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International Journal of Polymer Analysis and Characterization

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Contribution to the Study of the Enthalpy Relaxation of Polyesters by DSC Experiments

M. W. Khemici
a a b

, N. Doulache , A. Gourari & M. Bendaoud

Physics Faculty , University of Science and Technology Houari Boumediene (USTHB) , Algiers , Algeria
b

Physics Department, Sciences Faculty, University M'Hamed Bougara , Boumerds , Algeria Published online: 14 Jun 2012.

To cite this article: M. W. Khemici , N. Doulache , A. Gourari & M. Bendaoud (2012) Contribution to the Study of the Enthalpy Relaxation of Polyesters by DSC Experiments, International Journal of Polymer Analysis and Characterization, 17:5, 358-370, DOI: 10.1080/1023666X.2012.668641 To link to this article: http://dx.doi.org/10.1080/1023666X.2012.668641

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International Journal of Polymer Anal. Charact., 17: 358370, 2012 Copyright # Taylor & Francis Group, LLC ISSN: 1023-666X print=1563-5341 online DOI: 10.1080/1023666X.2012.668641

CONTRIBUTION TO THE STUDY OF THE ENTHALPY RELAXATION OF POLYESTERS BY DSC EXPERIMENTS M. W. Khemici,1,2 N. Doulache,1 A. Gourari,1 and M. Bendaoud1
Physics Faculty, University of Science and Technology Houari Boumediene (USTHB), Algiers, Algeria 2 Physics Department, Sciences Faculty, University MHamed Bougara, ` s, Algeria Boumerde
The differential scanning calorimetry (DSC) technique was used to study the enthalpy relaxation of weakly crystalline polyethylene naphatalate (PEN). The samples were examined under two different thermal histories inside the calorimeter. The rst method consists in annealing samples at temperature Ta below the glass transition temperature Tg, for different times Dta. The second one consists in cooling samples from a higher temperature than Tg to the room temperature using following cooling ratesb. In order to highlight the effect of thermal rigidity of molecular chains on the enthalpy relaxation of polyester, a comparative study between the enthalpy relaxation of polyethylene terephtalate (PET) and PEN with very close degrees of crystallinity vc was made. This study shows that the structural relaxation (physical aging) induces a decrease in the molecular mobility of the samples, which prevents the polymer from initiating a rapid return to the equilibrium state. On the other hand, the molecular chains in PEN are stiffer than in PET and hence relax less. Keywords: DSC; Enthalpy relaxation; Polyethylene naphtalate; Polyethylene terephthalate
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INTRODUCTION Highlighted for the rst time by Kovacs,[1] physical aging is a phenomenon directly related to the relaxation of volume or enthalpy. It is dened as any process leading to slow alteration of the material properties without any chemical modication and is related to the specic instability of glassy materials below their glass transition temperature Tg.[2] In fact, the glassy polymers are inherently unstable, their physical and mechanical properties changing with time so that the polymer reaches equilibrium state due to microstructural changes at the molecular scale.[2,3] We note that physical aging involves only reversible changes in materials properties without permanent change in their chemical structure and results either from conguration change by the macromolecular relaxation enthalpy or volume or the

Submitted 7 January 2012; accepted 9 February 2012. Correspondence: M. W. Khemici, Physics Department, Sciences Faculty, University MHamed ` s, Algeria. E-mail: wakkhemici@ Bougara, Avenue de Lindependence, 35000, (UMBB) Boumerde yahoo.fr 358

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phenomenon of transport (penetration of solvent migration of additives).[46] Its mechanism is summarized as follows: When a polymer is cooled from the liquid state to a temperature below Tg, the mobility of the amorphous phase is not sufcient to allow the material to stay in a thermodynamic equilibrium state. During cooling, the appearance of the glass transition phenomenon is associated with the fact that the speed of molecular rearrangement is slowed by the temperature diminution. When the polymer is in a supercooled liquid state, the molecular motions allow the structure to remain in equilibrium state for each value of T. However, this is not the case in the glass transition region. In fact, in this temperature region, the equilibrium state moves down in term of enthalpy or volume and the molecular motions of the chain are too slow: the polymer structure cant reach the equilibrium state and passes from a metastable equilibrium state to a nonequilibrium state (a glassy state) characterized by an excess of volume and enthalpy. At a temperature between Tg and Ta Tg 20 K, the residual mobility will allow the material to move towards the equilibrium state: this is the aging phenomenon by enthalpy relaxation. Then, we will cite some typical aspects of this phenomenon[6]: Physical aging is a consequence of the instability of the glassy state Physical aging is a reversible process: this can be highlighted by heating the aged material again to a temperature higher than its glass transition temperature Tg, whereupon the original state of thermodynamic equilibrium is recovered. . This phenomenon is independent with respect to the chemical nature of material.
. .

The aim of this work is to study the structural relaxation (physical aging) of polyethylene naphthalate (PEN) by differential scanning calorimetry (DSC) and to compare the obtained results to those obtained within polyethylene terephtalte (PET) published by Doulache et al.[4] Poly (ethylene therephthalate) PET and its concurrent poly (ethylene 2,6-naphtalate) PEN are two of the most widely used polymers in packaging applications because of their high performance in such areas as mechanical properties, transparency, and easy processing[7]. The excellent qualities of these materials are opening them up to a wide range of applications. However, for the optimal use of such materials, it is important to evaluate their lifetime in use, hence the need to study their structural relaxation. In this work, we will study rst the effect of physical aging induced by annealing PEN at temperature Ta below Tg, for different times Dta, and by cooling it from a higher temperature than Tg to room temperature using various cooling rates b by DSC experiments. Then, a comparative study between structural relaxation of PET and PEN is reported. EXPERIMENTAL SECTION Materials and Methods Experiments were carried out on commercial lms of poly(ethylene naphthalene 2,6-dicarboxylate) (PEN) under reference LS 308063 supplied by Goodfellow (U.K.) and biaxially stretched (PENbiax) with 125 mm thickness and 1.36 g=cm3 density. The initial crystallinity rate of the material was estimated by the DSC technique and is close to 49%.

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Samples with 5% of crystallinity degree (PEN5) were prepared by rapid quenching of the molten materials in ice water; 5% is the lowest degree of crystallinity we have obtained. The same value was found by Canadas et al.[8] Samples with 15% of crystallinity degree (PEN15) were prepared by quenching the material in ice water from temperature TQ 225 C lower than its melt temperature to T0 0 C. Physical aging of the samples was performed in two ways. The rst one consists in annealing the polymer at a temperature Ta lower than Tg for different times varying from 5 to 240 min. The second one consists in cooling the polymer from a temperature higher than Tg (140 C) to room temperature using various cooling rates b varying from 0.5 to 20 C=min. In all cases, before each measurement, an isothermal waiting at 140 C for a few minutes is used for each in order to erase the thermal history of the sample. Calorimetric measurements were made with a TA Instruments Q10. The calorimeter was previously calibrated with indium lead. DSC curves were obtained from 10 mg samples sealed in aluminum pans at 10 C=min controlled heating rate.

Phenomenological Description of Physical Aging During physical aging, the enthalpy relaxation is described in the model ToolNarayanasway model (TNM)[9,10] by means of the Kohlraush-Williams-Watt (KWW) law: "   # t b Ut exp 1 s0 b is a non-exponentiality factor that varies between 0 and 1. s0 represents a characteristic time that depends on two temperatures: the current temperature T and the ctive temperature Tf, which links any out-of-equilibrium state at temperature T with an equilibrium state. It is given by[11]: Tf t T0 DT 1 Ut t1 ; t 2

where t1 is the moment when a sudden change in temperature occurs. During quenching from the equilibrium state, the enthalpy H deviates rapidly from the equilibrium line at Tg according to the used cooling rate. The isothermal annealing or aging at a temperature Ta < Tg allows the enthalpy H to reduce this gap in order to gradually approach the equilibium enthalpy. The ctive temperature Tf is then dened as the abscissa of the intersection of the extrapolated equilibrium line at low temperatures with a line parallel to the linear variation of the glassy state passing through the point H (Ta), as shown in Figure 1. The nonlinearity aspect of the relaxation is introduced in this model through the expression of s0. Initially, Narayanasway[12] proposed a generalized version of the Arrhenius equation. Then, Moynihan[13] proposed rewriting it by the introduction of a positional parameter x that separates the thermal and structural contributions:   xDh 1 xDh s0 A exp 3 RT RTf

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Figure 1. Denition of the ctive temperature Tf.

where Dh is activation energy of the relaxation, A is pre-exponential factor, and x is parameter of nonlinearity, 0 < x < 1. RESULTS AND DISCUSSION In order to study the enthalpy relaxation of weakly crystalline PEN, the samples were investigated under two different thermal histories inside the calorimeter: various cooling rates and different glassy annealings. Effect of Cooling Rates This method involves subjecting the sample to a thermal cycle consisting of three steps: An isothermal hold at T0 140 C for several minutes in order to erase the thermal history of the sample. . Cooling of the sample at a constant rate b between T0 and Ti 95 C makes the material glassy, with a nonequilibrium structural state. This latter will depend on the value of b. . The sample is held one minute at temperature Ti in order to ensure good thermal stabilization, then the recording is run by DSC, the heating rate being xed at 10 C=min for all thermograms.
.

Changing the value of b will induce different nonequilibrium structural states. Figure 2 shows DSC curves recorded between Ti and T0. As in the PET case,[4] these thermograms show that for low cooling rates, an endothermic peak is superimposed on the jump of the heat capacity, located around 124 C, characteristic of the glass transition. Growth and shift of the peak towards higher temperatures are observed when the cooling rate decreases. Such an evolution of the endothermic peak associated with the enthalpy is explained by several authors[1418] as a reduction in molecular chain mobility.

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Figure 2. DSC curves recorded at 10 C=min between 95 and 140 C after cooling with rates indicated on the gure: (a) PEN5, (b), PEN15.

In fact, molecular mobility is the fundamental property strongly affected by physical aging. The thermally stimulated currents peak (TSC) resulting from the redistribution of electrical charges due to thermal agitation becomes less intense when aging becomes important. This means that aging is more pronounced when the molecular mobility becomes low, making the sample polarization more limited, resulting in a lower TSC peak[4,11,19]. Exploitation of the obtained thermograms enabled us to determine the enthalpy excess DH represented by the area under the endothermic peaks. Its variation versus the cooling rate b is represented in the left corner of Figure 2. It clearly appears through the evolution illustrated in Figure 3 that the endothermic peak is less pronounced in PEN15 than in PET with a close degree of crystallinity (14%). This result can be explained, in our opinion, by the increased thermal rigidity of PEN caused by its important aromaticity virtues.[7] Indeed, the molecular chains are stiffer than in PET and hence relax less, resulting in an endothermic peak less pronounced than the one appearing in the PETs relaxation. For a cooling rate higher than 5 C=min, the evolution of relaxation of PEN15 cannot be observed.

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Figure 3. Evolutions of enthalpy excess DH vs. cooling rate b:

&

PEN15, . PET.

The different structural states of the amorphous phase of the sample are characterized by a ctive temperature Tf.[11] Numerical calculations have permitted us to follow the evolution of Tf versus the temperature T for each cooling rate b, as represented in Figure 4. Figure 4 shows that the variation of Tf versus T has a behavior similar to that observed in the plots giving the evolution of the volume V and the enthalpy H as a function of temperature. We observed that for temperatures above Tg, the amorphous phase of the sample is in equilibrium liquid state for each value of b. At the beginning of heating, the material is in the glassy state and is characterized by a limit value Tf0 independent of T. More equilibrated state is reached for low cooling rates. Indeed, when the cooling rate is at the lowest value, the temperature Tf0 reaches the lowest value. The variation of ln (-b) according to 1=Tf0 is almost linear, as illustrated in the right corner of Figure 4. The slope of the obtained lines allows us to deduce the activation energy Dh associated with structural relaxation; its value is 1020 kJ.mol1 in PEN5 and 1240 kJ.mol1 in PEN15. Dh is less important in PET (875 kJ= mole)[4,20,21] than that found in PEN. This difference can also be due to the increased molecular rigidity in PEN. Analysis of the enthalpy relaxation induced by different cooling rates was made by applying the Tool model. In the following, we will describe, as an example, the relaxation of PEN5 using this model. The theoretical ctive temperature Tfth (T) dened in this model by Equation (2) is calculated by simulating an increase in temperature by 10 C=min between 90 and 140 C. An example of theoretical curves Tfth (T) obtained from the experimental curves Tfexp (T) with b 0.3 C=min is shown in Figure 5, after adjusting the parameters A, x, and b of the TNM model. The Tfth (T) variations allow the deduction of the corresponding theoretical normalized heat capacity Cpnth (T). Figure 6 displays an example of curves obtained for a slow cooling rate (b 0.3 C=min). The evolutions of A, x, and b of the TNM model as a function of the thermal history of the sample are shown in Figures 7, 8, and 9, respectively.

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Figure 4. Evolution of Tfexp as a function of the temperature T for each cooling rate b: (a) PEN5, (b) PEN15.

Figure 5. (&) Variations of Tfth(T) obtained during an increase at 10 C=min after cooling PEN5 at b 0.3 C=min; (- - -) variations of Tfexp(T) obtained after an increase in temperature under the same conditions. A 4 10139 s, x 0.8, b 0.5. (color gure available online).

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Figure 6. Example of adjustment of experimental normalized heat capacities CPN (- - -) and theoretical Cpn (&) according to the TNM model. b 0.3 C=min (PEN5).

Figure 7 shows a signicant reduction in the pre-exponential factor A from a cooling rate of about 5 C=min; this result suggests that the glass transition temperature of the material changes according to the thermal history of the sample. Figure 8 shows an invariance in the evolution of the parameter of nonlinearity x with regard to the cooling rate b. A similar result was found in PET study.[11,22] The non-exponentiality factor b evolves linearly when the cooling rate b varies in a semi logarithmic form in the same way as in the case of PET (see Figure 9). The evolutions of the parameters of the TNM model versus the cooling rate conrm the incapacity of this model to describe the enthalpy relaxation of a polyster by a single set of parameters, independent of the thermal history of the sample.

Figure 7. Evolution of the pre-exponential factor A of TNM model according to the cooling rate b.

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Figure 8. Evolution of the nonlinearity parameter x in the TNM model according to the cooling rate b.

Figure 9. Evolution of non-exponentiality b in the TNM model according to the cooling rate b.

Effect of Glassy Annealing We proceed now to the study of the inuence of PENs isothermal aging. The sample was aged at different temperatures Ta (105 C, 110 C, 115 C, and 120 C) during different times Dta. DSC thermograms were recorded at the temperature range 95 140 C. Figure 10 shows, as an example, the thermograms recorded for the performed aging at the temperature Ta 105 C. The observed endothermic peaks show jumps of heat capacity associated with the recoverable amount of structural relaxation for different annealings. The enthalpy excesses are calculated from areas under peaks of transition. They increase with aging times Dta, as illustrated in the left corner of Figure 10.

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Figure 10. DSC curves of PEN recorded at 10 C=min between 95 and 140 C after aging performed at Ta 105 C for different times Dta as indicated in the gure: (a) PEN5, (b) PEN15.

The evolution of ctive temperature Tfexp deduced from experimental thermograms recorded following various aging at Ta 105 C is illustrated in Figure 11. The increase of Dta induces the decrease of Tf0 value in a way comparable to the effects produced by the decrease of cooling rates. The evolution of Tf0 versus Dta is reproduced in the upper left corner of Figure 11. A maximal effect of glassy annealing is observed at Ta 110 C. In fact, the endothermic peak is less pronounced for aging temperatures above 110 C. According Bacharan,[11] annealing at 115 and 120 C could allow a portion of the amorphous phase to regain its equilibrium state during the time of annealing. Let us note that the maximum effect of the latter occurs at Ta Tg 15 C in PEN. The same result was found in the case of PET, with a maximum effect of annealing observed at Ta 65 C  Tg 15 C[4,11].

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Figure 11. Variation of the experimental ctive temperature Tfexp vs. the temperature T for each annealing time Dta at Ta 105 C: (a) PEN5, (b) PEN15.

CONCLUSION We have reported on the effects of physical aging of polyethylene naphthalate with two degrees of crystallinity following various annealings at Ta during different times Dta, and by cooling it following various cooling rates. A comparison of the obtained results with those of polyethylene terephtalate was made. According to the obtained results, it can be concluded that: Study of the effect of physical aging by different cooling rates or different annealed glass showed that the structural relaxation depends on the rigidity of molecular chains. . Different glassy annealing at temperatures Ta Tg 20 C and Tg 25 C could allow a portion of the amorphous phase of polyester (PET, PEN) to regain its equilibrium state during annealing.
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A maximal effect of glassy annealing is observed at a temperature closed to Tg 15 C in polyester. . Finally, we have shown the inability of the model of Tool to describe the enthalpy relaxation of a polyester by the same set of parameters.

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