A theoretical basis for understanding polymerization shrinkage of bone cement is presented based on density changes in converting monomer to polymer. Also, an experimental method, based on dilatometry and the Archimedes' principle is presented for highly precise and accurate measurement of unconstrained volumetric shrinkage of bone cement. Furthermore, a theoretical and experimental analysis of polymerization shrinkage in a constrained deformational state is presented to demonstrate that porosity can develop due to shrinkage. Six bone-cement conditions (Simplex-Ptrade mark vacuum and hand mixed, Endurancetrade mark vacuum mixed, and three two-solution experimental bone cements with higher initial monomer levels) were tested for volumetric shrinkage. It was found that shrinkage varied statistically (p< or = 0.05) from 5.1% (hand-mixed Simplex-Ptrade mark) to 6.7% (vacuum-mixed Simplex-Ptrade mark) to 10.5% for a 0.6:1 (polymer g/monomer mL) two-solution bone cement. Shrinkage was highly correlated with initial monomer content (R(2) = 0.912) but with a lower than theoretically expected rate. This discrepancy was due to the presence of residual monomer after polymerization. Using previously determined residual monomer levels, the theoretic shrinkage analysis was shown to be predictive of the shrinkage results with some residual monomer left after polymerization. Polymerization of a two-solution bone cement in a constrained state resulted in pores developing with volumes predicted by the theory that they are the result of shrinkage. The results of this study show that shrinkage of bone cement under certain constrained conditions may result in the development of porosity at the implant-bone cement interface and elsewhere in the polymerizing cement mantle.

Solutions of poly(methyl methacrylate) (PMMA) powder predissolved in methyl methacrylate (MMA) have been developed as an alternative to current powder/liquid bone cements. They utilize the same addition polymerization chemistry as commercial cements, but in mixing and delivering via a closed system, porosity is eliminated and the dependence of material properties on the surgical technique is decreased. Twelve different sets of compositions were prepared, with two solutions of constant polymer-to-monomer ratio (80 g of PMMA/100 mL of MMA) and all combinations of four benzoyl peroxide (BPO) initiator levels added to the first solution and three N, N-dimethyl-p-toluidine (DMPT) activator levels added to the second. These compositions were tested, along with Simplex-P bone cement, for effects of BPO and DMPT concentrations on polymerization exotherm, setting time, flexural strength, modulus, and maximum strain. The results show that each of these dependent variables was affected significantly by the individual concentrations of BPO and DMPT and their interactions. The flexural strength, modulus, and polymerization exotherm reached their maximums at about a 1:1 molar ratio of BPO to DMPT. Most compositions had exotherms, setting times, and maximum strains within the range of commercial cements and flexural strengths and moduli up to 54 and 43% higher than Simplex-P, respectively.

The glial scar formed at the site of traumatic spinal cord injury (SCI) has been classically hypothesized to be a potent physical and biochemical barrier to nerve regeneration. One longstanding hypothesis is that the scar acts as a physical barrier due to its increased stiffness in comparison to uninjured spinal cord tissue. However, the information regarding the mechanical properties of the glial scar in the current literature is mostly anecdotal and not well quantified. We monitored the mechanical relaxation behavior of injured rat spinal cord tissue at the site of mid-thoracic spinal hemisection 2 weeks and 8 weeks post-injury using a microindentation test method. Elastic moduli were calculated and a modified standard linear model (mSLM) was fit to the data to estimate the relaxation time constant and viscosity. The SLM was modified to account for a spectrum of relaxation times, a phenomenon common to biological tissues, by incorporating a stretched exponential term. Injured tissue exhibited significantly lower stiffness and elastic modulus in comparison to uninjured control tissue, and the results from the model parameters indicated that the relaxation time constant and viscosity of injured tissue were significantly higher than controls. This study presents direct micromechanical measurements of injured spinal cord tissue post-injury. The results of this study show that the injured spinal tissue displays complex viscoelastic behavior, likely indicating changes in tissue permeability and diffusivity.

Porous-free, two-solution bone cements have been developed in our laboratory as an alternative to commercial powder/liquid formulations. Each pair of solutions consist of poly(methyl methacrylate) (PMMA) powder dissolved in methyl methacrylate (MMA) monomer, with benzoyl peroxide (BPO) added to one solution as the initiator and N,N-dimethyl-p-toluidine (DMPT) added to the other as the activator. When mixed, the solutions polymerize via a free radical reaction, which is governed by the concentrations of initiator and activator and their molar stoichiometry. Previous work by the authors has demonstrated that these two-solution cement compositions are comparable to Simplex P bone cement in polymerization exotherm, setting time, and flexural mechanical properties. This study was designed to evaluate the effect of BPO and DMPT concentrations, along with their molar ratio, on the fracture toughness, fatigue strength, and residual monomer content of the experimental compositions. The results showed that fracture toughness and fatigue strength for the solution cements were comparable to Simplex P and were not significantly affected by the BPO concentration or the BPO:DMPT molar ratio; however, the highest DMPT concentration yielded significantly lower values for both variables. Residual monomer content was significantly affected by both the individual concentrations of BPO and DMPT and their molar ratios. The two-solution cements had significantly higher residual monomer contents versus Simplex P; however, this can be attributed to their higher initial monomer concentration rather than a lower degree of conversion.