4D Printing of Polyvinyl Chloride (PVC): A Detailed Analysis of Microstructure,Programming, and Shape Memory Performance

In this research, polyvinyl chloride (PVC) with excellent shape-memory effects is 4D printed via fused deposition modeling (FDM) technology. An experimental procedure for successful 3D printing of lab-made filament from PVC granules is introduced. Macro- and microstructural features of 3D printed PVC are investigated by means of wide-angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), and dynamic mechanical thermal analysis (DMTA) techniques. A promising shape-memory feature of PVC is hypothesized from the presence of small close imperfect thermodynamically stable crystallites as physical crosslinks, which are further reinforced by mesomorphs and possibly molecular entanglement. A detailed analysis of shape fixity and shape recovery performance of 3D printed PVC is carried out considering three programming scenarios of cold (T_g −45 °C), warm (T_g −15 °C), and hot (T_g +15 °C) and two load holding times of 0 s, and 600 s under three-point bending and compression modes. Extensive insightful discussions are presented, and in conclusion, shape-memory effects are promising,ranging from 83.24% to 100%. Due to the absence of similar results in the specialized literature, this paper is likely to fill a gap in the state-of-the-art shape-memory materials library for 4D printing, and provide pertinent results that are instrumental in the 3D printing of shape-memory PVC-based structures.     

Interlaboratory study on lipid oxidation during accelerated storage trials with rapeseed and sunflower oil analyzed by conjugated dienes as primary oxidation products

Accelerated storage tests are frequently used to assess the oxidative stability of foods and related systems due to its reproducibility. Various methods and experimental conditions are used to measure lipid oxidation. Differences between laboratories make it necessary to determine the repeatability and reproducibility of oxidation tests performed under the same conditions. The objective of the present interlaboratory study was to evaluate the outcome of a storage test for two different bulk oils, sunflower oil (SFO) and rapeseed oil (RSO), during a period of 9 weeks at 20°C, 30°C, 40°C, and 60°C. Sixteen laboratories were provided with bottled oils and conducted the storage tests according to a detailed protocol. Lipid oxidation was monitored by the formation of conjugated dienes (CD) and the activation energy (E_a) was determined for comparative purposes and statistically evaluated. An increase in CD formation was observed for both oils when the storage temperature was increased in all laboratories. The E_a,1 ranged from 47.9 to 73.3 kJ mol⁻¹ in RSO and from 27.8 to 62.6 kJ mol⁻¹ in SFO, with average values of 58.2 and 46.8 kJ mol⁻¹, respectively. The reproducibility coefficients were 10.9% and 18.2% for RSO and SFO, respectively. Practical applications: In order to compare results on oxidative stability of foods derived from different studies, the reproducibility of storage tests and methods employed to evaluate the oxidation level should be considered. This study provides fundamental data on the reproducibility of lipid oxidation under accelerated storage conditions and defines important parameters to be considered for the conduction of experiments.     

Valid parameter range analyses for chemical reaction kinetic models

The present work quantifies the relations between the structure of a chemical reaction kinetic model, its valid parameter range, and the truncation error tolerance of the model. General methods are presented to solve the three important problems of valid parameter range analysis: (1) identification of the valid parameter range of a kinetic model, (2) estimation of the error tolerance required when applying a kinetic model over a specified parameter range, and (3) improvement of existing model generation algorithms to construct more robust models. Finally, the relationship between a model's structure, its valid parameter range, and the truncation error tolerance are illustrated by the flexibility-tolerance-model graph. The new methods are applied to pyrolysis of methane/ethane mixtures.     

On‐line determination of the conversion in a styrene bulk polymerization batch reactor using near‐infrared spectroscopy

A fast on‐line method for measuring the monomer conversion of a styrene batch polymerization reaction with near‐infrared spectroscopy (NIR) has been developed. Multivariate calibration was performed, using polymer samples having temperatures around the set point of the batch reactor (75–85°C) and monomer conversions up to 35%. The calibration model was built in such a way that the effect of the temperature on the predicted conversion of the sample was minimized. The method was validated in a number of batch runs. In these runs, the batch temperature and molar mass distributions of the polymer were varied. At‐line size‐exclusion chromatography was used as a reference method for measuring the monomer conversion. Results show that on‐line conversion monitoring with NIR offered overall an excellent accuracy (～ 0.32% conversion). For high and low monomer conversions a small bias in the predicted conversion is present. The method proved to be insensitive to both relative large changes (10°C) of the batch temperature and to considerable changes of the molar mass distribution of the polymer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 90–98, 2002; DOI 10.1002/app.10241     

Modelling the Effective Thermal Conductivity in Polydispersed Bed Systems: A Unified Approach using the Linear Packing Theory and Unit Cell Model

A comprehensive, unified approach, using the Linear Packing Theory and Unit Cell Model, is proposed for calculating of the effective thermal conductivity of polydispersed packed beds. In this new approach, the effect of packing density is incorporated by the use of (i) an initial porosity to take into account the packing of mono‐sized particles, and (ii) the packing size ratio as a measure of the particle‐particle interaction. The proposed approach was validated with the experimental measurements of binary and ternary beds. This new approach demonstrates that the effective thermal conductivity of beds composed of polydispersed particles can be simulated for any composition without the need to measure the in situ porosity.     

Ecological aspects of the manufacture and application of highly pure liquid substances

The action mechanism for aggressive and highly pure media on fluoropolymer constructional elements is assumed to consist of two basic microeffects: destructive changes in the fluoropolymer and contamination of the environment. Our approach to a quantitative estimation of the physicochemical stability is based on logic similar to that of a thermodynamic model of a two‐component system. A fluoropolymer and changes in its microstructure are considered the first component of the system. The second component is composed of liquid media contaminated with fluoroorganic compounds extracted from the fluoropolymer. The proposed methods for delivering aggressive and highly pure fluids to consumers allow the exclusion of pollution from working areas with gaseous products through an exception to a number of intermediate stages of product transport. The discussed principles allow the creation of a modern, highly effective, and safe (with respect to the ecology and raw materials) production of aggressive liquid chemicals for consumers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 906–910, 2002     

Development of a comprehensive free radical photopolymerization model incorporating heat and mass transfer effects in thick films

A comprehensive kinetic model describing photopolymerization is developed which allows variation of temperature, species concentrations, and light intensity through the thickness of a photopolymerized film. Heat and mass transfer effects are included, as is the generation of heat by both reaction and light absorption. In addition to initiation, propagation, and termination mechanisms, both primary radical termination and inhibition are incorporated into the model. The possible presence and diffusion of an inert solvent are also accounted for. Thus, the model is useful for examining complex polymerization kinetics and behavior in industrially and commercially important thick film photopolymerizations, such as the curing of contact lenses, dental restorative materials, photolithographic resists, and optoelectronic coatings. The comprehensive model is used to predict polymerization rate, temperature, and conversion profiles in a variety of systems. The effects of heat generation and the thermal boundary conditions are explored, with the result that heat generation in thick samples leads to greatly increased conversions approaching 100 percent. Increased temperature in these samples also may lead to the appearance of two rate maxima, with the first due to the temperature increase and the second caused by the autoacceleration process. The magnitude of the temperature increase, along with the resultant effects, is more pronounced in insulated systems.     

以设计为中心的虚拟制造技术及在化工过程装备中的应用

简述了虚拟制造技术的内涵、关键技术及应用现状。在分析化工过程装备特点基础上 ,对过程装备虚拟制造技术平台的体系结构进行了探讨 ,以典型过程装备螺旋片导流式气液分离器为例 ,对其数字化建模方法、数值仿真技术、虚拟设计和制造环境进行了研究。初步结果表明 :以设计为中心的虚拟制造技术的应用 ,可以有效地减少产品开发的时间和成本 ,提高产品质量     

酯化反应偶联渗透汽化膜过程模型(Ⅰ)催化剂的影响

1 INTRODUCTION In former report, the kinetic model for anesterification process coupled by pervaporation wasestablished and the modeling result agreed well withthe experimental result[1].     

聚丙烯熔融指数软测量

采用机理和统计两种建模方法，建立聚丙烯生产过程熔融指数软测量模型。根据聚合反应机理和反应动力学，建立丙烯聚合过程的机理模型。统计模型则采用神经网络／部分最小二乘（NNPLS）方法。现场投运结果表明，模型计算速度和精度能满足工业现场在线实时运行的要求。