F. J. Gil

New aspects of the effect of size and size distribution on the setting parameters and mechanical properties of acrylic bone cements

The effect of the size and the size distribution of poly(methyl methacrylate) (PMMA) beads on the classical kinetic parameters, peak temperature and setting time, for acrylic bone cement formulations prepared with PMMA particles in the range 10-60 microns of average diameter and a relatively wide size distribution is analysed. In addition, the combined effects of the concentration of the free radical initiator benzoyl peroxide and the activator N, N-dimethyl-4-toluidine for the different particle sizes are studied and compared with those commercially available formulations like CMW or Rostal. The results obtained indicated that the use of PMMA particles with average diameter of 50-60 microns, and a relatively wide size distribution (10-140 microns diameter), significantly changes the curing parameters (peak temperature and setting time) of the cement formulations in comparison with the classical behaviour of the commercial systems of CMW and Rostal, without any noticeable loss in the mechanical properties, such as tensile strength, elastic moduli, and compressive strength and plastic strain.

PRODUCTION AND CHARACTERIZATION OF NEW CALCIUM PHOSPHATE BONE CEMENTS IN THE CAHPO4-ALPHA -CA3(PO4)2 SYSTEM : PH, WORKABILITY AND SETTING TIMES

The initial setting properties of calcium phosphate cements in the CaHPOv4–α-Ca3(PO4)2 (DCP–α-TCP) system have been investigated. Interest was focused on the pH, workability, cohesion time and initial and final setting times. The addition of CaCO3 modified the structure of the cement reaction product such that it became more similar to the apatite phase in bone mineral. The addition of 10% w/w of CaCO3 reduced the viscosity of the cement pastes resulting in an increase in initial and final setting times and improved injectability.

Improvement of the mechanical properties of new calcium phosphate bone cements in the CaHPO4-α-Ca3(PO4)2 system: Compressive strength and microstructural development

The hardening properties of calcium phosphate cements in the CaHPO4-alpha-Ca3(PO4)2 (DCP-alpha-TCP) system have been investigated with interest focused on the compressive strength and microstructure development. Previous studies have shown that the addition of CaCO3(CC) leads to a modification of the calcium-deficient apatite structure of the reaction product, which results in a material more similar to the apatite in bone mineral. The addition of 10% w/w of CC to the initial DCP-alpha-TCP powder mixture resulted, with time, in a retardation of the development of compressive strength. However, the optimum compressive strength reached values up to 40% higher than CC-free samples. This retarding effect also has been monitored as a function of the calcium to phosphorus (Ca/P) ratio of the DCP and alpha-TCP mixture, showing the importance of the final cement properties of the relative quantities of the reactants in the mixture.

Spatial organization of osteoblast fibronectin matrix on titanium surfaces: Effects of roughness, chemical heterogeneity and surface energy

We investigated the early events of bone matrix formation, and specifically the role of fibronectin (FN) in the initial osteoblast interaction and the subsequent organization of a provisional FN matrix on different rough titanium (Ti) surfaces. Fluorescein isothiocyanate-labelled FN was preadsorbed on these surfaces and studied for its three-dimensional (3-D) organization by confocal microscopy, while its amount was quantified after NaOH extraction. An irregular pattern of adsorption with a higher amount of protein on topographic peaks than on valleys was observed and attributed to the physicochemical heterogeneity of the rough Ti surfaces. MG63 osteoblast-like cells were further cultured on FN-preadsorbed Ti surfaces and an improved initial cellular interaction was observed with increasing roughness. 3-D reconstruction of the immunofluorescence images after 4 days of incubation revealed that osteoblasts deposit FN fibrils in a specific facet-like pattern that is organized within the secreted total matrix overlying the top of the samples. The thickness of this FN layer increased when the roughness of the underlying topography was increased, but not by more than half of the total maximum peak-to-valley distance, as demonstrated with images showing simultaneous reconstruction of fluorescence and topography after 7 days of cell culture.

Human-osteoblast proliferation and differentiation on grit-blasted and bioactive titanium for dental applications

Physico-chemical and topographical surface quality of commercially pure titanium (c.p. Ti) dental implants is one of the most influencing factors in the improvement of their osseointegration. In this sense, previously, a two-step method (2S) for obtaining bioactive blasted-rough titanium surfaces was developed for improving short-term (due to its bioactivity) and long-term (due to its roughness) osseointegration. This 2S-method consists of: (1) Grit blasting on titanium surface in order to roughen it, and (2) thermo-chemical (TCh) treatment in order to obtain a bioactive surface with bone-bonding ability. The aim of the present work is to evaluate the in vitro human-osteoblast response (proliferation, differentiation – ALP activity- and cell morphology-studied by environmental scanning electron microscopy) of rough c.p. Ti (grit blasted), bioactive c.p. Ti (thermo-chemically treated) and rough-bioactive c.p. Ti (2S-treated). Different grit materials (Al2O3 and SiC) have been used in order to investigate their influence. The results showed that cell adhesion was statistically higher for the rough and bioactive surfaces, whatever the grit used. Cells proliferated very well on all the c.p. Ti surfaces. If comparing groups with and without TCh (all other treatments being equal) the ALP was always higher in the groups with TCh, indicating stimulation of osteoblast differentiation because of TCh, more significantlly in the groups that were first blasted. Those ALP results were accompanied by a decrease in the value of proliferation, which shows the good behavior of the cells. This results suggest that a rough and bioactive-titanium surface obtained by 2S-treatment enhances adhesion and differentiation activity of human osteoblasts cells.

Effect of copper addition on the superelastic behavior of Ni-Ti shape memory alloys for orthodontic applications

Transformation temperatures and mechanical properties such as transformation stresses at different temperatures, superelasticity characteristics, and load cycling behavior have been investigated in NiTiCu orthodontic archwires with various copper concentrations. The results have been compared with the conventional NiTi orthodontic archwires. The addition of copper was effective in narrowing the stress hysteresis and in stabilizing the superelasticity characteristics against cyclic deformation, with the result that the slope of the load-deflection unloading curve of the alloy is lower than NiTi. Moreover, it produced greater stability of both the transformation temperature and the force applied to the teeth for a determined design and wire cross-section. On the other hand, the presence of copper in NiTi orthodontic archwires reduced the ageing effect. Studies of ion release in artificial saliva showed only small quantities after long periods of immersion.

Effect of porosity and environment on the mechanical behavior of acrylic bone cement modified with acrylonitrile-butadiene-styrene particles: I. Fracture toughness.

The elastomeric copolymer acrylonitrile-butadiene-styrene (ABS) was added to a conventional acrylic bone cement matrix. The results obtained show that although strength and stiffness decreased with an increasing second phase volume fraction, ductility and toughness both increased. The crack propagation became stable for specimens containing over a 5% volume fraction of the second phase. The fracture toughness increased up to 60% when the amount of ABS reached 20% (v/v). For larger amounts linear elastic fracture mechanics techniques could not be used properly. The effects of porosity and environmental conditions on the mechanical behavior were also studied. The mechanisms that control the fracture process were investigated by means of scanning electron microscopy.

The cement setting reaction in the CaHPO4‐α‐Ca3(PO4)2 system: An X‐ray diffraction study

The setting reactions of calcium phosphate cements in the CaHPO4-alpha-Ca3(PO4)2 (DCP-alpha-TCP) system have been investigated. X-ray diffraction (XRD) analyses were performed on DCP-alpha-TCP cement samples of varying calcium to phosphorus (Ca/P) ratios after setting for 24 h in Ringers solution at 37 degrees C. XRD measurements showed that the intensity of the DCP peaks decreased linearly as the Ca/P ratio of the mixture increased. However, the intensity of the peaks of a new calcium-deficient hydroxyapatite [CDHA; Ca9(HPO4)(PO4)5OH] precipitating phase increased linearly as the Ca/P ratio increased. Alpha-TCP was not detected after 24 h of setting in any sample. A two-phase mixture XRD model was applied to explain the results, and suitable fits were obtained between observed and expected values of the relevant peak heights. The method used for this study also can be applied to studies of the kinetic behavior of other cement systems.

Modified acrylic bone cement with high amounts of ethoxytriethyleneglycol methacrylate.

One cause of arthroplasty failure is the brittle mechanical behavior of bone cements. However, the improvement of cement formulations must also be accompanied by the maintenance of a wide variety of characteristics. New bone cements were obtained by the substitution of high percentages, up to 60% (v/v), of methyl methacrylate (MMA) by a higher molecular weight and more hydrophilic monomer, ethoxytriethyleneglycol methacrylate (TEG). The essential advantages of these materials were the decrease of maximum temperature together with a decrease in the residual monomer content with respect to conventional cement formulations. The water absorption process obeyed diffusion laws and the equilibrium water content increased by the introduction of higher percentages of the hydrophilic component. This characteristic had an appreciable effect on the viscoelastic behavior analyzed by DMTA. These modified bone cements had reduced polymerization shrinkage and similar levels of porosity. Tensile test revealed that the introduction of TEGMA gave rise to an important modification of the mechanical behavior, with a noticeable increase in the fracture strain. This fact was also confirmed by means of the analysis of the fracture surfaces by SEM.

Influence of the modification of P/L ratio on a new formulation of acrylic bone cement

The use of smaller powder/liquid (P/L) ratio favours the handling and wetting of poly(methyl methacrylate) (PMMA) beads in bone cement formulations. In this paper a P/L ratio of 1.86 is tested to overcome adhesion problems found in hydroxypropyl methacrylate (HPMA) modified bone cements and the influence on bone cement characteristics was analysed. The reduction of the P/L ratio leads to higher temperature peaks and shorter setting times, whereas the residual monomer content increases slightly. Water uptake obeys the diffusion laws, and the introduction of a more hydrophilic monomer gives rise to an increase of this parameter, which does not present significant changes with modification of the P/L ratio. Polymerization shrinkage is slightly greater because of the introduction of higher proportions of monomer in the formulation. Mechanical properties are similar to those obtained with conventional P/L ratios. The analysis of scanning electron microscopy (SEM) reveals an improvement of the adhesion between phases with respect to P/L = 2 formulations.