Dynamic glassy state

Luck, W.A.P. 1981. Structures of water in aqueous systems. In Water Activity Influences on Food Quality (L.B. Rockland and G.F. Stewart, eds), pp. 407 134. Academic Press, New York. Ludescher, R.D., Shah, N.K., McCaul, C.P., and Simon, K.V. 2001. Beyond Tg Optical luminescence measurements of molecular mobility in amorphous solid foods. Food Hydro colloids 15, 331-339. Ludwig, R. 2001. Water From cluster to the bulk. Angewandte Chem. Int. Ed. 40, 1808-1827. Maclnnes, W.M. 1993. Dynamic mechanical thermal analysis of sucrose solutions. In The Glassy State in Foods (J.M.V. Blanshard and PJ. Lillford, eds), pp. 223-248. Nottingham Univ. Press, Loughborough, Leicestershire. 

Roos, Y. and Karel, M. 1993. Effects of glass transitions on dynamic phenomena in sugar containing food systems. In Glassy State in Foods (J.M.V. Blanshard and P.J. Lillford, eds), pp. 207-222. Nottingham Univ. Press, Loughborough, UK. 

Concepts for the Dynamics of Viscous Liquids near an Ideal Glassy State. 

At low temperature the material is in the glassy state and only small ampU-tude motions hke vibrations, short range rotations or secondary relaxations are possible. Below the glass transition temperature Tg the secondary /J-re-laxation as observed by dielectric spectroscopy and the methyl group rotations maybe observed. In addition, at high frequencies the vibrational dynamics, in particular the so called Boson peak, characterizes the dynamic behaviour of amorphous polyisoprene. The secondary relaxations cause the first small step in the dynamic modulus of such a polymer system. 

Below Tg, in the glassy state the main dynamic process is the secondary relaxation or the )0-process, also called Johari-Goldstein relaxation [116]. Again, this process has been well known for many years in polymer physics [111], and its features have been estabhshed from studies using relaxation techniques. This relaxation occurs independently of the existence of side groups in the polymer. It has traditionally been attributed to local relaxation of flexible parts (e.g. side groups) and, in main chain polymers, to twisting or crankshaft motion in the main chain [116]. Two well-estabhshed features characterize the secondary relaxation. 

NMR has not been widely employed to study dynamics in block copolymer melts, although field gradient NMR can provide a wealth of information on the diffusion of block copolymer chains (Fleischer et al. 1993). The orientation of a deuterated homopolymer in a lamellar diblock copolymer (in a glassy state) was determined using 2H NMR by Valic et al. (1994,1995). Other applications of NMR to probe polymer chain dynamics and details of experimental protocols are described by Bovey and Jelinksi (1989). 

A review of the thermodynamics of block copolymer melts prior to the discovery of complex phases was presented by Bates and Fredrickson (1990). Ryan and Hamley (1997) have recently reviewed the morphology of block copolymers containing a glassy component, in the melt and glassy states, and a discussion of complex phases is included. Fredrickson and Bates (1996) and Colby (1996) have reviewed the dynamics of block copolymer melts, of which the former is a par-... 

Dynamic Relaxation Behavior of Hydrophilic Poly methacrylates and Polyacrylates in the Glassy State. 136... 

Of the diluents known to affect the dynamic relaxation behavior of polymers in the glassy state, water has so far received the greatest attention. Many polymers, which in the dry state are lacking any secondary relaxation process at temperatures from 77 to 273 K, e.g. poly(methyl methacrylate)135, polymethacrylamide136, cellulose and its derivatives137, collagen138, polysulfones139, poly(2,6-dimethylphenylene oxide)139, and others,... 

In the glassy state, these Ar-Al-PA exhibit local chain dynamics which are largely controlled by the chemical structure. Recently, the local motions that may occur in the glassy state and might take part in secondary transitions, have been investigated on a series of Ar-Al-PA of various chemical structures by using dielectric relaxation, 13C and 2H solid-state NMR and dynamic mechanical experiments [57-60]. 

Once the molecular motions occurring in the glassy state have been characterised and assigned through dielectric relaxation, 13C and 2H NMR, it is interesting to investigate their effect on the dynamic mechanical response of Ar-Al-PA [60,61],... 

To illustrate the transitions occurring in the glassy state, the temperature dependencies of the dynamic mechanical loss tangent at 1 Hz of the DGEBA/HMDA, DGEBA/tetramethylene diamine and DEBA/dodecamethyl-ene diamine systems [65] are shown in Fig. 93. They clearly exhibit two transitions ... 

Dynamic mechanical analysis and the 13C NMR experiments performed on pure aryl-aliphatic epoxy networks, as well as on antiplasticised systems, have led to a deeper insight into the molecular motions involved in the glassy state of these epoxy resins. 

The only approach presently available for getting this information deals with the atomistic modelling of the dynamics of ester groups in a glassy state cell of PMMA. Such a study has been recently performed [78]. 

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