Abstracts

№3, 2017

Fractal Dimensions of Carbon Black-Filled Polymers and Elastomers

P.1. Objects and Methods. Morphology

Chalych A.E. (Prof. D. Sc. [Chem.], Head of Lab.), Gerasimov V.K. (Assist. Prof. D. Sc. [Chem.], Lead. Res.), Gorshkova O.V. (Ph. D. [Chem.], Chief of Project. Office), Matveev V.V. (Jun. Res.)

Methods of preparation of objects are described. There are: carbon blacks (CB) Т1 and ХС-72 types, monodispersed polystyrene (PS), polyethylene (PE), as well as butadiene (SKD), isoprene (SKI-3), styrene butadiene (BSK) and butyl (BK) rubbers as objects. Two methods of preparation of filled samples are in use. In the first case (model systems) of filler and polymer are mixed in 1÷5% solution of PS in toluene. Content of CB was varied from 1 to 60 % . After mixing suspension was irradiated by ultrasound (US) (disperser UZDM-2T), frequency 44 khz, during 10 min. In the second case the standard sulfur vulcanizates were obtained. Morphology was studied by TEM (ЕМ-301, Japan) on thin films or with the use of etching in plasma of highfrequency oxygen discharge (vacuum reactor Edwards company). The technique of TEM image processing with the purpose to get information about the local and the global fractal dimension of the particles aggregates is described.

Key words: filled polymers, dispersion, ultrasound, structure, TEM, fractal dimension

Fractal Dimensions of Carbon Black-Filled Polymers and Elastomers

P.2. Fractal Dimensions of Carbon Black-Filled Systems

Chalych A.E. (Prof. D. Sc. [Chem.], Head of Lab.), Gerasimov V.K. (Assist. Prof. D. Sc. [Chem.], Lead. Res.), Gorshkova O.V. (Ph. D. [Chem.], Chief of Project. Office), Matveev V.V. (Jun. Res.)

Fractal dimensions characterizing internal structure and mechanisms of its formation in disperse systems are obtained. The dependencies for individual clusters and image in whole are usually linear in double logarithmic coordinates with angle of inclination between 1.38 and 1.82. All dependencies form two groups, for systems of low (below 10 %) and high (up 15 %) content of fillers, and correspondently, of relatively low (below 1,5) and high fractal dimensions and correspondent to different mechanisms of structure formation («clusters- clusters» and «clusters-particles»). Effect of irradiation (dose from 7 to 60 Mrad) on structure and fractal dimensions is studied. So the connectivity of carbon black aggregates is defined within the framework of fractal dimension concept. Dependence of the fractal dimension of the carbon-filled disperse systems on a preparation method and an external influences is shown.

Key words: filled polymers, structure, disperse systems, TEM, fractal dimension, irradiation, connectivity of elements

Effect of Mixture of Dealtom Multi-Walled Carbon Nanotubes with Carbon Black on the Properties of the Elastomer Composite

Mitryaeva N.S. (Postgrad. Student, assistant), Akimenko S.S. (Ph.D. [Chem], Senior Lecturer),

Myshlyavtsev A.V. (Prof., D. Sc. [Chem.], Deputy Head of Chair)(Leading Researcher), Zubarev A.V. (Ph.D. [Techn.], Gen Director)

Effect of concentration of multi-walled carbon nanotubes (MWCN) Dealtom on properties of elastomer composites as sole filler and in a mixture with carbon black (CB) has been studied. Rubber compounds and vulcanizates based on synthetic isoprene rubber SKI-3, two CB types N330, P278E as well as MWCN Dealtom were the objects of investigation. Vulcanization, strength, dynamic and electrical properties were measured. Tensile strength of control specimens (without MWCN) is of 13–30МPа and decrease at increase of MWCN content. Values of tgδ at temperature Т = + 40 °С is nearly constant at increase of MWCN content from 0,5 и 5,0 phr; at Т = 0 °С and –40 °С the slight increase of tgδ is shown. Specific electrical resistance decrease with MWCN content and is of minimum value at 0,5–3,0 phr. So the simultaneous use of CB and MWCN Dealtom as hybrid filler slightly improves electrical properties of elastomer composites.

Key words: multi-walled carbon nanotubes, carbon black, elastomer composite, synthetic isoprene rubber IR, strength properties, dynamic properties, electrical properties, dispersion

The Рossibility of Use the Complex Antioxidants for Rubber Compounds Based on Isoprene Rubbers Working under Extreme Conditions

Puchkov A.F. (Ph. D. [Techn.], Associate Prof.), Kablov V.F.(D. Sc. [Techn.], Prof.), Spiridonova M.P. (Ph. D. [Techn.], Dean), Tretyakova N.А. (Ph. D. [Techn.], Chief of Dep.), Vysochinskaya O.A. (Student of MA), Gerasimenko E.I. (Student of MA)

The influence of complex antioxidants on the characteristics of rubbers based on isoprene rubber under extreme conditions was studied. Data for rubber compounds containing only N-isopropyl-N-phenyl-n-phenylenediamine (IPPD) and a complex salt with ε-caprolactam (РRS-1N) in addition to IPPD are under comparison. Parameters determined are: tensile strength (fр), dynamic endurance using the «МRS-2» machine (N), abrasive wear using the «Grasselli» machine (), the amount of sol-fraction using viscometric method (ZF) and the equilibrium degree of swelling in toluene (Qр). IR-spectra by IR-Fourier spectrometer Nicolet-6700 and electron micrographs using the microscope EM-14 were obtained. Treatment of rubbers in critical for isoprene rubbers temperature conditions (140 ºC) for different time (τ) can significantly increase N and reduce a. The values of N are almost identical for rubber compounds with IPPD and PRS-1N, the maximum is achieved at τ = 25 hours. Values  are significantly less for rubber compounds containing PRS-1N. The results of ZF, Qр, IR-spectroscopy and electron microscopy confirmed the presence of specific temperature-time zones where physical and chemical processes occur moving away a catastrophic failure of the rubbers. The use complex antioxidant with a synergistic protective effect allows increasing the working time of the rubber goods before catastrophic failure.

Key words: isoprene rubber, complex antioxidant, extreme conditions, stability zones, abrasive wear, e-caprolactam, operational capability of rubbers

Impact Resistance of Compounds PP/NBR with Improved Compatibility

of Polymer Components Obtained in the Process of Reaction Compounding in the melt

Part 1. Influence of the Nature of the Polar Vinyl Monomer on Impact Resistance and Stress-Strain Properties of Compositions

Kazakov Yu.M. (Ph. D. [Techn.], Gen. Director), Volkov A.M. (Ph. D. [Chem.], Chief expert),

Ryzhikova I.G. (Ph.D. [Techn.], Chief expert), Volfson S.I. (Prof., Dr. Sc. [Techn.], Chief of chair)

Effect of components of modifying system on impact resistance and stress-strain properties of PP/NBR compositions of constructional purposes was investigated. Compositions containing 23 % (mas.) BNKS-18AMN and coagents of peroxide modifying system, namely polar vinyl monomers: maleic anhydrite (MA), half ester of MA and ethylene glycol (MEG), and complex of MEG with aromatic amine antioxidant Diafen FP (MEG+DFP). Simultaneously, preliminary synthesized compatibilizers based on PP and modified by MA or complex MEG+DFP grafting, including with the presence of elastomers of different polarity: NBR or EPDM, were introduced into the compositions. It was revealed that among the investigated coagents, the MEG+DFP provides the most effective dispergation of NBR phase in PP matrix. As the result the significant increase of impact-strength and elongation at break of the obtained compositions was found. Compatibilizers containing elastomeric phase: nonpolar EPDM in combination with MA and polar BNKS-18AMN combined with MEG+DFP, have the highest specificity and efficiency in the processes of reaction compounding of PP/NBR mixture. Peroxide modifying systems containing MEG and particularly MEG+DFP have to be used in the process.

Key words: PP, NBR, PP/NBR compositions, modifying system, peroxide/coagent, polymeric compatibilizer, reaction compounding

Impact Resistance of Compounds PP/NBR with Improved Compatibility of Polymer Components Obtained

in the Process of Reaction Compounding in the melt

Part 2. Influence of the Formulaition and Concentration of the Polymer Compatibilizer on the Composition Toughness.

Kazakov Yu.M. (Ph. D. [Techn.], Gen. Director) , Volkov A.M. (Ph. D. [Chem.], Chief expert),

Ryzhikova I.G. (Ph.D. [Techn.], Chief expert), Volfson S.I. (Prof., Dr. Sc. [Techn.], Chief of chair)

Toughness of PP/NBR compositions of constructional purposes was investigated. Compositions contain 23 %(mas.) BNKS-18AMN and coagents of peroxide modifying system, namely polar vinyl monomers: maleic anhydrite (MA), half ester of MA and ethylene glycol (MEG), and complex of MEG with aromatic amine antioxidant Diafen FP (MEG+DFP). Compositions contain also compatibilizers of different formulaition, synthesized in presence of 10 %(mas.) BNKS-18AMN. Data for toughness were obtained at +23 and –30 ºС. Concentration of compatibilizers in all studied compositions change from 3 to 20 %(mas.). At +23 ºС toughness have a maximum; at –30 ºС there is also a maximum under small concentrations. It was revealed that the highest values of toughness and relatively slow its decrease among the studied compositions take place for compositions with compatibilizer based on PP and synthesized in presence of 10%(mass) BNKS-18AMN with the use of complex coagent peroxide+MEG+DFP. These results may be due to increased volume and more homogeneous structure of interfacial transition layer formed under these compounding conditions. This in turn due to specific and effective nature of MEG molecules interaction with functional groups of NBR in interfacial region of these compositions, promoted by the presence of secondary aromatic amine associated with MEG.

Key words: PP, NBR, PP/NBR compositions, polymeric compatibilizer, reaction compounding, modifying system: peroxide/coagent

Rheometric Study of Vulcanization and Pore Formation of Foaming Elastomer Matherials

Shuvaeva A.V. (Ph.D. [Techn.], Chief of Lab.), Gordenko D.R. (Chief of Techn.Dep.),

Lyusova L.R. (Prof., D. Sc. [Techn.], Chief of Chair), Naumova Yu.A. (Prof., D. Sc. [Techn.])

Kinetic curves describing the processes of vulcanization and pore formation of foaming rubbers based on the butadiene-acrylonitrile rubbers are studied. Kinetic curves are obtained by vibration rheometer D-MDR 3000 (company «Mon Tech») with software MonControl, and provides the possibility to measure the pressure in the chamber at the same time as the torsional moment and tgδ. The investigated materials differ in stearic acid amount. The quantitative interpretation of the results of vulcanization and foaming processes in elastomer materials are presented. To approximate the curves of vulcanization and pore formation high adequacy mathematical models have been proposed. It is established that parameters of proposed models are related to vulcanization and foaming parameters. The effect of stearic acid on the formation of porous structure in foamed materials based on mixtures butadiene-acrylonitrile rubber containing acrylonitrile 27–30 %, and polyvinyl chloride is shown.

Key words: butadiene-acrylonitrile rubbers, vibrational rheometry, kinetics of vulcanization, vulcanization parameters, foamed rubber, pore formation, mathematical models

Аlternative Technology of Manufacturing of Rubber Products Using Recycling Tires Products

Kablov V.F. (Prof., D. Sc. [Techn.], Head of Chair), Perfil'ev A.V. (Postgrad. Student),

Shabanova V.P (Ph.D. [Techn.], Assist. Prof.), Perfil'ev A.A. (Undergrad. Student)

Prospects for the use of powder for manufacturing rubber products and features of various variants of powder technology with the use of powder and block rubbers are under consideration. Examples of practical application of powder technology at rubber industry enterprises as well as the press-powder technology of manufacturing of rubber products from secondary rubber crumb obtained during recycling of worn tires are presented. The variants of activation of the compressible composition are analyzed. The advantages of the use of microwave for the activation of rubber crumb before the manufacture are shown. This processing makes it possible to obtain products of improved properties. The increase of 30 % of the tensile strength of vulcanizates in this case is obtained. The vulcanization time reduced because of the homogeneous heating of the specimen. Press-crumb processing is recommended for manufacturing of different rubber mould articles on small enterprises in the case of absence of the standard mixing facilities.

Key words: rubber, rubber compound, powder technology, used tires, rubber crumb, activation, microwave irradiation, revulcanizates, product quality

Non-Isothermal Flow of Viscoelastic Elastomeric Compounds in Planar Channel

Baranov A.V.( Prof., D. Sc. [Phys.-Mat.]), Yunitskiy S.A.( Assist. Prof., Ph. D. [Phys.-Mat.])

Mathematical model of non-isothermal flow of non-Newtonian fluid in convergent channel is presented. These processes is realized at the flow of rubber compounds and other elastomer compositions in plane-slotted nozzle of extruders, and runner channels of mould at moulding, as well as at some processes of coat of heat-shieldung covers on surface of metal goods, and take place under sufficient changes of temperatures and pressure. All important factors to be taken into account in the development of the model have been noted in particular, viscoelasticity. Many assumptions were made on the basis of the fact that the flow occurs at low values of the Reynolds number and at a high Peclet number. Phan-Thien-Tanner model is used as a rheological model. Thermal boundary conditions of the first kind, temperature dependence of the viscosity and the energy dissipation are taken into account. From the momentum equation using this rheological model, the velocity profile is obtained as expressed in an explicit form. The solution of the energy equation was analyzed numerically by the finite difference method using an iterative scheme. Results of calculations have been presented. A significant effect of Weissenberg number on the velocity profile and pressure distribution along the channel has been shown.

Key words: mathematical modeling, non-Newtonian fluid, viscoelasticity, non-isothermal flow, elastomer composition

Effect of Impregnating Composition Type on Structure of Aramid Cords Threads

Andreykova L.N. (Ph. D. [Techn.], Jun. Res.), Bobrov S.P. (Ph. D. [Techn.], Deputy Director), Andriasyan Yu.O. (D. Sc. [Techn.], Chief of Basic Chair), Karpova S.G. (Ph. D. [Phys.-Mat.], Sen. Res.), Mihaylov I.A. (D. Sc. [Chem.], Director of Center of Collective Use)

Analysis of the publications on the effect of the type of impregnating composition on adhesive, mechanical, physical, and service properties of the aramid cord threads of brands Arom-75 (Rusar-75), Arom-175 (Rusar-175), Rusar-200 is carried out. According to the modern views the type of the impregnating compound influences on the adhesive, mechanical, and physical properties of an aramid cord as well as its structure. The impregnated cord threads Arom-75 and the non-impregnated thread (reference standard) were studied by EPR-spectroscopy. Parameters characterized the structure of the investigated samples: the correlation time (tc), the radical concentration and the ratio of the high-density amorphous region fraction to loose amorphous region fraction were determined. Data for cords based on threads Ruslan®, impregnate by two composition Р-151с12 and Р-138-12 as well as based on non-impregnated thread were under comparison. The possibility to change the structure of cord and therefore the properties of rubber industrial articles of aramid cord using the impregnating compounds of various types is shown.

Key words: aramid cords, impregnating composition, EPR, structure

7th RUSSIAN RUBBER CONFERENCE Rubber’2017: Traditions and Innovation (Moscow, Expocentre)

Reznichenko S.V. (Prof., D. Sc. [Techn.], Chief of Chair, Editor in Chief),

Konikova T.B. (Executive Director, Executive Secretary of the All- Russian Conference «Rubber-2017: Tradition and Innovations»),

Morozov Yu.L. (Prof., D. Sc. [Techn.], Deputy Editor)

Rеview of the papers presented on 7th All Russian Conference (International) «Rubber-2017: Traditions and Innovation» (Moscow, Expocenter, 25 – 26.04.17).

Key words: conference, rеview, Expocenter, raw materials, processing, tires, technical rubber goods, rubbers, equipment, recycling, ecology, innovations

Results of Exhibition «Tires & Rubber»

20-th International Specialized Exhibition

Post release on 20-th International Specialized Exhibition «Tires & Rubber» (Moscow, Expocenter, 24–27.04.17).

Key words: exhibition, post release, Expocenter, raw materials, processing, tires, technical rubber goods, rubbers