition temperature (T_i), the temperature at 5% mass loss (T_5%), the glass transition temperature (T_g), and the activation energy (E_a) of degradation of nanocomposites were determined and compared with each other and with those of unfilled PS. The T_i, T_5%, and degradation E_a values of nanocomposites were higher than those of neat PS, thus indicating a better heat resistance and lower degradation rate, and then a better overall thermal stability. The use of POSS with a symmetric structure, in the synthesis of PS based nanocomposite, showed a decrease of T_g value not only in respect to asymmetric POSS/PS nanocomposite but also in respect to neat polymer, thus suggesting an influence of filler structure in the thermal properties of the materials. POLYM. COMPOS., 33:1903–1910, 2012. © 2012 Society of Plastics Engineers     

Photon transmission method for studying film formation from polstyrene latexes with different molecular weights

A photon‐transmission method was used to probe the evolution of transparency during film formation from polystyrene (PS) particles with different molecular weights. The latex films were formed at room temperature from the PS particles having two different average molecular weights and annealed at elevated temperatures in various time intervals above the glass transition (T_g). Onset temperatures (T_H) at given times (τ_H) for the optical clarity of films formed from low (LM) and high molecular (HM) weight PS particles were used to calculate the healing activation energies for the minor chains and found to be 22.0 ± 0.5 and 27.0 ± 0.6 kcal/mol, respectively. The increase in the transmitted photon intensity, I_tr, above the T_H was attributed to increase in the number of interfaces that disappeared. The Prager–Tirrell (PT) model was employed to interpret the increase in crossing density at the junction surface. The backbone activation energies (ΔE) were measured and found to be 127.8 ± 2.5 kcal/mol for a diffusing polymer chain across the junction surface for LM and HM latex films. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 866–874, 2000     

Impact of molecular mass on the elastic modulus of thin polystyrene films

Surface wrinkling was used to determine the elastic modulus at ambient temperature of polystyrene (PS) films of varying thickness and relative molecular mass (M_n). A range of M_n from 1.2 kg/mol to 990 kg/mol was examined to determine if the molecular size impacts the mechanical properties at the nanoscale. Ultrathin films exhibited a decrease in modulus for all molecular masses studied here compared to the bulk value. For M_n > 3.2 kg/mol, the fractional change in modulus was statistically independent of molecular mass and the modulus began to deviate from the bulk as the thickness is decreased below ≈50 nm. An order of magnitude decrease in the elastic modulus was found when the film thickness was ≈15 nm, irrespective of M_n. However, an increase in the length scale for nanoconfinement was observed as the molecular mass was decreased below this threshold. The modulus of thin PS films with a molecular mass of 1.2 kg/mol deviated from bulk behavior when the film thickness was decreased below ≈100 nm. This result illustrates that the modulus of thin PS films does not scale with molecular size. Rather, the quench depth into the glass appears to correlate well with the length scale at which the modulus of the films deviates from the bulk, in agreement with molecular simulations from de Pablo and coworkers [31] and recent experimental work [35].     

Structural relaxation of polystyrene in nanolayer confinement

The physical aging of polystyrene (PS) confined in a multilayered film arrangement was explored using differential scanning calorimetry (DSC). The multilayered films were produced via multilayer coextrusion and consisted of alternating layers of PS and polycarbonate (PC), with PS layer thicknesses ranging from 50 nm to 500 nm. A 125 μm bulk control film of pure PS was also extruded and studied for comparison. The glass transition temperatures (T_g) of the PS in multilayered films did not appear to be systematically dependent on layer thickness, and T_g values in all PS/PC films were similar to the bulk value of 104 °C. Two approaches were used to investigate the structural relaxation of PS in the layered films. In the first method, PS layers were aged isothermally at 80 °C after annealing above the T_g of PS (135 °C for 15 min) to reset the thermal history and provide a well-defined starting point for aging experiments. Recovered enthalpy data for aged films (calculated from DSC thermograms) showed that the aging rate in the PS layers decreased with decreasing layer thickness. Calculated aging rates were also compared with the fraction of interphase material (which increases significantly with decreasing layer thickness), and the decrease in aging rate for films with thinner layers was found to correlate with an increase in interphase fraction. The elevated T_g of the interphase material (compared to pure PS) was suggested as a possible reason for reduced aging rates in the thin PS layers. In the second method, PS layers were cooled from above their T_g at different rates under confinement by PC layers. After this cooling step was performed, subsequent heating thermograms revealed that the enthalpy recovered upon reheating through the T_g of PS was similar for bulk and nanolayered films.     

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.     

A surface acoustic wave (SAW) probe for the thermomechanical characterization of selected polymers

Specially designed surface acoustic wave devices may be used to examine the physical characteristics of the surfaces of thin polymer samples. Both cast films and thin film samples may be employed. The devices uniquely offer an opportunity to study: (1) very thin films, (2) surface-segregated materials, (3) the effect of diffusion of vapor into the surface region, and (4) simultaneous measurements of exterior surfaces of laminates. No special sample preparation is required. The T_g, T_m, T(alpha-c), and beta transitions observed agree with values taken with more complex, time-consuming apparatus.     

Structural relaxation in chalcogenide glasses

The structural relaxation of chalcogenide glasses is discussed within Tool–Narayanaswamy–Moynihan (TNM) formalism. The TNM parameters for more than 70 different glassy compositions are compared on the basis of the relaxation rate defined as R_f(ΔT) = −(dT_f/dlogt)_i at the inflection point of the isothermal relaxation curve plotted on a logarithmic timescale. The R_f(ΔT) depends on the TNM parameter ß and the parameter σ, combining the nonlinearity parameter x, the effective activation energy h^* or the fragility m. It is shown that R_f(10) estimated at 10 K below T_g is useful for the prediction of structural relaxation kinetics in different amorphous materials. The chalcogenide glasses are, for example, compared with oxide glasses and organic polymers. For all these materials, the R_f(10) versus σ plot shows a well-defined pattern that is thoroughly discussed.     

Thermooxidative decomposition and its kinetics on chlorinated natural rubber from latex

Thermooxidative decomposition and its kinetics on chlorinated natural rubber (CNR) from latex are studied by thermal gravimetry (TG) analysis and TG coupled with FTIR spectroscopy. The thermooxidative decomposition of CNR is a two‐step reaction. The first step is the reaction of dehydrochlorination of which the reaction order (n) is 1.1; the reaction activation energy (E) increases linearly with the increment of the heating rate (B), and the apparent activation energy (E₀) is 101.7 kJ/mol. The initial temperature of weight loss (T₀) is 1.29B + 248.7, the final temperature of weight loss (T_f) is 0.86B + 312.4, and the temperature at the maximum weight loss ratio (T_p) is 1.05B + 286.2. The decomposition ratio at T_p (C_p) is not affected by B, and its average value is 38%. The decomposition ratio at T_f (C_f) is also not affected by B, and its average value is 60%. The second step is an oxidative decomposition reaction of the molecular main chain. The value of n is 1.1, E increases linearly with the increment of B, E₀ is 125.0 kJ/mol, the relation between B and T is similar to that of the first step, and C_f approaches 100%. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1305–1309, 2001     

Examination of the influence of cooperative segmental dynamics on the glass transition and coefficient of thermal expansion in thin films probed using poly(n-alkyl methacrylate)s

The thermal behavior of thin films of a homologous series of poly(n-alkyl methacrylate)s supported on silicon substrates was probed using spectroscopic ellipsometry. Deviations from bulk behavior for the glass transition temperature (T_g) and coefficient of thermal expansion (CTE) were observed for films thinner than approximately 60 nm, consistent with most observations for confinement effects in polymer films. However, the extent of the decrease of CTE and the deviation in T_g are significantly influenced by the alkyl chain length. As the alkyl chain length is increased from methyl to n-octyl, the deviation from bulk behavior is significantly suppressed. This behavior is similar to that observed by Torkelson and coworkers (Physical Review Letters 2004; 92: 095702) for polystyrene films as small molecule diluents were added; this behavior was attributed to the decrease in size of the cooperative segmental dynamics, ξ_i(CRR), with addition of solvent. ξ_i(CRR) decreases as the alkyl chain length is increased; this is consistent with the hypothesis for the relationship between ξ_i(CRR) and confinement effects in thin polymer films. However, a two order of magnitude difference between the thickness of nanoconfinement onset and ξ_i(CRR) for poly(n-octyl methacrylate) results in uncertainty for ξ_i(CRR) as the origin of the nanoconfinement effect.     

A study on the optical properties of three‐armed polystyrene and poly(styrene‐b‐isobutyl methacrylate)

Atom transfer radical polymerization (ATRP) of three‐armed polystyrene[PS] and poly(styrene‐b‐isobutyl methacrylate)[PS‐b‐PiBμMA] were accomplished using an initiator with tri‐active C‐Br end group function and cuprous (I) bromide/2,2′‐bipyridyne catalytic system. The characterization obtained by FT‐IR, ¹H‐NMR, and GPC techniques. The average molecular weight and polydispersity of PS and PS‐b‐PiBμMA were determined as 19,800, 29,300 and as 1.37 and 1.15, respectively, which indicates that the constant concentration of growing chains are present throughout the polymerization. The refractive index and extinction coefficient of the samples were determined in the visible range as a function of wavelength. The refractive index dispersion curves of the thin films were fitted by the Cauchy‐Sellmeier model. The width of localized states (E_u) values changed inversely with optical band gaps (E_g) of the films. While the calculated E_u values of films for initiator, PS and PS‐b‐PiBμMA were determined as 2.72, 2.98, and 2.94 eV, the E_g values were determined as 3.43; 3.11, and 3.16 eV, respectively. The dispersion parameters of thin films were determined. These parameters changed in the investigated wavelength ranges. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Thermodynamic properties of methanol–benzene mixtures at elevated temperatures

The total pressure and the compositions of the vapour and liquid phases of the methanol–benzene system have been determined under equilibrium conditions at 100°, 120°, 140°, 160°, 180°, 200° and 220° for ten levels of concentration. The corresponding activity coefficients of methanol and benzene are reported; their values indicate that the equilibrium data are thermodynamically consistent. An azeotrope is found at all temperatures, its methanol content increasing as the temperature is increased. The relationship log P_az = 6·5098—(1,766/T) expresses the interdependence of the azeotrope vapour pressure P_az(lb/in² abs.) and temperature T(°K). Estimates of integral heat of mixing (H^E) and entropy change due to mixing (S^E) as functions of liquid composition (x_meth) have been made from the excess free energy of mixing G^E,(T) x_meth functions. Both H^E and S^E at a given x are positive increasing functions of temperature. These phenomena are discussed in terms of the dissociation of methanol ‘polymer’ and the formation of benzene–methanol ‘complexes’.     

Correlation between the mechanical and dielectric responses in polymer films by a fractional calculus approach

A fractional calculus approach was used to study the correlation between the complex elastic modulus and the complex relative permittivity for a polystyrene (PS) film with thickness of ~80 μm. Experimental measurements were carried out using dynamic mechanical analysis and dynamic dielectric analysis. Experimental results show the mechanical and dielectric manifestations of the main relaxation (glass transition process), whose molecular mobility was analyzed by two innovative models: a mechanical fractional model and a dielectric fractional model. Parameters of fractional models show that, when temperature increases, the molecular mobility of the main relaxation also increases, but the cooperativity of mobility decreases. Besides, molecular mobility is greater in the mechanical manifestation of the main relaxation than in the electric manifestation. From theoretical results obtained from fractional models for the isochronal mechanic storage modulus, E′(T) , and the isochronal relative permittivity, , a correlation model for mechanical and dielectric properties of PS film was obtained. This correlation model describes in function of E′(T) . These results suggest that this correlation model can be used to study molecular mobility of mechanical and dielectric dynamic properties of the polymer films samples and predict changes in their behavior by modifying ambient conditions.     

Structure of the epoxy–chelate metal-containing matrices: Theoretical aspects

A theoretical analysis has been carried out of the structure of metalliferous epoxy–chelate polymers (MECP) based on diglycidyl ether of bisphenol-A (DGEBA) hardened with metal complexes of the formula [M(L)_n(X)_p], where M is the cation of the transition metal; R, a nitrogen-containing ligand; X, the anion of an organic acid; n, the number of the ligands in the complex molecule (n = 1 or 2), and p, the metal valency (p = 2 or 3). On the basis of the correlations between the tensile strength (σ_t) and tensile modulus (E_t), and flexural strength (σ_f) and flexural modulus (E_f), of MECP, σ_t = f(E_t)and σ_f = f(E_f), and supposing that when the condition $ \sigma _{_{t_A } }= \sigma _{_{t_B } } ,{\rm}\sigma _{_{f_A } }= \sigma _{f_B } ,{\rm}E_{t_A }= E_{t_B } ,{\rm}E_{f_A }= E_{f_B } $ is fulfilled, where A and B are complex hardeners of different structures but of the same class, the epoxy–chelate matrices have similar structures. The influence of the structural fragments of the hardener molecule (the metal, ligand, and anion) on the polymer properties was evaluated and it was found out that the biggest contribution to these properties belongs to the metal, the alteration of which changes the thermal stability (ΔM is the polymer mass loss after thermal treatment in air), deformability (ε), σ_f, E_f, and deflection temperature (DT) significantly. By this, the effect of the hardener structure change on the alteration of the MECP properties is maximal for ΔM, is minimal for the compressive strength (σ_c), and decreases in the series: ΔM > ε > DT > σ_f > E_f > σ_c. The type of the anion affects σ_c significantly, but the ligand type contributes the least to the polymer properties. The obtained dependencies of the MECP properties on the structural fragments of the complex hardeners allow preliminary evaluation of the structure of the chelates and epoxy–chelate compositions necessary to produce epoxy polymers with required properties. The new method of the theoretical investigation of the effect of the structural fragments (method of TIESF) of the polymer matrix on the polymer properties can be used to analyze the structures of the polymers of other classes and to predict the optimal structures, promising the production of the materials with the optimal properties. © 1993 John Wiley & Sons, Inc.     

Use of a dynamic mechanical analyzer to study supported polymers

The real and imaginary parts of the complex modulus of polymers which must be supported can be determined with the Du Pont Dynamic Mechanical Analyzer. Polymer coatings of equal thickness are laminated on both sides of a thin metal sheet. The flexural modulus of the laminate is given by E = E₁X³ + E₂(1 ? x³) where E₁ and E₂ are the moduli of the metal and the polymer, respectively, and x is the thickness fraction of metal. Under some conditions, the dynamic viscosity of the polymer can also be determined.     

How the infrared radiation affects the film formation process from latexes?

In this study, the effect of the infrared radiative heating (IRH) was investigated on the film formation from composites of polystyrene (PS) latex particles and poly vinyl alcohol (PVA). The films were prepared as a pure PS and a mixture of PS and PVA particles at equal compositions at room temperature and they were annealed at elevated temperatures above the glass transition temperature (T_g) of PS for 10 min by using IRH technique. Identical experiments were performed by using standard convectional heating technique in oven as comparison. It was shown that the activation energy for the film formation from PS latex particles decreased considerably in IRH annealing technique. Photon transmission (PT) and steady state fluorescence (SSF) techniques were used to monitor the film formation process at each sintering step. Minimum film formation temperature, T_o, and healing temperature, T_h, were determined by the data obtained from the SSF and the PT measurements for each heating processes. The film formation was modeled as a void closure and as an interdiffusion stage below and above T_h, respectively. Scanning electron microscopy (SEM) was used to examine the variation in morphological structure of annealed composite films. It was observed that IRH heating causes more homogenous and more flat film surface than films annealed in the oven. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43289.