Self-assembly of fibrous ZSM-5 zeolites in the presence of sodium alginate

ZSM-5 zeolites with a fibrous morphology were successfully self-assembled in the presence of sodium alginate. The effect of the sodium alginate concentration, Si/Al molar ratio in the synthesis gel, crystallization temperature and time, and the addition order of the sodium alginate on the morphology of the ZSM-5 zeolites was investigated. The possible formation mechanism of fibrous ZSM-5 zeolite crystals was also proposed. The results indicated that the carboxyl and hydroxyl groups of sodium alginate synergistically induced the self-stacking of ZSM-5 nanocrystals and thus the formation of the fibrous ZSM-5 zeolites. The Si/Al molar ratio of the fibrous ZSM-5 zeolites could be adjusted by controlling the amount of the NaAlO₂ additive; however, high Si/Al molar ratios also hindered the self-stacking of ZSM-5 nanocrystals. A high crystallization temperature (180 °C), a moderate sodium alginate concentration (8.33 g/L), and the addition of sodium alginate prior to tetraethoxysilane were necessary for the formation of fibrous ZSM-5 zeolites.     

Synthesis and characterization of NaA zeolite particle as intumescent fiame retardant in chloroprene rubber system

NaA zeolite with average particle size of 1 m was successfully synthesized by microwave heating. Inu-ences of pre-crystallization time,microwave power and microwave heating time on the synthesis of NaA zeolite were investigated. The as-synthesized sample was characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM) and particle size distribution(PSD) . Thermal and fiame retardant properties as intumescent fiame retardant(IFR) in chloroprene rubber(CR) system,such as thermo-gravimetry(TG),lim...     

An effective computational algorithm for rate-independent crystal plasticity based on a single crystal yield surface with an application to tube hydroforming

Up to now, several computational methods have been proposed for crystal plasticity models. The main objective of these computational methods has been to overcome the problem with the non-uniqueness of active slip systems during the plastic deformation of a single crystal. Crystal plasticity models based on a single crystal yield function have been proposed as alternative algorithms to overcome this problem. But the problem with these models is that they use a highly non-linear yield function for the crystal, which makes them computationally expensive. In this paper, a computational method is proposed that would modify a single crystal yield function in order to make it computationally efficient. Also to better capture experimental data, a new parameter is introduced into the single crystal yield function to make it more flexible. For verification, this crystal plasticity model was directly applied for the simulation of hydroforming of an extruded aluminum tube under complex strain paths. It was found that the current model is considerably faster than the previous crystal plasticity model based on a power-law type single crystal yield surface. Due to its computational efficiency, the current crystal plasticity model can also be used to calculate the anisotropy coefficients of phenomenological yield functions.     

Bending of single crystal microcantilever beams of cube orientation: Finite element model and experiments

The aim of this work is to investigate the microstructure evolution, stress-strain response and strain hardening behavior of microscale beams. For that purpose, two single crystal cantilever beams in the size dependent regime were manufactured by ion beam milling and beams were bent with an indenter device. A crystal plasticity material model for large deformations was implemented in a finite element framework to further investigate the effect of boundary constraints. Simulations were performed using bulk material properties of single crystal copper without any special treatment for the strain gradients. The difference between the slopes of the experimental and the simulated force displacement curves suggested negligible amount of strain gradient hardening compared to the statistical hardening mechanisms.     

Energetic dislocation interactions and thermodynamical aspects of strain gradient crystal plasticity theories

This paper focuses on the unification of two frequently used and apparently different strain gradient crystal plasticity frameworks: (i) the physically motivated strain gradient crystal plasticity models proposed by Evers et al. [2004a. Non-local crystal plasticity model with intrinsic SSD and GND effects. Journal of the Mechanics and Physics of Solids 52, 2379-2401; 2004b. Scale dependent crystal plasticity framework with dislocation density and grain boundary effects. International Journal of Solids and Structures 41, 5209-5230] and Bayley et al. [2006. A comparison of dislocation induced back stress formulations in strain gradient crystal plasticity. International Journal of Solids and Structure 43, 7268-7286; 2007. A three dimensional dislocation field crystal plasticity approach applied to miniaturized structures. Philosophical Magazine 87, 1361-1378] (here referred to as Evers-Bayley type models), where a physical back stress plays the most important role and which are further extended here to deal with truly large deformations, and (ii) the thermodynamically consistent strain gradient crystal plasticity model of Gurtin (2002-2008) (here referred to as the Gurtin type model), where the energetic part of a higher order micro-stress is derived from a non-standard free energy function. The energetic micro-stress vectors for the Gurtin type models are extracted from the definition of the back stresses of the improved Evers-Bayley type models. The possible defect energy forms that yield the derived physically based micro-stresses are discussed. The duality of both type of formulations is shown further by a comparison of the micro-boundary conditions. As a result, this paper provides a direct physical interpretation of the different terms present in Gurtin's model.     

Optimized synthesis and photovoltaic performance of TiO2 nanoparticles for dye-sensitized solar cell

This paper presents response surface methodology （RSM） as an efficient approach for modeling and optimizing TiO2 nanoparticles preparation via co-precipitation for dye-sensitized solar cell （DSSC） perfor- mance. Titanium （IV） bis-（acetylacetonate） di-isopropoxide （DIPBAT）, isopropanol and water were used as precursor, solvent and co-solvent, respectively. Molar ratio of water, aging temperature and calcina- tion temperature as preparation factors with main and interaction effects on particle characteristics and performances were investigated, Particle characteristics in terms of primary and secondary sizes, crys- tal orientation and morphology were determined by X-ray diffractometry （XRD） and scanning electron microscopy （SEM）. Band gap energy and power conversion efficiency of DSSCs were used for perfor- mance studies. According to analysis of variance （ANOVA） in response surface methodology （RSM）, all three independent parameters were statistically significant and the final model was accurate. The model predicted maximum power conversion efficiency （0.14%） under the optimal condition of molar ratio of DIPBAT-to-isopropanol-to-water of 1 ： 10：500, aging temperature of 36 C and calcination temperature of 400 ℃. A second set of data was adopted to validate the model at optimal conditions and was found to be 0.14 ± 0.015%, which was very close to the predicted value. This study proves the reliability of the model in identi（ving the optimal condition for maximum performance.     

疏液壁面上亲液杂质对滑移特性的影响

纳米流动系统具有高效、经济等优势,在众多领域具有广泛的应用前景.因该类系统具有极高的表面积体积比,致使界面滑移效应对流动具有显著影响.论文采用非平衡分子动力学模拟方法,研究了疏液壁面表层混入少量亲液原子时纳米通道内液体的滑移特性,并基于分子动理论解释了其影响机制.研究发现,亲液杂质(均布或集中)对液体法向密度振荡程度影响较弱,但会显著改变壁面附近类固体层的分布和液体滑移规律;随亲液杂质占比增加,液体类固体现象更趋明显,壁面处液体接触密度也线性增大,但通道内液体平均速度逐渐降低,滑移长度也迅速减小;相比于集中的亲液杂质,均匀分布亲液杂质对滑移的弱化效应更强.如当亲液杂质占比为28%时,其滑移长度比单纯疏液表面的降低率从50%扩大至56%.基于分子动理论的分析发现,亲液杂质会导致杂质原子附近第一液体层内的原子发生跃迁的能垒加大,即弱化了液体原子的流向跃迁行为,从而降低了滑移量;相比于集中杂质,均匀分布的杂质还会降低固液间的非公度性,致使滑移特性破坏更严重.     

Strain hardening in bent copper foils

A series of systematic tensile and microbend tests were conducted on copper foil specimens with different thicknesses. The specimens were made of a copper foil having almost unidirectional crystal orientations that was considered to be nearly single-crystal. In order to investigate the effects of slip system interactions, two different crystal orientations relative to the tensile direction were considered in the tests: one is close to coplanar double-slip orientation, and the other is close to the ideal cube orientation (the tensile direction nearly coincides to [0 0 1]) that yields multi-planar multi-slip deformation. We extended the microbend test method to include the reversal of bending, and we attempted to divide the total amount of strain-hardening into isotropic and kinematic hardening components. In the tensile tests, no systematic tendency of size dependence was observed. In the microbend tests, size-dependent kinematic hardening behavior was observed for both the crystal orientations, while size dependence of isotropic hardening was observed only for the multi-planar multi-slip case. We introduce an extended crystal plasticity model that accounts for the effects of the geometrically necessary dislocations (GNDs), which correspond to the spatial gradients of crystallographic slips. Through numerical simulations performed using the model, the origin of the size-dependent behavior observed in the microbend tests is discussed.     

3-D simulation of spatial stress distribution in an AZ31 Mg alloy sheet under in-plane compression

A complete 3-D crystal plasticity finite element method (CPFEM) that considered both crystallographic slip and deformation twinning was applied to simulate the spatial distribution of the relative amount of slip and twin activities in a polycrystalline AZ31 Mg alloy during in-plane compression. A microstructure mapping technique that considered the grain size distribution and microtexture measured by electron backscatter diffraction (EBSD) technique was used to create a statistically representative 3-D microstructure for the initial configuration. Using a 3-D Monte Carlo method, a 3-D digital microstructure that matched the experimentally measured grain size distribution was constructed. Crystallographic orientations obtained from the EBSD data were assigned on the 3-D digital microstructure to match the experimentally measured misorientation distribution. CPFEM captured the heterogeneity of the stress concentration as well as the slip and twin activities of a polycrystalline AZ31 Mg alloy during in-plane compression.     

方沸石大单晶及多晶粉饼力学性能的实验研究

报道了采用纳米压痕硬度计和Instron仪器分别对方沸石ANA大单晶和方沸石ANA多晶粉饼进行的力学性能测试工作。在纳米压痕实验中可实时测得连续载荷和随载荷连续变化而变化的位移,得到载荷-位移曲线图。根据W.C.O live算法,利用接触刚度连续测量(CSM)技术,实现了ANA沸石的硬度、弹性模量随压痕深度变化的连续测量,得到了ANA沸石单晶的硬度、弹性模量分别为0.25GPa和4GPa。用Instron仪器测得ANA多晶粉饼的弹性模量值为125MPa。对ANA沸石大单晶和ANA沸石多晶粉饼的力学性能进行了比较。     

A new crystal plasticity scheme for explicit time integration codes to simulate deformation in 3D microstructures: Effects of strain path,strain rate and thermal softening on localized deformation in the aluminum alloy 5754 during simple shear

The predominant deformation mode during material failure is shear. In this paper, a crystal plasticity scheme for explicit time integration codes is developed based on a forward Euler algorithm. The numerical model is incorporated in the UMAT subroutine for implementing rate-dependent crystal plasticity model in LS-DYNA/Explicit. The sheet is modeled as a face centered cubic (FCC) polycrystalline aggregate, and a finite element analysis based on rate-dependent crystal plasticity is implemented to analyze the effects of three different strain paths consisting predominantly of shear. Finite element meshes containing texture data are created with solid elements. The material model can incorporate information obtained from electron backscatter diffraction (EBSD) and apply crystal orientation to each element as well as account for texture evolution. Single elements or multiple elements are used to represent each grain within a microstructure. The three dimensional (3D) polycrystalline microstructure of the aluminum alloy AA5754 is modeled and subjected to three different strain rates for each strain path. The effects of strain paths, strain rates and thermal softening on the formation of localized deformation are investigated. Simulations show that strain path is the most dominant factor in localized deformation and texture evolution.     

沸石分子筛单晶体弹塑性双线性本构关系的实验研究与有限元确定

为研究两种沸石分子筛方钠石SOD和镁碱沸石FER的力学性能,采用纳米压痕技术,测得随载荷连续变化的位移,得到载荷-位移曲线图.根据Olive算法,利用接触刚度连续测量技术,得到这两种沸石分子筛的硬度及弹性模量.基于弹塑性双线性本构关系假定,用ANSYS有限元程序模拟纳米压痕实验过程,利用搜索法得到沸石大单晶SOD和FER的双线性本构关系.     

A novel constitutive model for semiconductors: The case of silicon

The photovoltaic industry relies heavily on solar-grade silicon multicrystals. Understanding their mechanical behavior requires the development of adequate constitutive models accounting for the effects of both high dislocation densities and complex loading situations in a wide range of temperature, strain rate, and impurity contents. The traditional model of Alexander and Haasen poses several limitations. We introduce in this work a novel constitutive model for covalent single crystals and its implementation into a rate-dependent crystal plasticity framework. It is entirely physically based on the dislocation generation, storage and annihilation processes taking place during plastic flow. The total dislocation density is segmented according to the dislocation mobility potential and their character. A dislocation multiplication law for the yield region more accurate than the one of Alexander and Haasen is proposed. The influence of additional dislocation sources created on forest trees, usually disregarded in models for semiconductors, is assessed. The dislocation velocity law combines three potentially rate-limiting mechanisms: the standard double kink mechanism, jog dragging and the influence of localized obstacles. The model is valid at finite strains, in multiple slip conditions and captures accurately the high temperature- and strain rate sensitivity of semiconductors. The experimental stress overshoot is qualitatively reproduced only when jog dragging is accounted for. Localized obstacles are shown not to have any significant effect on dislocation motion in silicon. The broader case of extrinsic semiconductors is discussed and the influence of dissolved oxygen on the upper yield stress of silicon monocrystals is successfully reproduced.     

A cyclic plasticity model for single crystals

The Armstrong–Frederick type kinematic hardening rule was invoked to capture the Bauschinger effect of the cyclic plastic deformation of a single crystal. The yield criterion and flow rule were built on individual slip systems. Material memory was introduced to describe strain range dependent cyclic hardening. The experimental results of copper single crystals were used to evaluate the cyclic plasticity model. It was found that the model was able to accurately describe the cyclic plastic deformation and properly reflect the dislocation substructure evolution. The well-known three distinctive regimes in the cyclic stress–strain curve of the copper single crystals oriented for single slip can be reproduced by using the model. The model can predict the enhanced hardening for crystals oriented for multislip, showing the model's ability to describe anisotropic cyclic plasticity. For a given loading history, the model was able to capture not only the saturated stress–strain response but also the detailed transient stress–strain evolution. The model was used to predict the cyclic plasticity under a high–low loading sequence. Both the stress–strain responses and the microstructural evolution can be appropriately described through the slip system activation.     

Deep learning-based on-line image analysis for continuous industrial crystallization processes

In situ microscopic imaging is a useful tool in monitoring crystallization processes, including crystal nucleation, growth, aggregation and breakage, as well as possible polymorphic transition. To convert the qualitative information to be quantitative for the purpose of process optimization and control, accurate analysis of crystal images is essential. However, the accuracy of image segmentation with traditional methods is largely affected by many factors, including solid concentration and image quality. In this study, the deep learning technique using mask region-based convolutional neural network (Mask R-CNN) is investigated for the analysis of on-line images from an industrial crystallizer of 10 m³ operated in continuous mode with high solid concentration and overlapped particles. With detailed label points for each crystal and transfer learning technique, two models trained with 70,908 and 7,709 crystals respectively are compared for the effect of training data amount. The former model effectively segments the aggregated and overlapped crystals even at high solid concentrations. Moreover, it performs much better than the latter one and traditional multi-scale method both in terms of precision and recall, revealing the importance of large number of crystals in deep learning. Some geometrical characteristics of segmented crystals are also analyzed, involving equivalent diameter, circularity, and aspect ratio.     

A stochastic model for the temporal aspects of flow intermittency in micropillar compression

Systematic experimental investigations have demonstrated that the plastic deformation of micropillar proceeds through a sequence of intermittent bursts, the sizes of which follow power-law statistics. In this study, a stochastic model based on the power-law distribution of burst size is formulated in the framework of crystal plasticity in order to investigate the temporal aspects of flow intermittency in micropillar compression. A Monte Carlo simulation scheme is developed to determine the burst size when a burst activity is captured. This burst size is considered as the displacement boundary condition of burst deformation. Three-dimensional finite element analysis of the model is performed and its predictions are validated by comparison with results from both micro-compression experiments and simulation tests of bulk crystals using the classic crystal plasticity finite element method (CPFEM). The model provides a reasonable prediction of stress–strain responses both at the macroscopic and microscopic scales. Finally, the capability of this model is shown with applications to the intermittent plastic deformation in micropillar compressions, in particular for their burst time durations and burst velocities. The results from such stochastic finite element analysis are shown to be consistent with earlier experimental findings and results of mean-field theory.     

A combined isotropic-kinematic hardening model for the simulation of warm forming and subsequent loading at room temperature

A coupled isotropic-kinematic hardening material model was developed based on phenomenological observations of performed two stage experiments on a medium carbon steel – SAE 1144, where the first deformation is performed at elevated temperatures and the second deformation at room temperature. Above all, deformations with orthogonal loading at various temperatures were investigated in order to determine the influence of the loading direction as well as of the temperature. Bergström’s theory of work hardening as well as the nonlinear kinematic hardening of an Armstrong–Frederick type were used as a basis for the model development. In the proposed model a relationship between material coefficients of the classical Bergström model and temperature was investigated. The aim of the new material model was to introduce the least possible amount of new parameters as well as to facilitate the mathematical determination of parameters during the fitting of the model with experimental data. The developed model was implemented in an in-house FE-Code in order to simulate the material behavior due to the dynamic strain aging and the hardening behavior after the dynamic strain aging process. Representative simulation results were compared with the experimental data in order to validate the efficiency and the application range of the model.     

On detonation behavior of mixed fuels

An experimental study of detonation was carried out for mixed fuels (, and ). The results obtained demonstrate that detonation velocities of mixed fuels agree very well with normal C-J velocity and that detonation limits were not extended by the addition of a small amount of . As for mixed fuel, detonation velocities and detonation limits as a function of the equivalence ratio of the whole mixture of mixed fuel coincided with those of single fuel. However, the detonation induction time of a mixture of with a lower sensitivity to detonation decreased considerably with the addition of a small amount of . In addition, the influence of mixed fuels on the quasi-detonation and the fast deflagration in the process of DDT was investigated, showing interesting and complicated features in mixed fuel. Received 20 December 1994 / Accepted 20 November 1995     

物理老化对玻璃态高聚物非线性蠕变行为的影响

在不同应力水平下对经历不同老化时间的有机玻璃(PMMA)进行常温蠕变测试,分析物理老化和应力对材料蠕变柔量函数的影响.分析表明,老化时间对PMMA蠕变行为的影响满足流变简单性规律,即不同老化时间的蠕变柔量曲线可以沿对数时间轴平移而叠加到参考曲线上.取最长的老化时间为参考状态,依时间-老化时间等效原理,得到了各应力水平下的蠕变柔量主曲线.老化移位因子与老化时间在双对数坐标图上呈现线性关系,其负斜率就是老化移位率.结果表明,老化移位率随应力的增高而减小.