Method for Simultaneously improving the thermal stability and mechanical properties of poly(lactic acid): effect of high-energy electrons on the morphological, mechanical, and thermal properties of PLA/MMT nanocomposites.

Nanocomposites derived from poly(lactic acid) (PLA) and organically modified montmorillonite (oMMT) have been cross-linked by high-energy electrons in the presence of triallyl cyanurate (TAC). The morphology of untreated and cross-linked PLA/MMT nanocomposites was characterized by wide-angle X-ray scattering (WAXS) and transmission electron microscopy (TEM). This treatment can improve both the thermal stability and the glass-transition temperatures of the PLA nanocomposites (e.g., PLA-MMT-TAC 30kGy, 50kGy, and 70kGy) because of the formation of cross-linking structures in the nanocomposites that will considerably reduce the mobility of polymers. Interestingly, at relatively low irradiation doses (e.g., 30 and 50 kGy) a good balance between tensile strength and elongation at break for the PLA nanocomposites could be achieved. These mechanical properties are superior to those of pure PLA. Therefore, combining nanotechnology and electron beam cross-linking is a promising new method of simultaneously improving the mechanical properties (toughness and tensile strength) and thermal stability of PLA.

Sterilization with electron beam irradiation influences the biomechanical properties and the early remodeling of tendon allografts for reconstruction of the anterior cruciate ligament (ACL).

Although allografts for anterior cruciate ligament (ACL) replacement have shown advantages compared to autografts, their use is limited due to the risk of disease transmission and the limitations of available sterilization methods. Gamma sterilization has shown detrimental effects on graft properties at the high doses required for sufficient pathogen inactivation. In our previous in vitro study on human patellar tendon allografts, Electron beam (Ebeam) irradiation showed less detrimental effects compared to gamma sterilization (Hoburg et al. in Am J Sports Med 38(6):1134-1140, 2010). To investigate the biological healing and restoration of the mechanical properties of a 34 kGy Ebeam treated tendon allograft twenty-four sheep underwent ACL replacement with either a 34 kGy Ebeam treated allograft or a non-sterilized fresh frozen allograft. Biomechanical testing of stiffness, ultimate failure load and AP-laxity as well as histological analysis to investigate cell, vessel and myofibroblast-density were performed after 6 and 12 weeks. Native sheep ACL and hamstring tendons (HAT, each n = 9) served as controls. The results of a previous study analyzing the remodeling of fresh frozen allografts (n = 12) and autografts (Auto, n = 18) with the same study design were also included in the analysis. Statistics were performed using Mann-Whitney U test followed by Bonferroni-Holm correction. Results showed significantly decreased biomechanical properties during the early remodeling period in Ebeam treated grafts and this was accompanied with an increased remodeling activity. There was no recovery of biomechanical function from 6 to 12 weeks in this group in contrast to the results observed in fresh frozen allografts and autografts. Therefore, high dose Ebeam irradiation investigated in this paper cannot be recommended for soft tissue allograft sterilization.

Inactivation Effect of Standard and Fractionated Electron Beam Irradiation on Enveloped and Non-Enveloped Viruses in a Tendon Transplant Model.

BACKGROUND: For increasing allograft tendon safety in reconstructive surgery, an effective sterilization method achieving sterility assurance including viruses without impairing the grafts properties is needed. Fractionated Electron Beam (Ebeam) has shown promising in vitro results. The proof of sufficient virus inactivation is a central part of the process validation. METHODS: The Ebeam irradiation of the investigated viruses was performed in an optimized manner (oxygen content < 0.1%, -78 °C). Using principles of a tendon model the virus inactivation kinetics for HIV-2, HAV, pseudorabies virus (PRV) and porcine parvovirus (PPV) were calculated as TCID(50)/ml and D(10) value (kGy) for the fractionated (10 × 3.4 kGy) and the standard (1 × 34 kGy) Ebeam irradiation. RESULTS: All viruses showed comparable D(10) values for both Ebeam treatments. For sufficient virus titer reduction of 4 log(10) TCID(50)/ml, a dose of 34 kGy of the fractionated Ebeam irradiation was necessary in case of HIV-2, which was the most resistant virus investigated in this study. CONCLUSION: The fractionated and the standard Ebeam irradiation procedure revealed comparable and sufficient virus inactivation capacities. In combination with the known good biomechanical properties of fractionated Ebeam irradiated tendons, this method could be a safe and effective option for the terminal sterilization of soft tissue allografts.

Development of multifunctional highly-efficient bio-based fire-retardant poly(lactic acid) composites for simultaneously improving thermal, crystallization and fire safety properties.

Currently, it is still a huge challenge to prepare high performance eco-friendly poly(lactic acid) (PLA) with high thermal stability, good processability, excellent crystallization behavior, good transparency and highly-efficient fire safety. In this paper, a novel bio-based nucleation agent N-(furan-2-ylmethyl)-P,P-diphenylphosphinic amide (FPPA) was prepared and used for the fabrication of fire safety PLA/FPPA composites. The chemical structure of FPPA was measured by FTIR, NMR and MS. Further, the crystallization behavior, thermal stability, fire safety and mechanical properties of PLA/FPPA composites were performed by TGA, DSC, polarization microscope, LOI, UL94, cone calorimeter, DMA and, SEM, Raman, GC-MS, and TGA-FTIR. The results showed that the multifunctional FPPA not only had a high thermal stability and was a good nucleation agent for PLA. Moreover, only loading of 3 wt% FPPA increased the LOI of PLA from 19.0 to 33.8 % with UL-94 V-0 classification. Furthermore, the heat release rate and total heat release values of PLA/3%FPPA composite reduced by 6.3 % and 15.3 % in cone-calorimeter test. Such high fire safety was mainly attributed to specific fire safety radicals due to thermal degradation of FPPA to interrupt composites burning in gas phase. Besides, transparency and mechanical properties were almost not changed because of low loading of FPPA in PLA. This multifunctional bio-based fire-retardant for PLA with good comprehensive performance promises broad application in engineering electronics, automobiles, 3D printing and construction materials.

Laccase-Enzyme Treated Flax Fibre for Use in Natural Fibre Epoxy Composites.

Natural fibres have a high potential as reinforcement of polymer matrices, as they combine a high specific strength and modulus with sustainable production and reasonable prices. Modifying the fibre surface is a common method to increase the adhesion and thereby enhance the mechanical properties of composites. In this study, a novel sustainable surface treatment is presented: the fungal enzyme laccase was utilised with the aim of covalently binding the coupling agent dopamine to flax fibre surfaces. The goal is to improve the interfacial strength towards an epoxy matrix. SEM and AFM micrographs showed that the modification changes the surface morphology, indicating a deposition of dopamine on the surface. Fibre tensile tests, which were performed to check whether the fibre structure was damaged during the treatment, showed that no decrease in tensile strength or modulus occurred. Single fibre pullout tests showed a 30% increase in interfacial shear strength (IFSS) due to the laccase-mediated bonding of the coupling agent dopamine. These results demonstrate that a laccase + dopamine treatment modifies flax fibres sustainably and increases the interfacial strength towards epoxy.

Polymer Electrolyte Membranes Prepared by Graft Copolymerization of 2-Acrylamido-2-Methylpropane Sulfonic Acid and Acrylic Acid on PVDF and ETFE Activated by Electron Beam Treatment.

Polymer electrolyte membranes (PEM) for potential applications in fuel cells or vanadium redox flow batteries were synthesized and characterized. ETFE (poly (ethylene-alt-tetrafluoroethylene)) and PVDF (poly (vinylidene fluoride)) serving as base materials were activated by electron beam treatment with doses ranging from 50 to 200 kGy and subsequently grafted via radical copolymerization with the functional monomers 2-acrylamido-2-methylpropane sulfonic acid and acrylic acid in aqueous phase. Since protogenic groups are already contained in the monomers, a subsequent sulfonation step is omitted. The mechanical properties were studied via tensile strength measurements. The electrochemical performance of the PEMs was evaluated by electrochemical impedance spectroscopy and fuel cell tests. The proton conductivities and ion exchange capacities are competitive with Nafion 117, the standard material used today.

A New Way of Toughening of Thermoset by Dual-Cured Thermoplastic/Thermosetting Blend.

The work aims at establishing the optimum conditions for dual thermal and electron beam curing of thermosetting systems modified by styrene/butadiene (SB)-based triblock copolymers in order to develop transparent and toughened materials. The work also investigates the effects of curing procedures on the ultimate phase morphology and mechanical properties of these thermoset⁻SB copolymer blends. It was found that at least 46 mol% of the epoxidation degree of the SB copolymer was needed to enable the miscibility of the modified block copolymer into the epoxy resin. Hence, an electron beam curing dose of ~50 kGy was needed to ensure the formation of micro- and nanostructured transparent blends. The micro- and nanophase-separated thermosets obtained were analyzed by optical as well as scanning and transmission electron microscopy. The mechanical properties of the blends were enhanced as shown by their impact strengths, indentation, hardness, and fracture toughness analyses, whereby the toughness values were found to mainly depend on the dose. Thus, we have developed a new route for designing dual-cured toughened micro- and nanostructured transparent epoxy thermosets with enhanced fracture toughness.

Evaluation of Electron Induced Crosslinking of Masticated Natural Rubber at Different Temperatures.

In this work, natural rubber (NR) was masticated using an internal mixer to fit the requirements of reactive blending with polylactide and characterized by size exclusion chromatography (SEC), Fourier-transform infrared (FT-IR) spectroscopy and dynamic rheology measurements. Subsequently, the effect of elevated temperatures (25 °C, 80 °C, and 170 °C) on the electron beam (EB) induced crosslinking and degradation of masticated natural rubber (mNR) in a nitrogen atmosphere without adding crosslinking agents has been investigated. The sol gel investigation showed that the gel dose of mNR slightly increased with increasing irradiation temperature, which is also confirmed by the swelling test. The chain scission to crosslinking ratio (Gs/Gx) was found to be less than 1 for irradiated mNR at 25 °C and 80 °C, suggesting a dominating crosslinking behavior of mNR. However, a significant increase of Gs/Gx ratio (~1.12) was observed for mNR irradiated at 170 °C due to the enhanced thermal degradation behavior at high temperature. A remarkably improved elasticity (higher complex viscosity, higher storage modulus, and longer relaxation time) for EB modified mNR was demonstrated by dynamic rheological analysis. Particularly, the samples modified at higher temperatures represented more pronounced elasticity behavior which resulted from the higher number of branches and/or the longer branched chains.

Why Should the "Alternative" Method of Estimating Local Interfacial Shear Strength in a Pull-Out Test Be Preferred to Other Methods?

One of the most popular micromechanical techniques of determining the local interfacial shear strength (local IFSS, τd) between a fiber and a matrix is the single fiber pull-out test. The τd values are calculated from the characteristic forces determined from the experimental force⁻displacement curves using a model which relates their values to local interfacial strength parameters. Traditionally, the local IFSS is estimated from the debond force, Fd, which corresponds to the crack initiation and manifests itself by a "kink" in the force⁻displacement curve. However, for some specimens the kink point is hardly discernible, and the "alternative" method based on the post-debonding force, Fb, and the maximum force reached in the test, Fmax, has been proposed. Since the experimental force⁻displacement curve includes three characteristic points in which the relationship between the current values of the applied load and the crack length is reliably established, and, at the same time, it is fully determined by only two interfacial parameters, τd and the interfacial frictional stress, τf, several methods for the determination of τd and τf can be proposed. In this paper, we analyzed several theoretical and experimental force⁻displacement curves for different fiber-reinforced materials (thermoset, thermoplastic and concrete) and compared all seven possible methods of τd and τf calculation. It was shown that the "alternative" method was the most accurate and reliable one, while the traditional approach often yielded the worst results. Therefore, we proposed that the "alternative" method should be preferred for the experimental force⁻displacement curves analysis.

Enhanced Interfacial Shear Strength and Critical Energy Release Rate in Single Glass Fiber-Crosslinked Polypropylene Model Microcomposites.

Continuous glass fiber-reinforced polypropylene composites produced by using hybrid yarns show reduced fiber-to-matrix adhesion in comparison to their thermosetting counterparts. Their consolidation involves no curing, and the chemical reactions are limited to the glass fiber surface, the silane coupling agent, and the maleic anhydride-grafted polypropylene. This paper investigates the impact of electron beam crosslinkable toughened polypropylene, alkylene-functionalized single glass fibers, and electron-induced grafting and crosslinking on the local interfacial shear strength and critical energy release rate in single glass fiber polypropylene model microcomposites. A systematic comparison of non-, amino-, alkyl-, and alkylene-functionalized single fibers in virgin, crosslinkable toughened and electron beam crosslinked toughened polypropylene was done in order to study their influence on the local interfacial strength parameters. In comparison to amino-functionalized single glass fibers in polypropylene/maleic anhydride-grafted polypropylene, an enhanced local interfacial shear strength (+20%) and critical energy release rate (+80%) were observed for alkylene-functionalized single glass fibers in electron beam crosslinked toughened polypropylene.

Preparation of Polymer Electrolyte Membranes via Radiation-Induced Graft Copolymerization on Poly(ethylene-alt-tetrafluoroethylene) (ETFE) Using the Crosslinker N,N'-Methylenebis(acrylamide).

Polymer electrolyte membranes (PEM) prepared by radiation-induced graft copolymerization are investigated. For this purpose, commercial poly(ethylene-alt-tetrafluoroethylene) (ETFE) films were activated by electron beam treatment and subsequently grafted with the monomers glycidyl methacrylate (GMA), hydroxyethyl methacrylate (HEMA) and N,N'-methylenebis(acrylamide) (MBAA) as crosslinker. The target is to achieve a high degree of grafting (DG) and high proton conductivity. To evaluate the electrochemical performance, the PEMs were tested in a fuel cell and in a vanadium redox-flow battery (VRFB). High power densities of 134 mW∙cm-2 and 474 mW∙cm-2 were observed, respectively.

Online Structural-Health Monitoring of Glass Fiber-Reinforced Thermoplastics Using Different Carbon Allotropes in the Interphase.

An electromechanical response behavior is realized by nanostructuring the glass fiber interphase with different highly electrically conductive carbon allotropes like carbon nanotubes (CNT), graphene nanoplatelets (GNP), or conductive carbon black (CB). The operational capability of these multifunctional glass fibers for an online structural-health monitoring is demonstrated in endless glass fiber-reinforced polypropylene. The electromechanical response behavior, during a static or dynamic three-point bending test of various carbon modifications, shows qualitative differences in the signal quality and sensitivity due to the different aspect ratios of the nanoparticles and the associated electrically conductive network densities in the interphase. Depending on the embedding position within the glass fiber-reinforced composite compression, shear and tension loadings of the fibers can be distinguished by different characteristics of the corresponding electrical signal. The occurrence of irreversible signal changes during the dynamic loading can be attributed to filler reorientation processes caused by polymer creeping or by destruction of electrically conductive paths by cracks in the glass fiber interphase.

Effect of electron beam irradiation on biomechanical properties of patellar tendon allografts in anterior cruciate ligament reconstruction.

BACKGROUND: Sterilization of anterior cruciate ligament (ACL) allografts is an important prerequisite to prevent disease transmission. However, mechanical tissue properties are compromised by most current sterilization procedures, so that uncompromised sterilization of allografts is difficult to achieve. Hypothesis/ PURPOSE: The aim of this study was to evaluate the effect of the novel electron beam sterilization procedure on the biomechanical properties of human patellar tendon allografts at various irradiation dosages. Electron beam sterilization may be an appropriate alternative to gamma sterilization. STUDY DESIGN: Controlled laboratory study. METHODS: Thirty-two human 10-mm wide bone-patellar tendon-bone grafts were randomized into 4 groups of sterilization with 15, 25, or 34 kGy of electron beam irradiation, respectively. The grafts' biomechanical properties were evaluated at time zero. Unsterilized grafts functioned as controls. Biomechanical properties were analyzed during cyclic and load-to-failure testing. RESULTS: Strain and cyclic elongation response showed no significant differences between the groups. Electron beam irradiation had no significant effect on stiffness and failure load with the exception of 34 kGy, which resulted in a significant decrease in failure load (1300.6 +/- 229.2 N) compared with unsterilized grafts (1630.5 +/- 331.1 N). CONCLUSION: This study showed that electron beam might be an appropriate alternative in sterilization of patellar tendon allografts with minimal effect on mechanical properties of tendon grafts in vitro. Future studies will have to evaluate the effect of the process on the biological properties of allografts in vitro and in vivo. CLINICAL RELEVANCE: Terminal sterilization of patellar tendon allografts with electron beam irradiation can ensure higher safety of transplanted grafts and hence improve patient safety and acceptance.

Melt spinning of poly(3-hydroxybutyrate) for tissue engineering using electron-beam-irradiated poly(3-hydroxybutyrate) as nucleation agent.

Electron-beam-irradiated poly(3-hydroxybutyrate) was used as a nucleating agent for poly(3-hydroxybutyrate) in a melt-spinning process. Molecular data and thermal properties of the irradiated samples were determined. The thermal properties of the nucleated melts were determined to assess the influence of the nucleation agents, and then spinning tests were carried out. Thermal and textile properties of the spun fibers were also determined. Estimations of the improvement of the crystallization in the spinline and of the inhibition of secondary crystallization in the fibers from the use of the described blood-compatible nucleation agents are given.

Immobilization of a hyperbranched polyester via grafting-to and electron beam irradiation.

Stable thin films of an aromatic-aliphatic hyperbranched polyester with hydroxyl groups were fabricated on silicon substrates using electron beam irradiation and a grafting-to approach. We present a detailed study on the influence of the dose, dose rate, and temperature on the film properties and degradation behavior of the polyester immobilized by electron beam irradiation. A patterned polyester film was prepared on the substrate using a masking technique. In the second part of this work, we report on a method for the strong binding of the hyperbranched polyester onto the surface of an "activated" silicon substrate without using any coupling agent. The results are compared with the grafting-to of the hydroxyl-terminated polyester using thin PGMA anchoring layers ( Reichelt et al. Macromol. Symp. 2007, 254, 240- 247 ). The optimal conditions and mechanism of the anchoring procedures were investigated. The surface and film properties of all immobilized polymer films were characterized by atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), electrokinetic measurements, contact-angle measurements by drop-shape analysis, spectroscopic and imaging ellipsometry, and infrared spectroscopy. It is shown that all immobilization methods can be optimized in such a way that the polymer surface properties remain unchanged compared to those of nongrafted polyesters.

Structural changes of UHMWPE after e-beam irradiation and thermal treatment.

Ultra-high molecular weight polyethylene (UHMWPE) was irradiated with accelerated electrons (1 MeV in air) using high dose rates (> 25 kGy/min) and thin specimens (thickness 1 mm). Parts of the specimens were remelted (200 degrees C for 10 min; 150 degrees C for 0, 2, 10, 30, 60 min). All specimens were stored in nitrogen in the dark at 5 degrees C. Supermolecular structure, extent of crosslinking, oxidative degradation, and macroradical content were studied by a number of methods (SAXS, WAXS, SEM, DSC, FTIR, ESR, TGA, solubility experiments, image analysis). The results obtained with irradiated samples were compared with those obtained with irradiated and remelted samples. It was confirmed that crosslinking predominates over chain scission at very high dose rates, even if the irradiation is performed in air. Discrepancies concerning supermolecular structure changes in UHMWPE after irradiation and thermal treatment, found in various studies in the literature, are discussed. A simple model, which describes and explains all supermolecular structure changes, is introduced. An effective way of eliminating residual macroradicals in UHMWPE is proposed.

Electron beam irradiation of poly(vinyl methyl ether) films: 1. Synthesis and film topography.

Temperature-sensitive hydrogel layers on silicon (Si) substrates were synthesized by electron beam irradiation of spin-coated poly(vinyl methyl ether) (PVME) films. The influences of the used solvent, the polymer concentration, and the spinning velocity on the homogeneity and the thickness of the PVME film were investigated. In the range of concentration c(p) = 1-15 wt% PVME in ethanol solution, homogeneous films with a thickness between d = 50 nm and 1.7 mum were obtained. The films were cross-linked by electron beam irradiation under inert atmosphere and analyzed by sol-gel-analysis. The results were compared with bulkgels formed by electron beam irradiation of PVME in the dry state. The film topography was analyzed by high-resolution field emission scanning electron microscopy and atomic force microscopy. An islandlike structure in the dry, swollen, and shrunken state of the hydrogel films was observed.

Effect of gamma irradiation on human cortical bone transplants contaminated with enveloped and non-enveloped viruses.

In the production of bone grafts intended for transplantation, basic safety measures to avoid the transmission of pathogens are selection and serological screening of donors for markers of virus infections. As an additional safety tool we investigated the effect of gamma irradiation on the sterility of human bone diaphysis transplants and evaluated its impact on the virus safety of transplants. Model viruses were included in the study to determine the dose necessary to achieve a reduction factor for the infectivity titres of at least 4 log(10) at a temperature of -30+/-5 degrees C. The following viruses were used: human immunodeficiency virus type 2 (HIV-2), hepatitis A virus (HAV), and poliovirus (PV-1), and the following model viruses: pseudorabies virus (PRV) as a model for human herpesviruses, bovine viral diarrhoea virus (BVDV) for HCV, and bovine parvovirus (BPV) for parvovirus B19. A first approach was to determine the D(10) values (kGy) for the different viruses (virus inactivation kinetics: BPV 7.3; PV-1 7.1; HIV-2 7.1; HAV 5.3; PRV 5.3; BVDV <3.0 kGy). Based on these results, inactivation of these viruses was studied in experimentally contaminated human bone transplants (femoral diaphyses). For BPV, the most resistant one of the viruses studied, a dose of approximately 34 kGy was necessary to achieve a reduction of infectivity titres of 4 log(10). We therefore recommend a dose of 34 kGy for the sterilisation of frozen bone transplants.