Intrinsic swelling

Water uptake capacity (swelling in bulk) and particle swelling (intrinsic swelling) may be considered the physical properties of tablet disintegrants that are more commmonly related to disintegrant efficiency... 

The methods for the evaluation of intrinsic swelling, i.e. individual particle volume increase, are mostly based on the microscopic observation of particles. This presents the obvious advantage of allowing the direct measurement of the increase in disintegrant particle dimensions due to water absorption lO-H. 

However, none of the proposed mechanisms satisfactorily explain all experimental findings ([48] and references therein). For instance, it was experimentally observed that some bcc alloys, such as the V-5Fe alloy, exhibit swelling rates which can be as high as 2%/dpa [53], which is not consistent with the hypothesis of an intrinsic swelling resistance of the bcc crystal structure. 

SAN resins show considerable resistance to solvents and are insoluble in carbon tetrachloride, ethyl alcohol, gasoline, and hydrocarbon solvents. They are swelled by solvents such as ben2ene, ether, and toluene. Polar solvents such as acetone, chloroform, dioxane, methyl ethyl ketone, and pyridine will dissolve SAN (14). The interactions of various solvents and SAN copolymers containing up to 52% acrylonitrile have been studied along with their thermodynamic parameters, ie, the second virial coefficient, free-energy parameter, expansion factor, and intrinsic viscosity (15). 

The solubiHty parameter of a polymer is a measure of its iatermolecular forces, and provides an estimate of the compatibiHty of a polymer with another polymer or a polymer with a solvent. Two components are compatible if they have similar solubiHty parameters. The solubiHty parameter can be determined by various methods, such as intrinsic viscosity and swelling measurements. The solubiHty parameters of various polymers and solvents are tabulated ia refereace handbooks (146,147). It also can be estimated from the stmcture of the polymer (148). 

In the studies by Skipper et al. the number of water layers (and thus molecules) was fixed on the basis of experimental evidence consequently, the stable states or degrees of swelhng were presumed. Quite differently, Karaborni et al. [44] determined, by means of a combination of GCMC and MD, the number of water molecules directly from a series of simulations in which the distance between montmorillonite planes was varied systematically. They observed that swelling proceeded from the dry state through the formation of one, three, and then five layers of water. This is very different from the usually beheved hydration sequence from one layer to two, then to three layers, and so on, which has been intrinsically assumed by Skipper and coworkers. The authors conclude that the complex swelling behavior accounts for many of the experimental facts. This work demonstrates impressively the power of the grand canonical simulation method. 

The influence of temperature on the copolymerization was investigated at constant absorbed dose of 0.12 and 0.16 KGy for copolymerization of AM-AANa [17,54] and AM-DAEA-HCl [22], respectively. The results are shown in Figs. 9 and 10, which show that the Rp values increase while the intrinsic viscosity and the degree of polymerization decrease with increasing the polymerization temperature. However, the increase in the temperature of the polymerization medium increases the swell-... 

In the present chapter we shall be concerned with quantitative treatment of the swelling action of the solvent on the polymer molecule in infinitely dilute solution, and in particular with the factor a by which the linear dimensions of the molecule are altered as a consequence thereof. The frictional characteristics of polymer molecules in dilute solution, as manifested in solution viscosities, sedimentation velocities, and diffusion rates, depend directly on the size of the molecular domain. Hence these properties are intimately related to the molecular configuration, including the factor a. It is for this reason that treatment of intramolecular thermodynamic interaction has been reserved for the present chapter, where it may be presented in conjunction with the discussion of intrinsic viscosity and related subjects. 

Materials Melt Index Die Swell, % Density, qm/cc Intrinsic Viscosity Haze, % Gloss Tear Strength, ms An 4.52 Anmr 4.5 5.05... 

For macroreticular CFPs, the accessibility of reagents and removal of the products is guaranteed by the intrinsic micrometer- and nanometer-scale morphology of the support. For gel-type CFPs, the same positive features are enabled by the proper choice of cross-linking degree and swelling medium. 

Polymer gels and ionomers. Another class of polymer electrolytes are those in which the ion transport is conditioned by the presence of a low-molecular-weight solvent in the polymer. The most simple case is the so-called gel polymer electrolyte, in which the intrinsically insulating polymer (agar, poly(vinylchloride), poly(vinylidene fluoride), etc.) is swollen with an aqueous or aprotic liquid electrolyte solution. The polymer host acts here only as a passive support of the liquid electrolyte solution, i.e. ions are transported essentially in a liquid medium. Swelling of the polymer by the solvent is described by the volume fraction of the pure polymer in the gel (Fp). The diffusion coefficient of ions in the gel (Dp) is related to that in the pure solvent (D0) according to the equation ... 

Note 2 For a polymer, the value of the solubility parameter is usually taken to be the value of the solubility parameter of the solvent producing the solution with maximum intrinsic viscosity or maximum swelling of a network of the polymer. 

Intraparticle diffusion limits rates in triphase catalysis whenever the reaction is fast enough to prevent attaiment of an equilibrium distribution of reactant throughout the gel catalyst. Numerous experimental parameters affect intraparticle diffusion. If mass transfer is not rate-limiting, particle size effects on observed rates can be attributed entirely to intraparticle diffusion. Polymer % cross-linking (% CL), % ring substitution (% RS), swelling solvent, and the size of reactant molecule all can affect both intrinsic reactivity and intraparticle diffusion. Typical particle size effects on the... 

Variation in % CL of the catalyst support most likely affects intraparticle diffusion more than it affects intrinsic reactivity. Increased cross-linking causes decreased swelling of the polymer by good solvents. Thus the overall contents of the gel become more polystyrene-like and less solvent-like as the % CL is increased. Fig. 5 shows the... 

Substantial variations of the organic solvent used in triphase catalysis with polystyrene-bound onium ions have been reported only for the reactions of 1-bromo-octane with iodide ion (Eq. (4))74) and with cyanide ion (Eq. (3)) 73). In both cases observed rate constants increased with increasing solvent polarity from decane to toluene to o-dichlorobenzene or chlorobenzene. Since the swelling of the catalysts increased in the same order, and the experiments were performed under conditions of partial intraparticle diffusional control, it is not possible to determine how the solvents affected intrinsic reactivity. 

The activity of polymer-supported crown ethers depends on solvent. As shown in Fig. 11, rates for Br-I exchange reactions with catalysts 34 and 41 increased with a change in solvent from toluene to chlorobenzene. Since the reaction with catalyst 34 is limited substantially by intrinsic reactivity (Fig. 10), the rate increase must be due to an increase in intrinsic reactivity. The reaction with catalyst 41 is limited by both intrinsic reactivity and intraparticle diffusion (Fig. 10), and the rate increase from toluene to chlorobenzene corresponds with increases in both parameters. Solvent effects on rates with polymer-supported phase transfer catalysts differ from those with soluble phase transfer catalysts60. With the soluble catalysts rates increase (for a limited number of reactions) with decreased polarity of solvent60), while with the polymeric catalysts rates increase with increased polarity of solvent74). Solvents swell polymer-supported catalysts and influence the microenvironment of active sites as well as intraparticle diffusion. The microenvironment, especially hydration... 

Host Lattices More Strongly Bonded in Two Dimensions Than in the Third. Host lattices in this group are numerous and varied in chemical nature. They may be placed in two subdivisions those layer structures which possess intrinsic porosity and those which must swell during uptake of guest molecules to accommodate them (Table IV). The list of guest molecules in Table IV is illustrative only guest molecules not referred to may be intercalated in various instances. 

It has to be emphasized that x2 is an intrinsic parameter of the network. Its value should be the same in the unswollen state and in the presence of any swelling solvent. 

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