Control of the temperature responsiveness of poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) copolymer using ultrasonic irradiation

Poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) (poly(NIPAM-co-HEMA)) is a temperature-responsive copolymer that is expected to be applicable as an advanced functional polymeric material in various fields. In this study, a novel method was developed to control the responsive temperature of poly(NIPAM-co-HEMA) using an ultrasonic polymerization technique. Initially, the behavior of the reaction was investigated using NIPAM and HEMA monomers under ultrasonic irradiation. A high ultrasonic power was found to produce a high reaction rate and low number average molecular weight of the copolymer. The polydispersity of the synthesized copolymer was approximately 1.5 for all ultrasonic powers examined. In the early stage of the reaction, the molar fraction of NIPAM in the copolymer was lower than the initial molar fraction of the monomers. It was concluded that ultrasonic irradiation affected the initiation reaction and polymer degradation, but did not affect the propagation reaction. Furthermore, the effect of the ultrasonic irradiation conditions on the temperature responsiveness of the copolymer was investigated. The lower critical solution temperature (LCST) of the copolymer was found to increase with increasing ultrasonic irradiation time. In addition, in the early stages of the reaction, the measured values of the LCST were higher than the estimated values using copolymer composition. This can be attributed to some parts of the copolymer chain possessing a higher NIPAM fraction than the overall fraction due to different reactivities of the monomers and terminated radicals. This hypothesis was indirectly verified by the synthesis of a block copolymer from the PNIPAM homopolymer and HEMA monomer.     

Silane-modified polymers as interphases in glass-fibre-reinforced composites: 2. Grafting and crosslinking of interphase materials

_—This paper presents an interphase engineering technique suitable for grafting silane-modified polymers onto glass fibres to be used in composites with enhanced impact tolerance. The silane-modified polymers include ethylene polymers grafted with γ-methacryloxypropyltrimethoxysilane (MPS) and a copolymer of butyl acrylate (BuA) and MPS. The grafting of functionalized interphase materials onto glass fibres is performed in solution. By changing the concentrations of the solutions, different amounts of polymer can be deposited on the fibres. Water crosslinking of the polymer gives the possibility of producing stabilised interfacial polymer coatings over a range of thicknesses. It is concluded that acidic conditions (1) promote the grafting of silane-modified polymers on glass fibres and (2) for a given reaction time, increase the amount of crosslinked polymer in the interphase, i.e. yield more stable interphases. It is also likely that preserving acidic conditions at the fibre/polymer interface is important for maintaining bonding across the interface. It is shown that polystyrene/glass-fibre composites having SEBS at the interface are promising candidates for high-impact-tolerance composites.     

GaN基LED低温空穴注入层的MOCVD生长研究

针对GaN基LED空穴注入效率低的问题,在量子阱与电子阻挡层之间插入低温空穴注入层（LT-HIL）,实验研究了MOCVD生长LT-HIL时二茂镁（Cp₂Mg）流量和生长温度的影响。结果表明：随着Cp₂Mg流量的增加,外延薄膜晶体质量下降,外延片表面平整度和均匀性降低;而受Mg掺杂时补偿效应的影响,主波长先红移后蓝移,芯片的输出光功率先升高后降低,正向电压先降低后升高。相比于无LT-HIL的样品,在20 mA工作电流下,Cp₂Mg流量为1.94 μmol/min时制备的芯片的输出光功率提升20.3%,而正向电压降低0.1 V。在Cp₂Mg流量较大时,LT-HIL的渐变式生长温度对外延质量有所改善,但不是主要影响因素。     

Protein adsorption properties of OEG monolayers and dense PNIPAM brushes probed by neutron reflectivity

The structure of dense poly(N-isopropylacrylamide) (PNIPAM) brushes and oligo(ethylene glycol) (OEG) monolayers has been probed using neutron reflectometry and ellipsometry. The PNIPAM brush is swollen below the Lower Critical Solution Temperature (LCST) of 32?^°C and is collapsed at 37?^°C. Neutron reflectivity shows that below the LCST, the brush is described by a two-layer model: an inner dense layer and a hydrated outer layer. Above the LCST the collapsed brush forms a homogenous layer. With a fully deuterated myoglobin protein to increase the neutron scattering length density contrast, the reflectivity data show no detectable primary adsorption on the grafted OEG surface. A bound on the ternary adsorption onto PNIPAM chains forming dense brushes below and above the LCST is obtained.     

Tuning of Lower Critical Solution Temperature (LCST) of Poly(N-Isopropylacrylamide-co-Acrylic acid) Hydrogels

Temperature-responsive hydrogel with a lower critical solution temperature (LCST) close to human body temperature was prepared. Crosslinked N-isopropylacrylamide (NIPAAm) and acrylic acid (AAc) copolymer networks were synthesized at various monomer ratios in the presence of ammonium persulfate (APS), N,N′-methylenebisacrylamide (NMBA) and N,N,N′,N′-tetramethylethylenediamine (TEMED) via a redox polymerization method. The resulting hydrogels possessed thermo- and pH-responsive characteristics. They were characterized in terms of swelling ratio, volume change, water uptake and diffusivity, water vapor uptake and diffusivity, and phase transition temperature. The water liquid and vapor diffusion coefficients for all the synthesized hydrogels were higher than the literature data, implying higher rates for drug release. The LCST of the hydrogel increased with higher AAc content in the copolymer. The gel containing 1.8% AAc exhibited an LCST similar to human body temperature, demonstrating a potential use in drug controlled release and biomedical applications.     

Fluorescence Investigations of “Smart” Microgel Systems

Fluorescence techniques, including lifetime, quenching, and time-resolved anisotropy measurements (TRAMS), were used to study microgel systems based upon N-isopropylacrylamide (NI-PAM) using pyrene as a fluorescent probe. These experiments have revealed that poly(N-isopropylacrylamide) (PNIPAM) nanoparticles undergo a phase transition at a lower critical solution temperature (LCST), of ca. 34°C, which involves collapse of the particles into compacted, hydrophobic spheres. A degree of control over the LCST has been achieved by copolymerization of NIPAM with varying amounts of dimethylacrylamide (DMAC). Incorporation of DMAC into the gel has the effect of changing the hydrophobic to hydrophilic balance and shifts the LCST to a higher temperature. Fluorescence methods indicate that the NIPAM/DMAC gels are of a more open, water-swollen nature above the LCST than that of their PNIPAM counterparts.     

Scalar dissipation rates in isothermal and reactive turbulent opposed-jets: 1-D-Raman/Rayleigh experiments supported by LES

Isothermal and reactive turbulent opposed flows are presented, which are appropriate to test the applicability and performance of models for turbulence, mixing, chemical reaction, and turbulence-chemistry interaction. Transient flow and scalar fields are measured using laser Doppler velocimetry and one-dimensionally resolved Raman/Rayleigh spectroscopy. Aside of statistical moments of temperature, mean species, and velocity components, scalar dissipation rate across the mixing and reaction layer is determined on a single-shot base. Using large eddy simulation in connection with a steady flamelet model, it is shown how numerical data can serve to estimate the influence of experimental noise upon a measured quantity, such as scalar dissipation. As a key result, it is shown that an increase in scalar rate of dissipation by chemical reactions is caused by a significant increase in the mixture fraction diffusivity, which outweighs the decrease in mixture fraction gradients. In mixture fraction space, local maxima of scalar dissipation rate are found on the rich side, which cannot be correctly reproduced by the steady flamelet model assuming equal species diffusivity. Furthermore, the impact of experimental noise on conditional probability density functions of scalar dissipation rate is shown (exemplary) to lead to erroneous conclusions from experimental data.     

Effect of unsteady pressure rise on flame propagation and near-cold-wall ignition

Thermodynamic pressure rise during combustion is a key feature in internal combustion engines. Yet, hardly any studies have been conducted to investigate the effects of transient pressure rise on flame propagation as well as on the ignition of the unburned gas. In this study, the effects of unsteady pressure rise were parametrically studied using a one-dimensional reacting flow model in which the thermodynamic pressure variation is an independent variable and thus its rate of rise can be controlled. It was determined that large rates of pressure rise can significantly increase the mass burning flux of a laminar flame and that this modification becomes more pronounced at higher pressure and temperature conditions. Furthermore, it was shown that the development of ignition near a cold wall, for mixtures that exhibit negative temperature coefficient behavior, is very sensitive to rate of change of pressure. The near-wall ignition behavior was found also to be rather sensitive to the prevailing pressures and temperatures whose values control whether ignition will occur in the main-gas or within the thermal boundary layer.     

Physical aspects of polymer combustion and the inhibition mechanism

The characteristics of polymer combustion were studied. The contributions from the conductive, convective, and radiation components of the total heat flow from the flame to the polymer surface were determined. The influence of inhibitors on the rate of chemical reactions in the preignition zone and on the rate of heat and mass exchange between the flame and the burning surface was estimated. It was shown that a change in the heat balance and heat and mass exchange accompanied by changing the optical properties of the flame and burning surface has a pronounced effect on the combustion rate at the flame edge. The formation of a protective coke layer reduces heat flow to the surface of a nonreacted polymer, leading to a decrease in the rate of evolution of the volatile combustible polymer-destruction products into the gas phase. As a result, the flame temperature decreases and it is extinguished.     

Surface energies and self-assembly of block copolymers on grafted surfaces

We present a theoretical analysis of the self-assembly of diblock copolymers on surfaces grafted with random copolymers. Our results demonstrate that the surface energies of homopolymeric components on grafted surfaces differ from the corresponding values for self-assembled morphologies. Moreover, grafted random copolymers are shown to adapt their conformations in response to the morphology of the overlaying block copolymer film to create chemical inhomogeneities which modulate the interfacial interactions. Consequently, the surface energy differences between the different components on the grafted substrate do not serve as a useful measure to predict the stability of self-assembly of the diblock copolymer film.     

Transport properties of a ferroelectric tunnel junction in bilayer ferroelectric/manganite structures

This paper presents the results of an experimental investigation of current flow through a ferroelectric nanolayer in a series of bilayer ferroelectric/manganite structures prepared by metalorganic aerosol deposition on a MgO substrate. It has been shown that a variation in the thickness of the ferroelectric layer in a bilayer ferroelectric/manganite structure leads to a change in the metal-insulator phase transition temperature of the manganite layer and also affects the transport properties of the ferroelectric/manganite structure. Based on the analysis of the experimental results, it is demonstrated that the ferroelectric layer up to 4 nm thick exhibits polarization properties. In the theoretical analysis, it is assumed that electrical conduction of bilayer structures is provided by a dual mechanism combining the electron tunneling through a ferroelectric barrier and the ohmic current flow in a manganite layer. The possibility of retaining the mechanism of charge carrier tunneling in a bilayer ferroelectric/manganite structure through the ferroelectric layer up to 6 nm thick is discussed.     

Temperature-induced phase transition and intramolecular charge-transfer process based on poly(N-isopropylacrylamide) hydrogel with covalently attached D-π-A type dye

A thermoresponsive poly(NIPAM-co-dye) copolymer with covalently attached D-π-A type dye was prepared by typical radical copolymerization. Software was used to calculate the electron density distribution of the push-pull, intramolecular charge transfer (ICT) operating in donor-π-conjugation-acceptor (D-π-A) configurations of dye monomer 3. It can be constructed an acid/base-induced molecular switch by modulation of intramolecular charge transfer with protonation/deprotonation. The lower critical solution temperature (LCST) behavior was investigated by means of UV-vis spectroscopy that allows the measurement of the phase transition from 25 to 40 °C in aqueous solution. The poly(NIPAM-co-dye) copolymer also exhibited color change when used an acid/base-induced molecular switch via control of intramolecular charge transfer (ICT). The morphology of the internal microstructure of the poly(NIPAM-co-dye) hydrogel was observed by scanning electron microscopy (SEM). The reversible switch could be obtained by thermal and acid/base stimuli.     

Influence of pressure-driven gas permeation on the quasi-steady burning of porous energetic materials

A theoretical two-phase-flow analysis is developed to describe the quasi-steady propagation, across a pressure jump, of a multi-phase deflagration in confined porous energetic materials. The difference, or overpressure, between the upstream (unburned) and downstream (burned) gas pressure leads to a more complex structure than that which is obtained for an unconfined deflagration in which the pressure across the multi-phase flame region is approximately constant. In particular, the structure of such a wave is shown by asymptotic methods to consist of a thin boundary layer characterized by gas permeation into the unburned solid, followed by a liquid-gas flame region, common to both types of problem, in which the melted material is preheated further and ultimately converted to gaseous products. The effect of gas flow relative to the condensed material is shown to be significant, both in the porous unburned solid as well as in the exothermic liquid-gas melt layer, and is, in turn, strongly affected by the overpressure. Indeed, all quantities of interest, including the burn temperature, gas velocity and the propagation speed, depend on this pressure difference, leading to a significant enhancement of the burning rate with increasing overpressure. In the limit that the overpressure becomes small, the pressure gradient is insufficient to drive gas produced in the reaction zone in the upstream direction, and all gas flow relative to the condensed material is directed in the downstream direction, as in the case of an unconfined deflagration. The present analysis is particularly applicable to those types of porous energetic solid, such as degraded nitramine propellants that can experience significant gas flow in the solid preheat region and which are characterized by the presence of exothermic reactions in a bubbling melt layer at their surfaces.     

移动物体导热和表面辐射耦合问题的数值计算

本文以炉渣冷却为应用背景,对移动物体导热和表面辐射耦合问题进行数值模拟,探讨其数值模拟方法及传输带速度、炉渣厚度等相关因素对炉渣换热及温度变化的影响。计算结果表明,当炉渣量一定时,提高带速可使出口处炉渣温度降低;当渣层厚度不变时,提高带速,出口处炉渣温度提高。计算还表明,对这种具有表面辐射的移动物体,需采用上风差分,且表面辐射计算要采用亚松弛。     

A molecular dynamics study on interfacial heat transport of alkanethiol surfactant coated nanofluids-effect of chain length and stiffness

The thermal transport across the alkanethiol surfactant layer at the nanoparticle/base fluid interface in nanofluids was investigated by molecular dynamics simulation, with consideration of the conformation of the surfactant layer with different surfactant chain lengths and backbone stiffness. The variation of temperature drop at nanoparticle-surfactant interface reveals that the interfacial thermal conductance was mediated by the chain length, possibly due to the difference in the adsorption density of surfactant on the surface of the nanoparticles, because of the blocking effect from the bending of the long alkyl chains. The intrinsic thermal conductivity of the surfactant layer increased with decreasing chain length and increasing chain stiffness because of the phonon scattering effect from the bending and cross-linking of the alkyl chains. We quantified the modes of heat flow across the surfactant layer and found that the contribution of intramolecular bonded interaction was much higher than that of atomic translation and nonbonded interaction separately. By analysing the variation of bonded interaction contrition with chain length and stiffness, it is demonstrated that the increased thermal conductivities benefited from the enhanced thermal transfer through the covalent bonds of surfactant molecules. The results can provide insights into the design of thermally conductive surfactants.     

Exploring Microstructures and Interphase Properties of Surface- Grafted Diblock Copolymers in a Homopolymer Melt by Self-Consistent Field Theory Simulations

Polymeric self-consistent field theory is used to investigate microstructures and interphase properties of diblock copolymers grafted onto solid surfaces in a homopolymer melt. The calculations show that the grafted diblock copolymers can self-assemble into hemispherical microstructures at low grafting densities of the diblock copolymers. The morphology transforms into hemicylinder-like and sandwich-like lamellar microstructures with an increase in the chain-grafting density. The effective thickness of the grafted block layer and the interphase width between the homopolymer melt and the grafted copolymers strongly depend on the physicochemical parameters of the system, such as the composition of the grafted copolymer, the chemical incompatibility between the different components, the length ratio of grafted copolymer to homopolymer, and the grafting density of the diblock copolymers. In addition, the above computational results of microphase-separated structures and interphase properties are qualitatively compared with our previous experimental observations. The comparison indicates that our theoretical results not only reproduce the general feature of the experimental observations, but also elucidate the internal structural information and complement the findings in the region of high grafting densities of diblock copolymers.     

管流中注入粒子的非定常波系的数值研究

使用二维有限体积方法,对在管流中固定位置处注入静止固体粒子的可压缩含灰气体流动进行数值模拟,讨论流场和粒子在过程中的耦合,研究质量增加和热量变化所产生的非定常波系,分析物理参数在过程中的变化.结果表明,在添质和加热过程中,流场会产生不同类型和不同强度的非定常波,在分析其物理规律的同时,讨论添质和加热相互作用导致的波系间转换,最后求解流场中各区域的热力学参数,得到不同的流场速度和粒子温度情况下各非定常波波强的相图,定量解释改变参数引起的非定常波变化规律.     

Second-harmonic generation in a layer with variable susceptibility

The weak nonlinearity limit of the second-harmonic generation in a medium with variable second-order susceptibility, changing along the direction of propagation of interacting waves according to the hyperbolic secant law, is considered. It is shown that the variation of the second harmonic’s normalized intensity with the spatial coordinate is given in terms of the solution to an auxiliary linear problem, which is known as the Rosen-Zener quantum two-level model. The final intensity of the second harmonic at the exit from the medium is calculated and analyzed. It is shown that, for the particular Rosen-Zener profile under consideration, because of its inherent properties, the variation range of the peak susceptibility of the layer for which the medium can be strictly considered as weakly nonlinear is narrower than the corresponding parameter range for a homogeneous medium.     

温度对Si衬底上低压MOCVD外延生长ZnS薄膜质量的影响

用低压MOCVD系统在(111)Si衬底上,用两步生长方法(改变/流量比)在300～400℃时外延生长了ZnS单晶薄膜。随着衬底温度的降低,ZnS薄膜结晶质量提高,并在300℃生长时获得结晶完整性较好的(111)ZnS单晶薄膜。文中讨论了衬底温度对薄膜质量的影响。     

ZnSe单晶薄膜的MOCVD法生长

本文研究了常压MOCVD法制备宽禁带材料ZnSe的生长机制。通过经验公式和烟雾实验,从理论上和实验上分析了反应室的气流状态。观测了滞流层厚度及生长速率与位置、气流速度及衬底温度的关系。实现了反应器设计最优化,在热壁、常压、DEZ源的系统中也生长出高质量的ZnSe单晶外延层。