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AZERBAIJAN CHEMICAL JOURNAL № 1 2019
UDC 541.64:678.7
METAL-CONTAINING NANOPARTICLES IN A MALEINIZED POLYETHYLENE MATRIX AS NANOFILLERS FOR POLYPROPYLENE
N.I.Kurbanova, Z.N.Huseynova, N.Y.Ishenko, A.T.Aliyev, T.M.Guliyeva,
S.K.Ragimova, S.A.Rzaeva
Institute of Polymer Materials, NAS of Azerbaijan [email protected] Received 29.06.2018
The effect of additives of metal-containing nanofillers including nanoparticles of zinc oxide stabilized on a polymer matrix of maleinized polyethylene on the properties of nanocomposites based on isotactic polypropylene by methods X-ray phase and thermogravimetric analyses was studied. The improvement of the strength and rheological indexes, as well as the thermooxidative stability of the nanocomposites obtained was revealed.
Keywords: isotactic polypropylene, metal-containing nanofillers, maleinized polyethylene matrix, physical and mechanical properties.
https://doi.org/10.32737/0005-2531-2019-1-54-58
Introduction
One of the most promising trends for the development of modern science is nanotechno-logy - the production and use of materials containing nanoparticles (NP).
In recent years, there has been a significant interest in composite materials on the basis of polymer matrices and metal nanoscale particles, which is due to a wide range of their applications - from catalysis to nanotechnology in information techniques.
The development of nanotechnology has opened the possibility of carrying out research in the field of composite nanomaterials, and has now made it possible to proceed to the development and use of promising polymeric materials for sensors, catalysis, nanoelectronics, etc. Metallopolymer composites are used mainly in the electronic and radio engineering industries, as well as in aviation and rocket construction [1-3].
It is known that in order to improve the performance of plastics, fillers are used in an amount of 30-50 mass. % by weight. Filled plastics are used, mainly, as a structural material [4].
In the world today, various types of polymer composite materials based on nanofillers actively replace the traditional materials [5]. Polymeric nanocomposites can be obtained in situ, i.e. by polymerization of the monomer in the presence of a nanofiller previously dispersed in the reaction medium [6]. The method
of introducing a nanofiller in the melt of polymers is more preferable. This method is most suitable for use in modern industry. It makes it possible to obtain nanocomposite polymers for a wide cross-section of producers, what makes this method promising and cost-effective [7].
The modification of polypropylene (PP) by the creation of various composite materials makes it possible to significantly expand the field of its application. The filled polypropylene ranks one of the first places among the filled thermoplastics. At present more attention is paid to the development of composites with na-nosized fillers. Such composite materials have higher characteristics than composite materials with micro- and macrofillers. The introduction of even a small amount of nanosize filler into polypropylene can significantly change the physical properties, enhance barrier qualities, thermal stability, electrical conductivity, etc. [8, 9].
The use of nanoparticles of d-valence metals (zinc, cobalt, nickel etc.) in polymers makes it possible to obtain fundamentally new materials that are widely used in radio and optoelectronics as magnetic, electrically conducting and optical media [2, 9].
The purpose of this work is to study the effect of additives of metal-containing nano-fillers (NF) on the physicomechanical, rheolog-ical, thermophysical and heatphysical properties of composites on the basis of isotactic PP.
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Experimental part
In the work isotactic PP of TPPF79FB brand (Russia) with a melt flow limit of 10-15 g/10 min, Vicat (T) softening (10N) no more than 1500C are used.
As NF there was used zinc oxide NP stabilized on a polymer matrix of maleinized high-density polyethylene, obtained by mechano-chemical method in a polymer melt. The content of nanoparticles is 5 mass % the size is 1117 nm, the degree of crystallinity is 35-45% [10]. The ratio of components of polymer mixtures (mass %): PP/NF = 100/(0.5, 1.0, 3.0).
Nanocomposite polymeric materials were obtained by mixing PP with zinc-containing NF on the laboratory mill at a temperature of 160-1650C. To carry out the mechanical tests, the obtained mixtures were pressed in the form of plates 1 mm thick at 1900C for 15 min and 10 MPa pressure.
The physico-mechanical properties of the obtained compositions were determined on the RMI-250 instrument, and the melt flow index (MFI) on the index of termoplasts melt (IIST) instrument at a temperature of 2000C, at a load of 5.00 kg.
X-ray phase analysis (XRD) of the obtained compositions was carried out on a "D2 Phaser" device from Bruker (Germany).
The thermostability of the test samples of thermoplastic elastomers was studied on a Q-1500D derivatograph manufactured by MOM (Hungary). The tests were carried out in an air atmosphere in a dynamic mode when the sample was heated to 5 deg/min from 20 to 5000C, weighed portion 100 mg, the sensitivity of the channels DTA-250 ^V, TG-100 mg, DTG-1 mV.
Results and its discussion
Nanocomposite polymer materials based on PP with metal-containing nanoparticles were obtained. The composition and structure of the obtained nanocomposites are studied.
The phase composition of the obtained nanocomposite was studied by X-ray diffraction analysis (RPhA). Phase identification was carried out from the data on interplanar distances, using the ASTM card file. It is shown that in the studied nanocomposites reflections from the planes of the crystal lattice of metals were observed, corresponding to the dhk/ series of zinc oxide (ZnO), according to the ASTM file (Figures 1, 2).
The effect of additives of metal-containing nanofillers on the physico-me-chanical, rheological, thermophysical and thermal properties of composites on the basis of isotactic PP has been studied. The physico-mechanical and rheological properties of the composites obtained are presented in Table 1.
As can be seen from the data in Table 1, the introduction into the composition 0.5-1.0 mass % of NF leads to a slight increase in the strength index from 21.6 to 32.7 MPa. Increase in the concentration of NF more than 1.0 mass % leads to a decrease in the strength of the composite (11.8 MPa), which is probably due to the aggregation of nanoparticles, which leads to the formation of microdefects in the bulk of the polymer matrix. An increase in the concentration of NF leads to a decrease in the strain at break of the composite, which, apparently, is due to blocking of the mobility of polymer segments by nanoparticles at the nanolevel.
The study of the by Vicat heat resistance by of the obtained compositions showed that the
Table 1. The physico-mechanical and rheological properties of the obtained composites
Composition Tensile strength, op, MPa Tensile strain, £p, % Vicat softening point, 0C Melt flow index (MFI), g/10 min
PP 21.6 46 165 9.5
PP/NF(0.5) 28.1 22 165 15.1
PP/NF(1.0) 32.7 80 165 19.7
PP/NF(3.0) 11.8 20 165 41.2
Fig.1. Diffractograms of the sample PP.
Fig.2. Diffractograms of the sample PP/NF.
AЗЕРБAЙДЖAHСКИЙ ХИМИЧЕСКИЙ ЖУРНАЛ № 1 2019
introduction of a nanofiller into the PP composition leads to the preservation of the heat resistance index at 1650C.
The study of the melt flow index (MFI) showed that increase in the NF content (1-3 mass %), contributes to the increase of MFI to 19.7 (1 mass %) and 41.2 g/10 min (3 mass %), what testifies to improvement of fluidity of the composition and the possibility of processing it by injection molding and extrusion.
The thermal stability of the test samples based on PP containing NF with NP of zinc oxide was estimated from the mass loss, value activation energy (Ea) of the decomposition of thermooxidative destruction, calculated by the double logarithm of the TG curve no the methods [11], and a temperature of 50% (T50) decay of the samples under study, and also by the time of their half-life - t1/2. The data obtained from derivatographic studies are shown in the Table 2.
Table 2. Thermal properties of the resulting composites
Composition T50, 0C T1/2, min. Melting point, 0C Ea, kJ/mol
PP 340 64 145 122.49
PP/NF(0.5) 360 68 145 170.23
PP/NF(1.0) 370 71 145 175.53
PP/NF(3.0) 360 69 145 173.12
As can be seen from the data in Table 2, the introduction of NF containing NP of zinc oxide into the composition contributes to an increase in the half-life temperature of the samples: T50 at 20-300C; the half lifetime t1/2 increases from 64 to 71 min., the activation energy (Ea) of the decomposition of the thermooxi-dative degradation of the resulting nanocompo-sites rises from 122.49 to 175.53 kJ/mol.
Derivatographic studies have shown that the introduction of NF containing NP of zinc oxide into the composition contributes to the enhancement of thermooxidative stability of the obtained nanocomposites.
Conclusions
The influence of a nanofiller containing nanoparticles of zinc oxide on the properties of composites on the basis of isotactic PP has been studied.
X-ray diffraction patterns confirm the presence of zinc oxide nanoparticles on the PP matrix.
The improvement of strength and rheolog-ical parameters, as well as thermooxidative stability of nanocomposites obtained, was revealed.
It is shown that nanocomposites based on PP can be processed both by pressing and injection molding method as well as extrusion method.
References
1. Suzdalev I.P., Suzdalev P.I. Nanoclusters and nanocluster systems // Adv. Chem. 2001. V. 70. No 3. P. 203-240.
2. Pomogailo A.D., Rosenberg A.S., Uflyand I.E. Nanoparticles of metals in polymers. M.: Chemistry. 2000. 672 p.
3. Tretyakov A.O. Polymer nanocomposites - materials of the XXI century. Equipment and tools for professionals. 2003. V. 37. No 2. P. 18-20.
4. The encyclopedia of polymers. M.: The Soviet. Encyclopedia. 1974. V. 2. P. 328.
5. Foster L. Nanotechnology. Science, innovation and opportunities. M.: Technosphere, 2008. 352 p.
6. Antipov E.M., Barannikov A.A., Gerasin V.A. et al. The structure and deformation behavior of nanocomposites based on polypropylene and modified clays // High-mol. comp. 2003. A. V. 45. No 11. P. 1885-1898.
7. Kovalchuk A.A., Shchegolikhin A.N., Dubnikova I.L. et al. Nanocomposites polypropylene/ multi-walled carbon nanotubes: in situ polymerization and properties // Plast. masses. 2008. № 5. P. 27-30.
8. Sister V.S., Ivannikova E.A., Lomakin S.M. Comparative analysis of thermal stability of polymer nanocomposites based on polypropylene // Nano-mater. nanotechnol. 2012. № 3. P. 13-28.
9. Gubin S.P., Yurkov G.Yu., Kosobudsky I.D. Na-nomater. based on metal-containing nanoparticles in polyethylene and other carbon-chain polymers // Int. J. Mater. Product Technol. 2005. V. 23. No 1-2. P. 2-25.
10. Kurbanova N.I., Alimirzoeva N.A., Guseinova Z.N., Nurullayeva D.R. Ecological Method of Preparation of Metal-Containing Nanoparticles in Polyethylene Matrix // 3st Int. Turkic World Conf. Chem. Sci. and Technol (ITWCCST 2017). Baku. 10-13 Sept. 2017. Abstract. P. 98.
11. Technic. properties of polymeric materials: Educational-reference manual // Under the general ed. prof. Kryzhanovsky V.K. SPb.: The profession, 2007. 240 p.
MALEiNLO§DiRlLMi§ POLiETiLEN MATRiSiNDO STABiLLO§DiRiLMi§ METALSAXLAYAN NANOHiSSOCiKLOR - POLiPROPiLENiN NANODOLDURUCUSU KiMi
N.i.Qurbanova, Z.N.Huseynova, N.Y.i^enko, A.T.Aliyev, T.M.Quliyeva, S.K.Rahimova, S.A.Rzayeva
Tarkibinda maleinla§dirilmi;j polietilen matrisinda stabill9§dirilmi§ sink oksid nanohissaciyi saxlayan nanodoldurucu-nun izotaktik polipropilen asasli nanokompozitin xassalarina tasiri rentgenfaza va termoqravimetrik analiz metodlari ila tadqiq edilmi§dir. Alinan nanokompozitlarin mohkamlik va reoloji gostaricilarin hamginin termooksidla§dirici sta-billiyinin yax§ila§masi a§kar edilmi§dir.
Agar sozlzr: izotaktik polipropilen, metaltarkibli nanodoldurucu, malemh§dirilmi§ polietilen matrisi, fiziki-mexaniki xassalar.
МЕТАЛЛСОДЕРЖАЩИЕ НАНОЧАСТИЦЫ В МАЛЕИНИЗИРОВАННОЙ ПОЛИЭТИЛЕНОВОЙ МАТРИЦЕ - НАНОНАПОЛНИТЕЛИ ПОЛИПРОПИЛЕНА
Н.И.Курбанова, З.Н.Гусейнова, Н.Я.Ищенко, А.Т.Алыев, Т.М.Гулиева, С.К.Рагимова, С.А.Рзаева
Методами рентгенофазового и термогравиметрического анализов исследовано влияние добавок - металлсодержащих нанонаполнителей, включающих наночастицы оксида цинка, стабилизированные на полимерной матрице малеинизированного полиэтилена, на свойствa нанокомпозитов, полученных на основе изотактического полипропилена. Выявлено улучшение прочностных и реологических показателей, а также термоокислительной стабильности полученных нанокомпозитов.
Ключевые слова: изотактический полипропилен, металлсодержащие нанонаполнители, матрица малеинизированного полиэтилена, физико-механические свойствa.
АЗЕРБАЙДЖАНСКИЙ ХИМИЧЕСКИЙ ЖУРНАЛ № 1 2019
