Thermal behaviour of polyethylene‐block‐poly(methyl methacrylate) block copolymer: effect of multiple heating and cooling rates versus mathematical artefact

The melting and crystallization behaviours of a polyethylene‐block‐poly(methyl methacrylate) (PE‐b‐PMMA) diblock copolymer and a PE homopolymer were investigated using multiple heating and cooling rate differential scanning calorimetry (DSC) experiments, and modelling of the crystallization kinetics and lamellar thickness distribution. This new model was first validated applying literature and experimental data. The model‐predicted morphology (n = 3.2) closely matched the spherulitic morphology (n = 3), which was determined using polarized optical microscopy. For each experimental cooling rate, the model predicted diblock copolymer crystallinity that well matched the entire DSC crystallinity curve, notably for an Avrami–Erofeev index of n = 2; and apparent crystallization activation energy that hardly varied with the cooling rates used, relative crystallinity (α), and crystallization temperature or time. This disfavours the concept of variable activation energy. The use of the right crystallization model and parameter estimation algorithm is important for addressing the mathematical artefact. Under non‐isothermal cooling, the PE‐b‐PMMA diblock copolymer, as per the model prediction, crystallized without confinement (n ≠ 1), preserving the cylindrical structure. From the characteristic shapes of the crystallization function f(α(T)) versus 1/T and crystallization rate versus α plots, the resulting T_cmax and narrow α_max range can guide the search for an appropriate crystallization model. The overall treatment illustrated in this study is not restricted to a PE homopolymer and a PE‐b‐isotactic PMMA block copolymer. It can be generally applied to crystalline homopolymers and copolymers (alternating, random and block), as well as their blends. The block copolymers and blends can be crystalline–amorphous as well as crystalline–crystalline. © 2014 Society of Chemical Industry     

种晶介导的二氧化铈球状粒子的形成

文章报道了一种以不同数量种晶介导合成CeO2多晶纳米颗粒的制备方法，分析以种晶介导球状的CeO2的形成机理。在生长阶段，CeO2粒子通过初级粒子在其表面的沉积来生长，从而降低了粒子的表面能，导致由许多初级粒子组成的次级粒子的形成。加入的一定量的紧密堆积的种晶聚集体优先作为初级粒子的沉积中心来降低它们的表面能，从而减小次级粒子的尺寸、增加其均匀性以及促进这些次级粒子的形成。     

Effect of Prolonged Duration of Gelatinization in Starch and Incorporation with Potassium Iodide on the Enhancement of Ionic Conductivity

Three systems of starch-based crust electrolytes were prepared using various gelatinization times, various weight percentages (wt%) of starch, and various wt% of starch incorporated into potassium iodide. All the samples were subjected to electrochemical impedance spectroscopy, X-ray diffraction spectroscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, and transference number measurements. Electrochemical impedance spectroscopy shows that 1.7?wt% of starch has maximized the room temperature conductivity of the electrolyte to 1.4587?×?10^?4?S?cm^?1. The conductivity was enhanced to 4.5278?×?10^?4?S?cm^?1 on the increment of starch’s wt% from 1.7 to 3.2. This conductivity was further enhanced to 3.4609?×?10^?3?S?cm^?1 on the addition of 0.3?wt% of potassium iodide. The conductivity enhancement was found due to the formation of glucosyl carboxonium ions. The effect of longer heating time in gelatinization is attributed to the formation of glucosyl carboxonium ions. X-ray diffraction spectroscopy affirms the reduction in crystallinity of starch. Scanning electron microscopy analysis shows the porous morphology of starch electrolyte, and addition of potassium iodide shows the morphology of bean nuts like particles seated on the pores. Fourier transform infrared confirms the degradation of starch. Transference number measurements of the crust electrolyte shows that ions are the dominant conducting species. All the results are authenticating that the conductivity enhancement in starch-based crust electrolyte is due to starch and the addition of inorganic salts.     

Going from green to white color electroluminescence through a nanoscale complex of Zinc (II)

In this paper, we report application of four novel Nano Zinc (II) complexes as the emitter dyes in organic light emitting diodes (OLEDs). The Nano Zinc (II) complexes emission, particularly its absorption, fluorescence spectra and quantum yield, tuned by varying sizes which affects environments of the Zinc (II) ion. OLED Devices with Nano Zinc (II) complexes were fabricated, giving rise to devices with peak emission ranging from 498 to 541 nm. Here, we have successfully employed sonoelectrochemical method for fabricating white OLEDs. The white emission ascribed to the exciton emission in Nano Zinc (II) complex emitter and from exciplex formation at the interface of PVK/Nano Zinc (II) complex. The experimental results demonstrate that this approach is ideal for color tuning of single and multilayer conducting semiconducting thin films used in the fabrication of organic electronic devices such as OLEDs.     

Patterns in melanocytic lesions: impact of the geometry on growth and transport inside the epidermis

In glabrous skin, nevi and melanomas exhibit pigmented stripes during clinical dermoscopic examination. They find their origin in the basal layer geometry which periodically exhibits ridges, alternatively large (limiting ridges) and thin (intermediate ridges). However, nevus and melanoma lesions differ by the localization of the pigmented stripes along furrows or ridges of the epidermis surface. Here, we propose a biomechanical model of avascular tumour growth which takes into account this specific geometry in the epidermis where both kinds of lesions first appear. Simulations show a periodic distribution of tumour cells inside the lesion, with a global contour stretched out along the ridges. In order to be as close as possible to clinical observations, we also consider the melanin transport by the keratinocytes. Our simulations show that reasonable assumptions on melanocytic cell repartition in the ridges favour the limiting ridges of the basal compared with the intermediate ones in agreement with nevus observations but not really with melanomas. It raises the question of cell aggregation and repartition of melanocytic cells in acral melanomas and requires further biological studies of these cells in situ.     

考虑导引头多约束的滑翔制导炮弹弹道规划

为提高制导炮弹在大着角情况下导引头捕捉目标的速度，减小末制导起始点角度偏差，在传统制导炮弹方案弹道规划方法(trajectory programming method, TPM)的基础上考虑末制导段，提出一种考虑导引头多约束的弹道规划方法(trajectory programming method-constraints of seeker, TPM-CS)。根据导引头最大探测距离建立末制导起始点约束，根据弹目几何关系和导引头视场角建立攻击路径约束，并建立最小化前置角和控制变量幅值的目标函数。为实现制导炮弹初始弹道倾角、偏角、火箭点火时间、滑翔启控时间、导引头开启时间等参数的最佳匹配，建立了5阶段弹道规划模型，并采用多阶段Radau伪谱法将该弹道规划问题转化为非线性规划问题，最后调用非线性规划求解器SNOPT进行求解。选取不同性能参数的导引头进行仿真，分析了导引头最大探测距离和导引头视场角对方案弹道的影响。将文中提出的弹道规划方法与传统弹道规划方法进行对比仿真，结果表明，相比于传统方法，文中所提方法规划方案弹道的末制导初始角度偏差缩小71.590%,导引头对目标保持照射状态的时间延长6...     

Ultrasound‐based,in‐line monitoring of anaerobe yeast fermentation: model,sensor design and process application

In order to implement process analytical technology in beer manufacturing, an ultrasound‐based in‐line sensor was developed which is capable to determine sound velocity and density via the multiple reflection method. Based on a systematic study of the ternary system water–maltose–ethanol, two models were established to estimate the critical process parameters: sugar and ethanol mass fraction. The sound velocity‐based model showed unreasonable high errors although temperature variations and deviations due to dissolved CO₂ were corrected. In contrast, the sound velocity–density–temperature model provided an average root mean square error of 0.53%g/g sugar and 0.26%g/g ethanol content for the main fermentation. Method, sensor and model showed the capability to capture the process signature which may be related to product and process quality.     

Peer impressions in open source organizations: A survey

In virtual organizations, such as Open Source Software (OSS) communities, we expect that the impressions members have about each other play an important role in fostering effective collaboration. However, there is little empirical evidence about how peer impressions form and change in virtual organizations. This paper reports the results from a survey designed to understand the peer impression formation process among OSS participants in terms of perceived expertise, trustworthiness, productivity, experiences collaborating, and other factors that make collaboration easy or difficult. While the majority of survey respondents reported positive experiences, a non-trivial fraction had negative experiences. In particular, volunteer participants were more likely to report negative experiences than participants who were paid. The results showed that factors related to a person's project contribution (e.g., quality and understandability of committed codes, important design related decisions, and critical fixes made) were more important than factors related to work style or personal traits. Although OSS participants are very task focused, the respondents believed that meeting their peers in person is beneficial for forming peer impressions. Having an appropriate impression of one's OSS peers is crucial, but the impression formation process is complicated and different from the process in traditional organizations.     

Peroxidation of Polymethylhydrogensiloxane and Cellulose by γ-Irradiation in Air and Grafting Induced by Their Decomposition

The peroxides of polymethylhydrogensiloxane, cellulose and a mixture of both were determined by ferrous ion method. The relation between the decomposition of the peroxide and the degree of grafting by standing at an elevated temperature after irradiation was examined.

The G-value for the peroxide formation of polymethylhydrogensiloxane was found to be 8.7, and the activation energy for the peroxide decomposition was determined from calculation to be 43 kcal/mol. The ratio of G-values of silicone between those terminated by methyl radical and by methyl radical is estimated to be about 2/1. It would thus appear certain that the rate of peroxidation is affected by the end group. The peroxidation is not a chain reaction at room temperature, and the peroxide is produced by the recombination of the peroxy radical. At least two types of peroxide are produced by irradiation in air, and one is decomposed at 80°C but the other is relatively stable.

On the other hand, the G-value for the peroxide formation of cellulose is equal to 5.6.

The tendency seen for the decrease of the peroxide corresponds to that of increasing degree of grafting, and it may be concluded that only 1/10 of the peroxides formed in the cellulose–silicone system results in grafting, since it has been calculated that the G-value for the grafting through the peroxide is about 1.0.     

Soot formation in high pressure laminar diffusion flames

The details of the chemical and physical mechanisms of the soot formation process in combustion remain uncertain due to the highly complex nature of hydrocarbon flames, and only a few principles are firmly established mostly for atmospheric conditions. In spite of the fact that most combustion devices used for transportation operate at very high pressures (e.g., aircraft gas turbines up to 40 atm, diesel engines exceeding 100 atm), our understanding of soot formation at these pressures is not at a desirable level, and there is a fundamental lack of experimental data and complementary predictive models. The focus of this review is to assess the experimental results available from laminar co-flow diffusion flames burning at elevated pressures. First, a brief review of soot formation mechanisms in diffusion flames is presented. This is followed by an assessment of soot diagnostics techniques, both intrusive and non-intrusive, most commonly used in soot experiments including the laser induced incandescence. Then the experimental results of soot measurements done at elevated pressures in diffusion flames are reviewed and critically assessed. Soot studies in shock tubes and in premixed flames are not covered. Smoke point fuel mass flow rate is revisited, and shortcomings in recent measurements are pointed. The basic requirements for tractable and comparable measurements as a function of pressure are summarized. Most recent studies at high pressures with aliphatic gaseous fuels show that the soot yield displays a unified behaviour with reduced pressure. The maximum soot yield seems to reach a plateau asymptotically as the pressure exceeds the critical pressure of the fuel. Lack of experimental data on the sensitivity of soot morphology to pressure is emphasized. A short summary of efforts in the literature on the numerical simulation of soot formation in diffusion flames at high pressures is the last section of the paper.