Polymeric Medical Devices Research Articles

Evaluation of Post-Processing on Additive Manufactured Bioresorbable Polymers for Medical Devices.

Additive manufacturing (AM) has seen massive growth in the medical device sector and an increase in the clearance of devices. Many challenges still exist in the design, development, and clinical use of AM-fabricated devices, notably the processing, annealing, and sterilization of resorbable polymers. In addition, the use of these materials continues to grow in medical devices and scaffold technologies for tissue engineering and regenerative medicine (TERM). Specifically, this study focused on the scaffold mechanical properties post-processing and throughout a simulated resorption (in vitro) study. Herein, we evaluated three (3) materials that span a range of mechanical properties and degradation rates relating to a range of tissue healing rates and mechanical properties affording the opportunity of biomimetic potentials, Caproprene 100M, Lactoflex 7415, and Lactoprene 100M. These bioresorbable polymers were additively manufactured into scaffold forms of Type V tensile bars to investigate post-processing parameters. A range of heat treatments were then performed after the AM process to induce a range of semicrystalline morphologies, and subsequently, two different sterilization techniques were performed, one based on super critical carbon dioxide and another using electron beam radiation. It was statistically shown that the heat treatment parameters and the sterilization method had statistically significant effects on the scaffold properties of each material. While material differences were responsible for the majority of the mechanical property breadth, techniques utilizing analysis of variance allowed the observation of significant effects and interactions associated with heat treatment, sterilization, and material parameters (alpha = 0.05). The characterization of the sample groups provided insight into the process-structure-property-performance relationships of the resorbable scaffold samples. It was established that the post-processing impacted the scaffold structures, and therefore, sterilization and heat treatment selections should be included within initial design considerations alongside material selection as critical for device development, especially when AM bioresorbable scaffolds for TERM.

Accelerated In Vitro Oxidative Degradation Testing of Ultra-High Molecular Weight Polyethylene (UHMWPE).

Nonabsorbable polymers used in biomedical applications are assumed to be permanently stable based on short-term testing, but some may be susceptible to oxidative degradation over several years of implantation. Traditional in vitro oxidative degradation screenings employ hydrogen peroxide (H2O2) solutions. However, the inherent instability of H2O2 can compromise the consistency of oxidative conditions, especially over extended periods and at elevated temperatures used for accelerated testing. In this study, an automated reactive accelerated aging (aRAA) system, which integrates an electrochemical detection method and a feedback loop, was utilized to ensure precise control of H2O2 concentrations during polymer oxidative degradation testing. The reproducibility of the aRAA system was evaluated by comparing four identical setups. Its efficacy as an oxidation challenge was demonstrated on (i) medical-grade vitamin E (VE) blended ultra-high molecular weight polyethylene (UHMWPE) and (ii) highly crosslinked (HXL) UHMWPE as model materials. The aRAA-aged VE-UHMWPE and HXL-UHMWPE samples were also compared against samples aged via an existing accelerated aging standard, ASTM F2003-02(2022). Samples were analyzed using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy to calculate their oxidation index per ASTM F2102-17. We observed that the aRAA system was more effective in oxidizing VE-UHMWPE and HXL-UHMWPE than the traditional ASTM F2003-02(2022) method. By providing a standardized and reliable approach to assess polymer oxidative degradation, the aRAA system could enhance the accuracy of long-term stability predictions for nonresorbable polymers in medical devices.

Effect of ethylene oxide and gamma sterilization on surface texture of films and electrospun poly(ε-caprolactone-co-p-dioxanone) (PCLDX) scaffolds

In the field of tissue engineering, synthetic and degradable polyesters like poly(ε-caprolactone) (PCL) and poly(ε-caprolactone-co-p-dioxanone) (PCLDX) are widely used as scaffolds. Our previous research revealed that thermal storage conditions could alter the surface texture of PCL and PCLDX scaffolds, which might influence cell-scaffold interactions in tissue engineering applications. These findings highlighted the importance of multi-scale characterization techniques to identify the scales most sensitive to external changes and the need for personalized surface texture analysis. Sterilization techniques, such as ethylene oxide and gamma radiation, are essential for ensuring the sterility of polymeric medical devices. However, these processes can significantly impact the bulk polymer properties and/or surface texture of the scaffolds, potentially affecting their biocompatibility, safety, and overall performance. Therefore, the influence of sterilization processes on the surface texture of PCLDX films and electrospun nanofibers and to correlate these findings with the thermal and physical properties of the polymer are essential and have been assessed. Our results demonstrated that ethylene oxide maintained the structural integrity and surface texture of PCLDX scaffolds, while gamma irradiation caused a significant reduction in molar mass and increased the number of hills (Shn) and dales (Sdn) on PCLDX samples. Despite these changes, both sterilization methods showed minimal effects on the thermal properties, such as melting temperature and degree of crystallinity, and surface wettability of the scaffolds. This comprehensive surface texture analysis highlights the importance of evaluating feature parameters such as Shn and Sdn for optimizing the performance and biocompatibility of polymeric scaffolds in tissue engineering.

Gamma, electron beam and X-ray irradiation effects on polymers in an advanced bone cement mixer device

The medical device industry has been investigating ways to increase the use of alternatives to cobalt-60 gamma radiation and ethylene-oxide gas sterilization, such as electron beam (E-beam) and X-ray radiation, due to regulatory and market pressures. One impediment to switching to E-beam or X-ray technology for sterilization is the lack of data on the effects of these radiation sources on medical device polymers. To provide such data this work considers irradiation and testing of a common single-use medical bone cement mixing system, the Stryker Advanced Cement Mixer (ACM®), that is composed of seven polymer materials. The ACM® devices considered here were processed to sterilization-relevant doses (15, 25, 50, and 70 kGy) using three radiation technologies: gamma, E-beam, and X-ray. The system and its polymer components were tested for product functionality, as well as mechanical and visual properties to determine how exposure effects may be influenced by radiation technology and dose level. We found that although there were instances of statistically significant differences in effects between the gamma-irradiated products and those irradiated with E-beam and X-ray, those effects were negligible in terms of retained functionality of the product and retained mechanical properties of the polymer components. Overall, results of this study demonstrate that, for of the effects studied, E-beam and X-ray are viable alternatives to cobalt-60 gamma radiation for sterilization of the polymer-based device investigated.

Modeling Degradation Behavior of Biodegradable Polymers for Medical Devices: A Comparative Review of Phenomenological and Stochastic Approaches

Modeling Degradation Behavior of Biodegradable Polymers for Medical Devices: A Comparative Review of Phenomenological and Stochastic Approaches

Radiopacity Enhancements in Polymeric Implant Biomaterials: A Comprehensive Literature Review.

Polymers as biomaterials possess favorable properties, which include corrosion resistance, light weight, biocompatibility, ease of processing, low cost, and an ability to be easily tailored to meet specific applications. However, their inherent low X-ray attenuation, resulting from the low atomic numbers of their constituent elements, i.e., hydrogen (1), carbon (6), nitrogen (7), and oxygen (8), makes them difficult to visualize radiographically. Imparting radiopacity to radiolucent polymeric implants is necessary to enable noninvasive evaluation of implantable medical devices using conventional imaging methods. Numerous studies have undertaken this by blending various polymers with contrast agents consisting of heavy elements. The selection of an appropriate contrast agent is important, primarily to ensure that it does not cause detrimental effects to the relevant mechanical and physical properties of the polymer depending upon the intended application. Furthermore, its biocompatibility with adjacent tissues and its excretion from the body require thorough evaluation. We aimed to summarize the current knowledge on contrast agents incorporated into synthetic polymers in the context of implantable medical devices. While a single review was found that discussed radiopacity in polymeric biomaterials, the publication is outdated and does not address contemporary polymers employed in implant applications. Our review provides an up-to-date overview of contrast agents incorporated into synthetic medical polymers, encompassing both temporary and permanent implants. We expect that our results will significantly inform and guide the strategic selection of contrast agents, considering the specific requirements of implantable polymeric medical devices.

Connecting radiation-driven changes in structural, thermal, and mechanical properties in several medical device polymers

Stemming from security threats and shortages in supply, a recent push has emerged to expand alternatives to radioisotope Cobalt-60 gamma radiation for sterilization of polymeric medical products, including electron beam (E-beam) and X-ray machine-based sources. However, before large-scale implementation, the effects of these non-isotope-based methods must be thoroughly investigated from several perspectives, involving their potential detrimental effects on the structural, thermal, and mechanical properties of polymers in medical devices. This paper investigates such effects in commonly used medical device polymers, including polypropylene homopolymer (PPH), polyolefin elastomer (POE), low-density polyethylene (LDPE), acrylonitrile butadiene styrene (ABS), and chlorobutyl rubber (CIIR). To connect radiation-driven changes in polymer structural and thermal properties and corresponding changes in mechanical properties, several characterization techniques were utilized, including gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR), dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). We found that the tensile strength of X-ray irradiated PPH, as well as X-ray, E-beam, and gamma irradiated CIIR decreases due to chain scission, which is corroborated by GPC and DMA. The GPC results of LDPE suggest chain scission, but interestingly without a corresponding decline in tensile strength. By comparison, POE and ABS appear to undergo further crosslinking with increasing irradiation dose, which generally strengthens them. Importantly, in the vast majority of the cases, there were small to no changes in properties upon changing radiation technologies (at a given dose), i.e., no radiation source dependence. However, in a few specific cases, radiation method dependencies did arise, for instance, in terms of the molecular weight of PPH being significantly increased upon X-ray irradiation, while the melting temperature, glass transition temperature, and elongation at break reduced compared to gamma. Overall, this study provides valuable insight into radiation-driven chemical and structural changes in polymers that produce changes in physical and functional properties.

Microtopographic superhydrophobic polymer surface to prevent urinary tract infections causing nosocomial drug-resistant bacterial adhesion

Catheter-associated urinary tract infections (CAUTIs) are one of the most prevalent forms of healthcare-associated infections worldwide. Recurrent episodes of infections and development of antibiotic resistance/tolerance among biofilm-forming bacteria are well documented. We developed a simple method of making superhydrophobic micro-structured antibacterial polymer surfaces for coating-free catheters. A two-step fabrication approach was used to turn the hydrophobic polydimethylsiloxane (PDMS) into superhydrophobic surfaces. The nanosecond pulsed Nd:YAG laser was used to fabricate two types of structures (holes and grooves) on a steel mold. The soft-molding technique was adopted to replicate these structures on PDMS films. The pillar structured PDMS surface exhibited a water droplet contact angle (WDCA) of 169○ ± 3° with a low sliding angle of 12○, whereas the grooved surface had 142○ ± 5° contact angle. Moreover, the Luria Broth which is media for bacterial growth shows contact angle of 141○ ± 2° and 120○ ± 3°, respectively. Theoretically, the micro-pillar structures with selected dimensions could sustain the Cassie–Baxter state. The crystal violet binding assay was used to assess the anti-biofilm activity of structured surfaces (grooved and pillared) against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), as well as clinical isolates of Klebsiella pneumonia (K. pneumoniae), E. coli, and S. aureus. Furthermore, the attachment and interaction of bacteria with surfaces were investigated through filed emission scanning electronic microscope (FE-SEM) and confocal microscopy. Overall, the pillar-structured surface reduces the average bacterial attachment more efficiently than a grooved surface (>80% vs. >50% reduction) compared to a plain PDMS surface due to its higher water-repellent property. This work will give new insights into the development of coating-free, long-lasting antibacterial surfaces for polymeric medical devices.

Antimicrobial Agent against Methicillin-Resistant Staphylococcus aureus Biofilm Monitored Using Raman Spectroscopy.

The prevalence of antimicrobial-resistant bacteria has become a major challenge worldwide. Methicillin-resistant Staphylococcus aureus (MRSA)-a leading cause of infections-forms biofilms on polymeric medical devices and implants, increasing their resistance to antibiotics. Antibiotic administration before biofilm formation is crucial. Raman spectroscopy was used to assess MRSA biofilm development on solid culture media from 0 to 48 h. Biofilm formation was monitored by measuring DNA/RNA-associated Raman peaks and protein/lipid-associated peaks. The search for an antimicrobial agent against MRSA biofilm revealed that Eugenol was a promising candidate as it showed significant potential for breaking down biofilm. Eugenol was applied at different times to test the optimal time for inhibiting MRSA biofilms, and the Raman spectrum showed that the first 5 h of biofilm formation was the most antibiotic-sensitive time. This study investigated the performance of Raman spectroscopy coupled with principal component analysis (PCA) to identify planktonic bacteria from biofilm conglomerates. Raman analysis, microscopic observation, and quantification of the biofilm growth curve indicated early adhesion from 5 to 10 h of the incubation time. Therefore, Raman spectroscopy can help in monitoring biofilm formation on a solid culture medium and performing rapid antibiofilm assessments with new antibiotics during the early stages of the procedure.

Influence of Surface Texturing on the Dry Tribological Properties of Polymers in Medical Devices.

There is a constant need to improve patient comfort and product performance associated with the use of medical devices. Efforts to optimise the tribological characteristics of medical devices usually involve modifying existing devices without compromising their main design features and functionality. This article constitutes a state-of-the-art review of the influence of dry friction on polymeric components used in medical devices, including those having microscale surface features. Surface tribology and contact interactions are discussed, along with alternative forms of surface texturing. Evident gaps in the literature, and areas warranting future research are highlighted; these include friction involving polymer Vs polymer surfaces, information regarding which topologies and feature spacings provide the best performing textured surfaces, and design guidelines that would assist manufacturers to minimise or maximise friction under non-lubricated conditions.

Modeling extraction of medical device polymers for biocompatibility evaluation

Extraction testing is critical for biocompatibility evaluation of medical devices, whether to generate samples for biological testing or form the basis for toxicological risk assessment. However, it is not always clear how to compare extraction testing between different extraction conditions and sample geometries. We employ a physics-based model to elucidate the theoretical impact of extraction conditions, sample geometry and material properties on extraction efficiency (M/M0) and extract concentration (C/C0) for single–step and iterative/exhaustive extraction test methods. The model is specified by three parameters: thermodynamic contributions (Ψ), kinetic contributions (τ), and number of extraction iterations (N). We find that over the range of typical parameters for single–step extractions, M/M0 only approaches one (complete exhaustion) for relatively large values of Ψ (≥10) and τ(≥1). Further, the model suggests that test article geometry and solvent volume can have a dramatic and sometimes opposing effect on M/M0 and C/C0. Our results imply that iterative extractions can be approximated as a single–step extraction with scaled parameters Ψ′ = ΨN and τ′ = τN. The model provides a framework to reduce the biocompatibility evaluation test burden by optimizing test article and extraction condition selection and guiding development of new test protocols.

The Effect of Sub- and Near-Critical Carbon Dioxide Assisted Manufacturing on Medical Thermoplastic Polyurethane.

Incorporating thermally labile active pharmaceutical ingredients for manufacturing multifunctional polymeric medical devices is restricted due to their tendency to degrade in the hot melt extrusion process. In this study, the potential of sub- and near-critical carbon dioxide (CO2) as a reversible plasticiser was explored by injecting it into a twin-screw hot melt extrusion process of Pellethane thermoplastic polyurethane to decrease its melt process temperature. Its morphological, throughput, thermal, rheological, and mechanical performances were also evaluated. The resultant extrudates were characterised using scanning electron microscopy, parallel plate rotational rheometer, differential scanning calorimetry, thermogravimetric analysis, and tensile testing. The process temperature decreased from 185 to 160 °C. The rheology indicated that the reduction in melt viscosity was from 690 Pa.s to 439 Pa.s (36%) and 414 Pa.s (40%) at 4.14 and 6.89 MPa, respectively. The tensile modulus in the elastomeric region is enhanced from 5.93 MPa, without CO2 to 7.71 MPa with CO2 at both 4.14 and 6.89 MPa. The results indicate that the employment of both sub- and near-critical CO2 as a processing aid is a viable addition to conventional hot melt extrusion and that they offer more opportunities for thermosensitive drugs to be more stable in the molten stream of Pellethane thermoplastic polyurethane.

“Self-Defensive” Antifouling Zwitterionic Hydrogel Coatings on Polymeric Substrates

In biomedicine fields, biofouling can easily occur on devices such as sensors and catheters, causing some iatrogenic infections, which menace the lives and health of patients greatly. Therefore, it is of great significance to solve the problems of bacterial infection on the surfaces of medical devices. In this paper, "self-defensive" and antifouling zwitterionic hydrogel coatings were prepared by network interpenetration of the hydrogel and the polymeric substrates. The zwitterionic polysulfobetaine methacrylate (PSBMA) hydrogel coatings resisted most of the bacteria to adhere on the substrates. When a few bacteria were lucky to escape the antifouling defense and adhered to the coatings, gentamicin sulfate (GS) would be released under the trigger of a weakly acidic environment caused by bacterial metabolism to kill these bacteria. Simultaneously, the coatings of the bacteria-adhering sites would be degraded by hyaluronidase secreted by these bacteria and peeled off to remove the bacteria and renew the antifouling surfaces. The antifouling properties and mechanism of the self-defensive behavior of the hydrogel coatings on polymeric substrates were investigated. Furthermore, the in vitro and in vivo antibacterial performances, as well as the biocompatibility of the coatings, were demonstrated. The results suggested that the self-defensive antifouling zwitterionic hydrogel coatings hold great potential to be used on the surfaces of polymeric medical devices.

3D-Printed PLA Medical Devices: Physicochemical Changes and Biological Response after Sterilisation Treatments.

Polylactic acid (PLA) has become one of the most commonly used polymers in medical devices given its biocompatible, biodegradable and bioabsorbable properties. In addition, due to PLA’s thermoplastic behaviour, these medical devices are now obtained using 3D printing technologies. Once obtained, the 3D-printed PLA devices undergo different sterilisation procedures, which are essential to prevent infections. This work was an in-depth study of the physicochemical changes caused by novel and conventional sterilisation techniques on 3D-printed PLA and their impact on the biological response in terms of toxicity. The 3D-printed PLA physicochemical (XPS, FTIR, DSC, XRD) and mechanical properties as well as the hydrophilic degree were evaluated after sterilisation using saturated steam (SS), low temperature steam with formaldehyde (LTSF), gamma irradiation (GR), hydrogen peroxide gas plasma (HPGP) and CO2 under critical conditions (SCCO). The biological response was tested in vitro (fibroblasts NCTC-929) and in vivo (embryos and larvae wild-type zebrafish Danio rerio). The results indicated that after GR sterilisation, PLA preserved the O:C ratio and the semi-crystalline structure. Significant changes in the polymer surface were found after HPGP, LTSF and SS sterilisations, with a decrease in the O:C ratio. Moreover, the FTIR, DSC and XRD analysis revealed PLA crystallisation after SS sterilisation, with a 52.9% increase in the crystallinity index. This structural change was also reflected in the mechanical properties and wettability. An increase in crystallinity was also observed after SCCO and LTSF sterilisations, although to a lesser extent. Despite these changes, the biological evaluation revealed that none of the techniques were shown to promote the release of toxic compounds or PLA modifications with toxicity effects. GR sterilisation was concluded as the least reactive technique with good perspectives in the biological response, not only at the level of toxicity but at all levels, since the 3D-printed PLA remained almost unaltered.

Is Green Tea All It Is Brewed Up to Be? Our Results Suggest It May Not Be

Abstract Inflammation underlies multiple disorders, including cardiovascular disease, diabetes mellitus, and cancer. Naturally occurring compounds are being investigated for potential medicinal benefit in the treatment of multiple disorders. The published literature indicates that epigallocatechin gallate (EGCG), derived from green tea leaves, has antioxidant, anti-inflammatory, anti-cancer, and antimicrobial properties. Through a series of cell-culture-based assays, EGCG was determined to be strongly proinflammatory at 10 µM and cytotoxic at 50 µM, concentrations utilized in multiple published reports, in both vascular endothelial cells and monocyte-derived macrophages. Furthermore, EGCG suppressed wound healing in vascular endothelial cells at both 10 and 50 µM. A 1-µM EGCG treatment appeared to have no effect on vascular endothelial cells or monocyte-derived macrophages when carried out for less than 3 days. Concentrations of 1, 10, and 50 µM EGCG were assessed for the ability to promote the biocompatibility of polymers using a THP-1 cell adhesion assay and a Chandler Loop ex vivo model of blood perfusion using whole equine blood. No significant changes in the number of adhered cells were seen in either assay, suggesting that EGCG does not promote the biocompatibility of commonly used polymers in medical devices. Taken together, our results indicate that EGCG is proinflammatory at the concentrations assessed and not suitable as a therapy to promote biocompatibility.

Role of Simulated Body Fluid in Biofilm Formation and Growth on a Polycarbonate Material

Bacteria form biofilms to facilitate colonization, and biofilm formation on polymeric medical devices is a common cause of hospital-acquired infection. Simulated body fluid (SBF) is a supersaturated calcium-phosphate solution with ionic composition nearly equal to that of human blood plasma, and has been used to test the bioactivity of materials. The purpose of this work was to understand whether SBF influenced surface structure on bacterial adhesion and biofilm formation on polycarbonate, a polymer commonly used in medical devices. In this study, polycarbonate coupons were immersed in a SBF solution at 37 oC for 7 and 14 days and air-dried for 30 minutes, and compared with deionized water immersion. Colony biofilms of P. aeruginosa were then investigated by growing bacteria on top surface of immersed coupons for 24 and 48 hours, and observed by the quantitative assay (areal cell density) and visualized using a field emission scanning electron microscopy (FESEM). Results stated that a prolonged immersion time of coupons in deionized water enhanced biofilm growth. Immersion in SBF for a period of 14 days showed a significant reduction in the viability following 24 hours of incubation compared to that in deionized water incubated for 48 hours. FESEM further demonstrated that P. aeruginosa had a tendency to form biofilm on a polycarbonate substrate, and was able to develop biofilms on both the SBF and deionized water. Significant cell clusters and bacterial adhesion was observed at 48-hour incubation. These insights can potentially assist in the establishment of infection and colonization of this opportunistic pathogen, and will aid the development of strategies to prevent biofilm formation.

Multiblock copolymers type PDC - A family of multifunctional biomaterials for regenerative medicine1.

Multiblock copolymers type PDC are polyetheresterurethanes composed of poly(ɛ-caprolactone) and poly(p-dioxanone) segments. They were designed as degradadable shape-memory polymers for medical devices, which can be implanted minimally-invasively. While providing structural support in the initial phase after implantation, they are capable to modulate soft tissue regeneration while degradation. In this perspective, we elucidate cell-material interactions, compatibility both in-vitro and in-vivo and biofunctionality of PDC, which represents a promising candidate biomaterial family especially for cardiovascular applications.

Developing Echogenic Materials as Catheters for Use with Ultrasound.

Patients with peripherally inserted central catheters (PICCs) are routinely discharged with the catheters in place. These patients experience complications due to undetected thrombosis or accidental dislodgement, with tracking through limited X-ray imaging. Developing catheters with the capability to be tracked without the need for X-ray imaging would greatly benefit these patients by decreasing patient stress, reducing time to diagnosis, and increasing nursing home capabilities. This study reports on the incorporation of echogenic microspheres into catheters to produce bulk echogenic effects for developments in the field of real-time ultrasound tracking of polymeric medical devices. The impact on elastic modulus, ultrasound contrast, and cytocompatibility of the polymer was analyzed when incorporating up to 10 wt % glass microspheres. Up to this loading level, the elastic modulus was found to remain constant. However, at 10 wt %, extrusion defects due to agglomeration, air bubbles, and shearing were numerous and deemed detrimental to ultrasound imaging. Successful, defect-free samples were produced with 5 wt % microsphere loading and when embedded in a soft tissue phantom revealed a significant increase in the signal-to-noise ratio as compared to the polymer alone. Preliminary results have shown a successful increase in polymer's echogenic properties, without undermining its mechanical and cytocompatibility properties.

Relations Between Dynamic Localization and Solute Diffusion in Polymers.

Various public health concerns can arise from the unintended leaching of additives and impurities from polymeric medical devices or food packaging, which is directly related to each solute's diffusivity D. Both experimental and simulation methods can be used to quantify D, but slow diffusion at physiologic temperature in glassy polymers can render these approaches impractical. Here, we investigate a simulation approach with the potential to more rapidly calculate D. Specifically, we examine links between dynamic localization, characterized by the Debye-Waller factor, ⟨u2⟩, and D in a variety of polymer/solute systems using atomistic molecular dynamics (MD) simulations. Using short, high-temperature MD simulations to estimate D at physiologic temperature, we find that the relation ln D ∝ 1/⟨u2⟩ quantitatively predicts D for small solutes and produces an upper-bound estimate of D for larger solutes. Upper-bound estimates are useful in certain contexts, and we compare our results with another approach for determining upper bounds, the Piringer model, to show where each method may be useful. Then, we examine a modified relation where the Debye-Waller factor is rescaled by the mode coupling temperature Tc, which can produce better estimates of D if Tc is carefully chosen. Last, we compare our approach with several other models that relate temperature or localized dynamics with diffusivity. Although each of these approaches can be used to model D across wide temperature ranges using one or more adjustable parameters, none of them are truly predictive in glassy polymers. Further developments are needed to predict the optimal values of the adjustable parameters a priori.

Direct comparison of gamma, electron beam and X-ray irradiation doses on characteristics of low-density polyethylene, polypropylene homopolymer, polyolefin elastomer and chlorobutyl rubber medical device polymers

There is a growing need for increased efficiency in the sterilization of single use medical devices and other products that contain polymer components. Gamma radiation is widely used for devices suited for radiation sterilization; however, safety, throughput and cobalt-60 source availability are challenging the prospect of relying on gamma radiation to meet the anticipated needs of the industry. Use of electron beam (e-beam) and X-rays as alternatives to gamma for radiation sterilization have been hampered in part by a concern that these modalities may adversely affect polymer integrity and performance relative to the gamma method, for which the industry has had much more experience. To address this concern, the effects of sterilization-relevant doses of e-beam, X-ray and gamma radiation were directly compared using common medical device polymers found in two prototypical commercial devices currently sterilized using cobalt-60 gamma irradiation. The Becton, Dickinson and Company (BD) Vacutainer™ Plus tube contains low-density polyethylene and chlorobutyl rubber components, while the BD Vacutainer™ Push Button Blood Collection Set contains polypropylene homopolymer and polyolefin elastomer components. Injection-molded samples prepared from the polymers used in these products were exposed to target doses of 15, 35, 50 and 80 kGy using gamma, e-beam and X-ray radiation. Changes in coloration, tensile properties and hardness were measured for each condition, and the effects of e-beam and X-ray irradiation compared with the effects of gamma irradiation on these properties. Both e-beam and X-ray appear as viable alternatives to gamma irradiation for sterilization of the polymers tested.