Two studies were carried out in an effort to gain a better understanding of how ketene dimers develop sizing. In the first study, eight ketene dimers with a range of melting points, vapor pressures, and molecular weights were evaluated for rate of sizing development. Ketene dimer melting point had a clear effect on the rate of sizing development. High melting ketene dimers initiated sizing at higher sheet moistures than low melting dimers. High melting dimers also developed their ultimate level of sizing faster than low melting ketene dimers. These results suggest that solid and liquid ketene dimers have different mechanisms of sizing development. Ketene dimer vapor pressure and molecular weight had no consistent effects on the rate of sizing development.
Pseudo first order rate constants for sizing development were then measured for a high melting solid ketene dimer and a liquid ketene dimer over dryer temperatures ranging from 55 °C to 85 °C. The rate constants measured for the liquid ketene dimer increased steadily as dryer temperature increased. An Arrhenius plot of the rate constants obtained for the liquid ketene dimer yielded an activation energy of 11 kcal per mole for sizing development. These results are consistent with the hypothesis that the chemical reaction of the lactone ring is the rate determining step in sizing development for liquid ketene dimers. The high melting solid ketene dimer followed more complex kinetics and probably developed sizing by a combination of mechanisms. It is likely that the differing sizing responses measured for the solid and liquid ketene dimers are due to differing sizing contributions from the unreacted and hydrolyzed ketene dimers.