The areas under the linear loss modulus versus temperature curves (loss area, LA) and tan δ versus temperature curves (TA) were evaluated for a number of acrylic, methacrylic, styrenic and butadiene based copolymers and interpenetrating polymer networks, IPNs, as a function of crosslink density and comliosition, and were compared with values predicted by group contribution analysis. The LAs of the sequential IPNs, cross‐poly(n‐butyl methacrylate)‐inter‐crosspolystyrene, were found to exhibit up to 30% larger LAs than the poly(n‐butyl metacrylate‐stat‐styrene) copolymers, which had LAs slightly less than the values predicted from the group contribution analysis. At constant chemical composition (50% n‐butyl methacrylate, 50% styrene), LA equals 14.4 GPa K for the IPN, attributed to a synergistic effect resulting from the IPN's microheterogeneous morphology, as compared with 10.7 GPa K for the single phase, miscible copolymer. Increases in the LA with increased concentration of polymer, network II were also observed for cross‐poly(ethyl acrylate)‐inter‐crosspolystyrene and cross‐polybutadiene‐inter‐cross‐polystyrene IPNs. On the other hand, cross‐polybutadiene‐inter‐cross‐poly(methyl methacrylate) IPNs had LAs much lower than were predicted by the group contribution analysis, which were attributed to lower miscibility in this system relative to the other systems evaluated. In general, decreased crosslink densities and lower concentrations of network II increased TA. These findings demonstrate how the morphology of a multiphase polymeric material can affect LA and TA, with significant increases In damping capability over the average of the component polymer values.

The shape of the glass transition plays a critical role in the engineering performance of polymers in sound and vibration damping, as well as other applications. The transition may be affected by fillers, plasticizers, blending, IPN formation, etc. A collection of data, both original and literature, is presented which illustrates how the phenomenon works. Emphasis is placed on the role of the area under the linear loss modulus-temperature curve, which may be evaluated in a fashion similar to other spectroscopic techniques. In addition, the loss area can be significantly affected by morphological factors.

SYNOPSISThe area under the linear loss modulus-temperature curves, LA, has been shown to be related to the chemical composition of the material. In addition, it can be significantly affected by morphology in multicomponent polymer systems. To characterize LA quantitatively, base-line corrections for instrumental contributions to LA were evaluated by several different methods and the results compared. In some instances, the calculation method affects only the LA magnitude, while general trends are unchanged whereas in others, qualitative differences also become important. Not all of the methods described can be utilized universally. However, a straight-line-type of base line, similar to that which is used in infrared spectroscopy and differential scanning calorimetry, provides a widely applicable means of quantifying the loss area.

SynopsisThe homopolymers, poly(3,3-bisethoxymethyl oxetane) (polyBEMO), poly(3,3-bisazidomethyl oxetane) (polyBAMO), and triblock copolymers based on these homopolymers and a statistical copolymer center block composed of BAMO and 3-azidomethyl-3-methyl oxetane AMMO were synthesized and characterized by differential scanning calorimetry, modulus-temperature, optical microscopy, membrane osmometry, and solution and melt viscosity. The values of K and a for the Mark-Houwink equation were found to be 7.29 x mL/g and 0.80, respectively, for polyBEMO at 25°C Using number-average molecular weights. Glass transition temperatures were in the range -25 to -40°C and melting temperatures were between 65 and 90°C for all polymers. The melting temperature was found to increase as expected with molecular weight. Melt viscosities of triblock copolymers with polyBAMO end blocks were at least an order of magnitude lower than those with polyBEM0 end blocks and clear optically, suggesting that the polyBAM0-based triblock copolymers formed one phase in the melt, while the polyBEMO-based triblock materials (milk white) phase separated. The addition of filler raised the melt viscosity to a level between that predicted by the Guth-Smallwood and the Mooney equations.

Interpenetrating polymer networks are combinations of two crosslinked polymers. Often, they exhibit dual phase continuity, meaning that both phases extend continuously throughout the sample. Recent research on IPNs has shown that both nucleation and spinodal decomposition mechanisms are important in the kinetics of phase separation.If the polymers are almost miscible, a microheterogeneous morphology will develop. Under these conditions, the glass transition of the IPN may be very broad, extending the range between the glass transition of the two homopolymers. Such materials are useful for sound and vibration damping. The loss and storage modulus, and tan δ behavior of polymers and IPNs in the glass transition region were evaluated on a quantitative basis, in order to characterize their damping behavior better. Corrections for background in dynamic mechanical spectroscopy studies will be discussed. The storage modulus of polystyrene at 25°C was selected as a standard. The development of a group contribution analysis of the integral area under the linear loss modulus‐temperature curves, the loss area, LA, is reviewed, and applied to a number of acrylic, styrenic, and vinyl statistical copolymers and IPNs. Each moiety in a polymer is shown to contribute to LA on a simple, additive basis.New research emphasizes the role of morphology and phase continuity in determining LA. The system cross‐poly(vinyl methyl ether)‐inter‐cross‐polystyrene was selected, because its phase diagram in the blend state is well known, and it has become both a model and interesting system to investigate. Midrange IPN compositions exist as two phases at room temperature, as illustrated by dynamic mechanical spectroscopy.