Jin-Chong Tan

Dynamic continuous recrystallization characteristics in two stage deformation of Mg-3Al-1Zn alloy sheet

Dynamic recrystallization (DRX) characteristics of a Mg/3Al/1Zn (AZ31) alloy sheet were investigated at temperatures ranging from 200� /450 8C and constant strain rates of 1/10 4 � /2/10 4 s 1 . The average grain size of the as-received alloy was 12 mm and can be refined to 6 mm via deformation at 250 8C, 1/10 4 s 1 to a strain level of 60%. Grain refinement was less effectiv ea t higher temperatures due to rapid grain growth. The grain refinement was attributed to dynamic continuous recrystallization which involves progressive increase in grain boundary misorientation and conversion of low angle boundaries into high angle boundaries. During DRX, subgrains were developed through the conversion of dislocation cell walls into subgrain boundaries. The presence of precipitates was not essential for dynamic recrystallization in the magnesium alloy being investigated because of its limited slip systems, low stacking fault energy and high grain boundary diffusion rate. # 2003 Elsevier Science B.V. All rights reserved.

Zeolitic imidazolate framework (ZIF-8) based polymer nanocomposite membranes for gas separation

As synthesised ZIF-8 nanoparticles (size ∼ 60 nm and specific surface area ∼ 1300–1600 m2 g−1) were directly incorporated into a model polymer matrix (Matrimid® 5218) by solution mixing. This produces flexible transparent membranes with excellent dispersion of nanoparticles (up to loadings of 30 wt%) with good adhesion within the polymer matrix, as confirmed by scanning electron microscopy, dynamic mechanical thermal analysis and gas sorption studies. Pure gas (H2, CO2, O2, N2 and CH4) permeation tests showed enhanced permeability of the mixed matrix membrane with negligible losses in selectivity. Positron annihilation lifetime spectroscopy (PALS) indicated that an increase in the free volume of the polymer with ZIF-8 loading together with the free diffusion of gas through the cages of ZIF-8 contributed to an increase in gas permeability of the composite membrane. The gas transport properties of the composite membranes were well predicted by a Maxwell model whilst the processing strategy reported can be extended to fabricate other polymer nanocomposite membranes intended for a wide range of emerging energy applications.

Chemical structure, network topology, and porosity effects on the mechanical properties of Zeolitic Imidazolate Frameworks.

The mechanical properties of seven zeolitic imidazolate frameworks (ZIFs) based on five unique network topologies have been systematically characterized by single-crystal nanoindentation studies. We demonstrate that the elastic properties of ZIF crystal structures are strongly correlated to the framework density and the underlying porosity. For the systems considered here, the elastic modulus was found to range from 3 to 10 GPa, whereas the hardness property lies between 300 MPa and 1.1 GPa. Notably, these properties are superior to those of other metal–organic frameworks (MOFs), such as MOF-5. In substituted imidazolate frameworks, our results show that their mechanical properties are mainly governed by the rigidity and bulkiness of the substituted organic linkages. The framework topology and the intricate pore morphology can also influence the degree of mechanical anisotropy. Our findings present the previously undescribed structure-mechanical property relationships pertaining to hybrid open frameworks that are important for the design and application of new MOF materials.

Structure and properties of an amorphous metal-organic framework.

ZIF-4, a metal-organic framework (MOF) with a zeolitic structure, undergoes a crystal-amorphous transition on heating to 300 degrees C. The amorphous form, which we term a-ZIF, is recoverable to ambient conditions or may be converted to a dense crystalline phase of the same composition by heating to 400 degrees C. Neutron and x-ray total scattering data collected during the amorphization process are used as a basis for reverse Monte Carlo refinement of an atomistic model of the structure of a-ZIF. The structure is best understood in terms of a continuous random network analogous to that of a-SiO2. Optical microscopy, electron diffraction and nanoindentation measurements reveal a-ZIF to be an isotropic glasslike phase capable of plastic flow on its formation. Our results suggest an avenue for designing broad new families of amorphous and glasslike materials that exploit the chemical and structural diversity of MOFs.

Hybrid Nanosheets of an Inorganic–Organic Framework Material: Facile Synthesis, Structure, and Elastic Properties

We report a new 2-D inorganic-organic framework material, MnDMS [Mn 2,2-dimethylsuccinate], featuring weakly bound hybrid layers in its bulk crystals that can be readily exfoliated into nanosheets via ultrasonication. The fully exfoliated hybrid nanosheets correspond to a unilamellar thickness of about 1 nm, while the partially exfoliated nanosheets (multilayer films) exhibit a typical thickness on the order of 10 nm. We used atomic force microscopy to characterize their surface topography and to map the variation of nanomechanical properties across the surface of the delaminated nanosheets. The morphology and crystallographic orientation of the exfoliated layers were further studied by transmission electron microscopy. Additionally, we investigated the elastic anisotropy underlying the bulk host material by means of single-crystal nanoindentation, from which the critical resolved shear stress (τ(crit)) needed for the micromechanical delamination of individual layers was determined to be relatively small (≲0.4 GPa).

Facile mechanosynthesis of amorphous zeolitic imidazolate frameworks.

A fast and efficient mechanosynthesis (ball-milling) method of preparing amorphous zeolitic imidazolate frameworks (ZIFs) from different starting materials is discussed. Using X-ray total scattering, N(2) sorption analysis, and gas pycnometry, these frameworks are indistinguishable from one another and from temperature-amorphized ZIFs. Gas sorption analysis also confirms that they are nonporous once formed, in contrast to activated ZIF-4, which displays interesting gate-opening behavior. Nanoparticles of a prototypical nanoporous substituted ZIF, ZIF-8, were also prepared and shown to undergo amorphization.

Porous materials for thermal management under extreme conditions

A brief analysis is presented of how heat transfer takes place in porous materials of various types. The emphasis is on materials able to withstand extremes of temperature, gas pressure, irradiation, etc., i.e. metals and ceramics, rather than polymers. A primary aim is commonly to maximize either the thermal resistance (i.e. provide insulation) or the rate of thermal equilibration between the material and a fluid passing through it (i.e. to facilitate heat exchange). The main structural characteristics concern porosity (void content), anisotropy, pore connectivity and scale. The effect of scale is complex, since the permeability decreases as the structure is refined, but the interfacial area for fluid–solid heat exchange is, thereby, raised. The durability of the pore structure may also be an issue, with a possible disadvantage of finer scale structures being poor microstructural stability under service conditions. Finally, good mechanical properties may be required, since the development of thermal gradients, high fluid fluxes, etc. can generate substantial levels of stress. There are, thus, some complex interplays between service conditions, pore architecture/scale, fluid permeation characteristics, convective heat flow, thermal conduction and radiative heat transfer. Such interplays are illustrated with reference to three examples: (i) a thermal barrier coating in a gas turbine engine; (ii) a Space Shuttle tile; and (iii) a Stirling engine heat exchanger. Highly porous, permeable materials are often made by bonding fibres together into a network structure and much of the analysis presented here is oriented towards such materials.

Reversible pressure-induced amorphization of a zeolitic imidazolate framework (ZIF-4).

We report the reversible pressure-induced amorphization of a zeolitic imidazolate framework (ZIF-4, [Zn(Im)(2)]). This occurs irrespective of pore occupancy and takes place via a novel high pressure phase (ZIF-4-I) when solvent molecules are present in the pores. A significant reduction in bulk modulus upon framework evacuation is also observed for both ZIF-4 and ZIF-4-I.

Mechanical Properties of Dense Zeolitic Imidazolate Frameworks (ZIFs): A High-Pressure X-ray Diffraction, Nanoindentation and Computational Study of the Zinc Framework Zn(Im)(2), and its Lithium-Boron Analogue, LiB(Im)(4)

The dense, anhydrous zeolitic imidazolate frameworks (ZIFs), Zn(Im)(2) (1) and LiB(Im)(4) (2), adopt the same zni topology and differ only in terms of the inorganic species present in their structures. Their mechanical properties (specifically the Youngs and bulk moduli, along with the hardness) have been elucidated by using high pressure, synchrotron X-ray diffraction, density functional calculations and nanoindentation studies. Under hydrostatic pressure, framework 2 undergoes a phase transition at 1.69 GPa, which is somewhat higher than the transition previously reported in 1. The Youngs modulus (E) and hardness (H) of 1 (E≈8.5, H≈1 GPa) is substantially higher than that of 2 (E≈3, H≈0.1 GPa), whilst its bulk modulus is relatively lower (≈14 GPa cf. ≈16.6 GPa). The heavier, zinc-containing material was also found to be significantly harder than its light analogue. The differential behaviour of the two materials is discussed in terms of the smaller pore volume of 2 and the greater flexibility of the LiN(4) tetrathedron compared with the ZnN(4) and BN(4) units.

Ball-Milling-Induced Amorphization of Zeolitic Imidazolate Frameworks (ZIFs) for the Irreversible Trapping of Iodine

The I2-sorption and -retention properties of several existing zeolitic imidazolate frameworks (ZIF-4, -8, -69) and a novel framework, ZIF-mnIm ([Zn(mnIm)2 ]; mnIm=4-methyl-5-nitroimidazolate), have been characterised using microanalysis, thermogravimetric analysis and X-ray diffraction. The topologically identical ZIF-8 ([Zn(mIm)2]; mIm=2-methylimidazolate) and ZIF-mnIm display similar sorption abilities, though strikingly different guest-retention behaviour upon heating. We discover that this guest retention is greatly enhanced upon facile amorphisation by ball milling, particularly in the case of ZIF-mnIm, for which I2 loss is retarded by as much as 200 °C. It is anticipated that this general approach should be applicable to the wide range of available metal-organic framework-type materials for the permanent storage of harmful guest species.