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A highly ordered cellulose nanocrystal (CNC) film was processed and characterized from a non-aqueous suspension. As a first step, by drawing upon the negative magnetic anisotropy of CNCs, a global order of the nanocrystals is achieved by magnetic field-assisted manipulation of a cholesteric suspension in n-methylformamide (NMF), and then the order is subsequently preserved into a solid-state film. We study the differences between the structures of the 4 T-dried film and the control film dried in the absence of magnetic field. Additionally, we compare the NMF-dried films to those dried from aqueous suspensions with and without magnetic field. Optical microscopy, cross-sectional imaging analysis, and sum frequency generation (SFG) spectroscopy show that the CNC-NMF film dried under magnetic field exhibited a highly ordered layered structure throughout the film, comparable to that observed when films were produced from aqueous suspensions. Extending the potential of the CNC alignment to non-aqueous systems will enable a broad spectrum of applications for CNC-based polymer composites.

Cellulose nanocrystals (CNCs) are rod-shaped particles that can self-assemble into a chiral nematic phase at certain contents. Due to their negative diamagnetic susceptibility and high aspect ratio, the structure of the chiral nematic phase of CNC suspensions can be manipulated using a magnetic field, which is a promising path to extending local order to a larger scale. The ability to manipulate CNCs in non-aqueous solvents is critically needed to incorporate them in a wide range of polymers. So far, magnetic field-induced manipulation of CNCs in suspension was reported for aqueous suspensions only, whereas a much-needed similar study for non-aqueous solvents has not been reported to the best of our knowledge. In this paper, we investigate the CNC ordering in n-methylformamide (NMF) under a 0.7 T magnetic field and compare it to the order achieved in H2O. The formation of a well-defined chiral nematic phase and its viscosity have a significant influence on the rate and extent of the field-induced orientation of CNCs. A clearly formed chiral nematic phase has a high potential for increased levels of field-induced ordering. And the chiral nematic phase with the lowest viscosity showed the largest increase in ordering when the magnetic field is applied before reaching equilibrium and plateauing. In contrast, the higher viscosity suspensions exhibited limited temporal changes after the initial field effect. These findings will facilitate the fabrication of globally ordered CNCs in a variety of polymers under a magnetic field, which is a necessary step to expanding the engineering applications of large-scale cellulose-based composites with anisotropic properties.

It is well known that the densification of oxide glass can occur at high contact pressure (typically >5 GPa) under normal indentation conditions. This study reports that when frictional shear is involved, the subsurface densification of glass can occur under low load conditions that would involve completely elastic deformation if the load is applied along the surface normal direction without any interfacial shear. This phenomenon was observed for a borosilicate glass rubbed with a smooth stainless-steel ball in liquid water at a nominal Hertzian contact pressure of ≤0.5 GPa. Under these frictional conditions, subsurface cracking is completely suppressed, and surface wear occurs through mechanochemical reactions. Since the mechanochemical wear track was sufficiently smooth, it was possible to employ a sub-glass transition temperature (sub-Tg) annealing method to measure the volume recovery of the densified subsurface region. The friction-induced subsurface densification of the wear track was also confirmed through nanoindentation measurements and dissolution tests in pH 13 aqueous solutions. Molecular dynamics (MD) simulations with a ReaxFF reactive force also suggested that the subsurface structural change can occur readily when friction is involved at low contact pressure conditions.

The US plan for high-level nuclear waste includes the immobilization of long-lived radionuclides in glass or ceramic waste forms in stainless-steel canisters for disposal in deep geological repositories. Here we report that, under simulated repository conditions, corrosion could be significantly accelerated at the interfaces of different barrier materials, which has not been considered in the current safety and performance assessment models. Severe localized corrosion was found at the interfaces between stainless steel and a model nuclear waste glass and between stainless steel and a ceramic waste form. The accelerated corrosion can be attributed to changes of solution chemistry and local acidity/alkalinity within a confined space, which significantly alter the corrosion of both the waste-form materials and the metallic canisters. The corrosion that is accelerated by the interface interaction between dissimilar materials could profoundly impact the service life of the nuclear waste packages, which, therefore, should be carefully considered when evaluating the performance of waste forms and their packages. Moreover, compatible barriers should be selected to further optimize the performance of the geological repository system. Immobilization of radionuclides in glass or ceramic forms in stainless steel in deep geological repositories is planned in the US for disposal of nuclear waste. Under simulated repository conditions, corrosion could be significantly accelerated at the interfaces of different barrier materials.

Hydrogen bonding interactions play an important role in many chemical and physical processes occurring in bulk liquids and at interfaces. In this study, hydrous species (H2O and Si-OH) on nano-porous alteration layers (gels) formed on a boroaluminosilicate glass called International Simple Glass corroded in aqueous solutions at pH 7 and pH 9, and initially saturated with soluble silicon-containing species were analyzed using linear and non-linear vibrational spectroscopy in combination with molecular dynamics simulations. The simulation results revealed various possible types of hydrogen bonds among these hydrous species in nanoconfinement environments with their populations depending on pore-size distribution. The nano-porous gels formed on corroded glass surfaces enhance hydrogen bond strength between hydrous species as revealed by attenuated total reflectance infrared spectroscopy. Sum frequency generation spectroscopy showed some significant differences in hydrogen bonding interactions on alteration layers formed at pH 7 and pH 9. The glass dissolution under the leaching conditions used in this study has been known to be ten times faster at pH 7 in comparison to that at pH 9 due to unknown reasons. The simulation and experimental results obtained in this study indicate that the water mobility in the gel formed at pH 9 could be slower than that in the gel formed at pH 7, and as a result, the leaching rate at pH 9 is slower than that at pH 7.

Although graphene is well known for super-lubricity on its basal plane, friction at its step edge is not well understood and contradictory friction behaviors have been reported. In this study, friction of mono-layer thick graphene step edges was studied using atomic force microscopy (AFM) with a Si tip in dry nitrogen atmosphere. It is found that, when the tip slides over a ‘buried’ graphene step edge, there is a resistive force during the step-up motion and an assistive force during the step-down motion due to the topographic height change. The magnitude of these two forces is small and the same in both step-up and step-down motions. As for the ‘exposed’ graphene step edge, friction increases in magnitude and exhibits more complicated behaviors. During the step-down motion of the tip over the exposed step edge, both resistive and assistive components can be detected in the lateral force signal of AFM if the scan resolution is sufficiently high. The resistive component is attributed to chemical interactions between the functional groups at the tip and step-edge surfaces, and the assistive component is due to the topographic effect, same as the case of buried step edge. If a blunt tip is used, the distinct effects of these two components become more prominent. In the step-up scan direction, the blunt tip appears to have two separate topographic effects elastic deformation of the contact region at the bottom of the tip due to the substrate height change at the step edge and tilting of the tip while the vertical position of the cantilever (the end of the tip) ascends from the lower terrace to the upper terrace. The high-resolution measurement of friction behaviors at graphene step edges will further enrich understanding of interfacial friction behaviors on graphene-covered surfaces.

Cellulose is synthesized into fibrils by enzyme complexes called cellulose synthase complexes (CSCs). We analyzed cellulose fibrils produced in a dividing unicellular freshwater alga Micrasterias with vibrational sum frequency generation (SFG) spectroscopy. It is known that cellulose in the daughter semi-cell of Micrasterias is synthesized by the isolated individual rosette-shape CSC, while cellulose in the mother semi-cell is produced by hexagonal arrays of rosette-shape CSCs. Comparing the SFG spectra of cellulose in these two regions of a single cell of Micrasterias showed intriguing correlations between the polymorphic structure and crystal size of cellulose and the shape and size of the CSCs. This information may provide a foundation needed to understand what determines the cellulose structure and crystallinity in plant cell walls.

The compression isotherm of a Langmuir film can provide information on the structural order and density of interfacial molecules. When nanoparticles are introduced to the Langmuir film at an air/li...

Mechanochemical reactions of adsorbed molecules at tribological interfaces can benefit or impede lubrication, depending on the type of reactions induced by the interfacial shear or friction. Shear-induced polymerization of oxidatively chemisorbed organic species can occur at tribological interfaces, and their products can mitigate the wear of the surface in the case of the intermittent cessation of the lubricant supply. In contrast, tribochemical reactions involving water molecules impinging from the ambient air could facilitate surface wear. In this study, we investigated how such processes are affected when a silicon oxide surface is exposed to the environment containing both water and polymerizable organic molecules. For the polymerizable organic moiety, allyl alcohol was chosen because it is known to have a good tribopolymerization activity and can compete with water for surface adsorption sites. The adsorbate composition can be divided into two regimes: water-rich and alcohol-rich. The tribopolymerization yield was found to be significantly enhanced, compared to the alcohol-only case, in both water-rich and alcohol-rich regimes. The coadsorbed water molecules appeared to be incorporated into the tribopolymerization product of allyl alcohol. The friction coefficient qualitatively correlated with the tribopolymerization yield. Surprisingly, a small degree of surface wear was observed in the alcohol-rich regime, although wear was completely suppressed in the water-rich regime and the alcohol-only condition. These results suggested that the wear prevention effect does not necessarily correlate with the tribopolymerization effects.

Atomic force microscopy (AFM) is typically used for analysis of relatively flat surfaces with topographic features smaller than the height of the AFM tip. On flat surfaces, it is relatively easy to find the object of interest and deconvolute imaging artifacts resulting from the finite size of the AFM tip. In contrast, AFM imaging of three-dimensional objects much larger than the AFM tip height is rarely attempted although it could provide topographic information that is not readily available from two-dimensional imaging, such as scanning electron microscopy. In this paper, we report AFM measurements of a vertically-mounted razor blade, which is taller and sharper than the AFM tip. In this case, the AFM height data, except for the data collected around the cutting edge of the blade, reflect the shape of the AFM tip. The height data around the apex area are effectively the convolution of the AFM tip and the blade cutting edge. Based on computer simulations mimicking an AFM tip scanning across a round sample, a simple algorithm is proposed to deconvolute the AFM height data of an object taller and sharper than the AFM tip and estimate its effective curvature.

The interaction of water with glass has a profound impact on its mechanical, chemical, and kinetic properties. Water can enter the glass network either as molecular form (H2O) or hydroxyl species (OH). The resulting impact of water on glass properties depends on the relative concentrations of hydroxyl to molecular species. While attenuated total reflection infrared (ATR-IR) spectroscopy can be used to determine the presence of these species in the subsurface region of glass, there is currently no approach to characterize their relative abundance in the glass surface. In this paper, we propose a calculating method for quantifying the ratio of hydroxyl to molecular water in silicate glasses based on a combination of ATR-IR spectroscopy and secondary ion mass spectrometry (SIMS). The technique is applied to leached soda lime silicate and sodium aluminosilicate glasses under a variety of process conditions. The method presented in this paper offers a new avenue for understanding the multiple roles of water in silicate glass network structure and topology.

Graphene has been recognized as an enhanced platform for biosensors because of its high electron mobility. To integrate active membrane proteins into graphene-based materials for such applications, graphene's surface must be functionalized with lipids to mimic the biological environment of these proteins. Several studies have examined supported lipids on various types of graphene and obtained conflicting results for the lipid structure. Here, we present a correlative characterization technique based on fluorescence measurements in a Raman spectroscopy setup to study the lipid structure and dynamics on epitaxial graphene. Compared to other graphene variations, epitaxial graphene is grown on a substrate more conducive to production of electronics and offers unique topographic features. On the basis of experimental and computational results, we propose that a lipid sesquilayer (1.5 bilayer) forms on epitaxial graphene and demonstrate that the distinct surface features of epitaxial graphene affect the structure and diffusion of supported lipids.

A fundamental understanding of how water interacts with glass is valuable for many practical concerns due to the myriad effects of water on glass properties. Topological constraint theory, which has been shown in prior studies to be an excellent model for various thermomechanical properties, is expanded herein to account for strain on the glass network, in this application due to unbonded interstitial species. Literature Tg data have been collected for silicate glasses containing various alkali and water contents and an expanded constraint theory model has been successfully applied to describe the effects of water on the glass transition temperature.

Cellulose is often described as a mixture of crystalline and amorphous material. A large part of the general understanding of the chemical, biochemical and physical properties of cellulosic materials is thought to depend on the consequences of the ratio of these components. For example, amorphous materials are said to be more reactive and have less tensile strength but comprehensive understanding and definitive analysis remain elusive. Ball milling has been used for decades to increase the ratio of amorphous material. The present work used 13 techniques to follow the changes in cotton fibers (nearly pure cellulose) after ball milling for 15, 45 and 120 min. X-ray diffraction results were analyzed with the Rietveld method; DNP (dynamic nuclear polarization) natural abundance 2D NMR studies in the next paper in this issue assisted with the interpretation of the 1D analyses in the present work. A conventional NMR model’s paracrystalline and inaccessible crystallite surfaces were not needed in the model used for the DNP studies. Sum frequency generation (SFG) spectroscopy also showed profound changes as the cellulose was decrystallized. Optical microscopy and field emission-scanning electron microscopy results showed the changes in particle size; molecular weight and carbonyl group analyses by gel permeation chromatography confirmed chemical changes. Specific surface areas and pore sizes increased. Fourier transform infrared (FTIR) and Raman spectroscopy also indicated progressive changes; some proposed indicators of crystallinity for FTIR were not in good agreement with our results. Thermogravimetric analysis results indicated progressive increase in initial moisture content and some loss in stability. Although understanding of structural changes as cellulose is amorphized by ball milling is increased by this work, continued effort is needed to improve agreement between the synchrotron and laboratory X-ray methods used herein and to provide physical interpretation of the SFG results.

This paper reviews principles, data interpretations, and applications of vibrational spectroscopic methods used for analysis of cellulose in the isolated state and in plant cell walls or lignocellulose biomass. The paper begins with reviewing the crystalline structures of crystalline cellulose polymorphs and the principles of three different vibrational spectroscopy methods—infrared (IR), Raman, and sum frequency generation (SFG)—complemented with density functional theory calculations. Then, it discusses the vibrational modes of crystalline celluloses, how the chain orientation in crystalline domain is analyzed in each method, and how the concentration and spatial distribution of crystalline cellulose domains interspersed in amorphous matrices are manifested or analyzed differently in these three methods. Lastly, the paper discusses examples of analyzing crystalline cellulose in plant cell walls or lignocellulose biomass with IR, Raman, and SFG including spectroscopic imaging. One review cannot cover all vibrational spectroscopy literatures on cellulose; this review aims at providing tutorial information, using selected literatures and experimental data, needed to interpret nano-, meso-, and micro-scale structures of cellulose in plant cell walls and lignocellulose biomass.

All liquids are topologically disordered materials; however, the degree of disorder can vary as a result of internal fluctuations in structure and topology. These fluctuations depend on both the composition and temperature of the system. Most prior work has considered the mean values of liquid or glass properties, such as the average number of topological degrees of freedom per atom; however, the localized fluctuations in properties also play a key role in governing the macroscopic characteristics of any glass-forming system. This paper proposes a generalized approach for modeling topological fluctuations in glass-forming liquids by linking the statistical mechanics of the disordered structure to topological constraint theory. In doing so we introduce the contributions of localized fluctuations into the calculation of the topological degrees of freedoms in the network. With this approach the full distribution of properties in the disordered network can be calculated as an arbitrary function of composition, temperature, and thermal history (for the nonequilibrium glassy state). The scope of this current investigation focuses on describing topological fluctuations in liquids, concentrating on composition and temperature effects.

A dielectric medium containing noncentrosymmetric domains can exhibit piezoelectric and second-harmonic generation (SHG) responses when an electric field is applied. Since many crystalline biopolymers have noncentrosymmetric structures, there has been a great deal of interest in exploiting their piezoelectric and SHG responses for electromechanical and electro-optic devices, especially owing to their advantages such as biocompatibility and low density. However, exact mechanisms or origins of such polarization responses of crystalline biopolymers remain elusive due to the convolution of responses from multiple domains with varying degrees of structural disorder or difficulty of ensuring the unidirectional alignment of noncentrosymmetric domains. In this study, we investigate the polarization responses of a noncentrosymmetric crystalline biopolymer, namely, unidirectionally aligned β-chitin crystals interspersed in the amorphous protein matrix, which can be obtained naturally from tubeworm Lamellibrachia satsuma (LS) tube. The mechanisms governing polarization responses in different dynamic regimes covering optical (>1013 Hz), acoustic/ultrasonic (103-105 Hz), and low (10-2-102 Hz) frequencies are explained. Relationships between the polarization responses dominant in different frequencies are addressed. Also, electromechanical coupling responses, including piezoelectricity of the LS tube, are quantitatively discussed. The findings of this study can be applicable to other noncentrosymmetric crystalline biopolymers, elucidating their polarization responses.

Exogenously-added LiCl has been shown to slightly accelerate the corrosion rate of a boroaluminosilicate glass called International Simple Glass (ISG) in aqueous solutions over forward- and residual-rate regimes, while KCl and CsCl impede. To understand the effect of exogenously added electrolytes on resulting hydrous species and the network structure of alteration layers, infrared spectroscopy was implemented. It was found that the fraction of molecular water relative to the surface-bound hydroxyl species is lower in the KCl and CsCl conditions compared to the LiCl and pure water conditions. An approximation for the spectral features of the thin surface films from an experimentally-obtained specular-reflectance infrared (SR-IR) spectrum was proposed; results indicate no significant difference in the Si-O bonding network of the alteration layers formed in the presence of exogenously added LiCl, KCl and CsCl. The observed change in corrosion rates might be linked to the relative abundance of molecular water species in the porous network, rather than the silicate bonding structure.

Borosilicate glasses are widely used to confine high-level radioactive wastes. The lifetime of these materials could reach hundreds of thousands of years if leaching of the glass into groundwater enables the formation of a passivating gel layer. Even in this regime, the glass will never stop corroding as thermodynamic equilibrium between glass and solution cannot be achieved. Therefore, accurate predictions of glass durability including passivation, require a deep understanding of the mechanisms controlling the so-called residual rate. However, despite tremendous efforts, these mechanisms remain poorly understood. Here, focusing on the behavior of the soluble elements of the International Simple Glass (B, Na, and Ca), we show that the residual rate is controlled by the behavior of B, a glass former supposed to dissolve instantaneously when in contact with water and thus widely considered as an ideal tracer. We then demonstrate that B release is controlled by multiple processes highly dependent on the pH. At the beginning of the passivating layer formation, the hydrolysis of B-O-Si linkages is rate-limiting and has an activation energy of ∼60 kJ mol−1, a value slightly lower than that for breaking Si-O-Si linkages. Once the fraction of closed pores resulting from gel restructuring is high enough, then diffusion of both reactants (water molecules) and some products (mainly Baq, Caaq) through the growing gel layer becomes rate-limiting. Consequently, B and Ca accumulate in an inner layer referred to as the active zone, with potential feedback on the B-O-Si hydrolysis. A new paradigm, including B as a key element of the system, is proposed to develop a comprehensive model for the corrosion of borosilicate glass.

We present direct photon-hadron correlations in 200 GeV/A Au+Au, d+Au, and p+p collisions, for direct photon pT from 5–12 GeV/c, collected by the PHENIX Collaboration in the years from 2006 to 2011. We observe no significant modification of jet fragmentation in d+Au collisions, indicating that cold nuclear matter effects are small or absent. Hadrons carrying a large fraction of the quark's momentum are suppressed in Au+Au compared to p+p and d+Au. As the momentum fraction decreases, the yield of hadrons in Au+Au increases to an excess over the yield in p+p collisions. The excess is at large angles and at low hadron pT and is most pronounced for hadrons associated with lower momentum direct photons. Comparison to theoretical calculations suggests that the hadron excess arises from medium response to energy deposited by jets.

A modern lubricant contains various additives with different functionalities and the interactions or reactions between these additives could induce synergistic or antagonistic effects in tribological performance. In this study, sum frequency generation (SFG) spectroscopy was used to investigate competitive adsorption of lubricant additives at a solid/base oil interface. A silica substrate was used as a model solid surface. The lubricant additives studied here included two oil-soluble ionic liquids (ILs, [N888H][DEHP] and [P8888][DEHP]), an antiwear additive (secondary ZDDP), an organic friction modifier (OFM), and a dispersant (PIBSI). Our results showed that for mixtures of ZDDP and IL in a base oil (PAO4), the silica surface is dominated by the IL molecules. In the cases of base oils containing OFM and IL, the silica/lubricant interface is dominated by OFM over [N888H][DEHP], while it is preferentially occupied by [P8888][DEHP] over OFM. The presence of PIBSI in the mixture of PAO4 and IL leads to the formation of a mixed surface layer at the silica surface with PIBSI as a major component. The SFG results in this investigation provide fundamental insights that are helpful to design the formulation of new lubricant additives of desired properties.

Cellulose in plant cell walls are synthesized as crystalline microfibrils with diameters of 3-4 nm and lengths of around 1-10 μm. These microfibrils are known to be the backbone of cell walls, and their multiscale three-dimensional organization plays a critical role in cell wall functions including plant growth and recalcitrance to degradation. The mesoscale organization of microfibrils over a 1-100 nm range in cell walls is challenging to resolve because most characterization techniques investigating this length scale suffer from low spatial resolution, sample preparation artifacts, or inaccessibility of specific cell types. Here, we report a sum frequency generation (SFG) study determining the mesoscale polarity of cellulose microfibrils in intact plant cell walls. SFG is a nonlinear optical spectroscopy technique sensitive to the molecular-to-mesoscale order of noncentrosymmetric domains in amorphous matrices. However, the quantitative theoretical model to unravel the effect of polarity in packing of noncentrosymmetric domains on SFG spectral features has remained unresolved. In this work, we show how the phase synchronization principle of the SFG process is used to predict the relative intensities of vibrational modes with different polar angles from the noncentrosymmetric domain axis. Applying this model calculation for the first time and employing SFG microscopy, we found that cellulose microfibrils in certain xylem cell walls are deposited unidirectionally (or biased in one direction) instead of the bidirectional polarity which was believed to be dominant in plant cell walls from volume-averaged characterizations of macroscopic samples. With this advancement in SFG analysis, one can now determine the relative polarity of noncentrosymmetric domains such as crystalline biopolymers interspersed in amorphous polymer matrices, which will open opportunities to study new questions that have not been conceived in the past.

Background Mechanical refining is a low-capital and well-established technology used in pulp and paper industry to improve fiber bonding for product strength. Refining can also be applied in a biorefinery context to overcome the recalcitrance of pretreated biomass by opening up the biomass structure and modifying substrate properties (e.g., morphology, particle size, porosity, crystallinity), which increases enzyme accessibility to substrate and improves carbohydrate conversion. Although several characterization methods have been used to identify the changes in substrate properties, there is no systematic approach to evaluate the extent of fiber cell wall disruption and what physical properties can explain the improvement in enzymatic digestibility when pretreated lignocellulosic biomass is mechanically refined. This is because the fiber cell wall is complex across multiple scales, including the molecular scale, nano- and meso-scale (microfibril), and microscale (tissue level). A combination of advanced characterization tools is used in this study to better understand the effect of mechanical refining on the meso-scale microfibril assembly and the relationship between those meso-scale modifications and enzymatic hydrolysis. Results Enzymatic conversion of autohydrolysis sugarcane bagasse was improved from 69.6 to 77.2% (11% relative increase) after applying mechanical refining and an increase in enzymatic digestibility is observed with an increase in refining intensity. Based on a combination of advanced characterizations employed in this study, it was found that the refining action caused fiber size reduction, internal delamination, and increase in pores and swellability. Conclusions A higher level of delamination and higher increase in porosity, analyzed by TEM and DSC, were clearly demonstrated, which explain the faster digestibility rate during the first 72 h of enzymatic hydrolysis for disc-refined samples when compared to the PFI-refined samples. In addition, an increased inter-fibrillar distance between cellulose microfibrils at the nano–meso-scale was also revealed by SFG analysis, while no evidence was found for a change in crystalline structure by XRD and solid-state NMR analysis.

Electromechanical coupling properties of biological materials, especially cellulose from plant cell walls and proteins from animals, are of great interest for applications in biocompatible sensors and actuators and ecofriendly energy harvesters. On the basis of their anisotropic nanostructures, cellulose and fibrous proteins such as collagen, silk, keratin, etc. are expected to be piezoelectric; however, this property does not necessarily translate to cellulose- or protein-containing bulk materials. In fact, the values of piezoelectric coefficients reported for cellulose and proteins in the literature vary over several orders of magnitude, which raises the question of whether these are truly intrinsic piezoelectric properties of biological materials or whether they are obscured with other electromechanical coupling processes such as electrostriction, flexoelectricity, electrochemical transport, or electrostatic deformation. This critical question about intrinsic and extrinsic electromechanical coupling mechanisms is reviewed in this article. The origin of piezoelectricity of cellulose and collagen (the most widely studied protein for piezoelectricity) is discussed based on their molecular structures. Key requirements to construct macroscopic piezoelectric biocomposites are addressed in terms of packing orders or arrangements of polar domains in composites. On the basis of this structural argument, truly piezoelectric responses of macroscopic materials fabricated with or containing cellulose and collagen are found to be extremely difficult to observe or quantify; most values reported in the literature as piezoelectric coefficients of such materials appear to originate from other electromechanical coupling mechanisms. Clarifying these mechanisms is important to properly design electromechanical devices using biobased materials.

A novel mathematical algorithm was developed to calculate refractive index (n + ik) from specular reflectance infrared (SR-IR) spectra in the strongly-absorbing glass network vibration region. The method is named as two-angle SR-IR (TASR-IR), since it is based on the Fresnel equations of specular reflectance at two incidence angles (10° and 45°). The results obtained from TASR-IR are comparable with the values obtained from spectroscopic ellipsometry. The TASR-IR method allows one to obtain the peak positions and intensities of fundamental network vibration modes of glass from the imaginary component (k) of complex refractive index without convolutions from the dispersion effect due to chains in the real component (n) of refractive index. The TASR-IR method is applied to silica, silicate, borosilicate, and boroaluminosilicate glasses; tentative peak assignments of glass network vibrations are proposed. The origin and concept of peaks in the vibrational spectra of glasses is discussed.

Most materials exposed to ambient air can adsorb water molecules and the adsorption capability strongly depends on the surface property. The water contact angle has been widely used as a measure for surface wettability; however, a question can still be asked whether the water contact angle can be used as an adequate sole predictor for water adsorption on the surface in humid air. In this paper, HF-etched silicon wafers were aged (oxidized) under different environmental conditions at room temperature to grow surface layers with varying water contact angles from ∼0° (fully hydrophilic) to ∼83° (highly hydrophobic), and water adsorption as a function of relative humidity (RH) was studied on such surfaces. The thickness and structure of the adsorbed water layer were found to depend on not only the surface wettability on each surface, but also the history of surface oxidation conditions. In particular, the silicon wafer surface oxidized in liquid water uptakes significantly more water from humid air than the fully-hydroxylated native oxide surface (SiOx/OH), even though its water contact angle is higher than that on the SiOx/OH surface. This could be attributed to the formation of a gel-like structure during oxidation in liquid water.

Vibrational sum frequency generation (SFG) spectroscopy was used to study how hydrogen bonding interactions of physisorbed water layers vary with the glass composition and surface condition. Three different glass materials were used: amorphous silica (fused quartz), sodium calcium silicate (also called soda lime silica), and calcium aluminosilicate (boron-/fluorine-free E-glass). Two different surface conditions were compared: (i) a mechanically polished, fire-polished, and then annealed surface and (ii) an acid-leached surface (pH 1, 90 °C, 24 h). Compositional and structural information obtained by X-ray photoelectron spectroscopy, spectroscopic ellipsometry, and attenuated total reflection infrared spectroscopy were correlated with SFG spectral features. The temperature dependence of SFG spectral features revealed that regardless of the glass composition, the glass surface is free of physisorbed water at 250 °C, and during cooling in ambient air, it starts absorbing water at a temperature corresponding...

This work investigated the decomposition of dilute N2O from gas streams with various oxygen contents by using a plasma-catalytic process over metal oxide catalysts supported on γ-Al2O3. Among the metals explored (Ru, Co, Cu, V, etc.), Ru was found to be the best catalyst for the decomposition of N2O in a plasma-catalytic reactor, and most of the experiments were conducted with alumina-supported Ru. The effects of applied voltage, reaction temperature, O2 content, gas flow rate and initial N2O content on the decomposition efficiency and byproducts formation were examined. Compared to the catalyst-alone case, the presence of plasma enhanced the decomposition efficiency by 30–50%, depending on the operating condition. The increase in the oxygen content from 0 to 20% largely decreased the catalytic decomposition efficiency, whereas in the presence of plasma N2O could be successfully decomposed even at 20% O2 content. The decomposition efficiency was not a strong function of the initial N2O concentration in the range of 225–1800 ppm, exhibiting pseudo first-order reaction kinetics. Without O2, there were negligible byproducts, but in the presence of O2, NO and NO2 were formed mainly due to the plasma-induced reactions between background molecules such as N2 and O2. The results obtained in this work showed the feasibility of plasma-catalytic process for the abatement of N2O.

The porosity and pore-size distribution in the glass play an important role in glass corrosion; however, such information is difficult to be obtained non-destructively. Here we report the use of spectroscopic ellipsometry (SE) under controlled humidity environments to determine those structural parameters in the alteration layers formed on international simple glass (ISG), a model nuclear waste glass, in aqueous corrosion conditions. The SE results show that the ISG sample corroded for nearly 4.5 years develops pores larger than 2 nm in diameter, while the alteration layers formed initially in less than 1 month do not have such large pores. The development of larger pores over a long period of corrosion time, while the overall thickness remains relatively constant, implies structural rearrangements of the silicate network occurring within the alteration layer, which could eventually affect the transport of reactants and products as well as the structural stability. Spectroscopy has been used to study the interfacial silica gel layer created during the corrosion of a model nuclear-waste glass. Understanding the way in which such materials degrade is of great importance because they are used to store radioactive waste. When international simple glass (ISG) corrodes an ‘alteration’ layer forms on its surface and now Seong H. Kim, from The Pennsylvania State University, and co-workers have used spectroscopic ellipsometry to characterize the thickness, porosity, and pore-size distribution of this layer after exposing it to different corrosive experimental conditions. Their data show that, although their alteration layers are of similar depths, the pore diameters in ISG samples corroded for 7 or 28 days are smaller than 2 nm whereas those corroded for 1625 days are larger, implying some restructuring of the layer over this time.

Sum frequency generation (SFG) vibrational spectroscopy can selectively detect and analyze noncentrosymmetric components interspersed in amorphous matrices; this principle has been used for studies of nanoscale structure and mesoscale assembly of cellulose in plant cell walls. However, the spectral information averaged over a large area or volume cannot provide regiospecific or tissue-specific information of different cells in plants. This study demonstrates spatially resolved SFG analysis and imaging by combining a broad-band SFG spectroscopy system with an optical microscope. The system was designed to irradiate both narrow-band 800 nm and broad-band tunable IR beams through a single reflective objective lens, but from opposite sides of the surface normal direction of the sample. The developed technique was used to reveal inhomogeneous distributions of cellulose microfibrils within single cell walls, such as cotton fibers and onion epidermis as well as among different tissues in Arabidopsis inflorescence stems and bamboo culms. SFG microscopy can be used for vibrational spectroscopic imaging of other biological systems in complement to conventional Fourier transform infrared spectroscopy and confocal Raman microscopy.

Mechanochemical reactions between adsorbate molecules sheared at tribological interfaces can induce association of adsorbed molecules, forming oligomeric and polymeric products often called tribopolymers). This study revealed the role or effect of surface chemistry of the solid substrate in mechanochemical polymerization reactions. As a model reactant, α-pinene was chosen because it was known to readily form tribopolymers at the sliding interface of stainless steel under vapor-phase lubrication conditions. Eight different substrate materials were tested-palladium, nickel, copper, stainless steel, gold, silicon oxide, aluminum oxide, and diamond-like carbon (DLC). All metal substrates and DLC were initially covered with surface oxide species formed naturally in air or during the oxidative sample cleaning. It was found that the tribopolymerization yield of α-pinene is much higher on the substrates that can chemisorb α-pinene, compared to the ones on which only physisorption occurs. From the load dependence of the tribopolymerization yield, it was found that the surfaces capable of chemisorption give a smaller critical activation volume for the mechanochemical reaction, compared to the ones capable of physisorption only. On the basis of these observations and infrared spectroscopy analyses of the adsorbed molecules and the produced polymers, it was concluded that the mechanochemical reaction mechanisms might be different between chemically reactive and inert surfaces and that the chemical reactivity of the substrate surface greatly influences the tribochemical polymerization reactions of adsorbed molecules.

Lithium-sulfur (Li-S) batteries are promising candidates for high-energy storage devices due to high theoretical capacities of both the sulfur cathode and lithium (Li) metal anode. Considerable efforts have been devoted to improving sulfur cathodes. However, issues associated with Li anodes, such as low Coulombic efficiency (CE) and growth of Li dendrites, remain unsolved due to unstable solid-electrolyte interphase (SEI) and lead to poor capacity retention and a short cycling life of Li-S batteries. In this work, we demonstrate a facile and effective approach to fabricate a flexible and robust hybrid SEI layer through co-deposition of aromatic-based organosulfides and inorganic Li salts using poly(sulfur-random-1,3-diisopropenylbenzene) as an additive in an electrolyte. The aromatic-based organic components with planar backbone conformation and π-π interaction in the SEI layers can improve the toughness and flexibility to promote stable and high efficient Li deposition/dissolution. The as-formed durable SEI layer can inhibit dendritic Li growth, enhance Li deposition/dissolution CE (99.1% over 420 cycles), and in turn enable Li-S batteries with good cycling stability (1000 cycles) and slow capacity decay. This work demonstrates a route to address the issues associated with Li metal anodes and promote the development of high-energy rechargeable Li metal batteries.

Mechanochemical reactions at gallium arsenide-silica (GaAs-SiO2) interface in micro-/nano-scales during ultra-precision manufacturing process offer novel phenomena of fundamental interests. Here, atomic structures, chemical, and mechanical properties of as-received, hydrochloric acid-etched, and ultraviolet-irradiated GaAs surfaces were characterized, and their roles in atomic attrition dominated by mechanochemical reactions were revealed at atomic scale. Experimental results suggested that, compared with water adsorption and mechanical property, oxidized structure plays a more crucial role in the mechanically-stimulated chemical reactions at GaAs–SiO2 interface. Analyzing the mechanochemical reactions with the stress-assisted Arrhenius-type kinetics model and contact mechanics implies that, the oxidized layer with thermodynamically more stable structure than GaAs crystal increases the energy barrier of mechanochemical reactions and suppresses the atomic removal. These finding provide a deep insight into the mechanochemical removal mechanism of GaAs and a broad cognition for regulating the mechanochemical reactions widely existing in scientific and engineering applications.

The effect of glass composition on surface layers formed through reaction between strong acid and several silicate and aluminosilicate glasses was studied through transmission-IR, ATR- IR, XPS, SIMS and nano-indentation analyses. It was shown that aluminum is depleted from the surface while molecular water is diffused into the surface layer of glasses with high levels of aluminum. Nano-indentation experiments indicated that the hardness of the surface layers were decreased compared with that of the bulk region and the degree of the softening was more significant in the high aluminum glass. This article is protected by copyright. All rights reserved.

Lithium metal is a promising anode candidate for the next-generation rechargeable battery due to its highest specific capacity (3860 mA h g−1) and lowest potential, but low Coulombic efficiency and formation of lithium dendrites hinder its practical application. Here, we report a self-formed flexible hybrid solid-electrolyte interphase layer through co-deposition of organosulfides/organopolysulfides and inorganic lithium salts using sulfur-containing polymers as an additive in the electrolyte. The organosulfides/organopolysulfides serve as “plasticizer” in the solid-electrolyte interphase layer to improve its mechanical flexibility and toughness. The as-formed robust solid-electrolyte interphase layers enable dendrite-free lithium deposition and significantly improve Coulombic efficiency (99% over 400 cycles at a current density of 2 mA cm−2). A lithium-sulfur battery based on this strategy exhibits long cycling life (1000 cycles) and good capacity retention. This study reveals an avenue to effectively fabricate stable solid-electrolyte interphase layer for solving the issues associated with lithium metal anodes., The practical application of lithium metal anodes suffers from the poor Coulombic efficiency and growth of lithium dendrites. Here, the authors report an approach to enable the self-formation of stable and flexible solid-electrolyte interphase layers which serve to address both issues.

This paper reports a comprehensive spectroscopic characterization of soda lime silica (SLS) glass surfaces with various thermal histories and dealkalization chemical treatments. While many studies have investigated elemental composition changes after dealkalization treatments, the work reported here focuses on identification and quantification of the associated structural changes in terms of non-bridging oxygen (NBO), bridging oxygen (BO) and hydrous species (Si OH and H 2 O). X-ray photoelectron spectroscopy (XPS) was used to determine the average areal densities of BOs, NBOs, and OH groups at the top 10 nm of the surface. Specular reflection infrared (SR-IR) spectroscopy was used to probe the Si O Si asymmetric stretch vibration mode of the silicate network of the top

Compositional changes in unleached and acid-leached soda-lime silicate surfaces were tracked with in-vacuo heating and X-ray Photoelectron Spectroscopy. Surface oxygen speciation was determined using a stoichiometry-based algorithm via elemental composition, instead of the typical O 1s peak-fitting approach. Accurate surface hydroxyl quantification is shown to require dehydration at temperatures near 200 °C. On the unleached surface, no change in surface hydroxyl density (~2.5 OH/nm2) is observed in the temperature range of 200 to 500 °C after the initial dehydration. However, repolymerization in the network (non-bridging oxygen → bridging oxygen) is observed due to volatilization of sodium. The acid-leached surface undergoes sodium out-diffusion from the bulk at sub-Tg temperatures with laterally-resolved inhomogeneity and shows a reduction in the concentration of hydroxyls from 4.5 OH/nm2 (200 °C) to 3.2 OH/nm2 (500 °C) accompanied by an increase in bridging oxygen. These results suggest that when [OH] > 2.5~3/nm2, vicinal OH undergo dehydroxylation with evolution of water, whereas when [OH] < 2.5/nm2, most OHs are non-interacting and isolated (at temperatures below Tg). Furthermore, at temperatures exceeding 300 °C, sodium has enough thermal energy to desorb in vacuum and diffuse from the bulk (depending on the abundance & local structure). This article is protected by copyright. All rights reserved.

In the IR spectra of silica and silicate glasses, the shifts of the maximum intensity position of the νSi-O-Si,as band upon heating or applying mechanical stress could be attributed to changes in the distribution of bond parameters such as bond length and bond angle. Upon heating, isotropic expansion occurs and the density changes; upon applying mechanical stress, anisotropic strain is induced and a significant change in the Si-O-Si bond angle is observed. From molecular dynamics simulations of silica glasses, we show that the peak position shift correlates better with the asymmetric change in the Si-O bond length distribution, rather than the Si-O-Si bridge angle, the O-Si-O tetrahedral angle, or the density change. This new finding provides an insight into how and why the νSi-O-Si,as IR peak of soda lime silica (SLS) glass shifts upon chemical strengthening via ion exchange and thermal tempering. This article is protected by copyright. All rights reserved.

Comprehensive interpretation of vibrational sum-frequency-generation (SFG) spectroscopic features of SFG-active nanodomains interspersed in amorphous bulk requires the knowledge of nonlinear susceptibility, χijk(2), of the SFG-active phase as a function of its spatial arrangement in the bulk as well as the polarizations of the probe lights. This study reports the full analysis of the azimuth angle and polarization dependence of SFG signals from a control sample consisting of uniaxially aligned cellulose Iβ crystals. The χijk(2) terms of cellulose were estimated from quantum mechanics calculations using time-dependent density functional theory (TD-DFT), and a simple structural model was built with truncated glucose dimers. The theoretical azimuth angle and polarization dependences of characteristic CH/CH2 and OH stretch modes of cellulose were compared with the experimentally observed trends. These comparisons revealed that the relative polarity of crystallites within the SFG coherence length, the random q...

For the encapsulation of biomolecules in inorganic materials, we have developed a unique enzyme-silicate conjugate material that consists of a self-assembled molecularly thin silicate layer on the surface of each individual enzyme molecule. The enzyme-silicate conjugate materials, called single enzyme caged nanoparticles (SECNs), were synthesized via the silica polymerization on the surface of enzyme molecule after solubilizing each enzyme molecule in hexane by using a tiny amount of surfactant, called “ion-pairing”. SECNs possess near native enzyme activity in aqueous media with minimal substrate diffusional limitations, and are highly stable under the protection of silicate network cage. Due to their nearly molecular size, SECNs can also be adsorbed into mesoporous silica materials to yield robust and easily-recyclable enzymatic systems that can be used in a number of potential biocatalytic applications such as diagnostics, biosensors, biotransformations, biofuel production, bioremediation and CO2 capture.

The organization of polysaccharides in plant cell walls is important for the mechanics of plant cells. Spectral analysis of cell walls by polarized IR can reveal polysaccharide organization, but may be complicated by dipoles not aligned with the backbone. For instance, analysis of uniaxially-aligned cellulose Iβ film revealed that the dipole transition vector of the 1160 cm−1 band involving stretch vibrations of glycosidic C1–O–C4 linkages is approximately at 30° with respect to the backbone of the cellulose chain, because of coupling with C5–O–C1 bonds in the six-membered rings. In the case of homogalacturonan, the dipole transition vector of the ester carbonyl group vibration (νC=O, 1745 cm−1) is expected to be nearly normal to the homogalacturonan backbone. Using this information and the dichroism equation, the change in net orientation of cell wall polymers upon mechanical stretch was determined by polarized IR analysis. Never-dried abaxial outer epidermal cell walls of the second scale of onion bulb were mechanically stretched along longitudinal or transverse directions with respect to the long axis of the cells and then dried while under mechanical stretch. The average orientations of both 1160 and 1745 cm−1 vibration transition dipoles were rotated by ~5° and ~4°, respectively, along the stretch direction from their initial random distributions upon longitudinal strain by 14%; and by ~4° and ~3°, respectively, upon transverse strain by 12%. These results imply that both cellulose microfibrils and pectins in the cell wall are passively realigned along the stretch direction by external mechanical force. The analytical methodology developed here will be useful to study how cell wall polymers might reorganize during cell wall growth and development.

The origins of run-in and ultralow friction states of a sliding contact of hydrogenated diamond-like carbon (H-DLC) and sapphire were studied with an in situ Raman tribometer as well as ex situ analyses of transmission electron microscopy (TEM), Raman spectroscopy, and nanoindentation. Prior to ultralow friction behavior, H-DLC exhibits a run-in period. During the run-in period in dry nitrogen atmosphere, the transfer film was formed and its uniformity and thickness as well as structure were varied. The duration and friction behaviors during the run-in depended on the initial surface state of the H-DLC coatings. A comparative study of pristine and thermally oxidized H-DLC revealed the role of surface oxide layer on run-in friction and transfer film formation. Attainment of the ultralow friction state appeared to correlate with the uniformity and structure of the transfer film evolved during the run-in, rather than its final thickness. TEM cross-section imaging of the wear track and the counter surfaces showed a trace of nanocrystalline graphite and a thin modified surface layer on both rubbing bodies. The comparison of hardness and reduced modulus of the wear tracks and the unworn surfaces as well as the ex situ Raman spectra suggested the densification of the wear track surfaces. Combining the in situ and ex situ analysis results, a comprehensive model was proposed for the formation and structure of the ultralow friction sliding contact of H-DLC.

Vibrational sum frequency generation (SFG) spectroscopy can selectively detect not only molecules at two-dimensional (2D) interfaces but also noncentrosymmetric domains interspersed in amorphous three-dimensional (3D) matrixes. However, the SFG analysis of 3D systems is more complicated than 2D systems because more variables are involved. One such variable is the distance between SFG-active domains in SFG-inactive matrixes. In this study, we fabricated control samples in which SFG-active cellulose crystals were uniaxially aligned in an amorphous matrix. Assuming uniform separation distances between cellulose crystals, the relative intensities of alkyl (CH) and hydroxyl (OH) SFG peaks of cellulose could be related to the intercrystallite distance. The experimentally measured CH/OH intensity ratio as a function of the intercrystallite distance could be explained reasonably well with a model constructed using the theoretically calculated hyperpolarizabilities of cellulose and the symmetry cancellation princi...

The thickness of cotton fiber cell walls is an important property that partially determines the economic value of cotton. To better understand the physical and chemical manifestations of the genetic variations that regulate the degree of fiber wall thickness, we used a comprehensive set of methods to compare fiber properties of the immature fiber (im) mutant, called immature because it produces thin-walled fibers, and its isogenic wild type Texas Marker-1 (TM-1) that is a standard upland cotton variety producing normal fibers with thick walls. Comprehensive structural analyses showed that im and TM-1 fibers shared a common developmental process of cell wall thickening, contrary to the previous report that the phase in the im fiber development might be retarded. No significant differences were found in cellulose content, crystallinity index, crystal size, matrix polymer composition, or in ribbon width between the isogenic fibers. In contrast, significant differences were detected in their linear density, cross-section micrographs of fibers from opened bolls, and in the lateral order between their cellulose microfibrils (CMFs). The cellulose mass in a given fiber length was lower and the CMFs were less organized in the im fibers compared with the TM-1 fibers. The presented results imply that the disruption of CMF organization or assembly in the cell walls may be associated with the immature phenotype of the im fibers.

Mechanical and tribological properties of barium boroaluminosilicate glass (commercial AF45® glass) treated with a thermal poling process employing 4 kV bias at 600 °C were studied. Compared to the pristine AF45 glass, the anode-side surface of the thermally poled glass has lower modifier ion concentrations and lower reduced modulus and hardness, while the cathode-side surface has increased modifier ion concentrations and shows an increase in reduced modulus and hardness. Both pristine and anode-side surfaces become more susceptible to wear as relative humidity (RH) of the surrounding environment increases from 20% to 90%; in contrast, the cathode-side surface exhibits a remarkable wear resistance at 90% RH. It was speculated that the increased wear resistance of the cathode-side surface at high RH conditions might be due to the accumulation of leachable modifier ions (especially sodium ions) in the subsurface region. These results may serve as a design rule to control the mechanochemical wear damage of optical glasses and optimize the tribological design of functional and engineering glasses in humid conditions.

In poly(vinylidene difluoride) (PVDF)-based polymers, the alignment of dipoles of the crystalline β phase with all-trans conformations is responsible for ferroelectricity; however, there is a lack of direct spectroscopic evidence for this phenomenon. We report in situ monitoring of the molecular orientations associated with ferroelectric responses of PVDF-based polymers using vibrational sum frequency generation (SFG) spectroscopy. The orientation of CH2 groups with respect to the −(CH2CF2)n– chain axis of the poled β domains in a PVDF copolymer was determined from the SFG dependence of an uniaxially aligned sample on the laser polarization and azimuthal angle. The relative intensities of CH2 symmetric and asymmetric stretch modes as well as their total intensities revealed the transformation of the all-trans conformation domains during the electrical poling of PVDF based co- and terpolymer films.

Vibrational sum-frequency-generation (SFG) spectroscopy is capable of selectively detecting crystalline biopolymers interspersed in amorphous polymer matrices. However, the spectral interpretation is difficult due to the lack of knowledge on how spatial arrangements of crystalline segments influence SFG spectra features. Here we report time-dependent density functional theory (TD-DFT) calculations of cellulose crystallites in intimate contact with two different polarities: parallel versus antiparallel. TD-DFT calculations reveal that the CH/OH intensity ratio is very sensitive to the polarity of the crystallite packing. Theoretical calculations of hyperpolarizability tensors (βabc) clearly show the dependence of SFG intensities on the polarity of crystallite packing within the SFG coherence length, which provides the basis for interpretation of the empirically observed SFG features of native cellulose in biological systems.

Hydrothermal treatment provides a unique way to reveal subsurface damage of soda lime silica (SLS) float glass. During the hydrothermal treatment, the penetration of water, ion-exchange, and hydrolysis reaction can take place. These reactions are accelerated at locations where subsurface damage exists. Interestingly, the hydrothermally-treated glass surface exhibits higher fracture toughness, lower hardness, and less resistance to mechanochemical wear at high humidity compared to the pristine SLS float glass. These property changes can be explained by the leaching and polymerization of the silicate network and the chemical environment of hydrous species in the surface region of SLS glass.