A new method to determine dispersive surface energy site distributions by inverse gas chromatography.

A computational model to predict the relative energy site contributions of a heterogeneous material from data collected by finite dilution-inverse gas chromatography (FD-IGC) is presented in this work. The methodology employed a multisolvent system site filling model utilizing Boltzmann statistics, expanding on previous efforts to calculate "experienced energies" at varying coverage, yielding a retention volume distribution allowing calculation of a surface free energy distribution. Surface free energy distributions were experimentally measured for racemic ibuprofen and ß-mannitol powders, the energies of each were found in the ranges 43-52 and 40-55 mJ/m(2), respectively, over a surface coverage range of 0-8%. The computed contributions to surface energy values were found to match closely with data collected on macroscopic crystals by alternative techniques (±<1.5 mJ/m(2)).

Correct specific retention volume determination in inverse gas chromatography.

Inverse Gas Chromatography (IGC) is an important technique for characterization of solids. Determining the specific retention volume of the injected probe molecule is the basis of the analysis for all the physico-chemical properties that the technique can determine, most importantly in Heat of Sorption, Glass Transition Temperature, Gibbs Adsorption Free Energy. Two equations have been used in the literature to calculate the specific retention volume; one normalizes the retention volume to 0 °C (standard temperature), which was previously proven to be thermodynamically incorrect, while the other calculates the retention volume at the measurement temperature. Here, we compare the heat of sorption for a series of alkanes on two substrates, micro crystalline cellulose and natural graphite, calculated using these two equations. This study shows that the specific retention volume is strongly dependent on the column temperature. Using the retention volume values normalised to 0 °C consistently overestimates the heats of sorption by up to 10%. Most importantly, correcting the retention volume to standard temperature will misrepresent the effect of temperature on the retention volume and the thermodynamic parameters derived from it.

Effect of milling on particle shape and surface energy heterogeneity of needle-shaped crystals.

PURPOSE: Milling and micronization of particles are routinely employed in the pharmaceutical industry to obtain small particles with desired particle size characteristics. The aim of this study is to demonstrate that particle shape is an important factor affecting the fracture mechanism in milling. METHODS: Needle-shaped crystals of the ß polymorph of D-mannitol were prepared from recrystallization in water. A portion of the recrystallized materials was ball-milled. Unmilled and milled sieved fractions of recrystallized D-mannitol were analyzed by dynamic image analysis (DIA) and inverse gas chromatography (IGC) at finite concentration to explain the breakage/fracture behavior. RESULTS: In the process of ball-milling, D-mannitol preferentially fractured along their shortest axis, exposing (011) plane with increased hydrophilicity and increased bounding rectangular aspect ratio. This is in contrary to attachment energy modeling which predicts a fracture mechanism across the (010) plane with increased hydrophobicity, and small change in particle shape. CONCLUSIONS: Crystal size, and more importantly, crystal shape and facet-specific mechanical properties, can dictate the fracture/cleavage behavior of organic crystalline materials. Thorough understanding of the crystal slip systems, combining attachment energy prediction with particle shape and surface characterization using DIA and IGC, are important in understanding fracture behavior of organic crystalline solids in milling and micronization.

Delignified wood aerogels as scaffolds coated with an oriented chitosan-cyclodextrin co-polymer for removal of microcystin-LR.

Nano-porous aerogels are an advantageous approach to produce low-density materials with high surface area, particularly when using biobased materials. Frequently, most biobased aerogels are synthesized through a bottom-up approach, which requires high energy inputs to break and rebuild the raw materials, and for elimination of water. To curb this, this work focused on generating aerogels by a top-down approach through the delignification of a wood substrate while eliminating water by solvent exchange. To diversify the surface chemistry for use in water treatment, the delignified wood-nanowood-was coated with a chitosan-cyclodextrin co-polymer and tested in the capture of microcystin-LR. The generated nanowood structure had 75% porosity after coating, with up to 339% water swelling and an adsorption capacity of 0.12 mg g-1 of the microcystin. This top-down technique enables the generation of low-cost aerogels by reducing steps, using a biobased self-assembled coating with hydrophobic active sites, and avoiding costly energetic input.

Effect of Polystyrene Synthesis Method on Water Sorption and Glass Transition.

Commodity PS is synthesized via free radical polymerization, whereas PS in block copolymers (BCPs) is typically synthesized via living anionic polymerization. The purpose of this work is to investigate how the synthesis method impacts important properties such as water sorption and glass transition temperature (Tg). Water sorption is important because the performance of nanostructured polymer membranes in various applications is known to be affected by environmental conditions such as humidity. Tg is important because it dictates processing conditions, both for commodity PS as well as BCPs such as thermoplastic elastomers. Water sorption in commercial PS was found to be 0.5 mgwater/gpolymer at the highest humidities investigated (about 80%), in agreement with literature. On the other hand, syndiotactic PS synthesized anionically at low temperature absorbed more water, up to 1.5 mgwater/gpolymer, due to higher free volume. The greatest impact on water sorption was due to addition of hydrophilic hydroxyl chain ends to atactic PS, which resulted in water sorption of up to 2.3 mgwater/gpolymer. In addition to measuring water sorption and dry Tg separately, the impact of relative humidity on PS Tg was examined. Combined differential scanning calorimetry and dynamic mechanical analysis show that on going from the dry state to high humidity, the Tg of PS decreases by 5 °C. Moreover, the tensile storage modulus of PS decreases from 1.58 GPa at 0% RH to 0.53 GPa at 40% RH. In addition to the practical relevance of this study, this report fills a gap in experimental literature by using a poor solvent system, PS/water, to examine plasticization in the pure polymer limit.

Probing Surface Characteristics of Rare Earth Minerals Using Contact Angle Measurements, Atomic Force Microscopy, and Inverse Gas Chromatography.

Rare earth minerals (REMs) such as bastnaesite, monazite, and xenotime are of considerable significance since they are the main commercial sources for rare earth elements (REEs) with cutting-edge applications. Fundamental understanding of surface properties of REMs is essential to identify the reactions taking place at different interfaces to develop more robust technologies for the recovery of REEs. The goal of this study is to provide a comprehensive investigation on the surface energy characteristics of bastnaesite and xenotime, as the primary sources of light and heavy rare earth elements, respectively. Crystal's orientation of REMs was identified using surface X-ray diffraction analysis, whereas the morphology and elemental composition were characterized using scanning electron microscopy and energy dispersive spectra analyses. Wettability of REMs was studied using sessile drop contact angle measurement technique, and the surface energy and its constituents were evaluated using Fowkes, van Oss-Chaudhury-Good, Owens-Wendt-Rabel-Kaelble, Zisman, and Neumann models. Atomic force microscopy (AFM) was used to compare the local surface properties and work of adhesion of REMs by analyzing the force profile between the mineral surfaces and a n-type silicon tip. Inverse gas chromatography (IGC) was employed to study the surface energy heterogeneity of REM powders and evaluate the dispersive and Lewis acid-base interactions. Results indicated that the dispersion forces have a larger contribution to the surface energy of both REMs in comparison with the polar interactions. The surface energy values obtained using contact angle measurements were lower than those obtained using IGC, however, the IGC results seemed to be closer to reality since the contact angle results showed a strong dependence on probe liquids, roughness, and local properties of the surfaces. Contact angle measurements and AFM analysis indicated that bastnaesite had higher hydrophobic character, whereas the IGC analysis revealed that the surface energy of xenotime was lower than that of bastnaesite at higher surface coverages. Despite the shortcomings of each method, results showed that a combination of these techniques could provide a deeper understanding of surface energy and wetting behavior of minerals.

The Effect of Polymorphism on Surface Energetics of D-Mannitol Polymorphs.

The aim of this work was to assess the effect of different crystalline polymorphism on surface energetics of D-mannitol using finite dilution inverse gas chromatography (FD-IGC). Pure α, ß and δ polymorphs were prepared via solution crystallisation and characterised by powder X-ray diffraction (P-XRD). The dispersive surface energies were found to range from 43 to 34 mJ/m2, 50 to 41 mJ/m2, and 48 to 38 mJ/m2, for α, ß, and δ, respectively, for surface coverage ranging from 0.006 to 0.095. A deconvolution modelling approach was employed to establish their energy sites. The primary sites corresponded to maxima in the dispersive surface energy of 37.1 and 33.5; 43.3 and 39.5; and 38.6, 38.4 and 33.0; for α, ß, and δ, respectively. This methodology was also extended to an α-ß polymorph mixture to estimate the amount of the constituent α and ß components present in the sample. The dispersive surface energies of the α-ß mixture were found to be in the range of 48 to 37 mJ/m2 with 40.0, 42.4, 38.4 and 33.1 mJ/m2 sites. The deconvolution modelling method extracted the energy contribution of each of the polymorphs from data for the polymorphic mixture. The mixture was found to have a ß-polymorph surface content of ∼19%. This work shows the influence of polymorphism on surface energetics and demonstrates that FD-IGC coupled with a simple modelling approach to be a powerful tool for assessing the specific nature of this energetic distribution including the quantification of polymorphic content on the surface.

In situ soft X-ray studies of ethylene oxidation mechanisms and intermediates on the Pt(111) surface.

In situ studies of ethylene oxidation on Pt(111) have been performed using a powerful combination of fluorescence yield soft X-ray methods for temperatures up to 600 K and oxygen pressures up to 0.01 Torr. Absolute carbon coverages have been determined both in steady-state and dynamic catalytic conditions on the Pt(111) surface. Fluorescence yield near-edge spectroscopy (FYNES) and temperature-programmed fluorescence yield near-edge spectroscopy (TP-FYNES) experiments above the carbon K edge were used to identify the structure and bonding of the dominant surface species during oxidation. TP-FYNES experiments of preadsorbed ethylene coverages in oxygen pressures up to 0.01 Torr indicate a stable intermediate is formed over the 215-300 K temperature range. By comparing the intensity of the C-H sigma resonance at the magic angle with the intensity in the carbon continuum, the stoichiometry of this intermediate has been determined explicitly. Based on calibration with known C-H stoichiometries, the intermediate has a C(2)H(3) stoichiometry for oxygen pressures up to 0.01 Torr, indicating oxydehydrogenation occurs before skeletal oxidation. FYNES spectra at normal and glancing incidences were performed to characterize the structure and bonding of this intermediate. Using FYNES spectra of ethylene, ethylidyne, and acetylene as reference standard, this procedure indicates the oxidation intermediate is tri-sigma vinyl. Thus, oxidation of ethylene proceeds through a vinyl intermediate, with oxydehydrogenation preceding skeletal oxidation.

Enhanced low-temperature CO oxidation on a stepped platinum surface for oxygen pressures above 10(-5) Torr.

The rate of CO oxidation has been characterized on the stepped Pt(411) surface for oxygen pressures up to 0.002 Torr, over the 100-1000 K temperature range. CO oxidation was characterized using both temperature-programmed reaction spectroscopy (TPRS) and in situ soft X-ray fluorescence yield near-edge spectroscopy (FYNES). New understanding of the important role surface defects play in accelerating CO oxidation for oxygen pressure above 10(-5) Torr is presented in this paper for the first time. For saturated monolayers of CO, the oxidation rate increases and the activation energy decreases significantly for oxygen pressures above 10(-5) Torr. This enhanced CO oxidation rate is caused by a change in the rate-limiting step to a surface reaction limited process above 10(-5) Torr oxygen from a CO desorption limited process at lower oxygen pressure. For example, in oxygen pressures above 0.002 Torr, CO(2) formation begins at 275 K even for the CO saturated monolayer, which is well below the 350 K onset temperature for CO desorption. Isothermal kinetic measurements in flowing oxygen for this stepped surface indicate that activation energies and preexponential factors depend strongly on oxygen pressure, a factor that has not previously been considered critical for CO oxidation on platinum. As oxygen pressure is increased from 10(-6) to 0.002 Torr, the oxidation activation energies for the saturated CO monolayer decrease from 24.1 to 13.5 kcal/mol for reaction over the 0.95-0.90 ML CO coverage range. This dramatic decrease in activation energy is associated with a simple increase in oxygen pressure from 10(-5) to 10(-3) Torr. Activation energies as low as 7.8 kcal/mol were observed for oxidation of an initially saturated CO layer reacting over the 0.4-0.25 ML coverage range in oxygen pressure of 0.002 Torr. These dramatic changes in reaction mechanism with oxygen pressure for stepped surfaces are consistent with mechanistic models involving transient low activation energy dissociation sites for oxygen associated with step sites. Taken together these experimental results clearly indicate that surface defects play a key role in increasing the sensitivity of CO oxidation to oxygen pressure.

Comparison of the properties of cellulose nanocrystals and cellulose nanofibrils isolated from bacteria, tunicate, and wood processed using acid, enzymatic, mechanical, and oxidative methods.

This work describes the measurement and comparison of several important properties of native cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs), such as crystallinity, morphology, aspect ratio, and surface chemistry. Measurement of the fundamental properties of seven different CNCs/CNFs, from raw material sources (bacterial, tunicate, and wood) using typical hydrolysis conditions (acid, enzymatic, mechanical, and 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO)-mediated oxidation), was accomplished using a variety of measurement methods. Atomic force microscopy (AFM), transmission electron microscopy (TEM), and 13C cross-polarization magic angle spinning (CPMAS) nuclear magnetic resonance (NMR) spectroscopy were used to conclude that CNCs, which are rodlike in appearance, have a higher crystallinity than CNFs, which are fibrillar in appearance. CNC aspect ratio distributions were measured and ranged from 148±147 for tunicate-CNCs to 23±12 for wood-CNCs. Hydrophobic interactions, measured using inverse gas chromatography (IGC), were found to be an important contribution to the total surface energy of both types of cellulose. In all cases, a trace amount of naturally occurring fluorescent compounds was observed after hydrolysis. Confocal and Raman microscopy were used to confirm that the fluorescent species were unique for each cellulose source, and demonstrated that such methods can be useful for monitoring purity during CNC/CNF processing. This study reveals the broad, tunable, multidimensional material space in which CNCs and CNFs exist.

An inorganic-organic proton exchange membrane for fuel cells with a controlled nanoscale pore structure.

Proton exchange membrane fuel cells have the potential for applications in energy conversion and energy storage, but their development has been impeded by problems with the membrane electrode assembly. Here, we demonstrate that a silicon-based inorganic-organic membrane offers a number of advantages over Nafion--the membrane widely used as a proton exchange membrane in hydrogen fuel cells--including higher proton conductivity, a lack of volumetric size change, and membrane electrode assembly construction capabilities. Key to achieving these advantages is fabricating a silicon membrane with pores with diameters of approximately 5-7 nm, adding a self-assembled molecular monolayer on the pore surface, and then capping the pores with a layer of porous silica. The silica layer reduces the diameter of the pores and ensures their hydration, resulting in a proton conductivity that is two to three orders of magnitude higher than that of Nafion at low humidity. A membrane electrode assembly constructed with this proton exchange membrane delivered an order of magnitude higher power density than that achieved previously with a dry hydrogen feed and an air-breathing cathode.

Determination of the surface energy distributions of different processed lactose.

Particulate interactions between drug and lactose carrier in dry powder inhaler formulations are affected by the heterogenous energy distribution on the surface of the individual compounds. A new method based on Inverse Gas Chromatography at finite concentration is applied to study the energy heterogeneity of untreated, milled, and recrystallized lactose of similar particle size distribution. Energy distributions for the dispersive surface energy and the specific free energy of ethanol are obtained. Milling causes an increase in surface energy due to formation of amorphous regions. Untreated and recrystallized materials have similar surface energies at low surface coverages but show clear differences in energy distribution.