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UDC 541.64:678.7
PREPARATION AND INVESTIGATION OF PROPERTIES OF THE POLYMER COMPOSITES ON THE BASIS OF POLYPROPYLENE AND ETHYLENE-PROPYLENE DIENE ELASTOMER WITH METAL-CONTAINING NANOPARTICLES
N.I.Gurbanova, A.T.Aliyev, A.M.Kuliyev, N.A.Alimirzoyeva, N.Ya.Ishenko
Institute of Polymer Materials, NAS of Azerbaijan ipoma@science. az Received 18.05.2016
The new nanocomposite thermoelastoplasts on the basis of isotactic polypropylene (PP) and ethylene-propylene diene rubber (EPDR) with application of nanofiller - nickel nanoparticles stabilized on polymer matrix have been prepared. The influence of nickel nanoparticles on properties of the prepared nanocomposites by the methods of X-ray phase (RPhA) and thermogravimetric (TGA) analyses has been investigated. It has been shown that an introduction of nanoparticles in PP/EPDR leads to the improvement of the rheological properties and increase of thermal stability of nanocomposites in keeping of their strength indices.
Keywords: nanocomposites, nickel nanoparticles, isotactic polypropylene, ethylene-propylene diene elastomer, RPhA, TGA.
Introduction
Intensive development of the world petrochemical branch intends a constant search for new materials possessing high consumer properties, ecological safety and simplicity of processing. Such materials are not without reason the thermoplastic elastomers (TPE) [1-3].
Recently, abroad it is rapidly developing the production and application of dynamically vulcanized thermoelastoplasts (TPV), combining the properties of vulcanized rubbers during exploitation and thermoplasts in the processing. Due to its relative low cost and sufficiently high exploitation characteristics TPV are one of the perspective classes of the polymer composition materials [3, 4].
In connection with severe requirement of the ecologists to increase of safety of the polymer materials and a mandatory waste utilization of production, the polyolefins were the most ecological in comparison with PVC, PS, PU, ABS-plastic, which were used for preparation of various types of TPE [4-6].
One of the most perspective directions of development of the modern science is the nano-technology - preparation and use of materials having nanoparticles in composition.
The development of nanotechnology opened up possibility of carrying out of the investigations in the field of composition nanomaterials and now it allowed to move to the creation and
use of perspective polymer materials for sensors, catalysis, nanoelectronics, etc. [7].
The permolecular structure of the polymer systems has been investigated in numerous works of school of the academician V.A.Kargin. The definition of place of polymers in nanochemistry opens possibility of use of nanostructured peculiarities of the polymers for properties and operational characteristics of composites. The development of a science of nanodimensional polymer and cluster metal-containing particles in the polymer matrices is stimulated by constantly growing interest to this problem in many fields of chemistry, physics and material study. The creation of metal-polymer composition materials, possessing specific physico-mechanical and operational characteristics: higher heat- and electro-conductivity, high magnetic susceptibility, ability to screen ionizing radiation in many ways favored development of such investigations [8-10].
There are known the works on preparation of thermoplastic elastomers of mixture (TPE) and dynamically vulcanized (TPV) with application of isotactic polypropylene (PP) as thermoplast, and as elastomer - ethylene-pro-pylene diene rubber (EPDR) or butadiene-nitrile rubber with use of various fillers or compatibili-zers for improvement of compatibility and also physical-mechanical and technological properties of compositions [11-13].
The use of metal nanoparticles of variable valence (copper, cobalt, nickel, etc.) in the polymers allows to prepare principally new materials, which find wide application in radio-and optoelectronics as the magnetic electro-conducting and optical media [8, 14].
There have been previously prepared the new TPE on the basis of PP/EPDR with application of nanofiller (NF) containing nanoparti-cle (NP) of copper oxide stabilized by matrix of polyethylene of high pressure [15]. It has been shown that an introduction of NP into TPE does not practically influence on melting temperature of the mixtures but leads to the increase of beginning temperature of thermooxidative destruction by 30-500C in keeping of mechanical characteristics of TPE.
This work has been devoted the preparation and investigation of properties of nano-composite mixture and dynamically vulcanized TPE on the basis of PP/EPDR with application of metal-containing nanoparticles stabilized on polymer matrix as a nanofiller.
Experimental
In work there were used: isotactic PP of mark 21030-16 (Russia) with M„=7.7104 and Mw=3.4 l05; density p=0.907 g/cm3; degree of crystallinity (K) 55%; melting temperature Tm= 1650C; the melt flow index (MFI)=2.3 g/10 min at T=1900C and loading 2.16 kg; EPDR - of mark Dutral TER 4044 with quantity of propylene links 35%, Mooney viscosity 44 (at 100X). In the composition of EPDR the diene component was 5-ethylidene-2-norbornene in a quantity of 4-5%.
As NF it were used NPs of nickel oxide (NiO), stabilized by polyethylene matrix prepared with application of titanium-phenolate of the catalytic system. Content on polymer matrix of NP of nickel oxide - 18%, sizes of NP - 11-15 nm, degree of crystallinity of NP - 25-45% [16].
A ratio of the initial components (mas. p.): PP/EPDR/NF = 50/50/1.
The polymer composites have been prepared by mixing in high-speed mixer of closed type "Brabender" at T=1900C and rotation rate of the rotor 100 rev/min for 10 min, and vulcanized - by a method of dynamic vulcanization in
the same conditions with application of sulphur-containing vulcanizing system, the composition of which includes the following ingredients (in mas p. per 100 mas. p. of rubber): elemental sulphur - 1.00, zinc oxide - 2.50, stearic acid -1.00, di(2-benzthiazolyl)disulfide - 0.25, tetra-methylthiuramdisulfide - 0.73 [17]. The samples for investigations were prepared by hot pressing as the plates by thickness of 0.35 mm at 1900C and pressure 10 MPa for 10 min with subsequent cooling to room temperature with rate 20 grad/min.
For investigation of the mechanical characteristics of the polymer mixtures from pressed plates there were cut the samples in the form of blades with sizes 35.00x5.00x0.35 mm. The uniaxial tension of the samples was performed on testing machine "Instron-1122" at room temperature and constant displacement rate of upper traverse 50 mm/min. From deformation diagram on initial site of curve the modulus of elasticity E, ultimate strength ap and specific elongation at break Sp were determined. The results were averaged on 10-14 samples. The error of measurement of modulus of elasticity and ultimate strength did not exceed 10%, and elongation at break - 20%. MFI was determined on capillary microviscosimeter IIRT-5 (Russia) at temperature 1900C and loads 2.16, 5.00 and 10.6 kg.
The dielectric properties of the prepared nanocomposites were carried out by measuring complex Concept 40 of firm Novocontrol (Germany). The measurement accuracy of dielectric permeability - 110-2, dielectric losses -110-5. The measurements were carried out at room temperature and limited by frequency range 10-2-106 Hz.
X-ray phase analysis (RPhA) of the prepared compositions has been carried out on apparatus "D2 Phaser" of firm Bruker (Germany).
The thermostablity of the investigated samples of thermoelastoplasts was studied on derivatograph of mark Q-1500D of firm MOM, Hungary. The tests have been carried out in air atmosphere in the dynamic regime at heating of the samples 5 grad/min from 20 to 5000C, the samples 100 mg, sensitivity of channels DTA -250 mkV, TG - 100, DTG - 1 mV.
Results and discussion
The physico-mechanical properties of mixture and dynamically vulcanized nanocom-posites on the basis of PP/EPDR, containing filler with nanoparticles of nickel oxide have been prepared and investigated. The mechanical characteristics and melt flow index MFI of the investigated systems are presented in Table 1.
Table 1. Properties of the investigated TPE and TPV
Composition E, MPa MPa 8» % MFI, g/10 min, r=190°C 8 K, %
2.16 kg 5.00 kg 10.6 kg
Unvulcanized TPE
PP/EPDR 395 11.0 170 0.9 3.7 14.8 2.0 53.7
PP/EPDR/NF 263 8.7 110 1.1 4.4 16.8 2.2 50.2
Dynamically vulcanized TPV
PP/EPDR 215 13.2 370 - - - 2.0 49.4
PP/EPDR/NF 114 12.8 340 - - - 2.4 50.0
E - modulus of elasticity, cD - tensile strength, Sp - elongation at break, MFI - melt flow index, K - crystallinity, s' - dielectric permeability.
As showed the carried out investigations in mixture TPE an application of NF containing nickel NPs leads to some decrease of modulus of elasticity of the system in keeping of tensile strength and specific elongation, however, favors increase of index of MFI in loading 10.6 kg in 1.22 times (Table 1).
As is seen from data of Table 1 in vulcanized compositions - TPV an application of NF containing nickel NPs leads to the decrease of value of modulus of elasticity E in 1.3 times in keeping of tensile strength and specific elongation. In this case, a system doesn't flow in loads in 2.16, 5.0 and 10.6 kg.
The decrease of modulus of elasticity of the composite has been probably stipulated by aggregation of NP leading to formation of mi-crodefects in a volume of the polymer matrix. The improvement of flow index of the composite has been apparently connected with increase of mobility of the polymer segments in interaction of NP with matrix on nanolevel. As a result of interaction of NF with macromole-cule segments a mobility of the latter ones is increased and the polymer flow is changed [18].
Thus, an introduction of metal-containing NF in TPE leads to the decrease of melt viscosity and thereby an index of MFI is increased.
This can be explained by formation of more fi-ne-spherulitic structure of filled compositions in comparison with initial one, apparently, NFs in concentration 1.0 mas. p. act as the structure-forming agents [19].
The investigations of electrical properties of the compositions of mixture and dynamically vulcanized TPE have been carried out. It was known that for initial PP a dielectric permeability - s' = 2.2-2.4 [20]. As showed our investigations for TPE PP/EPDR = 50/50, not containing NP, s' = 2.0 and with increase of frequency from 10-2 to 107 Hz the s' value is not changed. In introduction of NF containing NP of nickel in composition of mixture a value s' is slightly increased to 2.18 and is further not changed with frequency growth.
Dynamic vulcanization does not change the value of s' index of the initial composition. An introduction of NP containing NP of nickel in composition of TPE practically does not influence on s' value. The s' values obtained for investigated mixture and dynamically vulcanized TPE correspond to data for usual dielectrics. Thus, one can conclude that a quantity of the introduced NF (1 mas. p.) in composition of mixture or vulcanized TPE does not practically influence on electric properties of the compositions.
It has been carried out RPhA for mixture and dynamically vulcanized TPE on the basis of PP/EPDR, prepared with application of NF containing nickel NP. In Figures 1, 2 the diffracto-grams of RPhA PP/EPDR of the initial and with metal-containing nanofillers are presented. There have been shown the reflexes corresponding to PP: dm equal to 6.19929, 5.17135, 4.73608, 4.48713, 4.48707, 4.03424, 3.47038, 3.11297, 2.11651 A (Figure 1); reflexes characteristic for nickel-containing nanoparticles: dhki 1.48525, 2.10037, 2.42535 A (Figure 2), which corresponds on card file ASTM in a series dhki of nickel oxide.
The diffractograms of the investigated samples confirm the availability of NiO nano-particles on polymer matrix, a presence of which influences on properties of the prepared nanocomposites. In Table 1 the crystallinity value (K) of the investigated mixtures are presented. It is seen that the dynamic vulcanization
2Ttieta (Coupled TwoTheta/Theta) WL-1.54060
Fig.1. Diffractograms of the sample PP/EPDR.
Fig.2. Diffractograms of the sample PP/EPDR/NF.
of the initial mixture decreases K from 53.7 to 49.4%. An introduction of NF in composition of TPE favors decrease of K value from 53.7 to 49.9%, and in a case of TPV - to insignificant value increase of this index from 49.4 to 54.8%.
The thermostability of the investigated samples was estimated on activation energy (Ea) of decay of thermooxidative destruction calculated by a method of double logarithm on curve TG on methodology [21], on temperature of 10% ( T10 ), 20% (T2o ) and 50% (T50 ) decay of the investigated samples of TPE and TPV, and also on time of their half-decay - t1/2 . Data obtained as a result of the derivatographic investigations are presented in Table 2.
Table 2. Thermal properties of the investigated samples of TPE and TPV
Composition T10 T20 T50 T1/2, min Ea, kJ/mol
TPE
PP/EPDR 255 300 340 64 194.11
PP/EPDR/NF 275 325 385 70 223.86
TPV
PP/EPDR 275 315 355 68 215.38
PP/EPDR/NF 300 345 410 76 241.76
As is seen from data of Table 2 an introduction of filler, containing nanoparticle of nickel oxide, in composition of mixture and vulcanization thermoelastoplasts favors increase of decay temperature of the samples: T10 by 20-250C, T20 by 25-300C, T50 by 45-500C; half-decay time t1/2 is increased from 64 to 70 min for TPE and from 68 to 76 min for TPV, activation energy (Ea) of decay of thermooxidative destruction of the prepared nanocomposites is increased by 25-30 kJ/mol.
The derivatographic investigations showed that an introduction of filler containing na-noparticle of nickel oxide in composition of mixture and vulacanization thermoelastoplasts favors improvement of thermooxidative stabiliy of the prepared nanocomposites.
Conclusions
The influence of nanofiller containing nanoparticles of nickel oxide on peculiarities of the mixture and dynamically vulcanized TPE on the basis of isotactic PP and EPDR has been investigated. The diffractogarms of RPhA con-
firm the availability of nanoparticles of nickel oxide on matrix of TPE.
It has been shown that a small addition of nanofiller in a quantity of 1 mass p. does not practically influence on crystallinity and dielectric permeability of TPE and TPV. The prepared data of electrical properties of TPE correspond to indices of usual dielectrics. An introduction of nanofiller improves a flow of TPE, in this, it is decreased a modulus of elasticity of the investigated TPE and TPV in keeping of ultimate strength index and specific elongation.
The derivatographic investigations showed that the activation energy (Еа) of decay of thermooxidative destruction of the prepared nanocomposites is increased by 25-30 kJ/mol, which evidences about high thermooxidative stability of the prepared nanocomposites.
* This work has been executed at financial support of Science Development Fund under President of Azerbaijan - Grant № SDF-Mob-1-2013-1(7)-16/13/4
The authors express gratitude for Doctor of Chemistry, professor Prut E.V. for help in preparation and investigations of the properties of nanocomposite thermoplastic elastomers, Doctor of Chemistry Aliyeva R.V. for kindly given samples of nanofiller, Ph.D Gasimov V. for help in carrying out of RPhA.
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POLÎPROPÎLEN VO ETÎLENPROPÎLENDÎEN ELASTOMERl OSASINDA METALNANOHiSSOCiKLi POLlMER KOMPOZiTLORlN ALINMASI VO TODQiQi
N.i.Qurbanova, O.T.Aliyev, A.M.Quliyev, N.O.Olimirzayeva, N.Y.içenko
Tarkibinda nikel nanohissaciklari olan nanodoldurucudan istifada etmakla izotaktik polipropilen va etilenpropilendien elastomerlari asasinda yeni nanokompozit termoelastoplastlar alinmiçdir. Nikel nanjhissaciklarinin alinmiç nanokompozitlarin xassalarina tasiri rentgenfaza (RFA) va termoqravimetrik (TQA) usullann tadqiq olunmuçdur. Gôztarilmiçdir ki, nanohissaciklarin daxil edilmasi nanokompozitlarin môhkamlik gôstaricilarini saxlamaqla onlann reoloji xassalarini va termostabilliyini yuksaldir.
Açar sozlar: nanokompozitbr, nikel nanohissaciklari, izotaktik polipropilen, etilenpropilendien elastomeri, RFA, TQA.
ПОЛУЧЕНИЕ И ИССЛЕДОВАНИЕ СВОЙСТВ ПОЛИМЕРНЫХ КОМПОЗИТОВ НА ОСНОВЕ ПОЛИПРОПИЛЕНА И ЭТИЛЕНПРОПИЛЕНДИЕНОВОГО ЭЛАСТОМЕРА С МЕТАЛЛСОДЕРЖАЩИМИ НАНОЧАСТИЦАМИ
Р.И.Курбанова, А.Т.Алыев, А.М.Кулиев, Р.А.Алимирзоева, Н.Я.Ищенко
Получены новые нанокомпозитные термоэластопласты на основе изотактического полипропилена и этилен-пропилендиенового эластомера с применением нанонаполнителя, содержащего наночастицы никеля, стабилизированные на полимерной матрице. Исследовано влияние наночастиц никеля на свойства полученных нано-композитов методами рентгенофазового (РФА) и термогравиметрического (ТГА) анализов. Показано, что введение наночастиц в ПП-ЭПДК приводит к улучшению реологических свойств и повышению термостабильности нанокомпозитов при сохранении их прочностных показателей.
Ключевые слова: нанокомпозиты, наночастицы никеля, изотактический полипропилен, этиленпропилендиено-вый эластомер, РФА, ТГА.
