Size-exclusion chromatography of poly(ethylene 2,6-naphthalate).

A solvent mixture of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) and dichloroacetic acid (DCAA) is used to dissolve difficultly soluble poly(ethylene 2,6-naphthalate) (PEN). Solutions can be diluted and analyzed in a common size-exclusion chromatography (SEC) eluent, HFIP. The HFIP/DCAA mixture is better at dissolving PEN than either solvent individually and it is easier and safer to work with than phenolic and strongly acidic eluents. Dissolution temperatures between 50 and 60 °C are sufficiently low to minimize hydrolytic degradation of the polyester. PEN does not dissolve in the solvent mixture if the water concentration is greater than 0.76 wt%, and preferably the water content should be less than 0.13 wt% to eliminate minor prepeak artifacts. The procedure is suitable for PEN that is less than 48% crystalline, including prepolymers, oriented films and some solid-state polymerized materials. Highly crystalline polymers can be melt-quenched into a more amorphous state to render them soluble. The dilute solution conformational properties of PEN are compared to PET in HFIP, and molar mass-intrinsic viscosity scaling constants and unperturbed dimensions are calculated from SEC data.

Biological activity of polyethylene wear debris produced in the patellofemoral joint.

Polyethylene wear is considered a threat to the long-term survival of total knee replacements. The aim of this study was to investigate the contribution that resurfacing the patella makes to wear debris-induced osteolysis following total knee replacement. Ultra-high molecular-weight polyethylene wear particles were isolated from simulator lubricant. Particle shape, size, and volume distributions were recorded allowing the osteolytic potential of the wear debris produced in the patellofemoral joint to be estimated using the concept of specific biological activity and functional biological activity. Values were compared with those reported for the tibiofemoral joint. Specific biological activity for the patellofemoral joint was not significantly different from the values for the tibiofemoral joint of total knee replacement devices, and therefore, has a similar potential to stimulate osteolytic cytokine release from macrophages. Functional biological activity was significantly lower for the patellofemoral joint compared with the tibiofemoral joint. Functional biological activity was significantly lower for the patellofemoral joint compared with the fixed bearing and rotating platform total knee replacement devices. However, as patellar resurfacing is commonly fitted as part of a total knee replacement system, this results in a 20% increase in overall functional biological activity for the system. Therefore, implanting a patellar resurfacing will increase the potential for osteolysis in the knee.

An alternative route to dye-polymer complexation study using asymmetrical flow field-flow fractionation.

The goal of the present work is to apply the versatile asymmetrical flow field-flow fractionation (AF4) coupled to UV and light scattering detection for the characterization of hyperbranched poly(ethylene imine) decorated with maltose shell (PEI-Mal) and the polar dye Rose Bengal (RB) in respect to their complexation behaviour. The quantitative determination of the non-complexed dye was carried out using the ultra-filtration effect of AF4 during the focussing phase, whereas the non-bound RB is filtrated and transported out of the channel while the complex of RB and PEI-Mal remains inside. A calibration with UV detector (550 nm) was established and different parameters (e.g. membrane material, molecular weight cut-off and stability of both, pure RB and RB@PEI-Mal complexes in solution) were investigated and verified. Successful reproducibility tests were performed. First complexation studies with the developed method were applied successfully with different mixture compositions of RB and PEI-Mal.

Adsorption interaction parameter of polyethers in ternary mobile phases: the critical adsorption line.

It is shown that in LC of polymers, the interaction parameter in ternary mobile phases can be described by a plane, which is determined by the dependencies in binary mobile phases. Instead of a critical adsorption point, critical conditions are observed along a straight line of composition between the two critical points in binary mobile phases. Consequently, a separation of block copolymers under critical conditions for one block by an adsorption mechanism for the other block can be achieved in ternary mobile phases of different compositions, which allows an adjustment of the retention of the adsorbing block.

Identification of nanometre-sized ultra-high molecular weight polyethylene wear particles in samples retrieved in vivo.

Nanometre-sized particles of ultra-high molecular weight polyethylene have been identified in the lubricants retrieved from hip simulators. Tissue samples were taken from seven failed Charnley total hip replacements, digested using strong alkali and analysed using high-resolution field emission gun-scanning electron microscopy to determine whether nanometre-sized particles of polyethylene debris were generated in vivo. A randomised method of analysis was used to quantify and characterise all the polyethylene particles isolated. We isolated nanometre-sized particles from the retrieved tissue samples. The smallest identified was 30 nm and the majority were in the 0.1 microm to 0.99 microm size range. Particles in the 1.0 microm to 9.99 microm size range represented the highest proportion of the wear volume of the tissue samples, with 35% to 98% of the total wear volume comprised of particles of this size. The number of nanometre-sized particles isolated from the tissues accounted for only a small proportion of the total wear volume. Further work is required to assess the biological response to nanometre-sized polyethylene particles.

Preparation and properties of electrophoretic microcapsules for electronic paper.

This paper shows two types of microcapsules used for electrophoretic display. One is prepared by in-situ polymerization which is based on urea, melamine and formaldehyde and another by complex coacervation, which is composed of gelatin and gum Arabic. Microcapsules attract interests of many research groups for longer lifetime of electrophoretic display by reducing agglomerization or lateral movements of nanoparticles. The gelatin microcapsules were more attractive in providing more uniform microcapsule coverage on electrodes due to their flexibility as compared to the melamine-urea microcapsules. The properties of microcapsules were characterized by FTIR, OM, SEM and TGA. Migration of nanoparticles in the two types of microcapsules was also observed when an electric field was applied.

Characterization of high molecular weight polyethylenes using high temperature asymmetrical flow field-flow fractionation with on-line infrared, light scattering, and viscometry detection.

High temperature asymmetrical flow field-flow fractionation (HTAF4) coupled to infrared (IR), multi-angle light scattering (MALS), and viscometry (Visc) detection is introduced as a tool for the characterization of high molecular weight polyethylenes. The high molecular weight fraction strongly affects the rheological behaviour and processability of polyethylene materials and can often not be accurately resolved by current technology such as high temperature size-exclusion chromatography (HTSEC). Molecular weight (M), radius of gyration (Rg), and intrinsic viscosity [eta] of linear high density polyethylene (HDPE) and branched low density polyethylene (LDPE) samples are studied in detail by HTAF4 and are compared to HTSEC. HTAF4 showed a better separation and mass recovery than HTSEC for very high molecular weight fractions in HDPE and LDPE samples. As no stationary phase is present in an HTAF4 channel, the technique does not show the typical drawbacks associated with HTSEC analysis of high molecular weight polyethylenes, such as, exclusion effects, shear degradation, and anomalous late elution of highly branched material. HTAF4 is applied to study the relation between the molecular weight and the zero shear viscosity eta0 for high molecular weight HDPE. It was found that the zero shear viscosity values predicted from HTAF4 results are in good qualitative agreement with measured values obtained from dynamic mechanical spectroscopy (DMS) experiments, whereas eta0 values predicted from HTSEC do not show a strong correlation. The low molecular weight cutoff of HTAF4 is approximately 5x10(4) as a result of relatively large pores in the HTAF4 channel membrane. HTAF4 is, therefore, currently not suited to analyze low molecular weight materials.

Isolation and characterization of UHMWPE wear particles down to ten nanometers in size from in vitro hip and knee joint simulators.

There is currently considerable interest in the wear debris and osteolytic potential of different types of bearings used in total joint replacements. The biological activity of the wear debris is dependent on the size and volume of the particles produced. Wear volume also plays an important role in the functional biological activity of a joint replacement. In vitro studies have shown that crosslinking of ultra high molecular weight polyethylene (UHMWPE) acetabular cups and tibial trays produces a reduction in wear volume, and crosslinking has now been introduced clinically for both types of prostheses. Previous studies have identified both micron and submicron-sized polyethylene wear particles. The aim of this study was to characterize the wear and wear particles generated from moderately crosslinked GUR 1,020 GVF UHMWPE acetabular cups and tibial trays in hip and knee joint wear simulators down to 10 nanometers in size. The wear rates of the two prosthesis types were very similar at 25.6 +/- 5.3 mm(3) per million cycles for the hip prostheses and 22.75 +/- 5.95 mm(3) per million cycles for the knee prostheses. Nanometer-sized wear particles were isolated and characterized from both hip and knee simulator lubricants for the first time. Significantly higher numbers (p < 0.05) of particles in the nanometer (<0.1 microm) size range were produced by the hip prostheses compared to the knee prostheses. The knee prostheses produced larger particles, with the mode of particle size in the 0.1-1.0 microm size range, compared to <0.1 microm size range for the hip prostheses. In addition, the knee prostheses produced a greater volumetric concentration of wear particles in the 1.0-10 microm size range, and consequently lower specific biological activity and functional biological activity indices. These results indicated that the knee prostheses had a lower osteolytic potential compared to the hip prostheses.

Predictive functional control (PFC) and its application in chlorinated polyethylene process.

The main principle and the characteristic of Predictive Functional Control (PFC) strategy are presented in this paper and the corresponding control system aid design software APC-PFC is also introduced. For a chlorinated polyethylene (CPE) process, a design scheme of cascade predictive functional control system is described and the control performance is improved obviously.

Mechanical integrity of compression-moulded ultra-high molecular weight polyethylene: effects of varying process conditions.

Ultra-high molecular weight polyethylene (UHMWPE) bearing surfaces in knee and hip prostheses are frequently manufactured by direct compression moulding of the as-polymerised powder. A study was made of the important role of the temperature-time sequence in the melt state during processing, in determining the mechanical integrity of mouldings at 37 degrees C. Structural features were determined by calorimetry (for the degree of crystallinity), infra-red spectroscopy (for the degree of oxidation), density measurement, and scanning electron microscopy. Mechanical integrity was assessed by tensile tests at a constant nominal strain-rate of 10(-3) s(-1), with post-failure microscopic examination. For the whole range of melt temperatures 145-200 degrees C and times 10-90 min, essentially the same stress-strain path was followed, reflecting invariance of the degree of crystallinity. However, there were dramatic changes in elongation-to-break, from ca 10% for some mouldings at 145 degrees C to a mean of 560% at 175 degrees C where, at the 86% confidence level, there was evidence for a peak. The rise was explained by microscopy, that revealed two distinct types of fusion defect, of reducing severity with increasing temperature. Type 1 defects were voids arising from incomplete powder compaction, and persisted up to 165 degrees C. Type 2 defects were regions of enhanced deformability at inter-particle boundaries in apparently fully compacted mouldings, evidenced microscopically by localised relative displacements at particle interfaces, during the plastic deformation at 37 degrees C. They persisted up to 200 degrees C. Type 2 defects may be attributed to the slow self-diffusion of UHMWPE in the melt, leading to incomplete homogenisation. even after compaction is complete. The level of oxidation in the mouldings was small but rose with melt temperature, explaining the fall in elongation-to-break at temperatures higher than 175 degrees C.

Separation and characterization of polyethylene wear debris from synovial fluid and tissue samples of revised knee replacements.

A study was made of in vivo-generated polyethylene wear particles as separated from synovial fluid samples and from tissue samples surrounding total knee arthroplasty. A comparison of particle size and morphology between the two particle groups was made to assess any effects of selective tissue capture, and macrophage encapsulation and digestion. In addition, a Raman spectroscopy technique was evaluated that enables positive identification of individual wear particles. The particles of the same size range found in the synovial fluid and tissue samples exhibited a comparable morphology. Notably, submicron-sized debris was present in both the synovial fluid and tissue samples surrounding knees with osteolysis. The novel micro-Raman analysis of individual particles was successful in the categorizing of wear debris as polyethylene or nonpolyethylene.

Isolation of predominantly submicron-sized UHMWPE wear particles from periprosthetic tissues.

A method of tissue digestion using sodium hydroxide was applied to the isolation and recovery of ultra-high-molecular-weight polyethylene (UHMWPE) particles from tissues around failed total hip replacements. Density gradient ultracentrifugation of the digested tissues was performed to separate the UHMWPE from cell debris and other particulates. Fourier transform infrared spectroscopy and differential scanning calorimetry (DSC) verified that the recovered particles were UHMWPE. When viewed by scanning electron microscopy, individual particles were clearly observed and were either rounded or elongated. The majority were submicron in size. The application of this method to the study of particles from periprosthetic tissues may elucidate aspects of biomaterial particle size and shape that are important to the biologic response to, and clinical outcome of, total joint replacement.

Molecular weight distribution of a bulk ultra-high molecular weight polyethylene product--impax 5M + UHMW-NAT.

A bulk ultra-high molecular weight polyethylene product, IMPAX 5M + UHMW-NAT, was fractionated using an increasing-temperature sequential-extraction technique. In the presence of an inert atmosphere and an antioxidant, 5 g of material were methodically dissolved in decahydronaphthalene over the temperature range, 80-191 degrees C. Initially, intrinsic viscosities were measured in decalin at 135 degrees C by single point capillary viscometry. From this data the viscosity average molecular weights were estimated using a logarithmic expression. Results showed that the intrinsic viscosities (molecular weights) increased linearly with extraction temperature over a range from 10 to 40 dL/g (1 to 8 X 10(6)) and that the molecular weight distribution was log normal. Mass balances both before and after extraction indicated that less than 0.3% of the material had a molecular weight less than 10(6) and that less than 0.1% of the material was gel. Zero shear viscometry of bulk fractionated polymer and powdered whole polymers confirmed that capillary viscometry increasingly underestimates the true intrinsic viscosities as the polymer chain lengths (molecular shear forces) increase. Indeed, the actual molecular weights ranged from about 2-14 X 10(6). Knowledge of the molecular weight distribution of bulk products and the presence of either volatiles or crosslinked networks is critical for the continued design and development of superior wearing and fatigue-resistant implants.