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Physical Phenomena Related to Free Volumes in Rubber and Blends

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Advances in Elastomers II

Part of the book series: Advanced Structured Materials ((STRUCTMAT,volume 12))

Abstract

In the present chapter, different aspects related to free volumes and the physical phenomena involving free volumes in rubbers and blends are discussed. Experimental results were obtained using conventional experimental techniques (e.g. dynamic mechanical tests, differential scanning calorymetry and swelling) and principally a non-conventional one (positron annihilation lifetime spectroscopy—PALS). PALS has demonstrated a high capability to give direct information on free volumes. Due to its significant role in the study of nanoscopic effects in molecular systems (among them polymers), the physical grounds of the technique are explained. It is also illustrated how PALS detects free nanohole volumes and gives information on their changes as a consequence of different reactions induced in polymers. Based on the latest experience of the authors, some examples of PALS studies on NR and SBR rubbers and NR/SBR blends are presented. The results obtained are discussed using a modern scientific approach to the study of physicals processes in these elastomers; i.e. the analysis of the experimental information is given into the frame of well recognized theoretical models.

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Notes

  1. 1.

    Actually, from the analysis of PALS spectra a continuous distribution of the o-Ps lifetimes, and therefore of hole radii, is obtained. So, according to Ref. [23] from an estimation of the distribution of the inverse lifetime ξ(1/τ o-Ps ) the hole radius probability density fraction \( {f}(R) \) can be obtained as follows

    $$ f(R) = 2\delta R\left( {\cos \frac{2\pi R}{R + \delta R} - 1} \right)\frac{{\xi ({1 \mathord{\left/ {\vphantom {1 {\tau_{\sigma - Ps} )}}} \right. \kern-0pt} {\tau_{\sigma - Ps} )}}}}{{\left( {R + \delta R} \right)^{2} }} $$
    (3)

    Then, it is easy to obtain the hole volume density distribution as \( g(v_{h} ) = {{f(R)} \mathord{\left/ {\vphantom {{f(R)} {4\pi R^{2} }}} \right. \kern-0pt} {4\pi R^{2} }} \) which represents the volume fraction of holes as determined by o-Ps annihilation with volumes between v h and v h  + dv h is g(v h ) dv h [17, 24]. Then, from g(v h ) can be calculated the number fraction of holes.

    In Ref. [25] we studied the evolution of the free volume during vulcanization in SBR. In this work, for each sample instead of analyzing the o-Ps lifetimes as discrete ones we assumed the corresponding τo-Ps as continuum distributions and then, using Eq. (3) we obtained the different g(v h ). Then, we found that all g(v h ) consisted of one skewed peak and extended from about 20  to 450 Å3 approximately. Results are discussed in Sect. 4. Another example can be found in Ref. [19] in which the authors correlated the size, numerical concentration, and size distribution of free volumes with the nanostructure of different degree of crosslinkage cured polysiloxanes induced by thermal treatments. On the other hand, Dlubek et al. [17] estimated the free nanohole volume distribution in polycarbonate and polystyrene a room temperature.

    However, it is worth mentioning that for the analysis of the o-Ps lifetime component is normally accepted as a good approximation the use of the most probable free volume size as a representative parameter of g(v h ).

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Acknowledgments

This work was supported by Agencia Nacional de Promoción Científica y Tecnológica (PICT 2011-1088), Comisión de Investigaciones Científicas de la Provincia de Buenos Aires, SECAT (UNCentro) and University of Buenos Aires (Project UBACYT 2010–2012), Argentina.

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Authors and Affiliations

  1. LP&MC, Facultad de Ciencias Exactas y Naturales, Departamento de Física, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón I, C1428EGA, Buenos Aires, Argentina

    A. J. Marzocca

  2. IFIMAT, Universidad Nacional del Centro de la Provincia de Buenos Aires, Pinto 399, B7000GHG, Tandil, Argentina

    W. Salgueiro & A. Somoza

  3. Comisión de Investigaciones Científicas de la Provincia de Buenos Aires, Buenos Aires, Argentina

    W. Salgueiro & A. Somoza

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  1. A. J. Marzocca
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  2. W. Salgueiro
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Correspondence to A. J. Marzocca .

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Editors and Affiliations

  1. , Centre for Nanoscience and Nanotech., Mahatma Gandhi University, Priyadarshini Hills P. O., Kottayam, Kerlala, 686 560, India

    P. M. Visakh

  2. , Nanoscience and Nanotechnology, Mahatma Gandhi University, Priyadarshini Hills P. O., Kottayam, Kerala, 686 560, India

    Sabu Thomas

  3. Apollo Tyres Ltd., Gujarat, India

    Arup K. Chandra

  4. , Dept. Applied Physics and Mech. Eng., Lulea University of Technology, Lulea, 97187, Sweden

    Aji. P. Mathew

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Marzocca, A.J., Salgueiro, W., Somoza, A. (2013). Physical Phenomena Related to Free Volumes in Rubber and Blends. In: Visakh, P., Thomas, S., Chandra, A., Mathew, A. (eds) Advances in Elastomers II. Advanced Structured Materials, vol 12. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-20928-4_10

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