Expandable monomer Expansion

An interesting possibility is the formulation of a material with zero coefficient of thermal expansion by adding just enough expanding monomer to counteract the normal shrinkage of the resin. 

The electrostatic, induction, and dispersion terms can be expanded in a convergent series closely related to the multipole expansion, but fully accounting for the charge-overlap effects, the so-called bipolar expansion introduced by Buehler and Hirschfelder199,200. In the local coordinate systems with the origins located at the centers of masses of the monomers A and B, separated by the distance R, and with their x and y axes parallel and aligned along the z axes, the distance between two particles in space can be expressed as follows,... 

A general approach to the intramonomer correlation problem is known as the many-electron (or many-body) SAPT method88,141 213-215. In this method the zeroth-order Hamiltonian H0 is decomposed as H0 = F + W, where F = FA + FB is the sum of the Fock operators, FA and FB, of monomer A and B, respectively, and W is the intramonomer correlation operator. The correlation operator can be written as W = WA + WB, where Wx = Hx — Fx, X = A or B. The total Hamiltonian can be now be represented as H = F + V + W. This partitioning of H defines a double perturbation expansion of the wave function and interaction energy. In the SRS theory the wave function is obtained by expanding the parametrized Schrodinger equation as a power series in and A,... 

The Polymer. Amorphous Polystyrene. All of the expandable polystyrene referred to above is the amorphous type that is obtained by free radical initiation. This polymer is completely noncrystalline, and in the absence of impurities such as monomer and blowing agent it exhibits a glass-transition temperature of about 100°C. Both the rate of expansion and the extent of expansion are enhanced by reducing molecular weight, but the foam becomes less resistant to collapse on further steaming (63). Other polymeric modifications are discussed below. 

Bigger clusters have been formed, for instance, by the expansion of laser evaporated material in a gas still under vacuum. For metal-carbon cluster systems (including M C + of Ti, Zr and V), their formation and the origin of delayed atomic ions were studied in a laser vaporization source coupled to a time-of-flight mass spectrometer. The mass spectrum of metal-carbon cluster ions (TiC2 and Zr C j+ cluster ions) obtained by using a titanium-zirconium (50 50) mixed alloy rod produced in a laser vaporization source (Nd YAG, X = 532 nm) and subsequently ionized by a XeCl excimer laser (308 nm) is shown in Figure 9.61. For cluster formation, methane ( 15% seeded in helium) is pulsed over the rod and the produced clusters are supersonically expanded in the vacuum. The mass spectrum shows the production of many zirconium-carbon clusters. Under these conditions only the titanium monomer, titanium dioxide and titanium dicarbide ions are formed. 

If the monomer is a good solvent for the polymer, the latex particles might be assumed to expand indefinitely beeause of inhibition of monomer. An equilibrium monomer concentration and swelling equilibrium is reached, however, because the free energy decrease due to mixing of polymer and monomer is eventually balanced by the increase in surface free energy which accompanies expansion of the particle volume. 

Stable aqueous emulsions of poly(2-ethylhexyl acrylate) (PEHA) were also produced by RESAS from CO2 (68). In this case, a polymer suspension in CO2 was expanded instead of a dissolved solute. A C02-philic surfactant, Monasil PCA (PDMS-g-pyrrolidonecarboxylic acid), was utilized in dispersion polymerization to form a stable polymer suspension at 65°C and 345 bar. A hydrophilic surfactant, (e.g., SAM 185, Pluronic L61, or Pluronic L62), that is soluble in CO2 and CO2/2-EHA monomer mixtures as well as water was added to CO2 to stabilize the suspension after it had been rapidly expanded through a capillary into aqueous solution. The resulting aqueous emulsion with up to 15.6 wt % polymer content was stable for weeks with an average particle size of 2 to 3 pm. Another approach is to introduce the hydrophilic surfactant in the aqueous phase in addition to the surfactant in the CO2 phase. This approach is more general, since many hydrophilic surfactants are not soluble in CO2. During expansion of the suspension into an aqueous solution, the hydrophilic surfactant—for example, triblock Pluronic copolymers—dilfuses to the particle surface to provide stabilization. The resulting aqueous latexes were stable for 100 days for a polymer content reaching 12.7 wt %. 

In practical applications of the sapt approach to interactions of many-elect ron systems, one has to use the many-body version of sapt, which includes order-by-order the intramonomer correlation effects. The many-body SAPT is based on the partitioning of the total Hamiltonian as H = F+V+W, where the zeroth-order operator F = Fa + Fb is the sum of the Fock operators for the monomers A and B. The intermolecular interaction operator V = H — Ha — Hb is the difference between the Hamiltonians of interacting and noninteracting systems, and the intramonomer correlation operator W = Wa + Wb is the sum of the Moller-Plesset fluctuation potentials of the monomers Wx — Hx — Fx, X — A or B. The interaction operator V is taken in the non-expanded form, i.e., it is not approximated by the multipole expansion. The interaction energy components of Eq. (1) are now given in the form of a double perturbation series,... 

---