Pressure-induced phase transition in hydrogen-bonded supramolecular adduct formed by cyanuric acid and melamine

Single-crystal samples of the 1:1 adduct between cyanuric acid and melamine (CA·M), an outstanding case of noncovalent synthesis, have been studied by Raman spectroscopy and synchrotron X-ray diffraction in a diamond anvil cell up to pressures of 15 GPa. The abrupt changes in Raman spectra around 4.4 GPa have provided convincing evidence for pressure-induced structural phase transition. This phase transition was confirmed by angle dispersive X-ray diffraction (ADXRD) experiments to be a space group change from C2/m to its subgroup P2₁/m. On release of pressure, the observed transition was irreversible, and the new high-pressure phase was fully preserved at ambient conditions. We propose that this phase transition was due to supramolecular rearrangements brought about by changes in the hydrogen bonding networks.

Deformation induced phase transformation during machining of Ti-5553

Ti-5553 is a relatively new titanium alloy with applications particularly in the aerospace industry for such key structural components as landing gear. However, during machining of Ti-5553, the elevated temperature and high strain at tool-workpiece interface may alter workpiece microstructure and result in ß to a phase transformation. During phase transformation, some intermediated phase such as w phase may form which is brittle and hard to machine, and it could reduce the fatigue life of machined components. The aim of this research work is to optimize the machining condition for Ti-5553, in which its hot deformation behavior in terms of ß to a phase transformation could be fully understood. Analysis of variables such as micrographs of phase components and cutting zone temperature demonstrates that the cutting temperature governs the formation of final phase components and to some extent this variation has been quantified to allow for further and more detailed investigation.

High-pressure phase transition in cyclo-octane

Structural behaviour of cyclo-octane under high pressure is studied by using a synchrotron x-ray source in a diamond anvil cell (DAC) up to 40.2 GPa at room temperature. The cyclo-octane firstly solidifies to the triclinic phase at 0.87GPa. With the increasing pressure, the phase of cyclo-octane changes to the tetragonal phase at about 6.0 GPa and then transforms to amorphous phase above 18.2 GPa, which is kept till to 40.2 GPa. All the phase transitions of cyclo-octane are irreversible.

Nature of hardness evolution in nanocrystalline NiTi shape memory alloys during solid-state phase transition

Due to a distinct nature of thermomechanical smart materials' reaction to applied loads, a revolutionary approach is needed to measure the hardness and to understand its size effect for pseudoelastic NiTi shape memory alloys (SMAs) during the solid-state phase transition. Spherical hardness is increased with depths during the phase transition in NiTi SMAs. This behaviour is contrary to the decrease in the hardness of NiTi SMAs with depths using sharp tips and the depth-insensitive hardness of traditional metallic alloys using spherical tips. In contrast with the common dislocation theory for the hardness measurement, the nature of NiTi SMAs' hardness is explained by the balance between the interface and the bulk energy of phase transformed SMAs. Contrary to the energy balance in the indentation zone using sharp tips, the interface energy was numerically shown to be less dominant than the bulk energy of the phase transition zone using spherical tips.

Novel approach to trigger nanostructures in thermosets using competitive Hydrogen-Bonding-Induced Phase Separation (CHIPS)

A new route to prepare nanostructured thermosets by the utilization of intermolecular hydrogen-bonding interactions is demonstrated here. In this study, competitive hydrogen-bonding-induced microphase separation (CHIPS) in epoxy resin (ER) containing an amphiphilic block copolymer poly(ε-caprolactone)-block-poly(2-vinylpyridine) (PCL-b-P2VP) is investigated for the first time. The phase separation takes place due to the disparity in the hydrogen-bonding interactions in ER/P2VP and ER/PCL pairs leading to the formation of ordered nanostructures in the ER/block copolymer blends. SAXS and TEM results indicate that the hexagonally packed cylindrical morphology of neat PCL-b-P2VP block copolymer remains but becomes a core-shell structure at 10 wt % addition of ER, and changes to regular lamellae structures at 20-50 wt % then to disordered lamellae with 60 wt % ER. Wormlike structures are obtained in the blends with 70 wt % ER, followed by a completely homogeneous phase of ER/P2VP and ER/PCL. The formation of nanostructures and changes in morphologies depend on the relative strength of hydrogen-bonding interactions between each component block copolymer and the homopolymer. This versatile method to develop nanostructured thermosets, involving competitive hydrogen-bonding interactions, could be used for the fabrication of hierarchical and functional materials.

Synthetic hydrogels 2. Polymerization induced phase separation in acrylamide systems

Acrylamide hydrogels were synthesized in the presence of various non-solvents for linear polyacrylamide to examine phase separation during polymerization. The process was found to be dependent upon the segmental volume, the chemical structure, and the concentration of the non-solvent. The concept of conversion-phase diagram for linear polymer is introduced and used qualitatively to understand polymerization induced phase separation (PIPS), and to predict the onset of PIPS during hydrogel synthesis.

Fluorine-free superhydrophobic coatings with pH-induced wettability transition for controllable oil-water separation

We present a simple, environmentally friendly approach to fabricating superhydrophobic coatings with pH-induced wettability transition. The coatings are prepared from a mixture of silica nanoparticles and decanoic acid-modified TiO2. When the coating is applied on cotton fabric, the fabric turns superhydrophobic in air but superoleophilic in neutral aqueous environment. It is permeable to oil fluids but impermeable to water. However, when the coated fabric is placed in basic aqueous solution or ammonia vapor, it turns hydrophilic but underwater superoleophobic, thus allowing water to penetrate through but blocking oil. Therefore, such a unique, selective water/oil permeation feature makes the treated fabric have capability to separate either oil or water from a water-oil mixture. It may be useful for development of smart oil-water separators, microfluidic valves, and lab-on-a-chip devices.

Pressure-induced structural transitions in MOO3·xH2O (x = 1/2, 2) molybdenum trioxide hydrates : a raman study

The high-pressure behaviors of M_OO₃·1/2H₂O and M_OO₃·2H₂O have been investigated by Raman spectroscopy in a diamond anvil cell up to 31.3 and 30.3 GPa, respectively. In the pressure range up to around 30 GPa, both M_OO₃·1/2H₂O and M_OO₃·2H₂O undergo two reversible structural phase transitions. We observed a subtle structural transition due to O−H···O hydrogen bond in M_OO₃·1/2H₂O at 3.3 GPa. We found a soft mode phase transition in M_OO₃·2H₂O at 6.6 GPa. At higher pressures, a frequency discontinuity shift and appearance of new peaks occurred in both M_OO₃·1/2H₂O and M_OO₃·2H₂O, indicating that the second phase transition is a first-order transition. The frequency redshift of the O−H stretching bands of M_OO₃·1/2H₂O and M_OO₃·2H₂O are believed to be related to the enhancement of the O−H···O weak hydrogen bonds under high pressures.

Spectroscopic study of the effects of pressure media on high-pressure phase transitions in natrolite

Structural phase transitions in natrolite have been investigated as a function of pressure and different hydrostatic media using micro-Raman scattering and synchrotron infrared (IR) spectroscopy. Natrolite undergoes two reversible phase transitions at 0.86 and 1.53 GPa under pure water pressure medium. These phase transitions are characterized by the changes in the vibrational frequencies of four- and eight-membered rings related to the variations in the bridging T−O−T angles and the geometry of the elliptical eight-ring channels under pressure. Concomitant to the changes in the framework vibrational modes, the number of the O−H stretching vibrational modes of natrolite changes as a result of the rearrangements of the hydrogen bonds in the channels caused by a successive increase in the hydration level under hydrostatic pressure. Similar phase transitions were also observed at relatively higher pressures (1.13 and 1.59 GPa) under alcohol−water pressure medium. Furthermore, no phase transition was found up to 2.52 GPa if a lower volume ratio of the alcohol−water to natrolite was employed. This indicates that the water content in the pressure media plays a crucial role in triggering the pressure-induced phase transitions in natrolite. In addition, the average of the mode Grüneisen parameters is calculated to be about 0.6, while the thermodynamic Grüneisen parameter is found to be 1.33. This might be attributed to the contrast in the rigidity between the TO4 tetrahedral primary building units and other flexible secondary building units in the natrolite framework upon compression and subsequent water insertion.

Comparative studies of structural transition between AlN nanocrystals and nanowires

The structural transition of AIN nanocrystals and nanowires were investigated simultaneously under pressures up to 37.2 GPa by in situ angle dispersive high-pressure x-ray diffraction using synchrotron radiation source and a single diamond anvil cell. The size of hexagonal AIN nanocrystals and the diameter of nanowires are 45 nm on average. A pressure-induced wurtzite to rocksalt phase transition starts at 21.5 GPa and completes at 27.8 GPa for the nanocrystals and nanowires, respectively. The high-pressure behaviors of AlN nanocrystals the same as the AIN nanowires might arise from the similar size and diameter in nanocrystals and nanowires. Hexagonal AIN nanocrystals (45 nm) display an apparent volumetric contraction as compared to the AlN nanocrystals (10 nm) which might induce the difference of transition pressure.