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Horia PAVEN, Zina VULUGA, Raluca GABOR, Andy Cristian NICOLAE National Institute of Research and Development for Chemistry and Petrochemistry - ICECHIM, Bucharest, ROMANIA, email: htopaven@netscape.net Establishing appropriate end-use applications of composite materials with polymer-like matrix needs a careful consideration of both mechanical and thermal features. By using the dynamic mechanical thermal analysis (DMTA) technique, the primary quantities including the storage and loss moduli and the corresponding loss factor at given frequencies for a large temperature range are obtained, the results pointing out the influence of mechanical relaxation processes upon the dynamic stiffness as well as regarding the true damping capacity. Moreover, the use of different evaluation criteria is highlighted for various amounts of reinforcing component. Keywords: Dynamic mechanical thermal analysis, polypropylene, glass fibre, composites.
1. INTRODUCTION Obtaining materials with defined capacity to respond to a large spectrum of possible excitations represents an important actual task [1]. In case of polymer materials, including the composite ones - in which they are, as a rule, the major component - the consideration of native viscoelastic peculiarities are to be performed both from experimental and theoretical standpoints, resulting in balanced approaches [2]. When the dynamic conditions are taken into account, the framework of linear viscoelasticity offers either the variant of a sinusoidal strain, or that of a sinusoidal stress, as inputs. Accordingly, it is well known that in the former case the output, resulting in a stress is expressed by a modulus-like quantity providing in fact information on the dynamic stiffness, while in the later one, the resulting strain result in a compliancelike quantity make available a proper description of dynamic deformation capacity[3, 4]. In case of strain-controlled conditions, a complete set of viscoelastic characteristics include the primary ones (storage -, M , loss -, M , absolute modulus, M * , and loss factor, tan M) as well as the
corresponding secondary quantities (storage -, J M , loss -, J M , absolute compliance, J M * ). On the other hand, in case of stress-controlled conditions, the complete set of viscoelastic quantities contains as primary characteristics the storage -, J , loss -, J , absolute compliance, J * , and loss factor, tan J), while the
corresponding secondary ones include the storage -, M , loss -, M J , and absolute modulus, M J * [5, 6]. J
All these linear viscoelastic quantities are frequency-, , and temperature-, T, sensitive, and in case of composites the overall properties are, in principle, dependent on components properties, morphology and various physical and/or chemical interactions, the existing DMTA being a versatile tool of study [7].
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2. METHOD AND RESULTS Aiming at to better understand the interactions underlying the macroscopic properties of composite in terms of those of components, when the matrix is a semicrystalline polymer (e. g., polypropylene) and the filler is a short glass fibre, needs some comments concerning both the polymer related contribution as well as the polymer-fibre interaction. The dynamic mechanical thermal (DMT) characterization of semicrystalline polymers in case of strain-controlled, or stress-controlled conditions, respectively, when temperature-sweep and isochronal circumstances are taken into account, point out the existence of well defined peaks on the diagrams of loss modulus and loss factor in the former situation, or of loss compliance and loss factor ones in the later one, plotted versus temperature. Below the melting temperature, Tm, the so-called -, -, and -mechanical relaxations are located, the resulting peaks at temperatures T > T > T being associated with activation of corresponding dissipation processes which remains restrained below the appropriate temperature. Accordingly, the lower temperature -relaxation is attributed to the segmental motion, while intermediate, - one, is connected with transition of the bulk amorphous phase from glassy to rubbery state, and higher temperature, -relaxation, is connected with segment exchange arising between crystalline and amorphous domains, as well as to glass transition in the rigid amorphous phase - representing the part of the amorphous phase located in the close vicinity of crystalline lamellae whose mobility is restricted firmly by surrounding crystallites. In principle, when in the polymer matrix a second, stiffer component is introduced, the result is a composite presenting an overall higher stiffness, the interpretation of different variation trends due to the amount of filler being relatively simple only if the considered polymer is a single phase one. However, there are many practical cases when both an amorphous and a crystalline phase are present, the interest concerning such semicrystalline polymers appearing as the result of required sets of end-use properties. Of course, this is the natural consequence of interactions between the polymer phases, as well as those relative to each polymer phase and the filler. The considered components are a as received polypropylene - which is a commercial heterophase copolymer grade with standard properties including density ( = 980 kg/m3), melt flow rate (MFR = 80 g/10 min.) and heat distortion temperature (HDT = 93 C @ 0.45 N/mm2), the polymer presenting some special features regarding high impact strength and high stiffness. and a common standard glass fibre filler. The test specimens, obtained by injection moulding, have the nominal dimensions of 35104 mm3. The experimental system is a Q800 - DMTA (TA Instruments), the considered working conditions being defined by a dual cantilever clamping, such that a flexural deformation mode is involved. The multi-frequency alternative (f = 0.5; 1; 5; 10; 50 Hz), is concerned, at 3 C/min temperature-sweep rate in the range from -100 to 150 C. The raw data, from many available, are the storage modulus (SM), loss modulus (LM) and loss factor (TD) resulting for each fixed frequency, as temperature-dependent quantities. The essential targets are: - to obtain the SM(T), LM(T), and TD(T) in isochronal circumstances; - to present the effect of frequency on different SM(T), LM(T), and TD(T) dependences; - to identify the characteristic temperatures corresponding to mechanical relaxation peaks; - to detect the effects of LM and TD criteria on mechanical relaxations detection; - to point out the SM(f) dependences at different temperatures.
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Figure 1. The storage modulus vs. temperature at different frequencies for given amounts of glass fibres PP0 (wt. 0%), PP1 (wt. 30%), PP2 (wt. 40%).
Figure 2. The loss modulus vs. temperature at different frequencies for given amounts of glass fibres PP0 (wt. 0%), PP1 (wt. 30%), PP2 (wt. 40%).
Figure 3. The loss factor vs. temperature at different frequencies for given amounts of glass fibres PP0 (wt. 0%), PP1 (wt. 30%), PP2 (wt. 40%).
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PP0 L
Table 1. 1 Values of storage modulus at low temperatures Frequency Hz -100 -75 Temperature
o
C
-25 0
-50
3382 3251 2925 3404 3272 2961 3456 3324 3053 3476 3344 3093 3533 3401 3186 Values of storage modulus
2556 2091 2584 2129 2651 2222 2679 2261 2757 2358 at medium/high
Temperature
o
C
100 408 431 484 506 556 125 252 268 304 320 359
Table 2. 1 Values of storage modulus at low temperatures Frequency Hz -100 -75 Temperature
o
C
-25 0
-50
5629 5543 5084 5661 5569 5132 5740 5643 5265 5771 5673 5319 5857 5757 5458 Values of storage modulus
4540 4001 4577 4056 4677 4188 4718 4246 4837 4390 at medium/high
Temperature
o
C
100 1262 1313 1430 1479 1588 125 914 952 1041 1080 1172
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PP2 L
Table 3. 1 Values of storage modulus at low temperatures Frequency Hz -100 -75 Temperature
o
C
-25 0 6163 5581 6200 5632 6312 5785 6361 5840 6505 6010 at medium/high
-50
7398 7277 6810 7430 7303 6856 7517 7378 6988 7500 7420 7041 7709 7579 7226 Values of storage modulus
Temperature
o
C
100 1998 2070 2233 2301 2448 125 1476 1533 1664 1724 1860
The SM data (Figure 1) point out a typical decrease with temperature, the trends illustrating also stiffer values for higher amounts of filler. The frequency has a natural increase effect (see Table 1 to3), the SM(T) curves being shifted toward higher temperatures. The LM data (Figure 2) show characteristic peaks corresponding to intrinsic mechanical losses for different relaxations - elast (lower), beta (higher) - reflecting for the former an elastomer-like amorphous contribution, and for the later one, a typical plastomer-like relaxation. Furthermore, the effect of isochronal test is a positive shift if increasing frequencies are considered.The influence of filler amount is questionable for a 30% content, increasing significantly at an amount of wt. 40%. The TD data (Figure 3) indicate again distinct characteristic peaks - appearing at higher values of temperatures in comparison with those above quoted. However, it appears this TD criterion is by far less meaningful than the LM one, including a fewer justifiable superposition of loss factors for different amounts and/or frequencies, even if may appear there are some apparent similarities. Comparative effects of using LM and TD evaluation criteria are illustrated in Figures 4 and 5, distinguishing temperature-frequency- filler amount correspondences. The frequency dependence of dynamic stiffness at different temperatures (Figure 6) clarifies the influence of different amounts of fillers providing meaningful information upon end-use level terms.
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T LM elast
0 -10 -20 T(C) -30 -40 -50 -60 f(Hz) 0.5 1 5 10 50 PPO PP1 PP2
T TD elast
0 -10 -20 T(C) -30 -40 -50 -60 f(Hz) 0.5 1 5 10 50 PPO PP1 PP2
T LM beta
20 15 T(C) 10 5 0 0.5 1 5 f(Hz) 10 50
T TD beta
25 20 T(C) 15 10 5 0 0.5 1 5 f(Hz) 10 50 PPO PP1 PP2
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PP0
4000 3500 3000 2500 2000 1500 1000 500 0 0 10 20 30 f(Hz) 40 50 60
SM(MPa)
-75 C -25 C 25 C 75 C
PP1
7000 6000 5000 4000 3000 2000 1000 0 0 10 20 30 f(Hz) 40 50 60
SM(MPa)
- 75 C - 25 C 25 C 75 C
PP2
8000 7000 6000 5000 4000 3000 2000 1000 0 0 10 20 30 f(Hz) 40 50 60
SM(MPa)
- 75 C - 25 C 25 C 75 C
Figure 6 The frequency dependence of storage modulus at different temperatures in case of polypropylene matrix and the corresponding 30 and 40% glass fibre amount.
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CONCLUSIONS The comprehensive description of viscoelastic behavior needs the consideration of one or other of the two complete sets of M- or J-like characteristic quantities. The primary viscoelastic quantities are obtained by using a suitable experimental technique either in isochronal, temperature-dependent or in isothermal, frequency-dependent- circumstances, after that being calculated the corresponding secondary characteristics. The effects of using the glass fibre as reinforcing filler in a polypropylene matrix result, on the hand, in an significant increase of dynamic stiffness, which decrease with temperature The obtained values are higher at elevated frequencies, and the storage modulus versus temperature curves are shifted towards higher temperatures when the frequency increase. On the other hand, the existence of characteristic peaks corresponding to intrinsic mechanical relaxations may be revealed by the loss modulus or loss factor dependence on temperature, with a physical meaning bonus for the former quantity. The locations of the corresponding peaks are shifted towards higher temperatures with the amount of filler - at given frequency - or for an increase of the frequency - at fixed level of filler load.
REFERENCES
1. LAKES, R. S., Viscoelastic Solids, Cambridge Univ. Press, Cambridge, 2009. 2. van KREVELEN, D. W., te NIJENHUIS, K., Properties of Polymers, Elsevier, Amsterdam, 2009. 3. KARGIN, V. A., SLONIMSKY, G. A., Brief Essays on the Physics and Chemistry of Polymers, Himija, Moscow, (in Russian), 1967. 4. KRAUSZ, A. S., EYRING, G., Deformation Kinetics, Wiley, New York, 1975. 5. PAVEN, H., Explicit analytical relations for strain-controlled rheodynamical quantities in the case of Zener - Arrhenius model. I. Underlying relations, Materiale plastice, 47, 4, 523-526, 2010. 6. PAVEN, H., Explicit analytical relations for stress-controlled rheodynamical quantities in the case of Zener - Arrhenius model. I. Underlying relations, Materiale plastice, 48, 2, 2011 (in print). 7. DMTA Q 800, Thermal Analysis, TA Instruments, 2007.