Pub Date : 2020-10-27DOI: 10.6060/ivkkt.20206311.6276
G. Kozlov, I. Dolbin
Three schemes of modeling of reinforcement degree of nanocomposites polymer/2D-nanofiller with elastomeric matrix were proposed, differing principally from used ones earlier. These schemes do not used nominal characteristics of nanofiller (its modulus of elasticity, anisotropy degree), yet allow to obtain real (effective) values of these parameters. It has been shown, that modulus of elasticity of 2D-nanofiller aggregates in polymer matrix of nanocomposite is a function of stiffness of the indicated matrix. The other analogous model assumes the dependence of modulus of elasticity of 2D-nanofiller on its aggregation degree in polymer matrix, expressed by number of nanofiller separate platelets per one aggregate (“packet” or tactoid). The combination of these approaches allows to predict the real degree of nanofiller anisotropy and then reinforcement degree of nanocomposite. One more scheme uses the structure of nanofiller aggregates, characterized by its fractal dimension, for modeling of reinforcement degree of nanocomposites. The obtained real modulus of elasticity of 2D-nanofiller is in 5 orders of value smaller relatively to its nominal magnitude. The application of real (effective) characteristics of nanofiller allows to simulate reinforcement degree of nanocomposite within the framework of simple mixtures rule. Nanocomposites elastomer/2D-nanofiller are enough conservative systems, for which real anisotropy degree and structure of nanofiller aggregates do not depend on its content. This circumstance simplifies perceptibly prediction of mechanical properties of these nanocomposites.
{"title":"SIMULATION OF REINFORCEMENT DEGREE OF NANOCOMPOSITES ELASTOMER/2D-NANOFILLER","authors":"G. Kozlov, I. Dolbin","doi":"10.6060/ivkkt.20206311.6276","DOIUrl":"https://doi.org/10.6060/ivkkt.20206311.6276","url":null,"abstract":"Three schemes of modeling of reinforcement degree of nanocomposites polymer/2D-nanofiller with elastomeric matrix were proposed, differing principally from used ones earlier. These schemes do not used nominal characteristics of nanofiller (its modulus of elasticity, anisotropy degree), yet allow to obtain real (effective) values of these parameters. It has been shown, that modulus of elasticity of 2D-nanofiller aggregates in polymer matrix of nanocomposite is a function of stiffness of the indicated matrix. The other analogous model assumes the dependence of modulus of elasticity of 2D-nanofiller on its aggregation degree in polymer matrix, expressed by number of nanofiller separate platelets per one aggregate (“packet” or tactoid). The combination of these approaches allows to predict the real degree of nanofiller anisotropy and then reinforcement degree of nanocomposite. One more scheme uses the structure of nanofiller aggregates, characterized by its fractal dimension, for modeling of reinforcement degree of nanocomposites. The obtained real modulus of elasticity of 2D-nanofiller is in 5 orders of value smaller relatively to its nominal magnitude. The application of real (effective) characteristics of nanofiller allows to simulate reinforcement degree of nanocomposite within the framework of simple mixtures rule. Nanocomposites elastomer/2D-nanofiller are enough conservative systems, for which real anisotropy degree and structure of nanofiller aggregates do not depend on its content. This circumstance simplifies perceptibly prediction of mechanical properties of these nanocomposites.","PeriodicalId":14640,"journal":{"name":"IZVESTIYA VYSSHIKH UCHEBNYKH ZAVEDENII KHIMIYA KHIMICHESKAYA TEKHNOLOGIYA","volume":"13 2 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2020-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89930886","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2020-10-27DOI: 10.6060/ivkkt.20206311.6188
Yuliya V. Demidova, V. Potekhin, P. A. Demidov
Currently, the main method for producing N-(2-hydroxyethyl) piperazine in industry is the cyclization of ethylene glycols and ethanolamines in the presence of ammonia and hydrogen. The main disadvantage of this method is the production of a wide range of products and, as a consequence, low selectivity for N-(2-hydroxyethyl) piperazine. In this work, the object of study is the piperazine hydroxyethylation reaction in the presence of an “inert” solvent under the reaction conditions, as the most selective way to obtain N-(2-hydroxyethyl) piperazine. The solvent molecule acts as a homogeneous catalyst of the acid type and is characterized by the presence of a mobile proton for opening the oxirane ring of ethylene oxide by the acid-base mechanism. There was studied the dependence of the yield of reaction products on the parameters of the process in the temperature range of 60 - 130 ° C; solvent concentration (water, methylcellosolve) 1 - 75% wt. and molar ratio of reagents (ethylene oxide / piperazine) 0.2 - 1. Analysis of the reaction mass by gas-liquid chromatography showed that the main by-product is N, N'-bis (2-hydroxyethyl) piperazine - the product of the hydroxyethylation of N-(2-hydroxyethyl ) piperazine in the second amino group. The hydroxyl group of hydroxyethylation products are formed in a negligible amount. It was found that the composition and concentration of the solvent, as well as the temperature regime of hydroxyethylation, do not significantly affect the selectivity of the process. It was shown that piperazine hydroxyethylation is described by the kinetics of series-parallel reactions. The results obtained in the study may be of interest for the development of piperazine hydroxyethylation process technology, in terms of simplifying the mathematical model of the reactor unit by excluding from the description factors that do not significantly affect the selectivity of the formation of N-(2-hydroxyethyl) piperazine.
{"title":"ON REACTIVITY OF PIPERAZINE AMINOGRUPS IN INTERACTION WITH ETHYLENE OXIDE","authors":"Yuliya V. Demidova, V. Potekhin, P. A. Demidov","doi":"10.6060/ivkkt.20206311.6188","DOIUrl":"https://doi.org/10.6060/ivkkt.20206311.6188","url":null,"abstract":"Currently, the main method for producing N-(2-hydroxyethyl) piperazine in industry is the cyclization of ethylene glycols and ethanolamines in the presence of ammonia and hydrogen. The main disadvantage of this method is the production of a wide range of products and, as a consequence, low selectivity for N-(2-hydroxyethyl) piperazine. In this work, the object of study is the piperazine hydroxyethylation reaction in the presence of an “inert” solvent under the reaction conditions, as the most selective way to obtain N-(2-hydroxyethyl) piperazine. The solvent molecule acts as a homogeneous catalyst of the acid type and is characterized by the presence of a mobile proton for opening the oxirane ring of ethylene oxide by the acid-base mechanism. There was studied the dependence of the yield of reaction products on the parameters of the process in the temperature range of 60 - 130 ° C; solvent concentration (water, methylcellosolve) 1 - 75% wt. and molar ratio of reagents (ethylene oxide / piperazine) 0.2 - 1. Analysis of the reaction mass by gas-liquid chromatography showed that the main by-product is N, N'-bis (2-hydroxyethyl) piperazine - the product of the hydroxyethylation of N-(2-hydroxyethyl ) piperazine in the second amino group. The hydroxyl group of hydroxyethylation products are formed in a negligible amount. It was found that the composition and concentration of the solvent, as well as the temperature regime of hydroxyethylation, do not significantly affect the selectivity of the process. It was shown that piperazine hydroxyethylation is described by the kinetics of series-parallel reactions. The results obtained in the study may be of interest for the development of piperazine hydroxyethylation process technology, in terms of simplifying the mathematical model of the reactor unit by excluding from the description factors that do not significantly affect the selectivity of the formation of N-(2-hydroxyethyl) piperazine.","PeriodicalId":14640,"journal":{"name":"IZVESTIYA VYSSHIKH UCHEBNYKH ZAVEDENII KHIMIYA KHIMICHESKAYA TEKHNOLOGIYA","volume":"68 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2020-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86439921","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2020-10-27DOI: 10.6060/ivkkt.20206311.6252
Y. Ivanova, N. Mamardashvili, N. E. Kochkina
Aggregation of 13,17-diethyl-2,3,7,8,12,18-hexamethyl-5-(pyridin-4-yl) porphyrin (I), 13,17-diethyl-2,3,7,8,12,18-hexamethyl-5-(pyridin-3-yl)porphyrin (II) and 13.17-diethyl-2,3,7,8,12,18-hexamethyl-5-(pyridin-2-yl)porphyrin (III) in the presence of trans-bis(benzonitrile)palladium(II) dichloride was studied by dynamic light scattering and electronic absorption spectroscopy in dichloromethane at 293 K. The average aggregate size and the nature of their distribution were determined. Using scanning electron microscopy, it was determined the size and composition of clusters formed by aggregates of complexes of the palladium(II) cation with the studied porphyrins. It was shown that minimal acetic acid additions lead to the destruction of the corresponding clusters. At the same time, complete destruction of the aggregates does not occur even with a 100-fold molar excess of acid.We used the Zetasizer Nano ZS (model ZEN3600, Malvern Instruments), equipped with a 633nm laser and non-invasive backscattering (NIBS) technology when the scattered light detector is positioned at an angle of 173° to the incident light. Confirmation of porphyrin aggregation was performed by additional study of the structure using a Hitachi TM4000Plus desktop electron microscope equipped with a 4-segment highly sensitive semiconductor detector and a secondary electron detector for low vacuum mode. Elemental analysis of the obtained aggregates in the cluster was performed using a silicon drift detector with a working area of 30 mm2, combined with a Hitachi TM4000Plus microscope. It was found that aggregates consisting of a para-pyridyl derivative of alkylporphyrin and trans-bis (benzonitrile) palladium (II) dichloride are formed in dichloromethane at 293 K. The best results of porphyrin structures were observed for mixtures of 13,17-diethyl-2,3,7,8,12,18-5-hexamethyl-5-(pyridine-4-yl)porphyrin with TRANS-bis(benzonitrile)- palladium (II) dichloride in a ratio of 1:3, which is probably due to less spatial shielding of the reaction center of the macrocycle and, as a result, better stabilization of the resulting particles. The size of a cluster consisting of individual aggregates was measured using scanning electron microscopy. An elemental analysis of a single aggregate was obtained.
{"title":"AGGREGATION OF MS-MONOPYRIDYL-Β-OCTAALKYLPORPHYRINS IN DICHLOROMETHANE IN PRESENCE OF Pd(II)","authors":"Y. Ivanova, N. Mamardashvili, N. E. Kochkina","doi":"10.6060/ivkkt.20206311.6252","DOIUrl":"https://doi.org/10.6060/ivkkt.20206311.6252","url":null,"abstract":"Aggregation of 13,17-diethyl-2,3,7,8,12,18-hexamethyl-5-(pyridin-4-yl) porphyrin (I), 13,17-diethyl-2,3,7,8,12,18-hexamethyl-5-(pyridin-3-yl)porphyrin (II) and 13.17-diethyl-2,3,7,8,12,18-hexamethyl-5-(pyridin-2-yl)porphyrin (III) in the presence of trans-bis(benzonitrile)palladium(II) dichloride was studied by dynamic light scattering and electronic absorption spectroscopy in dichloromethane at 293 K. The average aggregate size and the nature of their distribution were determined. Using scanning electron microscopy, it was determined the size and composition of clusters formed by aggregates of complexes of the palladium(II) cation with the studied porphyrins. It was shown that minimal acetic acid additions lead to the destruction of the corresponding clusters. At the same time, complete destruction of the aggregates does not occur even with a 100-fold molar excess of acid.We used the Zetasizer Nano ZS (model ZEN3600, Malvern Instruments), equipped with a 633nm laser and non-invasive backscattering (NIBS) technology when the scattered light detector is positioned at an angle of 173° to the incident light. Confirmation of porphyrin aggregation was performed by additional study of the structure using a Hitachi TM4000Plus desktop electron microscope equipped with a 4-segment highly sensitive semiconductor detector and a secondary electron detector for low vacuum mode. Elemental analysis of the obtained aggregates in the cluster was performed using a silicon drift detector with a working area of 30 mm2, combined with a Hitachi TM4000Plus microscope. It was found that aggregates consisting of a para-pyridyl derivative of alkylporphyrin and trans-bis (benzonitrile) palladium (II) dichloride are formed in dichloromethane at 293 K. The best results of porphyrin structures were observed for mixtures of 13,17-diethyl-2,3,7,8,12,18-5-hexamethyl-5-(pyridine-4-yl)porphyrin with TRANS-bis(benzonitrile)- palladium (II) dichloride in a ratio of 1:3, which is probably due to less spatial shielding of the reaction center of the macrocycle and, as a result, better stabilization of the resulting particles. The size of a cluster consisting of individual aggregates was measured using scanning electron microscopy. An elemental analysis of a single aggregate was obtained.","PeriodicalId":14640,"journal":{"name":"IZVESTIYA VYSSHIKH UCHEBNYKH ZAVEDENII KHIMIYA KHIMICHESKAYA TEKHNOLOGIYA","volume":"20 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2020-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86614778","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2020-10-27DOI: 10.6060/ivkkt.20206311.6256
Y. Sokolova, Anton N. Chepikov
The oxidative roasting of industrial spent catalyst Co-Mo/Al2O3 for the hydrotreatment of diesel fuel with lime in an air atmosphere was studied. Using the data of DTA, TG and X-ray phase analysis, it was found that during roasting, the sulfur and carbon oxides forms CaSO4 and CaCO3, and Mo is converted to calcium molybdate. Using the filtering fixed bed of reagents, the kinetics of roasting was studied. It was found that in the temperature range of 550 – 600 °C with air, supply rate of 3 l/min the process ends in 38 - 44 min for ground and non-ground catalyst. The optimal parameters (lime consumption, temperature, and time of roasting) of the absorption of sulfur oxides during roasting were determined. The degree of sulfur and carbon oxides adsorption is 96 and 36%, respectively. Separation of roasting products using unmilled spent catalyst is proposed into a small fraction (contains a mixture of CaSO4, CaCO3 and CaO) and a coarse (consists of Al2O3, CaMoO4, CoO) fractions, and their separate processing. It has been shown that in the separate processing of roast fractions by a sodium carbonate solution, it is possible to separately obtain alumina (catalyst base) with cobalt oxide, a molybdenum-containing solution, and also a mixture of sulfate, carbonate and oxide calcium. The used method of roasting the spent hydrotreating catalyst with lime will allow hazardous waste of hazard class 3-4 to be disposed of without hazardous waste gas costs. It allows one to obtain, during further processing, molybdenum and cobalt compounds, as well as finely divided alumina.
{"title":"OXIDATIVE ROASTING OF INDUSTRIAL SPENT CATALYSTS CO-Mo/Al2O3 HYDROPROCESSING WITH LIM","authors":"Y. Sokolova, Anton N. Chepikov","doi":"10.6060/ivkkt.20206311.6256","DOIUrl":"https://doi.org/10.6060/ivkkt.20206311.6256","url":null,"abstract":"The oxidative roasting of industrial spent catalyst Co-Mo/Al2O3 for the hydrotreatment of diesel fuel with lime in an air atmosphere was studied. Using the data of DTA, TG and X-ray phase analysis, it was found that during roasting, the sulfur and carbon oxides forms CaSO4 and CaCO3, and Mo is converted to calcium molybdate. Using the filtering fixed bed of reagents, the kinetics of roasting was studied. It was found that in the temperature range of 550 – 600 °C with air, supply rate of 3 l/min the process ends in 38 - 44 min for ground and non-ground catalyst. The optimal parameters (lime consumption, temperature, and time of roasting) of the absorption of sulfur oxides during roasting were determined. The degree of sulfur and carbon oxides adsorption is 96 and 36%, respectively. Separation of roasting products using unmilled spent catalyst is proposed into a small fraction (contains a mixture of CaSO4, CaCO3 and CaO) and a coarse (consists of Al2O3, CaMoO4, CoO) fractions, and their separate processing. It has been shown that in the separate processing of roast fractions by a sodium carbonate solution, it is possible to separately obtain alumina (catalyst base) with cobalt oxide, a molybdenum-containing solution, and also a mixture of sulfate, carbonate and oxide calcium. The used method of roasting the spent hydrotreating catalyst with lime will allow hazardous waste of hazard class 3-4 to be disposed of without hazardous waste gas costs. It allows one to obtain, during further processing, molybdenum and cobalt compounds, as well as finely divided alumina.","PeriodicalId":14640,"journal":{"name":"IZVESTIYA VYSSHIKH UCHEBNYKH ZAVEDENII KHIMIYA KHIMICHESKAYA TEKHNOLOGIYA","volume":"21 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2020-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91186362","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2020-10-27DOI: 10.6060/ivkkt.20206311.6232
A. Golovanov, Nicolay V. Luparev, B. Sorokin
An influence of the conventional planar technology of the semiconductor surface treatment operations (photolithography, plasma-chemical surface cleaning in radio frequency low-pressure oxygen discharge, and thin metal films growth) on monocrystalline diamond surface topography and roughness is investigated. It is preliminary shown that photolithography without the plasma cleaning and magnetron deposition of an aluminum film do not induce any diamond surface changes which could be found by the optical profilometry, electron and optical microscopy. However, as a result of the lithography some organic contaminants can decrease the adhesion of the aluminum film and have to remove from the surface. Further, the influence of the above-listed surface treatment operations separately and in combinations on the synthetic diamond surface is investigated. It is found that an even short oxygen plasma cleaning during 5 min with a low bias power of 20 W leads to etching the grooves on the diamond surface The depth of the etching grooves varies by more than an order of magnitude in different experiments (0.3 - 19 nm), and by 10-20% within the same substrate under the influence of the poorly controlled external factors. Also, oxygen plasma treatment changes its secondary electron emission coefficient. Deposition of aluminum film after plasma cleaning does not induce noticeable changes in the diamond surface topography. The quality of diamond surface polishing (in “hard” of “soft” direction), the diamond’s type (IIa or IIb) as well as producing method (HPHT or homoepitaxial CVD) do not affect the result of grooves formation.
{"title":"MODIFICATION OF DIAMOND SURFACE DURING PHOTOLITHOGRAPHY, PLASMA-CHEMICAL CLEANING, AND MAGNETRON DEPOSITION","authors":"A. Golovanov, Nicolay V. Luparev, B. Sorokin","doi":"10.6060/ivkkt.20206311.6232","DOIUrl":"https://doi.org/10.6060/ivkkt.20206311.6232","url":null,"abstract":"An influence of the conventional planar technology of the semiconductor surface treatment operations (photolithography, plasma-chemical surface cleaning in radio frequency low-pressure oxygen discharge, and thin metal films growth) on monocrystalline diamond surface topography and roughness is investigated. It is preliminary shown that photolithography without the plasma cleaning and magnetron deposition of an aluminum film do not induce any diamond surface changes which could be found by the optical profilometry, electron and optical microscopy. However, as a result of the lithography some organic contaminants can decrease the adhesion of the aluminum film and have to remove from the surface. Further, the influence of the above-listed surface treatment operations separately and in combinations on the synthetic diamond surface is investigated. It is found that an even short oxygen plasma cleaning during 5 min with a low bias power of 20 W leads to etching the grooves on the diamond surface The depth of the etching grooves varies by more than an order of magnitude in different experiments (0.3 - 19 nm), and by 10-20% within the same substrate under the influence of the poorly controlled external factors. Also, oxygen plasma treatment changes its secondary electron emission coefficient. Deposition of aluminum film after plasma cleaning does not induce noticeable changes in the diamond surface topography. The quality of diamond surface polishing (in “hard” of “soft” direction), the diamond’s type (IIa or IIb) as well as producing method (HPHT or homoepitaxial CVD) do not affect the result of grooves formation.","PeriodicalId":14640,"journal":{"name":"IZVESTIYA VYSSHIKH UCHEBNYKH ZAVEDENII KHIMIYA KHIMICHESKAYA TEKHNOLOGIYA","volume":"6 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2020-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76421884","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2020-10-27DOI: 10.6060/ivkkt.20206311.6242
Maria Larionova, N. D. Solovieva, Elena A. Savelieva
It is studied the regeneration and utilization possibility of spent nitric acid solutions for copper and its alloys etching for the creating an environmentally clean closed-cycle production of regenerated electrolytes. It is established that some difficulties arise when using the electrochemical method in the regeneration process of these solutions: during copper electrodeposition from spent copper-containing nitric acid solutions, nitric acid decomposes with vigorous evolution of nitrogen dioxide, which prevents copper ions reduction. In order to suppress the side process, it was proposed to partially neutralize the solution, not reaching the pH of copper hydration (pH 4-5). It is revealed that a decrease in the concentration of metal cations occurs due to partial neutralization of the nitric acid contained in the solution by concentrated alkali solution. The pulsed electrolysis mode was used to increase the efficiency of the metal ions electrodeposition process from dilute solutions. It is established that the using of pulsed electrolysis can reduce diffusion difficulties that arise in a dilute spent nitric acid copper-containing solution, thereby intensify the process of copper electrodeposition. It is showed that the prospects of using ultrasound to increase the rate of the copper electrodeposition process and improve the quality of the resulting coating. It is studied the ultrasound field effect on nucleation during copper electrodeposition in a pulsed mode from a partially neutralized electrolyte simulating the spent nitrate solution of etching copper alloys on various materials by the potentiostatic. It is established an increase in the number of copper nucleus that form on the studied substrates (graphite, copper, steel) at the initial time under the action of an ultrasonic field. It is concluded that the use of ultrasound allows to intensify the process of metal electrodeposition. An increase in current efficiency during copper electrodeposition and an increase in the copper extraction degree using ultrasonic field are achieved at lower cathodic current densities in a pulse. It is substantiated using of graphite foil and steel as cathode materials in the copper extraction from the spent nitric acid etching solution.
{"title":"ELECTRODEPOSITION OF COPPER IN ULTRASONIC FIELD FROM SPENT ETCHING SOLUTIONS","authors":"Maria Larionova, N. D. Solovieva, Elena A. Savelieva","doi":"10.6060/ivkkt.20206311.6242","DOIUrl":"https://doi.org/10.6060/ivkkt.20206311.6242","url":null,"abstract":"It is studied the regeneration and utilization possibility of spent nitric acid solutions for copper and its alloys etching for the creating an environmentally clean closed-cycle production of regenerated electrolytes. It is established that some difficulties arise when using the electrochemical method in the regeneration process of these solutions: during copper electrodeposition from spent copper-containing nitric acid solutions, nitric acid decomposes with vigorous evolution of nitrogen dioxide, which prevents copper ions reduction. In order to suppress the side process, it was proposed to partially neutralize the solution, not reaching the pH of copper hydration (pH 4-5). It is revealed that a decrease in the concentration of metal cations occurs due to partial neutralization of the nitric acid contained in the solution by concentrated alkali solution. The pulsed electrolysis mode was used to increase the efficiency of the metal ions electrodeposition process from dilute solutions. It is established that the using of pulsed electrolysis can reduce diffusion difficulties that arise in a dilute spent nitric acid copper-containing solution, thereby intensify the process of copper electrodeposition. It is showed that the prospects of using ultrasound to increase the rate of the copper electrodeposition process and improve the quality of the resulting coating. It is studied the ultrasound field effect on nucleation during copper electrodeposition in a pulsed mode from a partially neutralized electrolyte simulating the spent nitrate solution of etching copper alloys on various materials by the potentiostatic. It is established an increase in the number of copper nucleus that form on the studied substrates (graphite, copper, steel) at the initial time under the action of an ultrasonic field. It is concluded that the use of ultrasound allows to intensify the process of metal electrodeposition. An increase in current efficiency during copper electrodeposition and an increase in the copper extraction degree using ultrasonic field are achieved at lower cathodic current densities in a pulse. It is substantiated using of graphite foil and steel as cathode materials in the copper extraction from the spent nitric acid etching solution.","PeriodicalId":14640,"journal":{"name":"IZVESTIYA VYSSHIKH UCHEBNYKH ZAVEDENII KHIMIYA KHIMICHESKAYA TEKHNOLOGIYA","volume":"35 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2020-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90927168","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2020-10-27DOI: 10.6060/ivkkt.20206311.6222
Natalya P. Rumyantseva, V. S. Belova, A. V. Balmasov
The article considers the effect of a nitrogen-containing inhibitory additive on the corrosion indicators of structural steels (Steel 20, 30ХГСА, 40ХН2МА, 18Х2Н4ВА). The effectiveness of the inhibitor was studied by conducting corrosion tests in a solution of 3% sodium chloride using gravimetric and electrochemical methods. The results of determining the current density and corrosion potential testify to the inhibition of the corrosion process after surface treatment of steels in an emulsion of cutting fluid used for machining parts. The introduction of a heterocyclic nitrogen-containing compound into the emulsion promotes surface passivation and enhances the inhibitory effect. Due to the introduction of additives for carbon steel 20, it is possible to reduce the corrosion current density by 2.5 times compared to machined samples and by 1.6 times compared to samples processed in an emulsion of cutting fluid without additives. After holding the studied steels in a solution of 3% sodium chloride a decrease in the iron content and an increase in the oxygen content are observed in the surface layer. For alloyed steels the surface is enriched with chromium. The results of gravimetric studies indicate that after processing the samples in a 3% emulsion of cutting fluid with the addition of a nitrogen-containing compound, the mass loss is reduced by almost 2.5 times for steels 20 and 18X2H4ВA, by 1.7 times in 30ХГСА, and by 1,3 times in 40XH2MA compared with samples after machining. The use of an inhibitor provides an increase in the duration of interoperational storage after machining of parts made from the investigated structural steels.
{"title":"INVESTIGATION OF INHIBITOR INFLUENCE ON CORROSION BEHAVIOR OF STRUCTURAL STEELS","authors":"Natalya P. Rumyantseva, V. S. Belova, A. V. Balmasov","doi":"10.6060/ivkkt.20206311.6222","DOIUrl":"https://doi.org/10.6060/ivkkt.20206311.6222","url":null,"abstract":"The article considers the effect of a nitrogen-containing inhibitory additive on the corrosion indicators of structural steels (Steel 20, 30ХГСА, 40ХН2МА, 18Х2Н4ВА). The effectiveness of the inhibitor was studied by conducting corrosion tests in a solution of 3% sodium chloride using gravimetric and electrochemical methods. The results of determining the current density and corrosion potential testify to the inhibition of the corrosion process after surface treatment of steels in an emulsion of cutting fluid used for machining parts. The introduction of a heterocyclic nitrogen-containing compound into the emulsion promotes surface passivation and enhances the inhibitory effect. Due to the introduction of additives for carbon steel 20, it is possible to reduce the corrosion current density by 2.5 times compared to machined samples and by 1.6 times compared to samples processed in an emulsion of cutting fluid without additives. After holding the studied steels in a solution of 3% sodium chloride a decrease in the iron content and an increase in the oxygen content are observed in the surface layer. For alloyed steels the surface is enriched with chromium. The results of gravimetric studies indicate that after processing the samples in a 3% emulsion of cutting fluid with the addition of a nitrogen-containing compound, the mass loss is reduced by almost 2.5 times for steels 20 and 18X2H4ВA, by 1.7 times in 30ХГСА, and by 1,3 times in 40XH2MA compared with samples after machining. The use of an inhibitor provides an increase in the duration of interoperational storage after machining of parts made from the investigated structural steels.","PeriodicalId":14640,"journal":{"name":"IZVESTIYA VYSSHIKH UCHEBNYKH ZAVEDENII KHIMIYA KHIMICHESKAYA TEKHNOLOGIYA","volume":"17 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2020-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"72839704","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2020-10-27DOI: 10.6060/ivkkt.20206311.6245
T. Shikova, S. Smirnov, Alexey I. Artyuhov
This paper presents the results of experimental study of the processes of destruction and changes in the composition of the surface layer of a Lexan 8010 polycarbonate (PC) film during treatment in a positive column of a DC glow discharge in argon, oxygen, and their mixtures. The mass loss rates of the polymer samples were measured depending on the parameters of the discharge and the composition of the plasma-forming gas. The IR spectra of the polymer films after plasma exposure were analyzed. It was shown that the most noticeable changes in the sample destruction rate and the chemical composition of the surface layer occur when the oxygen content in the mixture is up to 20%. With a further increase in the O2 content in the plasma-forming mixture, the changes are insignificant. The main gaseous products of PC destruction in the plasma of an argon-oxygen mixture are H2, CO, and H2O molecules. In the first second after the discharge is turned on, H2 molecules are released at maximum rate and at a lower CO rate. The formation of carbon monoxide and hydrogen molecules occurs without the direct participation of oxygen under the action of active particles of argon plasma without the participation of active oxygen. Exposure to argon plasma leads to an increase in the oxygen content on the sample surface. In this case, the destruction of С – О, О–С(=О)–О bonds, which are part of the structure of the polycarbonate elementary unit, and the formation of new oxygen-containing bonds are observed. Etching of the polymer with active plasma particles leads to a change in the micro relief of the sample surface. A change in roughness and an increase in the concentration of polar functional groups increases the wettability of the PC film surface. A discussion of the possible mechanisms of the processes is made, which allows us to describe the observed results.
本文研究了聚碳酸酯(PC)薄膜在氩气、氧气及其混合物的直流辉光放电正极柱下的破坏过程和表层成分的变化。根据放电参数和等离子体形成气体的组成，测量了聚合物样品的质量损失率。对等离子体辐照后聚合物薄膜的红外光谱进行了分析。结果表明，当氧含量达到20%时，试样破坏率和表层化学成分的变化最为显著。随着等离子体形成混合物中氧含量的进一步增加，这种变化是微不足道的。在氩氧混合物的等离子体中，PC破坏的主要气体产物是H2、CO和H2O分子。在开启放电后的第一秒，H2分子以最大速率和较低的CO速率释放。在没有活性氧参与的氩等离子体活性粒子的作用下，一氧化碳和氢分子的形成是在没有氧直接参与的情况下发生的。暴露在氩等离子体中会导致样品表面氧含量的增加。在这种情况下，观察到作为聚碳酸酯基本单元结构的一部分的С - О， О -С (=О) -О键的破坏，并形成新的含氧键。用活性等离子体粒子蚀刻聚合物会导致样品表面的微观起伏变化。粗糙度的变化和极性官能团浓度的增加增加了PC膜表面的润湿性。讨论了这些过程的可能机制，这使我们能够描述观察到的结果。
{"title":"KINETIC FEATURES OF PLASMA-CHEMICAL MODIFICATION OF POLYCARBONATE IN PLASMA IN ARGON - OXYGEN MIXTURE","authors":"T. Shikova, S. Smirnov, Alexey I. Artyuhov","doi":"10.6060/ivkkt.20206311.6245","DOIUrl":"https://doi.org/10.6060/ivkkt.20206311.6245","url":null,"abstract":"This paper presents the results of experimental study of the processes of destruction and changes in the composition of the surface layer of a Lexan 8010 polycarbonate (PC) film during treatment in a positive column of a DC glow discharge in argon, oxygen, and their mixtures. The mass loss rates of the polymer samples were measured depending on the parameters of the discharge and the composition of the plasma-forming gas. The IR spectra of the polymer films after plasma exposure were analyzed. It was shown that the most noticeable changes in the sample destruction rate and the chemical composition of the surface layer occur when the oxygen content in the mixture is up to 20%. With a further increase in the O2 content in the plasma-forming mixture, the changes are insignificant. The main gaseous products of PC destruction in the plasma of an argon-oxygen mixture are H2, CO, and H2O molecules. In the first second after the discharge is turned on, H2 molecules are released at maximum rate and at a lower CO rate. The formation of carbon monoxide and hydrogen molecules occurs without the direct participation of oxygen under the action of active particles of argon plasma without the participation of active oxygen. Exposure to argon plasma leads to an increase in the oxygen content on the sample surface. In this case, the destruction of С – О, О–С(=О)–О bonds, which are part of the structure of the polycarbonate elementary unit, and the formation of new oxygen-containing bonds are observed. Etching of the polymer with active plasma particles leads to a change in the micro relief of the sample surface. A change in roughness and an increase in the concentration of polar functional groups increases the wettability of the PC film surface. A discussion of the possible mechanisms of the processes is made, which allows us to describe the observed results.","PeriodicalId":14640,"journal":{"name":"IZVESTIYA VYSSHIKH UCHEBNYKH ZAVEDENII KHIMIYA KHIMICHESKAYA TEKHNOLOGIYA","volume":"6 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2020-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74844498","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2020-10-27DOI: 10.6060/ivkkt.20206311.6307
E. N. Egorov, N. I. Kol’tsov, N. F. Ushmarin, S. I. Sandalov
The article studies the effect of trans-polynorbornene, general and special-purpose rubbers and fillers on the vulcanization characteristics of a rubber mixture, physical, mechanical, operational and dynamic properties of vulcanizates based on butadiene methylstyrene caoutchouc. The investigated model rubber mixture included SKMS-30ARK rubber, sulfur, 2,2'-dibenzthiazole disulfide, guanide F, zinc white, stearic acid, phenyl-2-naphthalamine, N-isopropyl-N'-phenyl-para-phenylenediamine, carbon blacks of grades P 514 and N 220, shungite powder and other ingredients. The rubber mixture was produced on laboratory rolls LB 320 160/160. The first (basic) version of the rubber mixture contained industrial oil I-12A as a softener. The second version of the mixture contained a modifying additive based on trans-polynorbornene and industrial oil I-12A. The third, fourth and fifth versions were prepared on the basis of a combination of rubbers SKMS-30ARK, SKN-4065 and BK-1675, including a modifying additive, as well as polyisobutylene P-118 and sevilen 11808-340. The vulcanization characteristics of the rubber mixture were studied on an MDR 3000 Basic rheometer at 150 °C for 30 min. To determine the physical and mechanical properties of rubber, standard samples of all variants of the rubber mixture were vulcanized at a temperature of 143 °C for 30 min in a vulcanization press of the P-V-100-3RT-2-PCD type. Studies of the physical, mechanical, operational and dynamic properties of rubber were carried out in accordance with the existing standards for the rubber industry. It is shown that vulcanizates containing a modifying additive have lower values of conventional tensile strength, hardness and tear resistance compared to vulcanizate of the base version of the rubber mixture and are characterized by increased dynamic and performance properties. Rubber containing a combination of butadiene-nitrile, butadiene-methylstyrene caoutchoucs and butyl caoutchouc, 10.0 mass parts sevilen 11808-340, 20.0 mass parts of trans-polynorbornene composed of in the modifying additive and 55.0 mass parts of carbon black P 324, possesses improved physical, mechanical and dynamic properties, as well as high resistance in sea water.
{"title":"RESEARCH OF OPERATIONAL AND DYNAMIC PROPERTIES OF RUBBER FOR PRODUCTS WORKING IN SEA WATER","authors":"E. N. Egorov, N. I. Kol’tsov, N. F. Ushmarin, S. I. Sandalov","doi":"10.6060/ivkkt.20206311.6307","DOIUrl":"https://doi.org/10.6060/ivkkt.20206311.6307","url":null,"abstract":"The article studies the effect of trans-polynorbornene, general and special-purpose rubbers and fillers on the vulcanization characteristics of a rubber mixture, physical, mechanical, operational and dynamic properties of vulcanizates based on butadiene methylstyrene caoutchouc. The investigated model rubber mixture included SKMS-30ARK rubber, sulfur, 2,2'-dibenzthiazole disulfide, guanide F, zinc white, stearic acid, phenyl-2-naphthalamine, N-isopropyl-N'-phenyl-para-phenylenediamine, carbon blacks of grades P 514 and N 220, shungite powder and other ingredients. The rubber mixture was produced on laboratory rolls LB 320 160/160. The first (basic) version of the rubber mixture contained industrial oil I-12A as a softener. The second version of the mixture contained a modifying additive based on trans-polynorbornene and industrial oil I-12A. The third, fourth and fifth versions were prepared on the basis of a combination of rubbers SKMS-30ARK, SKN-4065 and BK-1675, including a modifying additive, as well as polyisobutylene P-118 and sevilen 11808-340. The vulcanization characteristics of the rubber mixture were studied on an MDR 3000 Basic rheometer at 150 °C for 30 min. To determine the physical and mechanical properties of rubber, standard samples of all variants of the rubber mixture were vulcanized at a temperature of 143 °C for 30 min in a vulcanization press of the P-V-100-3RT-2-PCD type. Studies of the physical, mechanical, operational and dynamic properties of rubber were carried out in accordance with the existing standards for the rubber industry. It is shown that vulcanizates containing a modifying additive have lower values of conventional tensile strength, hardness and tear resistance compared to vulcanizate of the base version of the rubber mixture and are characterized by increased dynamic and performance properties. Rubber containing a combination of butadiene-nitrile, butadiene-methylstyrene caoutchoucs and butyl caoutchouc, 10.0 mass parts sevilen 11808-340, 20.0 mass parts of trans-polynorbornene composed of in the modifying additive and 55.0 mass parts of carbon black P 324, possesses improved physical, mechanical and dynamic properties, as well as high resistance in sea water.","PeriodicalId":14640,"journal":{"name":"IZVESTIYA VYSSHIKH UCHEBNYKH ZAVEDENII KHIMIYA KHIMICHESKAYA TEKHNOLOGIYA","volume":"11 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2020-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73969475","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2020-09-09DOI: 10.6060/ivkkt.20206310.6275
S. Fedosov, M. Bakanov
This paper shows that, in many technological processes, raw materials are subjected to high-temperature heat treatment and, in most cases, they have a geometric shape of the canonical form: a plate, a cylinder and a sphere. The convection drying process is considered as a typical heat and mass transfer process. The processes occurring under heat treatment conditions are reduced to transfer problems for an unbounded plate, cylinder, and ball with boundary conditions of the first kind, when the transfer potential (temperature, moisture content) is set on the surface of a solid. A number of expressions for calculations in the context of arbitrary distribution of initial values of transfer potentials as well as for uniform distributions are presented. It is shown that, when modeling heat and mass transfer processes in which the thermophysical characteristics of a solid body change significantly in the course of thermal treatment thereof, the use of already known solutions that have been previously developed becomes problematic. The «zonal» method and the «micro-processes» method are considered herein. It is shown that, for both methods, on the basis of experimental data referring to the dynamics of temperature and mass (moisture) content of the material over the course of the process, their dependences on the average (for the «zone» or «micro - process») temperatures and mass contents are determined. The next stage for calculations using the «zonal» method is formalization of the results obtained in the form of histograms of the values of mass conductivity coefficients from the average values of mass contents. For the «micro-processes» method, the kinetic curve can be used in calculations simultaneously. The smaller the range of measured values of temperatures and mass contents is the greater is the adequacy of calculated experimental data. It is emphasized that, under uneven initial conditions, analytical solutions to the heat transfer problem are usually presented in the form of infinite Fourier series. The convergence of the Fourier series deteriorates with decreasing time intervals. The great relevance of the application of the considered methods can be traced when modeling heat and mass transfer with intensive processes of phase transitions.
{"title":"APPLICATION OF «MICRO-PROCESSES» METHOD FOR MODELING HEAT CONDUCTION AND DIFFUSION PROCESSES IN CANONICAL BODIES","authors":"S. Fedosov, M. Bakanov","doi":"10.6060/ivkkt.20206310.6275","DOIUrl":"https://doi.org/10.6060/ivkkt.20206310.6275","url":null,"abstract":"This paper shows that, in many technological processes, raw materials are subjected to high-temperature heat treatment and, in most cases, they have a geometric shape of the canonical form: a plate, a cylinder and a sphere. The convection drying process is considered as a typical heat and mass transfer process. The processes occurring under heat treatment conditions are reduced to transfer problems for an unbounded plate, cylinder, and ball with boundary conditions of the first kind, when the transfer potential (temperature, moisture content) is set on the surface of a solid. A number of expressions for calculations in the context of arbitrary distribution of initial values of transfer potentials as well as for uniform distributions are presented. It is shown that, when modeling heat and mass transfer processes in which the thermophysical characteristics of a solid body change significantly in the course of thermal treatment thereof, the use of already known solutions that have been previously developed becomes problematic. The «zonal» method and the «micro-processes» method are considered herein. It is shown that, for both methods, on the basis of experimental data referring to the dynamics of temperature and mass (moisture) content of the material over the course of the process, their dependences on the average (for the «zone» or «micro - process») temperatures and mass contents are determined. The next stage for calculations using the «zonal» method is formalization of the results obtained in the form of histograms of the values of mass conductivity coefficients from the average values of mass contents. For the «micro-processes» method, the kinetic curve can be used in calculations simultaneously. The smaller the range of measured values of temperatures and mass contents is the greater is the adequacy of calculated experimental data. It is emphasized that, under uneven initial conditions, analytical solutions to the heat transfer problem are usually presented in the form of infinite Fourier series. The convergence of the Fourier series deteriorates with decreasing time intervals. The great relevance of the application of the considered methods can be traced when modeling heat and mass transfer with intensive processes of phase transitions.","PeriodicalId":14640,"journal":{"name":"IZVESTIYA VYSSHIKH UCHEBNYKH ZAVEDENII KHIMIYA KHIMICHESKAYA TEKHNOLOGIYA","volume":"35 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2020-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85679029","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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