Mixed finite element method for coupled thermo‐hydro‐mechanical process in poro‐elasto‐plastic media at large strains

A mixed finite element for coupled thermo‐hydro‐mechanical (THM) analysis in unsaturated porous media is proposed. Displacements, strains, the net stresses for the solid phase; pressures, pressure gradients, Darcy velocities for pore water and pore air phases; temperature, temperature gradients, the total heat flux are interpolated as independent variables. The weak form of the governing equations of coupled THM problems in porous media within the element is given on the basis of the Hu–Washizu three‐filed variational principle. The proposed mixed finite element formulation is derived. The non‐linear version of the element formulation is further derived with particular consideration of the THM constitutive model for unsaturated porous media based on the CAP model. The return mapping algorithm for the integration of the rate constitutive equation, the consistent elasto‐plastic tangent modulus matrix and the element tangent stiffness matrix are developed. For geometrical non‐linearity, the co‐rotational formulation approach is utilized. Numerical results demonstrate the capability and the performance of the proposed element in modelling progressive failure characterized by strain localization and the softening behaviours caused by thermal and chemical effects. Copyright © 2005 John Wiley & Sons, Ltd.     

Micro‐Blooming: Hierarchically Porous Nitrogen‐Doped Carbon Flowers Derived from Metal‐Organic Mesocrystals

Synthesis of 3D flower‐like zinc‐nitrilotriacetic acid (ZnNTA) mesocrystals and their conformal transformation to hierarchically porous N‐doped carbon superstructures is reported. During the solvothermal reaction, 2D nanosheet primary building blocks undergo oriented attachment and mesoscale assembly forming stacked layers. The secondary nucleation and growth preferentially occurs at the edges and defects of the layers, leading to formation of 3D flower‐like mesocrystals comprised of interconnected 2D micropetals. By simply varying the pyrolysis temperature (550–1000 °C) and the removal method of in the situ‐generated Zn species, nonporous parent mesocrystals are transformed to hierarchically porous carbon flowers with controllable surface area (970–1605 m² g^?1), nitrogen content (3.4–14.1 at%), pore volume (0.95–2.19 cm³ g^?1), as well as pore diameter and structures. The carbon flowers prepared at 550 °C show high CO₂/N₂ selectivity due to the high nitrogen content and the large fraction of (ultra)micropores, which can greatly increase the CO₂ affinity. The results show that the physicochemical properties of carbons are highly dependent on the thermal transformation and associated pore formation process, rather than directly inherited from parent precursors. The present strategy demonstrates metal‐organic mesocrystals as a facile and versatile means toward 3D hierarchical carbon superstructures that are attractive for a number of potential applications.     

Solvent‐Induced Self‐Assembly Strategy to Synthesize Well‐Defined Hierarchically Porous Polymers

Porous polymers with well‐orchestrated nanomorphologies are useful in many fields, but high surface area, hierarchical structure, and ordered pores are difficult to be satisfied in one polymer simultaneously. Herein, a solvent‐induced self‐assembly strategy to synthesize hierarchical porous polymers with tunable morphology, mesoporous structure, and microporous pore wall is reported. The poly(ethylene oxide)‐b‐polystyrene (PEO‐b‐PS) diblock copolymer micelles are cross‐linked via Friedel–Crafts reaction, which is a new way to anchor micelles into porous polymers with well‐defined structure. Varying the polarity of the solvent has a dramatic effect upon the oleophobic/oleophylic interaction, and the self‐assembly structure of PEO‐b‐PS can be tailored from aggregated nanoparticles to hollow spheres even mesoporous bulk. A morphological phase diagram is accomplished to systematically evaluate the influence of the composition of PEO‐b‐PS and the mixed solvent component on the pore structure and morphology of products. The hypercrosslinked hollow polymer spheres provide a confined microenvironment for the in situ reduction of K₂PdCl₄ to ultrasmall Pd nanoparticles, which exhibit excellent catalytic performance in solvent‐free catalytic oxidation of hydrocarbons and alcohols.     

Fabrication and characteristics of porous NiTi shape memory alloy synthesized by microwave sintering

Porous nickel titanium (NiTi) shape memory alloy (SMA) was successfully fabricated by microwave sintering method. This method allows formation of porous structures without using any pore-forming agents. Moreover, microwave sintering of NiTi SMA can be successfully performed at a relatively low sintering temperature of 850 °C and a short sintering time of 15 min. The pore characteristics, microstructure, phase transformation and stress-strain behavior of the porous NiTi SMA were investigated. The porous NiTi SMA exhibited porosity ratios from 27% to 48% and pore sizes range from 50 to 200 μm when using different sintering temperatures and holding times. The predominant B2 (NiTi) and B19′ (NiTi) phases were identified in the porous NiTi SMA. A multi-step phase transformation took place on heating and a two-step phase transformation took place on cooling of the porous NiTi SMA. The irrecoverable strains decreased with increasing sintering temperature, but the holding time had little effect on the stress-strain behavior at 60 °C.     

PM‐Composites with Nickel‐Titanium Shape Memory Alloys

Starting from NiTi‐powders, composites of nickel‐titanium shape memory alloys (NiTi‐SMA) and different stainless steels as well as of different NiTi‐SMAs were produced by using the process of hot isostatic pressing (HIP). Metallographic investigations focussed on the interface between NiTi‐SMA and stainless steel with special emphasis placed on the characterization of the typical structure of the diffusion zones in both components.     

Ni含量对激冷贫镍TiNi形状记忆合金薄带相变行为的影

用激冷甩带法制备了Til-xNix(x=45％～49.8％)(原子分数)形状记忆合金(SMA)薄带,用示差扫描量热仪研究了Ni含量对铸态及450℃、500℃退火态TiNi SMA薄带相变行为的影响.结果表明,冷却/加热时,铸态和退火态Ti1-xNix(x=45％～49％)SMA薄带发生A→M/M→A一阶马氏体相变;当Ni含量为49.8％时,铸态和退火态TiNi SMA薄带冷却时发生A→ R→M两阶段相变,加热时发生M→A一阶段相变.随Ni含量增加,TiNi SMA薄带马氏体正、逆相变温度范围先增大后减小,Ni含量为48％时相变温度范围最宽.退火态比铸态TiNi SMA薄带相变温度范围窄.随Ni含量增加,TiNi SMA薄带马氏体正、逆相变温度升高,相变热滞增大.当Ni含量为49％时,SMA薄带的马氏体相变温度达最大值,当Ni含量为49.8％时马氏体相变温度迅速下降.     

Stepwise Crosslinking: A Facile Yet Versatile Conceptual Strategy to Nanomorphology‐Persistent Porous Organic Polymers

Both high surface areas and well‐orchestrated nanomorphologies are important for porous organic polymers (POPs). However, the two key characteristics are generally difficult to be satisfied simultaneously, because the common pore‐making procedures usually produce ill‐defined nanomorphologies or give rise to damage of precustomized nanomorphologies. Herein, a facile yet versatile stepwise crosslinking strategy for fabrication of POPs with an unusual nanomorphology‐persistent characteristic during pore‐making is reported. Polystyrene nanofibers and poly(styrene‐co‐divinylbenzene) nanosphere arrays are utilized as building blocks, and then transformed into nanofibrillar morphology‐persistent and ordered array morphology‐persistent POPs via stepwise crosslinking, respectively. The stepwise crosslinking strategy includes pre‐crosslinking and hypercrosslinking; the pre‐crosslinking in a carefully selected poor solvent of polystyrene forms a lowly crosslinked structure, which guarantees the stability of nanomorphology during the subsequent pore‐making via hypercrosslinking. The as‐obtained POPs can be used as precursors for novel well‐defined hyperporous carbon nanofibers and ordered carbon nanosphere arrays with excellent adsorption performances.     

Porous Polymers as Multifunctional Material Platforms toward Task‐Specific Applications

Exploring advanced porous materials is of critical importance in the development of science and technology. Porous polymers, being famous for their all‐organic components, tailored pore structures, and adjustable chemical components, have attracted an increasing level of research interest in a large number of applications, including gas adsorption/storage, separation, catalysis, environmental remediation, energy, optoelectronics, and health. Recent years have witnessed tremendous research breakthroughs in these fields thanks to the unique pore structures and versatile skeletons of porous polymers. Here, recent milestones in the diverse applications of porous polymers are presented, with an emphasis on the structural requirements or parameters that dominate their properties and functionalities. The Review covers the following applications: i) gas adsorption, ii) water treatment, iii) separation, iv) heterogeneous catalysis, v) electrochemical energy storage, vi) precursors for porous carbons, and vii) other applications (e.g., intelligent temperature control textiles, sensing, proton conduction, biomedicine, optoelectronics, and actuators). The key requirements for each application are discussed and an in‐depth understanding of the structure–property relationships of these advanced materials is provided. Finally, a perspective on the future research directions and challenges in this field is presented for further studies.     

TiNi Shape Memory Alloy Foams Synthesized by Spacer Sintering and their Properties

Titanium （Ti） and nickel （Ni） elemental powders were blended by ball milling and the ball milled powders were employed to fabricate TiNi shape memory alloy （SMA） foams by spacer sintering. Effect of ball milling time on phase constitutes of the sintered TiNi alloy foams was studied by X-ray diffraction （XRD） analysis. Scanning electron microscopy （SEM） was used to characterize the porous structure, and compressive tests were carried out to evaluate the mechanical properties of＇the foams. Results indicate that porosities of the TiNi alloy foams can be controlled by using the spacer sintering method, and the porosities show a significant effect on the mechanical properties and shape memory effect （SME）.     

Powder Metallurgical Near‐Net‐Shape Fabrication of Porous NiTi Shape Memory Alloys for Use as Long‐Term Implants by the Combination of the Metal Injection Molding Process with the Space‐Holder Technique

A new method was developed for producing highly porous NiTi for use as an implant material. The combination of the space‐holder technique with the metal injection molding process allows a net‐shape fabrication of geometrically complex samples and the possibility of mass production for porous NiTi. Further, the porosity can be easily adjusted with respect to pore size, pore shape, and total porosity. The influence of the surface properties of powder metallurgical NiTi on the biocompatibility was first examined using human mesenchymal stem cells (hMSCs). It was found that pre‐alloyed NiTi powders with an average particle size smaller than 45 μm led to the surface properties most suitable for the adhesion and proliferation of hMSCs. For the production of highly porous NiTi, different space‐holder materials were investigated regarding low C‐ and O‐impurity contents and the reproducibility of the process. NaCl was the most promising space‐holder material compared to PMMA and saccharose and was used in subsequent studies. In these studies, the influence of the total porosity on the mechanical properties of NiTi is investigated in detail. As a result, bone‐like mechanical properties were achieved by the choice of Ni‐rich NiTi powder and a space‐holder content of 50 vol% with a particle size fraction of 355–500 μm. Pseudoelasticity of up to 6% was achieved in compression tests at 37 °C as well as a bone‐like loading stiffness of 6.5 GPa, a sufficient plateau stress σ₂₅ of 261 MPa and a value for σ₅₀ of 415 MPa. The first biological tests of the porous NiTi samples produced by this method showed promising results regarding proliferation and ingrowth of mesenchymal stem cells, also in the pores of the implant material.     

Numerical Simulation of Mechanical Behaviors of the TiNi Shape Memory Alloy Welded Joints in the Precise Pulse Resistance Butt—Welding

The hysteresis unit system was introduced to mechanical structure behavior of the TiNi SMA joint based on the structure characteristics of the martensite variants in the joints, and some functions reflecting its inner structure characteristics and micro-behavior such as density function, phase transformation function were set up from micro-points. Finally, the structure behavior relationship and corresponding mathematic model reflecting the relationship among hysteresis strain, stress and phase transformation strain were provided, which could predict the stress-strain behavior of the TiNi SMA joint to large extent.     

Synthesis and characterization of novel biodegradable pentablock copolymers from L‐lactide,p‐dioxanone and poly (ethylene glycol)

ABCBA type pentablock copolymers, in which the A, B and C blocks are poly (p‐Dioxanone) (PPDO), poly (L‐Lactide) (PLLA), and polyethylene glycol (PEG), respectively, were synthesized via a two‐step ring‐opening polymerization in bulk using stannous octoate as the catalyst. PLA‐b‐PEG‐b‐PLA Triblock copolymer was synthesized at first and then p‐Dioxanone monomers as the other blocks were added to it. In the first step, poly ethylene glycol and, in the second step, triblock copolymer acts as the macro initiator. The obtained copolymers were identified by ?1&/sup;H&/I;, ?13&/sup;CNMR&/I; and IR&/I; spectroscopy. The intrinsic viscosity of copolymers was measured in chloroform/phenol (3/1 v/w) solution. The thermal properties, such as melting point, melting enthalpy and crystallinity, were studied. From the results of differential scanning calorimetry and thermal gravimetric analysis, it was observed that the PPDO blocks show similar crystallization behavior like homopolymer and also melting temperature of two PPDO end blocks raise with an increase in DON content in copolymer.     

Computational simulation of chemical dissolution‐front instability in fluid‐saturated porous media under non‐isothermal conditions

This paper primarily deals with the computational aspects of chemical dissolution‐front instability problems in two‐dimensional fluid‐saturated porous media under non‐isothermal conditions. After the dimensionless governing partial differential equations of the non‐isothermal chemical dissolution‐front instability problem are briefly described, the formulation of a computational procedure, which contains a combination of using the finite difference and finite element method, is derived for simulating the morphological evolution of chemical dissolution fronts in the non‐isothermal chemical dissolution system within two‐dimensional fluid‐saturated porous media. To ensure the correctness and accuracy of the numerical solutions, the proposed computational procedure is verified through comparing the numerical solutions with the analytical solutions for a benchmark problem. As an application example, the verified computational procedure is then used to simulate the morphological evolution of chemical dissolution fronts in the supercritical non‐isothermal chemical dissolution system. The related numerical results have demonstrated the following: (1) the proposed computational procedure can produce accurate numerical solutions for the planar chemical dissolution‐front propagation problem in the non‐isothermal chemical dissolution system consisting of a fluid‐saturated porous medium; (2) the Zhao number has a significant effect not only on the dimensionless propagation speed of the chemical dissolution front but also on the distribution patterns of the dimensionless temperature, dimensionless pore‐fluid pressure, and dimensionless chemical‐species concentration in a non‐isothermal chemical dissolution system; (3) once the finger penetrates the whole computational domain, the dimensionless pore‐fluid pressure decreases drastically in the non‐isothermal chemical dissolution system.     

State‐of‐the‐Art Advances and Challenges of Iron‐Based Metal Organic Frameworks from Attractive Features,Synthesis to Multifunctional Applications

Metal organic frameworks (MOFs), as an original kind of organic–inorganic porous material, are constructed with metal centers and organic linkers via a coordination complexation reaction. Among uncountable MOF materials, iron‐containing metal organic frameworks (Fe‐MOFs) have excellent potential in practical applications owing to their many fascinating properties, such as diverse structure types, low toxicity, preferable stability, and tailored functionality. Here, recent research progresses of Fe‐MOFs in attractive features, synthesis, and multifunctional applications are described. Fe‐MOFs with porosity and tailored functionality are discussed according to the design of building blocks. Four types of synthetic methods including solvothermal, hydrothermal, microwave, and dry gel conversion synthesis are illustrated. Finally, the applications of Fe‐MOFs in Li‐ion batteries, sensors, gas storage, separation in gas and liquid phases, and catalysis are elucidated, focusing on the mechanism. The aim is to provide prospects for extending Fe‐MOFs in more practical applications.     

Nanoarchitectured Design of Porous Materials and Nanocomposites from Metal‐Organic Frameworks

The emergence of metal‐organic frameworks (MOFs) as a new class of crystalline porous materials is attracting considerable attention in many fields such as catalysis, energy storage and conversion, sensors, and environmental remediation due to their controllable composition, structure and pore size. MOFs are versatile precursors for the preparation of various forms of nanomaterials as well as new multifunctional nanocomposites/hybrids, which exhibit superior functional properties compared to the individual components assembling the composites. This review provides an overview of recent developments achieved in the fabrication of porous MOF‐derived nanostructures including carbons, metal oxides, metal chalcogenides (metal sulfides and selenides), metal carbides, metal phosphides and their composites. Finally, the challenges and future trends and prospects associated with the development of MOF‐derived nanomaterials are also examined.     

人工食管用TiNi形状记忆合金的遗传毒性研究

针对人工食管用的TiNi形状记忆合金,实验研究了舍金的遗传毒性.用TiNi合金的加速降解方法模拟长期植入人体时的变化,并用小鼠骨髓嗜多染红细胞微核率试验对TiNi形状记忆合金的遗传毒性进行了评估.评估结果表明,TiNi形状记忆合金的遗传毒性呈阴性.具有良好的生物相容性的TiNi形状记忆合金可以作为人工食管的支撑材料.     

A stabilized finite element formulation for monolithic thermo‐hydro‐mechanical simulations at finite strain

An adaptively stabilized monolithic finite element model is proposed to simulate the fully coupled thermo‐hydro‐mechanical behavior of porous media undergoing large deformation. We first formulate a finite‐deformation thermo‐hydro‐mechanics field theory for non‐isothermal porous media. Projection‐based stabilization procedure is derived to eliminate spurious pore pressure and temperature modes due to the lack of the two‐fold inf‐sup condition of the equal‐order finite element. To avoid volumetric locking due to the incompressibility of solid skeleton, we introduce a modified assumed deformation gradient in the formulation for non‐isothermal porous solids. Finally, numerical examples are given to demonstrate the versatility and efficiency of this thermo‐hydro‐mechanical model. Copyright © 2015 John Wiley & Sons, Ltd.     

Toward Scalable Fabrication of Hierarchical Silica Capsules with Integrated Micro‐, Meso‐, and Macropores

Hierarchical porous structures are ubiquitous in biological organisms and inorganic systems. Although such structures have been replicated, designed, and fabricated, they are often inferior to naturally occurring analogues. Apart from the complexity and multiple functionalities developed by the biological systems, the controllable and scalable production of hierarchically porous structures and building blocks remains a technological challenge. Herein, a facile and scalable approach is developed to fabricate hierarchical hollow spheres with integrated micro‐, meso‐, and macropores ranging from 1 nm to 100 μm (spanning five orders of magnitude). (Macro)molecules, micro‐rods (which play a key role for the creation of robust capsules), and emulsion droplets have been successfully employed as multiple length scale templates, allowing the creation of hierarchical porous macrospheres. Thanks to their specific mechanical strength, these hierarchical porous spheres could be incorporated and assembled as higher level building blocks in various novel materials.     

A three‐dimensional model describing stress‐temperature induced solid phase transformations: solution algorithm and boundary value problems

An always increasing knowledge on material properties as well as a progressively more sophisticated production technology make shape memory alloys (SMA) extremely interesting for the industrial world. At the same time, SMA devices are typically characterized by complex multi‐axial stress states as well as non‐homogeneous and non‐isothermal conditions both in space and time. This aspect suggests the finite element method as a useful tool to help and improve application design and realization. With this aim, we focus on a three‐dimensional macroscopic thermo‐mechanical model able to reproduce the most significant SMA features (Int. J. Numer. Methods Eng. 2002; 55 : 1255–1264), proposing a simple modification of such a model. However, the suggested modification allows the development of a time‐discrete solution algorithm, which is more effective and robust than the one previously discussed in the literature. We verify the computational tool ability to simulate realistic mechanical boundary value problems with prescribed temperature dependence, studying three SMA applications: a spring actuator, a self‐expanding stent, a coupling device for vacuum tightness. The effectiveness of the model to solve thermo‐mechanical coupled problems will be discussed in a forthcoming work. Copyright © 2004 John Wiley & Sons, Ltd.     

溶胶—凝胶法合成了PZT—TiNi复合膜

以醋酸铅、异丙醇锆和钛酸正丁酯为先驱物,利用溶胶－凝胶在ＴｉＮｉ形状记忆合金箔基片上成功合成了ＰＺＴ铁电陶瓷薄膜,并研究了ＰＺＴ薄膜的晶化过程,结果表明,所得ＰＺＴ薄膜属钙钛矿结构无裂纹,与ＴｉＮｉ合金基结合牢固。