Comparison of the thermoformability of a PPE/PP blend with thermoformable ABS. Part II: Large deformation methods

Thermoforming involves stretching of a heat‐softened polymer sheet to large strains. This was simulated by uniaxial tensile stretching (UTS) experiments at different temperatures and strain rates. These experiments were used to identify an optimum window of thermoforming temperature and strain rate and to compare the thermoformabilities of a blend of polyphenylene ether (PPE) and polypropylene (PP) with thermoformable acrylonitrile butadiene styrene (ABS) resin. It was shown that the PPE/PP blend generally has a wider thermoforming window than ABS. Using Considere construction, it was shown that the PPE/PP blend underwent more homogeneous deformation than ABS. The higher homogeneity in deformation of the PPE/PP blend resulted in a higher uniformity in the distribution of draw ratios, which implies more uniform thickness distribution in thermoformed parts. Draw ratio and crystallization studies ruled out the possibility of postforming shrinkage in the PPE/PP blend under ambient temperature conditions. The PPE/PP blend was also found to have a higher shrinkage onset temperature than that of ABS. An attempt was also made to relate the small deformation viscoelastic properties with the large deformation UTS properties through the use of Deborah numbers. These results bring out the importance of studying both the small deformation and large deformation properties in conjunction, while comparing the thermoformabilities of different polymers. POLYM. ENG. SCI., 45:1377–1384, 2005. © 2005 Society of Plastics Engineers     

Water and water vapor sorption studies in polypropylene–zeolite composites

Water and water vapor sorption to porous polypropylene–zeolite composites prepared by hot pressing have been studied as a function of zeolite loading. This work presents the first report on the effect of the zeolite as a filler on the water‐sorption properties of PP composites. Water swelling experiments were conducted at 25°C using pure PP and PP–zeolite films samples having different zeolite loadings (6–40 wt %). Because PP is a hydrophobic polymer, it does not sorp any water, but the composites having 10, 20, 30, and 40% zeolites have sorbed 0.63, 1.00, 1.72 and 3.74% water, respectively. The zeolite itself at the same conditions sorbed 24.5% water. As the filler loading in the composites increased, equilibrium uptake values increased also. On the other hand, water vapor sorption and kinetics has been studied using a Cahn 2000 gravimetric sorption system. Within in the range of 0.35–0.95% water vapor was adsorbed by the composites containing 10–40 wt % zeolites. Experimental effective water vapor diffusivities of the composite films was about one order of magnitude higher (10‐fold) than the experimental water diffusion coefficient in composites. The transport of water in composites was slower than that in the liquid water due to the longer diffusion pathway and adsorption on the surface of the composites. Although the liquid water may fill all the voids in the composite, water vapor is adsorbed on the surface of the zeolite only. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3069–3075, 2003     

Instrumented thermoforming of advanced thermoplastic composites. II: Dynamics of double curvature part formation and structure development from PEEK/carbon fiber prepreg tapes

Poly(ether ether ketone) (PEEK) carbon fiber prepreg tapes (APC-2) have been thermoformed into a hemispherical double curvature part under a variety of processing conditions. Conventional matched die molding using aluminum molds (at 200°C) were not successful in thermoforming acceptable parts. Parts with severe wrinkling and folding were obtained. A novel three-piece (steel) mold with built-in sheet clamping arrangement was, therefore, designed and fabricated. This mold was used at 400°C temperature to thermoform parts from preheated preconsolidated laminates. More interestingly, using the above conditions, 8- and 16-ply unconsolidated laminates could be directly thermoformed into parts that were microstructurally sound and exhibited good shape conformity. Results suggest a cycle time of 15 min, with scope for further reduction, if mold cooling is employed. Notwithstanding the simplicity of the thermoforming process, such a short cycle time compares quite favorably with cycle times of several hours for conventional thermosetting resin based composites.     

A comparison of the thermoformability of a PPE/PP blend with thermoformable ABS. Part I: Small deformation methods

Different factors important in ascertaining the thermoformability of polymeric materials are identified and defined. These include resistance to sag, ease of flow, mold replication, deep draw capability, sensitivity to thermoforming temperature and speed, uniformity of thickness distribution, and post‐forming shrinkage and dimensional stability. Methods to study these properties can be classified into small deformation and large deformation methods. The small deformation methods, which are the subject of this paper, include dynamic temperature sweep tests, dynamic frequency sweep tests, stress relaxation time, and creep recovery tests. These tests were used to compare the thermoformabilities of a blend of polyphenylene ether (PPE) and polypropylene (PP) and thermoformable acrylonitrile butadiene styrene (ABS) resin. The dynamic temperature and frequency tests showed that the PPE/PP blend generally has a better viscoelastic balance than ABS implying a better balance between resistance to sag and ease of flow. Creep recovery tests suggested that the PPE/PP blend may offer better mold replication during thermoforming. Studies based on the stress relaxation time showed a lower residual stress build‐up in thermoformed PPE/PP blend than ABS implying better dimensional stability and a higher in‐service temperature window for the thermoformed PPE/PP blend than ABS. POLYM. ENG. SCI., 45:1369–1376, 2005. © 2005 Society of Plastics Engineers     

Water-swelling behavior of an ethylene–vinyl alcohol copolymer in the presence of sorbed sodium chloride

The swelling behavior of water in a poly(ethylene–vinyl alcohol) copolymer (70 mol % vinyl alcohol) has been characterized at 25°C by vapor and liquid sorption experiments over a range of water activities. The activity of the vapor phase has been varied by incrementing the pressure of the water vapor in the sorption cell. Alternatively, for the liquid phase experiments, aqueous sodium chloride solutions of different concentrations have been used to vary systematically the activity of the water in the salt solution and to introduce various concentrations of salt into the copolymer films. Relaxation-controlled sorption and Fickian diffusion have been observed as limiting cases of the water sorption behavior at high and low water activities, respectively. The effects of sorbed sodium chloride on water vapor sorption kinetics and equilibria were determined independently. A second salt phase forms within the previously homogeneous and seemingly single phase polymeric system, upon contacting the salt-loaded film with a water vapor activity above a threshold value corresponding to the activity of water in the salt solution used to introduce the salt into the films. The water and salt solubilities in the ethylene–vinyl alcohol copolymer have been measured systematically to describe the complex sorption equilibria associated with this three-component, multiphase system.     

Water vapor sorption and transport in dense polyimide membranes

The sorption and transport of water vapor in five dense polyimide membranes were studied by thermogravimetry. The sorption isotherms of water vapor in the polyimides could be successfully interpreted by both the dual‐mode sorption model and the Guggenheim–Anderson–de Boer equation. The water vapor diffusion behavior was found to be nearly Fickian at higher water vapor activities, whereas non‐Fickian diffusion was observed at lower water activities. The phenomena could be well described by the mechanism of combined Fickian and time‐dependent diffusion. The diffusion coefficient and water vapor uptake in the polyimides were strongly dependent on the polymer molecular structure. Except for the polyimide prepared from 3,3′,4,4′‐diphenylsulfone tetracarboxylic dianhydride and 1,3‐bis(4‐aminophenoxy) benzene, the permeability of water vapor in the dense polyimide membranes predicted from the sorption measurement at 30°C corresponded well with the water vapor permeability measured at 85°C. Among the polyimides studied, pyromellitic dianhydride–4,4′‐diaminophenylsulfone (50 mol%)/4,4′‐oxydianiline (50 mol%) showed both high water sorption and diffusion and, therefore, high water vapor permeability, which for vapor permeation membranes is necessary for the separation of water vapor from gas streams. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2306–2317, 2003     

Anomalous sorption kinetics in the methanol vapor–poly(methyl methacrylate) system

The non‐Fickian sorption kinetics of methanol vapor in poly(methyl methacrylate) films 8 and 51 μm thick at 25°C are presented. The behavior of the system was studied in series of interval and integral absorption runs. The relevant diffusion coefficient and viscous relaxation processes were studied separately by kinetic analysis of the first and second stages of sorption kinetic curves. The sorption isotherm concaved upward at high activities, this being typical of Flory–Huggins behavior, whereas it exhibited a convex‐upward curvature at low methanol vapor activities, this indicating sorption in the excess free volume of the polymer matrix. After excess free‐volume fill‐up, the concentration dependence of the diffusion coefficient was found to be well represented by the free‐volume theory of Vrentas and Duda. Relaxation frequencies calculated from the second stage of two‐stage curves exhibited a weak dependence on the concentration. Integral sorption experiments indicated that the system exhibited nearly case II kinetics at high methanol vapor activities. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1184–1195, 2005     

Structural modifications induced by recycling of polypropylene

The effect of numerous reprocessing cycles on transport properties of isotactic polypropylene (iPP) films was studied and related to the change of molecular weight and molecular weight distribution occurring during the recycling. Sorption curves of dichloromethane vapor in different samples of iPP were analyzed at 25°C to investigate the effect of structure modifications on the sorption mode. Moreover, gas permeability measurements were performed to evaluate the influence of reprocessing on the gas transport properties. The results obtained were attributed to modifications in the molecular structure of the polymer, evidenced from gel permeation chromatography (GPC), and to a different morphology of the films, as results from X-ray diffractograms and dynamic-mechanical thermal analysis (DMTA).     

Impact of cooling method and incoming sheet quality on final part surface quality in thick sheet paint film thermoformed parts

Thick sheet, “dry paint” film parts were thermoformed using different cooling methods and sheet temperatures to determine whether these two parameters had a direct effect on the surface quality of the final part. Although some thermoformers have claimed that applying chilled air after forming “dry paint” film parts improves the gloss of the parts, the data from this study showed that application of chilled air did not have an effect on either the parts' initial gloss or their gloss after time‐dependent hazing. The critical factor in maintaining surface quality in these parts was the maximum temperature reached by the “dry paint” film during heating. In addition, analysis of the data taken on the sheet prior to forming versus that taken on the part after forming demonstrated the importance of validating the surface quality of the as‐received sheet prior to conducting process versus appearance experiments. On the basis of these findings, a recommendation is made for incoming sheet surface quality levels for both process development studies and production applications. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

Sorption/desorption properties of ethanol,toluene, and xylene in poly(dimethylsiloxane) membranes

Sorption/desorption kinetics and sorption equilibria have been determined for ethanol, toluene, and xylene vapors in a poly(dimethylsiloxane) membrane containing about 32 wt % silica resin at 25°C. Dependence of diffusion coefficient on vapor activity and sorption isotherms have been compared to identify the transport mechanisms of those penetrants in the PDMS membrane. The analysis of Zimm–Lundberg clustering functions showed that all three penetrants had a tendency to form clusters and ethanol molecules might be immobilized by the residual silanol groups within the silica resin in the membrane. The diffusion coefficient of toluene was roughly constant and that of xylene slightly decreased as increasing the vapor activity due to the competing effects of penetrant clustering and solvent swelling of polymer. The diffusion coefficient of ethanol versus activity exhibited a maximum due to the effects of ethanol immobilization and cluster formation. The freevolume effect by solvent swelling to diffusion was obscured by either penetrant clustering or immobilization for the three penetrant–polymer systems. © 1994 John Wiley & Sons, Inc.     

Evaluation of Two Methods for Measuring Vapor Sorption in Polymers

In this paper, two methods for measuring the equilibrium vapor sorption in polymers are critically compared and data on sorption of toluene, p-xylene, hexane, cyclohexane, and heptane in low density polyethylene are reported. The vapor phase calibration method (VPC) was used to measure vapor sorption at low vapor activities in air (below 0.01), and the gravimetric method was used to measure sorption over wide range of activities of pure vapors (0.1–0.9). The Flory-Huggins interaction parameter (in amorphous phase) varied between 1.00 for cyclohexane and 1.19 for toluene. The resulting confidence intervals are conjunctive, indicating that both methods provide consistent results.     

Microencapsulation of ammonium polyphosphate: Preparation,characterization, and its flame retardance in polypropylene

Microencapsulated ammonium polyphosphate (MCAPP) with a melamine–formaldehyde (MF) resin coating layer was prepared by in situ polymerization. MCAPP was characterized by Fourier transform infrared, X‐ray photoelectron spectroscopy, and so on. The results show that the microencapsulation with MF resin leads to a decrease in the particles' size and water absorption. The flame retardant action and mechanism of MCAPP and ammonium polyphosphate (APP) in polypropylene are studied using limiting oxygen index (LOI) and UL 94 test, and their thermal stability is evaluated by thermogravimetric analysis. The LOI value of the PP/MCAPP composite at 30 wt% loading is 30.5%, whereas the corresponding value of the PP/APP composite is only 20%. Moreover, the LOI values of the PP/MCAPP/PER composites are higher than the ones of the PP/APP/PER composites. In the UL 94 test, the PP/MCAPP/PER composites with suitable ratios of MCAPP to PER can reach the V‐0 rating, and the best rating of the PP/APP/PER composites is V‐1. V‐1. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Toluene‐vapor sorption of chemically modified methyl methacrylate‐co‐chloromethyl styrene copolymers with N,N,‐dimethyl‐1,3‐propanediamine measured with a quartz crystal microbalance

The sorption properties of toluene vapor were measured for methyl methacrylate (MMA)‐co‐chloromethyl styrene (CMSt) copolymers chemically modified with N,N‐dimethyl‐1,3‐propanediamine (DMPDA) to develop a novel quartz crystal microbalance toluene‐vapor sensor coating. The influence of the structure of the comonomer, the composition of the copolymer, and the film thickness on the toluene sorption properties were investigated. The modified MMA–CMSt copolymers were capable of large, fast, and reversible sorption versus the modified styrene–CMSt copolymers. The largest sorption capacity was obtained for MMA–CMSt–DMPDA with a 96 mol % CMSt concentration. These behaviors were explained by a combination of the plasticization of the copolymers by the introduction of bulky DMPDA at lower CMSt concentrations and the formation of a loosely crosslinked structure at higher CMSt concentrations. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Study on rough-surface biaxially oriented polypropylene film. I. Formation of β-form crystals in sheet cast with T-die extruder

Sheets were cast by extruding polypropylenes (PP) which contained γ-quinacridone, a β-crystal nucleator, at levels of 0–10 ppm using a 30 mm ϕ extruder with a T-die at extrusion temperatures of 200–260°C and chill roll temperatures of 30–90°C. The influences of raw resin characteristics such as γ-quinacridone content and MFI of the base PP and casting conditions such as extrusion temperature and chill roll temperature on the amount of β-crystals formed in the sheet were studied. The amount of the β-crystals formed was larger as the γ-quinacridone content was higher and the extrusion temperature was lower and almost independent of the chill roll temperature. As for the influence of MFI of the base PP, the amount of the β-crystals formed was maximum at MFI ≑ 8 dg/min.     

Thermal,catalytic, antimicrobial,and chelating aspects of phenolic resin and its polychelates with f‐block elements

The polymeric ligand (resin) was synthesized by condensation of 2‐hydroxy‐4‐ethoxybenzophenone with ethane diol in the presence of polyphosphoric acid as a catalyst at 145°C for 10 h. The synthesized resin was used to study its ion exchange efficiency and to synthesize its polychelates with 4f‐block elements. The resin and its polychelates were characterized on the basis of elemental analyses, electronic spectra, magnetic susceptibilities, IR, NMR, and thermogravimetric analyses. The molecular weight was determined using number–average molecular weight (M_n ) by a vapor pressure osmometry (VPO) method. Ion‐exchange studies at various concentrations of different electrolytes, pH, and rate have been carried out for f‐block elements. Antimicrobial activity of all polychelates and catalytic activity of selected polychelates in organic synthesis have been studied. It is observed that resin can be used as an ion‐exchanger and polychelates are found to be an efficient catalysts and antimicrobial agents. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of N‐polyethereal polypyrroles and their application for the preconcentration of rare earth ions

Conducting polymers containing polyether pseudocages (P I , P II , P III ) have been synthesized via chemical oxidation of 1,5‐bis(1,1‐pyrrole)‐3‐oxabutane (M I ), 1,8‐bis(1,1‐pyrrole)‐3,6‐dioxahexane (M II ), and 1,11‐bis(1,1‐pyrrole)‐3,6,9‐trioxaundecane (M III ) using anhydrous FeCl₃ in CHCl₃. Because as obtained polymer resins did not give any response toward any cations, they were reduced (undoped) using chemical reducing agents. Tetrabutylammonium hydroxide was found to be more effective in undoping to obtain more reproducible and reusable polymer resins. The undoped polymer resins were tried in the extraction of rare earth metal ions from the aqueous medium. Among them, only P III resin removes La(III), Eu(III) and Yb(III) and can be employed for the preconcentration of these metal ions. For batch extraction of La(III), Eu(III) and Yb(III) at neutral pH values, percent recoveries of 98.0 ± 1.0, 90.7 ± 1.4, 87.3 ± 4.0, respectively, has been obtained. The sorption capacity is found as 1.3 mg of La(III) per gram of P III resin. The P III resin could be reused at least five times without significant change in its sorption capacity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Time and temperature dependent sorption in poly-ether-ether-ketone (PEEK)

The possible multimodal sorption mechanisms in glassy amorphous poly-ether-ether-ketone (PEEK) are presented. By varying the penetrant-polymer affinity, experimental temperature, and external solvent activity, a broad range of sorption behaviors from ideal Fickian diffusion to limiting relaxation controlled kinetics is observed. In particular, water, methylene chloride, and n-heptane sorption kinetics are analyzed and interpreted on the basis of the multiple transport mechanisms. Low uptake liquid n-heptane sorption follows ordinary Fickian diffusion. Analogously, water vapor at low activity, is sorbed in small amounts in the same limiting mode while, at higher activities, the moderately higher penetrant uptakes induce slow relaxation coupled with ideal Fickian diffusion. The highly interacting methylene chloride leads to ideal Fickian diffusion only at very low activities, while anomalous non-ideal Fickian diffusion and limiting Case II and diffusion controlled swelling are observed at moderate and at high solvent activities, respectively. Limiting Case II sorption of methylene chloride in PEEK has been observed only at a very low temperature (?32°C). The optical microscopy observations of cryogenically fractured samples contacted with liquid methylene chloride at 5, 20 and 36°C revealed the presence of a sharp front moving linearly with the square root of time. Solvent induced crystallization in methylene chloride swollen samples was detected by means of differential scanning calorimetry (DSC) and wide angle X-ray scattering (WAXS). Finally, sorption from liquid methylene chloride/n-heptane solutions with varying compositions are presented. The progressive increase of the more high sorbing methylene chloride concentration in the solutions, leads to the same wide variety of sorption behavior observed in the methylene chloride vapor sorptions. The gas chromatographic (GC) analysis indicated that the presence of methylene chloride enhanced the n-heptane sorption in the polymer.     

Vapor‐induced swelling of supported methacrylic and siloxane polymer films: Determination of interaction parameters

White light reflectance spectroscopy is applied to monitor vapor‐induced thickness changes of polymer films, supported on suitable silicon substrates. Assuming unidirectional swelling due to the constraining support, the equilibrium volume swelling of four methacrylic polymers and two siloxane‐based copolymers upon exposure to various activities of water, methanol, ethanol, and ethyl acetate vapor, at 30°C is evaluated. The deduced sorption isotherms were fitted to the Flory‐Huggins equation and interaction parameters, as well as solubility coefficients at infinite solute dilution, were deduced for each binary system. The relative sorption capacity of the different classes of polymers toward the four vapors are in line with the expected solubility interactions between solvent and solute. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Water vapor absorption and permeability of films based on chitosan and sodium caseinate

The objective of this work was to characterize the moisture sorption and water vapor permeation behavior of edible films made from sodium caseinate and chitosan for future applications as protective layers on foods. Glycerol was used as a plasticizer, and the films were obtained by a casting/solvent‐evaporation method. The moisture sorption kinetics and water vapor permeability (WVP) were investigated. The effect of the addition of glycerol on the WVP characteristics of the films was determined at 25°C with a relative humidity (RH) gradient of 0–64.5% (internal to external). Experimental data were fitted with an exponential function with two fitting parameters. WVP increased with increasing glycerol content in both films, chitosan samples being much more permeable than caseinate ones at any glycerol content. WVPs of sodium caseinate, chitosan, and chitosan/caseinate films with 28 wt % glycerol were also determined for two RH gradients, 0 to 64.5% and 100 to 64.5%, higher WVPs being measured at higher RHs. The moisture sorption kinetics of caseinate films prepared with various glycerol contents were determined by the placement of the films in environments conditioned at 20°C and 75% RH. Peleg's equation and Fick's second law were used to predict the moisture sorption behavior over the entire time period. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Equilibrium solubility and permeability of sulfur dioxide in epoxy resin of aliphatic diglycidyl ether

Equilibrium sorption isotherms were obtained for the sulfur dioxide-epoxy resin of aliphatic diglycidyl ether system over a temperature range of 1° to 45°C. The sorption isotherms indicated the presence of Langmuir sorption due to specific interaction. This is uncommon for rubbery polymers, though similar behavior was also observed previously. Zimm-Lundberg's clustering analysis indicated a slight tendency for clustering of the penetrant molecules at low temperatures and higher activities. The number of Langmuir sites for sorption was found to be independent of temperature. The mobilities of the molecules sorbed in Henry's law mode and the Langmuir mode were found to be approximately equal. Predictions of the permeability values for this system are presented and compared with other data from the literature. The temperature dependence of different sorption parameters is presented and discussed in detail.