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oastm_03 | Tail widths were calculated by taking the inverse gradient of the linear sub-bandgap section of a ln α vs E/eV plot. | [
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oastm_03 | Eu is found to correlate positively with N, indicating that the greater presence of charge carriers comes at the expense of structural defects, thought to be induced by the halide dopants. | [
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oastm_03 | This then accounts for the negative correlation between Eu and μ, where the greater presence of defects increases the number of scattering centres; ionised impurity scattering being the predominant scattering phenomenon in TCOs [32-34]. | [
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oastm_03 | A figure-of-merit (F.o.M.) value which accounts for both electrical and optical characteristics of the films has been included in Table 1. | [
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oastm_03 | This has been calculated from;σ/α=-RsheetlnT+R-1where T and R refer to transmittance and reflectance respectively. | [
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oastm_03 | A higher value denotes superior TCO properties [35]. | [
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oastm_03 | The data demonstrates an inverse relationship between halide size and effectiveness as a TCO material; the high I-TO value due to a thicker film. | [
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oastm_03 | Fluorine is thus the superior dopant demonstrating an F.o.M. value greater than the other halides. | [
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oastm_03 | Conclusions | [
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oastm_03 | We have elucidated an important reaction step in the formation of halide-doped SnO2 TCOs, namely a highly selective halide exchange process which takes place even in the most unfavourable of reaction conditions. | [
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oastm_03 | The resultant substituted tin-dopant precursor complex is thought to be an important marker in the formation of high-performing SnO2-based TCOs. | [
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oastm_03 | We have also demonstrated that high-performing TCOs can be obtained from doping SnO2 with halide dopants using AACVD. | [
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oastm_03 | The results reinforce the position of fluorine as the best halide dopant yielding the highest performing polycrystalline SnO2-TCOs of small crystallite dimensions, with carrier mobilities of 15cm3/V.s, carrier concentrations of 8.85×1020cm-3 and optical transmittance of 80% over visible light wavelengths. | [
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oastm_03 | These FTO thin films compare well with current commercial standards and can potentially be produced more safely and at lower cost. | [
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oastm_03 | Acknowledgements | [
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oastm_03 | IPP and NN thank the EPSRC for funding through the UCL MMMS Doctoral Training Centre. | [
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oastm_03 | substrates. | [
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oastm_04 | The mechanical properties and toughening mechanisms of an epoxy polymer modified with polysiloxane-based core-shell particles | [
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oastm_04 | Abstract | [
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oastm_04 | An epoxy resin, cured using an anhydride hardener, has been modified by the addition of pre-formed polysiloxane core-shell rubber (S-CSR) particles with a mean diameter of 0.18 μm. | [
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oastm_04 | The glass transition temperature, Tg, of the cured unmodified epoxy polymer was 148 °C, and this was unchanged after the addition of the S-CSR particles. | [
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oastm_04 | The polysiloxane rubber particles had a Tg of about -100 °C. | [
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oastm_04 | Atomic force microscopy showed that the S-CSR particles were well-dispersed in the epoxy polymer. | [
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oastm_04 | The addition of the S-CSR particles reduced the Young's modulus and tensile strength of the epoxy polymer, but at 20 °C the fracture energy, GIc, increased from 117 J/m2 for the unmodified epoxy to 947 J/m2 when 20 wt% of the S-CSR particles were incorporated. | [
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oastm_04 | Fracture tests were also performed at -55 °C, -80 °C, and -109 °C. | [
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oastm_04 | The results showed that the measured fracture energy of the S-CSR-modified epoxy polymers decreased significantly below room temperature. | [
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oastm_04 | For example, at -109 °C, a fracture energy of 481 J/m2 was measured using 20 wt% of S-CSR particles. | [
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oastm_04 | Nevertheless, this value of toughness still represented a major increase compared with the unmodified epoxy polymer, which possessed a value of GIc of 174 J/m2 at this very low test temperature. | [
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oastm_04 | Thus, a clear fact that emerged was that the addition to the epoxy polymer of the S-CSR particles may indeed lead to significant toughening of the epoxy, even at temperatures as low as about -100 °C. | [
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oastm_04 | The toughening mechanisms induced by the S-CSR particles were identified as (a) localised plastic shear-band yielding around the particles and (b) cavitation of the particles followed by plastic void growth of the epoxy polymer. | [
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oastm_04 | These mechanisms were modelled using the Hsieh et al. approach [33,49] and the values of GIc of the S-CSR-modified epoxy polymers at the different test temperatures were calculated. | [
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oastm_04 | Excellent agreement was found between the predictions and the experimentally measured fracture energies. | [
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oastm_04 | Further, the experimental and modelling results of the present study indicated that the extent of plastic void growth was suppressed at low temperatures for the S-CSR-modified epoxy polymers, but that the localised shear-band yielding mechanism was relatively insensitive to the test temperature. | [
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oastm_04 | Graphical abstract | [
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oastm_04 | Highlights | [
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oastm_04 | • | [
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oastm_04 | An epoxy polymer has been modified with polysiloxane core-shell rubber particles. | [
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oastm_04 | The epoxy had Tg of about 148 °C and the particles had a Tg of about -100 °C. | [
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oastm_04 | The addition of 20 wt% particles increased GIc from about 120 J/m2 to 950 J/m2. | [
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oastm_04 | • | [
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oastm_04 | The particles also significantly toughened the epoxy polymer even at about -100 °C. | [
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oastm_04 | Introduction | [
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oastm_04 | Epoxy polymers are a class of high-performance thermosetting polymers which are widely used for the matrices of fibre-reinforced composite materials and as adhesives. | [
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oastm_04 | They are known for their excellent engineering properties, such as high modulus, low creep, high strength, and good thermal and dimensional stabilities. | [
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oastm_04 | However, epoxy polymers have inherently low toughness and impact resistance due to their highly crosslinked structure. | [
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oastm_04 | This structure leads to brittle behaviour and causes the polymers to suffer from relatively poor resistance to crack initiation and growth. | [
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oastm_04 | To improve the toughness of epoxy polymers, it has been established that the incorporation of a second micro-phase of a dispersed rubber, e.g. | [
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oastm_04 | Ref. | [
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oastm_04 | They have been shown to increase the toughness of both bulk polymers and fibre composites, e.g. | [
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oastm_04 | Hayes and Seferis [16] have reviewed the use of CSR particles in thermoset polymers and composites; this review also discusses some of the other properties that can be affected by the incorporation of CSR particles. | [
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oastm_04 | It is generally accepted that the major toughening mechanism of rubber-toughened epoxies is based on a series of deformation processes, namely (a) localised plastic shear-band yielding around the rubber particles and (b) cavitation of the S-CSR particles followed by plastic void growth of the epoxy polymer. | [
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oastm_04 | It has been noted [1,3,5] that this second mechanism needs to be operative in order to typically achieve major increases in the toughness of the rubber-particle-modified epoxy polymer. | [
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oastm_04 | This suggests that using rubber particles with a relatively very low glass transition temperature, Tg, may enable cavitation of the rubber particles at very low test temperatures, and as a result allow plastic void growth of the epoxy polymer even at relatively low temperatures. | [
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oastm_04 | Hence, the present work used pre-formed polysiloxane core-shell rubber (S-CSR) particles which possess a relatively very low Tg of -100 °C to toughen an anhydride-cured epoxy polymer. | [
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oastm_04 | The room-temperature and low-temperature mechanical properties and fracture energy of these S-CSR particle-toughened epoxy polymers were determined. | [
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oastm_04 | Also, the blend morphology, structure/property relationship, and thermal-mechanical behaviour of the modified epoxy polymers were ascertained. | [
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oastm_04 | Further, the toughening mechanisms involved were also identified, and analytical models were used to predict the modulus, yield stress and fracture energy. | [
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oastm_04 | Experimental | [
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oastm_04 | Materials | [
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oastm_04 | An anhydride-cured epoxy polymer was used. | [
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} | oastm_04 | train4 | poly |
oastm_04 | The epoxy resin was a standard diglycidyl ether of bisphenol-A (DGEBA, Araldite LY556) with an epoxide equivalent weight (EEW) of 185 g/eq, supplied by Huntsman, UK. | [
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} | oastm_04 | train4 | poly |
oastm_04 | The curing agent was an accelerated methylhexahydrophthalic acid anhydride (Albidur HE600) with an anhydride equivalent weight (AEW) of 170 g/eq, supplied by Evonik Hanse, Germany. | [
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} | oastm_04 | train4 | poly |
oastm_04 | The polysiloxane core-shell rubber (S-CSR) particles used were supplied as a masterbatch of particles pre-dispersed at 40 wt% in a DGEBA also by Evonik Hanse. | [
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} | oastm_04 | train4 | poly |
oastm_04 | The rubber particles possessed a crosslinked polysiloxane core with a glass transition temperature, Tg, of about -100 °C. | [
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} | oastm_04 | train4 | poly |
oastm_04 | The shell consisted of a very thin skin of epoxy-functional molecules which had been grafted onto the crosslinked core. | [
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} | oastm_04 | train4 | poly |
oastm_04 | Up to 20 wt% of the S-CSR particles was used. | [
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} | oastm_04 | train4 | poly |
oastm_04 | Bulk plates of the unmodified and S-CSR-modified epoxy polymers were prepared. | [
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} | oastm_04 | train4 | poly |
oastm_04 | To vary the particle content, the S-CSR-modified resins were mixed with DGEBA to give the required concentration of S-CSR particles. | [
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} | oastm_04 | train4 | poly |
oastm_04 | The value of the EEW of the blend was calculated and a stoichiometric amount of the curing agent was added. | [
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} | oastm_04 | train4 | poly |
oastm_04 | The mixture was stirred, degassed and poured into release agent-coated (Frekote 700NC, Henkel, UK) steel moulds. | [
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} | oastm_04 | train4 | poly |
oastm_04 | The plates of the epoxy polymers were cured for 1 h at 120 °C followed by 2 h at 160 °C. | [
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oastm_04 | Dynamic-mechanical thermal analysis | [
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oastm_04 | The glass transition temperature, Tg, of all the bulk samples was measured using dynamic-mechanical thermal analysis (DMTA) with a Q800 DMA from TA Instruments, UK. | [
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oastm_04 | A double-cantilever mode at 1 Hz was employed using test specimens 60 × 10 × 3 mm3 in size. | [
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oastm_04 | The temperature range used was -100 °C to 200 °C with a heating rate of 4 °C/min. | [
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oastm_04 | The value of Tg was determined at the peak value of tan δ. | [
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oastm_04 | The number average molecular weight between cross-links, Mnc, was also calculated from the equilibrium modulus in the rubbery region, Er, using [20](1)Mnc=qρRT/Erwhere T is the temperature in K at which the value of Er was taken, ρ is the density of the epoxy at the temperature T, the term R is the universal gas constant, and q is the front factor. | [
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oastm_04 | As the density of the epoxy was only measured at room temperature, the value of the front factor, q, was taken to be 0.725, as in previous work [21]. | [
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oastm_04 | The density, ρ, of the epoxy was measured at room temperature according to BS ISO 1183-1 Method A [22] to be 1.20 g/m3 at 20 °C. | [
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} | oastm_04 | train4 | poly |
Subsets and Splits