Micro and macro approaches to tough polymers for composites

The progress to date on the development of techniques to toughen continuous thermoplastic composites is summarized. The work, using the approach of toughening the polycarbonate composite matrix with rubber particles, has focused on determining the differences between Double Cantilever Beam (DCB) samples molded inhouse and those molded by NASA. Specifically, an effort was made to account for the differences in fracture toughness observed between the various specimens. In addition, preliminary results of tensile dilatometry tests are described; these tests suggest that processes leading to increased volume and enhanced shear banding are occurring within the rubber toughened system. The results of the effort using another approach, the preparation of random block copolycarbonates, are presented. The synthetic route to these species was modified so that higher molecular weights of these materials can be obtained. In addition, an attempt is being made to determine the exact block length or the number of functional groups in the oligomers since this procedure also should lead to high molecular weight materials. Dynamic mechanical analysis of the copolymer prepared so far indicates that the scale of cooperative molecular motion of the PBA polycarbonate at sub-Tg temperatures is larger than five monomer units. Efforts to find a suitable rubber-toughener for a thermoset system (bismaleimides) is also discussed. Included is a description of the various tougheners intended for use or currently being used

Toughening mechanisms in thermoplastic-modified epoxies: 1. Modification using poly(phenylene oxide)

An epoxy based on the diglycidyl ether of bisphenol A (DGEBA) has been modified with poly(phenylene oxide) (PPO) and cured with piperidine. A two-phase alloy resulted, in which the DGEBA epoxy was the continuous phase. Several PPO loadings were investigated. The tensile yield strengths of these PPO-modified epoxies were found to be independent of PPO content. In contrast, the fracture toughness improved with PPO content in a linear fashion. The micromechanical mechanism responsible for the improvement in toughness was found to consist of crack bifurcation and microcracking. Some evidence of particle bridging was also observed, and it is thought that particle bridging may play an important role in the formation of a microcracked damage zone.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/30626/1/0000267.pd

Fatigue craze initiation in polycarbonate: study by transmission electron microscopy

Fatigue craze initiation in bulk, amorphous polycarbonate (PC) is investigated by means of transmission electron microscopy. The results agree very well with small angle X-ray scattering measurements of the same set of samples, and confirm that void generation is the main characteristic of the initiation process. The evolution of the initial void-like structures or `protocrazes' with dimensions of ~50 nm into crazes with dimensions of several micrometres is presented in considerable detail. It is found that some similarities exist between crazes induced by cyclic fatigue at room temperature and crazes produced in monotonic loading at temperatures close to the glass transition. The similarities suggest that disentanglement of polymer chains plays an important role in the fatigue craze initiation process in bulk, amorphous PC near room temperature.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/31430/1/0000348.pd

Positronium formation in semicrystalline poly(ethylene terephthalate)

The probability of positronium (Ps) formation in semicrystalline poly(ethylene terephthalate) (PET), has been investigated by means of positron annihilation lifetime spectroscopy (p.a.l.s.). The p.a.l.s. data are correlated with the structural characteristics of the samples, such as crystalline content, interlamellar spacing and lamella thickness. The results show an approximately linear decrease of the intensity (I3) of the long-lived orthopositronium (o-Ps) component with an increase in the crystalline content up to 53%, while the lifetime remains practically constant. It seems that the other structural parameters do not affect the Ps formation. The decrease of I3 cannot be completely accounted for if one assumes that o-Ps localizes in the amorphous phase only. It is suggested that the o-Ps also forms in the crystalline regions, due to the inhomogeneous electron density distribution along the c-axis of the PET lattice.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/31851/1/0000800.pd

Fatigue craze initiation in polycarbonate: study by small-angle X-ray scattering

The structural changes that occur during the incubation stage of tensile fatigue failure of glassy polycarbonate are investigated by means of small-angle X-ray scattering. The results are interpreted as the formation of voids, or `proto-crazes', with initial dimensions of ~60 nm and 150-200 nm in directions parallel and perpendicular to the load axis, respectively. These values are in the range expected for a void in a static equilibrium, and practically coincide with the initial void dimensions measured in glassy polymers stretched under monotonic loading.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/31378/1/0000291.pd

The novel mTOR inhibitor RAD001 (Everolimus) induces antiproliferative effects in human pancreatic neuroendocrine tumor cells

Background/Aim: Tumors exhibiting constitutively activated PI(3) K/Akt/mTOR signaling are hypersensitive to mTOR inhibitors such as RAD001 (everolimus) which is presently being investigated in clinical phase II trials in various tumor entities, including neuroendocrine tumors (NETs). However, no preclinical data about the effects of RAD001 on NET cells have been published. In this study, we aimed to evaluate the effects of RAD001 on BON cells, a human pancreatic NET cell line that exhibits constitutively activated PI(3) K/Akt/mTOR signaling. Methods: BON cells were treated with different concentrations of RAD001 to analyze its effect on cell growth using proliferation assays. Apoptosis was examined by Western blot analysis of caspase-3/PARP cleavage and by FACS analysis of DNA fragmentation. Results: RAD001 potently inhibited BON cell growth in a dose-dependent manner which was dependent on the serum concentration in the medium. RAD001-induced growth inhibition involved G0/G1-phase arrest as well as induction of apoptosis. Conclusion: In summary, our data demonstrate antiproliferative and apoptotic effects of RAD001 in NET cells in vitro supporting its clinical use in current phase II trials in NET patients. Copyright (c) 2007 S. Karger AG, Basel

Positron Emission Tomography-Computed Tomography Compared with Invasive Mediastinal Staging in Non-small Cell Lung Cancer: Results of Mediastinal Staging in the Early Lung Positron Emission Tomography Trial

IntroductionPatients with non-small cell lung cancer (NSCLC) require careful preoperative staging to define resectability for potential cure. 18Fluorodeoxyglucose positron emission tomography combined with computed tomography (18FDG PET-CT) is widely used to stage NSCLC. If the mediastinum is positive on PET-CT examination, some practitioners conclude that the patient is inoperable and refer the patient for nonsurgical treatment.MethodsIn this analysis of a previously reported trial comparing PET-CT with conventional imaging in the diagnostic work-up of patients with clinical stage I, II, or IIIA NSCLC, we determined the accuracy of PET-CT in mediastinal staging compared with invasive mediastinal staging either by mediastinoscopy alone or by mediastinoscopy combined with thoracotomy.ResultsAll 149 patients had mediastinal nodal staging at mediastinoscopy alone (14), thoracotomy alone (64), or both (71). The sensitivity of PET-CT was 70% (95% confidence interval [CI], 48–85%), and specificity was 94% (95% CI, 88–97%). Of 22 patients with a PET-CT interpreted as positive for mediastinal nodes, 8 did not have tumor. The positive predictive value and negative predictive value were 64% (95% CI, 43–80%) and 95% (95% CI, 90–98%), respectively. Based on PET-CT alone, eight patients would have been denied potentially curative surgery if the mediastinal abnormalities detected by PET-CT had not been evaluated with an invasive mediastinal procedure.ConclusionsPET-CT assessment of the mediastinum is associated with a clinically relevant false-positive result. Our study confirms the need for pathologic confirmation of mediastinal lymph node abnormalities detected by PET-CT

Principles and principals: Do customer stewardship and agency control compete or complement when shaping frontline employee behavior?

This article introduces customer stewardship control (CSC) to the marketing field. This concept represents a frontline employee's felt ownership of and moral responsibility for customers' overall welfare. In two studies, the authors show that CSC is a more encompassing construct than customer orientation, which reflects a frontline employee's focus on meeting customers' needs. They provide evidence that the former is more potent in shaping in- and extra-role employee behaviors. Moreover, they highlight how CSC operates in conjunction with an organization's agency control system: Stewardship's positive influence on in- and extra-role behavior is weaker in the presence of high agency control. They offer actionable advice about how to solve the resulting managerial control dilemma. Finally, the authors show that CSC depends on drivers that reside at the individual level (employee relatedness), the team level (team competence), or both levels of aggregation (employee and team autonomy). These findings show how to effectively design a frontline employee's work environment to ensure optimal frontline performance

How do validated measures of functional outcome compare with commonly used outcomes in administrative database research for lumbar spinal surgery?

Clinical interpretation of health services research based on administrative databases is limited by the lack of patient-reported functional outcome measures. Reoperation, as a surrogate measure for poor outcome, may be biased by preferences of patients and surgeons and may even be planned a priori. Other available administrative data outcomes, such as postoperative cross sectional imaging (PCSI), may better reflect changes in functional outcome. The purpose was to determine if postoperative events captured from administrative databases, namely reoperation and PCSI, reflect outcomes as derived by validated functional outcome measures (short form 36 scores, Oswestry disability index) for patients who underwent discretionary surgery for specific degenerative conditions of the lumbar spine such as disc herniation, spinal stenosis, degenerative spondylolisthesis, and isthmic spondylolisthesis. After reviewing the records of all patients surgically treated for disc herniation, spinal stenosis, degenerative spondylolisthesis, and isthmic spondylolisthesis at our institution, we recorded the occurrence of PCSI (MRI or CT-myelograms) and reoperations, as well as demographic, surgical, and functional outcome data. We determined how early (within 6 months) and intermediate (within 18 months) term events (PCSI and reoperations) were associated with changes in intermediate (minimum 1 year) and late (minimum 2 years) term functional outcome, respectively. We further evaluated how early (6–12 months) and intermediate (12–24 months) term changes in functional outcome were associated with the subsequent occurrence of intermediate (12–24 months) and late (beyond 24 months) term adverse events, respectively. From 148 surgically treated patients, we found no significant relationship between the occurrence of PCSI or reoperation and subsequent changes in functional outcome at intermediate or late term. Similarly, earlier changes in functional outcome did not have any significant relationship with subsequent occurrences of adverse events at intermediate or late term. Although it may be tempting to consider administrative database outcome measures as proxies for poor functional outcome, we cannot conclude that a significant relationship exists between the occurrence of PCSI or reoperation and changes in functional outcome