Research Progress of Bonding Agents and Their Performance Evaluation Methods

Bonding agents are an important type of additive that are used to increase the interfacial interaction in propellants. A suitable bonding agent can prevent the dewetting between the oxidant and binder, and thus effectively improve the mechanical properties of the propellant. In the current paper, the bonding mechanisms and research progress of different types of bonding agents such as alcohol amine bonding agents, borate ester bonding agents, aziridine bonding agents, hydantoin bonding agents, neutral polymer bonding agents, and so on, are reviewed and discussed. The evaluation methods of their bonding performances including molecular dynamic simulation, contact angle method, in situ loading SEM, characterization analysis, and mechanical analysis are summarized to provide design ideas and reference for future studies.

Evaluation of Cashew Nut Shell Liquid Borate Ester as Pour Point Depressant for Flow Assurance of Waxy Crude Oil

The development of chemical solutions to wax problems by modifying renewable natural products is an innovative response to the need for cheaper, eco-friendly pour point depressants for waxy crude oil flow improvement. Natural cashew-nut shell liquid (CNSL) was extracted from shells of Anacardium occidentale and derivatized into the borate ester. Pour point of oil doped with 500ppm CNSL borate ester was reduced by -24oC. The effect of borate ester addition on wax morphology was studied by cross-polarized microscopy. Analysis of micrographs using ImageJ software showed a decrease in Feret diameter, aspect ratio, and boundary fractal dimension of wax crystals in doped oil and increased crystal circularity and solidity, indicating the evolution of smaller, rounder, regular structures with smoother, even surfaces. At 10oC, oil shear stress and dynamic viscosity were reduced by 27.6% and 24.6%, respectively. Pour point depressant and flow improvement effects of additive were related to changes in crystal morphology.

XANES Study of Tribofilm Formation With Low Phosphorus Additive Mixtures of Phosphonium Ionic Liquid and Borate Ester

The development of low phosphorus engine oils is important to minimize phosphorus-induced exhaust catalyst poisoning and resulting in harmful emissions. In this study, low phosphorus oil formulations were prepared by using an ashless additive mixture of borate ester (SB) with ionic liquid composed of a phosphonium cation and phosphate anion (P_DEHP) at 350 and 700 ppm phosphorus. Tribological properties of this binary additive system were evaluated using a reciprocating cylinder on a flat test configuration. Favorable interaction between P_DEHP and SB resulted in a significant reduction in friction coefficient and wear volume, in particular for P_DEHP(700P) + SB oil blend. Time-scale analysis of tribofilm formation was determined by running the tribological experiments for 5, 15, and 60 min duration. Electrical contact resistance (ECR) results revealed that the addition of P_DEHP at 350 ppm of phosphorus to SB at 500 ppm of boron can reduce the incubation time from 300 to 100 s for stable tribofilm formation. X-ray absorption near-edge spectroscopy (XANES) analysis of tribofilms indicates that the tribofilm mechanism for additive mixtures of P_DEHP and SB initially involves the formation of boron oxide-based films, which later interact with phosphorus to form boron phosphates in addition to iron phosphates. Incorporation of the high amount of boron phosphates in addition to boron oxide/acid and iron phosphates in the tribofilms contributed to the improved tribological performance of P_DEHP(700P) + SB oil. XANES results reveal that tribofilms formed due to the interaction of SB and P_DEHP evolve to a cross-linked structure, wherein the chain length of polyphosphates is increased with the increase in rubbing time.

Electrically programmable adhesive hydrogels for climbing robots

Although there have been notable advances in adhesive materials, the ability to program attaching and detaching behavior in these materials remains a challenge. Here, we report a borate ester polymer hydrogel that can rapidly switch between adhesive and nonadhesive states in response to a mild electrical stimulus (voltages between 3.0 and 4.5 V). This behavior is achieved by controlling the exposure and shielding of the catechol group through water electrolysis–induced reversible cleavage and reformation of the borate ester moiety. By switching the electric field direction, the hydrogel can repeatedly attach to and detach from various surfaces with a response time as low as 1 s. This programmable attaching/detaching strategy provides an alternative approach for robot climbing. The hydrogel is simply pasted onto the moving parts of climbing robots without complicated engineering and morphological designs. Using our hydrogel as feet and wheels, the tethered walking robots and wheeled robots can climb on both vertical and inverted conductive substrates (i.e., moving upside down) such as stainless steel and copper. Our study establishes an effective route for the design of smart polymer adhesives that are applicable in intelligent devices and an electrochemical strategy to regulate the adhesion.

Synthesis and structure of a 1:1 co-crystal of hexamethylenetetramine carboxyborane and acetaminophen

Hexamethylenetetramine carboacetaminophenborane, a molecule with two pharmacophores attached to a central carboxyborate moiety, was synthesized and crystals were grown with an acetaminophen co-crystal former to result in the title 1:1 co-crystal [hexamethylenetetramine 4-acetamidophenyl 2-boranylacetate–4-acetamidophenol (1/1)], C15H22BN5O3·C8H9NO2. In the first of these molecules, both the borate-ester and acetylamino groups are considerably twisted away from the plane of the intervening benzene ring [dihedral angles = 76.89 (9) and 65.42 (9)°, respectively]. The extended structure of this co-crystal features N—H...O and O—H...O hydrogen bonds, which link the components into (100) sheets and weak C—H...O hydrogen bonds help to consolidate the structure.

Locating Methyl-Etherified and Methyl-Esterified Uronic Acids in the Plant Cell Wall Pectic Polysaccharide Rhamnogalacturonan II

Rhamnogalacturonan II (RG-II) is a structurally complex pectic polysaccharide that exists as a borate ester cross-linked dimer in the cell walls of all vascular plants. The glycosyl sequence of RG-II is largely conserved, but there is evidence that galacturonic acid (GalA) methyl etherification and glucuronic acid (GlcA) methyl esterification vary in the A sidechain across plant species. Methyl esterification of the galacturonan backbone has also been reported but not confirmed. Here we describe a new procedure, utilizing aq. sodium borodeuteride (NaBD4)-reduced RG-II, to identify the methyl esterification status of backbone GalAs. Our data suggest that up to two different GalAs are esterified in the RG-II backbone. We also adapted a procedure based on methanolysis and NaBD4 reduction to identify 3-, 4-, and 3,4- O-methyl GalA in RG-II. These data, together with matrix-assisted laser desorption/ionization–time-of-flight mass spectrometry (MALDI-TOF) MS analysis of sidechain A generated from selected RG-IIs and their NaBD4-reduced counterparts, suggest that methyl etherification of the β-linked GalA and methyl esterification of the GlcA are widespread. Nevertheless, the extent of these modifications varies between plant species. Our analysis of the sidechain B glycoforms in RG-II from different dicots and nonpoalean monocots suggests that this sidechain has a minimum structure of an O-acetylated hexasaccharide (Ara-[MeFuc]-Gal-AceA-Rha-Api-). To complement these studies, we provide further evidence showing that dimer formation and stability in vitro is cation and borate dependent. Taken together, our data further refine the primary sequence and sequence variation of RG-II and provide additional insight into dimer stability and factors controlling dimer self-assembly.