Effects of the lamination temperature on the properties of poly(ethylene terephthalate-co-isophthalate) in polyester-laminated tin-free steel can — II. Adhesion mechanism of poly(ethylene terephthalate-co-isophthalate) to TFS

The adhesion strength between poly(ethylene terephthalate-co-isophthalate) (co-PET) and tin-free steel (TFS) was investigated by varying the lamination temperature using a blister test. As the lamination temperature increased, the adhesion strength increased rapidly at the beginning and then saturated. The main reason for the increase of adhesion with the lamination temperature was an improved degree of wetting. This was manifested by the fact that the variation in the degree of wetting was very similar to that of the adhesion strength. The degree of wetting was dependent on the melt viscosity of co-PET. The results of differential scanning calorimetry (DSC) and rheometrics dynamic spectrometry (RDS) showed that the high extent of the crystalline phase increased remarkably the melt viscosity of co-PET, leading to incomplete wetting. When the co-PET/TFS joint was immersed in hydrochloric acid solution, the pattern of the front penetration line and the rate of penetration of hydrochloric acid solution into the co-PET/TFS interface were different, depending on the lamination temperature and the direction of penetration. The wet adhesion strength was found to increase with increasing lamination temperature because the size of voids at the co-PET/TFS interface resulting from incomplete wetting decreased.     

Effects of liquid–liquid phase separation on crystallization of poly(ethylene glycol) in blends with isotactic poly(methyl methacrylate)

To analyze the interplay between crystallization and liquid–liquid phase separation (LLPS), isothermal crystallization behavior of poly(ethylene glycol) (PEG) in blends with isotactic poly(methyl methacrylate) (i-PMMA) was investigated by differential scanning calorimetry (DSC). The blend system had an upper critical solution temperature (UCST) type phase diagram. When the crystallization occurred simultaneously with LLPS, the overall crystallization rate was enhanced at high crystallization temperatures T_c, relatively compared with that of neat PEG. This behavior was interpreted by the combination of the effects of spinodal quench depth ?T_s and usual supercooling degree ?T_c, according to the theory of Mitra and Muthukumar, namely, the crystallization rate is enhanced by the concentration fluctuation-assisted nucleation at high T_c. In the crystallization after LLPS proceeded, on the other hand, the overall crystallization rate was slow and less dependent on the blend composition. In addition, it was revealed by small-angle X-ray scattering measurements that amorphous i-PMMA was excluded from the interlamellar region of PEG crystals in SQ as well as WQ.     

Studies on thermodynamic properties of pure poly(ethylene glycol)-400 in the temperature range 299–363 K using volume expansivities

Dilatometric studies have been performed on the pure poly(ethylene glycol) of average molecular mass 400 g.mol^?1(PEG-400). From these studies, molar volumes and volume expansion coefficients (α) of this sample have been estimated at different temperatures. Using the data, a number of thermodynamic, thermo-acoustic and anharmonic parameters of the sample have been evaluated. All these parameters have been discussed to throw light on the internal structure, molecular order, anharmonicity and intermolecular interactions.     

Effects of storage on thermomechanical properties of poly(ɛ-caprolactone) blends containing poly(vinyl pyrrolidone/iodine)

Abstract

This study reports the effects of: the molecular weight ratio of poly(?-caprolactone) (PCL) in blends containing polymer of high (50 000 g mol^-1 ) and low (4000 g mol^-1 ) molecular weight; the concentration (0, 1, and 5 wt-%) of poly(vinyl pyrrolidone/iodine) (PVP/I); and storage at 30°C and 75% relative humidity; on the thermomechanical properties of films prepared by solvent evaporation from solutions containing both PCL and PVP/I. The tensile properties were found to be statistically dependent on the molecular weight ratio of PCL but not on the concentration of PVP/I. The reductions in tensile strength and elongation at break associated with increasing amounts of low molecular weight PCL were attributed to a reduction in the concentration of chain entanglements. No changes were observed in viscoelastic properties or the glass transition temperature. Following storage there were no changes in the tensile strength, glass transition temperature, or viscoelastic properties of the films; however, significant reductions in elongation at break were observed. It is suggested that this is due to hydrolytic chain scission of amorphous PCL. Inclusion of 5 wt-% PVP/I increased this process in films containing 100 : 0 and 80 : 20 high/low molecular weight PCL (but not 60 : 40), but the extent of this was small. This study highlighted significant aging properties of PCL in a moist atmosphere. Consequently, it is recommended that suitable packaging materials should be employed to control the exposure of PCL films to water during storage.     

Effects of molecular weight on poly(ω-pentadecalactone) mechanical and thermal properties

A series of poly(ω-pentadecalactone) (PPDL) samples, synthesized by lipase catalysis, were prepared by systematic variation of reaction time and water content. These samples possessed weight-average molecular weights (M_w), determined by multi-angle laser light scattering (MALLS), from 2.5 × 10⁴ to 48.1 × 10⁴. Cold-drawing tensile tests at room temperature of PPDL samples with M_w between 4.5 × 10⁴ and 8.1 × 10⁴ showed a brittle-to-ductile transition. For PPDL with M_w of 8.1 × 10⁴, inter-fibrillar slippage dominates during deformation until fracture. Increasing M_w above 18.9 × 10⁴ resulted in enhanced entanglement network strength and strain-hardening. The high M_w samples also exhibited tough properties with elongation at break about 650% and tensile strength about 60.8 MPa, comparable to linear high density polyethylene (HDPE). Relationships among molecular weight, Young's modulus, stress, strain at yield, melting and crystallization enthalpy (by differential scanning calorimetry, DSC) and crystallinity (from wide-angle X-ray diffraction, WAXD) were correlated for PPDL samples. Similarities and differences of linear HDPE and PPDL molecular weight dependence on their mechanical and thermal properties were also compared.     

Biological effects of poly(ethylene glycol) on the microbial poly(β-hydroxyalkanoates) produced by pseudomonads microorganisms

Poly(ethylene glycol) of M_n 200 g/mol (PEG-200) was added to cultivation media of Pseudomonas oleovorans and Pseudomonas putida during fermentation. The carbon source and the medium used were sodium octanoate and medium E*, respectively. It was discovered that PEG-200 can control product molecular weight as well as cell productivity for both microorganisms. However, PEG-200 had no significant effect on the polymer compositions. The introduction of PEG-200 in the second-stage culture for 24 hr did not result in any notable cellular toxicity-measured in terms of colony forming unit/mL. Increasing the PEG-200 concentration to 8%, however, caused a decrease in the total polymer yield, the cell productivity as the well as M_n values. Gas chromatography analysis of products indicated that the major repeat units were β-hydroxycaproate, β-hydroxyoctanoate, and β-hydroxydeca noate. Thus, this work initiates new research opportunities for the control of product molecular weight for in-vivo microbial polymer synthetic reactions.     

Effect of silicone dioxide and poly(ethylene glycol) on the conductivity and relaxation dynamics of poly(ethylene oxide)–silver triflate solid polymer electrolyte

The conducting and relaxation dynamics of Ag⁺ ions in poly(ethylene oxide) (PEO)–silver triflate (AgCF₃SO₃) solid polymer electrolytes (SPEs) containing nanosize SiO₂ filler and poly(ethylene glycol) (PEG) as a plasticizer were studied in the frequency range 10 Hz to 10 MHz and in the temperature range 303–328 K. The comparatively lower conductivity of the plasticized (PEG) PEO–AgCF₃SO₃–SiO₂ nanocomposite electrolyte system was examined by analysis of the Fourier transform infrared (FTIR) spectroscopy and conductivity data. The electric modulus (M″) properties of the SPE systems were investigated. A shift of the M″ peak spectra with frequency was found to depend on the translation ion dynamics and the conductivity relaxation of the mobile ions. The value of the conductivity relaxation time was observed to be lower for the PEO–AgCF₃SO₃ system only with nanofiller SiO₂. The scaling behavior of the M″ spectra showed that the dynamical relaxation processes was temperature-independent in the PEO–AgCF₃SO₃ and PEO–AgCF₃SO₃–SiO₂–PEG polymer systems, whereas they were temperature-dependent for the PEO–AgCF₃SO₃–SiO₂ system. However, the relaxation processes of all of theses systems were found to be dependent on their respective compositions. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Impact of organoclays on the phase morphology and the compatibilization efficiency of immiscible poly(ethylene terephthalate)/poly(ε-caprolactone) blends

Adding nanofillers Cloisite 30B (C30B) and Cloisite 15A (C15A) to poly(ethylene terephthalate) (PET)/poly(ε-caprolactone) (PCL) (70/30, wt/wt) blends via melt blending can improve their phase morphology and change their interface properties. The effects of the different selective localization of clay on the structure and the morphologies are studied and evaluated by theoretical and experimental methods. It is found that C30B is selectively localized in PET and at the PET-PCL interface, whereas C15A is mainly localized at the interface. Moreover, the changes in the rheological behavior of the blends are attributed to the formation of clay network-like structures. X-ray diffraction, scanning electron microscope, and transmission electron micrograph observations also evidenced an exfoliated and/or intercalated structure of C30B, and intercalated structure of C15A in the blend, together with significant morphology changes of the initially immiscible blend. The relative permeability to PET/PCL of the nanocomposites decreased with the increasing of nanoclays content. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48812.     

Effects of process parameters on the physical properties of poly (urea–formaldehyde) microcapsules prepared by a one-step method

The physical properties of microcapsules are strongly influenced by the synthetic conditions used for their preparation. To prepare microcapsules possessing a smooth surface morphology, high mechanical strength, and reduced permeability of the core material, in situ polymerization in an oil-in-water emulsion was performed using poly (urea–formaldehyde) and tetrachloroethylene as the shell and core materials, respectively. The influence of the synthetic conditions, including the initial pH value, concentration of wall material, concentration of NaCl, and heating rate, on the properties of the resulting microcapsules was investigated systematically by an orthogonal factorial design. The physical properties of the microcapsules were characterized using scanning electron microscopy and optical-photographic microscopy. The results showed that the concentration of shell material has a substantial effect on the mechanical strength of the microcapsules. Additionally, a slow heating rate and high initial pH value enhance the preparation of well-defined spherical microcapsules having excellent barrier properties. Finally, a moderate concentration of sodium chloride can remarkably improve the compactness of the capsule wall. The optimum conditions, determined on the basis of utilization of wall material, are as follows: initial pH value: 3.5; concentration of shell material: 3.6 × 10^?2 g/mL; heating rate: 0.5 °C/min; and concentration of sodium chloride: 5.0 × 10^?2 g/mL.     

Molecular weight effect on theta-gel formation in poly(vinyl alcohol)–poly(ethylene glycol) mixtures

Injectable hydrogel formulations that undergo in situ gelation at body temperature are promising for minimally invasive tissue repair. This work focuses on the investigation of injectable poly(vinyl alcohol) (PVA) and poly(ethylene glycol) (PEG) mixtures. The injectable PVA–PEG aqueous solutions form a hydrogel as temperature is reduced to near body temperature, while filling a defect in the injection site. Gamma sterilization of these solutions compromises injectability presumably due to crosslinking of PVA. We hypothesized that by modifying the PEG molecular weight and its concentration, injectability of radiation sterilized PVA–PEG hydrogels can be optimized without compromising the mechanical properties of the resulting gel. The use of a bimodal mixture of higher and lower molecular weight PEG (600 and 200 g/mol) resulted in lower PVA/PEG solution viscosity, better injectability, and higher gel mechanical strength. The PVA/bimodal-PEG had a lower viscosity at 2733 ± 149 cP versus a viscosity of 5560 ± 278 cP for PVA/unimodal-PEG (400 g/mol). The gel formed with the bimodal PEG mixture had higher creep resistance (61% total creep strain under 0.5 MPa) than that formed with unimodal PEG (84%). These hydrogel formulations are promising candidates for minimally invasive tissue repair. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermogelation properties of poly(N-isopropylacrylamide) – block – poly(ethylene glycol) – block – poly(N-isopropylacrylamide) triblock copolymer aqueous solutions

Low polydispersity PNIPAM–PEG–PNIPAM triblock copolymers with PEG blocks of 1–6 kDa and PNIPAM chains of 5–30 kDa were synthesized and their thermogelation behavior in aqueous solution as a function of their composition and block length was investigated for the first time. DSC, dynamic rheometry and the tube inverting method were employed to characterize the gelation process at various polymer concentrations, and their results were compared. The thermogelation process depended mainly on the length of both PNIPAM and PEG blocks. Both association and aggregation temperatures of the PNIPAM chains decreased with the MW of PNIPAM and increased with the length of the PEG block. The amplitude of these effects depended on the molecular weights of the blocks forming the copolymer as a consequence of the partial mixing of PNIPAM and PEG chains during the association/aggregation process, while the overall hydrophilicity of the entire copolymer played only a minor role. The length of the PEG block proved also to be the most important factor for the preparation of a stable gel in 20 wt.% solutions, while the hydrophilic groups/hydrophobic groups ratio had no importance.     

Effects of the molecular weight and CC functionality of poly 1-hexene on the properties of poly 1-hexene-based high impact polystyrene

Here we are aimed to unravel the effects of CC functionality and molecular weight of the rubber on the final properties of poly1-hexene-based high impact polystyrenes (HIPS). In this regard, various HIPS samples were synthesized by free radical polymerization of styrene in the presence of different weight fractions of various poly1-hexene-based impact modifiers including: (i) high molecular weight poly1-hexene (PHex), (ii) low molecular weight poly1-hexene (Olig), and (iii) 1-hexene/1,5-hexadiene copolymer (Copolym). Results showed that by increasing CC functionality from PHex to Oligm and Copoly, the degree of grafting increases which has its influence on the mechanical, thermal and morphological perspectives of the synthesized HIPSs. Besides CC unsaturation degree, the effect of rubber molecular weight on the final HIPS properties was studied as well. According to the results, molecular weight has significant effect on the final HIPS performance, too. Finally, our obtained results suggest new HIPS/Copolym sample as the one with the highest mechanical and thermal properties which is comparable well with commercial HIPS/polybutadiene grades. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47169.     

Effect of the reaction conditions on the properties of poly(4,4′-diphenylether-1,3,4-oxadiazole)s

Summary Poly(4,4-diphenylether-1,3,4-oxadiazole)s have been prepared by polycondensation of 4,4-diphenylether dicarboxylic acid and hydrazine sulphate, HS, in poly(phosphoric acid), PPA, under different reaction condictions. The products were characterized by viscometry, gel permeation chromatography, ¹H-NMR spectrometry and thermogravimetric analysis. Dense membranes have been prepared and submitted to gas transport and wide angle X-ray diffraction, WAXD, experiments. The differences found in permeability and selectivity parameters, as well as in density and WAXD results, are discussed in terms of their solution viscosities and hydrazide repeat unit contents.     

Studies on electrochemical properties of poly (ethylene oxide)-based gel polymer electrolytes with the effect of chitosan for lithium–sulfur batteries

Composite gel polymer electrolytes (CGPE), with different proportions of poly (ethylene oxide), plasticizers namely 1,3-dioxolane (DIOX)/tetraethelyneglygol dimethylether (TEGDME) and a lithium salt (LITFSI) with the addition of filler chitosan were prepared using the solution casting technique in an argon atmosphere. The membranes were subjected to various characterization techniques such as TG/DTA, FTIR and an ac impedance analysis. A lithium symmetric cell (Li/CGPE/Li) was assembled and the interfacial stability of the polymer electrolyte with a lithium anode was measured. The electrochemical stability and the transport properties of the high conducting sample were also measured. TG/DTA shows the thermal stability of the high conducting sample. The optimal value of the plasticizers was to be found in the ionic conductivity point of view.     

Modelling of poly(ethylene terephthalate) in injection stretch–blow moulding

Abstract

Simulations of the injection stretch–blow moulding process have been developed for the manufacture of poly(ethylene terephthalate) bottles using the commercial finite element package ABAQUS/standard. Initially a simulation of the manufacture of a 330 mL bottle was developed with three different material models (hyperelastic, creep, and a non-linear viscoelastic model (Buckley model)) to ascertain their suitability for modelling poly(ethylene terephthalate). The Buckley model was found to give results for the sidewall thickness that matched best with those measured from bottles off the production line. Following the investigation of the material models, the Buckley model was chosen to conduct a three-dimensional simulation of the manufacture of a 2 L bottle. It was found that the model was also capable of predicting the wall thickness distribution accurately for this bottle. In the development of the three-dimensional simulation a novel approach, which uses an axisymmetric model until the material reaches the petaloid base, was developed. This resulted in substantial savings in computing time.     

Crystallization and morphology of poly(ethylene succinate) and poly(β-hydroxybutyrate) blends

Summary The melting and crystallization behavior of poly(β-hydroxybutyrate) (PHB) and poly(ethylene succinate) blends has been studied by differential scanning calorimetry and optical microscopy. The results indicate that PHB and PES are miscible in the melt. Consequently the blend exhibits a depression of the melting temperature of both PHB and PES. In addition, a depression of the equilibrium melting temperature of PHB is observed. The Flory-Huggins interaction parameter (χ₁₂ ), obtained from melting point depression data, is composition dependent, and its value is always negative. Isothermal crystallization in the miscible blend system PES/PHB is examined by polarized optical microscope. The presence of the PES component gives a wide variety of morphologies. The spherulites exhibit a banded structure and the band spacing decreases with increase PES content. Received: 29 June 1998/Revised version: 31 August 1998/Accepted: 10 September 1998     

The effects of the preparation conditions on the electrochemical properties of graphite-CrO3 intercalation compounds in acid electrolyte—I. the studies on lower chromium oxides

A slow potentiodynamic method (10 mV min⁻¹) has been used to characterize the dilute intercalation compounds of graphite with CrO₃ (GIC-CrO₃'s) prepared by the dry and the impregnation-dry method from two kinds of natural graphite of different flake sizes. The characteristic anodic peak at 1.3–1.4 V vs nhe obtained for GIC-CrO₃'s in 0.25 M H₂SO₄ was evidenced to be associated with the oxidation of the lower oxides of Cr such as Cr₃O₈ and/or Cr₂O₅ remaining in the compounds after their treatment in hot 6 M HCl. The amount of these oxides and their electrochemical activity are dependent on the kind of graphite subjected to the intercalation process as well as the method of intercalation. The comparison of the results obtained for GIC-CrO₃'s with those achieved for the same compounds after heat treatment and with the physical mixture of pristine graphite with Cr₂O₃ led to assumption that lower oxides were formed due to the partial reduction of CrO₃ intercalated and that between them and the graphite structure, occurs the chemical interaction.     

Effect of immobilization of poly(γ-glutamic acid) on the biocompatibility of electrospun poly (L-lactide) mats

In this study, poly(L-lactide) (PLLA) non-woven mats were prepared by electrospinning technique, followed by treating with oxygen plasma and grafting with 3-aminopropyl triethoxysilane (APTES), then immersed in poly(γ-glutamic acid) (γ-PGA) solution to form a layer of γ-PGA on the surface. In so doing, hydrophobic PLLA would become highly hydrophilic. Through characterization of hydrophilicity and biocompatibility, the feasibility of these modified mats for wound dressing was evaluated. The results show that after the grafting of γ-PGA, the swelling ratio increased greatly from 7% for pristine PLLA mat to 321% for γ-PGA-grafted PLLA mat, and the contact angle decreased from 112° to 25°. In vitro cytocompatibility tests against L929 fibroblast show that γ-PGA-grafted PLLA was non-cytotoxic. In addition, the proliferation of fibroblasts was higher on γ-PGA-grafted PLLA than on pristine PLLA.     

The effect of sulfur evolution on the properties of high-temperature carbons—I. Thianthrene and thianthrene-anthracene precursors

The carbonization (525°C) and graphitization (up to 2500°C) of thianthrene, anthracene and a 17% wt thianthrene-83% wt anthracene mixture were investigated. The thianthrene carbons were found to be non-graphitizable and of low density. Upon heat-treatment from 1200–2500°C sulfur was evolved continuously and there was a further decrease in density due to an increase in closed porosity. The carbons produced from the mixture were found to be graphitizable and possessed similar crystal parameters to those carbons derived from anthracene after heat treatment to the same temperature. In contrast to the anthracene carbons, the mixed carbons showed a sharp decrease in density with heat treatment temperature. The principal reduction in sulfur content occurred between 1400–1600°C. The density change appears to be produced through the disruption of crystallite alignment which substantially increases the open pore volume for pores of less than 200 nm diameter. The behavior of the mixed carbon is similar to that reported for high sulfur petroleum cokes which can undergo an irreversible expansion (puffing) during graphitization.     

Synthesis,structure and behavior of new polycaprolactam copolymers based on poly (ethylene oxide)–poly (propylene oxide)–poly (ethylene oxide) macroactivators derived from Pluronic block copolymers

Novel series of poly (CL–co–Pluronic) polymers were successfully synthesized in situ by ring-opening polymerization (ROP) of ε-caprolactam (ε-CL). The copolymerization was activated by new type macroactivators (MAs) based on hydroxyl-terminated poly (ethylene oxide)-poly (propylene oxide)-poly (ethylene oxide) [PEO-PPO-PEO] triblock copolymers, known under the trade name Pluronic^®. Toluene-2,4-diisocyanate (TDI) was used to obtain the isocyanate-terminated Pluronic prepolymers. The corresponding MAs were synthesized in situ with an N-carbamoyllactam structure. As an initiator of the copolymerization processes was used sodium lactamate (NaCL). To confirm the influence over the copolymerization process, microstructure, composition and molecular weight of the polymeric products two new types MAs based on Pluronic (P123 and F68) have been varied from 2 to 10 wt.% (vs. the monomer ε-CL). The structure of the both Pluronic based macroactivators (MAs) and accordingly obtained two series poly (CL-co-Pluronic) polymers were confirmed by ¹H NMR and FT-IR analyses. Additionally, the structure, molecular weight, physicomechanical behavior, thermal stability and morphology of the new synthesized poly (CL–co–Pluronic) polymers have been investigated by Differential Scanning Calorimetry (DSC), Wide-Angle X-ray Diffraction (WAXD), Thermogravimetric Analysis (TGA) and Scanning Electron Microscopy (SEM) analysis.