Dielectric relaxations in amorphous polymers with complex chain architectures
By combining thermostimulated current and dynamic dielectric spectroscopies, the dielectric properties characteristic of the molecular mobility can be described over a very broad frequency range. The study of dielectric relaxations of phosphorus-containing dendrimers in the sub-glass transition region, and of poly(n-alkyl methacrylates) at and above the glass transition region allows us to gain insight into the molecular dynamics of complex architecture systems. From these sets of data we make an attempt to propose a structural interpretation of molecular mobility through the glass transition.
Dielectric study of the molecular mobility and the isothermal crystallization kinetics of an amorphous pharmaceutical drug substance.
During the development of new pharmaceutical products based on drug substances in their amorphous form, the molecular mobility of an amorphous active ingredient was characterized in detail within a very broad time-temperature range. The relation between the isothermal crystallization kinetics and the dynamics of this amorphous substance was investigated. First, dynamic dielectric spectroscopy (DDS) and the thermostimulated current (TSC) techniques were used to analyze the molecular mobility of the amorphous drug substance over a wide frequency and temperature range (the drug substance is referred to as SSR in this text and was chosen as a model glass-forming system). Two relaxation processes, corresponding to different molecular motions, were identified. The beta(a)-relaxation process, associated with intramolecular oscillation of small dipolar groups, followed Arrhenius temperature behavior over the entire time-temperature domain that was studied. However, the main alpha(a)-relaxation process, assigned to the dielectric manifestation of the dynamic glass transition of the amorphous phase, was described by Vogel-Fulcher-Tammann (VFT) and Arrhenius behavior above and below the glass transition temperature (T(g)) respectively. The physical meaning of these complex dynamics is explained in the context of the Adam and Gibbs (AG) model, by the temperature dependence of the size of cooperatively rearranging regions (CRR) that govern the time scale of delocalized molecular motions. The distinction between the molecular mobility and the structural relaxation of amorphous systems below T(g) is discussed. This work shows that the complementary nature of both DDS and TSC techniques is essential to directly analyze the intramolecular and molecular motions of disordered phases over a wide time-temperature range above and below the T(g). Second, real-time dielectric measurements were carried out to determine the isothermal crystallization kinetics of the SSR amorphous drug. Whatever the crystalline form obtained over time in the crystallization process, the decrease of the dielectric response of amorphous phase, which is characteristic of the isothermal crystallization, was studied to monitor the time dependence of the degree of crystallinity. The characteristic crystallization time, derived from Kohlrausch-Williams-Watt (KWW)-Avrami analyses performed at different temperatures, followed an Arrhenius temperature dependence. Behaviors specific to the molecular mobility of the amorphous drug substance were compared with the characteristic crystallization time. It was concluded that the crystal growth process of the SSR drug seems to be controlled by the intramolecular motions involving the beta(a)-relaxation mode and not by the molecular motions responsible for the alpha(a)-relaxation mode in the range of temperatures >T(g). Subsequent studies will focus on the crystallization process of the SSR drug in the glassy state (T < T(g)).
Hygroscopic Expansion of some Casting Investments
CREDIT is generally given to Taggart1 for introducing the cast gold inlay to the dental profession. Although he realized that gold shrinks when cooled from molten state to solid state of room temperature, the investment available to him did not supply sufficient compensation. In 1910, Van Horn2 published a paper dealing with a method by which he obtained the compensation by means of wax expansion. The next major research in connection with this problem was the work of Coleman3 at the National Bureau of Standards. He determined the gold shrinkage to be 1.25 per cent and presented a casting technic with compensation values of quantitative nature. The total compensation for the gold shrinkage was obtained by the combination of the setting and thermal expansion of the mold. This procedure is the general practice followed at the present time for compensation. There are some disadvantages to this method. Skinner has indicated the difficulty of obtaining smooth castings and the improper compensation for the casting shrinkage.4 It has been found by Hollenback5 and Scheu6a that castings made at a high temperature are rougher than those made at a low temperature (450° C.), depending upon the great difference in thermal expansion between plaster of Paris and silica, which causes a poor union of the fine particles. This may also result in friability and there may be some warpage due to the differential expansion. A method which provides sufficient compensation at a low mold temperature is the hygroscopic casting technic.b Wilson7 showed that certain plasters expand as much as 0.0044 inch to the inch by taking up moisture from the air. With this information at hand, Scheula, b tested some commercial investment to determine what results the addition of moisture would have. He found6b: (1) All of the casting investments that were tested expanded. (2) The thicker the mix, the greater the expansion. (3) A mix with hot water expanded more than one with cold water. (4) The time at which the mix is placed in the water is of great importance. It was found that if the mix is placed in the water early, it would not expand so much as when placed in a little later. It was also found that if the mix was placed in the water after a certain time, it could not expand to the maximal amount. (5) The temperature of the water in which the mix is placed is important, for two reasons; (a) the temperature of the water controls slightly the expansion of the investment, and (b) water at a temperature of 1000 F. slightly softens the wax pattern so that the fine margins are not marred while expansion is taking place. The mix should remain in the water at least 20 minutes to obtain the full expansion, after which time no further expansion is obtained.