R. Salovey

Effect of sterilization method and other modifications on the wear resistance of acetabular cups made of ultra-high molecular weight polyethylene. A hip-simulator study.

Background: Wear of ultra-high molecular weight polyethylene acetabular cups in hip prostheses produces billions of submicrometer wear particles annually that can cause osteolysis and loosening of the components. Thus, substantial improvement of the wear resistance of ultra-high molecular weight polyethylene could extend the clinical life span of total hip prostheses. It has become apparent that the conditions under which ultra-high molecular weight polyethylene cups have been sterilized can markedly affect their long-term wear properties, and new sterilization methods and other modifications have been developed to minimize the negative effects. Methods: In the present study, a hip-joint simulator was used to assess whether it is preferable to sterilize ultra-high molecular weight polyethylene cups without gamma irraSdiation, to avoid radiation-induced oxidative degradation, or to sterilize with gamma irradiation while the cups are packaged in a suitable low-oxygen atmosphere to minimize oxidation while retaining the increased wear resistance conferred by the radiation-induced cross-linking. Ion-implanted cups and cups made of a highly crystalline polyethylene (Hylamer) also were investigated. Cups made of each material were subjected to wear-testing prior to and after artificial thermal aging to accelerate oxidative degradation. Results: The results of the present study demonstrated that the cross-linking induced by gamma irradiation improves the wear resistance of ultra-high molecular weight polyethylene, while oxidation reduces it. Without thermal aging, the two types of cups that were sterilized with gamma irradiation while in low-oxygen packaging exhibited about a 50 percent lower rate of wear than did either the nonsterilized cups or the nonirradiated cups sterilized with gas plasma. There was a comparable advantage in the rate of wear after fourteen days of thermal aging. However, after thirty days of aging, the cups sterilized with gamma irradiation in low-oxygen packaging wore several times faster than did the nonirradiated cups. Ion-implanting improved the wear resistance without thermal aging, but after extensive thermal aging the oxidation and wear were greater than those of the controls. Hylamer cups (that is, those that were sterilized with gas plasma) exhibited wear properties very close to those of the nonsterilized ultra-high molecular weight polyethylene cups (the controls) with or without aging. Conclusions: Sterilizing an ultra-high molecular weight polyethylene acetabular cup without radiation (for example, with ethylene oxide or gas plasma) avoids immediate and long-term oxidative degradation of the implant but does not improve the inherent wear resistance of the polyethylene. Sterilizing with use of gamma irradiation with the implant packaged in a low-oxygen atmosphere avoids immediate oxidation and cross-links the polyethylene, thereby increasing its wear resistance, but long-term oxidation of the residual free radicals may markedly reduce the wear resistance. Ideally, cross-linking with gamma irradiation to reduce wear should be done in a manner that avoids both immediate and long-term oxidation. Clinical Relevance: The present study demonstrated how the fabrication and sterilization processes influence the resistance to oxidation and wear of the various types of ultra-high molecular weight polyethylene that are currently available. As an exact quantitative relationship between days of thermal aging and years of real-time aging (on the shelf and/or in vivo) has not yet been established, it is not possible to predict precisely when, if ever, the in vivo wear rate of cups sterilized with gamma irradiation while in low-oxygen packaging would exceed that of nonirradiated cups. Nevertheless, the results of these wear tests with use of a hip simulator suggest that, for at least ten years of clinical use, the in vivo wear rate of cups sterilized with gamma irradiation while in low-oxygen packaging will be substantially lower than that of cups sterilized without irradiation. The fundamental interactions among radiation, cross-linking, and oxidation exhibited by the specific materials included in the present study may also apply to acetabular cups of other types of polyethylene. Understanding these fundamental interactions will assist the surgeon in making an informed choice among the materials examined in the present study and among other types of modified polyethylene already in clinical use, including those sterilized with ethylene oxide, those sterilized with gamma irradiation in other forms of low-oxygen packaging, and the various new cross-linked and thermally stabilized polyethylenes.

Irradiation of chemically crosslinked ultrahigh molecular weight polyethylene

Acetabular cups for artificial hip joints were prepared by compression molding of ultrahigh molecular weight polyethylene in the presence of peroxide. Peroxide crosslinking led to a decrease in the degree of crystallinity, peak melting temperature, and recrystallization temperature, as well as decreased crystal perfection and size. Peroxide crosslinked cups were sterilized with gamma rays at room temperature in air atmosphere to an average dose of 3.4 Mrad. Irradiation produced further crosslinking in amorphous regions plus extensive chain scission of taut tie molecules and led to increased crystallinity and crystal perfection. A significant increase in carbonyl concentration was determined for irradiated specimens. In general, peroxide crosslinking reduces the effect of irradiation on the crosslinked network, because chemical crosslinking stabilizes chain fragments resulting from radiolytic scission and suppresses recrystallization of broken chains from amorphous regions. Wear rates were much lower for chemically crosslinked cups, which showed about one-fifth of the wear of control cups for the period from 0.5 to 1.0 million cycles.

Profile of oxidation in irradiated polyethylene

Following gamma irradiation in air which causes bond scission and yields large concentrations of peroxy radicals, maximum oxidation and an increase in crystallinity occurs on the surface of ultrahigh molecular weight polyethylene. Here, bimolecular reactions of peroxy radicals generate carbonyls, mostly ketones. On the polymer surface, peroxy radicals continue to react over time periods of years to generate carbonyls and chain scission. Peroxy radicals in the interior of the polymer abstract hydrogens and form hydroperoxides, inducing chain reactions and a slow but continue increase of ketone. Within the polymer sample, to a decreasing depth with increasing dose, a reduced concentration of oxygen is available to react with radiolytic radicals, so that more efficient crosslinking and a low level of hydroperoxide chain reaction occur. After long periods of time a surface maximum in carbonyl concentration is produced. Heating polyethylene in high pressures of oxygen accelerates the oxidative process.

Model filled polymers

SummaryPolyphenylene vinylene (PPV) coated polystyrene (PS) beads which have moderate conductivity when doped were prepared by mixing monodisperse crosslinked PS beads, the surfaces of which had been sulfonated to render them anionic, with cationic PPV precursor polymers. Two different PPV precursor polymers, poly (p-xylylidene tetrathiophenium chloride) and poly (p-xylylene-α-dimethylsulphonium chloride), were employed. Monodisperse crosslinked PS beads were sulfonated in the gas phase using fuming sulfuric acid to yield the surface activated monodisperse polystyrene sulfonic acid (PSSA) beads. Chemical doping with AsF5, of pellets prepared by pressing the coated beads resulted in conductivities as high as 10-1S/cm. The integrity of the polymer beads was determined by Scanning Electron Microscopy (SEM) and arsenic was found throughout the samples by examing fracture surfaces of the pressed coated pellets using EDXS.

Morphology of chemically crosslinked ultrahigh molecular weight polyethylene

Morphological characterization of chemically crosslinked ultrahigh molecular weight polyethylene was performed by differential scanning calorimetry and scanning electron microscopy. The lamellar thickness of nascent UHMWPE inferred from DSC endotherms showed a very broad distribution, which was reduced significantly after melting and recrystallizing in DSC. Peroxide crosslinking further reduced the lamellar thickness distribution compared to uncrosslinked samples. After gamma-irradiation, a slowly cooled peroxide-free sample showed a greater increase in lamellar thickness distribution. Examination of the morphology of freeze-fractured surfaces by SEM showed that a slowly cooled peroxide-free UHMWPE exhibited a rougher fracture while chemically crosslinked samples showed a smoother fracture. After compression molding at 300 degrees C for 2 h, the grain boundaries between particles disappeared for all UHMWPE samples, indicating a complete fusion of the original flakes.

Hydroperoxide formation in irradiated polyethylene

Spectroscopic analysis for hydroperoxide in irradiated ultrahigh molecular weight polyethylene, on the basis of the formation of a nitrate derivative after exposure to dilute nitric oxide, is examined. Hydroperoxide is found to be an important intermediate in the oxidation of polyethylene and is believed to result from hydrogen abstraction reactions by peroxy radicals in a polyethylene matrix. During γ irradiation in air, the rates of bimolecular combination of peroxy radicals on the surface to form ketones or hydrogen abstraction to form hydroperoxides are similar. However, as a result of bimolecular combination, the concentration of peroxy radicals decreases. After irradiation and storage in ambient air, isolated peroxy radicals below the polymer surface induce a slow chain reaction leading to a long-term increase in hydroperoxides and carbonyls. Differences in hydroperoxide and oxygen content for samples irradiated in air or vacuum are primarily confined to or near the surface.

“Continuous” emulsifier‐free emulsion polymerization for the synthesis of monodisperse polymeric latex particles

A continuous emulsifier-free emulsion copolymerization (CEFEP) of styrene and divinylbenzene (DVB) or methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDMA) has been devised to produce uniform polymeric microspheres of narrow size distribution from 74 nm to 2 μm, depending on reaction time. Monomer and crosslinker vapors were fed continuously into a small reactor. We suggest that after initial nucleation, subsequent CEFEP proceeds near the surfaces of growing particles in a monomer-swollen outer shell.

Model filled rubber. II. Particle composition dependence of suspension rheology

Monodisperse size colloidal particles varying in chemical composition were synthesized by emulsifier-free emulsion polymerization. Using a stress-controlled rheometer, the rheological behavior of colloidal suspensions in a low molecular weight liquid polysulfide was investigated. All suspensions exhibited shear thinning behavior. The shear viscosity, dynamic moduli, and yield stress increased as interactions between particles and matrix increased. The rheological properties associated with network buildup in the suspensions were sensitively monitored by a kinetic recovery experiment. We propose that interfacial interactions by polar and hydrogen bonding between particles and matrix strongly promote affinity of matrix polymer to the filler particles, resulting in adsorption or entanglement of polymer chains on the filler surface. A network structure was formed consisting of particles with an immobilized polymer layer on the particle surface with each particle floc acting as a temporary physical crosslinking site. As the interfacial interaction increases, the adsorbed layer thickness on the filler particles, hence, the effective particle volume fraction, increases. As a result, the rheological properties were enhanced in the order PS < PMMA < PSVP.

Static and dynamic light scattering studies of the crystallization of poly(ethylene oxide) from dilute solutions

Abstract We have monitored in situ the self-seeded crystallization of poly(ethylene oxide) from dilute toluene solutions by dynamic light scattering. In supercooled dilute solution, the radii (R) of the crystals grow linearly with time. the rate constant obtained from the slope of the plot Rversus time depends on the temperature and the molecular weight of the polymer, both of which determine the degree of the supercooling. The maximum crystal size obtained from solutions of fixed concentration also depends on the temperature and the polymer molecular weight. It appears that crystal growth is limited because of molecular weight fractionation. Static light scattering from suspensions of stable crystals provides information on the crystal morphology. A comparison of experimental and theoretical particle scattering functions suggests that the crystals form short cylinders and that the crystal growth from the seeds is primarily two-dimensional. Some comparisons to melt crystallization are possible. The preparation and use of tiny seed crystals is critical to the success of these studies.

Oligomer formation in the emulsifier-free emulsion polymerization of styrene

The formation of oligomers in emulsifier-free emulsion polymerization of styrene was characterized by means of gel permeation chromatography and surface tension measurements. GPC analysis showed incessant oligomer formation throughout the emulsion polymerization process. Oligomers spanned a molecular weight range of 200–1,500, have an Mw of 800–900, an Mn of 600–800 and a polydispersity index of 1.3. On average, the oligomers contain 4 to 6 styrene units. UV detection could not be utilized to acquire the weight ratio of oligomers to polymers without correction. Combination was the major mode of termination of free radicals in the aqueous phase, but disproportionation was not negligible: for every three-combination reactions there was about 1 disproportionation. Surface tension measurements showed that oligomers minimized the surface tension of the latex at about 50 min reaction to only 30 mN/m.