Nanosecond freezing of water under multiple shock wave compression: optical transmission and imaging measurements

Water samples were subjected to multiple shock wave compressions, generating peak pressures of 1-5 GPa on nanosecond time scales. This loading process approximates isentropic compression and leads to temperatures where the ice VII phase is more stable than the liquid phase above 2 GPa. Time resolved optical transmission and imaging measurements were performed to determine the solidification rate under such conditions. Freezing occurred faster at higher pressures as water was compressed further into the ice VII phase, in agreement with classical micleation theory. Water consistently froze when in contact with a silica window, whereas no solidification occurred in the presence of sapphire windows. The transition was determined to be a surface initiated process--freezing began via heterogeneous nucleation at the water/window interface and propagated over thicknesses greater than 0.01 mm. The first optical images of freezing on nanosecond time scales were obtained. These images demonstrate heterogeneous nucleation and irregular solid growth over 0.01-0.10 mm lateral length scales and are consistent with latent heat emission during the transformation. The combination of optical transmission and imaging measurements presented here provide the first consistent evidence for freezing on short time scales.     

Nanosecond rapid freezing of liquid benzene under shock compression studied by time-resolved coherent anti-Stokes Raman spectroscopy

Nanosecond time-resolved coherent anti-Stokes Raman spectroscopy is used to investigate the shock-induced liquid-solid phase transition and crystallization of liquid benzene. Temporal evolution of the Raman shift of the ring-breathing and C-H stretching modes is investigated. A metastable supercompressed state and a liquid-solid phase transition are observed under shock compression. Time-resolved Raman spectra reveal that the liquid state is initially a metastable state and rapidly transforms to the solid state within 25 ns under shock compression at 4.2 GPa.     

Heat of freezing for supercooled water: measurements at atmospheric pressure

Unlike reversible phase transitions, the amount of heat released upon freezing of a metastable supercooled liquid depends on the degree of supercooling. Although terrestrial supercooled water is ubiquitous and has implications for cloud dynamics and nucleation, measurements of its heat of freezing are scarce. We have performed calorimetric measurements of the heat released by freezing water at atmospheric pressure as a function of supercooling. Our measurements show that the heat of freezing can be considerably below one predicted from a reversible hydrostatic process. Our measurements also indicate that the state of the resulting ice is not fully specified by the final pressure and temperature; the ice is likely to be strained on a variety of scales, implying a higher vapor pressure. This would reduce the vapor gradient between supercooled water and ice in mixed phase atmospheric clouds.     

Ultrafast dynamics of self-assembled monolayers under shock compression: effects of molecular and substrate structure

Laser-driven approximately 1 GPa shock waves are used to dynamically compress self-assembled monolayers (SAMs) consisting of octadecanethiol (ODT) on Au and Ag, and pentanedecanethiol (PDT) and benzyl mercaptan (BMT) on Au. The SAM response to <4 ps shock loading and approximately 25 ps shock unloading is monitored by vibrational sum-frequency generation spectroscopy (SFG), which is sensitive to the instantaneous tilt angle of the SAM terminal group relative to the surface normal. Arrival of the shock front causes SFG signal loss in all SAMs with a material time constant <3.5 ps. Thermal desorption and shock recovery experiments show that SAMs remain adsorbed on the substrate, so signal loss is attributed to shock tilting of the methyl or phenyl groups to angles near 90 degrees. When the shock unloads, PDT/Au returns elastically to its native structure whereas ODT/Au does not. ODT evidences a complicated viscoelastic response that arises from at least two conformers, one that remains kinetically trapped in a large-tilt-angle conformation for times >250 ps and one that relaxes in approximately 30 ps to a nearly upright conformation. Although the shock responses of PDT/Au, ODT/Ag, and BMT/Au are primarily elastic, a small portion of the molecules, 10-20%, evidence viscoelastic response, either becoming kinetically trapped in large-tilt states or by relaxing in approximately 30 ps back to the native structure. The implications of the observed large-amplitude monolayer dynamics for lubrication under extreme conditions of high strain rates are discussed briefly.     

Ultrafast transformation of graphite to diamond: an ab initio study of graphite under shock compression

We report herein ab initio molecular dynamics simulations of graphite under shock compression in conjunction with the multiscale shock technique. Our simulations reveal that a novel short-lived layered diamond intermediate is formed within a few hundred of femtoseconds upon shock loading at a shock velocity of 12 kms (longitudinal stress>130 GPa), followed by formation of cubic diamond. The layered diamond state differs from the experimentally observed hexagonal diamond intermediate found at lower pressures and previous hydrostatic calculations in that a rapid buckling of the graphitic planes produces a mixture of hexagonal and cubic diamond (layered diamond). Direct calculation of the x-ray absorption spectra in our simulations reveals that the electronic structure of the final state closely resembles that of compressed cubic diamond.     

Molecular organization in protein-lipid film on the water surface studied by x-ray standing wave measurements under total external reflection

The x-ray standing wave method has been applied to study self-assembling processes in a protein-lipid film formed by injecting the protein-lipid mixture of alkaline phosphatase and phosphatidylinositol under the phospholipid monolayer preliminarily deposited on the water subphase by Langmuir method. X-ray standing wave measurements allowed to determine the composition of the protein-lipid film and to locate ions position in the direction normal to the film surface. The presence of trace Ni contamination incorporated in the protein-lipid film from the water subphase has been established. Numerical analysis of the X-ray standing wave fluorescence data revealed that after injection under the phospholipid monolayer, the protein-lipid mixture separated in a self-assembled manner to layered structure, molecules of alkaline phosphatase arranged themselves into a pure protein layer containing no phospholipid molecules.     

Photo-stability and Photo-damage of SPASER Nanoparticles under Nanosecond Pulsed-laser

SPASER nanoparticle(NP),with small size,ultranarrow spectral-line and good biocompatibility,is a potential biomedical nanoprobe.However,owning to the striking l...     

Bottom-up computational modeling of semi-crystalline fibers: from atomistic to continuum scale

A bottom-up computational approach involving Molecular Dynamics (MD) of silk fiber subunits and Finite Element (FE) simulations of whole spider silk fibers is presented. The approach is discussed with an emphasis on the benefits and bottlenecks of incorporating the atomistic and continuum models of crystalline and disordered domains in the fibers. The approach does not require any empirical parameters and it is applicable to similar semi-crystalline systems.     

Microgel adhesives for wet cellulose: measurements and modeling

Nanostructured adhesive layers were prepared by adsorbing and/or grafting polyvinylamine (PVAm) onto carboxylated poly(N-isopropylacrylamide) (PNIPAM) microgels that were then assembled between layers of wet oxidized cellulose. The wet delamination force was measured as functions of PVAm content, PVAm molecular weight, coverage (mass adhesive/joint area), and the distribution of carboxyl groups in the PNIPAM microgels. The use of microgels is attractive because simple physical adsorption onto the cellulose surfaces before lamination gives much higher adhesive content and strength compared to the corresponding adsorbed linear PVAm. Wet adhesion increased with PVAm content in the microgels and the quantity of microgels in the joint whereas adhesion was independent of PVAm molecular weight. Physical adsorption of the PVAm onto/into the microgels gave the same adhesion as covalently coupled PVAm. Finally, the roles of microgel diameter, elasticity, and coverage were simulated by a simple peel adhesion model in which the microgels were treated as ideal springs.     

Ultrafast shock compression of self-assembled monolayers: a molecular picture

Simulations of self-assembled monolayers (SAMs) are performed to interpret experimental measurements of ultrafast approximately 1 GPa (volume compression deltaV approximately 0.1) planar shock compression dynamics probed by vibrational sum-frequency generation (SFG) spectroscopy (Lagutchev, A. S.; Patterson, J. E.; Huang, W.; Dlott, D. D. J. Phys. Chem. B 2005, 109, XXXX). The SAMs investigated are octadecanethiol (ODT) and pentadecanethiol (PDT) on Au(111) and Ag(111) substrates, and benzyl mercaptan (BMT) on Au(111). In the alkane SAMs, SFG is sensitive to the instantaneous orientation of the terminal methyl; in BMT it is sensitive to the phenyl orientation. Computed structures of alkane SAMs are in good agreement with experiment. In alkanes, the energies of gauche defects increase with increasing number and depth below the methyl plane, with the exception of ODT/Au where both single and double gauche defects at the two uppermost dihedrals have similar energies. Simulations of isothermal uniaxial compression of SAM lattices show that chain and methyl tilting is predominant in PDT/Au, ODT/Ag and PDT/Ag, whereas single and double gauche defect formation is predominant in ODT/Au. Time-resolved shock data showing transient SFG signal loss of ODT/Au and PDT/Au are fit by calculations of the terminal group orientations as a function of deltaV and their contributions to the SFG hyperpolarizability. The highly elastic response of PDT/Au results from shock-generated methyl and chain tilting. The viscoelastic response of ODT/Au results from shock generation of single and double gauche defects. Isothermal compression simulations help explain and fit the time dependence of shock spectra but generally underestimate the magnitude of SFG signal loss because they do not include effects of high-strain-rate dynamics and shock front and surface irregularities.     

Moisture profile measurements of concrete samples in vertical water flow by gamma ray transmission method

Samples of concrete for popular habitation (0.1×0.03×0.1 m) and cellular concrete (0.1×0.05×0.1 m) were submitted to water vertical ascending infiltration. The moisture content spatial and temporal evolution of each sample it was monitored in three halfway positions in a same horizontal line, applying the gamma rays transmission method. The data were taken with a 137Cs (3.7×1010 Bq, 0662 MeV) source, Nal (Tl) of 2×2″ detector coupled to gamma ray spectrometry standard electronic with multichannel analyzer and a micrometric table. For the popular habitation concrete, there was a clear correlation between wetting profiles and concrete strength. The cellular concrete showed a wetting profile compatible to its greater porosity.     

Molecular dynamics simulation of shock compression of metals: Iron and iron-sulfur solutions

The embedded atom model potential suggested earlier was improved to correctly describe iron at high pressures and temperatures. Correction was introduced using the shock compression data. The properties of body- and face-centered cubic (BCC and FCC) lattices and liquid iron at compression degrees up to 50% of the normal volume and temperatures up to 10000 K were calculated. At degrees of compression 0.7–0.6 and 0 K, the FCC lattice is thermodynamically stable. The temperature of fusion increases to ≈9700 K at compression to 50% of initial volume (pressure 585 GPa). The pressure of pure iron at 5000 K and density 12.5 g/cm³ is ≈250 GPa and is substantially lower than in the center of the Earth according to the geophysical data (360 GPa). An embedded atom model potential for a 10 at % solution of sulfur in iron which allows the properties of the melt in the center of the Earth to be described correctly is suggested; the viscosity of the melt under these conditions is not high (0.0156 Pa s); these results are close to those obtained in ab initio calculations. The possibility of partial Earth core crystallization is shown.     

Spectral shifts in the fluorescence spectrum of anthracene under the influence of laser driven shock compression

We report spectral shifts in the fluorescence emission of a solution of anthracene in benzene under the influence of laser driven shock compression. Red-shifts of up to 800 cm⁻¹ are observed in the peak of the 0–1 vibronic band of anthracene corresponding to maximum pressures of =10 kbar. These results are in agreement with literature values of spectral shifts obtained under conditions of high static pressure. Laser driven shock provides an attractive alternative to conventional shock generation schemes when used in conjunction with optical spectroscopy as a probe of molecular level changes.     

Melting and freezing of water in cylindrical silica nanopores

Freezing and melting of H(2)O and D(2)O in the cylindrical pores of well-characterized MCM-41 silica materials (pore diameters from 2.5 to 4.4 nm) was studied by differential scanning calorimetry (DSC) and (1)H NMR cryoporometry. Well-resolved DSC melting and freezing peaks were obtained for pore diameters down to 3.0 nm, but not in 2.5 nm pores. The pore size dependence of the melting point depression DeltaT(m) can be represented by the Gibbs-Thomson equation when the existence of a layer of nonfreezing water at the pore walls is taken into account. The DSC measurements also show that the hysteresis connected with the phase transition, and the melting enthalpy of water in the pores, both vanish near a pore diameter D* approximately equal to 2.8 nm. It is concluded that D* represents a lower limit for first-order melting/freezing in the pores. The NMR spin echo measurements show that a transition from low to high mobility of water molecules takes place in all MCM-41 materials, including the one with 2.5 nm pores, but the transition revealed by NMR occurs at a higher temperature than indicated by the DSC melting peaks. The disagreement between the NMR and DSC transition temperatures becomes more pronounced as the pore size decreases. This is attributed to the fact that with decreasing pore size an increasing fraction of the water molecules is situated in the first and second molecular layers next to the pore wall, and these molecules have slower dynamics than the molecules in the core of the pore.     

Nanosecond field alignment of head group and water dipoles in electroporating phospholipid bilayers

To investigate the mechanism of biological cell membrane electroporation at the nanosecond and nanometer scale, we tracked pore-forming lipids and water in molecular dynamics simulations of a palmitoyloleoylphosphatidylcholine bilayer in a minimum porating electric field. Although the field-generated torque tilts the mean head group dipole a few degrees away from its equilibrium, zero-field position relative to the bilayer plane, this change in conformation does not appear to contribute directly to the development of the pore-initiating aggregation of lipid head groups and water that leads to the formation of a membrane-spanning hydrophilic pore. Field-directed rotation of the head group dipoles in the plane of the incipient pore wall, in combination with water dipole and solvation interactions at the aqueous-lipid interface, is one component in the coordinated ensemble of electroporation events.     

Determination of differences in free and bound water contents of beef muscle by DSC under various freezing conditions

The differences in bound water content of beef semimembranous muscle samples obtained from previously chilled (24 h at +4°C) middle-aged beef carcasses were determined by the use of DSC. Initially, samples obtained from fresh, unprocessed meat were frozen at –40, –50 or –65°C to determine their melting peaks for freezable water (free water) content with the use of DSC. The samples were then subjected to an environment with an ambient temperature of –30, –35, –40 or –45°C, with no air circulation, or with an air circulation speed of 2 m s^–1, until a thermal core temperature of –18°C was attained; this was followed by thawing the samples until a thermal core temperature of 0°C was reached. This process was followed by subjecting the samples to the ambient temperatures mentioned above, to accomplish complete freezing and thawing of the samples, with DSC, and thereby determination of the freezable water contents, which were then used to determine the peaks of melting. The calculated peak areas were divided by the latent heat of melting for pure water, to determine the freezable water contents of the samples. The percentage freezable water content of each sample was determined by dividing its freezable water content by its total water content; and the bound water content of each sample was determined by subtracting the percentage free water content from the total. In view of the fact that the free water content of a sample is completely in the frozen phase at temperatures of –40°C and below, the calculations of free and bound water contents of the samples were based on the averages of values obtained at three different temperatures.     

Shock-absorbing and failure mechanisms of WS2 and MoS2 nanoparticles with fullerene-like structures under shock wave pressure

The excellent shock-absorbing performance of WS2 and MoS2 nanoparticles with inorganic fullerene-like structures (IFs) under very high shock wave pressures of 25 GPa is described. The combined techniques of X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, thermal analysis, and transmission electron microscopy have been used to evaluate the diverse, intriguing features of shock recovered IFs, of interest for their tribological applications, thereby allowing improved understanding of their antishock behavior and structure-property relationships. Two possible failure mechanisms are proposed and discussed. The supershock-absorbing ability of the IF-WS2 enables them to survive pressures up to 25 GPa accompanied with concurrent temperatures of up to 1000 degrees C without any significant structural degradation or phase change making them probably the strongest cage molecules now known.