Paradigm shift in MRI for sciatica

In contrast with the intuitive feeling of physicians many worrisome MRI findings do not correlate with patient outcome in patients with sciatica. Physicians should for example not automatically ascribe persistent or recurrent symptoms of sciatica to the presence of abnormalities visible on MRI. This thesis enables physicians to reshape the mindset of many persons thinking that knowing imaging findings can only be good. Seeing MRI abnormalities of patients with sciatica should not always be believing.For this study funding was received from the Health Care Efficiency Research Program of Netherlands Organisation for Health Research and Development (ZonMw) and the Hoelen Foundation, The Hague.UBL - phd migration 201

Electron-Deficient N-Alkyloyl Derivatives of Thienopyrrole-4,6-dione Yield Efficient Polymer Solar Cells with Open-Circuit Voltages > 1 V

Poly(benzo[1,2-b:4,5-b′]dithiophene–thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymer donors yield some of the highest open-circuit voltages (VOC, ca. 0.9 V) and fill factors (FF, ca. 70%) in conventional bulk-heterojunction (BHJ) solar cells with PCBM acceptors. Recent work has shown that the incorporation of ring substituents into the side chains of the BDT motifs in PBDTTPD can induce subtle variations in material properties, resulting in an increase of the BHJ device VOC to ∼1 V. In this contribution, we report on the synthesis of N-alkyloyl-substituted TPD motifs (TPD(CO)) and show that the electron-deficient motifs can further lower both the polymer LUMO and HOMO levels, yielding device VOC > 1 V (up to ca. 1.1 V) in BHJ solar cells with PCBM. Despite the high VOC achieved (i.e., low polymer HOMO), BHJ devices cast from TPD(CO)-based polymer donors can reach power conversion efficiencies (PCEs) of up to 6.7%, making these promising systems for use in the high-band-gap cell of tandem solar cells

Dependence of Crystallite Formation and Preferential Backbone Orientations on the Side Chain Pattern in PBDTTPD Polymers

Alkyl substituents appended to the π-conjugated main chain account for the solution-processability and film-forming properties of most π-conjugated polymers for organic electronic device applications, including field-effect transistors (FETs) and bulk-heterojunction (BHJ) solar cells. Beyond film-forming properties, recent work has emphasized the determining role that side-chain substituents play on polymer self-assembly and thin-film nanostructural order, and, in turn, on device performance. However, the factors that determine polymer crystallite orientation in thin-films, implying preferential backbone orientation relative to the device substrate, are a matter of some debate, and these structural changes remain difficult to anticipate. In this report, we show how systematic changes in the side-chain pattern of poly(benzo[1,2-b:4,5-b′]dithiophene–alt–thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymers can (i) influence the propensity of the polymer to order in the π-stacking direction, and (ii) direct the preferential orientation of the polymer crystallites in thin films (e.g., “face-on” vs “edge-on”). Oriented crystallites, specifically crystallites that are well-ordered in the π-stacking direction, are believed to be a key contributor to improved thin-film device performance in both FETs and BHJ solar cells

Ring Substituents Mediate the Morphology of PBDTTPD-PCBM Bulk-Heterojunction Solar Cells

Among π-conjugated polymer donors for efficient bulk-heterojunction (BHJ) solar cell applications, poly(benzo[1,2-b:4,5-b′]dithiophene–thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymers yield some of the highest open-circuit voltages (VOC, ca. 0.9 V) and fill-factors (FF, ca. 70%) in conventional (single-cell) BHJ devices with PCBM acceptors. In PBDTTPD, side chains of varying size and branching affect polymer self-assembly, nanostructural order, and impact material performance. However, the role of the polymer side-chain pattern in the intimate mixing between polymer donors and PCBM acceptors, and on the development of the BHJ morphology is in general less understood. In this contribution, we show that ring substituents such as furan (F), thiophene (T) and selenophene (S)—incorporated into the side chains of PBDTTPD polymers—can induce significant and, of importance, very different morphological effects in BHJs with PCBM. A combination of experimental and theoretical (via density functional theory) characterizations sheds light on how varying the heteroatom of the ring substituents impacts (i) the preferred side-chain configurations and (ii) the ionization, electronic, and optical properties of the PBDTTPD polymers. In parallel, we find that the PBDT(X)TPD analogs (with X = F, T, or S) span a broad range of power conversion efficiencies (PCEs, 3–6.5%) in optimized devices with improved thin-film morphologies via the use of 1,8-diiodooctane (DIO), and discuss that persistent morphological impediments at the nanoscale can be at the origin of the spread in PCE across optimized PBDT(X)TPD-based devices. With their high VOC ∼1 V, PBDT(X)TPD polymers are promising candidates for use in the high-band gap cell of tandem solar cells

Improving the long-term stability of PBDTTPD polymer solar cells through material purification aimed at removing organic impurities

While bulk heterojunction (BHJ) solar cells fabricated from high Mn PBDTTPD achieve power conversion efficiencies (PCE) as high as 7.3%, the short-circuit current density (JSC) of these devices can drop by 20% after seven days of storage in the dark and under inert conditions. This degradation is characterized by the appearance of S-shape features in the reverse bias region of current–voltage (J–V) curves that increase in amplitude over time. Conversely, BHJ solar cells fabricated from low Mn PBDTTPD do not develop S-shaped J–V curves. However, S-shapes identical to those observed in high Mn PBDTTPD solar cells can be induced in low Mn devices through intentional contamination with the TPD monomer. Furthermore, when high Mn PBDTTPD is purified via size exclusion chromatography (SEC) to reduce the content of low molecular weight species, the JSC of polymer devices is significantly more stable over time. After 111 days of storage in the dark under inert conditions, the J–V curves do not develop S-shapes and the JSC degrades by only 6%. The S-shape degradation feature, symptomatic of low device lifetimes, appears to be linked to the presence of low molecular weight contaminants, which may be trapped within samples of high Mn polymer that have not been purified by SEC. Although these impurities do not affect initial device PCE, they significantly reduce device lifetime, and solar cell stability is improved by increasing the purity of the polymer materials

Flexural Fatigue Behavior of Cross-Ply Laminates: An Experimental Approach

Within an experimental approach we describe the mechanical behavior of different resin-epoxy laminates reinforced with cross-ply Kevlar and glass fibers under the conditions of static and cyclic three-point bending. In static tests, we consider the effect of stacking sequence, the thickness of 90°-oriented layers, reinforcement type on the mechanical behavior of laminates under loading and on realization of various damage modes leading to rupture. Cyclic loading studies have been performed in two steps. In the first stage, we inquire into the dependence of the behavior and durability of four glass fiber- reinforced laminate-types on the stacking sequence; the second stage is devoted to studying the dependence of cyclic strength and fatigue behavior of laminates on the reinforcement type. Fatigue tests are carried out in load-control regime for glass and hybrid (Kevlar + glass) fiber laminates. Fatigue curves are constructed in coordinates “stress - number of cycles until fracture” from the criteria corresponding to a drop in stiffness by 5 and 10%. Analysis of the results obtained permits evaluation of the effect of the stacking sequence and the reinforcement type on the behavior of cross-ply laminates in cyclic loading. The presence of Kevlar fibers accounts for nonlinear behavior of laminates in static tests and for low cyclic strength in fatigue tests under three-point bending.В рамках экспериментального подхода описано механическое поведение различных ламинатов с матрицей из эпоксидной смолы, перекрестно-армированных кевларовыми волокнами и стекловолокнами, в условиях статического и циклического трехточечного изгиба. При статических испытаниях рассматриваются последовательность укладки слоев и волокон, толщины слоев, ориентированных под углом 90° и влияние типа армирования на механическое поведение ламинатов в процессе нагружения, а также на реализацию различных режимов повреждения, приводящих к разрушению. Исследования при циклическом нагружении состоят из двух этапов. На первом этапе изучается влияние последовательности укладки слоев и волокон на поведение и долговечность четырех типов ламинатов, армированных стекловолокнами, на втором этапе - влияние типа армирования на циклическую прочность и сопротивление ламинатов при циклическом нагружении. Усталостные испытания выполнены в мягком режиме нагружения для ламинатов, армированных стекловолокнами и гибридными волокнами (кевлар+стекло). Кривые усталости были построены в координатах напряжение - число циклов до разрушения на основе критериев снижения жесткости на 5 и 10%. Анализ полученных результатов позволяет оценить влияние последовательности укладки слоев и типа армирования на поведение перекрестно-армированных ламинатов при циклическом нагружении. Наличие кевларовых волокон в ламинатах обеспечивает их нелинейное поведение при статических испытаниях и низкую циклическую прочность при усталостных испытаниях в условиях трехточечного изгиба.У рамках експериментального підходу описано механічну поведінку різних ламінатів із матрицею з епоксидної смоли, що перехресноармовані кевларо- вими волокнами і скловолокнами, в умовах статичного і циклічного три- точкового згину. При статичних випробуваннях розглядаються послідовність укладення шарів і волокон, товщини орієнтованих під кутом 90° шарів і вплив типу армування на механічну поведінку ламінатів у процесі навантаження, а також на реалізацію різних режимів пошкодження, що призводить до руйнування. Дослідження при циклічному навантаженні складається з двох етапів. На першому етапі розглядається вплив послідовності укладення шарів і волокон на поведінку і довговічність чотирьох типів армованих скловолокнами ламінатів, на другому етапі - вплив типу армування на циклічну міцність і опір ламінатів при циклічному навантаженні. Випробування на втому виконано у м ’якому режимі навантаження для армованих скловолокнами і гібридними волокнами (кевлар + скло) ламінатів. На основі критеріїв зниження жорсткості на 5 і 10% в координатах напруження - число циклів до руйнування побудовано криві утоми. Аналіз отриманих результатів дозволяє оцінити вплив послідовності укладення шарів і типу армування на поведінку перехресноармованих ламінатів при циклічному навантаженні. Наявність кевларових волокон у ламінатах запезчує їх нелінійну поведінку при статичних випробуваннях і низьку циклічну міцність при випробуваннях на втому в умовах триточкового згину