Nonisothermal crystallization behaviors of poly(3‐hexylthiophene)/reduced graphene oxide nanocomposites

Poly(3‐hexylthiophene) (P3HT)/reduced graphene oxide (rGO) nanocomposites were prepared through in situ reduction of graphene oxide in the presence of P3HT. The nonisothermal crystallization behaviors of P3HT and P3HT/rGO nanocomposites were investigated by differential scanning calorimetry. The Avrami, Ozawa, and Mo models were used to analyze the nonisothermal kinetics. The addition of rGO remarkably increased the crystallization peak temperature and crystallinity of P3HT, but the crystallization half‐time revealed little variation. The crystallization activation energies were calculated by the Kissinger equation. The results suggested that rGO plays a twofold role in the nonisothermal crystallization of P3HT, that is, rGO promotes the crystallization of P3HT as nucleating agent, and meanwhile, it also restricts the motion of P3HT chains. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Physical characterizations of semi-conducting conjugated polymer-CNTs nanocomposites

Carbon nanotubes (CNTs) were prepared using Alcholic Catalyst Chemical Vapor Deposition (ACCVD) technique in order to investigate the effects of their addition on the optical, electrical and mechanical properties of Poly(3-octylthiophene-2,5-diyl) (P3OT) matrix. The absorption spectra of the prepared CNTs and CNT-P3OT nanocomposites were measured in the spectral range 200 nm–3,000 nm at room temperature. The optical energy gap was determined from the obtained UV/Vis absorption spectrum. Optical results reveal that the prepared CNTs are almost single walled. Besides, the addition of CNTs to P3OT polymer matrix will decrease the optical energy gap and enhance the optical absorbance of P3OT matrix. On the other hand, the addition of CNTs to P3OT matrix will increase the electrical conductivity of P3OT matrix up to four orders of magnitude above the percolation threshold (0.44 wt% CNTs). Additionally, I–V characteristics indicate that the conduction mechanism is Ohmic at low applied voltage range while it is due to the trap charge limited at high applied voltage range. Furthermore, the behavior of dc conductivity with temperature was also investigated and the obtained results reveal that the activation energy decreases with CNTs content. Finally, mechanical results reveal that the elastic modulus values increase with the increasing of CNTs content in P3OT matrix.     

Butterfly nanostructures via regioregularly grafted multi‐walled carbon nanotubes and poly(3‐hexylthiophene) to improve photovoltaic characteristics

Butterfly nanostructures were designed using multi‐walled carbon nanotubes (CNTs) grafted with regioregular poly(3‐hexylthiophene) (RR‐P3HT) chains (CNT‐graft‐P3HT). The secondary crystallization of RR‐P3HT free chains onto CNT‐graft‐P3HT reflected the donor–acceptor supramolecules with a butterfly configuration, in which the CNT acted as the body of the butterfly and seeded crystallization of P3HT free chains resulted in the wings having a width of 37–38 nm. Butterfly supramolecules demonstrated high melting point (241.2 °C), fusion enthalpy (31.5 J g^?1) and crystallinity (85.13%). High photoluminescence quenching and thus donating–accepting property were also detected for the butterfly nanohybrids with a bandgap energy of 1.94 eV. Incorporation of butterfly nanostructures in the active layer of photovoltaic devices (P3HT:butterfly) conspicuously affected the system characteristics including short circuit current density (J_sc; 10.84 mA cm^?2), fill factor (FF; 56%) and power conversion efficiency (PCE; 3.94%). The inclusion of phenyl‐C71‐butyric acid methyl ester molecules as second acceptor in thin‐film active layers further increased the efficacy of systems, i.e. J_sc of 12.23 mA cm^?2, FF of 63%, open circuit voltage of 0.66 V and PCE of 5.08%, without considering external treatments and additives. © 2018 Society of Chemical Industry     

Vapor-assisted imprinting to pattern poly(3-hexylthiophene) (P3HT) film with oriented arrangement of nanofibrils and flat-on conformation of P3HT chains

Poly(3-hexylthiophene) (P3HT) film with a hierarchical ordered structure was fabricated by an approach combining vapor-assisted imprinting in a carbon disulfide (CS₂) atmosphere and thermal annealing treatment. In the hierarchical ordered structure, P3HT domains are vertically arranged and the domains are constituted by uniaxially aligned P3HT nanofibrils, furthermore, the chains in it adopted flat-on conformation. The vertically arranged domains are formed by the action of capillarity, the oriented nanofibrils are induced by the crystallization nucleation of P3HT and the directional evaporation of the solvent, and the flat-on conformation of P3HT chains are induced by the enhanced intermolecular interaction of the alkyl side chains in CS₂ atmosphere. The arrangement behavior of P3HT crystals and chains facilitate the bridging chains link neighboring grains with minimal distortion, while the enhanced intermolecular interaction enable the formation of larger P3HT crystals, and then reduce the quantity of grain boundary. As a result, this ordered structure provides more delocalized electrons along the direction that perpendicular to the substrate, which would result in an improvement of the carrier mobility along this direction.     

Semiconducting polymer-incorporated nanocrystalline TiO2 particles for photovoltaic applications

In this work, we study hybrid solar cells based on blends of the semiconducting polymer poly(3-octylthiophene-2,5-diyl)(P3OT) and [6,6]-phenyl C₆₁ butyric acid methyl (PCBM) coated titanium dioxide (TiO₂) nanocrystal film. The Fourier transform infrared spectra (FTIR), UV–vis absorption spectra and PL quenching researches show that the films had a stronger absorption in visible light range. The influence of the PCBM:P3OT ratio were researched and the optimized ratio of PCBM to P3OT (1:1.5) exhibit a short circuit current of 4.42 mA cm⁻², an open circuit voltage of 0.81 V, a fill factor of 0.73 and a light-to-electric conversion efficiency of 2.61% under a simulated solar light irradiation of 100 mW cm⁻².     

Thermal and mechanical properties of homogeneous ternary nanocomposites of regioregular poly(3‐hexylthiophene)‐wrapped multiwalled carbon nanotube dispersed in thermoplastic polyurethane: Dynamic‐ and thermomechanical analysis

An interesting correlation between initial loading and nature of wrapping of regioregular poly(3‐hexylthiophene) (rrP3HT) on multiwalled carbon nanotube and their combined effect on dynamic‐ and thermomechanical properties in ternary system (thermoplastic polyurethane as matrix) is highlighted. Wrapping of rrP3HT on carbon nanotube (CNT) makes the hexyl side chains thermally nonequivalent and composites more stable. Dynamic‐ and thermomechanical analysis ascertained the miscibility (single T_g = ?40°C), large mechanical reinforcement, and improved storage modulus of nanocomposites in the presence of CNT compared to its blends. Two breaks at ～ ?100 and ～ ?40°C for TPU‐P3HT composites (PHs) and TPU‐P3HT‐MWCNT composites (PHCs) in the loss modulus vs. temperature plot indicates two different types of transitions in P3HT chains. Dimensional stability by expansion probe technique measures low coefficient of thermal expansion of PHCs compared to its blends. Softening property by penetration probe technique suggests that 2.5 wt % loading of P3HT exhibits lowest degree of penetration compared to other nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Role of multi-wall carbon nanotube network in composites to crystallization of isotactic polypropylene matrix

The composites (iPP/CNTs) made of isotactic polypropylene (iPP) and multi-wall carbon nanotubes (CNTs) were prepared by solution blending. To improve compatibility between CNTs and iPP and to enhance dispersion of CNTs in iPP matrix, CNTs were chemically modified by grafting alkyl chains. The chemically modified CNTs had about 6 wt% grafted alkyl chains. Rheological measurements indicated that CNTs caused gelation in iPP/CNTs due to CNT network formation and the critical gelation CNT concentration was about 7.4 wt%, which was considered to be high due to the low CNT aspect ratio in this study. Crystallization behaviors of iPP/CNTs were studied by using optical microscopy (OM) and differential scanning calorimetry (DSC). Radial growth rates of spherulites during isothermal crystallization of iPP/CNTs with CNT concentrations less than 2.0 wt% measured by using OM showed decreasing trends with increasing CNT concentration. Avrami analysis of the exothermic heat flow curves during isothermal crystallization of iPP/CNTs measured by DSC indicated that crystallization rates were accelerated when CNT concentrations were lower than the critical gelation concentration, because CNTs mainly functioned as nucleating agents for crystallization, while crystallization rates did not change obviously when CNT concentrations were higher than the critical gelation concentration, because CNT network could form and mainly functioned to provide restriction to mobility and diffusion of iPP chains to crystal growth fronts.     

A comparative study on the influence of alkyl thiols on the structural transformations in P3HT/PCBM and P3OT/PCBM blends

Herein, we present a comparative study on the structural transformations in P3HT/PCBM and P3OT/PCBM blends using octane (C₈) and dodecane (C₁₂) thiols as solvent additives. Addition of dodecane thiol to the blends promotes needle-like PCBM crystal formation. These crystals are found abundant in P3OT/PCBM and less in P3HT/PCBM blend and are identified by SAXS, DSC and SEM measurements. Using polymer of two different tail lengths, the SAXS results provide the first experimental support on the recent findings on fullerene intercalation around the crystalline boundaries in a semi-crystalline polymer. The UV–Visible measurements reveal that the absorption maximum show an appreciable red-shift and photoluminescence spectra infers that the donor/acceptor interface is mostly retained, upon dodecane thiol addition. These needle-like PCBM crystals obtained by annealing free approach in the blends and their dependence on the alkyl tail length of the polymer, would pave way for more effective design of organic photovoltaic devices.     

High performance PEEK/carbon nanotube composites compatibilized with polysulfones-I. Structure and thermal properties

Poly(ether ether ketone) (PEEK)/single-walled carbon nanotube (SWCNT) composites incorporating polysulfones as compatibilizers were fabricated by melt-blending, after pre-processing based on ball milling and mechanical treatments in an organic solvent. Their structure, morphology and thermal properties have been investigated. Microscopic observations showed a uniform distribution of the CNTs and good miscibility between the compatibilizer and matrix phases. The incorporation of wrapped SWCNTs leads to a remarkable increase in the degradation temperatures of the matrix in comparison with non-compatibilized samples, attributed to the high thermal stability of the polysulfones and the compatibilizing effect. The addition of very small CNT loadings raises the crystallization temperature and the degree of crystallinity of PEEK. At higher concentrations, the inactive nucleating activity of the nanofillers, the confinement of the polymer chains within the CNT network and the presence of an amorphous compatibilizer moderately hinder PEEK crystallization. Synchrotron X-ray diffraction experiments indicate the existence of reorganization phenomena of the matrix crystals during the heating of the composites. Improved thermal properties are found for composites incorporating arc-purified SWCNTs, attributed to the higher degree of debundling and lower metal content of these CNTs. These compatibilized composites are new materials for potential high-temperature structural applications.     

Cocrystallization mechanism of poly(3-alkyl thiophenes) with different alkyl chain length

The crystallization rates of poly(3-alkyl thiophene) (P3AT) cocrystals having different alkyl chain length (e.g. hexyl and octyl) of the components are measured using differential scanning calorimetry (DSC) technique. Two pairs of cocrystals with varying compositions of the components viz. poly(3-octyl thiophene) (P3OT(R), regioregularity 89 mol%) and poly(3-hexyl thiophene) [P3HT(R), regioregularity 92 mol% and P3HT-2 regioregularity 82 mol%] are used. In both the systems the isothermal temperature range (TR) in the same time scale of crystallization is found to decrease with increasing alkyl chain length in the blends. The crystallization rate at the same T_c decreases with increasing alkyl chain length P3AT concentration and the Avrami exponent values of cocrystals are same with those of the component values. The low Avrami exponent values (0.23-1.16) in all the samples suggest the presence of rigid amorphous portion which can not diffuse out quickly from the crystal growth front (soft impingement). Analysis of crystallization rate using Laurintzen-Hoffman (L-H) growth rate theory indicates that there is regime-I to regime-II transition in all the samples. The product of lateral (σ) and end surface energy (σ_e) values are found to decrease with increasing the concentration of longer alkyl chain P3AT in the blend. Analysis of σ values according to a theory of Hoffman et al. [Hoffman JD, Miller RL, Marand H, Rotiman DR. Macromolecules 1992;25:2221. [14]] indicates that there is chain extension of the components in the melt of the blends, however, the entropy of cocrystallization has different sign to the two systems. Cocrystallization in P3HT(R)/P3OT(R) system is an entropy driven process but that in P3HT(2)/P3OT(R) system is entropy forbidden process. A possible explanation of cocrystallization in the later system has been attributed from small interaction between the components.     

Crystallization and stress relaxation behaviors of UHMWPE/CNT fibers

Crystallization and stress relaxation behaviors of ultrahigh molecular weight polyethylene (UHMWPE) doped with carbon nanotubes (CNTs) have been investigated by X‐ray diffraction, differential scanning calorimetry (DSC) and single strand strength testing. Compared with UHMWPE, crystallinity of the UHMWPE/CNT composites significantly increases from 71.95 to 82.92% while crystallization activation energy decreases from 679.4 to 535.8 KJ/mol. CNTs as the nucleating agent changes the nucleation type of UHMWPE from homogenous to heterogeneous and accelerates the nucleation and growing of crystalline grains. Above crystallization changes also affect the mechanical properties of the UHMWPE/CNTs composites. Stress relaxation testing indicates that the relaxation stability of UHMWPE/CNT composites increases while the relaxation rate decreases. J. VINYL ADDIT. TECHNOL., 24:229–232, 2018. © 2016 Society of Plastics Engineers     

Important thermodynamic characteristics of poly(3-hexyl thiophene)

Poly(3-hexyl thiophene) (P3HT) is widely studied as a model material in many electrical and photovoltaic applications, and has become the benchmark polymer when studying the physics of these devices. Despite its extensive use, its precise crystalline structure and thermodynamic characteristics, such as its enthalpy of melting of an ideal crystal, crystalline density, and amorphous density, are not well characterized. This work seeks to provide more certainty in defining these thermodynamic characteristics for regioregular P3HT. This is accomplished by determining the density of rr-P3HT with various thermal histories, and thus percent crystallinity. These densities are correlated to their melting enthalpy melting (ΔH_m) via DSC. This relationship estimates that ΔH₀ for P3HT is between 37 and 50 J/g, that the density of the amorphous portion of semicrystalline rr-P3HT is 1.094 g/cc, and that the density of crystalline P3HT is 1.12–1.14 g/cc. Interestingly, the density of the amorphous portion of rr-P3HT differs significantly from that of regio-random P3HT. This result indicates that the local packing of the segments differs in regio-random P3HT from that in the amorphous portions of rr-P3HT and that care must be expended when equating the behavior of these two phases.     

Melting behaviors and isothermal crystallization kinetics of poly(ethylene terephthalate)/mesoporous molecular sieve composite

Isothermal crystallization and subsequent melting behavior of mesoporous molecular sieve (MMS) filled poly(ethylene terephthalate) (PET) composites have been investigated at the designated temperature by using differential scanning calorimeter (DSC). The commonly used Avrami equation was used to fit the primary stage of the isothermal crystallization. The Avrami exponents n were evaluated to be 2<n<3 for the neat PET and composites. MMS particles acting as nucleating agent in composite accelerated the crystallization rate with decreasing the half-time of crystallization. The crystallization activation energy calculated from the Arrhenius' formula was reduced as MMS content increased. It is shown that the MMS particles made the molecular chains of PET easier to crystallize during the isothermal crystallization process. Subsequent differential scanning calorimeter scans of the isothermally crystallized samples exhibited different melting endotherms. It is found that much smaller or less perfect crystals formed in composites due to the interaction between molecular chains and the MMS particles. The crystallinity of composites was enhanced by increasing MMS content.     

Cellulose nanofibrils as templates for the design of poly(l-lactide)-nucleating surfaces

The abilities of surface-grafted cellulose nanofibrils for the nucleation of poly(l-lactide) (PLLA) were investigated. Cellulose nanofibrils with a width of ∼3 nm were obtained from wood cellulose via the oxidation using 2,2,6,6-tetramethylpiperidiniyl-1-oxyl as a catalyst and successive mechanical treatment. The cellulose nanofibril surfaces were selectively modified with amine-terminated poly(ethylene glycol) chains, via simple ionic bonds. The PEG-grafted cellulose nanofibril/PLLA composite films were prepared using a solvent casting method with chloroform. The isothermal and non-isothermal crystallization kinetics of the PLLA in the composites was studied using differential scanning calorimetry and polarized optical microscopy. The PEG chains were densely immobilized on the surface of the cellulose nanofibril templates, which had extraordinarily large specific surface areas. As a result, the surface-PEG layers effectively increased the rate of crystallization of the PLLA in the composites. Because of the increased degree of crystallinity after the isothermal crystallization, the composites showed better heat resistance than neat PLLA.     

Microstructure and properties of polypropylene/glass fiber composites grafted with poly(pentaerythritol triacrylate)

Isotactic polypropylene(PP)/glass fiber(GF) composites were modified by grafting polymerization of polyfunctional monomer, pentaerythritol triacrylate (PETA), in the presence of 2,5-dimethyl-2,5-di(tert-butylperoxy) hexane peroxide (DDHP) via melt extrusion. Fourier transform infrared spectroscopy (FTIR), melt strength test (MS), mechanical property test, differential scanning calorimetry (DSC) and X-ray diffraction (XRD) were used to characterize the microstructure and properties of the modified composites. The crystallization kinetics was investigated by Mo method while apparent activation energy of crystallization of the composites was determined by Kissinger method. The FTIR results showed that the acrylic polymers were grafted onto the polypropylene chains. The grafting made the melt strengths and the mechanical properties of the modified composites, and the interfacial adhesion between PP and glass fiber all enhanced. High melting and crystallization temperatures, high crystallization rate and large activation energy of crystallization were also obtained after grafting. In addition, the grafted acrylic polymers recovered the depressed crystallization of polypropylene and restrained α-β transition in fatigue experiment.     

Crystallization of i-PP/CaCO3 Composites and its Correlation with Tensile Properties

Abstract

Investigation of crystallization behaviour of isoatactic polypropylene (i-PP) in i-PP/CaCO₃ composites is carried out through Differential Scanning Calorimetry (DSC) and wide angle X-ray diffraction measurements. The effect of CaCO₃ and its surface treatment with titanate coupling agent on nucleation and growth rate of crystallization, crystallite size distribution and crystallinity, is determined from exothermic crystallization peaks of the composites. The filler concentration dependence of crystallinity determined by both the techniques shows good qualitative agreement. Tensile properties viz. tensile modulus, yield stress and elongation were also measured as functions of filler concentration for both untreated and treated CaCO₃ filled composites. Crystallinity, tensile strength and elongation decreased with increasing filler content in both the cases whereas tensile modulus increased. Crystallization parameters have been correlated with the tensile properties of i-PP/CaCO₃ composites.     

纳米CaCO3对FEP非等温结晶动力学的影响

采用熔融共混法制备了聚全氟乙丙烯（FEP）/纳米碳酸钙（nano-CaCO3）复合材料,利用差示扫描量热法研究了FEP及其复合材料的非等温结晶行为,并通过Avrami方程修正的Jeziorny法、Ozawa法以及Mo法对其非等温结晶动力学进行了处理分析。结果表明,Jeziorny法及Mo法均适用于处理FEP和FEP/nano-CaCO3的非等温结晶过程,但Ozawa法不合适;在同一降温速率下,FEP/nano-CaCO3复合材料的初始结晶温度、最大结晶温度均比相应的纯FEP高,且半结晶时间延长,这说明nano-CaCO3对FEP具有一定的诱导和促进成核的作用,但由于FEP/nano-CaCO3复合材料的长链分子结构及大的空间位垒导致FEP的结晶总速率下降。     

Graphene nanoplatelets dispersion in poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactic acid): preparation method and its influence on electrical,crystallinity and thermomechanical properties

Poly(l-lactic acid) (PLLA)/graphene nanoplatelets (GnP) nanocomposites were prepared through solvent casting and coagulation methods. The better dispersion of graphene was achieved by ultrasounds and its effect on crystallinity, thermomechanical and electrical properties of PLLA were studied and compared in both methods. Differential scanning calorimetry (DSC) was used to investigate the crystallinity of PLLA and its composites. Field emission gun scanning electron microscope (FEG-SEM) and wide-angle X-ray scattering (WAXS) were employed to characterize the microstructure of PLLA crystallites. Dynamic mechanical thermal analysis (DMTA) was performed to study the thermomechanical properties of the nanocomposites. FEG-SEM images illustrated finer dispersion of GnP in samples obtained by coagulation method with respect to solvent casting method. Graphene imparted higher electrical conductivity to nanocomposites obtained by solvent casting under ultrasound due to better formation of graphene network. DSC thermograms and their resulting data showed positive effects of GnP on crystallization kinetics of PLLA in both methods enhanced by the nucleating effect of graphene particles. Meanwhile, the effect of GnP, as nucleating agent, was more prominent in samples produced by coagulation method without utilization of ultrasounds. WAXS patterns represented the same characteristic peaks of PLLA in nanocomposite specimens suggesting similar crystalline structure of PLLA in presence of graphene, and the intensified peaks of nanocomposites compared to neat PLLA confirmed the DSC results regarding its improved crystallinity. Graphene increased storage modulus in rubbery region and glass transition temperature of nanocomposites in the coagulation method due to restricted mobility of PLLA chains.     

Effect of particle size and surface modification on mechanical properties of poly(para‐dioxanone)/inorganic particles

Poly(para‐dioxanone) (PPDO)‐based composites have been prepared by blending PPDO with three different types of CaCO₃ particles, CC1 (nano‐CaCO₃), CC2 (CaCO₃ whisker), and CC3 (silane‐coated CaCO₃ whisker). The effects of particles size, interface adhesion, and crystallinity of composites on mechanical properties were discovered through analysis of the morphology of fracture surfaces, thermal characteristics, and crystalline structure. DSC revealed that the CaCO₃ particles acted as a nucleating agent and promoted crystallinity of PPDO. The effect of CaCO₃ particles on crystallization of PPDO was clearly revealed by using the nucleating efficiency. Smaller size particles exhibit greater nucleating efficiency. Adhesion between PPDO and the CaCO₃ particles plays major roles on the mechanical properties of composites. The tensile strength of PPDO was improved over 54%. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers