International Journal of Science & Technology Volume 3, No 1, 37-42, 2008

Thermophysical Properties Of Blend Of Poly ( Vinyl Chloride ) With Poly ( Isobornyl Acrylate )
Mediha KOK1, Kadir DEMRELLI2 and Yildirim AYDOGDU1
2

Firat University, Department of Physics, Elazg, TURKIYE Firat University, Department of Chemistry, Elazg, TURKIYE yaydogdu@firat.edu.tr
(Received: 02.01.2008; Accepted: 28.02.2008)

Abstract: The immiscibility and thermophysical properties of poly(vinyl chloride )(PVC):poly(isobornyl acrylate) (PIBA) (50:50 by weight %) blend, which were prepared by solution method, were studied. The immiscibility was examined by DSC and TGA techniques. The thermophysical properties (thermal conductivity, specific heat capacity and thermal diffusivity) were measured by DSC. Thermophysical properties of PVC:PIBA (50:50 by weight %) blend and dependence on its miscibility were investigated.
Keywords: Poly(vinyl chloride ), poly(isobornyl acrylate), blend, miscibility, thermophysical property.

Poli ( Vinil Klorr )n Poli ( zobornil Akrilat) ile Karmn Termofiziksel zellikleri
zet: zelti yntemiyle hazrlanan poli(vinil klorr) (PVC):poli(izobornil akrilat) (PIBA) (50:50 arlka%) karmnn termofiziksel zellikleri karabilirlii incelendi. Karabilirlik ve termal iletkenlik, zgl s kapasitesi ve termal diffzivite, cams gei scakl termal bozunum gibi termofiziksel zellikleri belirlemek iin DSC ve TGA teknikleri kullanld.
Anahtar Kelimeler: Poli(vinil klorr), Poli(izobornil akrilat) (PIBA), karm, karabilirlik, termofiziksel zellik.

Introduction
Polymer blends are mixtures of two or more polymers that can either mix completely on a molecular scale or form two-phase structure. Polymer blends can exhibit new combinations of properties of component and strongly upon the morphology of the blended materials. This is synthetically somewhat easier than making copolymers because it allows the various polymer components to be produce by different polymerization methods [1,2]. Blending of polymers may either result in compatible ( miscible ) system or incompatible ( immiscible ) system. A miscible polymer blend means single phase system, an immiscible polymer blend means multi phase system [3]. Although polymer blending looks to be a very attractive way to obtain new materials, most polymers are immiscible and/or incompabitible. Reason for incompability are high interfacial tension and, consequently, poor interface adhesion [4]. By blending polymers, new material can be developed that combine physical and mechanical properties of their components, depending on the composition and level of compability. Polymer blends are currently receiving great attention because they offer low-cost alternatives to the development of entirely new materials with improved properties [5,6]. PVC; Poly (vinyl chloride) is extremely important with useful molecular structure and morphology every area for example, it is used thermoplastics due to its many valuable properties like low price, good process ability, chemical resistance and low flammability and Currently, PVC is one of the worlds leading synthetic polymers with global consumption of approximately 16 million tonnes per annum [7, 8]. Thermal conductivity, specific heat capacity, and thermal diffusivity are so important for the thermal transport properties in polymer industry that these three thermophysical properties have great significance in determining the heat transfer calculation [9,10].

M.Kok, K. Demrell and Y.Aydogdu

The thermophysical properties of materials as thermal conductivity (k), heat capacity at constant pressure (Cp), thermal diffusivity (), and density () are related to each other. This relation can be shown as follow: k= Cp (1)

heating rate and flow rate of 50 ml/min argon atmosphere. DSC curves were recorded at temperature range between 80 C and 140 C. DSC curves were used to investigate the miscibility of polymers. 2.4. Thermophysical Properties Perkin Elmer sapphire DSC was used to measure thermal conductivity and specific heat capacity. For the measurement of thermal conductivity of polymers and their blend, the method of Joseph H. Flynn and David M. Levin was used at the heating rate of 10 C/min and in flow of 50 ml/min argon atmosphere. According to this method; sensor materials, (Table 1), which have sharply melting peak in various temperature ranges, is selected and melting points of the sensor materials was used to calculate the thermal conductivity values. Following equations can be found out by using the above information. The thermal resistance of the polymers and blend, which were shaped as pellet, can be obtained from RS=R-R (2)

There have been many application concerning about blends. However only a few application have focused on thermophysical properties. At the former work, thermophysical properties of PVC were investigated [11]. This study describes thermal properties of PVC with blending a new polymer into PVC. Thermal conductivity, specific heat capacity, thermal diffusivity, and Thermogravimetric analysis of PIBA and its blend with PVC are investigated and the dependence of thermophysical properties of blend with PVC or PIBA is examined. 2. Experimental 2.1. Materials The homopolymerisation of IBA was prepared in 1,4-dioxane at 60 oC in the presence of AIBN. Predetermined amounts of the monomer, AIBN and the solvent were mixed in a polymerization tube. The mixture was degassed about 10 minute with argon gas and kept in a thermostated oil bath at 60 oC. After desired time, the mixture was cooled to ambient temperature. The homopolymer was precipitated into excess ethanol and purified by reprecipitation, and then it was dried under vacuum at 40 for 24 h. 2.2. Blend Preparation PVC:PIBA blend was prepared by solution tecnique. Equal weight rates of PIBA and PVC were mixed by using magnetic stirring in the THF. The solution was precipitated in to ethanol. First, the precipitate was dried at room temperature, then it was heated for 24 h at 40 C under vacuum to remove residue solvent. 2.3. DSC Measurements DSC studies, which are vital in polymer blends research, were made at the 10 C/min

and the thermal conductivity of the polymers k is obtained from

L L = AR S A R R

k=

(3)

where L is the thickness of polymers and A is the contact area between the sensor materials and the sheet. R is the thermal resistance between the heater and sensor material, Rl the thermal resistance between the heater and sensor material which also includes the resistance to heat flow of sample [12].
Table 1. List of sensor materials and their melting point
Sensor Materials Benzophenone 2,6 Dichloroprydine Fluorene Benzamid Indium Melting Point (C ) 48.0 86.0 112.0 127.0 156.6

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Thermophysical Properties Of Blend Of Poly ( Vinyl Chloride ) With Poly ( Isobornyl Acrylate )

Measurements of the specific heat capacity were made between 25 and 200 C temperature range at the heating rate of 10 C /min. The detail about measurement of the specific heat capacity was given another article [13,14] The bulk density of PVC, PIBA, and their blend were found by Archimedes principle (Table2). Founded thermal conductivity and specific heat capacity data were used to calculate thermal diffusivity by equation (1) .
Table 2. Determined bulk densities of polymers and blend
PVC (g/cm3) 1,089 PIBA (g/cm3) 0,984 Blend (g/cm3) 1.150

2.5. Thermogravimetric Analysis Thermogravimetric analysis were performed by using Perkin Elmer Diamond TG/DTA at the heating rate of 20 C/min from ambient temperature to 500 C in the air atmosphere. 3. Result and Discussions The glass-transition temperatures (Tg) of PIBA, PVC and PIBA-PVC blend were determined as inflexion point from DSC curves (Figure 1). The glass transition temperature of the PIBA and PVC are measured as 113 oC and 83 oC, respectively. That of blend polymer showed two transition at 110 oC and 80 oC, respectively. This means that PIBA and PVC have formed two phase and a immiscibility polymer. Thermal conductivity of polymers and its blend as a function of temperature are show in Figure 2-4. The thermal conductivity of PVC was measured beforehand [11]. The thermal conductivity of PVC at 48 C and 156 C was found to be 0.128 and 0.099 W/mC, respectively. The thermal conductivity of PIBA at 48 C and 156 C, was found to be 0.202 and 0.288 W/mC, respectively. On the contrary PVC, thermal conductivity of PIBA increased with increasing temperature after Tg. In addition, the thermal conductivity value is higher than PVC.

Fig.1. DSC thermograms of PVC, PIBA and PVC:PIBA (50:50 by weight%) heated at 10 C /min to 140 C.

The thermal conductivity of PVC:PIBA (50:50 by weight%) blend at 48 C and 156 C, was found to be 0.253 and 0.155 W/mC, respectively. Generally, when the thermal conductivity curve of blend is examined, it can be seen that the decreasing value with rising temperature until ~130 C shows similarity with PVC. But, at the point of near 50 C thermal conductivity value is the most high with comparing blend components. This is very important to development thermal properties of PVC.

Fig.2. Thermal conductivity of PVC as a function of temperature [11]

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M.Kok, K. Demrell and Y.Aydogdu

Fig.3. Thermal conductivity of PIBA as a function of temperature.

The heat capacity of samples show no peculiarities than other polymers. As other polymers, specific heat capacity increase with rising temperature and it is demonstrated jump at the point of Tg temperature. It should be noted here that the Tg of polymers and its blend can be observed by DSC as a stepped increase in the heat capacity sample during heating. When polymers are heated, absorbed heat is changed because of molecular motion in polymer. Afterwards the visible jumping the Cp value increase with former velocity. Dominant addition which is effect on specific heat capacity of most of solids arise from given energy into lattice vibrations. This is single addition for nonmagnetic insulating materials [16].

Fig.4.Thermal conductivity of PVC:PIBA(50:50) blend as a function of temperature.

Fig.5. Specific heat capacity curve of PVC with rising temperature [11].

The specific heat capacity curves of PVC, PIBA and PVC:PIBA (50:50 by weight) are illustrated Figure 5-7. From room temperature to 200 C, the heat capacities of PVC, PIBA and their blend were found in the range of 0.57-1.75 J/gC, 0,88-1,79 J/gC and 1.44-2.43 J/gC, respectively. The heat capacity (Cp) of PVC has been measured beforehand [11]. If Cp curve of PVC, PIBA and their blend are examined, it can be seen that Cp of blend is difference with its component. Because thermal properties of PVC were wanted to developed at this work. Heat capacity is a measure of the ability of a material to absorb heat from the external surroundings; it represents the amount of energy required to produce a unit temperature rise [15]. Therefore, high Cp value of blend means that the heat absorption of blend is better than PVC and PIBA.

Fig.6. Specific heat capacity curve of PIBA with rising temperature.

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Thermophysical Properties Of Blend Of Poly ( Vinyl Chloride ) With Poly ( Isobornyl Acrylate )

Fig.7. Specific heat capacity curve of PVC:PIBA (50:50 by weight) with rising temperature.

Fig.10. Thermal Diffusivity as a function of temperature: PVC:PIBA (50:50 by weight) blend.

Fig.8. Thermal Diffusivity temperature: PVC [11].

as

function

of

Fig.9. Thermal Diffusivity temperature: PIBA .

as

function

of

Figures 8-10 show the variation of the thermal diffusivity with temperature. Thermal diffusivity of PVC was measured beforehand [11]. This curves show similarity with thermal conductivity curve of PVC, PIBA and PVC:PIBA blend. Thermal diffusivity is a measure of rapidity of the heat propagation through a material and it is an important property in all problems involving non-steady state heat conduction [10]. As shown by Eq. (1), thermal diffusivity is the proportion of the product thermal conductivity times the reciprocal of the specific heat. As the test temperature goes up, the phonon vibration frequency will be quickened to make the collision possibility increase, so the mean free path decrease rapidly, which leads to the rapid decrease of its thermal diffusivity. Because its heat capacity ascends slowly, the thermal conductivity is dominated mainly by the phonon mean free path, and thermal conductivity decrease with increasing temperature [17]. To examine the thermal stability of mentioned above polymers, Thermogravimetric analysis (TGA, Figure 11) data under nitrogen flow were obtained, and the results were summarized in Table 3. The poly(IBA), PVC and blend polymer showed a decomposition curve with a two stages. If initial decomposition temperature has been assumed simply as a measurement of thermal stability, while poly(IBA) decomposes at 255 oC, PVC decomposes at 237 oC. Whereas that of blend polymer is about 245 oC. 50% of weight loss of poly(IBA) gives at 305 oC. The second stage (a

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M.Kok, K. Demrell and Y.Aydogdu

weight loss about 13%) of degradation of PIBA prepared by radicalic polymerization method consisted of slowly decomposition of side group and chain backbone. PVC starts decomposition at 237 oC and 50% of weight loss of poly(IBA) gives at 309 oC. The blend polymer decomposes more rapid according to PIBA and PVC homopolmers with increasing temperature.
Table 3. Degradation characteristics of PVC, PIBA and their blend.
Weight loss (%) at 300 oC PVC 236.73 17.29 PIBA 243.25 10.62 PVC:PIBA(50:50) 236.73 39.56 Polymer IDTa Weight loss (%) at 400 oC 64.74 81.25 69.71 Residue (%) At 500 o C 22.33 12.25 16.83

IDTa : Initial decomposition temperature

Fig.11. The TGA curves for PVC, PIBA and PVC:PIBA (50:50 by weight%) heated in air atmosphere 20 C /min to 500 C.

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