Pub Date : 2024-03-02DOI: 10.32362/2410-6593-2024-19-1-72-87
A. Kholodkova, A. V. Reznichenko, A. A. Vasin, A. V. Smirnov
Objectives. To examine the general principles and recent advances in the synthesis of high-purity and high-homogeneity barium titanate powders in the manufacture of electronic components.Results. The main publications regarding the synthesis of barium titanate powder, including the works of recent years, were analyzed. The technological advantages and disadvantages of various synthesis methods were identified. Groups of methods based on solid-state interaction of reagents and methods of “wet chemistry” were also considered. The possibilities of producing barium titanate particles of non-isometric shapes for creating textured ceramics were discussed separately.Conclusions. Barium titanate is a well-known ferroelectric with a high dielectric constant and low dielectric loss. It is used as a component in ceramic electronic products, for example, capacitors, memory devices, optoelectronic devices, and piezoelectric transducers. The possibilities of producing functional ceramics based on barium titanate powder largely depend on its state and morphological characteristics, determined during the synthesis stage. The most important factors affecting the functional characteristics of ceramics are the purity and morphology of the powder raw materials used.
{"title":"Methods for the synthesis of barium titanate as a component of functional dielectric ceramics","authors":"A. Kholodkova, A. V. Reznichenko, A. A. Vasin, A. V. Smirnov","doi":"10.32362/2410-6593-2024-19-1-72-87","DOIUrl":"https://doi.org/10.32362/2410-6593-2024-19-1-72-87","url":null,"abstract":"Objectives. To examine the general principles and recent advances in the synthesis of high-purity and high-homogeneity barium titanate powders in the manufacture of electronic components.Results. The main publications regarding the synthesis of barium titanate powder, including the works of recent years, were analyzed. The technological advantages and disadvantages of various synthesis methods were identified. Groups of methods based on solid-state interaction of reagents and methods of “wet chemistry” were also considered. The possibilities of producing barium titanate particles of non-isometric shapes for creating textured ceramics were discussed separately.Conclusions. Barium titanate is a well-known ferroelectric with a high dielectric constant and low dielectric loss. It is used as a component in ceramic electronic products, for example, capacitors, memory devices, optoelectronic devices, and piezoelectric transducers. The possibilities of producing functional ceramics based on barium titanate powder largely depend on its state and morphological characteristics, determined during the synthesis stage. The most important factors affecting the functional characteristics of ceramics are the purity and morphology of the powder raw materials used.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140082074","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 : 2024-03-02DOI: 10.32362/2410-6593-2024-19-1-61-71
A. A. Lukoshkova, A. T. Shulyak, E. E. Posypayko, N. A. Selivanov, A. V. Golubev, А. S. Kubasov, A. Bykov, A. P. Zhdanov, K. Zhizhin, N. Kuznetsov
Objectives. To develop methods for the synthesis of substituted derivatives of the octahydrotriborate anion. Such compounds can be considered as hydrogen storage, components of ionic liquids, precursors for the production of boride coatings using the traditional chemical vapor deposition method, and also as a building material for the production of higher boron hydrogen clusters.Methods. Since substitution reactions are sensitive to moisture and atmospheric oxygen, the syntheses were carried out in a direct flow of argon or in a dry, sealed SPEKS GB02M glove box with a double gas purification unit and two airlocks. The reaction was initiated by cooling to 0°C, in order to avoid the formation of by-products. All the results were characterized using infrared (IR) and nuclear magnetic resonance (NMR) spectroscopies.Results. The study presents a detailed study of the known methods for preparing substituted derivatives of the octahydrotriborate(1−) anion using dry hydrogen chloride as an electrophilic inductor and makes recommendations for improvement. In this method it is advisable to use cesium octahydrotriborate which facilitates the yield of the target product. New methods were proposed to initiate the substitution reaction in the [B3H8]−-anion using N-chlorosuccinimide and bromine. Using these inductors, new substituted derivatives of the octahydrotriborate anion with N-nucleophiles were obtained and defined by means of IR and NMR spectroscopies: [B3H7NCR], (R = Et, i-Pr, Ph) and [B3H7NH2R], (R = C9H19 (INA), Bn), [B3H7NHEt2], as well as Bu4N[B3H7Hal], Bu4N[B3H6Hal2], where Hal = Сl, Br. It was also established that hydrogen bromide is released during the reaction with bromine and amines. This immediately protonates the amine which requires additional heating of the reaction mixture. The study also established that the reaction mechanism with N-chlorosuccinimide is not radical.Conclusions. The main factors influencing the course of the substitution reaction are the possible occurrence of side interactions between the nucleophile and the inducer, steric possibilities, and subsequent isolation of the reactive reaction products.
{"title":"New approaches to the synthesis of substituted derivatives of the [B3H8]− anion","authors":"A. A. Lukoshkova, A. T. Shulyak, E. E. Posypayko, N. A. Selivanov, A. V. Golubev, А. S. Kubasov, A. Bykov, A. P. Zhdanov, K. Zhizhin, N. Kuznetsov","doi":"10.32362/2410-6593-2024-19-1-61-71","DOIUrl":"https://doi.org/10.32362/2410-6593-2024-19-1-61-71","url":null,"abstract":"Objectives. To develop methods for the synthesis of substituted derivatives of the octahydrotriborate anion. Such compounds can be considered as hydrogen storage, components of ionic liquids, precursors for the production of boride coatings using the traditional chemical vapor deposition method, and also as a building material for the production of higher boron hydrogen clusters.Methods. Since substitution reactions are sensitive to moisture and atmospheric oxygen, the syntheses were carried out in a direct flow of argon or in a dry, sealed SPEKS GB02M glove box with a double gas purification unit and two airlocks. The reaction was initiated by cooling to 0°C, in order to avoid the formation of by-products. All the results were characterized using infrared (IR) and nuclear magnetic resonance (NMR) spectroscopies.Results. The study presents a detailed study of the known methods for preparing substituted derivatives of the octahydrotriborate(1−) anion using dry hydrogen chloride as an electrophilic inductor and makes recommendations for improvement. In this method it is advisable to use cesium octahydrotriborate which facilitates the yield of the target product. New methods were proposed to initiate the substitution reaction in the [B3H8]−-anion using N-chlorosuccinimide and bromine. Using these inductors, new substituted derivatives of the octahydrotriborate anion with N-nucleophiles were obtained and defined by means of IR and NMR spectroscopies: [B3H7NCR], (R = Et, i-Pr, Ph) and [B3H7NH2R], (R = C9H19 (INA), Bn), [B3H7NHEt2], as well as Bu4N[B3H7Hal], Bu4N[B3H6Hal2], where Hal = Сl, Br. It was also established that hydrogen bromide is released during the reaction with bromine and amines. This immediately protonates the amine which requires additional heating of the reaction mixture. The study also established that the reaction mechanism with N-chlorosuccinimide is not radical.Conclusions. The main factors influencing the course of the substitution reaction are the possible occurrence of side interactions between the nucleophile and the inducer, steric possibilities, and subsequent isolation of the reactive reaction products.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140081928","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 : 2024-01-18DOI: 10.32362/2410-6593-2023-18-6-549-558
S. V. Romanov, O. A. Botvinova, E. A. Timakov, D. A. Rashchupkina, Y. T. Panov
Objectives. To improve the technology for obtaining polymer spray coatings based on polycarbodiimides (polyureas) by studying changes in the process and operational parameters due to the introduction of aspartic acid derivatives (AADs) into the composition.Methods. The process of the production of sprayed and contact polyureas involves a number of difficulties, not least in terms of the cost of the components and high-pressure equipment. For this reason, mathematical modeling was used to optimize experimental design. The curing time of the composition was measured under conditions simulated to be close to actual. After thermostating and mixing Components A and B in predetermined ratios, the gelation time was measured to represent the curing time of the composition. The hardness of the material was determined by the Shore method according to GOST 24621-91. Tensile strength and relative elongation were determined according to a standard method (GOST 30436-96).Results. The effect of three AADs on the properties of the finished polyurea was studied. It was found that the introduction of two of them (AAD-1 and AAD-2) into polyurea in an amount of up to 40 wt % produces slow-curing (>250 s) polyureas capable of manual application. The finished products have physical properties on par with machine-poured materials (breaking strength >73 MPa; tensile strength >23 MPa; elongation >500%). Compiled regression equations were used to construct graphs of equal levels showing the possible areas of directed modification of the studied compositions.Conclusions. AAD can be used as a modifying component for polyurea systems to obtain slow- curing polyureas with high performance properties, which can be purposefully controlled by mathematical modeling. The resulting products have commercial value due to their combination of valuable physical and mechanical properties.
{"title":"High-performance slow-curing polyurea compositions","authors":"S. V. Romanov, O. A. Botvinova, E. A. Timakov, D. A. Rashchupkina, Y. T. Panov","doi":"10.32362/2410-6593-2023-18-6-549-558","DOIUrl":"https://doi.org/10.32362/2410-6593-2023-18-6-549-558","url":null,"abstract":"Objectives. To improve the technology for obtaining polymer spray coatings based on polycarbodiimides (polyureas) by studying changes in the process and operational parameters due to the introduction of aspartic acid derivatives (AADs) into the composition.Methods. The process of the production of sprayed and contact polyureas involves a number of difficulties, not least in terms of the cost of the components and high-pressure equipment. For this reason, mathematical modeling was used to optimize experimental design. The curing time of the composition was measured under conditions simulated to be close to actual. After thermostating and mixing Components A and B in predetermined ratios, the gelation time was measured to represent the curing time of the composition. The hardness of the material was determined by the Shore method according to GOST 24621-91. Tensile strength and relative elongation were determined according to a standard method (GOST 30436-96).Results. The effect of three AADs on the properties of the finished polyurea was studied. It was found that the introduction of two of them (AAD-1 and AAD-2) into polyurea in an amount of up to 40 wt % produces slow-curing (>250 s) polyureas capable of manual application. The finished products have physical properties on par with machine-poured materials (breaking strength >73 MPa; tensile strength >23 MPa; elongation >500%). Compiled regression equations were used to construct graphs of equal levels showing the possible areas of directed modification of the studied compositions.Conclusions. AAD can be used as a modifying component for polyurea systems to obtain slow- curing polyureas with high performance properties, which can be purposefully controlled by mathematical modeling. The resulting products have commercial value due to their combination of valuable physical and mechanical properties.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139613890","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 : 2024-01-18DOI: 10.32362/2410-6593-2023-18-6-534-548
S. T. Mikhaylova, S. V. Reznichenko, E. A. Krasnikov, P. Tsygankov, N. Menshutina, I. D. Simonov-Emel’yanov
Objectives. To investigate the swelling of the main types of rubbers used in the rubber industry in carbon dioxide in a supercritical state (SC-CO2), in order to assess the possibility of obtaining elastomeric materials with porous structures using fluid technology, based on them.Methods. The process of swelling of rubbers in SC-CO2 and subsequent foaming was carried out according to a specially developed technique using the original installation. This is a high-pressure apparatus with transparent windows, allowing for the use of an optical technique to directly measure the geometric dimensions of samples during swelling and foaming using a digital video camera. The study of the porous structure of foamed rubbers was carried out using scanning electron microscopy.Results. The study established experimental curves of the swelling kinetics in SC-CO2 of isoprene, butadiene, styrene butadiene, ethylene propylene, chloroprene, ethylene acrylate, siloxane, and organofluorine rubbers. The influence of temperature and pressure on the rate and equilibrium degree of swelling was studied. The diffusion coefficients of SC-CO2 in rubbers of various chemical natures were also determined.Conclusions. It was shown that the equilibrium swelling degree of rubbers in SC-CO2 depends on the chemical nature of rubbers. It does not correlate with the value of their solubility parameters, changes directly proportional to the diffusion coefficient and increases with increasing temperature and pressure. It was found that irrespective of the degree of swelling in SC-CO2, all the rubbers studied are intensively foamed at a sharp pressure drop. The size of the pores formed is tens of microns: significantly smaller than the size of pores formed when chemical pore formers are used.
{"title":"Swelling of rubbers of different chemical natures in supercritical carbon dioxide","authors":"S. T. Mikhaylova, S. V. Reznichenko, E. A. Krasnikov, P. Tsygankov, N. Menshutina, I. D. Simonov-Emel’yanov","doi":"10.32362/2410-6593-2023-18-6-534-548","DOIUrl":"https://doi.org/10.32362/2410-6593-2023-18-6-534-548","url":null,"abstract":"Objectives. To investigate the swelling of the main types of rubbers used in the rubber industry in carbon dioxide in a supercritical state (SC-CO2), in order to assess the possibility of obtaining elastomeric materials with porous structures using fluid technology, based on them.Methods. The process of swelling of rubbers in SC-CO2 and subsequent foaming was carried out according to a specially developed technique using the original installation. This is a high-pressure apparatus with transparent windows, allowing for the use of an optical technique to directly measure the geometric dimensions of samples during swelling and foaming using a digital video camera. The study of the porous structure of foamed rubbers was carried out using scanning electron microscopy.Results. The study established experimental curves of the swelling kinetics in SC-CO2 of isoprene, butadiene, styrene butadiene, ethylene propylene, chloroprene, ethylene acrylate, siloxane, and organofluorine rubbers. The influence of temperature and pressure on the rate and equilibrium degree of swelling was studied. The diffusion coefficients of SC-CO2 in rubbers of various chemical natures were also determined.Conclusions. It was shown that the equilibrium swelling degree of rubbers in SC-CO2 depends on the chemical nature of rubbers. It does not correlate with the value of their solubility parameters, changes directly proportional to the diffusion coefficient and increases with increasing temperature and pressure. It was found that irrespective of the degree of swelling in SC-CO2, all the rubbers studied are intensively foamed at a sharp pressure drop. The size of the pores formed is tens of microns: significantly smaller than the size of pores formed when chemical pore formers are used.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139614991","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 : 2024-01-18DOI: 10.32362/2410-6593-2023-18-6-583-594
E. Savinkina, I. Karavaev, E. K. Bettels, G. A. Buzanov, A. S. Kubasov
Objectives. To date, compounds of rare earth nitrates with urea in a ratio of 1:4 and indium in a ratio of 1:6 have been synthesized and structurally characterized. However, there is a lack of research into similar compounds having a lower urea content. The purpose of this work was to continue the search for regularities of structure formation for complexes of various elements with urea.Methods. Novel coordination compounds were synthesized and characterized by powder- and single-crystal X-ray diffraction analysis, as well as infrared spectroscopy.Results. The interaction of indium, gadolinium and erbium nitrates with urea (Ur) in an aqueous solution under conditions of ligand deficiency produces the previously unknown coordination compounds cis-[In(Ur)4(NO3)2]NO3, [Gd(H2O)2(Ur)2(NO3)3], and [Er(H2O)2(Ur)(NO3)3]. The indium complex is shown to have an ionic structure, whereas the gadolinium and erbium complexes have a molecular structure. In the indium complex, the coordination number is 6; the cation has an octahedral structure; it involves two cis-arranged monodentate nitrate groups and four monodentate urea molecules. The coordination number of gadolinium is 10; here, the coordination polyhedron is a distorted pentagonal bipyramid at the vertices of which there are two water molecules, while in the internal polygonal base there are two monodentate urea molecules and three bidentate chelating nitrate groups oriented perpendicular to the polygonal base of the bipyramid. The coordination number of erbium is 9; the coordination polyhedron is a distorted tricapped trigonal prism.Conclusions. In contrast with the gadolinium complex, one urea molecule is coordinated in the erbium complex instead of two, decreasing the coordination number from 10 to 9. In the indium complex cation, the coordination number is 6; unlike the gadolinium and erbium complexes, the cation does not contain water, and the nitrate groups are monodentate.
{"title":"Coordination compounds of indium, gadolinium, and erbium nitrates with low urea content","authors":"E. Savinkina, I. Karavaev, E. K. Bettels, G. A. Buzanov, A. S. Kubasov","doi":"10.32362/2410-6593-2023-18-6-583-594","DOIUrl":"https://doi.org/10.32362/2410-6593-2023-18-6-583-594","url":null,"abstract":"Objectives. To date, compounds of rare earth nitrates with urea in a ratio of 1:4 and indium in a ratio of 1:6 have been synthesized and structurally characterized. However, there is a lack of research into similar compounds having a lower urea content. The purpose of this work was to continue the search for regularities of structure formation for complexes of various elements with urea.Methods. Novel coordination compounds were synthesized and characterized by powder- and single-crystal X-ray diffraction analysis, as well as infrared spectroscopy.Results. The interaction of indium, gadolinium and erbium nitrates with urea (Ur) in an aqueous solution under conditions of ligand deficiency produces the previously unknown coordination compounds cis-[In(Ur)4(NO3)2]NO3, [Gd(H2O)2(Ur)2(NO3)3], and [Er(H2O)2(Ur)(NO3)3]. The indium complex is shown to have an ionic structure, whereas the gadolinium and erbium complexes have a molecular structure. In the indium complex, the coordination number is 6; the cation has an octahedral structure; it involves two cis-arranged monodentate nitrate groups and four monodentate urea molecules. The coordination number of gadolinium is 10; here, the coordination polyhedron is a distorted pentagonal bipyramid at the vertices of which there are two water molecules, while in the internal polygonal base there are two monodentate urea molecules and three bidentate chelating nitrate groups oriented perpendicular to the polygonal base of the bipyramid. The coordination number of erbium is 9; the coordination polyhedron is a distorted tricapped trigonal prism.Conclusions. In contrast with the gadolinium complex, one urea molecule is coordinated in the erbium complex instead of two, decreasing the coordination number from 10 to 9. In the indium complex cation, the coordination number is 6; unlike the gadolinium and erbium complexes, the cation does not contain water, and the nitrate groups are monodentate.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139615020","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 : 2024-01-18DOI: 10.32362/2410-6593-2023-18-6-517-533
G. O. Stepanov, N. N. Rodionova, R. R. Konstantinov, K. Subbotin
Objectives. Ferroelectric triglycine sulfate (TGS) belongs to a group of crystals whose properties are sensitive even to minor changes in growth conditions. The mechanism of spontaneous polarization in TGS is associated with the adjustment of protons which participate in the formation of hydrogen bonds. Therefore, the state of the parent solution plays an important role in the crystal formation. The study aims to investigate the structural features of TGS crystals grown using aqueous alcoholic solutions of technologically processed antibodies to interferon-gamma, in comparison with those of the crystals grown using the control solutions (technologically processed phosphate-buffered saline and intact aqueous alcoholic solution).Methods. X-ray diffraction assay and Raman spectroscopy.Results. The effect of solutions of the technologically processed antibodies to interferongamma added to a parent solution on the growth of TGS single crystals is established. This effect manifests in the changing in occupancy of the proton sublattice of the crystal grown from the parent solution containing technologically processed antibodies to interferon-gamma, as compared with the crystals grown from the control solutions. In the case of the crystal grown from the solution containing technologically processed antibodies to interferon-gamma, this change in the occupancy of the proton lattice is expressed in an increase in the length of N2–C3 bonds.Conclusions. Adding the technologically processed antibodies in the parent solution before the crystal growth can affect the structure of TGS crystals.
{"title":"Effect of adding technologically processed antibodies to interferon-gamma into a parent solution on the structural features of triglycine sulfate crystals grown from this solution","authors":"G. O. Stepanov, N. N. Rodionova, R. R. Konstantinov, K. Subbotin","doi":"10.32362/2410-6593-2023-18-6-517-533","DOIUrl":"https://doi.org/10.32362/2410-6593-2023-18-6-517-533","url":null,"abstract":"Objectives. Ferroelectric triglycine sulfate (TGS) belongs to a group of crystals whose properties are sensitive even to minor changes in growth conditions. The mechanism of spontaneous polarization in TGS is associated with the adjustment of protons which participate in the formation of hydrogen bonds. Therefore, the state of the parent solution plays an important role in the crystal formation. The study aims to investigate the structural features of TGS crystals grown using aqueous alcoholic solutions of technologically processed antibodies to interferon-gamma, in comparison with those of the crystals grown using the control solutions (technologically processed phosphate-buffered saline and intact aqueous alcoholic solution).Methods. X-ray diffraction assay and Raman spectroscopy.Results. The effect of solutions of the technologically processed antibodies to interferongamma added to a parent solution on the growth of TGS single crystals is established. This effect manifests in the changing in occupancy of the proton sublattice of the crystal grown from the parent solution containing technologically processed antibodies to interferon-gamma, as compared with the crystals grown from the control solutions. In the case of the crystal grown from the solution containing technologically processed antibodies to interferon-gamma, this change in the occupancy of the proton lattice is expressed in an increase in the length of N2–C3 bonds.Conclusions. Adding the technologically processed antibodies in the parent solution before the crystal growth can affect the structure of TGS crystals.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139615592","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 : 2024-01-18DOI: 10.32362/2410-6593-2023-18-6-505-516
E. A. Kurganova, A. S. Frolov, S. A. Kanaev, G. N. Koshel, A. A. Petukhov, G. V. Rybina, V. V. Plakhtinskii, V. S. Kabanova, A. A. Smurova
Objectives. To investigate the regularities of the process of joint production of epoxycyclohexane, cyclohexanol, and cyclohexanone using the cyclohexene epoxidation reaction with cyclohexyl hydroperoxide in the presence of an ammonium paramolybdate catalyst, representing an alternative to the method of cyclohexanol and cyclohexanone synthesis by alkaline catalytic decomposition of cyclohexyl hydroperoxide.Methods. The qualitative and quantitative analysis of the obtained intermediate and target compounds was determined using modern physicochemical research methods: gas–liquid chromatography using the Chromatec-Crystal 5000.2 hardware and software complex with a flame ionization detector and infrared spectroscopy on an RX-1 infrared Fourier spectrometer. The content of hydroperoxide in the oxidation products was determined using iodometric titration, while the carboxylic acid content was determined by the titrimetric method based on the neutralization reaction.Results. The presented method for obtaining cyclohexanol and cyclohexanone together with epoxycyclohexane by the reaction of cyclohexene epoxidation with cyclohexyl hydroperoxide containing cyclohexane in the products of high-temperature liquid-phase oxidation is experimentally substantiated. The influence of various technological parameters on the process of liquid-phase oxidation of cyclohexane to hydroperoxide is described. The conditions for carrying out this reaction are determined to ensure the achievement of a content of cyclohexyl hydroperoxide of 1.5 wt % in the products of oxidation. The regularities of the epoxidation reaction of the synthesized cyclohexyl hydroperoxide with cyclohexene in the presence of an ammonium paramolybdate catalyst are analyzed.Conclusions. Epoxidation of cyclohexene with cyclohexyl hydroperoxide produced epoxycyclohexane at a yield of 80–90% and a conversion of cyclohexane hydroperoxide of 85%.
{"title":"Epoxidation of cyclohexene with cyclohexyl hydroperoxide","authors":"E. A. Kurganova, A. S. Frolov, S. A. Kanaev, G. N. Koshel, A. A. Petukhov, G. V. Rybina, V. V. Plakhtinskii, V. S. Kabanova, A. A. Smurova","doi":"10.32362/2410-6593-2023-18-6-505-516","DOIUrl":"https://doi.org/10.32362/2410-6593-2023-18-6-505-516","url":null,"abstract":"Objectives. To investigate the regularities of the process of joint production of epoxycyclohexane, cyclohexanol, and cyclohexanone using the cyclohexene epoxidation reaction with cyclohexyl hydroperoxide in the presence of an ammonium paramolybdate catalyst, representing an alternative to the method of cyclohexanol and cyclohexanone synthesis by alkaline catalytic decomposition of cyclohexyl hydroperoxide.Methods. The qualitative and quantitative analysis of the obtained intermediate and target compounds was determined using modern physicochemical research methods: gas–liquid chromatography using the Chromatec-Crystal 5000.2 hardware and software complex with a flame ionization detector and infrared spectroscopy on an RX-1 infrared Fourier spectrometer. The content of hydroperoxide in the oxidation products was determined using iodometric titration, while the carboxylic acid content was determined by the titrimetric method based on the neutralization reaction.Results. The presented method for obtaining cyclohexanol and cyclohexanone together with epoxycyclohexane by the reaction of cyclohexene epoxidation with cyclohexyl hydroperoxide containing cyclohexane in the products of high-temperature liquid-phase oxidation is experimentally substantiated. The influence of various technological parameters on the process of liquid-phase oxidation of cyclohexane to hydroperoxide is described. The conditions for carrying out this reaction are determined to ensure the achievement of a content of cyclohexyl hydroperoxide of 1.5 wt % in the products of oxidation. The regularities of the epoxidation reaction of the synthesized cyclohexyl hydroperoxide with cyclohexene in the presence of an ammonium paramolybdate catalyst are analyzed.Conclusions. Epoxidation of cyclohexene with cyclohexyl hydroperoxide produced epoxycyclohexane at a yield of 80–90% and a conversion of cyclohexane hydroperoxide of 85%.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139615967","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 : 2024-01-18DOI: 10.32362/2410-6593-2023-18-6-572-582
A. Dyachenko
Objectives. To study the technological features of a new fluoride technology for the production of titanium dioxide by the decomposition of titanomagnetite concentrate with ammonium fluorides.Methods. The chemical species of the titanium and iron components in the fluorination of titanomagnetite concentrate and sublimation separation of components were determined by means of X-ray powder diffraction analysis and inductively coupled plasma mass spectrometry. The kinetics of sublimation of the titanium component by the thermal decomposition of ammonium hexafluorotitanate was experimentally studied.Results. The products of the fluorination of titanomagnetite concentrate with ammonium bifluoride are compounds (NH4)2TiF6 and (NH4)3FeF6, as proven by chemical analysis and X-ray powder diffraction analysis. The subsequent sublimation separation of the titanium component produced the target product: a mixture of ammonium fluorotitanates. The desublimation of the titanium-containing fraction gave an NH4TiF5–(NH4)2TiF6–(NH4)3TiF7 mixture, the titanium content of which is 30.6% and the content of impurities (Fe, V, Si) is a minimum (0.45%). The activation energy of the heterogeneous reaction and the rate-limiting step of the process were also determined.Conclusions. A high-purity titanium product (a mixture of ammonium fluorotitanates) is obtained. This is a valuable commercial product for the industrial production of titanium dioxide pigment from titanomagnetite concentrate and ilmenite.
目标。研究通过氟化铵分解钛磁铁矿精矿生产二氧化钛的新型氟化技术的技术特点。通过 X 射线粉末衍射分析和电感耦合等离子体质谱法确定了钛磁铁矿精矿氟化和成分升华分离过程中钛和铁成分的化学种类。实验研究了六氟钛酸铵热分解钛成分升华的动力学。化学分析和 X 射线粉末衍射分析证明，钛磁铁矿精矿与氟化氢铵氟化的产物是 (NH4)2TiF6 和 (NH4)3FeF6 化合物。随后钛成分的升华分离产生了目标产品：氟钛酸铵混合物。含钛部分的升华得到了 NH4TiF5-(NH4)2TiF6-(NH4)3TiF7混合物，其中钛含量为 30.6%，杂质（Fe、V、Si）含量最低（0.45%）。此外，还测定了异相反应的活化能和该过程的限速步骤。获得了一种高纯度钛产品（氟钛酸铵混合物）。这是一种有价值的商业产品，可用于利用钛磁铁矿精矿和钛铁矿生产二氧化钛颜料。
{"title":"Fluorination of titanomagnetite concentrate with ammonium bifluoride","authors":"A. Dyachenko","doi":"10.32362/2410-6593-2023-18-6-572-582","DOIUrl":"https://doi.org/10.32362/2410-6593-2023-18-6-572-582","url":null,"abstract":"Objectives. To study the technological features of a new fluoride technology for the production of titanium dioxide by the decomposition of titanomagnetite concentrate with ammonium fluorides.Methods. The chemical species of the titanium and iron components in the fluorination of titanomagnetite concentrate and sublimation separation of components were determined by means of X-ray powder diffraction analysis and inductively coupled plasma mass spectrometry. The kinetics of sublimation of the titanium component by the thermal decomposition of ammonium hexafluorotitanate was experimentally studied.Results. The products of the fluorination of titanomagnetite concentrate with ammonium bifluoride are compounds (NH4)2TiF6 and (NH4)3FeF6, as proven by chemical analysis and X-ray powder diffraction analysis. The subsequent sublimation separation of the titanium component produced the target product: a mixture of ammonium fluorotitanates. The desublimation of the titanium-containing fraction gave an NH4TiF5–(NH4)2TiF6–(NH4)3TiF7 mixture, the titanium content of which is 30.6% and the content of impurities (Fe, V, Si) is a minimum (0.45%). The activation energy of the heterogeneous reaction and the rate-limiting step of the process were also determined.Conclusions. A high-purity titanium product (a mixture of ammonium fluorotitanates) is obtained. This is a valuable commercial product for the industrial production of titanium dioxide pigment from titanomagnetite concentrate and ilmenite.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139613814","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 : 2024-01-18DOI: 10.32362/2410-6593-2023-18-6-559-571
Y. Absalan, R. Alabada, M. R. Razavi, M. Gholizadeh, O. V. Avramenko, I. N. Bychkova, O. Kovalchukova
Objectives. To develop a new green method for the synthesis of nanosized materials of cobalt(II,III) oxide, with improved surface activity, using environmentally friendly precursors and solvents.Methods. A green method was proposed, in order to isolate Co3O4 nanoparticles with high surface activity. Instead of the usual organic solvents, three different natural sugars, including glycogen, sucrose, and glucose were used for the first time as templates. Water as a green solvent was used in all the steps. The polymorphic composition of the synthesized samples was determined by means of X-ray phase analysis. The morphology of the obtained crystallites was studied from micrographs of the oxide phases. Image Pro Plus 6 software was used to measure the size of nanoparticles. The surface activity of the isolated samples was studied using the Brunauer–Emmett–Teller method and the Langmuir method. The Barret–Joyner–Halenda method was used to determine the diameter, volume, and distribution of pores.Results. The crystallite sizes of the samples are 23 nm, 36 nm, and 30 nm for glucose, glycogen, and sucrose templates, respectively. Adsorption–desorption isotherms for samples obtained from complexes of glucose and sucrose correspond to type IV, indicating a strong interaction between the adsorbent and the adsorbed sample. The isotherm for the sample isolated from the complex with glycogen is of a different type and most likely indicates that this sample is almost completely mesoporous. The pore radii are found in the interval 1.2–1.6 nm.Conclusions. A new green method for the synthesis of nanosized particles of Co(II,III) oxide using natural saccharides and deionized water was developed. The composition, morphology, structure, and surface activity of the samples obtained were studied. It was shown that due to the polymeric structure of their metal complexes and the ability to bind active carbon on the surface of nanoparticles, natural saccharides can be used as matrices in the synthesis of nanosized metal oxides with high surface activity.
目的开发一种新的绿色方法，利用环境友好型前体和溶剂合成表面活性更好的纳米氧化钴（II,III）材料。为了分离出具有高表面活性的 Co3O4 纳米粒子，我们提出了一种绿色方法。首次使用了三种不同的天然糖，包括糖原、蔗糖和葡萄糖作为模板，而不是常用的有机溶剂。所有步骤均使用水作为绿色溶剂。合成样品的多晶体组成是通过 X 射线相分析法确定的。通过氧化物相的显微照片研究了所得晶体的形态。使用 Image Pro Plus 6 软件测量了纳米颗粒的尺寸。使用布鲁瑙尔-埃美特-泰勒法和朗缪尔法研究了分离样品的表面活性。Barret-Joyner-Halenda 法用于测定孔的直径、体积和分布。葡萄糖、糖原和蔗糖模板样品的结晶尺寸分别为 23 nm、36 nm 和 30 nm。葡萄糖和蔗糖复合物样品的吸附-解吸等温线符合 IV 型，表明吸附剂和被吸附样品之间存在强烈的相互作用。从与糖原的复合物中分离出来的样品的等温线则属于另一种类型，很可能表明该样品几乎完全是介孔的。孔隙半径在 1.2-1.6 nm 之间。利用天然糖原和去离子水合成纳米级氧化钴（II,III）颗粒的绿色新方法已经开发成功。研究了所得样品的组成、形态、结构和表面活性。结果表明，由于其金属复合物的聚合结构以及在纳米颗粒表面结合活性碳的能力，天然糖类可用作合成具有高表面活性的纳米级金属氧化物的基质。
{"title":"A green synthetic method for cobalt(II,III) oxide nanoparticles with high surface activity","authors":"Y. Absalan, R. Alabada, M. R. Razavi, M. Gholizadeh, O. V. Avramenko, I. N. Bychkova, O. Kovalchukova","doi":"10.32362/2410-6593-2023-18-6-559-571","DOIUrl":"https://doi.org/10.32362/2410-6593-2023-18-6-559-571","url":null,"abstract":"Objectives. To develop a new green method for the synthesis of nanosized materials of cobalt(II,III) oxide, with improved surface activity, using environmentally friendly precursors and solvents.Methods. A green method was proposed, in order to isolate Co3O4 nanoparticles with high surface activity. Instead of the usual organic solvents, three different natural sugars, including glycogen, sucrose, and glucose were used for the first time as templates. Water as a green solvent was used in all the steps. The polymorphic composition of the synthesized samples was determined by means of X-ray phase analysis. The morphology of the obtained crystallites was studied from micrographs of the oxide phases. Image Pro Plus 6 software was used to measure the size of nanoparticles. The surface activity of the isolated samples was studied using the Brunauer–Emmett–Teller method and the Langmuir method. The Barret–Joyner–Halenda method was used to determine the diameter, volume, and distribution of pores.Results. The crystallite sizes of the samples are 23 nm, 36 nm, and 30 nm for glucose, glycogen, and sucrose templates, respectively. Adsorption–desorption isotherms for samples obtained from complexes of glucose and sucrose correspond to type IV, indicating a strong interaction between the adsorbent and the adsorbed sample. The isotherm for the sample isolated from the complex with glycogen is of a different type and most likely indicates that this sample is almost completely mesoporous. The pore radii are found in the interval 1.2–1.6 nm.Conclusions. A new green method for the synthesis of nanosized particles of Co(II,III) oxide using natural saccharides and deionized water was developed. The composition, morphology, structure, and surface activity of the samples obtained were studied. It was shown that due to the polymeric structure of their metal complexes and the ability to bind active carbon on the surface of nanoparticles, natural saccharides can be used as matrices in the synthesis of nanosized metal oxides with high surface activity.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139615974","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 : 2023-11-27DOI: 10.32362/2410-6593-2023-18-5-471-481
Y. Mirgorod, N. A. Borsch, A. M. Storozhenko, L. S. Ageeva
Objectives. To establish expected emergent (unexpected) properties of magnetic materials when obtained in aqueous micellar solutions of surfactants (aqueous quantum materials), and their use in fine technologies.Methods. Chemical synthesis of magnetic nanoparticles in aqueous micellar solutions of surfactants of various nature. Characterization of magnetic solutions and nanoparticles by magnetic measurements, spectroscopy, diffractometry, small-angle X-ray diffraction, scanning probe microscopy, and others.Results. The term “water quantum material” refers to materials (micellar solutions) whose properties are mainly determined by the nuclear quantum effect on macroscopic scales (emergent property). Micellar solutions exhibit phenomena and functionality not always consistent with the classical theory of micellization. The article presents in detail the experimental results that suggest the manifestation of the emergent properties of magnetic materials obtained in aqueous micellar solutions of surfactants. In particular, Gd3+ ions in an aqueous micellar solution of sodium dodecyl sulfate exhibit paramagnetic properties, possibly indicating their random arrangement in solution contrary to the classical theory of micellization with an ordered adsorption layer on micelles. Hybrid Pt–Gd nanoparticles are formed in a quantum material with cetylpyridinium chloride as a matrix, although Gd3+ ions must be repelled by CP+ ions on micelles. Nanosized powders of cobalt ferrite and nickel ferrite obtained in a micellar solution of sodium dodecyl sulfate have superparamagnetic properties, although the presence of their precursor ions in the adsorption layer in classical micelles should lead to ferromagnetic properties.Conclusions. The synthesis of nanoparticles in a quantum material opens up the possibility of reducing ions of different signs in one stage during the processing of metallurgy waste, in order to obtain nanoparticles of various metals and their composites. Magnetic nanoparticles obtained in a quantum surfactant material self-assemble on various substrates, enabling the creation of materials whose residual magnetization and coercive field can be controlled at room temperatures.
目标。确定在表面活性剂胶束水溶液中获得的磁性材料（水性量子材料）的预期突发（意外）特性及其在精细技术中的应用。在不同性质的表面活性剂胶束水溶液中化学合成磁性纳米粒子。通过磁性测量、光谱法、衍射法、小角 X 射线衍射法、扫描探针显微镜等对磁性溶液和纳米粒子进行表征。所谓 "水量子材料"，是指其特性主要由宏观尺度上的核量子效应（突现特性）决定的材料（胶束溶液）。胶束溶液表现出的现象和功能并不总是与经典的胶束化理论一致。文章详细介绍了实验结果，这些结果表明在表面活性剂的胶束水溶液中获得的磁性材料具有显现特性。特别是，十二烷基硫酸钠胶束水溶液中的 Gd3+ 离子表现出顺磁性，这可能表明它们在溶液中的随机排列与胶束上有序吸附层的经典胶束化理论相反。以氯化十六烷基吡啶为基质的量子材料中形成了铂钯混合纳米粒子，但 Gd3+ 离子必须被胶束上的 CP+ 离子排斥。在十二烷基硫酸钠胶束溶液中获得的钴铁氧体和镍铁氧体纳米粉末具有超顺磁性，尽管它们的前体离子存在于经典胶束的吸附层中应该会导致铁磁性。在量子材料中合成纳米粒子为在冶金废料处理过程中在一个阶段还原不同符号的离子提供了可能性，从而获得各种金属的纳米粒子及其复合材料。在量子表面活性剂材料中获得的磁性纳米粒子可在各种基底上自组装，从而制造出可在室温下控制其剩余磁化和矫顽力场的材料。
{"title":"Emergent properties of magnetic ions and nanoparticles in micellar solutions of surfactants: Use in fine technologies","authors":"Y. Mirgorod, N. A. Borsch, A. M. Storozhenko, L. S. Ageeva","doi":"10.32362/2410-6593-2023-18-5-471-481","DOIUrl":"https://doi.org/10.32362/2410-6593-2023-18-5-471-481","url":null,"abstract":"Objectives. To establish expected emergent (unexpected) properties of magnetic materials when obtained in aqueous micellar solutions of surfactants (aqueous quantum materials), and their use in fine technologies.Methods. Chemical synthesis of magnetic nanoparticles in aqueous micellar solutions of surfactants of various nature. Characterization of magnetic solutions and nanoparticles by magnetic measurements, spectroscopy, diffractometry, small-angle X-ray diffraction, scanning probe microscopy, and others.Results. The term “water quantum material” refers to materials (micellar solutions) whose properties are mainly determined by the nuclear quantum effect on macroscopic scales (emergent property). Micellar solutions exhibit phenomena and functionality not always consistent with the classical theory of micellization. The article presents in detail the experimental results that suggest the manifestation of the emergent properties of magnetic materials obtained in aqueous micellar solutions of surfactants. In particular, Gd3+ ions in an aqueous micellar solution of sodium dodecyl sulfate exhibit paramagnetic properties, possibly indicating their random arrangement in solution contrary to the classical theory of micellization with an ordered adsorption layer on micelles. Hybrid Pt–Gd nanoparticles are formed in a quantum material with cetylpyridinium chloride as a matrix, although Gd3+ ions must be repelled by CP+ ions on micelles. Nanosized powders of cobalt ferrite and nickel ferrite obtained in a micellar solution of sodium dodecyl sulfate have superparamagnetic properties, although the presence of their precursor ions in the adsorption layer in classical micelles should lead to ferromagnetic properties.Conclusions. The synthesis of nanoparticles in a quantum material opens up the possibility of reducing ions of different signs in one stage during the processing of metallurgy waste, in order to obtain nanoparticles of various metals and their composites. Magnetic nanoparticles obtained in a quantum surfactant material self-assemble on various substrates, enabling the creation of materials whose residual magnetization and coercive field can be controlled at room temperatures.","PeriodicalId":12215,"journal":{"name":"Fine Chemical Technologies","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139228632","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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