Pregelation

The gelling temperature is an important factor for the characterization and application of pectins. The pectin consumer wants a pectin fulfilling his special requirements, this can mean either working with or without pregelation. Pregelation, the weakening of gel structure, occurs when pectin preparations are stressed below their gelation temperature so that the mechanical treatment leads to an irreversible destruction of the three-dimensional network. 

Fig. 38. A Degradation experiments with pregel polymers isolated prior to the onset of macrogelation in 1,4-DVB polymerization [209] Variation of Mw ( ) and dz (O) with the time of ultrasonic degradation. The polymer sample was prepared at 5 g/100 mL monomer concentration and its initial Mw was 2.2 X106 g/mol. The dotted horizontal line shows Mw of zero conversion polymers ( individual microgels ). B Variation of Mw with the polymerization time t and monomer conversion x in 1,4-DVB polymerization at 5 g/100 mL monomer concentration. The region 1 in the box represents the limiting Mw reached by degradation experiments. [Reprinted with permission from Ref. 209,Copyright 1995, American Chemical Society].

PAD ELECTRODE DEFIBRILLATOR 6X4.50" PREGELLED SELF-ADH DISP 200S 6515013838387 PG 40110 ... 

The linear relationship between H NMR transverse relaxation rate and (1 av) is shown in Figure 30 for pregelled potato starch (Hills et al., 1999). The change in slope at about 0.90 c/w corresponds to the bulk water break (i.e., the removal of bulk water) in a corresponding adsorption isotherm. Equation... 

The degree of polymerization of hard clusters increases with evolution of the system as a whole. The hard clusters already exist in pregel molecules. Before the macroscopic gel point of the system is reached they remain usually small. Later on, the hard clusters grow faster and eventually a gel point (percolation threshold) of the hard structure is reached. Below this point, clusters are embedded in the soft matrix beyond the percolation threshold, the hard and soft structures interpenetrate (Figure 5.7). Below the percolation threshold, hard clusters are essentially dendritic when the percolation threshold is surpassed, circuits (cycles) develop within the hard structure. 

Fig. 22. KMHS relationships for the fractions of end-linked 3-arm star-branched polystyrene molecules and of linear polystyrene fractions. The data refer to three samples of different in the pregel state and one from the sol fraction of a gel. The curves for the branched macromolecules coincide within experimental error in the high molar mass region. The deviations at lowM result from a different amount of non-reacted end-functionalized stars. The exponents of the end-linked and linear PS chains are a =0.42 0.02 while that of linear chains is 0.70 0.01 [95,120,123,124]. Reprinted with permission from [95]. Copyright [1997] American Society...

Fig. 26. Molar mass dependence of the g factor for three pregel and one postgel fraction of end linked PS stars. A good fit was obtained with the Zimm Stockmayer equation (Eq. 69) and an exponent in Eq. (70) of fi 0.63 [95] which agrees well with Kurata s estimation with b-0.6 [129]. Reprinted with permission from [129]. Copyright [1972] American Society...

In the same manner, with decreasing of diffusion coefficient and interaction parameter, the spinodal is reached during the evolution of the system in the pregel stage. The very low values of interfacial tension in rubber modified epoxies (interfacial tension of polymer-polymer-solvent system were reported in range of 10-4-10-1 mN/m) therefore lead to an NG mechanism for phase separation. 

It has also been found that polymers possessing functional groups such as amines and pyridines are soluble in pregelled sol solutions, especially, poly (2-vinjipyridine) and poly(A/-vinylpyrrolidinone) (PVP) (49). There, materials were made as part of a study of the synthesis of nonshrinking sol—gel-derived networks (49). 

Fig. 6. Linear swelling ratio measured for neutral NIPA gels prepared from the same pregel solution with different accelerators. S1-S3 Three different samples prepared with SB as an accelerator. 77-73 Three different samples prepared with TEMJ3D as an accelerator...

Another unique feature of ionized NIPA gel has been found recently both of the equilibrium swelling ratio a and the first-order transition temperature T0 depend strongly on the shape of samples [31]. The measurement of equilibrium a has been made on ionized NIPA gel rods of various diameters, and also on plates and cubes. The gel contained 680 mM NIPA, 20 mM acrylic acid (AA), and 8.6 mM BIS. All samples were prepared from the same pregel solution at the same time so as to guarantee that the composition and the structure of all samples were the same. 

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