Molecular design of interfacial layers based on conjugated polythiophenes for polymer and hybrid solar cells

In the past two decades, bulk heterojunction organic photovoltaic (OPV) devices have emerged as attractive candidates for solar energy conversion due to their lightweight design and potential for low‐cost, high‐throughput, solution‐phase processability. Interfacial engineering is a proven efficient approach to achieve OPV devices with high power conversion efficiencies. This mini‐review provides an overview of the key structural considerations necessary when undertaking the molecular design of conjugated polyelectrolytes, for application as interfacial layers (ILs). The different roles of ILs are outlined, together with the advantages and disadvantages of competing classes of IL materials. Particular emphasis is placed on the design and synthesis of water‐soluble polythiophene‐based IL materials and the influence of their structural characteristics on their performance as a promising class of IL material. Finally, the challenges and opportunities for polythiophenes as IL materials for OPV devices and other solution‐processed solar cell technologies (e.g. perovskite solar cells) are discussed. © 2017 Society of Chemical Industry     

Enhancing Photovoltaic Performance Using an All‐Conjugated Random Copolymer to Tailor Bulk and Interfacial Morphology of the P3HT:ICBA Active Layer

Bulk heterojunction (BHJ) solar cells are fabricated using active material blends of poly(3‐hexylthiophene) (P3HT) donor, indene‐C₆₀ bisadduct (ICBA) acceptor, and an all‐conjugated random copolymer (RCP) additive. By optimizing RCP loading, power conversion efficiencies (PCEs) up to 20% higher than those of a binary P3HT:ICBA mixture are achieved. The improved device characteristics are rationalized in terms of the differences between the photoactive thin film morphologies. Energy‐filtered transmission electron micro­scopy reveals that incorporation of the RCP improves the degree of structural order of the BHJ fibrillar network and increases the extent of microphase separation between P3HT and ICBA. Additionally, a combination of atomic force microscopy and X‐ray photoelectron spectroscopy analysis indicates segregation of the RCP at the free interface, leading to a shift in the surface potentials measured by Kelvin probe force microscopy. These changes, both in the bulk morphology and in the interfacial composition/energetics, are correlated to improved carrier collection efficiency due to a reduction of non‐geminate recombination, which is measured by charge extraction of photo­generated carriers by linearly increasing voltage.     

Synthesis of Janus polyaniline–polyelectrolyte complex membrane via in situ confined polymerization

Polyelectrolyte complex (PEC) membranes prepared from poly(styrene sulfonate) (PSS) and poly(diallyldimethylammonium chloride) (PDADMAC) were modified by crossflow polymerization of aniline (ANI). The PEC membranes were used as separators in a two-compartment setup where ANI monomer and ammonium persulfate (APS) oxidant diffused through the membranes to form polyaniline (PANI). APS and ANI having different distributions throughout the membranes, the reaction led to the asymmetric polymerization of PANI on one face of each PEC membrane thus producing Janus membranes. Due to the excess PANI content, the membrane displayed distinct asymmetric electrical conductivities on each face. Interestingly, very different ANI polymerizations were obtained when nonstoichiometric PEC membranes having different molar ratio of cationic and anionic polyelectrolytes (P⁺:P^? represents PDADMAC:PSS) were used and transport of APS was fastest through the 2:1 PEC when compared to the 1:2 PEC. In all experiments, the polymerization was most intense on the ANI side of the membranes. Also, the influence of NaCl both during PEC fabrication and during polymerization was studied and found to have some effect on the solute permeability. Results showed that a higher content of PANI was formed on PEC membranes having excess P⁺ and with no NaCl added during PEC fabrication. Although X-ray diffraction confirmed the presence of PANI on both sides of each membrane, scanning electron microscopy images demonstrated that both sides of each membrane had different PANI content deposited. Electrical conductivity measurements using a four-point probe setup also showed that the PEC–PANI exhibits asymmetric electrical property on different sides. © 2021 Society of Industrial Chemistry.     

Hydrodynamic Phonon Transport Perpendicular to Diffuse-Gray Boundaries

In this paper, we examine the application of an ideal phonon-hydrodynamic material as the heat transfer medium between two diffuse-gray boundaries with a finite temperature difference. We use the integral-equation approach to solve a modified phonon Boltzmann transport equation with the displaced Bose–Einstein distribution as the equilibrium distribution between two boundaries perpendicular to the heat transfer direction. When the distance between the boundaries is smaller than the phonon normal scattering mean free path, our solution converges to the ballistic limit as expected. In the other limit, we find that, although the local thermal conductivity in the bulk of the hydrodynamic material approaches infinity, the thermal boundary resistance at the interfaces becomes dominant. Our study provides insights into both the steady-state thermal characterization of phonon-hydrodynamic materials and the practical application of phonon-hydrodynamic materials for thermal management.     

Significant improvement for the functional properties of konjac glucomannan based on phase separation

Konjac glucomannan (KGM) serves as a stabiliser due to its high molecular weight and viscosity. However, these properties limit its addition in food products, especially in drinks. The main aim of this study was to improve the functional properties of KGM by a green and effective method, that is phase separation. It was found that increasing temperature accelerated phase separation of KGM/gum arabic mixture. KGM‐rich phase was characterised and its physical properties were investigated by different methods. Crystal property showed no significant changes after phase separation. Nevertheless, rheological properties indicated that the viscosities of samples after phase separation (FKGM) decreased dramatically. Their emulsifying capacities also improved. Moreover, the differences in molecular rearrangement at the oil–water interface were also studied by using interfacial rheology. These results suggested that FKGM with low viscosity had better interfacial properties, and thus may have potential applications as food ingredients.     

A study on the characteristics and pervaporation performance of polyamide thin‐film composite membranes with modified polyacrylonitrile as substrate for bioethanol dehydration

To improve the pervaporation performance in separating an aqueous ethanol solution, polyamide thin‐film composite (TFC) membranes (m‐tolidine‐H‐TMC/mPAN) were prepared through the interfacial polymerization reaction between trimesoyl chloride (TMC) and 2,2'‐dimethylbenzidine hydrochloride (m‐tolidine‐H) on the surface of a modified polyacrylonitrile (mPAN) membrane. The effects of the feed ethanol concentration on the pervaporation performance and the durability of m‐tolidine‐H‐TMC/mPAN TFC membranes were investigated. To choose the optimal mPAN membrane as the TFC substrate, the effect of hydrolysis time on the chemical properties and separation performance of an mPAN substrate was also studied. An appropriate hydrolysis time of 15 min was chosen to obtain the mPAN substrate due to the corresponding high permeation flux. The m‐tolidine‐H‐TMC/mPAN TFC membrane exhibited a high pervaporation performance for ethanol dehydration. A positron annihilation lifetime spectroscopy experiment was used to estimate the mean free‐volume radius of the m‐tolidine‐H‐TMC polyamide selective layer, which lay between the radii of the water and ethanol molecules. © 2013 Society of Chemical Industry     

STRUCTURAL TYPES IN PETROLEUM ASPHALTENES AS DEDUCED FROM PYROLYSIS/GAS CHROMATOGRAPHY/MASS SPECTROMETRY

ABSTRACT

An integrated technique has been developed for the study of the thermal chemistry of petroleum fractions—particularly the asphaltenes. The procedure involves the integrated use of a pyroprobe/gas chroma-tographic/mass spectrometric technique which offers information about the structuraI-types and distribution within the volatile products from the thermal decomposition of asphaltenes. The technique offers itself as an attractive on-line analytical method for the study of structural types that occur in asphaltenes as well as a technique for studying the parameters that can influence asphaltene decomposition. The concept of deducing “average” structures of asphaltenes is briefly discussed in terms of the observance of the lower molecular weight species in the volatile products of the thermal decomposition.     

Characterization of synthesized poly(aryldisulfide) through interfacial polymerization using phase-transfer catalyst

A new polysulfide polymer was synthesized from 1,4-bis(chloromethyl)-benzene and sodium disulfide by an interfacial polycondensation technique in the presence of tetrabutyl ammonium bromide, methyltributyl ammonium chloride and benzyl triethyl ammonium chloride as phase-transfer catalysts (PTC). The effect of PTC on the kinetics of polymerization was investigated. Structures of this aromatic polysulfide were confirmed through elemental analyses, attenuated total reflectance Fourier transform infrared spectroscopy, Raman spectroscopy, an X-ray diffraction technique, and a nuclear magnetic resonance spectroscopy method. The thermal behavior of this polymer was also characterized by differential scanning calorimetry and thermogravimetric analysis. The solubility of prepared polymer was critically dependent on the identity of the solvent.     

工艺参数对WC颗粒增强表层复合材料与钢基界面组织的影响

以45钢为基材,通过放电等离子烧结和铸造工艺成功制备了WC颗粒增强表层复合材料,研究不同浇铸工艺参数对表层WC/Fe复合材料与基材之间的界面结合及微观组织的影响。结果表明:随着浇铸量的增加,锭模的数值模拟温度可达1493 ℃,高温停留时间约734 s,为实现钢液与WC/Fe复合材料冶金结合提供有利条件,但是过高的浇铸量使WC/Fe复合材料的组织发生明显的变化,几乎观察不到WC增强相,组织出现大量鱼骨状碳化物Fe₃W₃C。当浇铸量控制在锭模体积的2/5时,可得到良好的WC/Fe复合材料与基材的宏观界面,界面反应产物Fe₃W₃C增加,但是增强颗粒仍保留了浇铸前的原始形貌。