Mass‐produced graphene—HDPE nanocomposites: Thermal,rheological, electrical,and mechanical properties

Economically viable high‐density polyethylene (HDPE)/graphene nanocomposites were produced using mass produced graphene powder and an industrial twin‐screw melt‐compounding machine. Rheological and electrical properties were investigated and scanning electron microscopy was carried out to investigate graphene dispersion and its network formation in the matrix. Mechanical properties of the nanocomposites were evaluated using tensile, flexural and impact tests. Differential scanning calorimetry analysis indicated that the crystalline structure of the polymer might be affected by high loadings of graphene. SEM evaluation revealed reasonable graphene dispersion in the matrix. In addition, the amount of graphene required to form a percolated network was similar for both rheological and electrical networks. The nanocomposites exhibited a significant increase in Young's and flexural moduli without a notable reduction in impact strength up to 14 wt% graphene loading. In these experiments, compounding graphene powder with HDPE produced a clear and distinct improvement in mechanical properties at an industrially suitable low cost. POLYM. ENG. SCI., 59:675–682, 2019. © 2018 Society of Plastics Engineers     

Polyurethane/amino‐grafted multiwalled carbon nanotube nanocomposites: Microstructure,thermal, mechanical,and rheological properties

A mixture of two different polyols, (polytetramethylene ether glycol and polydimethylsiloxane), were employed to synthesize a new structure of polyurethane (PU) with methylene diphenyl diisocyanate (MDI) and 1,4‐butanediol as chain extender. PU nanocomposites containing variable amount (0.3, 0.5, 1, and 3 wt %) of amino‐grafted multiwalled carbon nanotubes (NH₂‐MWNT) were prepared via in situ polymerization. The dispersion of NH₂‐MWNT into polymer matrix was investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Fourier transform infrared spectroscopy (FT‐IR) confirmed the urethane‐urea chemical bonding between the PU chains and the NH₂‐MWNT. Thermal stabilities of the nanocomposites were examined with thermogravimetric analysis (TGA) and the results indicated a remarkable improvement with increasing NH₂‐MWNT contents. The results of dynamic mechanical thermal analysis (DMTA) including storage modulus (E′) and glass transition temperature (T_g), as well as tensile properties demonstrated that the yield strength, strain‐at‐break, and young modulus were enhanced by increasing NH₂‐MWNT content. Rheological behavior including complex viscosity and storage and loss moduli of the PU nanocomposites improved with increasing NH₂‐MWNT loading, as well. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44411.     

Morphology and mechanical properties of nanostructured acrylic tri‐block‐copolymer modified epoxy

In this study, acrylic tri‐block‐copolymers of different compositions and constituents were used to modify an epoxy resin. In epoxy the block‐copolymers self‐assembled to generate different nanostructured phases. Spherical micelles and vesicles were formed due to preferential interactions among constituents of the blends. The effect of modifier concentration and morphology on the resulting mechanical properties was investigated. At a modifier content of 5 wt% a more than threefold increase in strain energy release rate was observed relative to the unfilled epoxy for the block‐copolymer/epoxy systems studied. This improvement was accompanied by slight reductions in tensile stiffness, strength and glass transition temperature of developed epoxy blends. Microstructural studies revealed that during crack propagation, vesicle and micelle structures respectively underwent debonding and cavitation followed by shear yielding of the substrate matrix. POLYM. ENG. SCI., 54:1047–1055, 2014. © 2013 Society of Plastics Engineers     

Synthesis and properties of elastic polyurethane‐imide

A new synthesis route for elastic polyurethane‐imides (EPUIs) has been established by a method involving the use of urea. Various EPUIs were synthesized from polyurethane‐urea, which was prepared from 4,4′‐diphenylmethane diisocyanate (MDI), polyoxytetramethylene glycol (PTMG) and 4,4′‐diphenylmethanediamine (MDA), and pyromellitic dianhydride in N‐methyl‐2‐pyrrolidone (NMP). Flexible films were cast from these solutions that had different inherent viscosities. Imidization of the EPUI films was completed at 200°C for 4 h in vacuo. The EPUIs were determined by FTIR, ¹H NMR, and ¹³C NMR spectra. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Aluminium‐filled low‐density polyethylene—structural,morphological, and mechanical properties

Low‐density polyethylene (LDPE) was filled with aluminium (Al) powder having concentrations of 1, 4, and 6% w/w. The samples in the form of disc containing the above concentration of Al powder were obtained using hot press molder. The structural properties have been investigated using density measurement and WAXD techniques. The morphology of pure LDPE and Al‐filled LDPE samples has been studied from scanning electron micrographs. The modulus of elasticity of the samples has been determined using Instron tensile tester. Results indicate that the crystallinity of LDPE component increases with the concentration of aluminium filler. Morphological changes also have been observed. The Young's modulus (Y) generally increases and becomes maximum for 4% Al‐filled LDPE sample. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis and characterization of ABA type tri‐block copolymers derived from p‐dioxanone,L‐lactide and poly(ethylene glycol)

A series of triblock co‐polymers, consisting of a poly(ethylene glycol) (PEG) central block joined to two blocks of random p‐dioxanone‐co‐L ‐lactide copolymers were synthesized by ring‐opening polymerization of p‐dioxanone (PDO) and L ‐lactide (LLA) initiated by PEG in the presence of stannous 2‐ethylhexanoate catalyst. The resulting copolymers were characterized by various techniques including ¹H and ¹³C NMR and FTIR spectroscopies, gel permeation chromatography, inherent viscosity, wide‐angle X‐ray diffractometry (WAXD) and differential scanning calorimetry (DSC). The conversion of PDO and L ‐lactide into the polymer was studied various mole ratios and at different polymerization temperature from ¹H NMR spectra. Results of WAXD and DSC showed that the crystallinity of PEG macroinitiator was greatly influenced by the composition of PDO and L ‐lactide in the copolymer. The triblock copolymers with low molecular weight were soluble in water at below room temperature. © 2003 Society of Chemical Industry     

Thermal,mechanical, and rheological properties of plasticized poly(L‐lactic acid)

Polylactide (PLA) is an attractive candidate for replacing petrochemical polymers because it is biodegradable. In this study, a specific PLA 2002D was melt‐mixed with a new plasticizer: glycerol monostearate (GMS). The PLA/GMS blends with different ratios were analyzed by dynamic mechanical analysis and differential scanning calorimetry. Although a slightly phase separation can be seen in DSC curves, the SEM micrographs of the impact fracture surfaces of PLA/GMS blends had a relatively good separation and this phenomenon was in good agreement with their higher impact strength. The result showed that the adding of GMS has enhanced the flexibility of PLA/GMS blends as compared to neat PLA. The relationship between complex viscosity and angular frequency of the PLA/GMS blends exhibits that the melt viscosity substantially lower than that of neat PLA. For example, at 10 rad/s, the melt viscosity of PLA/GMS (85/15) was reduced by about 7.2% compared to that of neat PLA. The impact strength was changed from 4.7 KJ/m² for neat PLA to 48.2 KJ/m² for 70/30 PLA/GMS blend. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of novel polystyrene‐block‐polyurethane‐block‐polystyrene tri‐block copolymers through atom transfer radical polymerization

Background: Radical polymerization is used widely to polymerize more than 70% of vinyl monomers in industry, but the control over molecular weight and end group of the resulting polymers is always a challenging task with this method. To prepare polymers with desired molecular weight and end groups, many controlled radical polymerization (CRP) ideas have been proposed over the last decade. Atom transfer radical polymerization (ATRP) is one of the successful CRP techniques. Using ATRP, there is no report on the synthesis of polystyrene‐block‐polyurethane‐block‐polystyrene (PSt‐b‐PU‐b‐PSt) tri‐block copolymers. Hence this paper describes the method of synthesizing these tri‐block copolymers. To accomplish this, first telechelic bromo‐terminated polyurethane was synthesized and used further to synthesize PSt‐b‐PU‐b‐PSt tri‐block copolymers using CuBr as a catalyst and N,N,N,N″,N″‐pentamethyldiethylenetriamine as a complexing agent. Results: The ‘living’ nature of the initiating system was confirmed by linear increase of number‐average molecular weight and conversion with time. A semi‐logarithmic kinetics plot shows that the concentration of propagating radical is steady. The results from nuclear magnetic resonance spectroscopy, gel permeation chromatography and differential scanning calorimetry show that the novel PSt‐b‐PU‐b‐PSt tri‐block copolymers were formed through the ATRP mechanism. Conclusion: For the first time, PSt‐b‐PU‐b‐PSt tri‐block copolymers were synthesized through ATRP. The advantage of this method is that the controlled incorporation of polystyrene block in polyurethane can be achieved by simply changing the polymerization time. Copyright © 2007 Society of Chemical Industry     

Morphology and photophysical properties of a thermally responsive fluorescent material based on a rod‐coil tri‐block copolymer

A thermally responsive rod‐coil poly[poly (N‐isopropylacrylamide)‐b‐polyfluorene‐b‐poly(N‐isopropylacrylamide)] triblock copolymer has been successfully synthesized by atom transfer radical polymerization from an end‐functionalized macroinitiator. The thermochromic behavior and relevant morphology of this polymer were investigated by UV‐vis spectra, DLS, and AFM, respectively, at various temperatures. A thermally responsive fluorescent material was achieved facilely by combining the optically active polyfluorene with temperature‐responsive poly(N‐isopropylacrylamide). All the measurements demonstrated that in the region of 25–45°C, the polymer underwent a phase transition and the corresponding change in optical properties in its water solution. However, the polymer did not show completely reversible behavior upon heating and cooling. On the basis of the comparison with two other thermally responsive conjugated polymers in literatures, a tentative mechanism has been proposed that π–π interaction induced rigid segments to remain chain conformation and packing styles as in collapsed state. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Long chain branched poly(butylene succinate‐co‐terephthalate) copolyesters using pentaerythritol as branching agent: Synthesis,thermo‐mechanical,and rheological properties

Incorporating long chain branching (LCB) structure into biodegradable copolyesters can effectively improve their melt strength and film blowing processability. However, branching also results in deterioration of crystallizability which is also important for copolyester properties and processing. In this study, pentaerythritol (PER) was used as branching agent (BA) instead of previous used in‐situ BA, diglycidyl 1,2,3,6‐tetrahydrophthalate (DGT), to synthesize LCB poly(butylene succinate‐co‐terephthalate) (PBST) copolyesters. The chain structure was characterized and the effects of branching on thermal transition, mechanical, and rheological properties were investigated. Similar to DGT, copolymerizing small amount of PER (0.1–0.4 mol %) generates LCB structure and, therefore, improves the melt elasticity or strength and tensile modulus but reduces the elongation at break. Differing from DGT, PER showed higher branching efficiency, and PER‐branched PBSTs exhibited unchanged or even improved crystallization ability compared with linear PBST. The improved melt strength coupled with good crystallizability will endow PER‐branched PBSTs with better film blowing processability. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44544.     

Synthesis and rheological properties of nickel‐zinc ferrite polymer nanocomposites

In this work, the ferrimagnetic nickel‐zinc ferrite nanopowder was synthesized via citrate‐ethylene glycol processing, followed by the preparation of the epoxy‐based nanocomposite. The materials were characterized using X‐ray diffraction (XRD), simultaneous thermal analysis (STA), alternative gradient force magnetometer (AGFM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results showed that the sample calcined at 1000°C for 1 h had the best crystallinity, and the calculated crystallite size of this sample was ～ 105 nm. The rheological properties and the magnetoviscous effect of the nanocomposites were studied by a standard rotating rheometer. The effects of the magnetic fields and shear rate with respect to time were investigated, and the results were discussed in terms of aggregates and magnetic field‐induced structures. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Morphological,thermal, rheological,and mechanical properties of PP/EVOH blends compatibilized with PP‐g‐IA

We prepared some blends of polypropylene (PP) and ethylene vinyl alcohol (EVOH) with and without a compatibilizer. As a new compatibilizer, we synthesized polypropylene grafted with itaconic acid (PP‐g‐IA) using Brabender mixing system. We investigated the morphological, thermal, rheological, and mechanical properties of a compatibilized blends (PP/EVOH/PP‐g‐IA) and not compatibilized blends (PP/EVOH). Our experiments showed that carboxylic acid groups in PP‐g‐IA and hydroxyl group in EVOH formed strong in situ hydrogen bond in the compatibilized blends, resulting in better morphological and mechanical properties of the compatibilized blends than those of not compatibilized blends. POLYM. ENG. SCI., 56:1240–1247, 2016. © 2016 Society of Plastics Engineers     

Synthesis and thermal properties of poly(methyl methacrylate)‐poly(L‐lactic acid)‐poly(methyl methacrylate) tri‐block copolymer

Poly(methyl methacrylate)‐poly(L ‐lactic acid)‐poly(methyl methacrylate) tri‐block copolymer was prepared using atom transfer radical polymerization (ATRP). The structure and properties of the copolymer were analyzed using infrared spectroscopy, gel permeation chromatography, nuclear magnetic resonance (¹H‐NMR, ¹³C‐NMR), thermogravimetry, and differential scanning calorimetry. The kinetic plot for the ATRP of methyl methacrylate using poly(L ‐lactic acid) (PLLA) as the initiator shows that the reaction time increases linearly with ln[M]₀/[M]. The results indicate that it is possible to achieve grafted chains with well‐defined molecular weights, and block copolymers with narrowed molecular weight distributions. The thermal stability of PLLA is improved by copolymerization. A new wash‐extraction method for removing copper from the ATRP has also exhibits satisfactory results. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and characterization of low density polyethylene‐agar biocomposites: Torque‐rheological,mechanical, thermal and morphological properties

Low density polyethylene (LDPE) and agar were blended by using the former as an internal mixer and varying the amount of agar. Resulting blends were hot pressed and characterized with regard to their torque‐rheological, mechanical, dynamic‐mechanical, thermal, and morphological properties. The torque rheological properties were determined using classical power law model. Tensile properties of LDPE‐agar biocomposites showed that agar improves the tensile modulus (stiffness), but compromise the tensile strength and elongation at break. Viscoelastic behavior of the matrix is clearly influenced by the presence of agar biofiller as shown by the dynamic mechanical analysis (DMA). Thermal behavior of the biocomposites was also investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Morphological observations by scanning electron microscopy (SEM) show the ductile to brittle fracture of LDPE‐agar biocomposites subjected to tensile test. This work is an initial reference to identify potential applications of biocomposites based‐on agar as a biofiller. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

The rheological behavior and dynamic mechanical properties of syndiotactic 1,2‐polybutadiene

The rheological behavior and the dynamic mechanical properties of syndiotactic 1,2‐polybutadiene (sPB) were investigated by a rotational rheometer (MCR‐300) and a dynamic mechanical analyzer (DMA‐242C). Rheological behavior of sPB‐830, a sPB with crystalline degree of 20.1% and syndiotactic content of 65.1%, showed that storage modulus (G′) and loss modulus (G″) decreased, and the zero shear viscosity (η₀) decreased slightly with increasing temperature when measuring temperatures were lower than 160°C. However, G′ and G″ increased at the end region of relaxation curves with increasing temperature and η₀ increased with increasing temperature as the measuring temperatures were higher than 160°C. Furthermore, critical crosslinked reaction temperature was detected at about 160°C for sPB‐830. The crosslinked reaction was not detected when test temperature was lower than 150°C for measuring the dynamic mechanical properties of sample. The relationship between processing temperature and crosslinked reaction was proposed for the sPB‐830 sample. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Influence of some additives on state‐of‐mix,rheological, tensile,and dynamic mechanical properties in SBR compounds

The influence of some additives (Flexon processing oil, Struktol WB 16 slipping agent, and Struktol NS 60 homogenizing resin) on state‐of‐mix, rheological, tensile, and dynamic mechanical properties were investigated. It was found that extrudate swell of the rubber compounds with either processing oil or NS 60 is governed mainly by the state‐of‐mix, but by wall slip in the case of compounds with WB 16. As for the dynamic mechanical properties, the plasticizing effect is the major factor controlling the properties in the case of processing oil, while the degree of crosslink and dilution effect are the main factors in the case of NS 60. Both degree of crosslink and state‐of‐mix are responsible for the dynamic mechanical properties in the case of WB 16. In addition, it was found that the tensile properties are controlled mainly by the plasticizing effect in the case of processing oil, but by the degree of crosslink in the cases of WB 16 and NS 60. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2474–2482, 2001     

Influence of screw speed on the mechanical and rheological properties of poly(ethylene‐co‐vinyl acetate)—organomodified montmorillonite nanocomposites

Poly(ethylene‐co‐vinyl acetate) (EVA) and organophilic montmorillonite clay nanocomposites were manufactured in a co‐rotating twin‐screw extruder using screw speeds ranging between 200 and 800 rpm. The morphology and thermal‐mechanical and rheological properties were studied to establish processing–morphology–property relationships. Particularly for samples produced under higher screw speed ranges, X‐ray diffraction and transmission electron microscopy revealed a tendency of increased exfoliated clay. Although the mechanical properties improved by the presence of clay, they were not altered by the screw speed. The rheological behavior in the solid and melt states were evaluated and showed that the storage modulus of neat EVA subjected to higher screw speed undergoes more pronounced decrease in the storage modulus than the nanocomposites, suggesting that the clay minimizes the effect of the screw speed. This minimization effect could be explained in the light of the assessment of relaxation times that showed stronger physical interactions with the nanocomposites in the molten state. POLYM. COMPOS., 36:854–860, 2015. © 2014 Society of Plastics Engineers     

Bleached extruder chemi‐mechanical pulp fiber‐PLA composites: Comparison of mechanical,thermal, and rheological properties with those of wood flour‐PLA bio‐composites

An environmentally friendly bleached extruder chemi‐mechanical pulp fiber or wood flour was melt compounded with poly(lactic acid) (PLA) into a biocomposite and hot compression molded. The mechanical, thermal, and rheological properties were determined. The chemical composition, scanning electron microscopy, and Fourier transform infrared spectroscopy results showed that the hemicellulose in the pulp fiber raw material was almost completely removed after the pulp treatment. The mechanical tests indicated that the pulp fiber increased the tensile and flexural moduli and decreased the tensile, flexural, and impact strengths of the biocomposites. However, pulp fiber strongly reinforced the PLA matrix because the mechanical properties of pulp fiber‐PLA composites (especially the tensile and flexural strengths) were better than those of wood flour‐PLA composites. Differential scanning calorimetry analysis confirmed that both pulp fiber and wood flour accelerated the cold crystallization rate and increased the degree of crystallinity of PLA, and that this effect was greater with 40% pulp fiber. The addition of pulp fiber and wood flour modified the rheological behavior because the composite viscosity increased in the presence of fibers and decreased as the test frequency increased. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44241.     

Polyamide‐6‐b‐polybutadiene block copolymers: Synthesis and properties

Polyamide‐6 (PA6)/polybutadiene (PB) block copolymers were synthesized with macroactivators (MAs) based on hydroxyl‐terminated polybutadiene functionalized with diisocyanates and having three N‐acyllactam chain‐growing centers per molecule. Two different diisocyanates, hexamethylene diisocyanate and isophorone diisocyanate, were applied as precursors for the MAs. The sodium salt of ε‐caprolactam was chosen as an initiator. The influence of the MA type and concentration on the anionic ring‐opening polymerization of ε‐caprolactam at 180°C was studied. A large percentage of the gel fraction in the copolymers was estimated, indicating crosslinked macromolecules. The structure and phase behavior of the copolymers were investigated with differential scanning calorimetry, wide‐angle X‐ray scattering, thermogravimetric analysis, and dynamic mechanical thermal analysis. In the copolymers, only the PA6 chains crystallized, and the crystallinity depended on the PB content. Different glass‐transition temperatures for the PB blocks and PA6 blocks were observed, indicating microphase separation in the copolymers. The mechanical properties of the copolymers were studied by notched impact testing and hardness measurements. The impact strength increased linearly with the soft component concentration up to 10 wt % and reached values six times higher than those of the PA6 homopolymer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 711–717, 2003     

Blends of high‐density polyethylene with chlorinated polyethylene: Morphology,thermal, rheological,and mechanical properties

Blends of high‐density polyethylene (HDPE) with chlorinated polyethylene (CPE) were generated using melt mixing. CPE of two different chlorination contents was used and its amount in the blends was varied from 1% till 30%. The rheological, thermal, mechanical, and morphological properties of the blends were characterized along with miscibility analysis. In general, better mixing of the CPE polymer in HDPE was observed at lower CPE concentration and reduced mixing or immiscibility occurred at higher concentration of CPE. However, the extent of immiscibility was different in both CPE25 and CPE35 systems. The rheological analysis of the data using Cole‐Cole, Han‐Chuang and van Gurp plots confirmed the miscibility of CPE25 blends (except for 30% CPE25 blend at lower frequency) whereas CPE35 blends with 10–30% CPE content were immiscible. Highest increase in the rheological properties (complex moduli) was observed at 2% CPE content. The mechanical properties of the CPE25 blends were superior than the corresponding CPE35 blends especially at higher CPE concentration where effects of immiscibility as well as matrix plasticization played a role. The morphology characterization using TEM indicated change in the crystalline features of the polymer in the case of CPE35 blends. The optical microscopy also confirmed the better mixing of CPE25 polymers in HDPE than CPE35. The CPE25 blends exhibited uniformly dispersed CPE phase which was also confirmed by the rheological analysis. However, the blends of CPE35 with 10% CPE content onwards had significant phase immiscibility. POLYM. ENG. SCI., 54:85–95, 2014. © 2013 Society of Plastics Engineers