Morphological reorganization and mechanical enhancement in multilayered polyethylene/polypropylene films by layer multiplication or mild annealing

Shortly after processing, Polyethylene/Polypropylene (PE/PP) multilayer films demonstrate an increase in tensile modulus and other mechanical properties when the individual layer thickness is below 0.5 µm. Subsequent annealing at 60 °C for 16 h brings the properties of all other samples to similar values. WAXD characterization of the layered films identified a prevalence of mesophase in the thicker PP layers. In samples with increased layer numerosity or subjected to annealing, WAXD detected its conversion to α crystalline phase that correlates with improved mechanical properties. SSNMR and DSC detailed the defective nature of α iPP crystallites. Comonomers, detected by NMR in the commercial polymers used for the films, are the source of “tunable disorder” that dictates the formation of the PP mesophase and the low temperature of conversion to the mechanically stronger defective α phase. Soft intrafilm layer interfaces instead enable nucleation and localized polymer chain rearrangement even without annealing. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 520–531     

Nafion®/(organically modified silicate) nanocomposites via polymer in situ sol–gel reactions: Mechanical tensile properties

A series of Nafion®/[organically modified silicate (ORMOSIL)] hybrid materials have been created by in situ sol–gel copolymerizations of tetraethylorthosilicate and semiorganic silicon alkoxide monomers. The trends in the mechanical tensile properties of these hybrid materials were largely rationalized in terms of the entrapment of the long sulfonic acid side chains in silicate or ORMOSIL structures. There is a significant increase in the mechanical strength relative to that of unfilled Nafion®, except in one case. Young's modulus is enhanced relative to that of unfilled acid form Nafion® in a number of cases, although the degree of ductility is reduced relative to that of unfilled Nafion®. The filler fractions are beneath a critical value that would reflect percolation of a glassy, direct load‐bearing silicate phase. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2237–2247, 2002     

Melting behavior in blends of isotactic polypropylene and a liquid crystalline polymer

The influence of low contents of a liquid crystalline polymer on the crystallization and melting behavior of isotactic polypropylene (iPP) was investigated using electron and optical microscopy, differential scanning calorimetry, and X-ray diffraction. In pure iPP, the α modification was found, whereas for iPP/Vectra blends at Vectra concentration <5%, both α and β forms were observed. The amount of β phase varied from 0.23 to 0.16. Optical microscopy showed that Vectra was able to nucleate both α and β forms. Non-isothermal crystallization produces a material with a strong tendency for recrystallization of the α and β forms (αα′ and ββ′ recrystallization) leading to double endotherms for both crystalline forms in DSC thermograms. Melting thermograms after isothermal crystallization at low temperatures showed a similar behavior. At values of T_c > 119 °C for the α form and T_c > 125 °C for the β form, only one melting endotherm was observed because enough perfect crystals, not susceptible to recrystallization, were obtained. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1949–1959, 2004     

Effect of chemical functionalization on the mechanical properties of polypropylene hollow fiber membranes

Chemical treatment of polymeric hollow fiber membranes (HFMs) is used to prepare their exterior surfaces for coatings. Typical treatments can cleave both C? C and C? H bonds of polypropylene, leading to lower mechanical strength of the fibers. This study evaluated the yield strength, maximum strain, ultimate tensile strength, and burst strength of HFMs treated with each of three common oxidizing reagents: ozone as a gas phase system, aqueous solutions of potassium persulfate, and ammonium persulfate for liquid phase systems. The yield strength and ultimate tensile strength of HFMs decreased continuously with increasing ozonation time. Batch treatments with aqueous oxidizing systems showed limiting values of the yield and ultimate tensile strengths with time. Swelling the hollow fibers with methanol prior to oxidation caused less reduction of the mechanical properties after persulfate treatment. Fibers pretreated with methanol showed lower losses of mechanical properties strength with aqueous oxidation systems. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1366–1373     

Mechanical property tuning of semicrystalline network polymers by controlling rates of crystallization and crosslinking

Semicrystalline network polymers were obtained by the Diels–Alder (DA) reaction of furyl‐telechelic poly(ε‐caprolactone) and tris(2‐maleimide ethyl)amine. Controlling the rates of crystallization and crosslinking reaction gave materials with various properties. Curing at a temperature much below T_m of poly(ε‐caprolactone), at which crystallization proceeded first followed by DA reaction, gave a hard and stiff material, whereas curing above T_m gave a soft and stretchable one. When crystallization and crosslinking were promoted simultaneously, tough and ductile materials were obtained. Structural analysis of the network polymers showed that the variation in the properties was derived from the difference in the crystallinity, crystallite size, and network structure. Therefore, materials with various mechanical properties, from soft to hard, could be obtained by simple thermal treatment. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Thermal and mechanical analysis of metallocene‐catalyzed ethene–α‐olefin copolymers: The influence of the length and number of the crystallizing side chains

Copolymers of ethene and 1‐octene, 1‐dodecene, 1‐octadecene, and 1‐hexacosene were carried out with [Ph₂C(2,7‐di‐^tertBuFlu)(Cp)]ZrCl₂/methylalumoxane as a catalyst to obtain short‐chain branched polyethylenes with branch lengths of 6–26 carbon atoms. This catalyst provided high activity and a very good comonomer and hydrogen response. In this study, the influence of the length and number of the side chains on the mechanical properties of the materials was investigated. The crystalline methylene sequence lengths of the copolymers and lamellar thicknesses were calculated after the application of a differential scanning calorimetry/successive self‐annealing separation technique. By dynamic mechanical analysis, the storage modulus as an indicator of the stiffness and the loss modulus as a measure of the effect of branching on the α and β relaxations were studied. The results were related to the measurements of the polymer density and tensile strength to determine the effect of longer side chains on the material properties. The hexacosene copolymers had side chains of 24 carbons and remarkable material properties very different from those of conventional linear low‐density polyethylenes. The side chains of these copolymers crystallized with one another and not only parallel to the backbone lamellar layer, depending on the hexacosene concentration in the copolymer. The side chains crystallized even at low hexacosene concentrations in the copolymer. A transfer of these results to 16 carbons side chains in ethene–octadecene copolymers was also possible. © 2006 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1600–1612, 2006     

Copolymerization: A new tool to selectively induce poly(butylene naphthalate) crystal form

Poly(butylene/diethylene naphthalate) copolymers (PBN‐PDEN) were synthesized in bulk according to the polycondensation procedure and examined by NMR, GPC, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and XRD. At room temperature they appeared as semicrystalline materials; the copolymerization caused a lowering in the T_g value, a decrement of T_m and of the crystallization rate. Pure α or β′ form was obtained at low and high DEN unit content, respectively; crystalline form transition never occurred in the solid state, analogously to PBN. After cooling from the melt, the pure α form was always evidenced in PBN‐PDEN10 and PBN‐PDEN20, whereas the pure β′ crystal phase develops in the copolymer containing 40 mol % DEN units, independently on the cooling rate. In the case of PBN‐PDEN30 a pure α or β′ form was obtained at low and high cooling rate, respectively. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1356–1367, 2009     

Influence of crystal polymorphism on mechanical and barrier properties of poly(l-lactic acid)

The effect of crystal polymorphism on barrier and mechanical properties of PLLA is detailed in this contribution. PLLA films containing different amounts of α and α′ crystal forms were prepared by annealing quenched PLLA at different temperatures. The polymorphic structure of the films was analyzed by X-ray diffraction. Mechanical properties and permeability to water vapor were investigated as a function of degree of crystallinity (w_C) and related to crystal polymorphism developed during annealing. The polymorphic structure of PLLA significantly affects mechanical and barrier properties. The α crystal modification provides a better barrier to water vapor and a higher Young’s modulus, compared to films containing the α′ modification, but a lower elongation at break. The varied barrier and mechanical properties were correlated to the different packing of PLLA chains in the two analyzed polymorphs. The conformational disorder of the α′ form makes this structure a mesophase (condis crystal), with remarkable effects on material properties.     

Nanoconfinement as a tool to study early stages of polymer crystallization

This article promotes the idea that crystallization experiments under confinement can be an interesting tool to learn more about the early stages of polymer crystallization in bulk systems. Based on various results from the recent literature, it is demonstrated that crystalline forms that are metastable, transient, or inaccessible in bulk samples can be easily obtained and studied in nanoscopic compartments. This is interesting in the light of the recent discussion about thermodynamic reasons for the temporary occurrence of a mesophase at the growth front of crystals in bulk polymers, in particular, about a hexagonally packed mesophase in polyethylene. The experimental findings for nanoconfined methylene sequences seem to support indirectly thermodynamic approaches explaining the occurrence of a mesophase based on the small thickness of the crystal at the growth front. A first estimate for the critical crystal thickness d_mc defining the transition from hexagonal to orthorhombic packing in case of confined methylene sequences is provided based on results for side chain polymers. Further perspectives of crystallization experiments on confined systems are discussed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1556–1561, 2008     

Vibration-induced change of crystal structure in isotactic polypropylene and its improved mechanical properties

In order to understand the formation of different crystal structures and improve the mechanical properties of isotactic polypropylene (iPP), melt vibration technology, which generally includes shear vibration and hydrostatic pressure vibration, was used to induce the change of crystal structure of iPP. iPP forms α crystal structure in traditional injection molding. Through melt vibration, crystal orientated and its size became smaller, and a change of crystal structure of iPP from α form to β form and γ form was achieved. Therefore, the mechanical properties of iPP were improved. At high melting temperature (230 °C), only β form can be induced. At low melting temperature (190 °C), either β form or γ form can be induced, depending on the combination of frequency and vibration pressure. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2385–2390, 2004     

Poly(vinyl alcohol) hydrogels: Reinforcement of radiation-crosslinked networks by crystallization

Aqueous poly(vinyl alcohol) solutions were crosslinked via electron-beam irradiation to form transparent hydrogels of varying crosslinking densities. Typical crosslinked hydrogels with M _c between 3500 and 8000 were weak, easily shattered, nonextensible materials with very low tensile moduli (up to 70 psi) and tensile strengths at break (less than 10 psi). Reinforcement by induction of partial crystallization was accomplished by a two-stage drying process, consisting of a slow dehydration stage at room temperature and an annealing stage at elevated temperatures, which was mainly responsible for the introduction of the crystallites. The swollen hydrogels after the annealing process had crystallinities widely varying between 30 and 65% and polymer volume fractions between 30 and 60%, depending on the temperature-time history of the specimen. These materials showed greatly improved mechanical properties (modulus, ultimate tensile strength, tear strength), as compared to the uncrystallized hydrogels.     

Effect of carbon nanotubes on the crystallization and properties of polypropylene

The effect of different concentrations of single‐walled carbon nanotubes (SWNTs) on the nonisothermal crystallization kinetics, morphology, and mechanical properties of polypropylene (PP) matrix composites obtained by melt compounding was investigated by means of X‐ray diffraction, differential scanning calorimetry, optical and scanning electron microscopy, and dynamic mechanical thermal analysis. Microscopy showed well‐dispersed nanotube ropes together with small and large aggregates. The modulus was found to increase by about 75% at a level of 0.5 wt % nanotubes. The SWNTs displayed a clear nucleating effect on the PP crystallization, favoring the α crystalline form rather than the β form. The crystallization kinetics analysis showed a significant increase in activation energy on incorporating nanotubes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2445–2453, 2005     

Molecular weight dependency of crystallization and melting behavior of β‐nucleated isotactic polypropylene

Compounds of isotactic polypropylene (iPP) and β‐nucleating agent were used to investigate the relationship between the development of β phase and molecular weight in iPP under quiescent crystallization conditions by using wide angle X‐ray diffraction and differential scanning calorimetry techniques. In all cases, the dependency of the formation of β phase in iPP on molecular weight of iPP at a defined crystallization temperature range was found. The iPP with high molecular weight possessed a wide range of crystallization temperature in inducing rich β phase. However, poor or even no β phase was obtained for the samples with low molecular weight in the same range. In addition, an upper critical crystallization temperature of producing dominant β phase was found at 125 °C. Beyond this temperature, a phenomenon of prevailing α phase became obvious. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1301–1308     

A novel method for a high‐strength electrospun meta‐aramid nanofiber by microwave treatment

Electrospun nanofibers have attracted great attention as potential reinforcements in composite application due to their high specific surface area, high porosity, and versatility. Because the electrospun nanofibers exhibit relatively low mechanical strength due to low crystallinity and random alignment, many researchers have tried to enhance the mechanical strength through various approaches, such as heat treatment and fiber orientation control. These methods, however, are difficult to control and require the use of high temperatures and sophisticated apparatuses, and high costs. In this study, we investigate a novel microwave technique to fabricate high‐strength electrospun meta‐aramid nanofiber mats. To optimize the microwave irradiation conditions, the electrospun nanofiber was treated at varying levels of moisture and for different irradiation times. Field emission scanning electron microscopy was used to observe the surface morphology of the electrospun nanofiber mats at the different irradiation times. The changes in the crystallinity and thermal properties were investigated using X‐ray diffraction and thermogravimetric analysis measurements. Tensile tests were performed to measure the mechanical strength of the meta‐aramid nanofiber mats with respect to each parameter. As a result, any residual solvents and salts were removed, and the degree of crystallization was dramatically increased by microwave irradiation under wet conditions. These effects led to a 2.8‐fold increase in the tensile strength of the nanofiber mats compared with an untreated mat. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 807–814     

Effect of strain‐induced molecular ordering on mechanical performance and barrier properties of polylactide nanocomposites

Plastic deformation of polylactide has been known as a self‐reinforcement alternative to improve mechanical and barrier properties. In this study, the structural evolution was investigated during a hot‐drawing process, at different initial strain rates and temperatures above T_g of polylactide. The drawing process at T_g +10 °C, led to the formation of an intermediate molecular ordering, between the crystalline and amorphous phases. A lower fraction of this mesomorphic phase was found to develop with the addition of nanoparticles. An increase in the stretching temperature to T_g +30 °C, caused an improvement of the crystallization kinetics, compared to that of thermally activated crystallization. A strain hardening behavior was observed in the presence of mesophase during a stretching process of the hot‐drawn films at room temperature. Permeability was discerned to its basic components, diffusivity, and solubility coefficients. The matrix degradation influenced the permeability components. The diffusivity decreases in the presence of the impermeable matters. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1865–1876     

Effects of functionalized multiwalled carbon nanotubes on the morphologies and mechanical properties of PP/EVA blend

The maleic anhydride‐grafted multiwalled carbon nanotubes (MWCNTs‐g‐MA) have been introduced into polypropylene/ethylene‐co‐vinyl acetate (PP/EVA) blend. To clearly describe the effects of MWCNTs‐g‐MA on the morphology and mechanical properties of PP/EVA blends, the selective distribution of MWCNTs‐g‐MA in the blends is realized through different sample preparation methods, namely, MWCNTs‐g‐MA disperse in EVA phase and MWCNTs‐g‐MA disperse in PP matrix. The results show that the distribution of MWCNTs‐g‐MA has an important effect on the final morphology of EVA and the crystallization structure of PP matrix. Compared with PP/EVA binary blend, distribution of MWCNTs‐g‐MA in PP matrix induces the aggregation of EVA phase at high EVA content and the decrease of spherulite diameters of PP matrix simultaneously. However, when MWCNTs‐g‐MA are dispersed in the EVA phase, they induce more homogeneous distribution of EVA, and the crystallization behavior of PP is slightly affected by MWCNTs‐g‐MA. The corresponding mechanical properties including impact strength and tensile strength are tested and analyzed in the work. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1481–1491, 2009     

Crystallization of tethered polyethylene in confined geometries

Ordered poly(ethylene)‐poly(vinylcyclohexane) (PE‐PVCH) block copolymers are employed to study the crystallization of tethered PE in confined geometries. The high T_g of the PVCH component of these materials forces PE chains to crystallize in well‐defined geometries dictated by the mesophase structure of the block copolymer. Effects of chain tethering on crystallization are examined through comparison of singly‐tethered PE chains in PE‐PVCH (EV) diblocks and doubly‐tethered PE in PVCH‐PE‐PVCH (VEV) triblocks. Crystallinity is independent of the block copolymer mesophase structure in both the EV and VEV systems, although crystallinity in VEV depends on the molecular weight of the PE block of the copolymer. Melting temperature data indicate that spatial confinement reduces crystallite size in EV and VEV, and that the double tethering of PE chains in VEV reduces crystallite size further through topological constraints. Crystal nucleation and growth depend strongly on the type of microstructure in both EV and VEV block copolymers. Differences in the overall rate of crystallization are correlated with the dimensional continuity of the PE microdomains. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37:2053–2068, 1999     

Dialdehyde starch‐crosslinked chitosan films and their antimicrobial effects

For improved mechanical and water‐swelling properties of chitosan films, a series of transparent films were prepared with dialdehyde starch as a crosslinking agent. Fourier transform infrared and X‐ray analysis results demonstrated that the formation of Schiff's base disturbed the crystallization of chitosan. The mechanical properties and water‐swelling properties of the films were significantly improved. The best values of the tensile strength and breaking elongation were 113.1 MPa and 27.0%, respectively, when the dialdehyde starch content was 5%. All the crosslinked films still retained obvious antimicrobial effects toward S. aureus and E. coli, and they showed potential for biomedical applications. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 993–997, 2003     

Impact of cellulose nanocrystal aspect ratio on crystallization and reinforcement of poly(butylene adipate‐co‐terephthalate)

Cellulose nanocrystals (CNCs) are appealing nanomaterials for the reinforcement of polymeric materials. It is now well established that high mechanical properties are obtained when preparing the nanocomposite by casting/evaporation methods and using CNC contents above the percolation threshold. This phenomenon results from the formation of a stiff CNC network within the matrix meaning that the properties of the matrix play only a limited role on the mechanical properties of the material when the matrix is in the rubbery state. In subpercolation concentration or when using a different processing technique, the level of understanding is less clear, mainly when the CNC‐induced crystallization of the matrix interferes with the reinforcing mechanism. In this study, we used CNCs with different aspect ratios to prepare nanocomposites by extrusion with polybutyrate adipate terephthalate as matrix. The impact of CNC on the crystallinity of the matrix and mechanical properties of the nanocomposite has been investigated. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2284–2297     

Photo‐induced thiol‐ene polysulfide‐crosslinked materials with tunable thermal and mechanical properties

Photo‐induced thiol‐ene crosslinked polymeric networks have been extensively explored in constructing a variety of new materials with enhanced mechanical properties for optical, biomedical, and sensing applications. Toward the broad applications, however, tunable mechanical properties are greatly desired. Here, an effective approach utilizing high‐molecular‐weight methacrylate copolymers having pendant thiol and vinyl groups (MCPsh and MCPenes) to modulate thermal and mechanical properties of photo‐induced thiol‐ene crosslinked materials is reported. The MCP copolymers are synthesized by an industrially friendly polymerization method, followed by post‐modification including either a facile coupling reaction or reductive cleavage. Upon UV irradiation, thiol‐ene reactive blends of MCPsh and MCPenes yield highly crosslinked materials through the formation of flexible sulfide linkages. These polysulfide‐crosslinked materials based on rigid MCP backbones exhibit enhanced mechanical properties. Further, their thermal and mechanical properties are tuned by modulating monomer compositions of MCPs as well as varying numbers of pendant SH or vinyl groups (i.e., extent of crosslinking densities). This approach is versatile and effective for development of high performance polymeric materials. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3060–3068