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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Cellulose Nanocrystals are a Renewable and Biocompatible Nanocarrier of Agrochemicals Directly to Plant Cells

More sustainable agricultural practices are critical to meeting humanity's food needs while minimizing adverse environmental impacts. Engineered nanomaterials used as nanocarriers promise to reduce the volume of agrochemicals required for crop production but concerns about nanocontamination of agricultural products necessitate the discovery of naturally occurring alternatives. Here, in this study, plant‐derived cellulose nanocrystals (CNC) as a “green” alternative to man‐made nanomaterials for the economical delivery of agrochemicals to plants are suggested. Using confocal microscopy and fluorescently labeled CNC, it is demonstrated that CNC can successfully penetrate the plant cell wall and enter cells without causing any negative effects on the overall plant phenotype, genome, and metabolome. The efficiency of CNC to deliver chemicals is demonstrated through in vitro tests involving CNC covalently conjugated with 2,4‐dichlorophenoxyacetic acid (2,4‐D). Plant cell culture experiments confirmed that CNC can be used as a 2,4‐D nanocarrier and reduces the volume of plant growth regulators needed to cultivate plant cells. This work creates a new platform for cyclical agricultural practices where CNC extracted from agricultural waste can be used for the direct delivery of agrochemicals to crops, thereby reducing the environmental burden created by both agricultural waste and excess herbicides.

Cellulose nanocrystals↗
DOE OSTI2023

Relaxation dynamics of water in the vicinity of cellulose nanocrystals

Water molecules near cellulose nanocrystals (CNCs; produced via the sulfuric acid-catalyzed hydrolysis of wood pulp) are believed to relax slower than those in the bulk liquid, which may result in unique properties of CNC aqueous dispersions. Herein this study analyzed the polarization behavior of water molecules in CNC aqueous dispersions and other reference samples using a dielectric relaxation spectroscopy (DRS) technique in the microwave frequency range (0.2–20 GHz). As the CNC concentration increases, two slow relaxation components become prominent. The comparison with DRS data of aqueous dispersions of nanoporous silica, polyvinyl alcohol (PVA), and hairy CNC (HCNC) with amorphous chains protruding from both ends suggested that these slow relaxation modes of water near CNC surfaces cannot be attributed to direct hydrogen bonding interactions with the hydroxyl (OH) groups exposed and immobilized at the solid surface. Instead, they are similar to the water molecules interacting with OH groups attached to flexible polymer chains. Molecular dynamics (MD) simulations of the polarization behavior of water near the (110) facet of cellulose Iβ crystals confirmed that the interactions of water molecules with the cellulose crystal surface do not cause slower relaxations in the frequency range studied via the DRS. These results indicated that the CNC surface cannot be depicted with the crystallographic facets of cellulose Iβ; instead, it resembles a polymer-brush surface on which the short glucan residues or fragments of the strong acid-catalyzed hydrolysis process are swollen and extended into the aqueous phase.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Cylindrical Confinement of Nanocolloidal Cholesteric Liquid Crystal

The organization of nanocolloidal liquid crystals in constrained geometries has fundamental and practical importance, since under confinement, liquid crystals contain stable topological defects that can serve as templates for nanoparticle organization. Three-dimensional confinement of cholesteric (Ch) liquid crystals formed by cellulose nanocrystals (CNCs) have been extensively studied; however, their two-dimensional confinement remains underinvestigated. In this work, we report the results of systematic experimental studies of two-dimensional confinement of Ch–CNC liquid crystal in cylindrical capillaries with varying inner diameters. Confinement resulted in phase separation of the Ch–CNC liquid crystal into a Ch shell formed by concentric CNC pseudolayers with the helicoidal axis perpendicular to the inner surface of the capillary walls, and a micrometer-diameter isotropic core thread running parallel to the long axis of the capillary. The morphology of the confined Ch–CNC liquid crystal varied when progressively increasing the degree confinement. Finally, we show that phase separation of the Ch–CNC liquid crystal into a Ch shell and an isotropic core is preserved in flexible capillary tubing, suggesting the applicability of this system for the fabrication of flexible optical waveguides.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Ion-Conducting Thermoresponsive Films Based on Polymer-Grafted Cellulose Nanocrystals

Mechanically robust, thermo-responsive, ion-conducting nanocomposite films are prepared from poly(2-phenylethyl methacrylate) grafted cellulose nanocrystals (MxG-CNC-g-PPMA). One-component nanocomposite films of the polymer grafted nanoparticle (PGN) MxG-CNC-g-PPMA are imbibed with 30 wt% imidazolium-based ionic liquid, to produce flexible ion-conducting films. These films with 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (MxG-CNC-g-PPMA/[H]) not only displays remarkable improvements in toughness (>25 times) and tensile strength (>70 times) relative to the corresponding nanocomposites consisting of the ionic liquid imbibed in the two component CNC/PPMA nanocomposite, but also shows higher ionic conductivity than the corresponding neat PPMA with the same wt.% of ionic liquid. Notably, the one-component film containing 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (MxG-CNC-g-PPMA/[E]) exhibits temperature responsive ionic conduction. The ionic conductivity decreases at around 60°C as a consequence of the lower critical solution temperature (LCST) phase transition of the grafted polymer in the ionic liquid, which leads to phase separation. Moreover, holding the MxG-CNC-g-PPMA/[E] film at room temperature for 24 hours returns the film to its original homogenous state. These materials exhibit properties relevant to thermal cutoff safety devices (e.g., thermal fuse) where a reduction in conductivity above a critical temperature is needed.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Chemically Cross-Linked Cellulose Nanocrystal Aerogels for Effective Removal of Cation Dye

In this study, porous aerogels were prepared by directional freeze-drying via cross-linking cellulose nanocrystals (CNCs) with poly(methyl vinyl ether-co-maleic acid) (PMVEMA) and poly(ethylene glycol) (PEG). The thermal properties and physical adsorption performance toward cation methylene blue dye of the obtained CNC aerogels were investigated. The maximum degradation temperature was increased from 324°C of CNCs to 355°C of cross-linked CNC aerogels. The dye adsorption isotherm results showed that the maximum methylene blue adsorption capacity of CNC aerogels was 116.2 mg g −1 , according to the Langmuir model, which was mainly due to the electrostatic attractions between negatively charged carboxyl groups or sulfonate groups on the CNC aerogles and cation MB molecules. The reusability test showed that the CNC aerogels contained the same dye adsorption performance in five adsorption/desorption cycles. Overall, this study described an ideal alternative for water purification with high dye adsorption capacity and enhanced physical performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Computer-controlled finishing via dynamically constraint position-velocity-time scheduler

In a Computer Numerical Controlled (CNC) finishing process, the target material removal from an optical surface is guided by the convolution between the influence function of a machine tool and its dwell time at certain points over the surface. To reduce dynamics stressing and increase machining efficiency, the dwell time must be converted to varying velocities, which are the actual inputs to the machine tool controller. Conventionally, the conversion assumed constant acceleration and relied on linear motion interpolation, which caused discontinuities in velocities. This unsmooth motion affects the material removal distribution, and, thus, the accuracy of the finished surface shape. Many modern CNC machines support the smoother, cubic-polynomial interpolated Position-Velocity-Time (PVT) motion mode; however, the conventional scheduler may fail to provide suitable velocities for the PVT. Here in this study answers this challenge by proposing a novel PVT-based velocity scheduler that achieves smooth motion while considering CNC dynamic limits. Firstly, the principle of the PVT is explained, and the PVT-based velocity scheduler is formulated. Secondly, a quadratic programming is used to optimize the velocities by imposing the CNC dynamic constraints and the C 1 continuities (zeroth and first derivatives are continuous) simultaneously. Thirdly, the smoothness and accuracy of the scheduled velocities are studied on different kinds of tool paths via simulation. Finally, a sub-0.3 nm level surface finishing experiment using ion beam figuring is demonstrated to verify the feasibility of the proposed method. The PVT-based scheduler and simulator code is open-sourced.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Minimizing Oxygen Permeability in Chitin/Cellulose Nanomaterial Coatings by Tuning Chitin Deacetylation

The demand for packaging materials with low gas permeabilities is increasing, but commonly used petroleum-derived single-use plastics are not renewable, biodegradable, or easy to recycle. Nanomaterials composed of chitin and cellulose, which are abundant in nature, have high crystallinities and low oxygen permeabilities (OP), providing a viable alternative. In this work, we explore how deacetylation conditions of crab shell chitin can be used to tune the charge and size of resulting chitin nanowhiskers (ChNWs) and the resulting OP of layered film structures. Three deacetylation factors, the concentration of sodium hydroxide (%NaOH), temperature (T), and reaction time, were explored using a three-factor three-level Taguchi design with an orthogonal array. Furthermore, the resulting ChNW suspensions were sequentially spray-coated with suspensions of cellulose nanocrystals (CNCs) onto cellulose acetate (CA) films to form a multilayer structure. We show that ChNWs prepared under more aggressive deacetylation conditions inside the original orthogonal array (higher %NaOH, T, and time) had shorter lengths but the surface charge was significantly influenced only by more aggressive deacetylation outside of the original design conditions. With only ~10% decrease in the ultimate tensile strength and no significant loss in failure strain, the ChNW-CNC coating resulted in ~20% decrease in WVTR in comparison to uncoated CA films. The optimization of process conditions resulted in CA-ChNW-CNC films with a 91-99% decrease in OP (132-16.7 cm 3 ∙μm/m 2 /day/kPa versus 1553 cm3∙μm/m2/day/kPa for uncoated CA).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Lignocellulosic Biomass-Derived Nanocellulose Crystals as Fillers in Membranes for Water and Wastewater Treatment: A Review

The improvement of membrane applications for wastewater treatment has been a focal point of research in recent times, with a wide variety of efforts being made to enhance the performance, integrity and environmental friendliness of the existing membrane materials. Cellulose nanocrystals (CNCs) are sustainable nanomaterials derived from microorganisms and plants with promising potential in wastewater treatment. Cellulose nanomaterials offer a satisfactory alternative to other environmentally harmful nanomaterials. However, only a few review articles on this important field are available in the open literature, especially in membrane applications for wastewater treatment. This review briefly highlights the circular economy of waste lignocellulosic biomass and the isolation of CNCs from waste lignocellulosic biomass for membrane applications. The surface chemical functionalization technique for the preparation of CNC-based materials with the desired functional groups and properties is outlined. Recent uses of CNC-based materials in membrane applications for wastewater treatment are presented. In addition, the assessment of the environmental impacts of CNCs, cellulose extraction, the production techniques of cellulose products, cellulose product utilization, and their end-of-life disposal are briefly discussed. Furthermore, the challenges and prospects for the development of CNC from waste biomass for application in wastewater treatment are discussed extensively. Finally, this review unraveled some important perceptions on the prospects of CNC-based materials, especially in membrane applications for the treatment of wastewater.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

A machining digital twin for hybrid manufacturing

Hybrid manufacturing consisting of metal additively manufactured preforms and computer numerical control (CNC) machining has been established to be an effective method for high material use rates. However, hybrid manufacturing introduces unique challenges. Near-net shape designs are typically selected, which result in a smaller margin for part placement within the stock and stringent requirements for work coordinate system identification. Additionally, less stock material reduces the preform stiffness, which limits the material removal rates during machining. This paper demonstrates a digital twin for CNC machining of a wire arc additively manufactured preform that implements: 1) structured light scanning for stock model identification and tool path generation; 2) a fused filament fabrication apparatus to attach temporary fiducials and scan targets to the preform that enable coordinate system definition for both the CAM and CNC machine; 3) preform and tool tip frequency response function measurements to enable stable milling parameter selection; and 4) post-manufacturing measurements of geometry, surface finish, and structural dynamics to confirm designer intent. These efforts define key components of the machining digital twin for hybrid manufacturing.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Enhanced Ion Conductivity through Hydrated, Polyelectrolyte-Grafted Cellulose Nanocrystal Films

Here,iIonically conductive, hydrated polyelectrolyte nanocomposites are prepared from iodomethane-treated poly(2-vinylpyridine) (mPV)-grafted cellulose nanocrystals (MxG-CNC-g-mPV). These polyelectrolyte-grafted nanoparticle (PEGN) films exhibit an order-of-magnitude higher iodide ion conductivity relative to mPV films and a high in-plane/through-plane anisotropy. The PEGN architecture prevents CNC aggregation, maximizing the CNC/polyelectrolyte interface. PEGN films were prepared with varying polymer graft density (0.03-0.12 chains/nm 2 ) and molecular weight (7k-30k g/mol). The greatest ion conductivity enhancement is observed with lower molecular weight, higher density grafts: ca. 89 ± 6 mS/cm (140 ±10 mS/cm accounting for the volume of the CNC) versus 3.3 ± 0.4 mS/cm for ungrafted mPV. Poly(styrene-block-2-vinylpyridine)-grafted CNCs were prepared in which the insulating polystyrene block or the conducting mPV block was directly attached to the CNCs; only the films with the mPV block closest to the CNCs exhibited an enhancement in conductivity relative to mPV. Together, these data point to beneficial CNC/polyelectrolyte interfacial effects, resulting in significant ionic conductivity enhancement along the length of the CNCs in these films.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Effect of Graft Molecular Weight and Density on the Mechanical Properties of Polystyrene-Grafted Cellulose Nanocrystal Films

In this work, polymer-grafted nanoparticle (PGN) films were prepared from polystyrene (PS) grafted to rodlike cellulose nanocrystals (MxG-CNC-g-PS) with a controllable grafting density (0.03–0.25 chains/nm 2 ) and molecular weight (5–60 kg/mol). These nanorod-based PGNs are solution- and melt-processible, permitting access to one-component composite films with high nanofiller loadings (with up to 55 wt %). The impact of both grafted polymer density and molecular weight on the mechanical properties of the films was investigated and related to the polymer brush conformation: concentrated polymer brush (CPB), semidilute polymer brush (SDPB), or CPB core with SDPB corona (CPB/SDPB). The rubbery regime storage modulus (above $T_g$) showed 2 orders of magnitude increase, maximizing at a low degree of polymerization (N) and low grafting density (σ). Fracture toughness was maximized in samples with the grafted polymer in the SDPB or CPD/SDPB (higher N and relatively low σ) regime and showed enhancement relative to PS of molecular weight similar to the graft. In line with prior computation predictions, optimizing for both rubbery modulus and fracture toughness in such nanorod-based PGN films requires the polymers in the SDPB regime and CNC loading levels (ca. 50–60 wt %) that are difficult to attain in more traditional two-component CNC composites.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Surface-Functionalized Cellulose Nanocrystals as Nanofillers for Crosslinking Processes: Implications for Thermosetting Resins

Understanding the response of fillers in the epoxy resin crosslinking process and characterizing polymer–filler dynamics are the key features that guide the engineering of new thermosetting resin composites. Here, in this work, X-ray photon correlation spectroscopy (XPCS) is used as a thermal analysis tool to track the microscopic changes occurring during the cure of a functionalized cellulose nanocrystal (mCNC)–epoxy composite. In contrast, traditional methods such as differential scanning calorimetry (DSC) and curing rheology are used to understand the kinetics and properties on macroscopic length scales. Of interest is the influence of the mCNC on the curing kinetics and properties of the thermosetting resin. Two levels of modification (increasing hydrophobicity) were chosen to observe the effect of functionalization. Before cure, the highly functionalized CNC (mCNC3) shows a 44% increase in complex viscosity (η*), while the less functionalized CNC (mCNC2) shows a η* value similar to that of the neat resin. As the cure cycle progresses, results from DSC, rheology, and XPCS further show the enhancement in dispersion for mCNC3. The results show a clear difference in the maximum drift velocity, maximum heat flow, and complex viscosity during the ramp to the isothermal cure temperature (T cure ). Such results suggest that mCNC3 contains a well-dispersed network of particles due to the higher level of functionalization. During T cure , a transition in elastic modulus (G') occurs only for the highly functionalized CNC particle system. We believe that heat-induced aggregation occurs, and the crosslinked resin ultimately dominates the macroscopic properties of the final cured system for all samples. The results from the three techniques are in good agreement and showcase XPCS as a beneficial experimental tool for characterizing the microscopic dynamics of particulate-filled thermosetting resins. Hence, we envision this to be a fundamental curing study for the design of thermosetting resin composites.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Mechanically tunable elastomer and cellulose nanocrystal composites as scaffolds for in vitro cell studies

Considering the range of properties that various materials offer for tissue engineering it has come clear that no one size fits all, as no one material can be fully effective for all types of cell and ensuing tissues. Scaffolds need to address the delicate balance between cell-scaffold interactions and the particular requirements of different cell types. To address the specific needs for the controlled growth of tissues it is imperative to match scaffold stiffness and elasticity to cells and tissues of interest to promote regeneration success. We here report an efficient method for creating scaffolds of tunable elasticity by generating a range of composites based on ε-caprolactone-D,L-lactide-based elastomer with cellulose nanocrystals (CNC). Two specific composites with different Young's modulus (E) values (~5 MPa and ~15 MPa) were selected and fully evaluated by tensile tests, Fourier Transform-Infrared (FT-IR), Scanning Electron Microscopy (SEM), contact angle measurements, and X-ray scattering. As a proof of concept this work studies how matching the scaffold's mechanical properties to neuroblastomas and fibroblasts cells affects cell behavior. Specifically, the composite with lower E, by design with less CNC content, is more suitable for neuroblastomas, whereas the one with higher E via higher CNC content is more suited for human dermal fibroblasts. The approach of matching cells with appropriate mechanical environments can provide important insights into fundamental cell behaviors.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Rapid Commissioning of Large Machine Tools Using Finite Element-Based Correction of Geometric Errors

Large computer numerical control (CNC) machine tools derive their stiffness from monolithic cast iron bases or weldments that are sometimes integral to machine motion systems like box ways or guideways. However, the sheer size of castings and even floor flatness deviations result in dimensional errors in these systems, which manifest as machine motion errors. Typical geometric alignment processes rely on an iterative approach, where measurements are taken to assess alignment (straightness, squareness, and parallelism), followed by adjustment of the machine supports (fixators or leveling pads), which can take weeks even for an experienced operator. Conversely, a novel method is proposed to shorten the correction time by eliminating the trial-and-error process in favor of a more deterministic approach guided by a finite element (FE) method. A feasibility study is conducted on a CNC polymer hybrid machine, with a steel weldment frame, supported by six leveling pads. An FE model of the frame is utilized to obtain recommended leveling pad adjustments, based on measurement of machine errors taken using a laser tracker. After a single adjustment cycle, measurements reveal that geometric errors of the machine tool are reduced from 2.22 mm of flatness deviation to 0.32 mm, achieving an 85.6% reduction. Furthermore, the entire process including measurement, adjustment, and assessment is completed in just 6 h by two operators who are not professional service engineers. In conclusion, this methodology demonstrates feasibility for scaling up, especially to large, high-precision CNC machine tools with bases mounted by fixators, offering the capability for bidirectional adjustment.

42 ENGINEERING↗
DOE OSTI2023

Manufacturing Demonstration Facility: Development and Evaluation of Hybrid Manufacturing Toolpaths

The integration of additive manufacturing (AM) capabilities on Computer Numerical Control (CNC) systems allows for the expansion of additive manufacturing to a wide range of part and tool repair operations. This multi-tasking integration, termed hybrid manufacturing, has been researched by others in the past, and Autodesk has been critical in developing process planning and toolpath algorithms for hybrid systems. Objectives and Tasks: Hybrid manufacturing systems enable both additive and subtractive capabilities in a single manufacturing workcell. These systems have the potential to impact a variety of industries, including the tool and die industry due to their repair, refurbishment, and complex geometry manufacturing capabilities. While there has been significant development of toolpath planning for both subtractive and additive processes independently, there has been little, if any, development of hybrid toolpath planning to integrate both processes during the manufacturing design and toolpath generation stage of a product’s lifecycle. Furthermore, additive toolpath planning has been limited to planar manufacturing, but this limitation could be overcome as hybrid CNC machines have multi-axis control. The objectives of this research include: - Development and demonstration of independent three-, four-, and five-axis toolpath generation algorithms for both additive and subtractive processes, and - Development, demonstration, and integration of three-, four-, and five-axis hybrid process planning and toolpath generation algorithms for hybrid additive and subtractive processes. The team will leverage the widely used Autodesk Fusion 360 product design and manufacturing (CAD/CAM) platform to achieve these objectives. Autodesk will provide the expertise in CAD tools, as well as access to their new CAD/CAM manufacturing tools (3-, 4-, and 5-axis milling, additive toolpath generation). ORNL will provide expertise in additive manufacturing toolpath generation, process planning, and manufacturing validation. By the end of the program, the team will have developed and validated multi-axis milling, additive manufacturing, and hybrid manufacturing on an industrial hybrid CNC system (Mazak 500-VC).

42 ENGINEERING↗
DOE OSTI2023

LCA-based environmental sustainability assessment of hybrid additive manufacturing of a turbine blade

In this paper, a cradle-to-gate life cycle assessment (LCA) method is used to compare the overall energy consumption and environmental impact of hybrid additive manufacturing (HAM) and the traditional CNC milling process with a case study of turbine blade manufacturing. Six environmental impacts are assessed in this study: acidification potential (AP), eutrophication potential (EP), global warming potential (GWP), photochemical ozone creation potential (POCP), ozone depletion potential (ODP), and abiotic depletion potential (ADP). The results suggest that HAM can not only reduce energy consumption and material waste but also reduce the environmental impact by 53% from a life cycle perspective. Specifically, the results of GWP, AP, EP, ODP, POCP and ADP of the HAM are only 32.2%, 34.6 %, 44.7%, 27.2%, 25.6%, and 24.7 % of that in traditional CNC machining.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

pH‐ and Redox‐Responsive Pickering Emulsions Based on Cellulose Nanocrystal Surfactants

Abstract Nanoparticle surfactants (NPSs), formed by using dynamic interactions between nanoparticles and complementary ligands at the liquid‐liquid interface, have emerged as “smart emulsifiers” with attributes of high emulsification efficiency, long‐term stability, and on‐demand emulsification/demulsification capabilities. However, only pH‐responsiveness can be adopted for the assembly of reported NPSs formed by electrostatic interactions. Here, we propose an alternative design strategy, by taking advantage of the ferrocenium (Fc + ) sulfate ion pair, to develop a new type of cellulose nanocrystal (CNC) surfactant. The Fc + groups are sensitive to pH, redox reagents and voltage, imparting the CNC surfactants and derived Pickering emulsions with multi‐stimuli‐responsiveness, and showing promising applications in controllable delivery, release, and biphasic biocatalysis.

Yang, Yang↗
DOE OSTI2023

pH- and Redox-Responsive Pickering Emulsions Based on Cellulose Nanocrystal Surfactants

Nanoparticle surfactants (NPSs), formed by using dynamic interactions between nanoparticles and complementary ligands at the liquid-liquid interface, have emerged as “smart emulsifiers” with attributes of high emulsification efficiency, long-term stability, and on-demand emulsification/demulsification capabilities. However, only pH-responsiveness can be adopted for the assembly of reported NPSs formed by electrostatic interactions. Here, we propose an alternative design strategy, by taking advantage of the ferrocenium (Fc + ) sulfate ion pair, to develop a new type of cellulose nanocrystal (CNC) surfactant. In conclusion, the Fc + groups are sensitive to pH, redox reagents and voltage, imparting the CNC surfactants and derived Pickering emulsions with multi-stimuli-responsiveness, and showing promising applications in controllable delivery, release, and biphasic biocatalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗