A Dissipative Reaction Network Drives Transient Solid–Liquid and Liquid–Liquid Phase Cycling of Nanoparticles

Transient states maintained by energy dissipation are an essential feature of dynamic systems where structures and functions are regulated by fluxes of energy and matter through chemical reaction networks. Perfected in biology, chemically fueled dissipative networks incorporating nanoscale components allow the unique properties of nanomaterials to be bestowed with spatiotemporal adaptability and chemical responsiveness. We report the transient dispersion of gold nanoparticles in water, powered by dissipation of a chemical fuel. A dispersed state that is generated under non-equilibrium conditions permits fully reversible solid–liquid or liquid–liquid phase transfer. The molecular basis of the out-of-equilibrium process is reversible covalent modification of nanoparticle-bound ligands by a simple inorganic activator. Activator consumption by a coupled dissipative reaction network leads to autonomous cycling between phases. The out-of-equilibrium lifetime is tunable by adjusting the pH value, and reversible phase cycling is reproducible over several cycles.     

Dendronized Hyperbranched Macromolecules: Soft Matter with a Novel Type of Segmental Distribution

Dendronization of a hyperbranched polyester with different generation dendrons leads to pseudo‐dendritic structures. The hyperbranched core is modified by the divergent coupling of protected monomer units to the functional groups. Compared to dendrimers, the synthetic effort is significantly less, but the properties are very close to those of high‐generation dendrimers. The number of functional groups, molar mass, and rheology behavior even in the early generation (G1–G4) pseudo‐dendrimers strongly resembles the behavior of dendrimers in higher generations (G5–G8). Comparison of the segmental and internal structure with perfect dendrimers is performed using SANS, dynamic light scattering and viscosity analysis, microscopy and molecular dynamics simulation. The interpretation of the results reveals unique structural characteristics arising from lower segmental density of the core, which turns into a soft nano‐sphere with a smooth surface even in the first generation.     

Polybenzimidazole dendrimer containing triazine rings-based high-temperature proton exchange membranes with high performances over a wide humidity range

A high-temperature proton exchange membrane with high proton conductivity over a wide humidity range still remains a challenge. PBI dendrimer containing triazine rings (TPBI) was synthesized to approach this aim considering its high content of hygroscopic terminal groups and of larger free volume. A novel proton conductor previously synthesized (zirconium 3-sulfopropyl phosphonate, ZrSP) was doped due to its good proton conductivity over a wide humidity range. TPBI was post-crosslinked with a tetrafunctional epoxy resin (N,N,N′,N′-tetraglycidyl-4,4′-diaminodiphenylmethane, TGDDM) to enhance the mechanical stability at low cross-linking degrees, which allowed high doping levels of ZrSP, and thus, high conductivity. The prepared membranes (TPBI-TGDDM/ZrSP) showed good thermal stability, high proton conductivity over wide humidity range, and good dimensional stability. At suitable degrees of branching, TPBI-TGDDM/ZrSP exhibited superior mechanical property, oxidative stability, methanol barrier property, and membrane selectivity than its linear analog (mPBI-TGDDM/ZrSP). As ZrSP instead of PA was applied as the proton conductor, TPBI-TGDDM/ZrSP showed good durability of proton conductivity, especially in comparison with TPBI-TGDDM/PA, which highly retarded decline in conductivity caused by PA leaking. The proton conductivity at 180 °C of TPBI(20)-TGDDM(10)/ZrSP(50) achieved 142, 84.2 and 23.6 mS cm^?1 at 100%, 50%, and 0 RH, respectively.     

Simulating Light Scattering Behavior of Branched Molecules

Monte Carlo simulations reveal long chain branching (LCB) topology based on kinetics of systems like low‐density polyethylene (ldPE). Examining the topologies computed shows the majority of branch arms to be short as compared to backbone length, while also a significant branch‐on‐branch fine structure is observed. Until now, predicting scattering function P ⁻¹(θ) from LCB has only been successful for structures like simple combs or stars. Topologies in graph theoretical form are used to predict scattering function P ⁻¹(θ) and by summating intramolecular distances, accounting for branching and excluded volume. Experimental size exclusion chromatography with multiangle light scattering can be brought in line with the predicted branching character. Branching is less than predicted due to a different fine structure in ldPE leading to stronger size contraction.     

Measurement of energy release rate and energy flux of rapidly bifurcating crack in Homalite 100 and Araldite B by high-speed holographic microscopy

High-speed holographic microscopy is applied to take three successive photographs of fast propagating cracks in Homalite 100 or in Araldite B at the moment of bifurcation. Crack speed at bifurcation is about 540 m/s on Homalite 100, and about 450 m/s on Araldite B. From the photographs, crack speeds immediately before and after bifurcation are obtained, and it is found that discontinuous change of crack speed does not exist at the moment of bifurcation in the case of Homalite 100, but exists in the case of Araldite B. From the photographs, crack opening displacement (COD) is also measured along the cracks as a function of distance r from the crack tips. The measurement results show that the CODs are proportional to √r before bifurcation. After bifurcation, the CODs of mother cracks are proportional to √r, though the CODs of branch cracks are not always proportional to √r. The energy release rate is obtained from the measured CODs, and it is found that energy release rate is continuous at bifurcation point in both cases of Homalite 100 and Araldite B. Energy flux that shows the energy flow toward a crack tip is also obtained.     

Influence of long-chain branches in polyethylenes on linear viscoelastic flow properties in shear

 This contribution presents a survey on the influence of long-chain branching on the linear viscoelastic properties zero shear-rate viscosity and steady-state recoverable compliance of polyethylene melts. The materials chosen are linear and slightly long-chain branched metallocene-catalyzed polyethylenes of narrow molecular mass distribution as well as linear and highly long-chain branched polyethylenes of broad molecular mass distribution. The linear viscoelastic flow properties are determined in shear creep and recovery experiments by means of a magnetic bearing torsional creep apparatus. The analysis of the molecular structure of the polyethylenes is performed by a coupled size exclusion chromatography and multi-angle laser light scattering device. Polyethylenes with a slight degree of long-chain branching exhibit a surprisingly high zero shear-rate viscosity in comparison to linear polyethylenes whereas the highly branched polyethylenes have a much lower viscosity compared to linear samples. Slightly branched polyethylenes have got a higher steady-state compliance in comparison to linear products of similar polydispersity, whereas the highly branched polyethylenes of broad molecular mass distribution exhibit a surprisingly low elasticity in comparison to linear polyethylenes of broad molecular mass distribution. In addition sparse levels of long-chain branching cause a different time dependence in comparison to linear polyethylenes. The experimental findings are interpreted by comparison with rheological results from literature on model branched polymers of different molecular topography and chemical composition. Received: 12 July 2001 Accepted: 30 October 2001     

Influence of molar mass distribution and long-chain branching on strain hardening of low density polyethylene

Low-density polyethylenes (LDPE) were synthesized in a laboratory-scale autoclave under high pressure. These samples were found to possess a high molar mass tail, resulting in a distinctly bimodal molar mass distribution and a lower concentration of long-chain branching than typical of commercial LDPEs. Rheological experiments in elongation showed that these samples exhibit a very pronounced strain hardening, which could be favorable for distinct processing operations. Although the samples have a rather high molar mass ( g/mol), their zero shear-rate viscosities η ₀ and their shear thinning behavior are still in a range, where thermoplastic processing is possible. A qualitative understanding of the experimental results is tried by the model of the Cayley tree.

A Tree-valued Markov Process Associated with an Admissible Family of Branching Mechanisms

Let E?R be an interval. By studying an admissible family of branching mechanisms{ψt,t ∈E} introduced in Li [Ann. Probab., 42, 41-79(2014)], we construct a decreasing Levy-CRT-valued process {Tt, t ∈ E} by pruning Lévy trees accordingly such that for each t ∈E, Tt is a ψt-Lévy tree. We also obtain an analogous process {Tt*,t ∈E} by pruning a critical Levy tree conditioned to be infinite. Under a regular condition on the admissible family of branching mechanisms, we show that the law of {Tt,t ∈E} at the ascension time A := inf{t ∈E;Tt is finite} can be represented by{Tt*,t∈E}.The results generalize those studied in Abraham and Delmas [Ann. Probab., 40, 1167-1211(2012)].     

EAST快速极紫外光谱仪绝对强度的原位标定

磁约束等离子体中杂质(特别是高Z杂质)的存在将大大增强等离子体辐射功率损失，破坏等离子体的约束性能。杂质行为的定量研究首先要求对杂质测量的光谱诊断系统进行绝对强度标定，获得灵敏度响应曲线。介绍了EAST托卡马克上的快速极紫外光谱仪系统绝对强度的原位标定方法。在波长范围20～150Å内，通过对比极紫外(EUV)波段连续轫致辐射强度的计算值和测量值得到光谱仪的绝对强度标定。在此过程中，首先由(523±1) nm范围内可见连续轫致辐射强度的绝对测量值计算出有效电荷数Z_eff，进而结合电子温度和密度分布计算EUV波段连续轫致辐射强度；EUV波段连续轫致辐射强度的测量值即为不同波长处探测器的连续本底计数扣除背景噪声计数值。对于较长波段范围130～280Å，通过对比等离子体中类锂杂质离子(Fe23+，Cr21+，Ar15+)和类钠杂质离子(Mo31+，Fe15+)发出的共振谱线对(跃迁分别为1s22s 2S_1/2-1s22p 2P_{1/2, 3/2}及2p63s 2S_1/2-2p63p 2P_{1/2, 3/2})强度比的理论和实验值进行相对强度标定。其中共振谱线对强度比的理论值由辐射碰撞模型计算得到，模型中处在各个能级的离子数主要由电子碰撞激发，去激发以及辐射衰变三个过程决定。两种方法相结合，实现了光谱仪20～280Å范围的绝对强度标定。考虑轫致辐射、电子温度及电子密度的测量误差，绝对标定误差约为30%。在绝对标定的基础上，我们对杂质特征谱线强度进行绝对测量，并将测量结果与杂质输运程序结合ADAS(Atomic Data and Analysis Structure)原子数据库计算得到的模拟值进行比较，进而估算等离子体中的杂质浓度。     

Set-valued stochastic intergrals and stochastic inclutions 1

We present the concepts of set - valued stochastic integrals and stochastic inclusions. The main result of the paper deals with a selection property of set - valued stochastic integrals. This property is a fundamental one for stochastic inclusions.