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Reticular chemistry concerns the linking of molecular building blocks into predetermined structures using strong bonds. We have been working on creating and developing the conceptual and practical basis of this new area of research. As a result, new classes of crystalline porous materials have been designed and synthesized: metal-organic frameworks, zeolitic imidazolate frameworks, and covalent organic frameworks. Crystals of this type have exceptional surface areas (2,000−6,000 m2/g) and take up voluminous amounts of hydrogen (7.5 wt% at 77 K and 3−4 × 106 Pa), methane (50 wt% at 298 K and 2.5 × 106 Pa), and carbon dioxide (140 wt% at 298 K and 3 × 106 Pa). We have driven the basic science all the way to applications without losing sight of our quest for understanding the underlying molecular aspects of this chemistry. The presentation was focused on the design concepts, synthesis, and structure of these materials, with emphasis on their applications to onboard energy storage.
The coarsening of polyhedral grains in a liquid matrix was calculated using crystal growth and dissolution equations used in crystal growth theories for faceted crystals. The coarsening behavior was principally governed by the relative value of the maximum driving force for growth (Δgmax), which is determined by the average size and size distribution, to the critical driving force for appreciable growth (Δgc). When Δgmax was much larger than Δgc, pseudonormal grain coarsening occurred. With a reduction of Δgmax relative to Δgc, abnormal grain coarsening (AGC, when Δgmax ≥ Δgc) and stagnant grain coarsening (SGC, when Δgmax < Δgc) were predicted. The observed cyclic AGC and incubation for AGC in real systems with faceted grains were explained in terms of the relative value between Δgmax and Δgc. The effects of various processing and physical parameters, such as the initial grain size and distribution, the liquid volume fraction, step free energy, and temperature, were also evaluated. The calculated results were in good agreement with previous experimental observations.
Successful growth of vertically aligned carbon nanotube (CNT) arrays on copper substrate by thermal chemical vapor deposition is reported in this paper. The effects of Ti, Ni, and Ni–Cr intermediate layers have been studied to eliminate cracking of the copper surface during the synthesis of CNTs. It was found that these intermediate layers play a critical role in achieving vertical alignment of CNTs on copper substrates. The effects of other reaction parameters such as flow rate of ethylene, concentration of water vapor, and deposition temperature have also been studied. Scanning electron microscopy, transmission electron microscopy, and micro-Raman spectroscopy were used to evaluate the quality and nature of the CNT formed.
Mg-Li-Al alloy was prepared by ingot casting and then underwent subsequent reactive ball milling. A Mg-Li-Al-H complex hydride was obtained under a 0.4 MPa hydrogen atmosphere at room temperature, and as high as 10.7 wt% hydrogen storage capacity was achieved, with the peak desorption temperature of the initial step at approximately 65 °C. The evolution of the reaction during milling, as well as the effect of Li/Al ratio in the raw materials on the desorption properties of the hydrides formed, were studied by x-ray diffraction and simultaneous thermogravimetry and differential scanning calorimetry techniques. The results showed that mechanical milling increases the solubility of Li in Mg, leading to the transformation of bcc β(Li) solid solution to hcp α(Mg) solid solution, the latter continues to incorporate Li and Al, which stimulates the formation of Mg-Li-Al-H hydride. A lower Li/Al ratio resulted in faster hydrogen desorption rate and a greater amount of hydrogen released at a low temperature range, but sacrificing total hydrogen storage capacity.
A Cu- and Ni-free Zr-based metallic glass with high glass-forming ability was found in the Zr-Al-Co ternary system. The eutectic Zr56Al16Co28 alloy could be cast into glassy cylindrical rods with diameters up to 18 mm. The glassy alloy exhibited high tensile fracture strength of 1830 MPa and low Young's modulus of 83 GPa in conjunction with better corrosion resistance compared with the glassy Zr57Nb5Al10Ni12.6Cu15.4 in a simulated body fluid. Hydrothermal-electrochemical treatment in the aqueous 5M-NaOH solution resulted in the formation of amorphous sodium cobaltate layer on the surface of glassy Zr56Al16Co28 alloy. Hydroxyapatite was spontaneously formed on the surface of the alloy, indicating bioactivity after surface modification. The discovery of a Cu- and Ni-free Zr-based metallic glass with a critical diameter larger than 1 cm in conjunction with excellent mechanical properties, superior corrosion resistance, and good bioactivity may open up the application field as biomaterials.
The wettability of Pb-free Sn-based solder over the Cu-based Cu60Zr30Ti10 bulk metallic glass surface was investigated. We observed that the as-polished surface was nonwetting for the solder, which was due to the surface oxide layer of ZrOx formed in air. After complete removal of the oxide layer, a thin layer of Ag was deposited on the clean Cu60Zr30Ti10 surface. The Ag-covered Cu60Zr30Ti10 surface showed relatively high resistivity to the reoxidation even in air, and thus the wettability of the Cu60Zr30Ti10 surface for the Sn-based solder was greatly improved.
A new method is proposed to determine the elastic modulus and residual stress of freestanding thin films based on nanoindentation techniques. The experimentally measured stiffness-displacement response is applied to a simple membrane model that assumes the film deformation is dominated by stretching as opposed to bending. Dimensional analysis is used to identify appropriate limitations of the proposed model. Experimental verification of the method is demonstrated for Al/0.5 wt% Cu films nominally 22 µm wide, 0.55 µm thick, and 150, 300, and 500 µm long. The estimated modulus for the four freestanding films match the value measured by electrostatic techniques to within 2%, and the residual stress to within 19.1%. The difference in residual stress can be completely accounted for by thermal expansion and a modest change in temperature of 3 °C. Numerous experimental pitfalls are identified and discussed. Collectively, these data and the technique used to generate them should help future investigators make more accurate and precise measurements of the mechanical properties of freestanding thin films using nanoindentation.
The ignition and reaction processes of the thermal explosion reaction from the Ti–B4C system in air were studied. The thermal explosion reaction for the formation of TiC and TiB2 can be initiated at a relatively low temperature with the incorporation of air. Generally, the ignition process in air is suggested to be a chemical oven rather than gas transport, and the reaction process is proposed to be dissolution and precipitation.
Superalloys are unique high-temperature materials used in gas turbine engines, which display excellent resistance to mechanical and chemical degradation. This book presents the underlying metallurgical principles which have guided their development and practical aspects of component design and fabrication from an engineering standpoint. The topics of alloy design, process development, component engineering, lifetime estimation and materials behaviour are described, with emphasis on critical components such as turbine blading and discs. The first introductory text on this class of materials, it will provide a strong grounding for those studying physical metallurgy at the advanced level, as well as practising engineers. Included at the end of each chapter are exercises designed to test the reader's understanding of the underlying principles presented. Solutions for instructors and additional resources are available at www.cambridge.org/9780521859042.
This is a clear account of the application of electron-based microscopies to the study of high-Tc superconductors. Written by leading experts, this compilation provides a comprehensive review of scanning electron microscopy, transmission electron microscopy and scanning transmission electron microscopy, together with details of each technique and its applications. Introductory chapters cover the basics of high-resolution transmission electron microscopy, including a chapter devoted to specimen preparation techniques, and microanalysis by scanning transmission electron microscopy. Ensuing chapters examine identification of superconducting compounds, imaging of superconducting properties by low-temperature scanning electron microscopy, imaging of vortices by electron holography and electronic structure determination by electron energy loss spectroscopy. The use of scanning tunnelling microscopy for exploring surface morphology, growth processes and the mapping of superconducting carrier distributions is discussed. Final chapters consider applications of electron microscopy to the analysis of grain boundaries, thin films and device structures. Detailed references are included.
This 2003 book relates the complete set of strength characteristics of constituent atoms to their electronic structures. These relationships require knowledge of both the chemistry and physics of materials. The book uses both classical and quantum mechanics, since both are needed to describe these properties, and begins with short reviews of each. Following these reviews, the three major branches of the strength of materials are given their own sections. They are: the elastic stiffnesses; the plastic responses; and the nature of fracture. This work will be of great value to academic and industrial research workers in the sciences of metallurgy, ceramics, microelectronics and polymers. It will also serve well as a supplementary text for the teaching of solid mechanics.
Understanding the dynamics of reactive polymer processes allows scientists to create new, high value, high performance polymers. Chemorheology of Polymers provides an indispensable resource for researchers and practitioners working in this area, describing theoretical and industrial approaches to characterising the flow and gelation of reactive polymers. Beginning with an in-depth treatment of the chemistry and physics of thermoplastics, thermoset and reactive polymers, the core of the book focuses on fundamental characterization of reactive polymers, rheological (flow characterization) techniques and the kinetic and chemorheological models of these systems. Uniquely, the coverage extends to a complete review of the practical industrial processes used for these polymers and an insight into the current chemorheological models and tools used to describe and control each process. This book will appeal to polymer scientists working on reactive polymers within materials science, chemistry and chemical engineering departments as well as polymer process engineers in industry.