Density Of Amorphous Phase Research Articles

Retrospecting the relationship between interlamellar amorphous structure and intrinsic modulus of semicrystalline polymers via in-situ positron annihilation lifetime spectroscopy and in-situ X-ray scattering

The structure-property relationship of the interlamellar amorphous phase in semicrystalline polymers has been a fundamental yet controversial topic in polymer physics for several decades. The intricate hierarchical structure and limited availability of experimental techniques pose significant challenges in quantitatively characterizing the evolution of the amorphous structure and establishing its connection to the mechanical behavior. In this work, the unannealed and annealed isotactic polypropylene hard-elastic films composed of idealized series-arranged lamellar stacks are studied to simplify the mechanical coupling between the two phases. By utilizing the synchrotron-based in-situ small and wide-angle X-ray scattering (SAXS/WAXS) techniques, the apparent modulus and overall volumetric strain of the amorphous phase are estimated. Moreover, with our significant progress in the counting rate of positron annihilation lifetime spectroscopy (PALS), the minute-scale structure evolution of amorphous phase (free-volume pores) during the tensile process is now feasible to be captured. Combing in-situ X-ray scattering and in-situ PALS results, in the elastic regime, it is found that triaxial stress in the amorphous phase leads to the expansion of free-volume pores (about 23% volume increase for the annealed sample, 35% volumetric strain for the unannealed one) and density decrement within occupied volume by overcoming Van Der Waals force. Our quantitative analysis also reveals that the annealing process not only enhances the crystallinity and aspect ratio of lamellae but also weakens the intrinsic modulus and chain packing density of amorphous phase.

Peculiarities of structure and dielectric relaxation in ferroelectric vinylidene fluoride-tetrafluoroethylene copolymer at different crystallization conditions

Vinylidene fluoride (VDF)/tetrafluoroethylene (TFE) 94/6 copolymer films obtained by low-temperature crystallization from acetone solution and by melt-crystallization under high pressure were studied. As shown in the X-ray diffraction patterns, β- and γ- phases coexist in the sample crystallized from a solution. At melt-crystallization, a number of γ-crystals decrease and spherulitic supramolecular structure is formed. It is accompanied by a decrease of the amorphous phase density in the intra- and inter-spherulite regions, which leads to an increase in the glass transition temperature. Differential scanning calorimetry data indicate a smaller fraction of the amorphous phase for the sample crystallized from the melt. At the same time, the relaxation strength of the mobility in the amorphous phase in this sample is higher. This contradiction is explained by the increased ratio of isomers in planar zigzag conformation, as shown by IR spectroscopy.

Temperature-induced amorphization in CaCO3 at high pressure and implications for recycled CaCO3 in subduction zones

Calcium carbonate (CaCO3) significantly affects the properties of upper mantle and plays a key role in deep carbon recycling. However, its phase relations above 3 GPa and 1000 K are controversial. Here we report a reversible temperature-induced aragonite-amorphization transition in CaCO3 at 3.9–7.5 GPa and temperature above 1000 K. Amorphous CaCO3 shares a similar structure as liquid CaCO3 but with much larger C-O and Ca-Ca bond lengths, indicating a lower density and a mechanism of lattice collapse for the temperature-induced amorphous phase. The less dense amorphous phase compared with the liquid provides an explanation for the observed CaCO3 melting curve overturn at about 6 GPa. Amorphous CaCO3 is stable at subduction zone conditions and could aid the recycling of carbon to the surface.

In situ X-Ray Diffraction of Shock-Compressed Fused Silica

Because of its widespread applications in materials science and geophysics, SiO_{2} has been extensively examined under shock compression. Both quartz and fused silica transform through a so-called "mixed-phase region" to a dense, low compressibility high-pressure phase. For decades, the nature of this phase has been a subject of debate. Proposed structures include crystalline stishovite, another high-pressure crystalline phase, or a dense amorphous phase. Here we use plate-impact experiments and pulsed synchrotron x-ray diffraction to examine the structure of fused silica shock compressed to 63GPa. In contrast to recent laser-driven compression experiments, we find that fused silica adopts a dense amorphous structure at 34GPa and below. When compressed above 34GPa, fused silica transforms to untextured polycrystalline stishovite. Our results can explain previously ambiguous features of the shock-compression behavior of fused silica and are consistent with recent molecular dynamics simulations. Stishovite grain sizes are estimated to be ∼5-30 nm for compression over a few hundred nanosecond time scale.

Polyamorphism in Aluminum Nitride: A First Principles Molecular Dynamics Study

The high‐pressure behavior of amorphous aluminum nitride is investigated for the first time by means of ab initio molecular dynamics simulations. It is found to undergo two successive first‐order phase transformations with the application of pressure. The first one is a polyamorphic phase transition in which the low‐density amorphous phase transforms into a high‐density amorphous phase having an average coordination number of about 4.6. The high‐density amorphous structure transforms back to a low‐coordinated amorphous network upon pressure release but its density is higher than that of the original low‐density amorphous phase. The second phase change is the crystallization of the high‐density amorphous state into a rocksalt structure. A careful analysis suggests that the hexagonal‐like nanoclusters presented in amorphous aluminum nitride prevent the formation of a very dense amorphous phase (about sixfold coordinated) during the first phase transition and they act as a nucleation center for the crystallization process.

Effects of modulation period on microstructure, mechanical properties of TiBN/TiN nanomultilayered films deposited by multi arc ion plating

TiBN/TiN multilayered coating with different modulation periods (bilayer thickness) have been synthesized using typical cathodic arc plasma deposition equipment. The objective of this work is to study the influence of modulation period on the microstructure, mechanical and tribological properties. TiBN/TiN multilayer coatings exhibited a TiN (111), (200), (220) and TiB2 (220) crystallographic orientations and preferred TiN (111) orientation. With the decrease of modulation period from 12 nm to 1.9 nm, the mole ratio of B increased from 0.079 to 0.162 in addition to the average mole ratio of N was about 0.39 steadily, while the mole ratio of Ti decreased from 0.506 to 0.407. The microstructure of TiBN/TiN multilayered coating evolves form nanocrystalline TiN/a-BN to nanocomposite Ti(B,N) with an dense amorphous BN phase, The maximum values of hardness and elastic modulus reached 31.6 GPa and 336 GPa with a bilayer period of 1.9 nm and B:Ti ratio of 2:5.

Phase densities and lamellar morphologies of semicrystalline polyethylenesviaabsolute small-angle X-ray scattering measurements

With the crystalline volume fraction from small-angle X-ray scattering (SAXS) and the density of the crystalline phase from wide-angle X-ray diffraction, the amorphous phase density of two representative polyethylenes was calculated as a function of temperature using the absolute total SAXS scattering power or invariant. The density of the amorphous phase in semicrystalline polyethylene is crystallinity independent and is lower than melt-extrapolated values reported in the literature. Model-independent SAXS-based crystallinity values can be calculated with the aid of the densities of the crystalline and amorphous phase and the absolute SAXS invariant. Such model-independent crystallinity values can be used in SAXS curve-shape analysis procedures to obtain the average thickness of the crystalline and amorphous layers also in the case of non-ideal lamellar semicrystalline polymer morphologies for which the number-average long period cannot be retrieved from the maxima in correlation functions or interface distribution functions.

Comparative study of phase transformations in carbon at different schemes of shock compression

A comparative study of phase transformations in carbon-base materials at shock compression has been carried out according to two different schemes: in cylindrical ampoules with a central rod at a direct contact of explosives with the ampoule and in ampoules without the central rod with throwable outer shells. It has been found that in the shock compression on the second scheme a higher absolute output of diamond is achieved, but as opposed to the first scheme, the shock compression products do not virtually contain lonsdaleite or dense amorphous phase. The analysis shows that in the second case the states with lower pressures but higher temperatures, which lead to a transformation of metastable phases into stable diamond, are realized.

Pressure-induced transformations in amorphous silicon: A computational study

We study the transformations between amorphous phases of Si through molecular simulations using the environment dependent interatomic potential (EDIP) for Si. Our results show that upon pressure, the material undergoes a transformation from the low density amorphous (LDA) Si to the high density amorphous (HDA) Si. This transformation can be reversed by decompressing the material. This process, however, exhibits clear hysteresis, suggesting that the transformation LDA ↔ HDA is first-order like. The HDA phase is predominantly five-fold coordinated, whereas the LDA phase is the normal tetrahedrally bonded amorphous Si. The HDA phase at 400 K and 20 GPa was submitted to an isobaric annealing up to 800 K, resulting in a denser amorphous phase, which is structurally distinct from the HDA phase. Our results also show that the atomic volume and structure of this new amorphous phase are identical to those of the glass obtained by an isobaric quenching of the liquid in equilibrium at 2000 K and 20 GPa down to 400 K. The similarities between our results and those for amorphous ices suggest that this new phase is the very high density amorphous Si.

Effect of the Structural State of Graphitic Materials on Their Phase Transformations under Shock Compression

The effect of structural disordering of graphitic materials on their phase transformations into dense modifications of carbon under shock compression conditions (P shock = 30 GPa, T shock = 3000 K) is studied. It is shown that a lower degree of three-dimensional ordering of initial structure (P3) first decreases and then increases the overall yield of dense phases, reaching the maximum at P3 = 0. The content of lonsdaleite simultaneously decreases and that of the dense amorphous phase (C am) increases. The results obtained are attributed to gradual change of the predominant martensite transformation mechanism to predominant diffusion-controlled mechanism, and also to the fact that the metastable phases (lonsdaleite and C am) that form at the initial transformation stage partly transform into a stable diamond phase.

Volume Expansion Measurements in Metallic Liquids and Their Relation to Fragility and Glass Forming Ability: An Energy Landscape Interpretation

Recent studies of Cu-Zr glasses have reported a rapid variation in the amorphous phase density near the optimal glass forming compositions, supporting the belief that the densest liquids are also the best glass formers. Here, we show that the measured densities of the Cu-Zr liquids at higher temperatures are not peaked sharply near these compositions, but the volume expansivities are. Theoretical studies have shown that the expansivity correlates with fragility near T(g); the experimental results presented here show that at high temperature they become anticorrelated. From energy landscape arguments, this indicates the existence of a crossover temperature for the expansivity-fragility correlation that scales inversely with the liquid fragility. These results lead to an improved understanding of the high temperature properties of liquids that form glasses and suggest a new method for identifying the best glass forming compositions within an alloy system from the properties of the equilibrium liquids.

Calcium Carbonate Mineralization: X-ray Microdiffraction Probing of the Interface of an Evaporating Drop on a Superhydrophobic Surface

The liquid/air interface of calcium bicarbonate solution drops was probed by synchrotron radiation microbeam scattering. The drops were deposited on a nanopatterned superhydrophobic poly(methyl methacrylate) surface and raster-scanned during evaporation by small-angle and wide-angle X-ray scattering. The appearance of about 200-nm-size calcite crystallites at the interface could be spatially resolved at the onset of crystallization. Diffuse scattering from the interface is attributed to a dense nanoscale amorphous calcium carbonate phase. Calcite was found to be the major phase in the solid residue with vaterite as minor phase.

Structure of the dense amorphous carbon phase synthesized in a mixture with diamond as a result of shock compression of carbon black

Soft X-ray emission and absorption spectroscopy methods were used in the present work to study experimentally the electronic structure of the dense amorphous carbon phase synthesized in a mixture with diamond as a result of shock compression of carbon black. The X-ray emission C Kα bands, representing the energy distribution of the C 2p-like states, have been recorded for the amorphous carbon phase and, for comparison, for diamond, lonsdaleite, graphite, and carbon black. For the amorphous carbon phase, diamond and lonsdaleite the spectra of quantum yields of the X-ray photoeffect in the area of the C K absorption edge have been recorded as well. Total and partial densities of states of the carbon H-6 and bct-4 phases, diamond and lonsdaleite have been calculated using the first-principles self-consistent full potential linearized augmented plane wave (FP-LAPW) method. Comparison on a common energy scale of the X-ray emission C Kα bands and C K quantum yields of the dense amorphous carbon phase as well as the theoretical curves of partial C 2p-like states of the carbon H-6 and bct-4 phases reveals that, the electronic structure of the amorphous carbon phase under consideration is well described by that of the carbon bct-4 phase. The experimental X-ray emission and absorption spectroscopy data indicate that the amorphous carbon phase studied is metallic, being in agreement with the results of the theoretical FP-LAPW calculations.

HYDRATION OF 3CaO•Al2O3 AND 4CaO•Al2O3•Fe2O3 IN PORTLAND CEMENT

Hydration process of many kinds of cement paste is investigated by powder X-ray diffraction (XRD)/Rietveld analysis. The parameters of the present study are type of cement (Ordinary Portland cement, Low heat cement, and Eco-cement), water to cement ratio (0.50, 0.35), and curing temperature (283, 293, 313K). In this contribution, reaction of aluminate phase (3CaO•Al2O3) and ferrite phase (4CaO•Al2O3•Fe2O3) is focused and evaluated. Experimental results show that the reaction of both aluminate phase and ferrite phase is affected by the temperature and presence of calcite. When system includes calcite, monocarbonate aluminate is mainly produced, rather than ettringite. And in the case of high curing temperature, Al2O3 is reacted as amorphous. Regarding ferrite phase, the reaction degree at the age of 1 year decrease as curing temperature increases, this can be presumed due to dense amorphous phase around cement minerals. Based on these experimental facts, simple hydration model is presented to evaluate development of hydration degree of aluminate phase and ferrite phase.

Ostwald ripening of clusters during protein crystallization.

Contrary to classical nucleation theory, protein crystals can nucleate via a two-step process in which the molecular arrangement of the ordered solid phase is preceded by nucleation of a dense amorphous phase. We study the growth of these precrystalline clusters in lysozyme using a combination of dynamic light scattering, optical microscopy, and microfluidics. Clusters display Ostwald ripening growth kinetics but deviate from this trend after nucleation of the crystal phase. This behavior arises from the metastable relationship between clusters and the ordered solid and is explained numerically using a population balance model.

Preparation of Ru thin film layer on Si and TaN/Si as diffusion barrier by plasma enhanced atomic layer deposition

The growth behavior of plasma enhanced atomic layer deposited (PEALD) ruthenium (Ru) thin film was systematically studied in the context of its application to a copper diffusion barrier. The Ru layer was grown on bare Si and a 30 nm bottom wide nano-patterned trench with an aspect ratio of 4. Bis(ethylcyclopentadienyl)ruthenium [Ru(EtCp) 2] was used as a precursor and NH 3 was used as a plasma enhanced reactant, respectively. To obtain optimal deposition conditions, a Ru thin film was grown on non-patterned bare Si and ALD grown TaN substrate. The process parameters were precisely controlled, resulting in a uniform Ru film layer at 8-inch full wafer scale with a growth temperature of 290 °C and 230 mTorr of working pressure. The experimental results showed typical ALD grown thin film characteristics with a linear relation between film thickness and number of cycles. The growth rate was saturated at 0.35 Å/cycle for TaN and 0.33 Å/cycle for Ru. Based on the optimal conditions obtained from the non-patterned wafer, Ru thin film was deposited on 30 nm bottom width nano-patterned Si and TaN/Si trench with an aspect ratio of 4 to investigate the conformity. The conformity was measured to be 0.86 on Si and 0.97 on the TaN/Si trench, which indicates excellent step coverage. The physical properties of the Ru/TaN bilayer studied by X-ray diffraction and transmission electron microscopy (TEM) showed that a dense amorphous phase Ru thin film layer was successfully grown using PEALD. Our study indicated that reliable self-limited ALD characteristics and excellent conformal deposition of the Ru/TaN bilayer on both bare substrate and the 30 nm wide nano-patterned trench.

Clustering versus Percolation in the Assembly of Colloids Coated with Long DNA

We report an experimental study in which we compare the self-assembly of 1 mum colloids bridged through hybridization of complementary single-stranded DNA (ssDNA) strands (12 bp) attached to variable-length double-stranded DNA spacers that are grafted to the colloids. We considered three different spacer lengths: long spacers (48 500 bp), intermediate length spacers (7500 bp), and no spacers (in which case the ssDNA strands were directly grafted to the colloids). In all three cases, the same ssDNA pairs were used. However, confocal microscopy revealed that the aggregation behavior is very different. Upon cooling, the colloids coated with short and intermediate length DNAs undergo a phase transition to a dense amorphous phase that undergoes structural arrest shortly after percolation. In contrast, the colloids coated with the longest DNA systematically form finite-sized clusters. We speculate that the difference is due to the fact that very long DNA can easily be stretched by the amount needed to make only intracluster bonds, and in contrast, colloids coated with shorter DNA always contain free binding sites on the outside of a cluster. The grafting density of the DNA decreases strongly with increasing spacer length. This is reflected in a difference in the temperature dependence of the aggregates: for the two systems coated with long DNA, the resulting aggregates were stable against heating, whereas the colloids coated with ssDNA alone would dissociate upon heating.

Shock-induced growth and metastability of stishovite and coesite in lithic clasts from suevite of the Ries impact crater (Germany)

The microtextures of stishovite and coesite in shocked non-porous lithic clasts from suevite of the Ries impact structure were studied in transmitted light and under the scanning electron microscope. Both high-pressure silica phases were identified in situ by laser-Raman spectroscopy. They formed from silica melt as well as by solid-state transformation. In weakly shocked rocks (stage I), fine-grained stishovite (≤1.8 μm) occurs in thin pseudotachylite veins of quartz-rich rocks, where it obviously nucleated from high-pressure frictional melts. Generally no stishovite was found in planar deformation features (PDFs) within grains of rock-forming quartz. The single exception is a highly shocked quartz grain, trapped between a pseudotachylite vein and a large ilmenite grain, in which stishovite occurs within two sets of lamellae. It is assumed that in this case the small stishovite grains formed by the interplay of conductive heating and shock reverberation. In strongly shocked rocks (stages Ib–III, above ∼30 GPa), grains of former quartz typically contain abundant and variably sized stishovite (<6 μm) embedded within a dense amorphous silica phase in the interstices between PDFs. The formation of transparent diaplectic glass in adjacent domains results from the breakdown of stishovite and the transformation of the dense amorphous phase and PDFs to diaplectic glass in the solid state. Coesite formed during unloading occurs in two textural varieties. Granular micrometre-sized coesite occurs embedded in silica melt glass along former fractures and grain boundaries. These former high-pressure melt pockets are surrounded by diaplectic glass or by domains consisting of microcrystalline coesite and earlier formed stishovite. The latter is mostly replaced by amorphous silica.

Influence of submonolayer sodium adsorption on the photoemission of the Cu(111)/water ice surface

Photoemission from an ice film deposited on Cu(111) as a function of thickness has been observed in the presence and absence of sodium atoms at the surface-vacuum interface. For either adsorbate alone and photon energies below 4 eV, two-photon photoemission from the Cu(111) substrate dominates. The Cu(111) photoelectron spectrum is perturbed by low coverages of Na, and its intensity is strongly attenuated by a few monolayers of ice. For a low density amorphous ice film, strong charging effects are observed. For ice films annealed to yield either the dense amorphous or crystalline phase, this effect is absent. Deposition of only 0.02 monolayer of Na leads to a dramatic decrease in the threshold for photoemission to 2.3+/-0.2 eV. Thus, photoelectrons are generated by visible radiation in a one-photon process with a cross section that exceeds 10(-18) cm(2). The initial state for the photoemission is identified as a metastable surface trapped electron, which decays thermally with an activation energy of 10+/-2 kJ mol(-1). Quantum calculations are described which support this model and show that the Na atom is accommodated in the first layer of the ice surface.

Amorphous Phase of Propylene/Ethylene Copolymers Characterized by Positron Annihilation Lifetime Spectroscopy

Recent advances in catalyst technology make it possible to synthesize high molecular weight propylene copolymers with a high degree of isotacticity and high levels of an α-olefin comonomer. The primary objective of this study is to systematically characterize the rubbery amorphous phase of propylene/ethylene (P/E) copolymers over a range in comonomer content. A series of new experimental P/E copolymers prepared with a group IV transition metal-based post-metallocene catalyst are compared with a series of P/E copolymers prepared with a conventional metallocene catalyst. Positron annihilation lifetime spectroscopy (PALS) is used to obtain the temperature dependence of the free volume hole size. The PALS measurements are supplemented with bulk volume−temperature measurements. It is found that the free volume hole size and the amorphous phase density at ambient temperature strongly depend on crystallinity. Densification of the amorphous phase is attributed to constraint imposed on rubbery amorphous chain segm...