International Interlaboratory Comparison of Thermogravimetric Analysis of Graphene-Related Two-Dimensional Materials.

Research on graphene-related two-dimensional (2D) materials (GR2Ms) in recent years is strongly moving from academia to industrial sectors with many new developed products and devices on the market. Characterization and quality control of the GR2Ms and their properties are critical for growing industrial translation, which requires the development of appropriate and reliable analytical methods. These challenges are recognized by International Organization for Standardization (ISO 229) and International Electrotechnical Commission (IEC 113) committees to facilitate the development of these methods and standards which are currently in progress. Toward these efforts, the aim of this study was to perform an international interlaboratory comparison (ILC), conducted under Versailles Project on Advanced Materials and Standards (VAMAS) Technical Working Area (TWA) 41 "Graphene and Related 2D Materials" to evaluate the performance (reproducibility and confidence) of the thermogravimetric analysis (TGA) method as a potential new method for chemical characterization of GR2Ms. Three different types of representative and industrially manufactured GR2Ms samples, namely, pristine few-layer graphene (FLG), graphene oxide (GO), and reduced graphene oxide (rGO), were used and supplied to ILC participants to complete the study. The TGA method performance was evaluated by a series of measurements of selected parameters of the chemical and physical properties of these GR2Ms including the number of mass loss steps, thermal stability, temperature of maximum mass change rate (Tp) for each decomposition step, and the mass contents (%) of moisture, oxygen groups, carbon, and impurities (organic and non-combustible residue). TGA measurements determining these parameters were performed using the provided optimized TGA protocol on the same GR2Ms by 12 participants across academia, industry stakeholders, and national metrology institutes. This paper presents these results with corresponding statistical analysis showing low standard deviation and statistical conformity across all participants that confirm that the TGA method can be satisfactorily used for characterization of these parameters and the chemical characterization and quality control of GR2Ms. The common measurement uncertainty for each parameter, key contribution factors were identified with explanations and recommendations for their elimination and improvements toward their implementation for the development of the ISO/IEC standard for chemical characterization of GR2Ms.

X-ray computed tomography using partially coherent Fresnel diffraction with application to an optical fiber.

A reconstruction algorithm for partially coherent x-ray computed tomography (XCT) including Fresnel diffraction is developed and applied to an optical fiber. The algorithm is applicable to a high-resolution tube-based laboratory-scale x-ray tomography instrument. The computing time is only a few times longer than the projective counterpart. The algorithm is used to reconstruct, with projections and diffraction, a tilt series acquired at the micrometer scale of a graded-index optical fiber using maximum likelihood and a Bayesian method based on the work of Bouman and Sauer. The inclusion of Fresnel diffraction removes some reconstruction artifacts and use of a Bayesian prior probability distribution removes others, resulting in a substantially more accurate reconstruction.

Bubble Point Measurements of Neopentane + Ethane Mixtures.

Bubble point measurements have been taken on three compositions of the neopentane + ethane system. The results are modeled with a Peng-Robinson equation with symmetrical mixing rule and a Helmholtz-energy-based 4-parameter model. Interaction parameters for all fits are provided. The results are consistent with other similar mixture systems (neopentane + propane and ethane + pentane) and demonstrate near ideal mixing.

Bubble-Point Measurements and Modeling of Binary Mixtures of Linear Siloxanes.

The bubble-point pressures of three binary mixtures of linear siloxanes have been measured. The binary mixtures consist of hexamethyldisiloxane (MM) which is mixed with either octamethyltrisiloxane (MDM), decamethyltetrasiloxane (MD2M), and dodecamethylpentasiloxane (MD3M). For each mixture, three compositions were measured where MM was present in approximately 25 mol%, 50 mol%, and 75 mol%. The bubble-point pressures were measured over a temperature range of 270 K to 380 K for all mixtures. Large uncertainties are observed for the lower temperatures (below 320 K) due to non-condensable impurities. A detailed analysis is performed to determine the effect of non-condensable gases on the measured bubble-point pressure data. The newly obtained bubble-point pressure data is used to determine new binary interaction parameters for the multicomponent Helmholtz energy model. The data used for the fitting of the binary interaction parameters are weighted by the relative uncertainty, this ensures that data points with high uncertainty contribute less to the final binary interaction parameter. In this work, a description of the experimental apparatus and measurement procedure is given, as well as the measured bubble-point pressure data and newly obtained binary interaction parameters.

Quantification of Carbon Nanotubes in Environmental Matrices: Current Capabilities, Case Studies, and Future Prospects.

Carbon nanotubes (CNTs) have numerous exciting potential applications and some that have reached commercialization. As such, quantitative measurements of CNTs in key environmental matrices (water, soil, sediment, and biological tissues) are needed to address concerns about their potential environmental and human health risks and to inform application development. However, standard methods for CNT quantification are not yet available. We systematically and critically review each component of the current methods for CNT quantification including CNT extraction approaches, potential biases, limits of detection, and potential for standardization. This review reveals that many of the techniques with the lowest detection limits require uncommon equipment or expertise, and thus, they are not frequently accessible. Additionally, changes to the CNTs (e.g., agglomeration) after environmental release and matrix effects can cause biases for many of the techniques, and biasing factors vary among the techniques. Five case studies are provided to illustrate how to use this information to inform responses to real-world scenarios such as monitoring potential CNT discharge into a river or ecotoxicity testing by a testing laboratory. Overall, substantial progress has been made in improving CNT quantification during the past ten years, but additional work is needed for standardization, development of extraction techniques from complex matrices, and multimethod comparisons of standard samples to reveal the comparability of techniques.

Bubble-Point Measurements of n-Propane + n-Decane Binary Mixtures with Comparisons of Binary Mixture Interaction Parameters for Linear Alkanes.

To develop comprehensive models for multicomponent natural gas mixtures, it is necessary to have binary interaction parameters for each of the pairs of constituent fluids that form the mixture. The determination of accurate mixture interaction parameters depends on reliably collected experimental data. In this work, we have carried out an experimental campaign to measure the bubble-point pressures of mixtures of n-propane and n-decane, a mixture that has been thus far poorly studied with only four existing data sets. The experimental measurements of bubble-point states span a composition range (in n-propane mole fraction) from 0.269 to 0.852, and the bubble-point pressures are measured in the temperature range from 270 K to 370 K. These data, in conjunction with data from a previous publication on mixtures of n-butane + n-octane and n-butane + n-nonane, are used to determine binary interaction parameters. The newly-obtained binary interaction parameters for the mixture of n-propane and n-decane represent the experimental bubble-point pressures given here to within 8% (coverage factor, k=2), as opposed to previous deviations up to 19%.

Predicting enzyme adsorption to lignin films by calculating enzyme surface hydrophobicity.

The inhibitory action of lignin on cellulase cocktails is a major challenge to the biological saccharification of plant cell wall polysaccharides. Although the mechanism remains unclear, hydrophobic interactions between enzymes and lignin are hypothesized to drive adsorption. Here we evaluate the role of hydrophobic interactions in enzyme-lignin binding. The hydrophobicity of the enzyme surface was quantified using an estimation of the clustering of nonpolar atoms, identifying potential interaction sites. The adsorption of enzymes to lignin surfaces, measured using the quartz crystal microbalance, correlates to the hydrophobic cluster scores. Further, these results suggest a minimum hydrophobic cluster size for a protein to preferentially adsorb to lignin. The impact of electrostatic contribution was ruled out by comparing the isoelectric point (pI) values to the adsorption of proteins to lignin surfaces. These results demonstrate the ability to predict enzyme-lignin adsorption and could potentially be used to design improved cellulase cocktails, thus lowering the overall cost of biofuel production.

Findings and Recommendations from the NIST Workshop on Alternative Fuels and Materials: Biocorrosion.

In 2013, the Applied Chemicals and Materials Division of the National Institute of Standards and Technology (NIST) hosted a workshop to identify and prioritize research needs in the area of biocorrosion. Materials used to store and distribute alternative fuels have experienced an increase in corrosion due to the unique conditions caused by the presence of microbes and the chemistry of biofuels and biofuel precursors. Participants in this workshop, including experts from the microbiological, fuel, and materials communities, delved into the unique materials and chemical challenges that occur with production, transport, and storage of alternative fuels. Discussions focused on specific problems including: a) the changing composition of "drop-in" fuels and the impact of that composition on materials; b) the influence of microbial populations on corrosion and fuel quality; and c) state-of-the-art measurement technologies for monitoring material degradation and biofilm formation.

Morphological and Electrical Characterization of MWCNT Papers and Pellets.

Six types of commercially available multiwall carbon nanotube soot were obtained and prepared into buckypapers by pellet pressing and by filtration into a paper. These samples were evaluated with respect to thickness, compressibility and electrical conductivity. DC conductivity results by two-point and four-point (van der Pauw) measurement methods as a function of preparation parameters are presented. Topology was investigated qualitatively by way of scanning electron microscopy and helium ion microscopy and from this, some generalizations about the nanotube structural properties and manufacturing technique with respect to conductivity are given.

Determination of nanoparticle surface coatings and nanoparticle purity using microscale thermogravimetric analysis.

The use of nanoparticles in some applications (i.e., nanomedical, nanofiltration, or nanoelectronic) requires small samples with well-known purities and composition. In addition, when nanoparticles are introduced into complex environments (e.g., biological fluids), the particles may become coated with matter, such as proteins or lipid layers. Many of today's analytical techniques are not able to address small-scale samples of nanoparticles to determine purity and the presence of surface coatings. Through the use of an elevated-temperature quartz crystal microbalance (QCM) method we call microscale thermogravimetric analysis, or µ-TGA, the nanoparticle purity, as well as the presence of any surface coatings of nanomaterials, can be measured. Microscale thermogravimetric analysis is used to determine the presence and amount of surface-bound ligand coverage on gold nanoparticles and confirm the presence of a poly(ethylene glycol) coating on SiO2 nanoparticles. Results are compared to traditional analytical techniques to demonstrate reproducibility and validity of µ-TGA for determining the presence of nanoparticle surface coatings. Carbon nanotube samples are also analyzed and compared to conventional TGA. The results demonstrate µ-TGA is a valid method for quantitative determination of the coatings on nanoparticles, and in some cases, can provide purity and compositional data of the nanoparticles themselves.

Hybrid phospholipid bilayer coatings for separations of cationic proteins in capillary zone electrophoresis.

Protein separations in CZE suffer from nonspecific adsorption of analytes to the capillary surface. Semipermanent phospholipid bilayers have been used to minimize adsorption, but must be regenerated regularly to ensure reproducibility. We investigated the formation, characterization, and use of hybrid phospholipid bilayers (HPBs) as more stable biosurfactant capillary coatings for CZE protein separations. HPBs are formed by covalently modifying a support with a hydrophobic monolayer onto which a self-assembled lipid monolayer is deposited. Monolayers prepared in capillaries using 3-cyanopropyldimethylchlorosilane (CPDCS) or n-octyldimethylchlorosilane (ODCS) yielded hydrophobic surfaces with lowered surface free energies of 6.0 ± 0.3 or 0.2 ± 0.1 mJ m(-2) , respectively, compared to 17 ± 1 mJ m(-2) for bare silica capillaries. HPBs were formed by subsequently fusing vesicles comprised of 1,2-dilauroyl-sn-glycero-3-phosphocholine or 1,2-dioleoyl-sn-glycero-3-phosphocholine to CPDCS- or ODCS-modified capillaries. The resultant HPB coatings shielded the capillary surface and yielded reduced electroosmotic mobility (1.3-1.9 × 10(-4) cm(2) V(-1) s(-1) ) compared to CPDCS- and ODCS-modified or bare capillaries (3.6 ± 0.2 × 10(-4) cm(2) V(-1) s(-1) , 4.8 ± 0.4 × 10(-4) cm(2) V(-1) s(-1) , and 6.0 ± 0.2 × 10(-4) cm(2) V(-1) s(-1) , respectively), with increased stability compared to phospholipid bilayer coatings. HPB-coated capillaries yielded reproducible protein migration times (RSD ≤ 3.6%, n ≥ 6) with separation efficiencies as high as 200 000 plates/m.

Stabilized phospholipid membranes in chromatography: toward membrane protein-functionalized stationary phases.

Transmembrane protein (TMP)-functionalized materials have resulted in powerful new methods in chemical analysis. Of particular interest is the development of high-throughput, TMP-functionalized stationary phases for affinity chromatography of complex mixtures of analytes. Several natural and synthetic phospholipids and lipid mimics have been used for TMP reconstitution, although the resulting membranes often lack the requisite chemical and temporal stability for long-term use, a problem that is exacerbated in flowing separation systems. Polymerizable lipids with markedly increased membrane stability and TMP functionality have been developed over the past two decades. More recently, these lipids have been incorporated into a range of analytical methods, including separation techniques, and are now poised to have a significant impact on TMP-based separations. Here, we describe current methods for preparing TMP-containing stationary phases and examine the potential utility of polymerizable lipids in TMP affinity chromatography.

Transmission electron imaging and diffraction of asbestos fibers in a scanning electron microscope.

Test protocols for airborne clearance of asbestos abatement sites define the collection, imaging and quantification of asbestos with transmission electron microscopy (TEM). Since those protocols were developed 35 years ago, scanning electron microscope (SEM) capabilities have significantly improved and expanded, with improvements in image spatial resolution, elemental analysis, and transmission electron diffraction capabilities. This contribution demonstrates transmission electron imaging and diffraction using NIST Asbestos Standard Reference Materials and a conventional SEM to provide comparable identification and quantification capabilities in the SEM as the current regulatory methods based on TEM techniques. In particular, we demonstrate that the 0.53 nm layer line spacing that is characteristic of asbestos can be quantified using different detection methods, and that other identifying diffraction signatures of chrysotile are readily obtained. The results demonstrate a viable alternative to the current TEM-based methods for asbestos identification and classification.

Universalized and robust length separation of carbon and boron nitride nanotubes with improved polymer depletion-based fractionation.

Partitioning nanoparticles by shape and dimension is paramount for advancing nanomaterial standardization, fundamental colloidal investigations, and technologies such as biosensing and digital electronics. Length-separation methods for single-walled carbon nanotubes (SWCNTs) have historically incurred trade-offs in precision and mass throughput, and boron nitride nanotubes (BNNTs) are a rapidly emerging material analogue. We extend and detail a polymer precipitation-based method to fractionate populations of either nanotube type at significant mass scale for four distinct nanotube sources of increasing average diameter (0.7 nm to >2 nm). Such separations result in a supernant phase containing shorter nanotubes and a pellet phase containing the longer nanotubes, with the threshold length for depletion decreasing with increasing polymer concentration. Cross-comparison through analytical ultracentrifugation, spectroscopy, and microscopy versus applied polymer concentration show tailorable and precise length fractionation for 100 nm through >1 µm rod lengths, with fractionation also designable to remove non-nanotube impurities. The threshold length of depletion is further found to increase for decreasing nanotube diameter at fixed polymer concentration, a finding consistent with scaling attributable to nanotube radial excluded volume. The capabilities demonstrated herein promise to significantly advance nanotube implementation within the scientific community.

Statistical sampling of carbon nanotube populations by thermogravimetric analysis.

Carbon nanotubes are one of the most promising nanomaterials available with applications in electronics devices, sensing, batteries, composites and medicine. Strict control of the carbon nanotube chemistry and properties is necessary as the applications proceed into more specialized areas. Thermogravimetric analysis (TGA) is one analytical method currently utilized for the characterization of carbon nanotubes. Though TGA can provide quantitative measurements of the composition of a sample, many researchers do not ensure the variance of the sample is properly captured. This research demonstrates for four single-wall carbon nanotube (SWCNT) samples how to statistically evaluate the material with TGA to ensure that the variance within the material is represented. SEM results are used to help reach conclusions about purity of the material by providing a visual means for inspection. This data is used to select the SWCNT material with the lowest variability and highest quality, as evaluated by composition and reproducibility.

Detailed Analysis of the Synthesis and Structure of MAX Phase (Mo0.75V0.25)5AlC4 and Its MXene Sibling (Mo0.75V0.25)5C4.

MAX phases with the general formula Mn+1AXn are layered carbides, nitrides, and carbonitrides with varying stacking sequence of layers of M6X octahedra and the A element depending on n. While "211" MAXphases (n = 1) are very common, MAX phases with higher n, especially n ≥ 3, have hardly been prepared. This work addresses open questions regarding the synthesis conditions, structure, and chemical composition of the "514" MAX phase. In contrast to literature reports, no oxide is needed to form the MAX phase, yet multiple heating steps at 1,600 °C are required. Using high-resolution X-ray diffraction, the structure of (Mo1-xVx)5AlC4 is thoroughly investigated, and Rietveld refinement suggests P-6c2 as the most fitting space group. SEM/EDS and XPS show that the chemical composition of the MAX phase is (Mo0.75V0.25)5AlC4. It was also exfoliated into its MXene sibling (Mo0.75V0.25)5C4 using two different techniques (using HF and an HF/HCl mixture) that lead to different surface terminations as shown by XPS/HAXPES measurements. Initial investigations of the electrocatalytic properties of both MXene versions show that, depending on the etchant, (Mo0.75V0.25)5C4 can reduce hydrogen at 10 mA cm-2 with an overpotential of 166 mV (HF only) or 425 mV (HF/HCl) after cycling the samples, which makes them a potential candidate as an HER catalyst.

Quartz crystal microbalances for microscale thermogravimetric analysis.

A new method for analyzing the chemical purity and consistency of microscale samples with a quartz crystal microbalance (QCM) sensor platform is described. The QCM is used to monitor submicrogram changes in the mass of a deposited thin film as a function of temperature, in a manner similar to that of a conventional thermogravimetric analyzer (TGA). Results correlated well with TGA measurements for a wide range of representative materials, including organic compounds, ionic detergents, oxidizing and inert powders, carbon nanotubes, and various mixtures of these samples. In each case, the sample mass was on the order of a few micrograms, compared to the need for several milligrams for conventional TGA analysis. This work illustrates the effectiveness of this approach for analysis of nanoparticles, thin films, and highly purified specimens on the microgram scale.

Applications of TGA in quality control of SWCNTs.

Carbon nanotubes exhibit a range of chemistries, including mixtures of different nanotube diameters, lengths, and chiralities coupled with various concentrations of metallic and non-nanotube-carbon impurities. The performance of a given material for a specific application depends on the chemistry, which is dictated in large part by the manufacturing process. Here, thermogravimetric analysis is utilized as a bulk characterization method for determining nanotube quality after manufacturing. The application of thermogravimetric analysis for quantifying basic nanotube chemistry is described (e.g., carbon-to-metal content, homogeneity). In addition, extension of the method to analyze specific nanotube properties (i.e., length and diameter) is reported. Results indicate that thermogravimetric analysis is sufficiently sensitive to enable quality control at both the macro-scale (carbon-to-metal ratio) and nano-scale (single-walled to multi-walled) and can detect subtle modifications in manufacturing processes.

Exfoliated transition metal dichalcogenide nanosheets for supercapacitor and sodium ion battery applications.

Growing concerns regarding the safety, flammability and hazards posed by Li-ion systems have led to research on alternative rechargeable metal-ion electrochemical storage technologies. Among the most notable of these are Na-ion supercapacitors and batteries, motivated, in part, by the similar electrochemistry of Li and Na ions. However, sodium ion batteries (SIBs) come with their own set of issues, especially the large size of the Na+ ion, its relatively sluggish kinetics and low energy densities. This makes the development of novel materials and appropriate electrode architecture of absolute significance. Transition metal dichalcogenides (TMDs) have attracted a lot of attention in this regard due to their relative ease of exfoliation, diverse morphologies and architectures with superior electronic properties. Here, we study the electrochemical performance of Mo-based two-dimensional (2D) layered TMDs (e.g. MoS2, MoSe2 and MoTe2), exfoliated in a superacid, for battery and supercapacitor applications. The exfoliated TMD flakes were interfaced with reduced graphene oxide (rGO) to be used as composite electrodes. Electron microscopy, elemental mapping and Raman spectra were used to analyse the exfoliated material and confirm the formation of 2D TMD/rGO layer morphology. For supercapacitor applications in aqueous electrolyte, the sulfide-based TMD (MoS2) exhibited the best performance, providing an areal capacitance of 60.25 mF cm-2. For SIB applications, TMD electrodes exhibited significantly higher charge capacities than the neat rGO electrode. The initial desodiation capacities for the composite electrodes are 468.84 mAh g-1 (1687.82 C g-1), 399.10 mAh g-1 (1436.76 C g-1) and 387.36 mAh g-1 (1394.49 C g-1) for MoS2, MoSe2 and MoTe2, respectively. Also, the MoS2 and MoSe2 composite electrodes provided a coulombic efficiency of near 100 % after a few initial cycles.

Enzymes in Commercial Cellulase Preparations Bind Differently to Dioxane Extracted Lignins.

Commercial fungal cellulases used in biomass-to-biofuels processes can be grouped into three general classes: native, augmented, and engineered. Colorimetric assays for general glycoside hydrolase activities showed distinct differences in enzyme binding to lignin for each enzyme activity. Native cellulase preparations demonstrated low binding of endo- and exocellulases, high binding of xylanase, and moderate binding for ß-D-glucosidases. Engineered cellulase formulations exhibited low binding of exocellulases, very strong binding of endocellulases and ß-D-glucosidase, and mixed binding of xylanase activity. The augmented cellulase had low binding of exocellulase, high binding of endocellulase and xylanase, and moderate binding of ß-D-glucosidase activities. Bound and unbound activities were correlated to general molecular weight ranges of proteins as measured by loss of proteins bands in bound fractions on SDS-PAGE gels. Lignin-bound high molecular weight bands correlated to binding of ß-D-glucosidase activity. Whereas ß-D-glucosidases demonstrated high binding in many cases, they have been shown to remain active. Bound low molecular weight bands correlated to xylanase activity binding. Contrary to other literature, exocellulase activity did not show strong lignin binding. The variation in enzyme activity binding between these three classes of cellulases preparations indicates that it is possible to alter the binding of specific glycoside hydrolase activities during the enzyme formulation process. It remains unclear whether or not loss of endocellulase activity to lignin binding is problematic for biomass conversion.