BORON AND BORON-NITROGEN CONTAINING FUEL AND LUBRICANTS

The article is devoted to a current problem - the synthesis of new compounds and their study as anti-wear and proto-pressure additives for lubricating oils. The purpose of this work is to obtain sulfur-phosphorus-containing compounds that could have tribological properties. Based on liter-ature data and experience in this field, the authors synthesized derivatives of dithiophosphoric acids, which were further studied as extreme pressure and anti-wear additives for lubricating oils. The synthon for the synthesis of compounds was the sodium salt of diisopropyl and allyl dithiophosphoric acids, obtained by reacting the corresponding dithiophosphoric acids with a 40% solution of sodium hydroxide. By reacting the sodium salt of diisopropyl, sodium allyl di-thiophosphate with toluene sulfonamide, obtained by reacting toluene sulfonamide with 5-phosphorus chloride, toluene sulfonisopropyl and allyl dithiophosphates were obtained. The re-sulting compounds have high extreme pressure properties. It has been shown that the extreme pressure properties of the compound depend on the structure of the fragments included in the compound. You should pay attention to the calculated indicator scuff index (Si), which indicates the effectiveness of extreme pressure properties; the higher this indicator, the higher the extreme pressure properties. 4-phenoxycarbonyl methyl ester of diispropyl dithiophosphoric acid was obtained by reacting the sodium salt of diisopropyl dithiophosphoric acid with phenyl chloroace-tate; similarly, by adding 5-methyl-2-hydroxy-γ-chloroacetophenone to the diisopropyl dithio-phosphate salt, 5-methyl-2-hydroxyphenylcarbonyl methyl ester of diisopropyl dithiophosphoric acid was obtained. These compounds also have high extreme pressure properties; in addition, they are superior to toluene sulfonic acid derivatives of dithiphosphoric acids in anti-wear prop-erties, which is fully explained by the large amount of sulfur in the composition of the latter. The structure of all synthesized compounds was proven by IR spectral analysis, the study of physicochemical properties and elemental analysis. Extreme pressure and anti-wear properties were studied on a four-ball friction machine (FFM-1). The evaluation of extreme pressure prop-erties was carried out according to the load wear index (LWI), according to the critical load (CL) and according to the welding load (WL), anti-wear properties by the diameter of the wear scar (Wd). Keywords: sulfur-phosphorus-containing compounds, tribological properties, allyl dithiophos-phate, anti-wear

Metalworking fluids (MWFs) are the primary source of organic contaminants in oily wastewater at many manufacturing facilities. Such facilities, including those in the automotive industry, face the continuing challenge of improving wastewater treatment for organics. Hydraulic fluids (HFs), chemically similar to MWFs, have been a major source of costly soil contamination at industrial and commercial facilities.A better understanding of these organics is essential to the treatment of oily wastewater and HF decontamination. Therefore, two aspects were reviewed: (1) current and historical organic chemical compositions of MWFs and HFs and (2) existing and emerging analytical methods. Base mineral oils were emphasized, as they are the primary ingredient of these fluids and the main contaminant in oily wastewater and HF-contaminated soil. Hydrocarbon compositions of “naphthenic” (cycloalkanes) and “paraffinic” (straight and branched noncyclic alkanes) mineral oils were described, as were the chemical nature of the various MWF and HF additives.Analytical methods for gross organic measurements, individual organics, and structure- and sizebased fractions and distributions were reviewed. Most promising for characterizing the base oil fraction were gas chromatography (GC) coupled with two soft ionization mass spectrometry detection methods and comprehensive 2-dimensional GC. These methods can provide complete distributions of hydrocarbon structures and sizes and are potentially useful to monitor hydrocarbon fate in wastewater treatment, soil/sediment remediation, or other applications involving complex hydrocarbon mixtures.

1. In steel-on-steel friction in a four-ball machine, oil additives of the sulfur-containing phosphorus acid ester type are not greatly superior to sulfur-free esters as regards antiseizing and antiwear properties. 2. Among the esters investigated,the best antiseizing properties are displayed by acid esters and trialkyl trithiophosphite. Complete esters are good antiwear additives, but do not greatly reduce the stringency of seizing, which has a violent character at moderate loads. 3. In the oxidation of oils, complete esters of phosphoric, phosphorous, and thiophosphorous acids are antioxidizers, whereas their acid esters and complete esters of phosphinic acid are strong oxidizers. 4. Acid esters of phosphorous and dithiophosphoric acids and phosphinites can cause corrosion of nonferrous alloys. 5. In the selection of phosphorus-containing additives for oils, account must be taken of not only their antiwear and antiseizing properties, but also their thermochemical stability, antioxidizing properties, and corrosion activity with respect to metals.

Tests were performed on two different four‐ball testers. The first was used to determine antiwear (AW) and extreme pressure (EP) properties at sliding friction. The second was used to assess the surface fatigue (pitting) life at rolling movement. Lubricating oils of various chemical compositions were tested. A base mineral oil was blended with two different commercial packages of lubricating additives of AW and EP types. The AW additives contained ZDDP and were blended with the base oil at 0.2 and 3wt %. The EP additives were organic compounds of sulphur and phosphorus, blended with the base oil at 1 and 10wt %. It is shown that AW additives not only improve AW and EP properties but also — at 0.2% — are beneficial for the fatigue life. An increase in the concentration of AW additives leads to an improvement of AW and EP properties but — for one of the packages — reduces the fatigue life. EP additives — at 1% concentration — significantly improve EP properties, and to a lesser extent AW properties. Such a concentration of EP additives has no influence on the fatigue life. An increase in the concentration of EP additives leads to a further improvement of EP and AW properties. However, this is accompanied by a considerable decrease in the fatigue life. By using a scanning electron microscope and energy dispersive spectrometer for analysis of the worn surface, mechanisms of action of various lubricating additives under different friction conditions were identified. Copyright © 2006 John Wiley & Sons, Ltd.

Three biodegradable/ecofriendly polyalkylene glycol esters 1,4-PTHC3, 1,4-PTHC6 and 1,4-PTHC8 [polyglycol containing 1:4 mol fraction of propylene oxide (PO) and tetrahydrofuran (THF)] esterified with propionic acid (C3 fatty acid), hexanoic acid (C6 fatty acid) and octanoic acid (C8 fatty acid) were synthesized via two-step reaction mechanism. Initially, propylene oxide and tetrahydrofuran were polymerized in 1,2 dichloroethane to obtain a polymer 1,4-PTH (polyglycol containing 1:4 mol fraction of PO and THF) with molecular weight ( $$\overline{{M_{n}}}$$ ) 1070.7. Finally, esterification of 1,4-PTH was done with varied fatty acids, i.e., C3, C6 and C8 fatty acid catalyzed by p-toluenesulfonic acid and toluene as solvent to obtain final products 1,4-PTHC3, 1,4-PTHC6 and 1,4-PTHC8 having the molecular weights ( $$\overline{{M_{n}}}$$ ) 1154.78, ( $$\overline{{M_{n}}}$$ ) 1192.86 and ( $$\overline{{M_{n}}}$$ ) 1220.91, respectively. The molecular structure and crystallinity of the synthesized poly(propyleneoxide-co-tetrahydrofuran) ester was studied by FT-IR, X-ray diffraction and DSC. The physicochemical properties like; pour point (ASTM 97), kinematic viscosity (ASTM 445), viscosity index (ASTM 2270), refractive index, density, thermal stability, autoignition temperature (IS 7895), corrosion stability and oxidation stability (IP 48) were determined. The extreme pressure (IP 239) and antiwear properties (ASTM D 4172) were also evaluated in terms of weld load and average wear scar diameter, respectively. Hence all the properties so determined were compared with the specifications of lube oils and it was revealed that these poly(propyleneoxide-co-tetrahydrofuran) esters, i.e., 1,4-PTHC3, 1,4-PTHC6 and 1,4-PTHC8 had suitable physical and tribological properties to be used as base stock for compressor lubricant, metal working fluid and fire-resistant hydraulic fluid.

ObjectivesMetalworking has been associated with bladder cancer risk in many studies. Metalworking fluids (MWFs) are suspected as the putative exposure, but epidemiologic data are limited. Based on state-of-the-art, quantitative exposure...

We adapted previously developed decision rules from the New England Bladder Cancer Study (NEBCS) to assign occupational exposure to straight, soluble, and synthetic metalworking fluids (MWFs) to participants of the Spanish Bladder Cancer Study (SBCS). The SBCS and NEBCS are case-control studies that used the same lifetime occupational history and job module questionnaires. We adapted published decision rules from the NEBCS that linked questionnaire responses to estimates of the probability (<5, ≥5 to <50, ≥50 to <100, and 100%), frequency (in h week-1), and intensity (in mg m-3) of exposure to each of the three broad classes of MWFs to assign exposure to 10 182 reported jobs in the SBCS. The decision rules used the participant's module responses to MWF questions wherever possible. We then used these SBCS module responses to calculate job-, industry-, and time-specific patterns in the prevalence and frequency of MWF exposure. These estimates replaced the NEBCS-specific estimates in decision rules applied to jobs without MWF module responses. Intensity estimates were predicted using a previously developed statistical model that used the decade, industry (three categories), operation (grinding versus machining), and MWF type extracted from the SBCS questionnaire responses. We also developed new decision rules to assess mineral oil exposure from non-machining sources (possibly exposed versus not exposed). The decision rules for MWF and mineral oil identified questionnaire response patterns that required job-by-job expert review. To assign MWF exposure, we applied decision rules that incorporated participant's responses and job group patterns for 99% of the jobs and conducted expert review of the remaining 1% (145) jobs. Overall, 14% of the jobs were assessed as having ≥5% probability of exposure to at least one of the three MWFs. Probability of exposure of ≥50% to soluble, straight, and synthetic MWFs was identified in 2.5, 1.7, and 0.5% of the jobs, respectively. To assign mineral oil from non-machining sources, we used module responses for 49% of jobs, a job-exposure matrix for 41% of jobs, and expert review for the remaining 10%. We identified 24% of jobs as possibly exposed to mineral oil from non-machining sources. We demonstrated that we could adapt existing decision rules to assess exposure in a new population by deriving population-specific job group patterns.

Mineral oil metal working fluids (MWFs)—development of practical criteria for mist sampling

Not all mineral oil metalworking fluids (MWFs) in common use form stable airborne mists which can be sampled quantitatively onto a filter. This much has been known for some time but no simple method of identifying oils too volatile for customary filter sampling has been developed. Past work was reviewed and experiments were done to select simple criteria which would enable such oils to be identified. The sampling efficiency for a range of commercial mineral oil MWF were assessed by drawing clean air through spiked filters at 2 l. min−1 for periods up to 6 h before analysis. The physical properties of MWF are governed by their composition and kinematic viscosity was found to be the most practical and easily available index of the potential for sample loss from the filter. Oils with viscosities greater that 18 cSt (at 40°C) lost less than 5% of their weight, whereas those with viscosities less than 18 cSt gave losses up to 71%. The losses from the MWF were mostly aliphatic hydrocarbons (C10–C18), but additives such as alkyl benzenes, esters, phenols and terpene odorants were also lost. The main recommendation to arise from the work is that filter sampling can be performed on mineral oils with viscosities of 18 cSt (at 40°C) or more with little evaporative losses from the filter. However, sampling oils with viscosities less than 18 cSt will produce results which may significantly underestimate the true value. Over a quarter of UK mineral oil MWFs are formulated from mineral oils with viscosities less than 18 cSt (at 40°C). The problem of exposure under-estimation and inappropriate exposure sampling could be widespread. Further work is being done on measurement of mixed phase mineral oil mist exposure.

The American Conference of Governmental Industrial Hygienists (ACGIH) has recommended that the threshold limit value (TLV) for mineral oil mists be dramatically lowered, based on epidemiological evidence of respiratory health effects among machinists exposed to various metalworking fluid mists. A review of the literature regarding respiratory health effects from either metalworking or non-metalworking fluids suggest that machinists may have experienced slightly higher prevalence of common respiratory symptoms and mild and reversible cross-shift changes in some measures of pulmonary function. However, the inconsistency and potential for both random and systematic error in this body of literature argue against drawing definitive conclusions. There is also no substantive evidence that any of these effects led to permanent disease or impairment. The most likely causal agents for respiratory effects in these workers are microbial contaminants in water-based metalworking fluids, not straight mineral oils. This is consistent with the epidemic outbreaks of hypersensitivity pneumonitis, bronchitis, and asthma reported at some work sites using water-based metalworking fluids. This highlights the importance of frequent cleaning and fluid changes for metalworking fluid reservoirs, as part of a systematic approach to managing metalworking fluid aerosol exposures. A dramatic drop in the TLV for mineral oil mists would not resolve this problem.

This paper summarizes the analytical and occupational hygiene findings from a recent survey of occupational exposure to metalworking fluids (MWFs) in the engineering industry. The aim of the survey was to link MWF mist exposure measurements with particular engineering processes and controls, and utilize the data obtained to develop exposure standards. At the same time the opportunity was taken to assess fluid management and control, including bacterial and fines contamination in the machine sumps. In general, occupational exposure to mineral oil MWF mist was controlled to <3 mg/m(3) (8 h time-weighted average) and to <1 mg/m(3) for water-mix MWF mist (in terms of the concentrate). These exposure values do not necessarily represent best practice, but are believed to be achievable and representative of industry as a whole. Gravimetric analysis of the total inhalable particulate was found to be a good predictor of mineral oil MWF mist but not for water-mix MWF mist. Grinding and drilling operations produced higher exposures than turning and milling for water-mix fluids. There were insufficient data to compare machining operations for mineral oil MWFs. On the whole, fluid management was found to be poor, with most sites failing to meet industry good practice or Health & Safety Executive (HSE) standards. Some of the operating procedures utilized were deficient or unsatisfactory. Poor standards of fluid management were found at all sizes of company. High levels of bacteria, endotoxin and fines were found in sumps, and control of other factors, such as water-mix fluid concentration, was often poor. Mineral oils had higher levels of fines than water-mix fluids (medians of 395 and 18 mg/l, respectively), and grinding produced high levels of fines in both types of MWF. Many water-mix sumps contained bacterial levels of >1 x 10(6) CFU/ml, and endotoxin levels of >100 000 EU/ml were not uncommon. The median values were 109 000 CFU/ml and 8039 EU/ml, respectively. Mists could potentially contain extensive contamination from bacteria and endotoxin. Analysis of the data suggests that sumps operating under typical conditions for machining (a temperature of 20 degrees C, a pH of 9 and a fluid strength below 10%), also appear to provide optimum conditions for the proliferation of bacteria. Low levels of benzo[a]pyrene (median 0.03 micro g/g) were found in the mineral oils, and low levels of N-nitrosodiethanolamine (median 0.4 micro g/ml) were found in the water-mix MWFs. The results of this work will contribute to guidance from the HSE, setting out accepted industry good practice, including guide values for MWF mist and sump fluid contaminants, with significant emphasis on sump fluid management (maintenance and monitoring), as well as control issues.

Ashless and non-corrosive disulfide compounds as excellent extreme pressure additives in naphthenic oil

Lubricants play vital role in tube hydroforming (THF) process to reduce friction between tool and die wall interface which helps to enhance the quality of finished product. The process parameters and quality of components is influence by the friction between the tube and inner surface of the die. Excellent lubricant reduces the problem of wrinkling, buckling and premature failure of the component. Extreme pressure, Anti-wear, and frictional properties of fluid influence the performance of tube hydroforming process. In this paper EP (extreme pressure), anti-wear and friction properties of hydroforming lubricating oils as Enklo68, Enklo46, Enklo32 and Enklo100 are investigated. Test method as per ASTM standards is used for the measurement of EP and wear preventive properties of hydroforming fluids by using Ball Tester TR – 30L under atmospheric pressure of lubricating oil at 392 N load and 75°C temperature with constant speed of 1770 rpm. From experimental investigations it is observed that as Enklo68 is more suitable hydroforming fluid as compared to Enklo46, Enklo32 and Enklo100 as its observed coefficient of friction (i.e. 0.10581) is very less.

This article reports on an investigation of the mutual effects on the antiwear, extreme pressure, and antioxidant properties of mineral oils from the addition of the methylbenzyl ester of diisobutyldithiophosphoric acid and antioxidant additives of the phenol and amine types: Ionol, 2,6,-di-tert-butyl-4-methylphenol; NG-2246,2,2'-methylenebis(4-methyl-6-tert-butyphenol); MB-1,4,4'-methylene-bis(2,6di-tert-butylphenol); AO-20, a mixture of products from the alkylation of phenols with styrene; and Neozone A. Finds that of the additives studied, the greatest mutual effect is shown by the AO-20 and the methylbenzyl diisobutyldithiophosphate. The joint addition of these products improves the antiwear, extreme-pressure, and antioxidant properties of the tested mineral oil.

Cutting fluid is crucial in ensuring surface quality and machining accuracy during machining. However, traditional mineral oil-based cutting fluids no longer meet modern machining’s health and environmental protection requirements. As a renewable, pollution-free alternative with excellent processing characteristics, vegetable oil has become an inevitable replacement. However, vegetable oil lacks oxidation stability, extreme pressure, and antiwear properties, which are essential for machining requirements. The physicochemical characteristics of vegetable oils and the improved methods’ application mechanism are not fully understood. This study aims to investigate the effects of viscosity, surface tension, and molecular structure of vegetable oil on cooling and lubricating properties. The mechanisms of autoxidation and high-temperature oxidation based on the molecular structure of vegetable oil are also discussed. The study further investigates the application mechanism and performance of chemical modification and antioxidant additives. The study shows that the propionic ester of methyl hydroxy-oleate obtained by epoxidation has an initial oxidation temperature of 175 ℃. The application mechanism and extreme pressure performance of conventional extreme pressure additives and nanoparticle additives were also investigated to solve the problem of insufficient oxidation resistance and extreme pressure performance of nanobiological lubricants. Finally, the study discusses the future prospects of vegetable oil for chemical modification and nanoparticle addition. The study provides theoretical guidance and technical support for the industrial application and scientific research of vegetable oil in the field of lubrication and cooling. It is expected to promote sustainable development in the manufacturing industry.