Gas permeation of polymer blends. III. Poly(vinyl chloride) (PVC)/chlorinated polyethylene (CPE)

The permeability P, diffusivity D, and activation energy for diffusion, E_D, of He, O₂, N₂, and CO₂ were determined for blends of PVC/chlorinated polyethylene (CPE), where the chlorine content of the CPE components varied: 36 wt-% for CPE-1, 42 wt-% for CPE-2, and 48 wt-% for CPE-3. The difference in thermal expansion coefficients Δα above and below the glass transition temperature T_g of the polymers and the fractional free volume V_g of the polymers at their T_g were determined. Density and crystallinity measurements for the blends were also carried out as in the earlier work (Shur and Rånby, J. Appl. Polym. Sci., 19 , 1337 (1975)). Dynamic mechanical measurements of the blends were made using a torsion pendulum at about 1 Hz. P and D decreased, but E_D increased with increasing CI content of CPE in the blends. P and D for the blends showed no additivity. The permeability indicated phase inversion for blend compositions at about 10% of CPE-1 and CPD-2 by weight. The experimental and the calculated densities were largely the same for PVC/CPE-1 blends; but for PVC/CPE-2 and PVC/CPE-3 blends, the experimental values were higher than the calculated ones. The Δα and V_g values for PVC and the three CPE samples decreased with increasing CI content in the polymers. Dynamic mechanical measurements indicate that PVC/CPE-1 and PVC/CPE-2 blends form largely incompatible blends, while PVC/CPE-3 blends are compatible to some extent. There is some weak interaction between PVC and CPE-3 giving a low level of compatibility. The solubility of gases obtained from time-lag measurements of diffusion for 50/50 blends decreased for He, O₂, and N₂, but increased for CO₂ with increasing Cl content in CPE. The solubility of He, O₂ and N₂ shows a positive correlation with the Lennard-Jones force constant ?/k. However, a deviation from the linear relation between ?/k and In S was observed for CO₂ and the deviation became larger with increasing Cl content in CPE. The abnormally high solubility of CO₂ is probably due to the high polarizability of this gas. The heat of solution ΔH_s indicates that for He the sorption process may be a molecular slip process (endothermic), but for other gases the sorption may proceed by a dissolution process (exothermic). There is a large difference between the calculated solubility for the blends assuming incompatibility and the experimental values from time-lag measurements. This may partly be due to the uncertainty of sorption values obtained from the time-lag method and/or partly to changes of sorption modes by interaction between PVC and CPE in the blends. The resulting transport behavior of the blends is discussed on the basis of the free volume concept and of phase–phase interaction in the blends.     

Uptake of aromatic solvents by polyethylene films

The sorption properties of the solvents benzene, toluene, and xylene in polyethylene films at 40, 60, and 80°C were investigated. The diffusion coefficient increased with an increase in the sorption temperature for the solvents and was highest for xylene and least for benzene. The inability of xylene to show a definite order of the diffusion coefficients at the investigated temperatures was attributed to the presence of two methyl side groups in the molecule. The solubilities of the solvents in polyethylene increased with an increase in the sorption temperature, and the following order of the solubilities could be observed: xylene > toluene > benzene. The permeabilities of the solvents in polyethylene depended on the sorption temperature, and the following order of the permeabilities was observed: xylene > toluene > benzene. The calculated activation energies of sorption in polyethylene films were all positive; benzene had the highest energy of sorption, and xylene had the lowest. The calculated enthalpies of sorption (ΔH_S) were also positive for the three solvents and were in the following order: xylene > toluene > benzene. The calculated entropies of sorption (ΔS) were negative for the solvents and showed trends similar to the variation of ΔH_S among the solvents. The change in the Gibbs free energies of sorption (ΔG_S), evaluated with the expression ΔG_S = ΔH_S ? TΔS (where T is the Kelvin temperature), were all positive, and this was an indication of the nonspontaneity of the solubility of polyethylene in the aromatic solvents at 313 K. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3849–3854, 2007     

Sorption and diffusion of water into melamine–formaldehyde‐incorporated poly(vinyl acetate)–polyester nonwoven fabric composites

A series of composites were fabricated by impregnating a polyester nonwoven fabric with melamine–formol (MF)‐incorporated poly(vinyl acetate) (PVAc) latex. The effect of different weight ratios of MF/PVAc, i.e. 0/100, 5/100, 10, 100, 15/100 and 20/100 (dry, wt/wt), on the water sorption and diffusion into the composites was evaluated. Water sorption studies were carried out at different temperatures, i.e. 30, 50 and 70 °C, based on the immersion weight gain method. From the sorption results, the diffusion (D) and permeation (P) coefficients of water penetrant were calculated. A significant increase in the diffusion and permeation coefficients was observed with an increase in the temperature of sorption. Drastic reductions in diffusion and permeation coefficients were noticed with increasing MF content in the composites. Attempts were made to estimate the empirical parameters like n, which suggests the mode of transport, and K, a constant which depends on the structural characteristics of the composite in addition to its interaction with water. The temperature dependence of the transport coefficients was used to estimate the activation energy parameters for diffusion (E_D) and permeation (E_p) processes from Arrhenius plots. Copyright © 2006 Society of Chemical Industry     

Diffusion of benzene vapor in blends of poly(vinyl acetate) and poly(methyl acrylate)

Sorption and diffusion of benzene in miscible blends of poly(vinyl-acetate), PVAc, and poly(methyl acrylate), PMA, have been studied. The polymer-polymer interaction parameter values calculated from equilibrium vapor sorption data were all negative, indicating favorable interaction between the two polymers. The sorption of benzene vapor into these blends was measured at a temperature above the T_g's of the pure polymers and found to obey Fickian kinetics. The mutual diffusion coefficients were estimated from the initial slopes of the sorption curves. The concentration dependent diffusion coefficients were fitted to the empirical relation D = D_o exp(αC) which satisfactorily correlated the data. Values of the constant D_o were found to vary continuously with blend composition, while the α values did not. These experimental data were analyzed employing Fujita's free volume theory. It was found that the data was consistent with this theory. If the f_o values for the blends are assumed to be the weighted average of the component polymers, then the β parameter values for the blends also obey the additivity rule.     

Sorption and transport studies of water in Kapton polymide. I

Sorption isotherms and diffusion coefficients of water in a 0.3-mil Kapton polyimide film at 30, 45, and 60°C are reported. The data are well described by the dual mode sorption and transport models at low activities. At high penetrant activities, clustering of water is suggested by a Zimm–Lundberg analysis of the sorption data and the fact that the diffusion coefficient for water decreases with increasing external vapor activity. The effect of temperature on the diffusion coefficients at infinite dilution and the dual mode sorption parameters k_D, b, and C are presented and discussed. The magnitude of the activation energy of the diffusion coefficient at infinite dilution, 5.4 kcal/mol, is smaller than the corresponding activation energy in more flexible chain polymers, perhaps suggesting that rather small backbone motions are associated with diffusion of water through the Kapton matrix. The predictions for the isosteric enthalpy of sorption from the dual mode model are presented and compared with the values determined from graphical analysis of the sorption isotherms performed independently without reference to the dual mode sorption model.     

Castor oil‐based polyurethane–polyester nonwoven fabric composites: Mechanical properties,chemical resistance,and water sorption behavior at different temperatures

Castor oil‐based polyurethane (PU)–polyester nonwoven fabric composites were fabricated by impregnating the polyester nonwoven fabric in a composition containing castor oil and diisocyanate. The effects of different diisocyanates such as toluene‐2,4‐diisocyanate (TDI) and hexamethylene diisocyanate (HMDI) on the mechanical properties have been studied for neat PU sheets and their composites with polyester nonwoven fabric. Chemical resistance of the PU composites has been assessed by exposing the specimens to different chemical environments. Percentage water absorption of composites and neat PU sheets has been determined both at room temperature and in boiling water. Both TDI‐ and HMDI‐based PU composites showed a marginal improvement in tensile strength retention at 100°C heat ageing. Water sorption studies were carried out at different temperatures, viz, 30, 50, and 70°C, based on immersion weight gain method. From the sorption results, the diffusion (D) and permeation (P) coefficients of water penetrant have been calculated. Attempts were made to estimate the empirical parameters such as n, which suggests the mode of transport (non‐Fickian), and K, a constant which depends on the structural characteristics of the polymer in addition to its interaction in boiling water. The temperature dependence of the transport coefficients has been used to estimate the activation energy parameters for diffusion (E_D) and permeation (E_p) processes from Arrhenius plots. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effect of poly(vinyl chloride)/chlorinated polyethylene blend composition on thermal stability

Blends of poly(vinyl chloride) (PVC) with different ratios of chlorinated polyethylene (CPE) were degradated by the thermogravimetric method under dynamic conditions (50–600°C) in an inert atmosphere. The effect of the miscibility and composition of the PVC/CPE blends on the thermal stability were investigated. DSC curves of the blends show neither a shift of the PVC glass transition temperature nor a shift of the CPE melting temperature, which means that these blends are heterogeneous. The characteristics of the TG curves were determined, some of which (T_1%,T_5%, Δm₁) can be used as indicators of the thermal stability of the blend. The apparent activation energy of PVC dehydrochlorination in the blends was also calculated. Comparison of the experimental TG curves and TG curves predicted by the additivity rule indicates the existence of the components' interaction in the PVC/CPE blends. The addition of CPE improves the thermal stability of PVC for all the investigated blends in the temperature range where α_calc is greater than α_exp. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 166–172, 2000     

Sorption and diffusion of acrylonitrile monomer through crosslinked nitrile rubber

As the first step for the preparation of interpenetrating polymer networks from nitrile rubber and polyacrylonitrile, the sorption and diffusion of acrylonitrile monomer through nitrile rubber crosslinked by three different vulcanization systems—conventional (CV), dicumyl peroxide (DCP), and a mixture consisting of sulfur and peroxide (mixed)—were studied in the temperature interval of 30–70°C. Kinetic curves have been generated for these systems to compute diffusion and sorption coefficients. The equilibrium sorption is found to be maximum for the CV system. The molar mass between crosslinks (M_c) has estimated and compared with affine and phantom models. It was found that the M_c values follow the affine model. The diffusion coefficient values are highest for DCP and lowest for CV. It was observed that the kinetics of liquid sorption followed an anomalous behavior. The temperature dependence of the transport parameters was followed by an Arrhenius relationship, from which the activation energy for diffusion, permeation, and sorption were calculated. It is found that temperature activates diffusion in all cases. The polymer–solvent interaction parameter was determined. The amount of polysulfidic linkages in the rubber network was also estimated. The experimental results were compared with theoretical predictions. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 941–952, 2000     

Gas permeation of polymer blends. IV. Poly(vinyl chloride) (PVC)/acrylonitrile–butadiene–styrene (ABS) terpolymer

The transport behavior of He, O₂, N₂, and CO₂ in membranes of poly(vinyl chloride) (PVC)/acrylonitrile–butadiene–styrene (ABS) blends has been studied at 25°C. The blends were further characterized by dynamic mechanical measurements, differential thermal analysis (DTA), density measurements, and x-ray diffraction. The equilibrium sorption of CO₂ and N₂ was measured directly at atmospheric pressure using an electromicrobalance and compared with sorption values obtained as P/D ratios from permeation measurements. The rates of permeation (P) and diffusion (D) increase with increasing ABS content in the blends. The P and D values are not additive, and only slight indications of phase inversion in the blends are observed at 5–10 wt-% ABS in the blends. Experimental densities of the blends are higher than calculated densities assuming volume additivity. The data are interpreted to mean that the PVC/ABS blends form a two-phase system composed of a soft polybutadiene (rubber) phase and a rigid PVC/styrene–acrylonitrile copolymer (SAN) phase of mutually compatible components. DTA and dynamic mechanical measurements also show a two-phase system. Sorption values of CO₂ and N₂ by equilibrium sorption measurements increase with increasing ABS content in the blends without the large fluctuations which have been observed for the sorption values obtained from the time lag method. Comparison of the two types of sorption values (from direct measurements and from P/D ratios) show larger deviations for CO₂ than for N₂. This suggests that the time lag method is not valid for permeants with polar character in heterogeneous two-phase systems where chemical immobilizing effect on the permeant molecules occurs.     

Interaction of crosslinked ethylene–propylene–diene terpolymer blends with chlorinated organic penetrants

The sorption and diffusion of halogenated hydrocarbon penetrants through different ethylene–propylene–diene terpolymer (EPDM) blends, such as EPDM/natural rubber, EPDM/bromobutyl rubber, and EPDM/styrene butadiene rubber (50/50 w/w), were studied. The diffusion coefficient of halogenated penetrants fell in the range 1.5–14.52 × 10^?7 cm²/s in the temperature range of 25–60°C. Transport data were affected by the nature of the interacting solvent molecule rather than its size and also by the structural variations of the EPDM blends. 1,2‐Dichloroethane showed a lower mass uptake compared to other penetrants. The temperature dependence of the transport coefficient was used to estimate the activation parameters, such as the activation energy of diffusion (E_D) and the activation energy of permeation (E_p) from Arrhenius plots. The activation parameters for E_D of aliphatic chlorinated organic penetrants was in the range 7.27–15.58 kJ/mol. These values fell in the expected range for rubbery polymers, well above their glass‐transition temperature. Also, the thermodynamic parameters, such as enthalpy and entropy, were calculated and fell in the range 2–15 kJ/mol and 3–54 J/mol/K, respectively. Both first‐ and second‐order transport kinetics models were used to investigate the transport kinetics, and first‐order kinetics were followed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1366–1375, 2003     

Molecular Sorption by Heterogeneous Natural Rubber/Poly(ethylene-co-vinyl acetate) Blend Systems

The sorption of n-alkanes, viz. hexane, heptane and octane by cross-linked natural rubber/poly(ethylene-co-vinyl acetate) (NR/EVA) blends has been studied at 28, 38, 48 and 58°C, with special reference to the effects of EVA content, cross-linking systems, penetrant nature and temperature. The solvent transport was found to decrease with increase in EVA content in the blends. The effects of blend ratio on the transport characteristics have been correlated with the phase morphology of the blends, using scanning electron micrographs and optical micrographs. Among the three vulcanising systems, viz. sulphur (S), dicumyl peroxide (DCP) and a mixed system (S + DCP) employed for the matrix, the DCP cross-linked blends exhibited the lowest solvent uptake. Octane has been found to show higher interaction with the blends than hexane and heptane, probably owing to the closer solubility parameter values. The computed transport coefficients, viz. diffusion coefficient and permeability coefficient, were found to decrease with increase in EVA content in the blends. At room temperature, the mechanism of diffusion was found to deviate slightly from the regular Fickian trend for all blend systems. The blend–solvent interaction parameter and the activation energy for transport were also determined from the sorption data.     

Gas permeation of polymer blends. II. Poly(vinyl chloride)/acrylonitrile–butadiene copolymer (NBR) blends

The transport behavior of He, O₂, N₂, and CO₂ in a series of PVC/NBR polymer blends with varying acrylonitrile (AN) content in the NBR component has been studied at 25° and 50°C. In addition, measurements of density, crystallinity, and thermal expansion coefficients were carried out. The transport behavior of these blends is similar to previous result for PVC/EVA.¹. With increasing AN content in NBR, the permeability (P) and diffusivity (D) of the permeants decreased while the activation energy for diffusion (E_D) increased. For the polymer blends, better additivity of permeability and diffusivity was observed with increasing AN content in the NBR component. The polymer blends also showed increasing volume contraction with increasing AN content in the NBR component. These effects have been discussed as due mainly to increased polymer–polymer interaction causing reduced segmental mobility and increased compatibility of the two polymers. The sorption values calculated from P/D ratios were largely irregular and fluctuated with the blend composition. They were less reproducible than other transport parameters, i.e., P and D measured separately. Several reasons for the irregular sorption behavior were proposed.     

Dielectric relaxation and thermodynamic properties of polyvinylpyrrolidone using time domain reflectometry

Temperature‐dependent values of dielectric permittivity ε′ and dielectric loss ε″ of polyvinylpyrrolidone (PVP, commercialized as PVP K‐60) solution of average molecular weight 160 000 g mol^?1 were measured. The measurements were carried out in the frequency range 10 MHz to 20 GHz using time domain reflectometry at temperatures from 25 to 0 °C. The dielectric spectra can be described by the Davidson‐Cole model. Dielectric parameters such as the static dielectric constant ε₀, the high frequency limiting dielectric constant ε_∞, the relaxation time τ₀ and the distribution parameter β and thermodynamic parameters such as the free energy of activation ΔF_τ, the enthalpy of activation ΔH_τ and the entropy of activation ΔS_τ were determined. The average free energy of activation was found to be in the range 12.55–14.65 KJ mol^?1 and the enthalpy of activation was found to be 6.86 KJ mol^?1. Entropies of activation were found to be positive at all the measured temperature values and these large positive values of entropies reveal a less ordered structure of the PVP solution. The Kirkwood correlation factor g and the dipole moment µ were also determined for PVP solution. The results were compared with the results of the PVP‐water system studied previously. Copyright © 2011 Society of Chemical Industry     

Sorption and transport of gases in miscible poly(methyl acrylate)/poly(epichlorohydrin) blends

The sorption and the transport of He, Ar, N₂, CH₄, and CO₂ in miscible poly(methyl acrylate)(PMA)/poly(epichlorohydrin)(PECH) blends from 1 to 20 atm at 35°C are reported. For He, Ar, N₂, and CH₄, the permeabilities and the diffusion time lags are independent of the upstream pressure, if the compaction effect resulting from compression of the polymer membrane onto the supporting medium is eliminated. The permeability of CO₂ increases with upstream pressure but solubility follows a simple Henry's law behavior. For all five gases, the dependence of solubility, diffusion coefficient, and permeability on blend composition are compared with theoretical mixing rules with the conclusion that both the interaction energy density and the excess activation energy for gas diffusion in the blends are near zero. The fact that the specific volumes of the blends exactly follow linear additivity also confirms that only very weak interactions exist between PMA and PECH.     

Immobilization influence on the water sorption and diffusion in poly(3-hydroxybutyrate)

The temperature dependency of water vapor sorption and diffusion in poly(3-hydroxybutyrate) (PHB) was studied for the first time. Equilibrium sorption and diffusion kinetics were determined by a quartz McBain's vacuum microbalance technique in the temperature range of 303–333 K. A probability of water molecule interaction with the polymer matrix was analyzed for wet PHB films by FTIR spectroscopy technique. Sorption isotherms are interpreted as the solution of free water molecules estimated by the Flory–Huggins equation and the sorption of water molecules immobilized on the carbonyl groups of PHB. The immobilization effect was described by a Langmuir-type equation. The dependency of diffusivity on water concentration was described in the frames of Fujita's immobilization model in which the growing function D_w versus C_w characterized the filling degree of carbonyl groups as sites of immobilization in the polymer. Enthalpy of free water sorption (12 kJ/mol) and water immobilization (42 kJ/mol), as well as the activation energy of water diffusion coefficients (71 kJ/mol), in noncrystalline areas of PHB were determined. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 981–985, 1999     

Humid aging of polyetherimide. I. Water sorption characteristics

The sorption and desorption kinetics of water into polyetherimide (ULTEM 1000) were studied at various temperatures ranging from 20 to 100°C. The water equilibrium concentration increases slightly with temperature from 1.39% (by weight) at 20°C to 1.50% at 100°C. The solubility coefficient, S, calculated from these data, and the water vapor pressure decrease with temperature. The calculated heat of dissolution H_s is close to −43 kJ mol⁻¹, which explains the low effect of temperature on the equilibrium concentration. The diffusion coefficient, D, varies from about 1.10⁻¹² m² · s⁻¹ at 20°C to about 16.10⁻¹² m² · s⁻¹ at 100°C. The apparent activation energy of diffusion, E_D, and the heat of dissolution, H_s, of water in the polymer have opposite values (respectively, +43 and −42 kJ · mol⁻¹). From this observation and a comparison of these data with water diffusion characteristics in other glassy polar polymers, it is hypothesized that the transport rate of water is kinetically controlled by the dissociation of water–polymer complexes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1439–1444, 2000     

Disperse dyeing of polyester fibers: Kinetic and equilibrium study

The effect of temperature on the dyeing rate constant k, diffusion coefficient D, and time of half‐dyeing t_1/2 was evaluated for the dyeing of polyester fibers with two disperse dyes, an azo and an anthraquinone dye. Activation energies of diffusion E were calculated. The polyester dyeing equilibrium was also studied and the partition coefficient K and standard affinity Δμ° at various temperatures were determined for the anthraquinone dye. Standard enthalpy ΔH° and standard entropy ΔS° of dyeing were also obtained. The same equilibrium parameters were not obtained for the azo dye because of its dyeing behavior. A similar kinetic and equilibrium study was made for the pure azo and anthraquinone compounds free from the dispersing agents present in the commercial dyes and the results are discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 123–128, 2002     

Diffusion and solubility of n-alkanes in polyolefines

The diffusion and partition coefficients (relative solubility constants) of n-alkanes (from carbon nos. 12–32) have been determined by a permeation method (pouch method) for the polyolefines LDPE, HDPE, and PP–copolymer, and PP–homopolymer at room temperature. The activation energies for the diffusion are interpreted in the meaning of the rate transition theory. Correlations exist between the activation energy ΔE and the heat of vapourization Δ_vH_s as well as between the activation energy ΔE and the Arrhenius preexponential factors D₀. These correlations are useful for the prediction of the diffusion coefficients of n-alkanes with carbon numbers larger than 32.     

Magnetite‐loaded calcium‐alginate (MLCA) particles as potential sorbent for removal of Ni(II) from aqueous solution

This work is focused on the removal of Ni(II) from aqueous solutions by sorption onto newly developed magnetite‐loaded calcium alginate particles. The uptake of Ni(II) by these magnetite particles, with their mean geometrical diameter 84 and 508 μm, is best described by the Freundlich isotherm and the constants K_F and 1/n were found to be 3.491 mg g^?1, 0.731 and 0.793 mg g^?1 and 0.907, respectively. The mean sorption energy, as determined by Dubinin‐Radushkevich isotherm for 508‐ and 84‐μm sized particles was evaluated to be 8.9 and 8.0 kJ mol^?1, respectively, thus, suggesting the ion‐exchange mechanism for uptake process. Of the various kinetic models proposed, the kinetic Ni(II)‐uptake data were best interpreted by “Simple Elovich” and “Power function” as suggested by their higher regression values. The almost linear nature of plots of log(% sorption) versus log(time) was indicative of intraparticle diffusion. The values of intraparticle diffusion coefficients K_id were found to be 63.49 × 10^?2 and 94.35 × 10^?2 mg l^?1 min^0.5. The intraparticle diffusion was also confirmed by Bangham equation. Finally, various thermodynamic parameters were evaluated. The negative ΔG° indicated spontaneous nature of uptake process while positive ΔH° value suggested exothermic nature of the sorption process. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Enthalpy relaxation in bisphenol‐A polycarbonate/poly(methyl methacrylate) blends

Bisphenol‐A polycarbonate (PC)/poly(methyl methacrylate) (PMMA) blends (PC/PMMA) were prepared by melt mixing with and without a trans‐esterification catalyst (tetrabutylammoniun tetraphenylborate), which is able to promote inter‐exchange reactions between PC and PMMA. Evidences of the ester–ester exchange reaction taking place were pointed out via Fourier Transform Infra‐Red and size exclusion chromatography analyses. A series of enthalpy relaxation measurements were carried out for the pure polymers and for blends thereof. The data were analyzed on the basis of the Tool–Narayanaswamy–Moynihan/Kohlraush–Williams–Watts model. This model characterizes the structural relaxation in the glass transition region by means of four parameters: the apparent activation energy (Δh*), the nonlinearity (x), the nonexponentiality (β), and the pre‐exponential factor (τ₀). The apparent activation energy can be determined from the cooling rate dependence of the fictive temperature (T_f) measured using DSC. Δh* values of homogeneous blend and of the starting polymers were determined in this way, while an estimation of x, β and τ₀ was proposed. Comparisons were made between a single glass transition temperature PC/PMMA blend and homopolymers data. The experimental values of Δh* suggest that the degree of cooperativity decreases on going from the starting polymers to the blend. POLYM. ENG. SCI., 47:218–224, 2007. © 2007 Society of Plastics Engineers.