Molecular and macroscopic properties of PMMA bone cement: free-radical generation and temperature change versus mixing ratio.

The molecular and macroscopic changes occurring during the polymerization of poly(methyl methacrylate) (PMMA) bone cement have been investigated. Electron paramagnetic resonance (EPR) spectroscopy was used to monitor free-radical generation and this was compared to temperature changes occurring in the cement for various ratios of polymer powder to liquid monomer (P/L ratio) used in the sample preparation. Both the concentration and the characteristic growth time of the free radicals associated with the polymerization of the bone cement depended on the P/L ratio used. Larger P/L ratio resulted in shorter characteristic growth time for the free radicals as well as a shorter time for the occurrence of the peak sample temperature. Smaller P/L ratios gave smaller maximum concentrations of free radicals and larger peak temperatures. These results are explained on the basis of (1) more initiators present at higher P/L ratios resulting in faster polymerization and (2) less initiators and more monomers present at smaller P/L ratios resulting in fewer radicals but more exothermic reactions. The free radicals present in the bone cement due to the manufacturer's sterilization process were found to be proportional to the fraction of powder used in the preparation, indicating negligible monomer loss during sample mixing.