基于特征正交分解的一类瞬态非线性热传导问题的新型快速分析方法

提出了一种基于特征正交分解(POD)和有限元法的瞬态非线性热传导问题的模型降阶快速分析方法, 建立了导热系数随温度变化的一类瞬态非线性热传导问题有限元格式的POD降阶模型. 在隐式时间推进方法的基础上有效结合单元预转换方法和多级线性化方法发展了一种加速求解瞬态非线性热传导降阶模型的新型计算方法,并通过二维和三维算例验证了该方法的准确性和高效性. 研究结果表明: (1)降阶模型解的均方根误差在经过初始时段轻微的脉动后稳定于0.01%以下, 而其计算效率比有限元全阶模型提高2$\sim $3个数量级, 并且自由度数量(DOFs)愈大提高的幅度也愈加显著; (2)新型算法解决了常规算法在计算非线性降阶模型时加速性能差的问题, 即使是在DOFs比较小的时候也能够明显提高计算效率; (3)常数边界条件下得到的POD模态可以用来建立相同求解域在各种复杂时变边界条件下的瞬态非线性热传导降阶模型, 并对其传热过程和温度场进行快速准确的分析与预测, 具有很好的工程应用价值.      

System-size effect on the friction at liquid-solid interfaces

The friction at the liquid-solid interfaces is widely involved in various phenomena ranging from nanometer to micrometer scales. By the molecular dynamic(MD)simulation, the friction properties of liquid-solid interfaces at the molecular level are calculated via the Green-Kubo relation. It is found that the system size will influence the value of the friction coefficient, especially for the solid surfaces with the larger polar charge. The value of the friction coefficient decreases with the increase in the system size and converges at large system sizes. The large polar charge will lead to a significant friction coefficient. However, the diffusion of water molecules on this surface is almost a constant, indicating that the diffusion coefficient seems to be independent of the system size and polar charge. This work provides insights for the selection of the system size in modeling the frictional properties of hydrophobic/hydrophilic surfaces.     

Synthesis,Electrochemistry, and Photophysics of Aza‐BODIPY Porphyrin Dyes

The synthesis of dyad and triad aza‐BODIPY‐porphyrin systems in two steps starting from an aryl‐substituted aza‐BODIPY chromophore is described. The properties of the resulting aza‐BODIPY‐porphyrin conjugates have been extensively investigated by means of electrochemistry, spectroelectrochemistry, and absorption/emission spectroscopy. Fluorescence measurements have revealed a dramatic loss of luminescence intensity, mainly due to competitive energy transfer and photoinduced electron transfer involving charge separation followed by recombination.     

Synthesis of poly(n‐butyl acrylate) homopolymer and poly(styrene‐b‐n‐butyl acrylate‐b‐styrene) triblock copolymer via AGET emulsion ATRP using a cationic surfactant

Cationic emulsions of triblock copolymer particles comprising a poly(n‐butyl acrylate) (PⁿBA) central block and polystyrene (PS) outer blocks were synthesized by activator generated by electron transfer (AGET) atom transfer radical polymerization (ATRP). Difunctional ATRP initiator, ethylene bis(2‐bromoisobutyrate) (EBBiB), was used as initiator to synthesize the ABA type poly(styrene‐b‐n‐butyl acrylate‐b‐styrene) (PS‐PⁿBA‐PS) triblock copolymer. The effects of ligand and cationic surfactant on polymerizations were also discussed. Gel permeation chromatography (GPC) was used to characterize the molecular weight (M_n) and molecular weight distribution (MWD) of the resultant triblock copolymers. Particle size and particle size distribution of resulted latexes were characterized by dynamic light scattering (DLS). The resultant latexes showed good colloidal stability with average particle size around 100–300 nm in diameter. Glass transition temperature (T_g) of copolymers was studied by differential scanning calorimetry (DSC). © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 611–620     

Role of the Bridge in Photoinduced Electron Transfer in Porphyrin–Fullerene Dyads

The role of π‐conjugated molecular bridges in through‐space and through‐bond electron transfer is studied by comparing two porphyrin–fullerene donor–acceptor (D–A) dyads. One dyad, ZnP–Ph–C₆₀ (ZnP=zinc porphyrin), incorporates a phenyl bridge between D and A and behaves very similarly to analogous dyads studied previously. The second dyad, ZnP–EDOTV–C₆₀, introduces an additional 3,4‐ethylenedioxythienylvinylene (EDOTV) unit into the conjugated bridge, which increases the distance between D and A, but, at the same time, provides increased electronic communication between them. Two essential outcomes that result from the introduction of the EDOTV unit in the bridge are as follows: 1) faster charge recombination, which indicates enhanced electronic coupling between the charge‐separated and ground electronic states; and 2) the disappearance of the intramolecular exciplex, which mediates photoinduced charge separation in the ZnP–Ph–C₆₀ dyad. The latter can be interpreted as a gradual decrease in electronic coupling between locally excited singlet states of D and A when introducing the EDOTV unit into the D–A bridge.     

A new Monte Carlo model for predicting the mechanical properties of fiber yarns

Understanding the complicated failure mechanisms of hierarchical composites such as fiber yarns is essential for advanced materials design. In this study, we developed a new Monte Carlo model for predicting the mechanical properties of fiber yarns that includes statistical variation in fiber strength. Furthermore, a statistical shear load transfer law based on the shear lag analysis was derived and implemented to simulate the interactions between adjacent fibers and provide a more accurate tensile stress distribution along the overlap distance. Simulations on two types of yarns, made from different raw materials and based on distinct processing approaches, predict yarn strength values that compare favorably with experimental measurements. Furthermore, the model identified very distinct dominant failure mechanisms for the two materials, providing important insights into design features that can improve yarn strength.     

Synthesis and liquid crystalline behavior of bulky poly(methacrylamide)s

N‐(Bis(4‐(2‐ethylhexyloxy)phenyl)(phenyl)‐methyl)methacrylamide was synthesized and polymerized via reversible addition‐fragmentation chain‐transfer (RAFT) polymerization. The chain‐transfer agent (4‐cyano‐4‐(phenylcarbonothioylthio) pentanoic acid (CPADB)), combined with a chiral additive, and a radical initiator yielded polymers with dispersities between 1.2 and 1.4. At low concentrations, the polymers are soluble in hexanes and chloroform while at higher concentrations they swell in these solvents. Characterization of the polymers by wide‐angle X‐ray scattering (WAXS) revealed an interplanar distance of 19.0 Å. The WAXS data combined with polarized optical microscopy support a lamellar crystallization and lyotropic liquid crystalline behavior in hexanes and chloroform. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2563–2568     

Synthesis of tertiary amine‐based pH‐responsive polymers by RAFT Polymerization

Well‐defined tertiary amine‐based pH‐responsive homopolymers and block copolymers were synthesized via reversible addition‐fragmentation chain transfer (RAFT) polymerization using 4‐cyanopentanoic acid dithiobenzoate (CPAD) as the RAFT agent for homopolymers and a poly(ethylene glycol) (PEG) macro‐RAFT agent for the block copolymers. ¹H NMR and gel permeation chromatography results confirmed the successful synthesis of these homopolymers and block copolymers. Kinetics studies indicated that the formation of both the homopolymers and the block copolymers were well defined. The pKa titration experiments suggested that the homopolymers and the related block copolymers have a similar pKa. The dynamic light scattering investigation showed that all of the block copolymers underwent a sharp transition from unimers to micelles around their pKa and the hydrodynamic diameter (D_h) was not only dependent on the molecular weight but also on the composition of the block copolymers. The polymer solution of PEG‐b‐PPPDEMA formed the largest micelle compare to the PEG‐b‐PDPAEMA and PEG‐b‐PDBAEMA with a similar molecular weight. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1010–1022     

Butylated hydroxytoluene enediyne: access to diradical and electrophilic quinone methide intermediates

A theoretical study was carried out on the unimolecular reaction of an enediyne with a fused butylated hydroxytoluene to internally scavenge the p‐benzyne diradical sites formed after the Bergman cyclization. The calculations revealed that the conversion of the p‐benzyne diradical (2‐tert‐butyl‐4‐methyl‐5,8‐didehydro‐1‐naphthalenol) to p‐quinone methide is favored over the conversion to a phenoxy/benzene diradical 4 in an approximate 95:5 ratio. Based on this model, the Bergman cyclization leads in a bifunctional manner to intermediates for competing reactivity with intermolecular H‐atom abstraction. Copyright © 2015 John Wiley & Sons, Ltd.