Structure‐property relationships in commercial polyetheretherketone resins

Key relationships between molecular structure and final properties are reported for standard flow and high flow grades of commercially‐available polyetheretherketone (PEEK) resins that differ primarily in molecular weight and molecular weight distribution. Despite similar chemistry and composition, the molecular size‐dependent structural differences associated with the PEEK resins in this study are shown to influence the crystallization rate, final crystallinity, and melt rheology during processing, which subsequently affects mechanical properties, including strength, ductility, and impact resistance. These structure‐property relationships provide fundamental understanding to aid in the design and manufacturing of industrial and medical devices that leverage both the advantages common to all PEEK resins, including chemical and thermal resistance, mechanical strength, and biocompatibility, as well as more subtle differences in crystallization kinetics, melt rheology, ductility, and impact resistance. POLYM. ENG. SCI., 57:955–964, 2017. © 2016 Society of Plastics Engineers     

Structure–property relationships of medium‐density polypropylene foams

This paper is focused on the production and characterization of a collection of polypropylene (PP) foams with relative densities ranging from 0.3 to 0.6. Samples were foamed using the improved compression moulding method. The process allows controlling density and cellular structure independently as well as obtaining PP foams without fillers, crosslinking or using special PP grades. The influence of blowing agent content, density, cellular structure and foaming conditions on the mechanical response measured in compression, tensile, bending and Charpy impact tests was determined. Results show that density, open cell content and blowing agent concentration have a significant influence on the mechanical performance of medium‐density PP foams. © 2013 Society of Chemical Industry     

Structure‐property relationships in copolyester elastomer‐layered silicate nanocomposites

While the field of polymer–clay nanocomposites is reaching maturity, some parts of the studied systems still present researchers with possibilities for the improvement of material properties. This study entails the understanding of the relationships in copolyester elastomer/organically modified layered silicate nanocomposite and the structure–property relationships within the system of the nanocomposite. A series of these nanocomposites was prepared via twin‐screw extrusion melt compounding. The experiments included the following three types of synthetic organosilicates: high aspect ratio Somasif (ME100) fluoromica and two lower aspect ratio Laponite synthetic hectorites, (WXFN) and (WXFP). These organosilicates were modified with quaternary octadecyltrimethylammonium bromide (ODTMA) and were used to prepare the nanocomposites. The nanocomposite structure on a micro‐ and nanometre scales was evaluated by two techniques, such as X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The mechanical properties of the nanocomposites were examined to determine the impact aspect ratio of the nanofiller and wt % loading have on performance. The addition of the 2 wt % high aspect ratio of ME100‐ODTMA, in particular, showed statistically improved tensile strength, tear resistance, creep resistance, and water vapor permeation barrier enhancement. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41742.     

Structure–property relationships of polycarbonate diol‐based polyurethanes as a function of soft segment content and molar mass

Segmented thermoplastic polyurethanes (PUs) have been synthesized with polycarbonate diol as soft segment and 4,4′‐diphenylmethane diisocyanate and butanediol as hard segment. Two different series employing two different soft‐segment molar mass, 1000 and 2000 g/mol, and by changing the hard‐segment content from 32 to 67% have been investigated with the aim to elucidate the effect of the different content variations on the properties. Morphological, thermal, and mechanical properties have been studied by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), wide angle X‐ray diffraction, atomic force microscopy, tensile and tear strength, hardness, and specific gravity tests. Properties have been explained from the standpoint of miscibility between hard‐ and soft‐segment microdomains of the tailored segmented PUs through an exhaustive analysis. FTIR, DSC, and DMA measurements revealed that miscibility between hard and soft microdomains increases as the molar mass of the macrodiol decreases. An increase in hard‐segment content entailed the formation of larger hard domains with higher crystallinity what results in superior mechanical properties such as higher tensile stress and tear strength, and hardness. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41704.     

Structure–property relationships of composite films

Coextruded multifilms of varying chemical composition and structure were studied by the dynamic mechanical technique. The films studied were two- and three-ply combinations of a polyimide (Kapton) and fluorinated ethylene–propylene copolymer (FEP) and four other two-ply polyethylene and modified polyethylene composites: low-density polyethylene (LDPE)–ionomer, rubber-modified high-density polyethylene (HDPE)–ionomer; ethylene–vinyl acetate (EVA) copolymer–LDPE, and EVA-modified HDPE–LDPE. The mechanical spectra of individual film components were also obtained at 110 Hz between ?120° and 120°C (220°C for the Kapton–FEP system). Mechanical relaxations were examined to determine the degree of interaction between adjacent films and correlate them with tensile and ultimate properties of the composite.     

Structure‐property relationships of LLDPE—highly filled with aluminum hydroxide

The mechanical performance, rheological behavior, and phase morphology of linear low‐density polyethylene (LLDPE) highly loaded with aluminum hydroxide [Al(OH)₃] were investigated. It was found that titanate surface‐active agent and ethylene‐vinyl acetate copolymer (EVA) improve the processing and ductile properties of the composite remarkably but are accompanied by the deterioration of the tensile strength. Addition of vinyl triethoxy silane (VTEO) and dicumyl peroxide (DCP) improves the tensile strength of the composite because of the silane crosslinking structure introduced. A synergistic effect of interface modifying and silane crosslinking method in improving mechanical performance of the composite is presented. Phase morphology of the LLDPE/Al(OH)₃ composites was studied by means of scanning electron microscopy (SEM) technique. SEM micrographs indicate that a core‐shell type with Al(OH)₃ as a core and EVA as a shell is formed in the composite. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2485–2490, 2002     

Structure–property relationships in PVC compression moldings

Compression moldings were produced from two rigid PVC compounds at a range of temperatures. The tensile and impact properties of these moldings depended primarily on the level of particle fusion as assessed by extrusion rheometry. Properties were not related to the level of primary crystallization measured by X-ray diffraction, but the particle fusion process appears to be at least partly due to recrystallization. Fusion occurred more readily in the mass PVC compound than in the suspension PVC compound. Annealing the sheet produced at 200°C caused changes in crystallinity which resulted in small property changes. The maximum annealing effect occurred at 110°C.     

Structure–property relationships of thermally bonded polypropylene nonwovens

The effect of fiber structure and morphology on the resultant mechanical and low load deformation properties of thermally bonded nonwoven polypropylene fabrics has been studied. Commercially available staple polypropylene fibers varying in linear density and draw ratio (Herculon and Marvess staple fibers) were used in this study. The orientation of these fibers was characterized by birefrigence measurements. Differential scanning calorimetry measurements were made to determine the heat of fusion and melting point of fibers. Experiments confirm that tensile strength and stiffness of the fabrics correlate with this fiber structure. Under the same bonding conditions fabrics made from fibers with low draw ratios show higher tensile strength and stiffness than do fibers with high draw ratios. The mechanical properties of fabrics were found to be greatly affected by the thermal bonding temperature. The tenacity and flexural rigidity of fabrics made from poorly oriented fibers show higher values than those made from highly oriented fibers. The shrinkage of the fabrics was observed to increase with increasing bonding temperature in both machine and cross machine directions. The changes in fabric thickness due to the thermal bonding are considerably lower for poorly oriented fibers.     

Structure‐property relationships of degradable polyurethane elastomers containing an amino acid‐based chain extender

A series of degradable polyurethanes of variable soft segment chemistry and content were synthesized and characterized. An amino acid‐based diester chain extender was used to confer degradability and both polycaprolactone diol (PCL) and polyethylene oxide (PEO) were used as soft segments. In addition, the diisocyanate component was a potentially nontoxic diisocyanate (2,6‐diisocyanato methyl caproate, LDI). The physicochemical properties of these unique series of polyurethanes were investigated. It was found that the PEO containing polyurethanes were generally weak, tacky amorphous materials. In contrast, the PCL polyurethanes were relatively strong, elastomeric materials which ranged from completely amorphous to semicrystalline as noted by differential scanning calorimetry. The PCL containing polyurethanes exhibited increasing tensile strength, modulus, and ultimate strain with increasing PCL molecular weight because of increasing phase separation and increasing soft segment crystallinity. Fourier transform infrared analysis showed significant hard segment urea and urethane hydrogen bonding which increased with hard segment content, although interphase bonding is believed to be significant for the PCL polyurethanes. Surface characterization carried out by contact angle analysis and X‐ray photoelectron spectroscopy indicated soft segment surface enrichment for all of the polyurethanes. The PEO‐based polymers were very hydrophilic whereas the PCL‐based polymers displayed significantly higher contact angles, indicating greater surface hydrophobicity. The observed diversity in material properties suggests that these polyurethanes may be useful for a wide range of applications. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1522–1534, 2000     

Structure–property relationships in bibenzoxazole polymers containing fluorocarbon linkages

A series of bibenzoxazole polymers with general formula where R′f and Rf are fluorocarbon-containing linkages has presented a unique opportunity to determine relationships between physical transitions and molecular structure. The results of oscillatory thermomechanical experiments (～1 Hz) show two glassy-state and a glass transition as amorphous transitions for each material above ?180°C. Each glassy-state transition is correlated with onset of motion of specific linkages, the flexibilities of which depend on the structure and molecular positions of the linkages. The glass transition temperatures depend on the two relaxations (T < T_g) in a systematic manner.     

Thermal property and miscibility of polycarbonate/copolyester blends

Summary The thermal property and the miscibility of polycarbonate (PC)/copolyester blends were investigated. For the study, different copolyesters were synthesized from terephthalic acid (TPA) and various mixtures of ethylene glycol (EG) and cyclohexane dimethanol (CHDM). Various blends of PC and copolyester were prepared by melt mixing and thermal properties of the blends were studied employing differential scanning calorimeter. It was found that the blends of the PC and the copolyesters were partially miscible when the glycol in the copolyester was composed of 10, 20, or 30 mole % CHDM. However, the blends of the PC and the copolyesters were miscible in all proportions when the glycol in the copolyester was composed of 50 or 70 mole % CHDM. Miscibilities of the PC/copolyester blends depending on the composition of the copolyester are discussed based on the thermal properties of the blends.     

Structure–physical property relationships in peroxide-cured butadiene–styrene copolymers

Structure–physical property relationships in high-vinyl butadiene–styrene copolymers have been determined for samples cured with dicumyl peroxide under the same conditions. Three different structures, butadiene–styrene–butadiene (B–S–B) triblocks, butadiene–styrene (B–S) diblocks, and random butadiene–styrene copolymers, have been examined. Flexural modulus increases with increasing styrene content owing to the inherent stiffness of a polystyrene backbone. Swelling increases whereas hardness and heat distortion temperature decrease with increasing styrene content. This behavior is explained by the decrease in crosslink density with increasing styrene content in all structures. Heat distortion temperatures of the B–S–B and B–S networks are superior to the heat distortion properties of the random structures. The B–S–B structure is the most solvent resistant, followed by the random copolymers, with the B–S structures swelling to the greatest extent. Swelling differences between the B–S–B and random networks decrease with increasing styrene content, while swelling differences between the B–S–B and B–S networks increase with increasing styrene content. These results are explained by the nature of the crosslinking reaction and the number of loose ends present in each network.     

Structure–property relationships for liquid transport in modified polypropylene membranes

In view of the intensifying interest in the application of polymeric membranes in mixture separation processes, the permeation and permselective properties of polypropylene films toward several candidate organic liquids and vapors were investigated. Polymer films were subjected to solvent and thermal treatments, and the effects of these treatments on film morphology and transport properties were studied. Structure–property relationships for membrane permeation were then developed. Polypropylene films were found to be selective toward toluene, relative to isooctane, and p-xylene relative to o-xylene. Liquid flux rates were found to depend primarily upon the solubility of the permeants in the films and the absolute difference in the solubility parameters of the polymer–liquid pair provided a good basis for correlation of this effect. Considering liquids of closely similar solubility parameters, fluxes were found to be dependent upon the apparent molecular cross sections of the permeants. Films annealed in various organic solvents at temperatures of 60–100°C exhibited enhanced permeability, with up to fifteenfold increase relative to untreated membranes, but with reduced selectivity towards the permeants. A mechanism to account for these effects through consideration of the influence of treating solvent type on polymer morphology is proposed. It postulates the formation of more open or coarser spherulitic structures as a result of recrystallization in the presence of solvent during annealing. The enhanced flux rates in the treated films are attributed to the changes in the spherulite textures and to diminished intercrystalline tie chain constrainment within the spherulitic substructure.     

Structure–property relationships for azo disperse dyes on polyurethane fibre

Using two series of monoazo disperse dyes, the relationships between the molecular structure of dye and its dyeing properties, such as adsorption behaviour, fastness properties and distribution on polyurethane–polyester blends, were thoroughly investigated. Correlation analysis of experiment data revealed that the partition coefficient between octanol and water (CLogP) is the main factor affecting dye sorption. A greater level of CLogP tends to have a greater isotherm coefficient and better rubbing and washing fastness on polyurethane fibre, as well as a greater distribution ratio between the components of the blend. The dye dipole moment is negatively correlated with various degrees of washing fastness. The dye with two terminal hydroxy groups exhibited notable sorption on the polyurethane component and has the largest partition ratio on polyurethane–polyester in the blend. Corresponding regression analysis equations were identified.     

Structure–property relationships in some composite systems. Deformation mechanism

In the present paper, we report the photoelastic behavior of composite elastomeric systems. The samples were obtained by vulcanizing mixtures of cis-polybutadiene and a polar monomer. The polar monomer used was methacrylic acid or magnesium methacrylate. The photoelastic analysis was carried out on samples with different monomer amount and in different swelling conditions. This kind of analysis gives informations about the deformation mechanism of these systems.     

Structure–property relationships in thermally aged cellulose fibers and paper

The research presented in this paper investigates the effect of thermally accelerated aging on the submicrostructure of cellulose and attempts to relate such changes to the well‐documented loss of mechanical strength in aged paper. Filter paper and ramie fibers samples were aged in vacuo at 160°C. Small angle X‐ray scattering (SAXS) was used to study void structure within the fibers and hydration used as a structural probe. On hydration, the void radius of gyration and area decrease, while the void aspect ratio and overall void fraction increase. After aging, the wet structure more closely resembles the dry, suggesting that water cannot expand the structure to the same extent. It is postulated that increases in local ordering on aging create a structure more resistant to disruption by water. The use of additional techniques, namely Fourier transform IR spectroscopy, wide angle X‐ray scattering, scanning electron microscopy (SEM), environmental SEM, and measurement of water retention value, provided additional indirect support for the postulated model. There is no direct evidence for significant crystallinity changes in aged material, suggesting that if structural rearrangements occur, they will be local in nature. There is also no evidence for the formation of covalent crosslinks or new chemical species on aging. Water retention values and wet SAXS results concur, highlighting the importance of water in the cellulose structure and the reduced capacity for water sorption in aged samples. SEM observations show that the failure mechanism in paper changes with age from fibers pull out (i.e., interfiber bond failure) to fiber failure, and wide and zero span tensile tests indicate a weakening of the fibers. These results are consistent with previous reports, and we attribute them primarily to chain scission, although the increased intrafiber bonding may have an influence on the values obtained. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1465–1477, 1999     

Novel phthalocyanine/polyol high-solids coatings: Structure—property relationships

A convenient synthetic procedure for preparing nickel carboxylated phthalocyanine is reported. Upon further hydroxylation, such metal phthalocyanine moieties are incorporated into several melamine-based polyester high-solids systems and the structure—property correlations are examined. Molecular level spectroscopic FTIR analysis and mechanical testing are correlated in an effort to establish structure—property relations in these coatings. It is found that the presence of metal phthalocyanine macrocycle as a cross-linking agent enhances such properties as adhesion, hardness, and impact resistance. © 1993 John Wiley & Sons, Inc.     

Structure–property relationships for sulfonated poly(butylene terephthalate)

Structure–property relationships have been developed for sulfonated poly(butylene terephthalate) copolymers. The compositional variables investigated were sulfonate content, molecular weight, and polymer endgroup composition, and the fundamental polymer properties evaluated were melt viscosity, crystallization kinetics, and impact strength. It was found that all compositional variables significantly affect all of the polymer properties of interest. The most interesting effect is the influence of polymer endgroup composition on polymer properties. The trends indicate that the carboxylic acid endgroups form intermolecular interactions with sodium sulfonate groups, resulting in a decrease in the strength of intermolecular ionic interactions between sodium sulfonate groups. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4662–4771, 2006     

Photosensitive polynorbornene based dielectric. I. Structure–property relationships

In the microelectronics industry, the drive for increasing device speed, level of functionality and shrinking size has placed significant demands on the performance characteristics of polymer dielectrics. In this study, a negative acting, photodefinable dielectric formulation based on a copolymer of decylnorborne (decylNB) and epoxynorbornene (AGENB) was investigated for use in electronics packaging. The structure–property relations of this copolymer were investigated. Copolymer composition and processing conditions were shown to significantly affect the properties of the final polymer films. A lower content of AGENB results in lower moisture absorption, dielectric constant, modulus and residual stress, but it compromises multilayer capability. High crosslink density lowers the dielectric constant but increases the modulus and residual stress. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3023–3030, 2004     

Reprocessing acrylonitrile–butadiene–styrene plastics: Structure–property relationships

Acrylonitrile–butadiene–styrene (ABS) plastics from computer equipment housings have been reprocessed, some under various conditions of temperatures and shearing rates and others for multiple numbers of cycles. Structural changes in these reprocessed materials were investigated by infrared spectroscopy (FTIR), gel permeation chromatography, and dynamic mechanical thermal analysis. Gas chromatography/mass spectrometry was used to analyze extracts from the ABS plastics. These studies were related to measurements of the mechanical properties of the reprocessed materials, and the fracture surfaces were examined using scanning electron microscopy. It was found that impact strength was much more significantly affected than tensile properties by reprocessing. Within the range of reprocessing parameters studied, temperature had a more significant effect than shear rate on mechanical properties. Significant reductions in impact strength and slight increases in stiffness and strength, particularly following reprocessing at the highest temperature of 270°C and multiple reprocessing, were linked to loss of small molecules (including lubricants), degradation (crosslinking and scission) of the rubber phase, and changes in the morphology seen in the fracture surfaces. POLYM. ENG. SCI., 47:120–130, 2007. © 2007 Society of Plastics Engineers