Sulfur-containing Additives Research Articles

ChemInform Abstract: Baker′s‐Yeast‐Mediated Reduction of Sulfur‐Containing Compounds

AbstractReview: 149 refs.

Studies of the Effect of Varying Prop-1-Ene-1,3-Sultone (PES) Concentration on Li-Ion Batteries

Introduction Electrolyte additives are the most effective way to improve the calendar life and cycling performance of lithium-ion batteries. Vinylene carbonate (VC) is perhaps the most well-known additive for Li-ion batteries and has been shown to be useful during the solid electrolyte interphase (SEI) formation [1], which can result in longer calendar life and reduced irreversible capacity (IRC). However, it has been shown that the performance of cells containing VC decreases at high temperatures and high voltages. Sulfur-containing additives have been studied in hopes to overcome the temperature sensitivity of VC. Prop-1-ene-1,3-sultone (PES) was found to have smaller IRC than VC-containing cells and was suggested to be an SEI forming additive [2]. In this study, we show that PES is a useful additive for Li-ion pouch cells and suggest that PES, when used in combination with other additives, may be more effective than VC at achieving long lifetimes and high cycling performance. Experimental Li[Ni1/3Mn1/3Co1/3]O2 (NMC)/graphite pouch cells made with 1M LiPF6in EC:EMC 3:7 (by weight) and varying amounts of PES were studied using ultra high precision coulometry and storage experiments. In addition, gas evolution measurements employing Archimedes principle and electrochemical impedance spectroscopy (EIS) measurements were performed. The PES-containing cells were compared to the same control electrolyte containing 2% VC. Results Figure 1 shows a preliminary set of results from both storage and cycling experiments of PES-containing cells compared with control electrolyte and 2% VC-containing cells. The dotted line in Figures 1a, d, and e indicates the value for 2% VC. Figure 1a shows the gas evolution during formation at 40°C and Figures 1b and c show gas evolution during storage at 60°C and 40°C, respectively. Cells containing 2, 4 and 6% PES show smaller gas during formation than that of 2% VC and all concentrations of PES studied show significantly smaller gas during 40°C and 60°C storage than VC-containing cells. The most prominent advantage of PES compared to VC is the extremely low gas evolution during high temperature storage. Figure 1d shows the voltage drop during storage from 4.2 V at 40°C for 500 hours. Figure 1e shows the average coloumbic inefficiency (CIE) during the last three cycles of cycling between 2.8 V and 4.2 V at C/20 and 40°C. Through the voltage drop and CIE, it is clear that 2% PES appears to be as good as 2% VC. This work suggests that PES is a viable alternative to VC and is superior during high temperature storage. PES may also prove to be beneficial in combination with other additives.

The Impact of High-Voltage Electrolyte Additives and Solvents to 4.7 V Determined Using Isothermal Microcalorimetry

The use of electrolyte additives in lithium ion batteries can extend cycle life, increase coulombic efficiency, and reduce parasitic reactions [1]. Here, high resolution isothermal microcalorimetry [2, 3] is used to determine the impact of high-voltage electrolyte additives and solvents as a function of voltage up to 4.7 V in Li[Ni0.4Mn0.4Co0.2]O2(NMC442)/graphite pouch cells.Transitioning to increasingly higher upper cutoff voltages has proved difficult as many additives and solvents are unstable at such high potentials and the parasitic degradation of these components result in severely decreased lifetimes. The voltage-dependent impact of electrolyte additives, additive blends, and solvents that have shown to result in high coulombic efficiencies, reduced electrolyte oxidation, and other parasitic reactions, will be explored. Such components include additives such as vinylene carbonate (VC), methylene methanedisulfonate, ethylene sulfate, trimethylene sulfate, and others, as well as a variety of fluorinated solvents. By comparing the heat flow of cells that vary only in electrolyte composition during cycling and open circuit conditions, the effect of the additive on the parasitic heat during the entire potential range is obtained in a short, simple experiment. A TA instruments TAM III isothermal calorimeter equipped with twelve microcalorimeters was used for these measurements. The accuracy of the microcalorimeter used (< ±1 mW) allows for a highly sensitive differentiation between cells.Figure 1 shows the heat flow versus voltage for four machine-made 260 mAh NMC442/graphite pouch cells cycling at 10 mA (C/26) at 40oC with different additive blends. At this current, the contributions of entropy and polarization to the total heat flow are nearly identical between cells, such that any differences in measured heat are attributable to differences in parasitic heat. Figure 1 shows exceptional differences in the heat flow between the first charge (left) and subsequent charges (the fourth charge is shown as an example, right). The cells which produce the most heat during the first charge to 4.7 V have the smallest heat flow at the same potential for subsequent cycles. This is attributed to passivation-type reactions which, while initially producing vast amounts of heat, result in a reduction of parasitic reactions over the remainder of the cell life. Figure 1 also shows that the electrolyte blends with sulfur-containing additives reduce parasitic reactions compared to 2% VC-containing cells above 4.4 V, and continue to reduce these reactions with increasing state of charge. Similar results will be presented for a variety of high-voltage additives and solvents.While these electrolyte additives and solvents can reduce the heat due to parasitic reactions, the overall parasitic heat is still substantial at high potentials, as seen in Figure 1 by the dramatically increasing heat flow above 4.4 V. The results presented here clearly show the impact of high-voltage electrolyte additives and solvents and directly determine their optimal potential ranges to minimize parasitic reactions and therefore extend cell lifetimes.

Tribological properties of phenolic resin bonded abrasive tools filled with two inclusion complexes of β-cyclodextrin and sulfur-containing additives

In this work, three kinds of phenolic resin bonded abrasive tool specimens containing β-cyclodextrin or its two complexes with dialkyl pentasulfide and sulfurized isobutylene at different contents were prepared by a cold compression method, respectively. The tribological properties of these abrasive tool specimens at different speeds and loads were investigated under water lubrication. The results indicated that filling of the complexes could improve the friction and wear performance of the abrasive tools. The minimum friction coefficient and wear rate were obtained when the content of the filler was about 15–20 wt.%. The friction coefficient of the abrasive tool decreased with the increase of speed and load, while the wear rate showed a reverse trend. X-ray photoelectron spectroscopy (XPS) analysis was employed to investigate the self-lubricating mechanism of the abrasive tool. It was found that the additives were released along with the decomposition of the complexes. The enhanced tribological properties of these abrasive tools were believed to stem from the formation of a self-lubricating layer that constituted by sulfide film and carbon deposited film, which had significant influence on the phenolic resin transfer process from substrate to the counter steel surface, and also had functions of anti-friction, anti-wear, and an improvement of surface quality.

Protection of low-carbon steel in phosphoric acid solutions by mixtures of a substituted triazole with sulfur-containing compounds

Based on IFKhAN-92 inhibitor, which is a substituted triazole, and sulfur-containing additives, efficient mixtures have been developed that protect low-carbon steel in phosphoric acid solutions in a broad range of acid concentrations (2.0–8.0 M) and temperatures (0–95C).

Experiences from a Novel Sensor for Fireside Corrosion Monitoring during Grate Combustion of Corn Stover/Wood Chip Blends

The operation of a pilot-scale online corrosion sensor system was studied at VTT’s 100 kW grate pilot plant. The feedstock composition in tests was varied from 100% wood chips to a blend that also contained 40 en-% d.b. corn stover. The mass flow of alkali chlorides was varied with sulfur-containing additives. The measurements included electrical resistance (ER) of deposit and linear polarization resistance (LPR) for both St45.8 and AISI347H alloys. The number of fine particles (online data), alkali chloride mass flow, chloride content of the deposit, and flue gas composition (online data) were simultaneously measured to study how the furnace conditions correlate with the ER and LPR signals. Information on the risky furnace conditions can be obtained with these methods. The decrease in sensor signals after starting to feed in fuel blended with corn stover indicated increasing corrosion. The ER and LPR values started to increase again after changing the fuel back to 100% wood chips. The deposit composition, alkali chloride flow, and corrosion sensor signals predicted a low corrosion rate on the alloys with the corn stover-containing blend, when the mass flow of additive was sufficient to destroy the corrosive alkali chlorides before meeting the probe.

Mechanical and physico-chemical study of sulfur additives effect in milling of high strength steel

Most machining operations require the presence of a cutting fluid in order to ensure their success due to the intensity of thermal and mechanical conditions generated on the cutting tools. In some cases of severe machining, the fluid contributes to lubrication in a physicochemical way thanks to the additives it contains. This study aims to analyze the tribochemical mechanisms of lubrication during milling operations and subsequently at optimizing the lubricant formulation. The objective of this study is also to identify and to compare, the performance of various extreme pressure (EP) sulfur-containing additives, and to understand their action mechanisms in metal cutting. Physico-chemical analyses are carried out by means of Auger Electron Spectroscopy (AES) and X-ray Photoelectron Spectroscopy (XPS) with the purpose of detecting the nature of additive reaction products on the surfaces involved in cutting and correlating them with the milling results. The polysulfide additive is found to exhibit the best efficiency (decrease of specific cutting energy and tool wear) in the tested milling conditions. A correlation is found between the additive chemical reactivity and the milling test results.

Investigation of the Mechanisms of Heat Exchanger Corrosion in a Municipal Waste Incineration Plant by Analysis of the Raw Gas and Variation of Operating Parameters

The detailed mechanism of high temperature chlorine corrosion, the dominant cause of corrosion in a municipal solid waste incinerator (MSI), has still to be clarified. Upon its way through the boiler the raw gas is subject to various physical and chemical processes and interactions. Of these, sulfation of chlorides is supposed to have the major impact on chlorine corrosion. The physical and chemical mechanisms of corrosion were investigated at a municipal solid waste incinerator. Both the particulate and gas phases of the flue gas were chemically and physically analyzed during their way through the boiler, at temperatures from close to 1000°C down to 200°C. The raw gas composition was analyzed during normal operation and during the soot blowing cleaning routine. Additionally, operating parameters of the plant were varied, and deposition processes were evaluated with the aim to find out primary measures to reduce corrosion rates. The particle mass concentration exhibits a bimodal size distribution with maxima at approximately 0.5 μ m—growing by duration of travel—and 100 μ m. First results show that sulfation of the particles can be observed upon travel through the boiler and on the fouling. Sulfur-containing additives increased the sulfation of the particles during flight, though not to completion.

Acid corrosion of iron in the presence of mixtures of anionic additives and compounds of the reaction series of o-hydroxyazomethine derivatives with nucleophilic substituents

The effects of halide-and sulfur-containing additives on iron corrosion in 1 M H2SO4 in the presence of nucleophilic o-hydroxyazomethine derivatives are studied. Dependences of the inhibition factor (as well as its sensitivity to a change in the polarity of the substituents) and the effective activation energy on the nature and concentration of both the groups of additives are interpreted in terms of the Linear Gibbs Energy Relation (LGER) and the principle of Hard and Soft Acids and Bases (HSAB).

Polyfunctional complex sulfur-containing additives to SKI-3 rubber and vulcanizates thereof

The performance of new polyfunctional additives containing bis(2,6-di-tert-butyl-4-hydroxyphenyl) polysulfide and dicyclopentadiene-sulfur copolymer was studied with respect to SKI-3 and vulcanizates thereof. These additives act not only as stabilizers but also as vulcanizing agents improving a number of physicomechanical characteristics of the vulcanizates.

Cotton and Weed Response to Glyphosate Applied with Sulfur-Containing Additives

Field studies were conducted to assess two sulfur-containing additives for use with glyphosate applied postemergence to glyphosate-resistant cotton for the control of sicklepod and yellow nutsedge. Neither diammonium sulfate (AMS) nor ammonium thiosulfate (ATS), both applied at 2.24 kg/ha, increased control of either species. Effective control of both species was dependent on glyphosate (isopropylamine salt) rate alone, with optimum control at 1.26 kg ae/ha. Plant-mapping data further indicated that sulfur-containing additives generally had no effect on either cotton fruiting patterns or yield. However, applying glyphosate at any rate did increase seed cotton yield in 2 of 3 yr vs. no glyphosate. In addition, applying glyphosate at any rate resulted in an increase in the number of bolls vs. no glyphosate in the following plant-mapping responses: total number of bolls per plant, number of abcised bolls per plant, bolls at the top five sympodial nodes, and bolls at positions 1 and 2 on the sympodia. Glyphosate absorption and subsequent translocation, as influenced by the addition of the sulfur-containing additives, was evaluated using radiotracer techniques. Glyphosate absorption after 48 h was 86, 63, and 37% of amount applied in cotton, sicklepod, and yellow nutsedge, respectively. Absorption by sicklepod and yellow nutsedge was not affected by the addition of either of the additives. Absorption by cotton was reduced by ATS but was not affected by AMS. In yellow nutsedge and cotton, glyphosate concentration in the treated area and adjacent tissue was not affected by either additive. A greater portion of glyphosate was translocated away from the treated area in sicklepod with glyphosate plus AMS (32%) than with glyphosate plus ATS (21%). AMS and ATS may be used in glyphosate-resistant cotton without the risk of either crop injury or yield reduction. However, their use for increased control of annual weed species, such as sicklepod and yellow nutsedge, may not be warranted.

Effect of Chemisorbed Oxide Layers Modified by Nitrogen and Sulfur Atoms on the Catalytic Properties of Platinum Metal Electrodes: A Quantum-Chemical Approach

Electrocatalytic properties of platinum metal electrodes and their dependence on nitrogen- and sulfur-containing additives to electrolyte are studied by an Xαdiscrete variation method. It is shown that rhodium catalysts are the most promising, while iridium is unsuitable for the synthesis of percompounds.

The surface and tribological chemistry of chlorine- and sulfur-containing lubricant additives

A model for the operation of chlorinated hydrocarbon extreme-pressure additives is outlined in which the chlorinated hydrocarbon thermally decomposes at the hot (~1000 K) interface forming a chloride+carbon film, which is simultaneously worn from the surface. Assuming that seizure occurs when the chloride film thickness decreases to zero reproduces the experimentally measured seizure load vs. additive concentration results. A similar model is found to apply to sulfur-containing additives. The thermal decomposition of model chlorinated hydrocarbons is investigated in ultrahigh vacuum (UHV) using constant-flux molecular beams and reveals that these react with similar activation energies as at higher pressures, forming films of identical compositions to those found tribologically. This allows the surface reaction chemistry of model extreme-pressure additives and the tribological properties of the films to be investigated separately in UHV. In this vein, measurements of the tribological properties of thin KCl films grown on iron in UHV show that the friction coefficient drops from a clean-surface value of ~1.9 to ~0.27 after completion of the first monolayer.

Hydrogen coevolution and permeation in nickel electroplating

Nickel coatings were electrodeposited onto a steel membrane in a conventional Devanathan cell in order to measure the diffusion rate of hydrogen into the steel substrate during electrodeposition. In most cases a Watts' solution containing various organic additives was used: butyne-2 diol-1, 4; saccharine or thiourea. The structure of the electrodeposits was studied by X-ray and Transmission electron microscopy (TEM). It was shown that the electrodeposition parameters (pH, composition of the bath, additives) have a strong effect on hydrogen permeation. The use of organic additives during Ni plating increased the penetration of hydrogen into the substrate. In particular, sulfur-containing additives cause a fast initial increase of the permeation rate, which is attributable to a high surface concentration of Hads when steel is not totally covered with nickel. By performing permeation experiments with Ni coatings during hydrogen charging from a H2SO4 solution, it was shown that hydrogen permeation through nickel coatings is influenced by their fibre texture and by their grain sizes. A low permeation rate was observed in coatings plated in the presence of butyne-2 diol-1,4, which exhibit a strong 100 texture with large grains and a low density of defects. Conversely, the hydrogen diffusion rate is very high in coatings plated in the presence of thiourea or saccharine. These coatings exhibit a weak texture with very small grains.

Antiwear Tribofilm Formation on Steel Surfaces Lubricated With Gear Oil Containing Borate, Phosphorus, and Sulfur Additives

The formation of antiwear tribofilms plays a critical role in the longevity of automotive gears. The focus of this experimental study was on the lubrication efficacy of gear oils with different contents of borate-, phosphorus-, and sulfur-containing additives leading to the formation of protective tribofilms. Experiments were performed with AISI 52100 steel balls sliding against AISI 52100 steel disks in baths of different oils at ambient (∼32 °C) and elevated (∼100 °C) temperatures under load and speed conditions favoring sliding in the boundary lubrication regime. Friction coefficient responses accompanied by electrical contact voltage measurements provided real-time information about the formation and durability of the antiwear tribofilms. The wear resistance of the tribochemical films was quantified by wear rate data obtained from surface profilometry measurements of wear tracks on the disk specimens and sliding tests performed at ambient temperatures after the formation of the tribofilms during elevated-temperature sliding. Results indicate a strong dependence of tribofilm formation on temperature and type of additives. The slightly lower friction and higher wear resistance obtained at elevated temperatures with blended oils is attributed to the increased chemical reactivity of additives containing borate, phosphorus, and sulfur, leading to the formation of durable tribofilms. Relatively higher wear resistance and faster tribofilm formation were obtained with the borate-enriched gear oil formulations. Presented as a Society of Tribologists and Lubrication Engineers Paper at the ASME/STLE Tribology Conference in Cancun, Mexico October 27–30, 2002

Hydrogenated Benzoin Photo-stabilizers. (Part 2). Hydrogenated Benzoins Having Hydroxyl Substituents on Phenyl Groups.

Hindered amine light stabilizers (HALS) are handicapped in that they cannot be used together with sulfur-containing additives which are often utilized for the stabilization of plastics. In this study, three hydrogenated benzoins having hydroxyl substituents on phenyl groups were synthesized, in order to multi-functionalize hydrogenated benzoins, which were proposed as substitutes free of shortcomings of HALS. 2,2'-Dihydroxy and, especially, 4,4'-dihydroxy derivatives, worked solo as an excellent radical scavenger, while the effect of 3,3'-dihydroxy derivative was unknown, attributed to lack of experimental data. 4,4'-Dihydroxy and, especially, 3,3'-dihydroxy derivatives exhibited higher abilities than HALS, to give hydrogens to p-benzoquinone, resulting in the formation of corresponding phenolic compounds. 2,2'-Dihydroxy derivative showed less activity to trap radicals and lower ability to give hydrogens to p-benzoquinone, but it was found that the product formed after the donation of hydrogens could work again as a photo-stabilizer, because its chemical structure is similar to that of benzophenone-type UV absorbers.

Tribochemically assisted wear of silicon nitride ball

The response of silicon nitride balls to different chemical additives contained in a diamond slurry was studied in a high speed four-ball machine. It was found that there are two effective inorganic chemical additives: acid additive (A) and alkaline additive (B). Use of A or B in the diamond slurry resulted in a high material removal rate and a rough surface. With an increase in the size of the diamond particles contained in the slurry, the material removal rate and the roughness of the surface also increased. Addition of sulfur-containing additives into the diamond slurries produced a decrease in the material removal rate but a smoother surface. The presence of water in the oil-based diamond slurry gave an increase in the material removal rate and a relatively smooth surface. In the ester-containing slurry, there was an increase in the material removal rate and the roughness of the surface.

Sulfur-containing additives based on polythiodiglycol

Sulfur-containing additives based on polythiodiglycol

Colorimetric and volume-graphic methods for investigating interaction of sulfur-containing additives in lubricating oils

Colorimetric and volume-graphic methods for investigating interaction of sulfur-containing additives in lubricating oils

Interaction of sulfur-containing additives with metals

Interaction of sulfur-containing additives with metals