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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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15,536
['Exp_Characterization', 'Experiment']
QUAL_MEASUREMENT
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oastm_03
train1
semi
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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15,537
15,725
['Results']
QUAL_MEASUREMENT
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oastm_03
train1
semi
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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15,726
15,962
['Background', 'Results', 'Background_PriorWork']
QUAL_MEASUREMENT
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oastm_03
train1
semi
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
train1
semi
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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16,102
16,216
['Background', 'Exp_Characterization', 'Experiment']
O
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oastm_03
train1
semi
oastm_03
A higher value denotes superior TCO properties [35].
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16,217
16,269
['Background', 'Background_PriorWork']
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oastm_03
train1
semi
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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16,270
16,415
['Results']
QUAL_MEASUREMENT
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oastm_03
train1
semi
oastm_03
Fluorine is thus the superior dopant demonstrating an F.o.M. value greater than the other halides.
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16,416
16,514
['Conclusion']
O
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oastm_03
train1
semi
oastm_03
Conclusions
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16,515
16,526
['Background', 'Heading']
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oastm_03
train1
semi
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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16,527
16,738
['Conclusion']
O
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oastm_03
train1
semi
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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16,739
16,883
['Explanation']
O
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oastm_03
train1
semi
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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16,884
17,001
['Conclusion']
QUAL_MEASUREMENT
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oastm_03
train1
semi
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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17,002
17,308
['Conclusion']
MEASUREMENT
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oastm_03
train1
semi
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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17,309
17,439
['Conclusion']
QUAL_MEASUREMENT
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oastm_03
train1
semi
oastm_03
Acknowledgements
[ "Acknowledgements" ]
17,440
17,456
['Heading']
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oastm_03
train1
semi
oastm_03
IPP and NN thank the EPSRC for funding through the UCL MMMS Doctoral Training Centre.
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['Metadata']
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oastm_03
train1
semi
oastm_03
substrates.
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17,579
17,590
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oastm_03
train1
semi
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
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oastm_04
Abstract
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oastm_04
train4
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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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136
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['Experiment', 'Exp_Preparation']
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oastm_04
train4
poly
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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317
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['Results']
MEASUREMENT
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oastm_04
train4
poly
oastm_04
The polysiloxane rubber particles had a Tg of about -100 °C.
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oastm_04
train4
poly
oastm_04
Atomic force microscopy showed that the S-CSR particles were well-dispersed in the epoxy polymer.
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oastm_04
train4
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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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MEASUREMENT
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oastm_04
train4
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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
train4
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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
train4
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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
train4
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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
train4
poly
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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['Conclusion']
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oastm_04
train4
poly
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
train4
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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
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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
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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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[ "•" ]
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An epoxy polymer has been modified with polysiloxane core-shell rubber particles.
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The epoxy had Tg of about 148 °C and the particles had a Tg of about -100 °C.
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['Conclusion']
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[ "•" ]
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AFM showed that the particles were well-dispersed in the epoxy polymer.
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[ "•" ]
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The addition of 20 wt% particles increased GIc from about 120 J/m2 to 950 J/m2.
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['Conclusion']
MEASUREMENT
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The particles also significantly toughened the epoxy polymer even at about -100 °C.
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Introduction
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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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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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However, epoxy polymers have inherently low toughness and impact resistance due to their highly crosslinked structure.
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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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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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Refs.
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[1-5], or a thermoplastic polymer, e.g.
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Ref.
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[6-8], can increase the toughness.
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Here the rubber or thermoplastic particles are typically about 0.1-5 μm in diameter with a volume fraction of about 5-20%.
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The particles are typically well-dispersed, and formed by reaction-induced phase-separation.
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However, the particle size is difficult to control as it is dependent on the curing conditions, and hence cannot be varied systematically without changing the properties of the epoxy polymer.
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An alternative route to increase the toughness of epoxy polymers is to use core-shell rubber (CSR) particles.
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These particles comprise a soft rubbery core within a harder shell.
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The particles are typically formed by emulsion polymerisation, and then dispersed in the epoxy resin.
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Hence, it is readily possible to produce particles with a controlled particle size, unlike with phase-separating rubbers.
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A range of core and shell materials may be used, and multilayer particles are common [9].
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The shell is chosen to be compatible with the epoxy polymer, and poly(methylmethacrylate), which is sometimes functionalised, is often used.
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Typical core materials include polybutadiene [10] and acrylate-polyurethane rubbers [11].
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They have been shown to increase the toughness of both bulk polymers and fibre composites, e.g.
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Refs.
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[12-15].
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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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However, although the properties of these rubber-toughened epoxy polymers have been investigated extensively, only a few studies have reported the low-temperature performance of these rubber-toughened epoxies.
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In general, the literature [5,17-19] reports that the fracture toughness of rubber-toughened epoxy polymers decreases as the temperature decreases, except at very low temperatures (possibly having passed the β-transition of the polymer) where the fracture toughness appears to increase somewhat again.
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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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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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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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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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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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Also, the blend morphology, structure/property relationship, and thermal-mechanical behaviour of the modified epoxy polymers were ascertained.
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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
train4
poly
oastm_04
Experimental
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oastm_04
train4
poly
oastm_04
Materials
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7,061
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oastm_04
train4
poly
oastm_04
An anhydride-cured epoxy polymer was used.
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MEASUREMENT
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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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7,610
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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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O
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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
train4
poly
oastm_04
Dynamic-mechanical thermal analysis
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oastm_04
train4
poly
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
train4
poly
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
train4
poly
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
train4
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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
train4
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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
train4
poly
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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MEASUREMENT
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oastm_04
train4
poly
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
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poly