Andrzej Kulczycki

Butanol/Biobutanol as a component of an aviation and diesel fuel

This paper describes the analysis and conclusions regarding the use of butanol/biobutanol as a component of – biobutanol is interesting as biocomponent of gasoline, diesel fuel as well as aviation fuels. This is especially important in case of air transport, which is the carbon dioxide emission source of the fastest growth. gasoline, including aviation ones, but there are no information about biobutanol added to mineral Jet fuel as well as diesel fuel. Direction of research conducted by leading aviation companies indicates that hydrocarbon biocomponent will be main biofuel used as aviation turbine fuel. One of reported technology is focused on use of butane-1-ol as semi-finished products for isoparaffinic hydrocarbons generation that then would be used for aviation turbine fuels production. In order to do such analysis the preliminary lab testing of blends of butanol isomers with aviation fuel Jet A-1 and diesel fuel were performed. The paper contains the results of standard tests for blends of mineral fuels with butane-1-ol and butane-2-ol added in concentration of 0-20 % regarding the use of such component of mineral fuels are pr significantly influence on conductivity of Jet fuel. In case of aviation fuel for turbine engines, and diesel fuel, the restrictions regarding direct use of butanol are important. However, butanol can be treated as semi-finished material for synthesizing of biohydrocarbons used in above applications.

On the mechanism of catalysis induced by mechano-activation of solid body

The paper presents a new model of the mechanism of mechanocatalysis and tribocatalysis. The reason for the increase in heterogeneous catalysis effect after mechanical activation of a catalyst has not been fully understood yet. There is no known theory, which would explain the mechanism of the influence of mechanical energy introduced to catalyst particles on the rate of chemical reaction. All existing theories are based on Arrhenius equation and assume that catalysts increase reaction rate due to decreasing of activation energy Ea. We hypothesize that both for standard and catalyzed heterogeneous reactions the same Ea (real activation energy) is needed to trigger the reaction processes and the catalytic effect is the result of energy introduced to the reaction system, its accumulation by a catalyst and then emission of high flux of energy to the space near the catalyst particles. This energy emitted by molecules of reagents can reach a value equal to the value of Ea at lower ambient temperature than it would result from Arrhenius equation. This hypothesis is based on αi model described in previous papers by Kajdas and Kulczycki as well as the results of tribochemical research described by Hong Liang et al., which demonstrate that the reaction rate is higher than that resulting from temperature.

The influence of oxygenates on lubricity of fuels for CI engines

Lubricity of fuels for CI engines becomes one of very important parameter since the sulphur content was decreased to 50 and actually 10 ppm. To provide effective lubrication of fuel pumps and unit injectors elements, in case fuel does not contain organic sulphur compounds, the oxygen containing organic compounds are added as lubrication additives. Biocomponents are usually introduced into mineral diesel fuel containing additives package, which includes lubricating additive (organic acid). The aim of this paper is investigation of the influence of polar oxygenates added to petroleum diesel fuel in concentration between 5 and 20% (V/V) on lubricating additive effectiveness in protective layer creation. The results of HFRR tests obtained for blends of commercial diesel fuel containing lubricating additive with biobuthanol models (MB) leads to conclusion that: − generally the buthanol isomers addition increases wear of upper ball of HFRR apparatus, − wear of upper ball of HFRR apparatus depends on the average film thickness and does not depend on tested fuels viscosity at 40°C, − dilution of commercial diesel fuel by biobuthanol models and consequently decreasing of lubricating additive concentration cannot be the only reason of deterioration of tested blends lubricity. It was concluded, that the possible reason of lubricity deterioration by buthanol added to commercial diesel fuel in concentration between 5 and 20% (V/V) are antagonistic interactions between oxygenates (buthyl alcohol) and lubricating additive. These antagonistic interactions depend on the structure of buthanol isomers.

THE IMPACT OF THE TYPE OF CUTTING FLUID ON THE TURNING PROCESS

This article compares the test results concerning the wear of cutting tools after face turning under dry friction conditions and lubricated friction conditions with biodegradable cutting fluid or mineral-oil based emulsion. The turning was performed using a CTX 310 ECO machine tool. The wear of the cutting tools was measured by means of stereo zoom microscopy (SX80), while the elements were identified through scanning electron microscopy (JSM 7100F). The tribological tests were conducted for a ball-on-disc configuration in sliding contact using a T-01M tribometer. The surface textures of the face turned specimens were measured with a Talysurf CCI Lite optical profiler. The study also involved determining the foaming tendency and corrosive effects of both cutting fluids. The use of the biodegradable cutting fluid with low foaming tendency resulted in lower wear and higher corrosion resistance of the tool. Słowa kluczowe: biodegradowalna ciecz obróbkowa, toczenie, tarcie, zużycie. Streszczenie W artykule przedstawiono wyniki badań zużycia narzędzi skrawających po procesie toczenia czołowego w warunkach tarcia technicznie suchego, ze smarowaniem biodegradowalną cieczą obróbkową oraz emulsją opartą na oleju mineralnym. Badania wykonano na tokarce CTX 310 ECO. Po obróbce zmierzono zużycie narzędzi za pomocą stereoskopowego mikroskopu inspekcyjnego SX80, a identyfikację pierwiastków przeprowadzono z użyciem skaningowego mikroskopu elektronowego JSM 7100F. Testy tribologiczne wykonano na urządzeniu T-01M. Pomiary struktury geometrycznej powierzchni elementów toczonych czołowo wykonano profilometrem optycznym Talysurf CCI Lite. Dodatkowo przeprowadzono badania pienienia i korozji cieczy obróbkowych. Zastosowane w badaniach biodegradowalne chłodziwo wpłynęło na zmniejszenie wybranych wskaźników opisujących zużycie narzędzia, a także zapewniło lepsze właściwości przeciwkorozyjne oraz przeciwpienne. ∗ Kielce University of Technology, Faculty of Mechatronics and Mechanical Engineering, al. Tysiąclecia Państwa Polskiego 7, 25-314 Kielce, Poland. ∗∗ Air Force Institute of Technology, ul. Księcia Bolesława 6, 01-494 Warszawa, Poland, e-mail: andrzej.kulczycki@itwl.pl. INTRODUCTION Metalworking processes require the use of cutting fluids, which act both as coolants and lubricants. Their functions are numerous; they include cooling the cutting zone, lubricating the chip-tool-workpiece interface and removing chips from the cutting zone [L. 1, 2]. Conventional cutting fuels are based on mineral oil, which is hardly biodegradable and as such contributes to environmental pollution. Globally, more than 2,000,000 m3 of cutting fluids are used each year. Approximately 85% of them contain mineral oil. Improper disposal of spent cutting fluids leads to the pollution of surface water, groundwater, air, and soil, which, in consequence, affects food safety [L. 3–5, 6]. Metalworking fluids that are harmful to the environment and human health need to be replaced with ones that are safe and can be recycled or regenerated. The service properties of mineral oil-based cutting fluids are improved by introducing special-purpose additives, which generally are non-biodegradable and toxic to the ecosystem [L. 7, 8]. Cutting fluids also contain antiseptics to kill bacteria and fungi; prolonged or repeated exposure to these irritants may lead to occupational diseases such as skin inflammation, oil acne, respiratory tract infections, allergies, and even cancers [L. 9]. Chemists and tribologists have created new blends to be used instead of mineral oil-based cutting 120 ISSN 0208-7774 T R I B O L O G I A 3/2017 fluids. Alternatives include vegetable oils, which are renewable, nontoxic, environmentally friendly, and easily biodegradable [L. 10]. They are also characterized by good lubrication, low volatility, low emission of hydrocarbons, and good thermal properties [L. 11, 12]. Currently, much research is devoted to cutting fluids based on vegetable oils, for example, soya bean oil, castor oil, palm oil, coconut oil, and rapeseed oil [L. 13, 14]. The analysis presented in [L. 15] focuses on the effects of a cutting fluid based on neem oil. The results obtained for the alternative fluid were compared with those reported for a conventional cutting fluid and also those obtained under dry machining conditions. The turning process was performed using a TEX TRENCIN SN40B machine tool with tool bits made of HS6-5-2C high-speed steel (12x200 mm). The machining was carried out for three workpieces made of mild steel using different cutting depths and different spindle speeds. At the end of the process, the temperature was measured with a thermocouple. A PEL C960 digital camera was used to take photographs of the tools before and after turning in order to analyse their wear. The workpieces were cut into small pieces and then photographs were taken to examine their surfaces. The results show that the temperatures reported in machining with the neem oil-based cutting fluid were lower than those obtained during dry turning or turning with a conventional cutting fluid. From the analysis of the properties of the neem oil, it was evident that it is well-suited to be used as a metalworking fluid. The workpiece surface quality after turning with this alternative fluid was comparable with that obtained for a traditional cutting fluid.

THE USE OF BIODEGRADABLE CUTTING FLUIDFOR THIN AND HARD a-C:H AND TiAlN COATINGS

This paper presents results of tribological tests performed under lubricated friction conditions using a T-01M analyser. The lubricant was biodegradable cutting fluid containing a special-purpose additive – zinc aspartate. The discs for the ball-on-disc configuration were made of HS6-5-2C steel. The study involved testing coated and uncoated steel specimens. The a-C:H and TiAlN coatings were produced using physical vapour deposition (PVD). The structure of the coatings was analysed before and after the tribological tests with a JSM-7100F scanning electron microscope. The coating hardness was measured using a CSM Instruments nano-hardness tester (NHT). The coating surface texture of the coated and uncoated discs was determined by means of a Talysurf CCI Lite profilometer. The thin boundary films that formed in the friction area prevented the surfaces from coming into direct contact. The films improved the motion resistance and provided anticorrosive protection during the tests. The biodegradable cutting fluid used in the study had no negative effect on the environment. Słowa kluczowe: biodegradowalne ciecze obróbkowe, powłoka a-C:H i TiAlN, tarcie, zużycie. Streszczenie W artykule zestawiono wyniki badań tribologicznych wykonane na testerze T-01M w warunkach tarcia ze smarowaniem biodegradowalną cieczą chłodząco-smarującą zawierającą dodatek uszlachetniający – asparginian cynku. Tarcze były wykonane ze stali HS6-5-2C bez i z naniesioną powłoką a-C:H oraz TiAlN techniką fizycznego osadzania z fazy gazowej PVD. Obserwacje struktury powłok przed testem tribologicznym wykonano mikroskopem skaningowym SEM JSM-7100F. Twardość powłok przed testem tribologicznym zmierzono za pomocą nanotwardościomierza NHT CSM Instrument. Natomiast analizę struktury geometrycznej powierzchni tarcz bez powłoki i z powłokami przed oraz po testach tribologicznych wykonano profilometrem optycznym Talysurf CCI Lite. W miejscu tarcia powstały warstwy graniczne, które zabezpieczyły przed bezpośrednim kontaktem powierzchni współpracujących tarciowo. Warstwy te przyczyniły się do zmniejszenia oporów ruchu oraz zapewniły ochronę antykorozyjną w czasie prowadzenia testów. Ponadto użyta do badań ciecz chodząco-smarująca jest biodegradowalna i nie wykazała negatywnego wpływu na środowisko. * Kielce University of Technology, Faculty of Mechatronics and Mechanical Engineering, al. Tysiąclecia Państwa Polskiego 7, 25-314 Kielce, Poland, e-mails: ozimina@tu.kielce.pl, mmadej@tu.kielce.pl, jkowalczyk@tu.kielce.pl. ** Air Force Institute of Technology, ul. Księcia Bolesława 6, 01-494 Warsaw, Poland e-mail: andrzej.kulczycki@itwl.pl. INTRODUCTION With the industry sector expanding very fast, we observe higher energy consumption requirements and greater environmental pollution posing serious risks to human health. The environmental issues need to be addressed, not only with new legislation, but also environmentally friendly technologies [L. 1]. Machining, which is the most common manufacturing process found in practically all industries, involves removing material from the workpiece to achieve a desired final shape [L. 2]. Machining operations generally require applying cutting fluids, which may have a direct impact on the environment [L. 3]. In many countries, ‘spent’ fluids are classified as toxic or ‘hazardous waste’ [L. 4]. With the above factors taken into consideration, dry cutting is performed whenever possible. In some cases, however, the use of a cutting fluid is necessary to prevent seizure at the tool/workpiece interface, reduce tool wear, or control the workpiece thermal deformation. Narrow tolerances on dimensions and form may not allow dry cutting. Under such circumstances, special solutions are required. 46 ISSN 0208-7774 T R I B O L O G I A 6/2017 Machining performed under dry conditions means consuming much more energy. As the world energy consumption increases every day, future research should focus on energy savings. On average, there is a 15% rise in energy consumption every five years (Fig. 1). 0 100 200 300 400 500 600 700 800 90

The influence of the chemical structure of synthetic hydrocarbons and alcohols on the lubricity of CI engine fuels and aviation fuels

The paper covers the mechanism of lubrication layer formation by fuels containing synthetic hydrocarbons and alcohols. Development of alternative fuels containing FAME, alcohols, and synthetic hydrocarbons has increased the interest in the mechanism of lubrication of fuelling systems parts. Fuel lubricity tests have been conducted using the HFRR and BOCLE testing rigs. Fuels under testing, both for CI engines and for aviation turbine ones, contained synthetic components: saturated hydrocarbons both of even and odd number of carbon atoms, and butanol, isomers. These components have been added to conventional fuels, such as diesel fuel and Jet A-1 fuel at the concentration of 0–20% (V/V). All fuels under testing contained commercially available lubricity improvers (carboxylic acid). Test results were analysed using model αi described in [L. 6, 7]. As a result of the analysis, it has been found that the liquid phase, which is a lubricating film, should contain agglomerates or molecular clusters responsible for the transport of energy introduced into lubricating film by electrons emitted from metal surface. The mechanism enabling a description of the effect of base fuel without lubricity improvers on efficiency of such additives has been suggested. Słowa kluczowe: paliwa, smarność paliw, syntetyczne węglowodory, klastry molekularne. Streszczenie Przedmiotem artykułu jest mechanizm tworzenia warstwy smarującej przez paliwa zawierające syntetyczne węglowodory i alkohole. Rozwój paliw alternatywnych spowodował wzrost zainteresowania mechanizmem smarowania elementów układów zasilania silników. Badania smarności paliw prowadzono z użyciem aparatów HFRR i BOCLE. Badane paliwa do silników o ZS i paliwa do turbinowych silników lotniczych zawierały trzy serie syntetycznych komponentów: węglowodory parafinowe o parzystej liczbie atomów węgla, węglowodory parafinowe o nieparzystej liczbie atomów węgla oraz izomery butanolu. Powyższe syntetyczne komponenty były dodawane do mineralnych paliw: oleju napędowego i paliwa Jet A1 w ilości 0–20% (V/V). Wszystkie badane paliwa zawierały komercyjnie dostępne dodatki smarnościowe (kwas karboksylowy). Wyniki badań eksperymentalnych były analizowane z zastosowaniem modelu αi opisanego w publikacjach [L. 6, 7]. W rezultacie przeprowadzonej analizy stwierdzono, że faza ciekła – film smarny powinna zawierać aglomeraty lub klastry molekularne, które są odpowiedzialne za transport energii wprowadzanej do filmu smarnego przez elektrony emitowane z powierzchni metalu. Zaproponowano mechanizm, który może wyjaśnić wpływ paliwa bazowego (bez dodatków smarnościowych) na efektywność działania dodatków smarnościowych. 92 ISSN 0208-7774 T R I B O L O G I A 3/2017 • The chemical reaction of additive with surface material (additives create the “extreme pressure” /EP

Problems in fuelling spark ignition engines with dimethyl ether

This paper discusses briefly the production technology of dimethyl ether, taking into account plant raw materials and the physical and chemical properties of DME as compared to diesel fuel. The benefits and disadvantages of DME as a fuel are presented and changes in the emission of harmful substances characterised as compared to the combustion of diesel fuel. Also, basic usage problems are addressed, e.g. the wear of engine’s elements, cavity and leakages in the fuel system.

The method, based on storage simulator and IR – VIS spectroscopy, for predicting the allowable time of storage of biocomponents for CI engines

The paper presents the results of investigations concerning a new method used for predicting the allowable time of storage of biocomponents – FAME. The method was based on laboratory research carried out with the use of a storage tank simulator. The aging process was carried out in the conditions increasing the reaction rate – at high temperature. There are several methods/procedures used for predicting the allowable time of storage of fuels and biocomponents – FAME, but all of them are based on tests at the temperature so high that the mechanism of aging process is different than the one observed in storage tanks. It was assumed that the aging process could be divided into two stages: at the first stage, the aging precursors are created and at the second stage, precursors are converted into the fuel aging products. These products lead to changes in fuel properties. The kinetics of precursor creation determines the rate of all reactions, which lead to the final aging products. It was found that the rate of reaction at the first stage of fuel aging can be effectively increased by an increase in temperature and even relatively high temperature does not change the mechanism of the creation of aging precursors. The method that has been worked out makes it possible to control the mechanism of aging process during quick laboratory tests. The products of aging processes were detected with the use of the IR-VIS spectrometry. The allowable time of storage was determined for several FAME samples on the basis of quick laboratory tests. The results of laboratory quick tests were verified by comparing them with the results of the aging process of FAME in storage tanks. On the basis of the test results, the algorithm of allowable time of FAME storage calculation was worked out.

THE INFLUENCE OF FUELS CHEMICAL COMPOSITION ON ITS LUBRICITY – NEW VIEWS ON THE MECHANISM OF PROTECTION LAYER CREATION DURING TRIBOLOGICAL PROCESS

The aim of this paper is to examine the current views on the mechanism of the formation of a protective film by mineral fuels and biocomponents (FAMEs and alcohols). As the experimental data show, the ability of fuels / biofuels to form a protective film under different conditions is very important to the efficient operation of fuel pumps. The mating parts of pumps are protected against wear and seizure because of the interactions between the metal surfaces and the lubricant (fuel / biofuel) at the molecular level. The tribochemical research focuses on the tribochemical reactions of lubricating additives because the base fuel is frequently treated as a solvent only. Today, most fuels for CI engines contain FAME, a biocomponent that may differ in the chemical structure depending on the type and properties of the vegetable oil used. The current trend is to produce fuels from biomass hydrocarbons, which are blended with mineral diesel fuel. It has been found that the chemical structure of biohydrocarbons is responsible for changes in the lubricity of the blends. Lubricity is determined using a standard high frequency reciprocating rig (HFRR) test because of one parameter, i.e. the wear of the ball. The results of the authors’ previous studies were used to create a new model of the protective film formation by fuels containing biocomponents (oxygenates) and biohydrocarbons. The model makes it possible to describe the tribochemical processes quantitatively. The quantitative analysis is based on the parameter αi, which is the measure of reactivity of lubricating additives and/or biocomponents related to the properties of the mating parts and the operating conditions in a tribological system. The new approach to the mechanism of the protective film formation, based on the quantitative description of tribochemical reactions, enables us to begin research on new criteria for the lubricity of fuels containing lubricating additives and biocomponents.

THE NEW STAND FOR AGING OF BIOCOMPONENTS AND BIOFUELS PROCESS TESTING AT RELATIVELY SHORT TIME

In the paper, the concept of a model bench for accelerated ageing of bio-components and biofuels was presented. It is used to simulate the ageing process of biofuels and components of vegetable or animal origin, taking place during storage in the storage tanks. The construction of the bench’s essential elements and its equipment were designed and implemented in such a way as to mostly reflect actual storage conditions in large capacity tanks. An additional and unprecedented function of the bench includes the possibility to simulate the product transport conditions. Furthermore, a method of the test, with the use of simultaneously performed traditional tests on the physical and chemical properties monitored in the process of storage was presented. An analysis of the relation between values of the parameters obtained with different methods (on the model bench and under laboratory conditions) was conducted. In addition, their usefulness to assess the impact of logistic processes on the product quality was presented. In the paper, the results of the work executed within the framework of the project “Development of a prototype of the monitoring system the ageing rate and degree of bio-components and biofuels” within the Program Innovative Economy Operational Programme, Measure 1.4. “Support for goal-oriented projects” were used.