Deuterated polymer chains

To obtain Rg and the correlation lengdi ( ) of the concentration fluctuations we make use of die SANS high concentration isotope labeling method [12-14], which allows the determination of bodi parameters for semidilute polymer solutions. The coherent scattering cross section (dSd 2 in units of cm ) of an inctxnpressible mixture of identical protonated and deuterated polymer chains dissolved in a solvent is given by [4,5,14] ... 

The main experimental techniques used to study the failure processes at the scale of a chain have involved the use of deuterated polymers, particularly copolymers, at the interface and the measurement of the amounts of the deuterated copolymers at each of the fracture surfaces. The presence and quantity of the deuterated copolymer has typically been measured using forward recoil ion scattering (FRES) or secondary ion mass spectroscopy (SIMS). The technique was originally used in a study of the effects of placing polystyrene-polymethyl methacrylate (PS-PMMA) block copolymers of total molecular weight of 200,000 Da at an interface between polyphenylene ether (PPE or PPO) and PMMA copolymers [1]. The PS block is miscible in the PPE. The use of copolymers where just the PS block was deuterated and copolymers where just the PMMA block was deuterated showed that, when the interface was fractured, the copolymer molecules all broke close to their junction points The basic idea of this technique is shown in Fig, I. 

Significant experimental support for these relations and the minor chain repta-tion model has been obtained from neutron reflection and SIMS experiments using specially deuterated polymers... 

We present here a simple experiment, conceived to test both the reptation model and the minor chain model, by Welp et al. [50] and Agrawal et al. [51-53]. Consider the HDH/DHD interface formed with two layers of polystyrene with chain architectures shown in Fig. 5. In one of the layers, the central 50% of the chain is deuterated. This constitutes a triblock copolymer of labeled and normal polystyrene, which is, denoted HDH. In the second layer, the labeling has been reversed so that the two end fractions of the chain are deuterated, denoted by DHD. At temperatures above the glass transition temperature of the polystyrene ( 100°C), the polymer chains begin to interdiffuse across the... 

We consider an incompressible (m-l-1) multicomponent mixture of polymers consisting of m different types of polymer chains within a matrix referred to as 0 . Components may be either homopolymers of a given chemical species or, e.g. homopolymer sections in block copolymers. Hydrogenated and deuterated species of the same homopolymer are considered as different components. In this context a diblock copolymer is a two-component polymer system. A mixture of partially protonated diblock chains hA-dB with deuterated diblock chains is consequently regarded as a four-component system. 

Zhao and Brittain [280-282] reported the LCSIP of styrene on planar silicon wafers using surface modifications of 2-(4-(ll-triethoxysilylundecyl)phenyl-2-methoxy-propane or 2-(4-trichlorosilylphenyl)-2-methoxy-d3-propane respectively. Growth of PS brushes from these SAMs has been successfully achieved factors that influence PS thickness included solvent polarity, additives and TiC concentration. Sequential polymerization by monomer addition to the same silicate substrate bearing the Hving polymer chains resulted in thicker PS films. FTIR-ATR studies using a deuterated initiator indicated that the initiator efficiency is low, and the... 

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). 

In the polymerization of allyl acetate, transfer to monomer produces an unreactive radical which fails to re-initiate growth of the polymer chain. Bartlett and Tate (31) compared the rates of polymerization for the unlabelled monomer and.the deuterated monomer CH2 CH-CD2 0-CO CH3. The deuterated monomer polymerized more rapidly giving a product of higher molecular weight. These observations suggest that the rate of polymerization and the molecular weight of the polymer are controlled by the reaction... 

While it cannot be said that all of the assignments in the spectrum of PVdC are satisfactorily established, it would seem that the majority are. The important ones from the standpoint of the chain structure are the v (CC12) modes, and the present evidence on their assignment supports the correctness of the Fuller structure. A study of a partially deuterated polymer might be of further assistance in this respect. What is also clearly needed is a more detailed study of the skeletal modes to be expected from the proposed chain structure, since these clearly contribute significantly to the spectrum. Finally, knowledge of the crystal structure might permit more to be said on the nature of interchain interactions and their effect on the spectrum. 

By using a selective deuteration, 2H NMR allows investigation of motions of specific groups within a polymer chain. 

In all the five methods, complete dissociation of the polymer chains was expected and therefore complete deuteriation except for the hydroxyl groups buried in the central core of the triple-stranded molecule. Complete dissociation was not obtained even when using increasingly severe deuteration techniques. 

The Doi-Edwards, reptation based model makes specific predictions for the relaxation dynamics of different portions of a polymer chain. Specifically, the relaxation of the chain ends is predicted to be substantially faster than the relaxation of the center. This is a result of the reptation dynamics, which have the ends first leaving the confines of the tube. Using polymer chains that were selectively deuterated either at the ends or at the middle, Ylitalo and coworkers [135] examined this problem and found that the Doi-Edwards model was able to successfully predict the observed behavior once the effects of orientational coupling was included. The same group further explored the phenomena of orientational coupling in papers that focused on its molecular weight [136] and temperature [137]... 

The necessity to label (deuterate) the systems under study may appear as a practical drawback. It often prevents working with real (industrially designed) materials. A way to circumvent this problem is to use labelled molecules as 2H NMR probes whose behaviour reflects that of the rubber matrix. These molecules may be solvent molecules or even polymer chains chemically identical to the rubber matrix itself. This approach is described in Section 15.4 and is illustrated by a few examples. 

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