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CHAPTER 1. STATUS OF THE ISSUE, PURPOSE AND TASKS OF RESEARCH.
1.1. Analysis of studies of clay soils treated with stabilizers.
1.2. Experience practical application in road construction of clay soils treated with stabilizers.
CHAPTER 2. THEORETICAL INVESTIGATIONS OF SOILS TREATED WITH STABILIZERS.
2.1. Modern ideas about the nature of structural bonds and properties of clay soils.
2.2. Theoretical prerequisites for choosing the type of stabilizer - surfactants and binders for clay soils.
2.3. Theoretical studies processes of structure formation during the treatment of clay soils with stabilizers - surfactants without and together with binders.
CHAPTER 3. EXPERIMENTAL STUDIES OF SOILS TREATED WITH STABILIZERS.
3.1. Characteristics of the materials used.
3.2. Sample Preparation Method.
3.3. Selection of the optimal composition of mixtures.
3.4. Analysis of the results of the study of clay soils treated with stabilizers without and together with binders
3.4.1. Optimal humidity.
3.4.2. Water resistance.
3.4.3. Frosty swelling.
3.4.4. Filtration coefficient.
3.4.5. strength and deformability.
3.5. Technological features of processing clay soils with stabilizers.
CHAPTER IV
4.1. Road construction objects.
4.2. Volumetric structures.
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Introduction to the thesis (part of the abstract) on the topic "The use of surfactants (stabilizers) to improve the properties of cohesive soils in road construction"
Modern trends in road construction: increasing traffic intensity and carrying capacity of road transport, expanding the network of roads, including local ones, put forward the tasks of the need not only to increase the durability of road structures, but also to use local materials and soils in the construction of roads. Given that many regions of Russia are experiencing a shortage of materials for the construction of foundations, and their delivery is associated with additional transportation costs, the relevance of using local soils in pavement structures becomes obvious.
It is known that clayey soils of various ages and genesis are most widespread in Russia. The main deterrent to the widespread use of which in road construction is the change in their physical and mechanical characteristics for the worse when moistened. Strengthening clay soils with various binders, such as cement, lime, bitumen, and others, as a rule, is associated with a significant consumption of the binder, which can lead to an increase in construction costs.
For a directed change in the properties of clay soils, it is possible to use surfactants of a special action - stabilizers. Stabilizers currently produced do not fully meet the goals of road construction: their range is small, many of them are toxic, mainly intended for acidic soils, have a fairly high cost, and most of them are produced abroad.
In this regard, the study of the effect of special domestic stabilizers on the properties of carbonate clay soils and the creation of materials with desired properties based on clay soils treated with such stabilizers, as well as the development of technology for the use of the obtained materials in the construction of roads are topical issues. The solution of these issues will contribute not only to the expansion of the road network using local clay soils, but also to an increase in the bearing capacity of road structures.
Recently, there has been an increased practical interest in methods of physical and chemical stabilization of soils using hydrophobizing surfactants, which make it possible to eliminate the ability of clay soils to interact with water due to the neutralization of the forces of surface attraction of water. A hydrophobic surfactant film does not allow water molecules to enter the contact zones of the mineral particles of the soil, and thereby protects the soil from soaking. Changes at the level of microstructure lead not only to the stable preservation of the physical and mechanical properties of natural clay soil, but also to their improvement (for example, strength increases, swelling decreases, etc.). In addition, the prospects for the use of surfactants, especially of domestic production in road and airfield construction, are due to their relatively low cost.
Generalization and analysis of theoretical and practical results of research on the use of cohesive soils treated with surfactants as bearing and underlying layers of pavements shows that certain success has been achieved in this area. However, there are a number of tasks that have not yet been solved. For example, the mechanism of interaction of surfactants with clay soils, the nature and relationship of the physical and chemical processes occurring in this case are not clear enough, the general patterns of changes in the structure of natural clay soil after processing it with surfactants are not fully understood, there is no method for predicting the properties of clay soils and etc. Therefore, theoretical and experimental studies aimed at solving these and other problems that make it possible to increase the durability of road and airfield pavements and reduce the cost of their maintenance and repair are relevant.
Theoretical and experimental studies presented in the dissertation work were carried out on clay soils treated with the surfactant "Status", developed by the Department of "Engineering Geology and Geotechnics" MADI (GTU) and first proposed for these purposes.
The purpose of the dissertation. Scientific substantiation and development of compositions of mixtures of clay soils treated with new surfactants (stabilizers) for pavement bases.
The following results are presented for defense:
Refinement of the theoretical method for selecting a new effective surfactant - a directional stabilizer to improve the properties of clay soils;
Features of the structure formation of clay soils treated with the stabilizer "Status";
The compositions of clay soils treated with the stabilizer "Status";
Features of the technology of processing and application of clayey soils treated with the Status stabilizer in the construction of highway foundations.
Scientific novelty and reliability of the obtained results are as follows:
The use of a new effective surfactant - stabilizer "Status" to improve the properties of clay soil with the possibility of predicting the properties of the treated soil is substantiated;
The features of the structure formation of clay soil treated with the stabilizer "Status" have been established;
The advantage of using the specified stabilizer in comparison with other types of surfactants is shown;
The features of the technology for processing clay soils with surfactant - stabilizer "Status" (without and in combination with a binder) are revealed.
The reliability of the theoretical results is confirmed by modern methods of scanning electron microscopy.
The reliability of the results obtained experimentally is confirmed by processing methods based on probability theory and mathematical statistics.
Practical significance of the results of the dissertation research.
The practical significance lies in the fact that on the basis of the theoretical justification for the selection of surfactants to improve the properties of clay soils, a new anionic stabilizer "Status" was chosen.
Optimal compositions of mixtures based on clayey soils of carbonate varieties treated with the Status stabilizer for use in pavement bases have been developed.
The technical feasibility of using mixtures of clay soils treated with a stabilizer in the bases of pavements using the technological equipment available in road facilities, as well as the economic efficiency of using these materials, has been established.
Implementation of work. The materials of the dissertation work were used by: the Avtodortekh company during the construction of the second category highway Stavropol - Mineralnye Vody - Kraynovka in Stavropol Territory;
Stroyprojectindustry LLC, a design and construction company, during the construction of a garage foundation in the Yuzhnoye Butovo area;
SPC Avtodortekh LLC during the construction of an impervious screen at the solid waste landfill in the village of. Preobrazhenskoye, Samara region.
Approbation of work and publication. The main research results were reported at 60, 61 Scientific and Methodological and Scientific and Technical Conferences of MADI (GTU) in 2002, 2003.
Workload. The dissertation work consists of an introduction, four chapters, general conclusions, a list of references and an appendix. The work contains 165 pages of typewritten text, including 26 tables and 35 figures. The list of references includes 133 titles, 4 of which are in foreign languages.
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Dissertation conclusion on the topic "Design and construction of roads, subways, airfields, bridges and transport tunnels", Fedulov, Andrey Aleksandrovich
148 - GENERAL CONCLUSIONS
1. An analysis of the prerequisites for the choice of surfactants made it possible to substantiate the criteria for the selection of surfactants for the treatment of clay soils. Given the low level of knowledge of anionic surfactants, as well as the widespread occurrence of carbonate varieties of clay soils, a new universal stabilizer "Status" of a-ionic action was chosen. The theoretical prerequisites for the choice are confirmed by modern electron microscopy methods, with the help of which it was found that the introduction of the Status stabilizer into the clay soil in a small amount leads to the formation of a hydrophobic enveloping film around the mineral grain. In this case, a denser structure of soil microaggregates is formed. The use of a small amount of cement (up to 2%) allows, along with hydrophobic films, to create new bonds of a cementation nature, which indicates a change not only in water-colloidal properties, but also in strength characteristics. It has been established that due to more ordered, symmetrical forms of microaggregates, a more stable structure of the material is formed.
2. On the basis of clay soils of carbonate varieties, optimal compositions of mixtures were developed using the Status stabilizer, which can be used in pavement structures. It has been established that with an increase in the content of clay particles in the soil (during the transition from sandy loam to loam and clay), the optimal content of the stabilizer decreases, and the efficiency of its use increases. At the same time, for sandy loam, the optimal amount of stabilizer is 170 ml/m3, for loams and clays - 100-120 ml/m3.
3. The increase in the density of dry soil with the addition of a stabilizer reaches 5-7% for clay, 3-5% for loam, and 2-3% for sandy loam.
Compared to the use of the "Raodbond" stabilizer, the introduction of which does not change the optimum moisture content, the use of the "Status" stabilizer reduces the optimum moisture content of sandy loam by 4%.
It has been established that the soaking rate of samples from clay soil without a stabilizer is 1.5-2 times higher than that of soil treated with the Status stabilizer.
4. The study of heaving processes during freezing showed the feasibility of using the Status stabilizer. So, in the treated soil, the value of heaving deformation is 35% less than in the untreated one.
The introduction of a stabilizer into the soil also reduces the filtration coefficient by up to 10 times, while the addition of cement does not affect the water permeability of the treated soil.
5. It has been established that after treatment with a stabilizer, the specific cohesion of sandy loam due to a significant increase in water-colloidal forces increases by 1.2 times, and loam by 1.5 times. The deformation modulus of the initial clay soil, equal to 25.6 MPa, increased to 29.8 MPa after the application of the stabilizer in combination with the addition of cement.
6. It has been established that the technological gap from the moment the mixture is prepared to its compaction should not exceed 1.5-2 hours. At the same time, the order of adding components (stabilizer or cement) does not significantly affect the water-physical and physical-mechanical properties of the material.
7. The research results were tested during the construction of three facilities in 1999-2002. Thus, clayey soils treated with the Status stabilizer were used as the bottom layer of the base of the highway, as well as in the construction of the base of the foundation for the garage and the base of the solid waste impervious screen. During the period of operation, no damage or deformation was found.
8. The economic efficiency of using local clay soils treated with surfactants in the foundation structures of various structures is due to a decrease in volumes and transportation costs for the delivery of imported expensive materials. In addition, construction organizations for the construction of such foundations do not need to additionally purchase special mechanisms, which is currently of great importance for road construction.
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Memories of Academician of the Academy of Sciences of the USSR Petr Alexandrovich Rebinder, Head of the Department of Colloidal Chemistry, Faculty of Chemistry, Moscow state university them. M.V. Lomonosov from 1942 to 1972, about the period of his work in a new building on the Lenin Hills (1953-1972), I began to write on the eve of the next Rebinder readings, which are traditionally held at the Faculty of Chemistry of Moscow State University on the birthday of Peter Alexandrovich on October 3 . This time (1997) the meeting was dedicated to the memory of Dr. chemical sciences E.E. Segalova in connection with the 80th anniversary of her birth. E.E.Segalova worked a lot and fruitfully at the Department of Colloidal Chemistry with Petr Alexandrovich in the field of structure formation of mineral binders.
At the 23 Rebinder readings, reports by E.D. Shchukin "Development of P.A. Rebinder's theory of condensation structure formation" and a report by V.N. P.V. Nussa, A.N. Ovchinnikova "Relaxation characteristics of water during hardening of cement in the presence of nonionic surfactants (according to NMR data)", which is the development of the teachings of P.A. Rebinder and E.E. Segalova about coagulation and condensation -crystallization structure formation in disperse systems.
Many of the authors personally knew Petr Alexandrovich and worked with him, others learned from his works. Apparently, among the authors of the reports, I knew Pyotr Aleksandrovich before anyone else. This is due to the fact that my father, Professor Izmailov Nikolai Arkadievich (Head of the Department of Physical Chemistry at Kharkov State University (KhSU) from 1945 to 1961) was familiar with Petr Aleksandrovich for a long time, and in our house they often remembered Petr Aleksandrovich and spoke of him as an interesting person with encyclopedic knowledge and as a brilliant scientist.
Pyotr Aleksandrovich was bound scientific interests with many scientists of Kharkov (prof. Ya.E. Geguzin, O.P. Mchedlov-Petrosyan, S.S. Urazovsky, I.M. Livshits, L.S. Palatnik, S.G. Teletov - head of the department of colloidal Chemistry at KhSU and many others). When Pyotr Alexandrovich came to KSU, he was surrounded by a "multilayer" (to use the term of colloidal chemistry from the adsorption section) by venerable and novice scientists who discussed their scientific problems with P.A., and P.A. instantly grasped the essence and gave priceless advice. When there were obvious "mistakes" and erroneous judgments, P.A. always found a mild form that did not humiliate the "misguided discoverer."
Pyotr Aleksandrovich was a deeply decent, courageous, honest and fair scientist. In this I could see for myself in very difficult and anxious days for my father. It was 1952. "Pseudo-scientists" ran amok in the scientific community. They defeated the geneticists in biology and turned to the chemists, trying to destroy the scientists who developed the theory of resonance. This seemed not enough, and here we already got to the theory of solutions, which was developed by my father N. A. Izmailov.
On November 20, 1952, an extended meeting of the Academic Council of the Faculty of Chemistry of KhSU was scheduled to discuss the use of thermodynamics to describe the properties of solutions. In fact, my father was accused of "idealism". Among the members of the extended academic council (with the invitation of professors in the humanities), only my father and his colleagues were specialists in the problem under discussion. In those days, serious questions could be decided, including the theory of activity in solutions, simply by a majority of votes.
For the father, it was necessary to enlist the support of authoritative scientists - experts in the field of activity theory. At the family council, it was decided that I (then a fourth-year student of the Faculty of Chemistry of KhSU) should go to Moscow to P. A. Rebinder, A. N. Frumkin and V. K. Semenchenko and ask, if possible, to reflect their attitude in writing to the theory of activity and the coefficient of activity. All scientists immediately wrote about the usefulness of such an approach in the theory of solutions and thus supported and saved my father and all physical chemistry from pogroms.
When I arrived in Moscow, I first went to Pyotr Alexandrovich's home. He and his family [wife - Elena Evgenievna, daughters Alya (Elena Petrovna) and Maryasha (Marianna Petrovna), mother (Anna Petrovna)] greeted me very warmly. Pyotr Aleksandrovich said, pointing at me, look how young she is and is already helping her father. And then he said, as soon as you graduate from KSU, come to my graduate school at Moscow State University. This visit actually determined my fate. I did just as Peter Alexandrovich said, and I never regretted it.
Petr Alexandrovich began to dictate to Elena Evgenievna a letter, which was read at the enlarged Council of KSU, which practically decided the vote of the members of the enlarged Council. The authority of P. A. Rebinder was very great. The letter of Academician P.A. A. M. Gorky, Kharkov 1953, pp. 282-283.
The discussion at KSU was completed, the work of N.A. Izmailov developed further, I was preparing to enter graduate school with Petr Aleksandrovich Rebinder. I passed the entrance exams in September-October 1953. This year, for the first time, classes began in a new building on the Lenin Hills. The dean of the Faculty of Chemistry was Acad. A. V. Novoselova. Spacious rooms, beautiful furniture, new custom-made instruments, many of which are still used in the colloid chemistry workshop (determination of the contact angle, measurement of surface tension by the method of the highest pressure in bubbles and drops, determination of adsorption and calculation of the specific surface of activated coal, determination of the zeta potential from measurements of electrophoretic mobility, sedimentation analysis, etc.). The head of the workshop was Assoc. B.Ya. Yampolsky, who did a lot to equip it.
P. A. Rebinder and E. E. Segalova were my supervisors for the preparation of my PhD thesis. The topic of the dissertation work was discussed for the first time with P. A. Rebinder in the Botanical Garden of Moscow State University on October 20, 1953. It was a clear, warm, sunny day, the trees were painted in all the colors of the rainbow. P.A. very quickly moved from tree to bush, raised beautiful leaves, pointed to flowers and spoke about a new direction - structure formation in mineral binders, related to physical and chemical mechanics, which, together with E.E. Segalova, he will develop in soon. Interspersed P.A. talked about the merits of rose cuttings, which he bought for the dacha in Lutsino.
The topic of my Ph.D. thesis was "Investigation of the processes of crystallization structure formation in suspensions of semi-aqueous gypsum".
Delivered by P.A. Rebinder and E.E. Segal's goal of the work was to study the physical and chemical patterns and mechanism of the processes of structure formation during the hardening of semi-aqueous gypsum. The main task was to elucidate the causes and conditions for the emergence of a strong hardening structure, as well as ways to control the strength of this structure. Various views available in the literature led to the general conclusion that the crystallization of gypsum dihydrate from a supersaturated solution formed by the dissolution of gypsum hemihydrate or preformed colloidal dihydrate particles leads to the formation of a crystalline intergrowth, which is the hardening structure.
For the scientific school of P.A. Rebinder was characterized by the use of several research methods that allow a comprehensive consideration of the phenomenon.
Detailed studies of the processes of structure formation in suspensions of semi-aqueous gypsum, carried out by the staff and graduate students of P.A. Rebinder, made it possible to distinguish three stages of gypsum hardening:
1) The induction period of structure formation, corresponding to the appearance in the suspension of the coagulation structure of the initial crystals of semi-aqueous gypsum and the resulting neoplasms - dihydrate crystals.
2) The emergence and development of the crystallization structure of gypsum dihydrate, which, unlike the primary coagulation structure, is irreversibly destroyed by mechanical action.
3) Decreased strength of the resulting crystallization structure under wet storage conditions due to internal stresses and recrystallization phenomena (dissolution of small crystals and growth of large ones). Hardening structures are thermodynamically unstable; in humid conditions, crystallization contacts (intergrowth areas between crystals) are spontaneously and irreversibly destroyed as a result of dissolution.
PA Rebinder was always interested in the influence of surfactants. In our work, it was shown that surfactants introduced into water lengthen the induction period of gypsum structure formation, allow increasing strength by reducing the water-solid ratio (W/T). At constant W/T, surfactant additions generally reduce strength by blocking crystal-to-crystal contacts.
The main regularities discovered in the study of gypsum hardening (1957) later appeared in the study of cement (hardening processes) and individual monomineral binders that make up cements, in the work of graduate students and applicants under the guidance of P.A. Rebinder and E.E. Segalova ( until 1965) (E.A. Amelina, S.I. Kontorovich, B.I. Smirnov, Z.D. Tulovskaya, T.K. Brutskus, E.S. Solovieva, R.R. Sarkisyan, Jerzy Stoklos (Poland), Du Yu Zhu (China) and others).
Pyotr Aleksandrovich was very fascinated by these works and often discussed them. Sometimes these discussions took place in the House of Scientists, of which he was chairman for many years. Usually it was in the evening in the beautiful dining room of the House of Scientists on the second floor. Pyotr Aleksandrovich was always waited by a waitress with lunch (cooked to P.A.'s taste, since he was allergic to some foods). PA Rebinder shared his dinner with Evgenia Efimovna Segalova and me. In the same place, he told various "mixers".
Pyotr Alexandrovich classified the names of people he knew according to various criteria: insects (Pchelin, Mukhin, Osin, Komarov, Blokhin, Muravyov); harmful (Shkodin, Zlobin, Kaverzneva); chess (Peshkov, Shakhova, Konev, Korolev); illegitimate children (Colonels, Tsarevs, Captains, Majors, Soldiers). Once Komarov, Bloch and Lovlya brought an article to P.A. The article was published with a list of the authors of "Catching, Bloch and Komarov".
Petr Alexandrovich was always interested in the regularities of structure formation of macromolecular substances and macromolecular substances in a colloidal state. Major scientists were invited to the Department of Colloidal Chemistry of Moscow State University to give lectures to students and graduate students: Acad. V.A. Kargin, prof. V.A. Pchelin, prof. S.S. Voyutsky.
In 1955 V.A. Kargin, being a professor at the Department of Colloidal Chemistry, organized and headed the department macromolecular compounds at the Faculty of Chemistry of Moscow State University. P.A. Rebinder provided the premises (before the construction of building A) and transferred a number of tasks from the workshop on colloid chemistry (viscometry, swelling). For some time the Department of Colloidal Chemistry and the Department of Macromolecular Compounds had a common Komsomol, trade union and party organization. Petr Alexandrovich loved and warmly treated the first students of V.A. Kargin (now academicians of the Russian Academy of Sciences V.A. Kabanov, N.A. Plate and N.F. Bakeev), was an opponent for the doctoral dissertation of N.F. Bakeev. At this defense, interesting and deep discussions took place on the issues of phase transformations in high-molecular systems. Dissenting points of view were in no way transferred to the results of voting and to the high scientific assessment of the dissertation.
At the same time, Petr Aleksandrovich wanted to develop the colloidal chemistry of macromolecular compounds at his own department, and he invited Professor V.A. Pchelin, a specialist in the field of surface phenomena in protein systems, to the department. After graduating from graduate school, I was assigned to the department in the group of prof. V.A.Pchelina. P.A. Rebinder took an active part in the development of programs for the main directions in the development of colloidal chemistry of protein substances. Among them were the issues of solubilization of practically insoluble in water organic compounds protein macromolecules; the dependence of solubilization on the nature of the protein, conformational state, etc. At that time, the assumption prevailed that when proteins come into contact with an organic phase, proteins denature.
On these issues, I made a report at the department in the office of P.A., prepared a lot and, as it seemed to me, answered in detail all the questions asked of me. Prylyudno P.A. He praised me, and then said that if I read so much and look for answers from other people's published materials, I would never be able to come up with my own original. I pass on this advice of Petr Aleksandrovich to all graduate students and graduate students who specialize in the colloidal chemistry of protein substances. Indeed, we, together with graduate students (G.P. Yampolskaya and A.V. Volynskaya), discovered the patterns of solubilization, and managed to prove by a number of methods that proteins do not denature upon contact with an organic phase. Moreover, if these are enzymes, then after the solubilization of organic matter, only the Michaelis constant changes, while the catalytic constant remains the same.
Second important direction development of colloidal chemistry of protein substances P. A. Rebinder defined "structure formation in protein systems". P.A. Rebinder believed that one of the most important problems of colloidal chemistry (physical chemistry of dispersed systems and surface phenomena in them) should be considered the formation of spatial structures of various kinds in dispersed systems and the control of the processes of structure formation and the properties of dispersed structures, primarily their mechanical properties. (deformation and strength). The development of this section of colloidal chemistry has greatly contributed to the emergence of an independent field of chemical science - physical and chemical mechanics of disperse structures and materials. The task of a new field of knowledge, uniting a number of problems of rheology, molecular physics, solid state physics, mechanics of materials and technology of their production, P.A. Rebinder saw first of all the establishment of the mechanism and regularities of the processes of formation, deformation and destruction of various types of dispersed structures.
P.A. Rehbinder said that the solution of this problem would make it possible to obtain dispersed high-strength materials and structured systems with desired properties using optimal technological processes for processing various substances as feedstock.
Repeatedly at lectures and scientific seminars, P.A. Rebinder said that chemical science faces two most important tasks: the synthesis of new substances by chemical transformations and the processing of these substances into final materials and products. The second problem is solved by physicochemical mechanics of materials. Petr Alexandrovich believed that phase equilibria in high-molecular systems, especially those containing crystallizing polymers, can be no less complex than in metal alloys, silicate or salt systems. Physicochemical analysis and the study of phase equilibria should become an equally obligatory auxiliary research method in "polymer science" - the study of polymeric materials, as they have long ago become in metal science, silicate chemistry, gallurgy, technology of fats and hydrocarbon systems. Without exact knowledge of all the features of the state diagrams of the studied high-molecular-weight systems, it is impossible to correctly assess the nature of the structural transformations observed in such systems, most often associated with the formation of new dispersed phases.
Gels and jellies of various nature have long been the subject of study in colloidal chemistry. The appearance of a framework in the structure determines the specific mechanical properties of gels, such as strength, reversible deformation, absence of flow, and elasticity. However, the nature of this emerging network, the nature of bonds and contacts, the mechanism of gel formation, and the thermodynamic properties of gels are still the subject of study by many researchers.
In the last (posthumous "Science" 1974) monograph by V.N. Izmailova and P.A. Rebinder "Structure formation in protein systems", summarizing our work, including postgraduate students G.P. Yampolskaya, A.F. El-Shimi, L.E. Bobrova, A.S. Zholbolsynova, M .N. Pankratova, B. Falyazi, the regularities of the formation of spatial dispersed structures in protein systems were considered, which made it possible to note the important features of the processes of formation of a new dispersed phase from supersaturated polymer solutions. Thus, gelation is always associated with conformational changes in macromolecules, leading to a decrease in the solubility of polymers. As a result, aggregates of macromolecules, i.e., particles of a new lyophilic phase, arise from supersaturated solutions. Their accumulation subsequently causes the appearance of strong disperse structures. Splicing of particles of a new polymer phase with the formation a large number contacts between them (hydrogen, van der Waals or hydrophobic interactions) and leads to the appearance of gel structures of various types, characterized by solid mechanical properties.
The strength properties of polymer disperse structures can be controlled by changing the nature of macromolecules (which is provided by the possibilities of chemical modification), as well as by changing the pH of the medium, concentration, ionic strength of the solution, temperature, and the addition of modifying agents. Studies of the kinetics of gelation of biopolymers have shown that the rate of increase in the strength of gels is the greater, the higher the concentration of a macromolecular substance in the system, and depends on the charge of the macromolecule and the temperature of gel formation. Moreover, the assessment of the enthalpy of contacts that occur during gelation (as shown in the example of gelatin) makes it possible to trace the change in the number and nature of bonds between the elements of the gel structure.
Almost all employees of the Department of Colloidal Chemistry of Moscow State University, the Department of Dispersed Systems of the Institute of Physical Chemistry of the USSR Academy of Sciences and colleagues from other republics took part in the development of the new science created by P.A. Rebinder - physical and chemical mechanics. Petr Alexandrovich skillfully coordinated and directed the development of colloidal chemistry and physicochemical mechanics in the USSR. This coordination was carried out through the Scientific Council on Colloid Chemistry and Physicochemical Mechanics, chaired by P. A. Rebinder, at numerous scientific conferences, where P. A. Rebinder was invariably the organizer and simply in his daily work.
Once Prof. Mikhail Ilyich Usanovich (Head of the Department of Physical Chemistry of the University in Alma-Ata). Pyotr Aleksandrovich invited me to this conversation. It was about organizing a department of colloidal chemistry at Alma-Ata University. Prof. M.I.Usanovich said that there is a capable young man, a candidate of chemical sciences, who can head the department of colloidal chemistry, if he is helped. This young man was, now a professor, Dr. Kh. n., head of the Department of Colloid Chemistry and Enzymology K.B. Musabekov, who has already trained doctors of chemical sciences S.B. Aidarov and Zh.A. Abilov and many candidates of sciences. Some of them worked at the Department of Colloidal Chemistry of Moscow State University (A.Kenzhebekov). Students from Kazakhstan were sent to the Department of Colloidal Chemistry of Moscow State University by K.B. .
The main provisions of the scientific direction of the Department of Colloid Chemistry at the University of Alma-Ata were later published in our joint monograph (K.B. Musabekov, B.A. Zhubanov, V.N. Izmailova, B.D. Summ "Interfacial layers of polyelectrolytes (synthetic polymers) ", "Science" of the Kazakh SSR Alma-Ata, 1987)
Academician of the Academy of Sciences of the Uzbek SSR Karim Sadykovich Akhmedov - a prominent scientist in the field of colloid chemistry, physicochemical mechanics and physicochemistry of polymers, the founder of the school of colloid chemists in Uzbekistan, as well as his students (I.N. Shpilevskaya, L.Yu. Yunusov , S.S. Khamraev, E.A. Aripov, F.L. Glekel, G.N. Virskaya, S.A. Zainutdinov, I.K. Sataev, Z.U. Usmanov, I.K. N. Aminov, A.T. Akhmedzhanova) at the departments of colloid chemistry of Tashkent University and Tashkent Polytechnic Institute, the Institute of Chemistry of the Academy of Sciences of Uzbekistan of the USSR maintained a close relationship with Petr Alexandrovich Rebinder. For many, Petr Aleksandrovich or his students were scientific consultants at work, opponents at the defense, teachers underwent an internship at the Department of Colloidal Chemistry of Moscow State University, employees of the Department (MSU) lectured in Tashkent.
In Ukraine, on the territory Soviet Union was the only institute for colloid chemistry and water chemistry. Academician of the Academy of Sciences of the Ukrainian SSR F. D. Ovcharenko was its director for many years. The actual leader of colloid chemistry and physico-chemical mechanics in Ukraine was Fedor Danilovich Ovcharenko, a student of Academician Anton Vladimirovich Dumansky - as he is now called the "grandfather of colloid chemistry". Every year on June 22, the birthday of Acad. A.V. Dumansky held conferences on colloid chemistry and physico-chemical mechanics. They were attended by colloid scientists from the entire Soviet Union, everything was organized on a grand scale and there was a kind of review scientific achievements. Pyotr Alexandrovich talked a lot in an informal setting with Fedor Danilovich, and they helped each other in solving many problems. At one time, Fedor Danilovich was the secretary of the Central Committee of the Communist Party of Ukraine, and naturally, he had additional opportunities to influence the development of colloid chemistry and physico-chemical mechanics both in Ukraine and in the Soviet Union. One can write a separate memory about the personality of Fyodor Danilovich, and it will also cause only pleasant emotions for both the writer and the reader.
In 1957, a scientific center was organized in Novosibirsk. For the development of the colloid-chemical direction, Pyotr Alexandrovich sent his friend and prof. A. B. Taubman, a student of A.F. Koretsky, and then P.M. Kruglyakov (student of Prof. P.R. Taube) went there. Young scientists successfully worked, created a workable team, defended their Ph.D. dissertations, there were many interesting practical developments. A.F. Koretsky, using P.A. Rebinder’s theory of lyophilic disperse systems based on surfactant compositions, prepared microemulsion systems (with a phase inversion temperature of about 50 o C), which were repeatedly used (resource-saving technology) for washing tankers from oil. In those years, oil was transported to Cuba, and sugar returned in the same containers.
Frequent welcome guests at the Department of Colloidal Chemistry at Petr Alexandrovich were, then still very young, now head. cafe in colloid chemistry at St. Petersburg University and chairman of the Scientific Council on colloid chemistry and physico-chemical mechanics of the Russian Academy of Sciences, acad. RAS A.I.Rusanov and prof. A.A. Abramzon (Professor of the St. Petersburg Institute of Technology). It seems to me that their work was influenced by communication with Peter Alexandrovich. I can judge from the posts. In conversations with me, A.A. Abramzon always emphasized that he considers himself a student of Pyotr Alexandrovich, and that he is just as romantic.
Petr Alexandrovich was always interested in the problems of colloidal chemistry in the oil industry. He had many contacts with various scientists in the USSR. I remember the meetings of P.A. Rebinder with prof. I.L.Markhasin (Ufa, Oil Institute).
With the author of the book "Colloid Chemistry of Synthetic Latexes" (1984) prof. R.E. Neiman (Voronezh University) Petr Alexandrovich was connected both by professional interests and by the organization of the All-Union Conference in Voronezh in 1968.
Self-giving P.A. Rehbinder at conferences is worthy of emulation by current and future scientists. He listened to all reports, asked questions and participated in discussions. P. A. Rebinder’s own speeches were always very bright, understandable, he possessed oratory and gathered huge audiences.
This applies to the reports of P.A.Rebinder and at international conferences. In 1968, in August, at the V International Congress on Surfactant Chemistry (Barcelona, Spain), P.A. Rebinder had a plenary report. This time coincided with the August events in Czechoslovakia. Boycott announced at many international conferences Soviet participants, but not where the delegation of scientists was headed by P.A. Rebinder.
The Congress was held in a special building with a complex of large and small auditoriums, with TVs in the halls broadcasting meetings of all sections. The building and auditoriums were decorated with the flags of participants from all countries. Pyotr Aleksandrovich delivered his report in excellent French. At first, the audience listened to the report with reserved attention. Petr Alexandrovich during the report, if necessary, to transfer the slide to another demonstration, he usually said "merci", but this time, apparently, something "stuck", he again said "merci", again the slide did not change, then P .BUT. said in Spanish "mucha gracias" and the slide was changed. The hall exploded with applause, listened with delight.
We were all proud to work with such a great scientist. The benevolence and respectful attitude of scientists from all over the world towards Petr Aleksandrovich were transferred to us. At the conference, P.A. introduced us, then still young employees, to well-known scientists.
Report by P.A. Rehbinder at a congress in Spain was called "Interaction of surface and bulk properties of surfactant solutions". The report contained 9 points. One of them refers to the problems of colloid chemistry in biology and medicine: "Surfactants with their remarkable ability to form adsorption layers at the phase boundaries are becoming increasingly greater value for scientific justification the most physiologically (pharmacologically) active substances that effectively affect the activity of a living organism. Surface activity can be highly dependent on the nature of the interface, so it should be measured for a "model", liquid boundary closest to the real one at the site of action. Such is the water solution/oil (lipoid medium) interface, which models the phase separation in the living structure of an organ.
The most intense physiological action corresponds to saturation of the adsorption layer. It is achieved at the lower concentration of the substance in the volume of the solution, the higher its surface activity.
This general principle valid for such active substances as anesthetics and analgesics, drugs, substances that activate or, conversely, depress the respiratory function. The same principle - the natural development of Traube's views - obviously constitutes the basis for the action of active substances on living organisms in a very small (homeopathic) concentration. Surfactant additives contribute to the absorption and digestion of food and, above all, fats. In this regard, the most typical biological surfactants, bile cholic acids, are of decisive importance. Many vitamins have a pronounced surface activity and promote the absorption of food. The dispersing (peptizing) effect of surfactants increases the permeability of living cell membranes in relation to physiologically active and nutrients, promoting the growth of body tissues and cell division. If the pores of the membrane are hydrophobic, then the surfactant can increase the permeability by exhibiting a wetting effect, i.e., changing the sign of capillary pressure towards capillary absorption on the menisci in thin pores. The surfactant itself always has an increased permeability due to surface diffusion, i.e. the tendency of the molecules of the adsorption layer to spread over the largest possible surface.
Many of these biological applications of surfactants are determined not by the reduced interfacial tension itself, but by the formation of an adsorption layer of surfactant at the phase boundary associated with it, with all the consequences determined by the properties of this layer. The interfacial tension itself acquires the main role only when it becomes very small. At an interfacial tension of the order of tenths or hundredths of mJ/m 2, as is known, at ordinary temperature a condition arises close to spontaneous dispersion - a colloidal emulsion or suspension is formed under the influence of such minor influences as, for example, convection flows in a liquid dispersion medium caused by local temperature changes. Such spontaneous dispersion under the influence of additives of soap-like surfactants leads to the formation of emulsions that are well absorbed by organisms and are therefore particularly effective in terms of toxic (pesticides) or pharmacological action (drug emulsions) or, finally, as food emulsions.
This is the conclusion of the report by P.A. Rebinder is modern and refers to the colloid-chemical problems of life science "Life science", which are still being developed at the department (V.N. Izmailova, G.P. Yampolskaya "Properties of Protein Layers of Liquid Interfaces. Monograph in "Proteins at Liquid Interfaces, in" Studies of Interface Science D. Mobius and R. Miller (Eds) vol 7, Elsevier, Amsterdam, Elsevier, 1998, p.103-148).
During the conference in Spain, all participants were invited to a bullfight. Pyotr Alexandrovich refused and said: "I am an animal lover." But when we were in the Prado Museum and in the Escurial Palace, Petr Alexandrovich enjoyed the paintings of El Greco, Goya, Velazquez, Murillo. He was happy to talk about the plots of the paintings and the work of the great masters. Excellent P.A. Rebinder knew the history of Spain, however, as well as many other countries.
The great contribution of P.A. Rebinder introduced the stability factor formulated by him - "Structural-mechanical barrier". The entry into science of the "Structural-mechanical barrier according to Rehbinder" as a strong stabilization factor was not easy. In 1961, discussion articles on the problem of stability were published on the pages of the Colloid Journal. In the article by P.A. "The problem of aggregative stability is without a doubt the main and most peculiar problem of colloidal chemistry. At the same time, this main problem is the least developed and still causes heated discussions, despite the extensive experimental material of both laboratory research and industrial-technological nature."
At this time prof. S.S. Voyutsky prepared the textbook "Course of colloidal chemistry". Petr Alexandrovich asked me to be the scientific editor of this textbook and especially drew my attention to the fact that S.S. Voyutsky in ch. IX "Stability and coagulation of colloidal systems" correctly reflected the position on the structural-mechanical barrier.
With great pleasure I accepted the offer of P.A. Rebinder and S.S. Voyutsky to be the scientific editor of the textbook. For me it was a chance to work on the problems of colloidal education with such eminent scientists in an informal setting. The work proceeded as follows. At first I read the textbook and made all sorts of comments. Then they were coordinated with P.A. Rebinder and S.S. Voyutsky. The result was that S.S. Voyutsky included in Ch. IX ideas about the structural-mechanical barrier of stability, edited by P.A. Rebinder.
My comments and suggestions to the textbook by S.S. Voyutsky were set out on 74 pages of typewritten text. With the final version of the comments, we worked with Pyotr Aleksandrovich at the dacha in Lutsino. They played tennis during the day. Elena Evgenievna took care of us, a meal was held on the large veranda with the same compote of rhubarb and well-brewed tea. At the feet of Pyotr Alexandrovich, a German shepherd named Urs fawned over. All this impressed me very much. Pyotr Alexandrovich read my opus and said that everything was well written and business-like.
The discussion on the structural-mechanical barrier in the stability of disperse systems led to the fact that my first PhD student from Egypt, A.F. El-Shimi, together with P.A. And already in 1966 in Berlin at the III International Congress on Surfactants, we presented a report in which there were results on the correlation of the lifetime of elementary gas bubbles and drops (according to the method proposed by P.A. Rehbinder and E.K. Venstrem in 1932) and the rheological parameters of the interfacial adsorption layers of gelatin (determined on the Rebinder and Trapeznikov apparatus) with a wide variation in concentration, pH, temperature, and additions of low molecular weight surfactants to the oil phase.
At the conference in Berlin, we were met by Dr. H. Sonntag (previously he worked at the Department of Colloidal Chemistry of Moscow State University in 1957-1958). His works are devoted to the issues of stability, including stabilization by macromolecular compounds. In "Colloids and Surfaces" in 1998, in the issue dedicated to the memory of H. Sonntag in 1998, the article "V. Izmailova, G. Yampolskaya "Concentrated emulsions stabilized by macromolecules and the contributions of Hans Sonntag to this scientific field" should be published. Colloids and Surfaces A: Physicochemical and Engineering Aspects 1998.
While traveling through Germany (GDR) in Saxon Switzerland, Pyotr Alexandrovich, unexpectedly for everyone, climbed onto the railing of the bridge, which was laid over the abyss, and walked along the railing without losing his balance. I still have a photo of this episode, when I look at it, it takes my breath away.
At a conference in Berlin, P.A. Rebinder and his collaborators met as old friends with the Bulgarian scientists A.D. Sheludko, D. Platikanov and D. Exerova. Now D. Platikanov is the head of the Department of Physical Chemistry at Sofia University, and D. Exerova is the head of a department at the Institute of Physical Chemistry of the BAN. In 1997 they organized the 9th International Conference on Surface and Colloidal Chemistry in Sofia. This conference was dedicated to the memory of Academician A.D. Sheludko.
At the conference in Sofia there was a report by ED Shchukin "Development of physical and chemical mechanics in the works of Petr Aleksandrovich Rebinder and his school". My report "Rheological Properties of Interfacial Adsorption Layers of Proteins" also demonstrated the development of PA Rehbinder's ideas on the determining role of the rheological parameters of interfacial layers of a stabilizer in the stability of films, emulsions and foams. Many speakers recalled the name of Peter Alexandrovich.
The conditions for the implementation of the structural-mechanical barrier of stability according to Rehbinder include the adsorption of the stabilizer on the interfacial boundary with the formation of an interfacial layer with mechanical properties, and the simultaneous lyophilization of the interfacial boundary. It is known that the adsorption of proteins is accompanied by a decrease in surface and interfacial tension, and a sufficiently high water content in the interfacial layer allows us to assume that the complex Hamaker constant is close to the corresponding value of water (10 -21 J). Thus, the structural-mechanical barrier can manifest itself at the stages of coagulation and coalescence. The stabilizing effect of the structural-mechanical barrier in the stability of foams and emulsions was also investigated in the study of the corresponding thin films (free and emulsion), as well as macrodispersions - foams and emulsions. It is known that the stability of primary (ordinary) free black films stabilized by low molecular weight surfactants is described by the DLVO theory. The reasons for the stability of secondary (Newtonian) foam films have not been established.
AT last years life of P.A. Rebinder repeatedly discussed the problem of the stability of these systems with A.D. Sheludko, and as a result of the discussions, an impression was formed about the decisive role of the rheological properties of adsorption layers and films in the stability of secondary foam films. In 1971, an agreement was signed on the creative community between Moscow and Sofia universities. Already after the death of Petr Alexandrovich, within the framework of this agreement, which continues to this day (1998), black films of proteins were first obtained and studied in joint work.
Pyotr Alexandrovich Rebinder was also valued at the Academy of Sciences of the USSR. Petr Alexandrovich together with Academician M.V. Keldysh was invited to the celebration of the 50th anniversary of the Swedish Academy of Sciences. Pyotr Aleksandrovich enthusiastically spoke about the reception. On the same visit to Sweden, he was presented with a book with a genealogical tree of the entire Rebinder family. The first mention of the Rebinders dates back to 1100 (Johan Rebinder). After 800 years, an entry was made in the book about the birth of Peter Alexandrovich.
In 1996, when I was at the All-Russian Conference on Surfactants in Shebekino, prof. B.E. Chistyakov took me to the museum of Belgorod. In the museum, a special room is set aside for a gallery of portraits of the Rebinders.
At the Faculty of Chemistry of Moscow State University, Petr Alexandrovich was an invariable participant in the meetings of the methodological commission. At that time, I was the deputy chairman of the Methodological Commission of the Faculty of Chemistry, and therefore I could observe the work of P.A. Rebinder. Important questions of chemical education were solved. With related faculties (mathematics - prof. L.A. Tumarkin, physics - prof. V.F. Kiselev), sections of mathematics and physics necessary for teaching chemistry, especially for physical and colloidal chemistry, were selected. Here, the knowledge of P.A. Rebinder as a physicist and mathematician was used (he graduated from the Faculty of Physics and Mathematics of Moscow University in 1924). Representatives of all departments gathered: physical chemistry (corresponding member Ya.I. Gerasimov and prof. A.V. Kiselev), analytical chemistry(Academician I.P. Alimarin, Associate Professor Z.F. Shakhova and Prof. V.M. Peshkova), electrochemistry (Prof. N.V. Fedorovich), inorganic chemistry (Academician V.I. Spitsin and Prof. L .I.Martynenko), general chemistry (prof. K.G.Khomyakov, prof. G.D.Vovchenko, prof. E.M.Sokolovskaya), colloid chemistry (academician P.A.Rebinder and prof. V.N. Izmailova), organic chemistry (academician A.N. Nesmeyanov, prof. R.Ya. Yuryeva and prof. Yu.K. Yuryev), chemical technology (academician S.I. V.A. Kargin). P.A.Rebinder paid great attention to the development of the colloid chemistry course curriculum, which was discussed at the Methodological Committee of the Faculty of Chemistry, and then approved by the Ministry of Higher Education and became a model for the chemical faculties of State Universities.
In this regard, the content of the program was correlated with the content of the programs of courses in physical chemistry, organic chemistry and macromolecular substances. For example, adsorption phenomena, the structure and properties of surfactant adsorption layers, the basics of adsorption thermodynamics, the Gibbs equation are discussed in detail in the course of colloid chemistry, and adsorption from the gas phase is described in detail in the course of physical chemistry. The electrical properties of dispersed systems and electrokinetic phenomena in connection with the stability of dispersed systems are read in the course of colloid chemistry, and the fundamentals of the theory of the structure of the double electric layer are presented both in the course of colloid chemistry and in the course of physical chemistry (this section in the course of colloid chemistry is considered earlier than course in physical chemistry).
The synthesis of surfactants is read in courses of organic chemistry, and their properties and their role in the stability of foams, emulsions, suspensions, the Rebinder effect, colloid-chemical methods for cleaning water areas in courses of colloid chemistry.
High-molecular substances that are in a colloidal state during phase separation at the phase boundaries, due to their large role in stability - ("structural-mechanical barrier according to Rehbinder"), constitute an independent section in colloidal chemistry and are naturally considered in the course of colloidal chemistry.
The results of these discussions are reflected in the article by P.A. Rebinder "Colloid Chemistry" in the Great Soviet Encyclopedia.
The methodological commission of the Faculty of Chemistry also solved the problems of the sequence of teaching individual disciplines of chemistry. Once they decided to try to teach students physical chemistry first, and then organic. The experiment failed, I had to put everything back in its place. In the 1960s another experiment was set up. A long-term industrial practice for 5th year students was introduced into the curriculum. The total duration of training was increased to 5.5 years. Students worked for one year at workplaces in different institutes, received a salary, and studied in the evening (16 hours a week). P.A. Rebinder did a great job in organizing jobs for students (only Academician Ya.M. Kolotyrkin, director of the L.Ya. Karpov Institute of Physics and Chemistry, could compare with him). In such training of qualified chemists, there were more minuses than pluses, and this was abandoned after 2 years. Petr Alexandrovich warned about this and was for reasonable conservatism in fundamental education.
The happiness of those students, graduate students and doctoral students who were lucky to study with Petr Aleksandrovich is to listen to his lectures.
I listened to all the lectures of Petr Alexandrovich - all 20 years of my study and work at the Department of Colloid Chemistry. For two years I was a lecture assistant to Pyotr Aleksandrovich.
At the lectures of P.A. Rebinder listeners received information about the latest achievements of P.A. Rebinder himself. He was very generous in this regard, and his lectures attracted not only students but scholars from many institutions. P.A. Rebinder was an excellent lecturer, his lectures and reports, full of deep content, were full of examples from the practice and theory of science.
Was brief summary lectures on colloidal chemistry (compiled by Associate Professor K.A. Pospelova). The lectures were problematic. Theoretical and mathematical substantiation of the basic laws was given. The lectures were illustrated with experiments and posters. They contained a historical note, which scientist was the discoverer, who took part in the development of ideas. The state of development of science today was brought to the attention of students. What tasks and problems need to be solved in the near future were indicated. A possible practical use was pointed out.
For relaxation, to relieve fatigue from students P.A. taught them correct Russian speech: “You can’t talk about yourself, I eat, but I need to eat, and when you invite me, you need to say eat. but your wife.
Lectures Petr Aleksandrovich read in a well-trained voice with a surprisingly pleasant timbre. The speech was accompanied by pauses, there was also a different volume, all this contributed to the increased attention of students.
At the lecture there was always a flask with strong tea, which E.P. Arsentyeva has been brewing for more than 30 years.
Students traditionally asked two questions: 1) What do you drink? And then P.A. was distracted and talked about the dangers of alcohol. 2) Do you like chess? P.A. answered that the mental energy of talented chess players would be better directed to scientific research.
Pyotr Alexandrovich was always strictly dressed (suit, shirts with a tie) in any, even very warm weather, thereby emphasizing respect for others.
The lecture demonstrations thought out and staged under Pyotr Alexandrovich are still shown by A.M. Parfenova, the keeper of these experiments. Pyotr Alexandrovich, when the experiment was successful, especially the movement of the boat on the surface of the water due to two-dimensional pressure, the dance of camphor (dance "twist"), he said: "What a charm, it's better not to go to the Tretyakov Gallery once again and look at the experiments."
The history of chemistry and colloidal chemistry P.A. always sought to convey to the audience, showing the relationship and mutual influence of discoveries in different areas of natural science. One of the doctoral students of P.A. Rebinder prof. N.A. Figurovsky headed the cabinet of the history of chemistry and lectured on history. Under the guidance of prof. N.A. Figurovsky and Art. n. with. T.A. Komarova (graduate of the Department of Colloid Chemistry in 1946) defended several papers on the history of colloidal chemistry (T.T. Orlovskaya, T.V. Bogatova).
Lectures by P.A. Rebinder had a great aftereffect. Corresponding Member I.V. Berezin, the founder of the Department of Chemical Enzymology, said at one of the Rebinder readings that the ideas of micellar catalysis of enzymes placed in reverse surfactant micelles were inspired when I.V. Berezin listened to Petr Alexandrovich's lectures as a student.
P.A. Rebinder and G. Hartley (USA) (1933) were the founders of modern theories of micellization. They simultaneously (and independently) proposed the idea of the structure of spherical micelles in aqueous solutions of surfactants.
Once, when I was at Petr Aleksandrovich's house, he showed me the yellowed newspaper "Pravda" for 1937, where the basement was dedicated to micelles of surface-active substances (surfactants) and it was written that Petr Aleksandrovich juggles surfactant molecules, then their "tails" together in water, then "heads" in non-aqueous solvents, and as a result - that P.A. is a spy for all counterintelligence of all imperialist powers.
Further P.A. said that after the publication of the newspaper, the telephone went silent, no one spoke to him, everyone avoided meetings, and only Alexander Naumovich Frumkin at night on the phone, so that no one could hear, discussed the question "What to do?" Pavel Ignatievich Zubov saved the situation. He was then a member of the Central Committee of the Communist Party and stood up for Pyotr Alexandrovich. Pyotr Alexandrovich was grateful all his life and Acad. A.N. Frumkin, and prof. P.I. Zubov.
In the article by A.N. Frumkin "In memory of a friend" [P.A. Rebinder. Selected works. Surface phenomena in disperse systems. colloidal chemistry. "Science" M. 1978 p.13], written in one breath, contains words of pain from the loss of a friend and gives a high assessment of the activities of Pyotr Alexandrovich: "Peter Alexandrovich was an outstanding scientist, one of the best representatives of Soviet science. If our country has firmly taken a leading position in the science of surface phenomena, one of the most important branches of modern physical chemistry, this is primarily his merit.
Public speeches of Peter Alexandrovich were distinguished by their originality. Only, in his characteristic manner, he expressed his thoughts in such a way that one thought was contained in another, another in a third, and so on. and at the same time, a complexly subordinate sentence, was complete. I had a geometric image of such thinking of Pyotr Alexandrovich from the field of Chinese art of bone carving, when different patterned, lacy bone balls are carved one into the other.
The statements of P.A. and definitions of people close to him in the service, in this case we are talking about the Faculty of Chemistry of Moscow State University.
All chemists of the older generation remember the figurative speech of P.A. I.F. Lutsenko (June 7, 1972), when P.A. Rebinder said: "You are a great ironist."
Petr Alexandrovich had good business relations with the entire administration of the Faculty of Chemistry.
Deputy Dean for Administrative and Economic Work A.A. Simatsky invited P.A.Rebinder to the vernissages of his own paintings, he drew well. After the death of P.A. Rebinder, on the memorial marble plaque, which is installed at the Department of Colloidal Chemistry, a beautiful font of letters was made by A.A. Simatsky.
WORKED HERE
OUTSTANDING PHYSICAL CHEMIST
HERO OF SOCIALIST LABOR
ACADEMICIAN
PETER ALEKSANDROVICH
REBINDER
HEAD OF THE DEPARTMENT OF COLLOID CHEMISTRY
In 1942 - 1972
In front of the watchmen at the entrance P.A. Rebinder always took off his hat. To all P.A. addressed to you and by name and patronymic (students too). He exchanged strong handshakes with men, and kissed the hands of women, not raising the lady's hand, but bowing. He asked young mothers: "How is your baby doing?"
In the years I was reviewing, there were many young people (undergraduate and graduate students) at the Department of Colloid Chemistry. Petr Aleksandrovich knew all the topics of diploma and postgraduate works and often came to defend theses.
Employees, graduate students and graduate students worked selflessly, enthusiastically from morning until late evening. Pyotr Alexandrovich often came to the department late in the evening, after all sorts of business at the academy, institute, etc., opened all the doors of the laboratories, greeted each other, exchanged a few words, and was very surprised if at 9 pm one of his employees was not there in place.
After defending dissertations, there was a special ritual. Pyotr Alexandrovich was a toastmaster, spoke the necessary words to the defender, his leaders and opponents, and then the traditional toast was raised "to those who are on the way", that is, who, according to P.A., is already ready for defense. It was nice to hear your name.
In 1997 the Russian Foundation Basic Research in accordance with the decision of the Council for Grants of the President of the Russian Federation, supported the leading scientific school of the Russian Federation "Physical and chemical mechanics of solids and disperse systems". The head of the school was the head of the Department of Colloidal Chemistry, Faculty of Chemistry, Moscow State University, Professor B. D. Summ. Receiving a grant convincingly underlines the respectful attitude of scientists (grant distributors) to the scientific heritage of P.A. Rebinder.
P.A. Rehbinder did create a school of thought from whose founding works modern trends arose. Generations of young scientists will still learn from his work and open up new opportunities for the development of colloid chemistry and physico-chemical mechanics, created by Petr Alexandrovich.
Petr Alexandrovich Rebinder was very loved, respected and bowed before his encyclopedic knowledge, goodwill, respected for the development and solution of educational and methodological problems in higher education, for his fundamental contribution to the development of colloidal chemistry, physical and chemical mechanics and natural science in general, and for his pedagogical skills, many outstanding scientists.
And I will finish my pleasant memories with the fact that the author of these lines was lucky to be a student of Pyotr Alexandrovich and work under his leadership for 20 happy years. Years of joint work are forever illuminated by his scientific generosity, kindness and friendly attitude.
Speaking shortly before his death in front of graduate students of the Faculty of Chemistry of Moscow State University. M.V. Lomonosov (July 4, 1972), Pyotr Aleksandrovich uttered inspired words - an appeal to young researchers to give strength and knowledge to work, the purpose of which is to preserve health, performance and prolong creative life person. Pyotr Alexandrovich saw this as the main task of a humanist scientist.
Chapter I. Literature Review
§ 1 The main reactions of liquid-phase oxidation of hydrocarbons
§2. Kinetic regularities of liquid-phase oxidation
§3. Catalyzed hydrocarbon oxidation
§4: Surfactants and microheterogeneous systems
§5. Effect of Surfactants on Hydrocarbon Oxidation
Chapter P. Experimental part
Reagents
Experimental methodology
Analysis Methods
Chapter III. Phenomenology of ethylbenzene autooxidation in the presence of surfactants
3.1. Influence of cationic surfactant - cetyltrimethylammonium bromide on the decomposition of a-phenylethyl hydroperoxide
3.2. Influence of anionic surfactant - sodium dodecyl sulfate on the accumulation and decomposition of a-phenylethyl hydroperoxide.
Chapter IV. Combined effect of compounds of metals of variable valence and surfactants on the oxidation of ethylbenzene and the decomposition of its hydroperoxide
4.1. Effect of the combination of SDS-Co(acac)2 on the oxidation of ethylbenzene and on the decomposition of α-phenylethyl hydroperoxide.
4.2. Effect of the AOT-Co(acac)2 combination on the oxidation of ethylbenzene and on the decomposition of α-phenylethyl hydroperoxide.
4.3. Catalysis of the oxidation of ethylbenzene with cetyltrimethylammonium bromide in combination with cobalt(II) acetylacetonate
Introduction thesis in chemistry, on the topic "Oxidation of ethylbenzene in microheterogeneous systems formed by additives of surfactants"
The oxidation of hydrocarbons with molecular oxygen is one of the most attractive directions in the petrochemical synthesis of peroxides, ketones, acids, and other oxygen-containing products. On the other hand, an urgent task is to protect organic materials, such as food and technical oils, fuels, cosmetics, etc., from thermal-oxidative degradation under the action of atmospheric oxygen. The scientific basis for controlling oxidation processes is the theory of liquid-phase oxidation, developed in relation to homogeneous and heterogeneous processes. At the same time, many real systems are microheterogeneous, water-organic, or become so during operation. Additives of surface-active substances (surfactants) to hydrocarbons regulate the microstructure of the medium, prevent the release of water, dissolved and formed during the oxidation process. The effect of surfactants on the oxidizability of hydrocarbon substrates has not been practically studied, although a priory one can expect significant effects associated with the possibility of association of surfactants and oxidation products containing polar oxygen-containing groups, the involvement of inhibitors, including hydrophilic fragments, in these associates, and, consequently, changes in their reactivity and even directions of reactions involving these compounds.
In this work, in order to reveal the nature and scale of the influence of microheterogeneity and kinetic heterogeneity, caused by the addition of surfactants to a hydrocarbon medium, on the kinetics and mechanism of hydrocarbon oxidation, the features of the kinetics and mechanism of ethylbenzene oxidation in microheterogeneous systems are studied. As initiators of microaggregation, we used the most well-known and least reactive surfactants in radical-chain oxidation processes, cationic and anionic surfactants, including saturated hydrocarbon fragments, nonionic surfactants - ethoxylated hydrocarbons, and solid microdispersed TiO2 and SiO2 oxides.
The process of oxidation of ethylbenzene is carried out in industry in order to obtain hydroperoxide and some other products. The kinetics and mechanism of the ethylbenzene oxidation process are well studied in a wide temperature range, which makes it possible to consider this reaction as one of the basic models in the theory of liquid-phase oxidation.
Of particular interest is the combined effect of variable valence metals and surfactants on oxidation processes, since such compositions can control the reaction rate and the composition of oxidation products over a wide range.
Objective
To study the effect of individual surfactants of various nature and microdispersed oxides on the oxidation of ethylbenzene. To reveal the nature and scale of the influence of microheterogeneity and kinetic inhomogeneity of the medium on the kinetics and mechanism of ethylbenzene oxidation and decomposition of α-phenylethyl hydroperoxide.
Evaluate the possibilities of creating effective catalysts for the oxidative transformation of hydrocarbons by combining surfactants with homogeneous metal complex catalysts.
Dissertation conclusion on the topic "Physical chemistry"
1. The phenomenon of catalysis of the oxidation of ethylbenzene (RH) and the decomposition of α-phenylethyl hydroperoxide (ROOH) by the addition of surfactants has been established. It has been shown that the nature of the surfactant has a strong influence on the mechanism of the catalytic action.
2. It has been established that the mechanism of catalysis of the oxidation of ethylbenzene by a cationic surfactant - cetyltrimethylammonium bromide (CTAB) is based on the acceleration of the decomposition of hydroperoxide into free radicals in joint ROOH-CTAB aggregates. The kinetic characteristics of the catalytic process in the presence of surfactants were determined.
3. It is shown that an anionic surfactant - sodium dodecyl sulfate (SDS) heterolytically decomposes ROOH into phenol and acetaldehyde. This leads to a specific autosynergism of the inhibitory action of SDS during the oxidation of ethylbenzene: the heterolytic decomposition of ROOH with the formation of a free radical scavenger, phenol, makes SDS an extremely effective antioxidant for ethylbenzene.
4. Combinations of ionic surfactants with compounds of metals of variable valence as catalytic systems have been studied, which make it possible to regulate the rate of the process and the composition of ethylbenzene oxidation products over a wide range.
5. Three types of synergistic interaction of surfactants with cobalt (I) acetylacetonate (Co(acac)2) during the catalytic decomposition of α-phenylethyl hydroperoxide were found.
In the case of a combination of CTAB and Co(acac)2, the mechanism of cobalt-bromide catalysis of ROOH decomposition and ethylbenzene oxidation in microaggregates formed by CTAB and ROOH is realized. Due to the concentration of reagents in microaggregates, sufficiently high oxidation rates are achieved at relatively low catalyst concentrations, which ensure the selective oxidation of ethylbenzene to acetophenone.
In the combination of Co(acac)2 with AOT, which does not form joint aggregates with ROOH, a synergistic effect in the decomposition of ROOH is achieved due to the solubilization of the formed water in AOT inverted micelles, which prevents the deactivation of Co(acac)2.
Anionic SDS and Co(acac)2 in the absence of oxygen form a new catalytic system that facilitates the formation of phenylacetate upon the decomposition of ROOH.
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How do you mix immiscibles like water with oil? To connect the unconnectable, you need an intermediary. It is not at all necessary for him to penetrate deeply into the mass of both substances, it is enough to be distributed in a uniform, at least monomolecular, layer on the surface of their contact. Such intermediaries, substances capable of accumulating on the interfacial surface of contact between two bodies, are called surface-active.
Laundry is the most obvious example of the use of surfactants. But they are even more widely used in industry. To prepare a lubricant from dissimilar components, to distribute a polar filler in a non-polar polymer (see Polymers), to separate valuable ore from waste rock - none of these technical problems could be solved if people did not know how to use surfactants.
The simplest of these substances is ordinary soap, i.e., sodium and potassium salts of higher carboxylic acids, for example, stearic C17H35COOH or oleic C17H33COOH; they are obtained by hydrolysis (saponification) of natural fats under the action of aqueous solutions of alkalis. It has long been learned to obtain detergents (they are also surfactants) by the action of sulfuric acid on natural oils. The French chemist E. Fremy was the first to prepare such preparations in 1831 from olive and almond oils. AT late XIX in. Russian chemist G.S. Petrov, by the action of sulfuric acid on oil refining products, obtained surfactants - alkylsulfonates, which are widely used to this day. And finally, in the middle of the XX century. organic substances with the general formula were added to the list of basic surfactants:
C n H 2n+1 -CH 4 -O (-CH 2 CH 2 O-) x -CH 2 CH 2 OH
All currently used surfactants are characterized by an amphiphilic structure of molecules: each molecule contains atomic groups that differ greatly in the nature of interaction with environment. Thus, one or more hydrocarbon radicals in a molecule have a chemical affinity for hydrocarbons and oils, i.e., they are oleophilic. The other part of the molecule has an affinity for water, that is, it is characterized by hydrophilicity. The oleophilic groups that interact weakly with water determine the tendency of the molecule to move from an aqueous (polar) medium to a hydrocarbon (non-polar) one. Hydrophilic groups of atoms, on the contrary, hold the molecule in a polar environment. That is why such substances can play, for example, the role of intermediaries between water and oil.
According to the type of hydrophilic groups, surfactants are divided into ionic, or ionic, and non-ionic, or non-ionic. Ionic surfactants decompose in water into ions, some of which have surface activity, others are inactive. If anions are active, the surfactants are called anionic; if cations are active, these substances are called cationic. Anionic surfactants are organic acids and their salts; cationic - bases and their salts.
Depending on the purpose and chemical composition, surfactants are produced in the form of solid products (pieces, flakes, granules, powders), liquids and semi-liquid substances (pastes, gels).
The most important areas of application of surfactants: the production of soaps and detergents, textile auxiliaries used for the treatment of fabrics, paint and varnish products. Surfactants are used in many technological processes of the chemical, petrochemical, chemical-pharmaceutical, and food industries.
The general theory of the action of surfactants was developed by the Soviet physical chemist Academician P. A. Rebinder (see Colloid Chemistry).
