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Influence of Ringer's solution on creep resistance of hydroxyapatite reinforced polyethylene composites.

In vitro creep studies of polyethylene, both unfilled and filled with hydroxyapatite at 0.20 and 0.40 volume fraction, have been performed. The samples were immersed in Ringer's solution at 37 degrees C for 1, 7, 30, 90 and 150 days prior to isochronous and creep tests in the same condition. The creep properties of unfilled polyethylene is unaffected by the immersion, but the isochronous modulus and the creep resistance of filled polyethylene were reduced. The effect increased with increasing volume fraction and time of immersion. This reduction is related to the penetration of the solution into the material, softening the interface.

Journal Article↗

In vitro complement activation after contact with pyrolytic carbon-coated and uncoated polyethylene terephthalate.

This study was undertaken to evaluate whether the pyrolytic carbon coating of polyethylene terephthalate induces complement activation. Complement activation induced by pyrolytic carbon-coated polyethylene terephthalate (PET+PC) in comparison with uncoated polyethylene terephthalate (PET) was assessed on whole blood collected with heparin. The activation of the classic pathway was evaluated by C4d fragment enzyme immunoassay. The activation of the alternative pathway was evaluated with Bb fragment enzyme immunoassay. The results show that uncoated PET activates the alternative pathway, but not the classic one. PET+PC does not induce complement activation, not even through the alternative pathway. Pyrolytic carbon coating therefore contributes to improving blood compatibility.

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High-pressure synthesis of crystalline polyethylene using optical catalysis.

Polymerization processes are probably the most relevant example of a chemical reaction activated by catalysts or radical initiators. Among polymers, polyethylene is by far the most common and largely produced. Here we present a high-pressure synthesis of high-density crystalline polyethylene by using only physical tools such as pressure and light. Low-density polyethylene is obtained by compressing ethylene at room temperature above 3 GPa in the ordered crystal phase, and a highly crystalline polymer is produced in the fluid phase at pressures lower than 1 GPa by using continuous-wave laser lines (lambda < or = 460 nm) as an optical catalyst. The photo-activation is based on a two-photon absorption process to pi* antibonding states, where the change in molecular geometry favours the polymeric chain formation. The high yield and crystallinity of the polymer recovered by the photoinduced reaction and the simplicity of the synthesis make this process appealing for large-scale applications.

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Combinations of chiral and prochiral singlet radical-pairs in reaction cavities of polyethylene films. Control and analysis of radical tumbling and translation.

The regio- and stereo-chemistries of combination products from chiral 1-naphthoxy/(R)-2-phenylpropanoyl and prochiral 1-naphthoxy/1-phenylethyl singlet radical-pairs (radical-pairs A and B, respectively) have been studied at different temperatures in polyethylene (PE) films with different crystallinities. The radical-pairs have been generated as intermediates along the photo-Fries reaction course of 1-naphthyl (R)-2-phenylpropanoate ((R)-1) and the photo-Claisen reaction course of 1-naphthyl (R)-1-phenylethyl ether ((R)-2). Radical-pair was produced directly upon lysis of the first excited singlet state of (R)-2 and indirectly after irradiation of (R)-1 and subsequent decarbonylation of the 2-phenylpropanoyl radical of radical-pair A. Comparison of the fates of the directly and indirectly formed radical-pairs provides detailed information about the nature of the reaction cavities within the polyethylene hosts and how the combinations of the radical-pairs are influenced by their initial locations within a cavity. The results, especially when taken with those from irradiations in n-alkanes, indicate that the cavities are "templated" by the (R)-1 and (R)-2 guest molecules and that the templated shapes are retained in some form for periods that are at least as long as the time required for decarbonylation of a 2-phenylpropanoyl radical. In addition, the enantiomeric excesses of the decarbonylated photoproducts from (R)-1(2, 2-(1-phenylethyl)-1-naphthol (2BN), and 4-(1-phenylethyl)-1-naphthol (4BN)) or 2BN and 4 BN from (R)-2 indicate different influences of temperature on translational and tumbling motions of the radicals of radical-pairs B within their polyethylene cages.

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Microscopic calculation of the energetics of charged states in amorphous polyethylene.

Polarization energies are calculated for a single excess charge on a polyethylene chain in amorphous polyethylene using (i) local segment and nonlocal distributed molecular polarizabilities, (ii) material structures simulated by both general-purpose and specialist Monte Carlo software, and (iii) uniform and Gaussian distributions of charge with different extents of charge delocalization. Local and distributed response lead to results that are essentially the same except that they correspond to different mean polarizabilities. With increasing delocalization of the charge along the chain, the polarization energies shift to higher values and the width of their distribution decreases, the differences being more pronounced for the uniform distribution. The polarization energies for charges delocalized over 10-20 methylene units form a distribution some 14 eV wide centered around 1 eV, narrowing significantly for more homogeneous polymer melts. The calculations are relevant to trapping of charge in polyethylene. They also yield the microscopic variation in the potential along the polymer chain caused by the polarization energy difference, and so may provide useful inputs to theories of electronic conduction in polymer materials.

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Trapping of excitons at chemical defects in polyethylene.

In a previous paper we studied an injected electron-hole pair in crystalline polyethylene (PE) and found that the exciton becomes weakly self-trapped in a narrow interchain pocket comprised between two gauche defects. Despite the large energy stored in the trapped excitation, there did not appear to be a direct nonradiative channel for electron-hole recombination. Actual polyethylene systems of practical use are, however, neither crystalline nor pure. To understand the fate of an electron-hole pair in the impure case, we studied by ab initio simulations the evolution of an exciton trapped on three common chemical defects found in polyethylene: a grafted carbonyl (C=O); an intrachain vinyl group (C=C); a grafted carboxyl (COOH). Ab initio simulations lead to predict three different outcomes: trapping, nonradiative recombination, and homolitic bond-breaking, respectively. This suggests that extrinsic self-trapping of electron-hole pairs over chemical defects inside the quasicrystalline fraction of PE could be relevant for electrical damage in high-voltage cables.

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Why do polyethylene crystals have sectors?

High-resolution (3.7 A in optical diffraction) electron microscope images have been obtained from a series of n-paraffin monolamellar crystals with chain lengths from n-C36H74 to n-C82H166. The higher molecular weight specimens, which do not undergo chain folding, form sectorized crystals and the molecular packing is found to include alternate bands of untilted and tilted chains along <130>. Their widths are consistent with those of Bragg fringe widths in bright-field images obtained at lower magnification. The chain tilt axis is near d*110. Lower molecular weight paraffins form nonsectorized crystals where the chains are generally untilted with occasional small inclinations around nonspecific axes. Surface decoration of the longer alkanes with polyethylene crystallites, first of all, reveals three preferred polyethylene crystal rod orientations ([100] plus two perpendicular to [110]) instead of the two commonly found for the lower alkane. Control studies on solid-solution crystals reveal that the third [100] orientation is a result of slight surface roughness due to unequal chain lengths or surface protrusions of chains; the new decoration is also randomly distributed. For pure n-C60H122 lamellae, however, suggestions of regular bands containing rods along [100], due to surface discontinuities along <130>, can also be seen. In contrast with polyethylene, these data suggest that crystal sectorization may be a function of chain-stem packing alone and that chain folds may play merely a secondary role in the polymer--e.g., by directing the collapse of pyramidal crystals on a flat surface.

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Quantitative Assessment of Polyethylene Component Position in a Mobile-Bearing Prosthetic Knee, Using a Single Radiograph.

Rationale and Objectives. To reduce tibio-femoral misalignment, the polyethylene bearing-component of a new knee prosthesis was allowed limited motion on the underlying metallic component. The object of the work presented here was to develop a suitable radiographic technique for quantifying the in-vivo position of the bearing. By collecting these data at discrete flexion angles, the functional operation of the prosthesis could be determined. Methods. The known geometries between landmarks on the two components were used to produce algorithms for reconstructing their spatial positions from a single radiograph. A custom-designed computer program utilized these algorithms to determine the relative translation and rotation of the polyethylene component. Results. This technique produced typical errors of 0.54 mm translation and 0.56 degrees rotation between the polyethylene component and the underlying metallic component. Conclusions. A practical method has been developed for assessing mobile-bearing motion, in vivo. This method can be applied to other prosthetic devices, or combinations of components, once the requirement for identifiable landmarks has been addressed. Clinical Relevance. Skeletal and soft-tissue changes in the pathological knee may produce abnormal rotations and translations in the transverse tibial plane. This technique is intended both to validate the design philosophy of a mobile-bearing prosthesis and to provide additional data on any pathological motions, which will have implications for future prosthetic designs.

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Surface states and negative electron affinity in polyethylene.

First-principles calculations are used to investigate the electronic properties of the surfaces of polyethylene. The calculations support the experimental evidence of a negative electron affinity, with calculated values of -0.17 eV and -0.10 eV for surfaces with chains perpendicular and parallel to the surface normal, respectively. Both surfaces exhibit a surface state with binding energy -1.2 +/- 0.5 eV with respect to the bulk polyethylene conduction band minimum. Implications of these findings on spectroscopy, as well as on the transport and aging properties of polyethylene for high-voltage applications, are discussed.

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Protection of cellulose synthesis in detached cotton fibers by polyethylene glycol.

Detachment of the cotton fiber cell from the ovule results in loss of over 90% of the in vivo capacity for synthesis of [(14)C]cellulose from [(14)C]glucose. However, over 50% of the capacity for cellulose synthesis in the detached fiber population is protected when polyethylene glycol 4000 is present during detachment and incubation. Radioautography shows that approximately full capacity is restored in about half the fibers, whereas the other half of the population are incapable of cellulose synthesis from supplied glucose. The rate of cellulose synthesis in such fibers has a pH optimum of 6 and the optimum polyethylene glycol 4000 concentration is 0.06 molal (-9 bars). Cellulose synthesis in such detached fibers is synergistically stimulated by Ca(2+) and Mg(2+) and inhibited by K(+).Evidence is presented which indicates that the protection by polyethylene glycol 4000 is due to its ability to promote membrane resealing, which seems to be required for protecting cellulose synthesis in the detached fiber; however, the requirement for membrane integrity is not exclusively involved in the maintainence of an energy generating system for the synthesis. The possibility that a membrane potential may be required for maintaining an active cellulose synthesizing system is discussed.

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Effect of polyethylene glycol exclusion on the water potential of solution-saturated filter paper.

Solutions of high molecular weight polyethylene glycol are often used to control water potential in seed germination studies. There is an implicit assumption that the seed support materials do not alter the water potential of the osmotic solution. Filter paper, however, contains a hydrophylic volume fraction that is inaccessible to high molecular weight polymers. Water absorbed by filter paper fibers was found to concentrate polyethylene glycol and lower water potential in solution-filter paper mixtures. The magnitude of this concentration effect is a function of the original concentration of polyethylene glycol and the ratio of solution volume to filter paper weight.

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Degradation of degradable starch-polyethylene plastics in a compost environment.

The degradation performance of 11 types of commercially produced degradable starch-polyethylene plastic compost bags was evaluated in municipal yard waste compost sites at Iowa State University (Ames) and in Carroll, Dubuque, and Grinnell, Iowa. Masterbatches for plastic production were provided by Archer Daniels Midland Co. (Decatur, Ill.), St. Lawrence Starch Co. Ltd. (Mississauga, Ontario, Canada), and Fully Compounded Plastics (Decatur, Ill.). Bags differed in starch content (5 to 9%) and prooxidant additives (transition metals and a type of unsaturated vegetable oil). Chemical and photodegradation properties of each material were evaluated. Materials from St. Lawrence Starch Co. Ltd. and Fully Compounded Plastics photodegraded faster than did materials from Archer Daniels Midland Co., whereas all materials containing transition metals demonstrated rapid thermal oxidative degradation in 70 degrees C-oven (dry) and high-temperature, high-humidity (steam chamber) treatments. Each compost site was seeded with test strips (200 to 800 of each type) taped together, which were recovered periodically over an 8- to 12-month period. At each sampling date, the compost row temperature was measured (65 to 95 degrees C), the location of the recovered test strip was recorded (interior or exterior), and at least four strips were recovered for evaluation. Degradation was followed by measuring the change in polyethylene molecular weight distribution via high-temperature gel permeation chromatography. Our initial 8-month study indicated that materials recovered from the interior of the compost row demonstrated very little degradation, whereas materials recovered from the exterior degraded well. In the second-year study, however, degradation was observed in several plastic materials recovered from the interior of the compost row by month 5 at the Carroll site and almost every material by month 12 at the Grinnell site. The plastic bags collected from each community followed a similar degradation pattern. To our knowledge, this is the first scientific study demonstrating significant polyethylene degradation by these materials in a compost environment.

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Polyethylene particles from a hip simulator cause (45)Ca release from cultured bone.

Periprosthetic osteolysis is a dominant factor in the success or failure of total hip prostheses. Polyethylene wear debris has been implicated in the process of bone resorption and subsequent implant loosening. The present study is the first to examine the effect of ultra high molecular weight polyethylene (UHMWPE) wear debris produced by a hip simulator on calvarial bone resorption in vitro. (45)Ca release was measured in cultured mouse calvarial bone samples. Although short-term exposure to UHMWPE particles (2 h) decreased (45)Ca release, longer-term exposure for 1-2 days increased release in a dose-dependent manner. After one-day exposure to 7.5 x 10(6) particles per mL, 18% more (45)Ca was released from cultured calvarial bone than from control samples. It was concluded that UHMWPE wear particles either directly or indirectly stimulated osteoclasts to activate bone resorption. Polyethylene wear debris contributes to the osteolytic process at the bone-implant interface.

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Use of vegetative furrows to mitigate copper loads and soil loss in runoff from polyethylene (plastic) mulch vegetable production systems.

The transport of runoff with high copper concentrations and sediment loads into adjacent surface waters can have adverse effects on nontarget organisms as a result of increased turbidity and degraded water quality. Runoff from vegetable production utilizing polyethylene mulch can contain up to 35% of applied copper, a widely used fungicide/bactericide that has adverse effects on aquatic organisms. Copper is primarily transported in runoff with suspended particulates; therefore, implementation of management practices that minimize soil erosion will reduce copper loads. Replacing bare-soil furrows with furrows planted in rye (Secale cereale) significantly improved the sustainability of vegetable production with polyethylene mulch and reduced the potential environmental impact of this management practice. Vegetative furrows decreased runoff volume by >40% and soil erosion by >80%. Copper loads with runoff were reduced by 72% in 2001, primarily as a result of reduced soil erosion since more than 88% of the total copper loads were transported in runoff with suspended soil particulates. Tomato yields in both years were similar between the polyethylene mulch plots containing either bare-soil or vegetative furrows. Replacing bare-soil furrows with vegetative furrows greatly reduces the effects of sediments and agrochemicals on sensitive ecosystems while maintaining crop yields.

Agriculture↗

Failure of the Ring polyethylene uncemented acetabular cup.

We report a high rate of failure of the Ring polyethylene cementless cup caused largely by granulomatous osteolysis. We have reviewed 126 prostheses inserted from 1986 to 1992 at from 11 to 90 months after surgery. There was radiological evidence of osteolytic granulomas adjacent to the external surface of the cup in 32%, appearing on average at three years from operation. In a subgroup of 59 prostheses followed for at least four years the incidence of such changes was 54%. A total of 27 cups (22%) have required revision, 21 for granulomatous loosening at an average follow-up of five years. In the retrieved prostheses there was obvious polyethylene abrasion and histological examination confirmed the presence of polyethylene wear debris. We found no significant correlation of osteolysis with cup size, although smaller cups were predominant among those having revision.

Acetabulum↗

Solution technique to incorporate polyethylene oxide and other water-soluble polymers into surfaces of polymeric biomaterials.

A simple solution technique was used to incorporate polyethylene oxide (PEO, of 5000, 10,000, 18,500, and 100,000 g/mol) and other water-soluble polymers such as polyvinylpyrrolidone and polyethyl oxazoline into the surfaces of commonly used biomedical polymers such as polyethylene terephthalate, a polyurethane (Pellethane 2363-80AE), and polymethylmethacrylate. The presence of the water-soluble polymers on these surfaces was verified by using contact angle analysis and ESCA. Protein adsorption studies, fibroblast adhesion assays, and whole blood perfusions over these polymers showed that the surface modified with PEO 18,500 was the most effective in reducing all the tested biological interactions. It was concluded that PEO 18,500 had a chain length that was optimal, using this technique for surface incorporation, to reduce protein adsorption and hence prevent protein-mediated biological interactions.

Adsorption↗

Intrinsic stability of unused and retrieved polyethylene glenoid components.

The surface geometry of polyethylene components can be altered by in vivo use. The purpose of this investigation is to document the effects of these changes on the intrinsic stability provided by the glenoid component. We validated a method of measuring the intrinsic stability of glenoid components as indicated by the balance stability angle (the maximal angle between the glenoid centerline and the resultant humeral force before dislocation of the humeral head occurs). We compared observed values with those predicted for unused glenoid components for which the geometry was known. We then applied this method to retrieved glenoid components in which the surface geometry had been altered by in vivo use. The balance stability angles measured in retrieved glenoids were often substantially reduced: 11 of 24 glenoids had diminished balance stability angles of at least 30% in at least one direction. We concluded that the surface geometry of polyethylene glenoid components can be altered by in vivo use in a manner that may compromise their contribution to glenohumeral stability.

Arthroplasty, Replacement↗

Endothelial cell binding to Dacron modified with polyethylene oxide and peptide.

Polyethylene oxide (PEO) was incorporated into the surface of Dacron (PET) vascular prosthetic material (crimped Bionit I, BNl) followed by covalent attachment of an endothelial cell (EC) adhesion peptide; Gly-Arg-Glu-Asp-Val-Tyr (GREDVY). This procedure provides the possibility of a surface selective for EC adherence. Optimal PEO incorporation with minimal fiber damage was achieved from 78% (vol) trifluoroacetic acid (TFA) as characterized by scanning electron microscopy, nuclear magnetic resonance, bromphenol blue staining, and tensile testing. By weight, there was 4.4 times as much 18.5kD PEO as 1.5kD PEO incorporated into PET, but there were 2.8 times as many molecules of low molecular weight PEO. Attachment of 125I-GREDVY to substrates increased as follows: BNJ < BNI - 18.5 kD PEO < BNI - 1.5 kD PEO. Polyethylene oxide size affected EC binding with high molecular weight material decreasing binding and low molecular weight PEO increasing attachment. GREDVY modification of BNI or either of the two BNI-PEOs gave small but consistently increased EC binding compared with the same preparation without GREDVY. In contrast, human fibroblasts cultured from umbilical vein showed decreased binding when GREDVY was attached to BNI or PEO modified BNI. These results indicate that selective EC binding to PET vascular prostheses can be achieved.

Amino Acid Sequence↗