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16-羟基封端的环氧树脂-Cryogenic mechanical properties of epoxy resin toughened by hydroxyl-terminated polyurethane
16-羟基封端的环氧树脂-Cryogenic mechanical properties of epoxy resin toughened by hydroxyl-terminated polyurethane
16-羟基封端的环氧树脂-Cryogenic mechanical properties of epoxy resin toughened by hydroxyl-terminated polyurethane
Tong Wu, Yu Liu, Na Li, Gui-Wen Huang, Cheng-Bing Qu, Hong-Mei Xiao
PII: S0142-9418(18)31224-8
DOI: https://doi.org/10.1016/j.polymertesting.2018.11.048
Reference: POTE 5724
Please cite this article as: T. Wu, Y. Liu, N. Li, G.-W. Huang, C.-B. Qu, H.-M. Xiao, Cryogenic
mechanical properties of epoxy resin toughened by hydroxyl-terminated polyurethane, Polymer Testing
(2019), doi: https://doi.org/10.1016/j.polymertesting.2018.11.048.
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hydroxyl-terminated polyurethane
Tong Wua,b, Yu Liua, Na Lia, Gui-Wen Huanga, Cheng-Bing Qua,*, Hong-Mei Xiaoa,**
a
Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing
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100190, China
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b
University of Chinese Academy of Sciences, Beijing 100190, China
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* Corresponding author.
** Corresponding author.
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Tel./fax: +86 10 82543755. E-mail address: quchengbing@mail.ipc.ac.cn
ABSTRACT
In this work, we evaluated the room temperature (RT) and cryogenic temperature
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toluene diamine (DETDA) system modified by two kinds of hydroxyl-terminated
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of investigating the influence of phase structure on the overall resin performances.
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The morphological changes with different contents of HTPU were examined by
scanning electron microscopy (SEM) and two phase structures of homogeneous phase
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and sea-island structure were proved to be successfully obtained by introducing of
solution theory. The mechanical properties of the two kinds of modified resins were
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resulted in higher enhancing effects on impact and tensile properties, while the
sea-island structure showed better retention in the glass transition temperature (Tg) of
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the mixture. The mechanism of these property differences depended on the phase
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structure were discussed in detail and the conclusions achieved in this work could be
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reference valuable for the design and apply of modified resins with difference phase
1. Introduction
Epoxy resin (EP) is widely used as adhesive, coating and matrix of composites in
cryogenic engineering areas due to their wide curing temperature range, low
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coefficient of thermal expansion (CTE), high insulation resistance and good resistance
to chemical corrosion [1-4]. However, a higher cross-link density of the epoxy resins
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would lead to low absolute strength and poor fracture toughness, limiting its
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applications in mechanical components for cryogenic engineering applications [5-7].
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temperature [8, 9]. It is considered as an extensive and efficient method to toughen
epoxy resin by incorporating heterogeneous phase with some additive such as rigid
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inorganic particles [10-19], liquid rubber elastomer [20-23], some block copolymers
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[24] and hyperbranched polymers [25]. Especially, polyurethane (PU) modified epoxy
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resin has attracted wide attention due to excellent toughness improvement coming
(DDS) system [27, 28]. Results show that comparing to the amine-terminated
polyurethane (HTPU) can form a more uniform distribution of particle diameter with
EP and result in a highest efficiency in toughness. Further reports show the epoxy
resin can form homogeneous phase or heterogeneous phase with the different
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molecular weights and the different contents of PU [29, 30]. And in the heterogeneous
phase, epoxy resin composited with lower content of PU can form a sea-island
structure, and also can form a co-continuous phase by increasing the content of PU to
produce interpenetrating polymer network (IPN) [31-33]. Zielinski et al. [34] have
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reported that the size and distribution of second phase rubberlike particles of PU have
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a significant influence in the improvement of mechanical properties of epoxy resin.
However, few works in regard to the cryogenic mechanical properties of epoxy resin
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toughed by different molecular weight and contents of HTPU have been reported.
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In this study, we used two kinds of HTPU as modifiers namely HTPU1 and
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HTPU2 to toughen DGEBA/DETDA system. HTPU1 and HTPU2 have different
molecular weights through adjusting the proportion of polyester and polyether in the
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polyurethane. The impact and tensile properties were examined at RT and 77K for
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HTPU modified epoxy resins. Moreover, dynamic thermal mechanical analysis was
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employed to investigate the thermal properties of epoxy resins with various contents
2. Experimental section
2.1 Materials
The epoxy resin used in this work was DGEBA (WSR615, from BLUESTAR
Nantong Star Synthetic Materials Co., Ltd. Nantong, China). The curing agent was
DETDA (from Albemarle Corporation Charlotte, USA). The HTPU1 and HTPU2 was
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(Beijing, China). All components were commercial products, and they were used as
received, without previous purification. Fig.1(a) and Fig.1(b) show the molecular
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structures of HTPU, in which A denotes epoxy group, carboxyl group or hydroxyl
group and the M1, M2 and M3 mean polyester, polyurethane and polyether, receptively.
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Fig. 1. Structural formula of (a) DGEBA, (b) DETDA and (c) HTPU
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HTPU2 with different amount (weight ratios to DGEBA 5 phr, 10 phr, 20 phr) was
poured into the DGEBA. Then curing agent (DETDA) was added into the
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DGEBA/HTPU mixture with the weight ratio to DGEBA 25:100 to get mixed
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receptively. In addition, the control group only contained DGEBA and DETDA with
the weight ratio 100:25. The mixture was then treated under magnetic stirring for 30
minutes to get homogeneous solution. Then the clear homogeneous solution was
degassed by a vacuum rotary pump at 60 °C for 30 minutes, because the air bubbles
which dissolved in mixture could affect the properties of the specimen by creaking
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voids in the epoxy mixture. After the air bubbles were completely removed, mixture
was poured into a preheated stainless steel mold which was coated with Frekote ®
770-NC release agent in advance. Then the mold with mixture were placed in a hot air
oven at 80 °C for 8 hours following with 130 °C for 12 hours to obtain test specimens.
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Table 1
Formulations of EP/HTPU composites
HTPU content (phr) DGEBA (g) DETDA (g) HTPU1 (g) HTPU2 (g)
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Control group 0 100 25 0 0
EP/HTPU1-05 5 100 25 5 0
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EP/HTPU1-10 10 100 25 10 0
EP/HTPU1-20 20 100 25 20 0
EP/HTPU2-05 5 100 25 0 5
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EP/HTPU2-10 10 100 25 0 10
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EP/HTPU2-20 20 100 25 0 20
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2.3 Characterization
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The fracture surfaces of the specimens after tensile test at RT or 77K were
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sputter coated with gold and observed using scanning electron microscopy (SEM,
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S-4800, HITACHI, Japan) under low vacuum mode (operating voltage 10 kV).
In order to investigate the influence of toughening agent on the alpha and beta
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The temperature at which the beta secondary relaxation of epoxy resin occurs is about
– 50 °C according to the reference [28]. So the DMA tests were implemented using in
temperature range from -100 °C to 200 °C with frequency of 1 Hz and heating rate of
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5 °C/min under single cantilever bending mode. The samples were cut into dimension
Fourier Transform infrared spectra (FTIR) was conducted using Excalibur 3100
(Varian, America) to characterize the effect of functional groups of the additive on the
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epoxy during curing process. The spectrometer was equipped with an attenuated total
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reflectance (ATR) sampling accessory for the test of solid specimens. After solid
specimens were cleaned by ethyl alcohol, the spectra of solid specimens were
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determined by FTIR-ATR. The test wavenumber of solid specimens ranged from 600
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cm-1 to 4000 cm-1. And the liquid mixture was dropped on the potassium bromide
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(KBr) tablets by plastic straw for the test. The test wavenumber of the liquid mixture
ranged from 400 cm-1 to 4000 cm-1. Each specimen was scanning 64 times to weaken
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HTPU1 and HTPU2 were conducted using Q-Exactive (Thermo Fisher Scientific,
modes (pESI). The HTPU1 and HTPU2 were dissolved in methanol for testing.
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distribution of these two types of HTPU which contains same molecular structures.
2.4 Tests
to ASTM D256-10. In the 77K test, specimens were immersed in the liquid nitrogen
for 20 minutes. Then the specimen was one by one quickly taken out to the
experimental machine and finished test in 5 seconds. Consideration for data accuracy,
the test result was the average of at least 10 test specimens under 77K and RT tests,
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respectively.
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The tensile properties of specimens were determined by universal material testing
machine (Instron 5882, USA) testing dog bone shaped specimens according to ASTM
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D638-14. The specimen was tested at a crosshead speed of 2 mm/min. For the test at
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77K, in order to ensure the temperature uniformity of the sample, the tensile
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specimens were first immersed in liquid nitrogen for 20 minutes, and the entire tensile
test was completed in a liquid nitrogen container. The test result was the average of at
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solution theory that in our epoxy resin system phase separation is primarily caused by
the difference of molecular weight of additive [35]. The result is an equation for the
Gibbs free energy change for mixing a polymer A with a solvent B. The Gibbs mixed
∆ =∆ − ∆ = + 1− + 1− (1)
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%&
χ= 2"#$ − "## − "$$ = (# − ($ (2)
'
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where z is the coordination number. V0 is the volume of the polymer unit. The uAB, uAA
and uBB are the energy of the molecular interactions in the A-B, A-A and B-B,
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respectively.
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EP
Fig. 2. The schematic diagram of epoxy resin mixing with HTPU and the SEM images of cured
mixture. Insets show the digital photographs of materials.
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Gibbs mixed free energy consists of two parts, the entrogy and the energy. For
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the entrogy part, it always promotes the hybrid. Due to molecular weight of HTPU2 is
EP/HTPU1 [36-38]. Thus, the Gibbs mixed free energy of EP/HTPU2 becomes
the curing process, the mixture of EP/HTPU2 is unstable and phase separation takes
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Fig. 3. FTIR spectra obtained from (a) liquid mixture (before curing) of EP/HTPU1, (b) liquid mixture
(before curing) of EP/HTPU2, (c) solid specimen (after curing) of EP/HTPU1, (d) solid specimen (after
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shown in Fig. 3(a), due to the presence of the DETDA and DGEBA, the double peak
of amino group at 3389 and 3462 cm-1 (-NH2 asymmetric stretching vibration) and the
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peak of epoxy group at 912 cm-1 (C-O stretching vibration) are observed in the liquid
mixture [39]. During curing process, only these two peaks are absent from the
spectrum of the specimen in the Fig. 3(c), because amino groups react with epoxy
groups. Besides, Fig. 3(b) and Fig. 3(d) show the similar phenomenon for EP/HTPU2.
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Comparing to the spectra of EP/HTPU1, there are no any other changes in the spectra
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of EP/HTPU2. As mentioned above, it is proved that the HTPU do not participate in
the curing reaction and the phase separation of EP/HTPU2 is not caused by the curing
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reaction of EP. Furthermore, Fig. 3(e) and Fig. 3(f) show that the HTPU1 and HTPU2
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exist the same peaks. The peaks of the 3466 (3449) cm-1 (O-H stretching vibration)
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and the peaks of 1107 (1110) cm-1 (C-O stretching vibration) indicate that there
existed hydroxyl groups in the molecular structure of the HTPU [40]. The epoxy
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group and carboxyl group of the molecular structure are absent in FTIR spectra,
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which results from much less amount these two groups than hydroxyl group. Even if
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both HTPU1 and HTPU2 have hydroxyl groups, since HTPU2 precipitates after
curing, only HTPU1 can form a stable hydrogen bond with EP and dissolves in it.
EP
Thus, FTIR indicates that functional groups are not the factor of the phase separation
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Fig. 4 shows the characteristic spectra of the HTPU1 and HTPU2 analyzed via
FTMS-pESI. The base peaks of the HTPU1 and HTPU2 are 447.2918 m/z and
1375.4525 m/z, respectively. It is worth noting that the base peak of the HTPU2 is
exactly three times that of the HTPU1. Besides, the peaks of 924.6312 m/z and
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447.2913 m/z observed in the spectrum of HTPU2 are double and equal of the base
peak (447.2918 m/z) of HTPU1. Combining with FTIR spectra, it indicates that the
HTPU1 and HTPU2 have the same basic molecular structures but are different in
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Fig. 4. FTMS-pESI for a methanolic solution of HTPU with range of the 150-2000 m/z (a) HTPU1 and
(b) HTPU2
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Fig. 5. DMA tests of the EP composited with different contents of HTPU: (a) storage modulus of
EP
EP/HTPU1, (b) storage modulus of EP/HTPU2, (c) tanδ of EP/HTPU1, (d) tanδ of EP/HTPU2, (e) Tg
of EP/HTPU1 and EP/HTPU2 and (f) full width at half maxima (FWHM) of EP/HTPU1-α and
EP/HTPU2-α in tanδ
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DMA tests have been performed to investigate whether the presence of the
HTPU affects the crosslink density and the Tg of epoxy resin. Continuous temperature
sweep tests have been performed in a wide range of temperature from -100 °C to
200 °C to characterize the viscoelasticity of the materials. Fig. 5 shows the curves of
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storage modulus and tanδ in DMA tests. As shown in Fig. 5(a), there exists an unusual
phenomenon that in the range from -20 °C to 20 °C, the storage modulus of the
control group is the lowest compared to any other EP/HTPU1 with different contents
of HTPU1. This may be due to the strong hydrogen bonds interaction between
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hydroxyl groups of HTPU1 and EP [26,42]. However, Fig. 5(b) shows that the storage
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modulus of EP/HTPU2 with all different contents are lower than the control group in
a wider temperature range from -100 °C to 160 °C. This may be due to the rubber
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aggregate phase formed by the precipitation of HTPU2 after curing process. [43]. Fig.
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5(c) and Fig. 5(d) give the tanδ of EP/HTPU1 and EP/HTPU2, respectively. The tanδ
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of EP/HTPU1 in Fig. 5(c) shows the α-relaxation peak and β-relaxation peak shift to
lower temperature with the increase of HTPU1 contents. However, the α-relaxation
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peak and β-relaxation peak of EP/HTPU2 in Fig. 5(d) change very little with the
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temperature (Tg,β) of EP/HTPU1 and EP/HTPU2 with different HTPU contents are
given in Fig. 5(e). The results show when the HTPU1 content increased from 0 to 20
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phr, the Tg,α and Tg,β of EP/HTPU1 decreased from 158.6 °C and -51.1 °C to
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101.4 °C and -61.5 °C, respectively. But under the same conditions, Tg,α and Tg,β of
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EP/HTPU2 only decreased from 158.6 °C and -51.1 °C to 155.9 °C and -52.1 °C,
respectively. Because of the dissolution of the HTPU1 in the epoxy systems, the
presence of the flexible chains causes the decrease of the entire cross-linked network
density between DGEBA and DETDA, and the motion of the network can become
more easily under external forces, finally showing the decrease in Tg [27,44]. But
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because most HTPU2 will precipitate after curing process, the Tg of EP/HTPU2
change little. Fig. 5(f) shows the full width at half maxima (FWHM) of EP/HTPU1-α
and EP/HTPU2-α measured in the peaks of tanδ, which indicates as increasing the
contents of HTPU1, the FWHM of EP/HTPU1 increases. On the contrary, the FWHM
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of EP/HTPU2 is far different from EP/HTPU1. The differences of the FWHM
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between EP/HTPU1 and EP/HTPU2 prove that higher miscibility and interaction exist
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3.3 Mechanical properties results and analyses
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The overall mechanical performance of epoxy resin is much possibly influenced
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by homogeneous phase and sea-island structure formed by EP/HTPU1 and
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EP/HTPU2, respectively. Hence emphasis has been given to provide an insight on the
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epoxy resin microstructure in the control group, EP/HTPU1 and EP/HTPU2 tested at
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RT and 77K. Fig. 6 shows three zones of tensile fracture morphologies of EP/HTPU1
and control group which represents three stages of tensile fracture. In the first mirror
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area named crack initiation shown in Fig. 6(S1), this area macroscopically presents a
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flat smooth semicircular mirror that normally appears at the edges or corners of the
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specimen. The morphology is a smooth surface with no rough parts, lumps or holes.
And in the second misty area named crack propagation shown in Fig. 6(S2), river
patterns are observed at RT test. The river patterns are radioactively extended from
the initiation of the crack and presents approximately parallel, slightly curved, wavy
stripes. But the morphology of the tensile fracture at 77K is completely different with
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which were tested at RT. As shown in Fig. 7(from a-S2 to d-S2) and Fig. 8(from a-S2
to d-S2), the crease of the fracture morphology at 77K is not observed compared with
RT. This area is flat but not reflective compared with the mirror area. And there are
some parabolic patterns in this area with the axis pointing to the crack initiation. The
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difference of the misty area between RT and 77K indicates that the molecular chains
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of the epoxy resin are frozen at cryogenic temperatures and results in matrix more
brittle. Finally, in the last area named instantaneous fracture shown in Fig. 6(S3),
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there is fill of dimples which are round or oval pit that is approximate in size. More
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importantly, Fig. 7(from a-S3 to d-S3) and Fig. 8(from a-S3 to d-S3) show that the
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crease of the fracture morphology at 77K is not observed. As dimples become larger,
it can absorb more fracture energy to achieve toughening. However, these three areas
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are partially covered up and interrupted by the presence of the second phase particles
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of HTPU2. The similar phenomenon of these three stages is not observed in the
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Fig. 6. The schematic diagram of the tensile fracture morphology divided into three areas: (S1) SEM of
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the first mirror area, (S2) SEM of the second misty area and (S3) SEM of the instantaneous fracture
area
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Fig. 7. SEM images of the tensile fracture morphologies under 77K tests with the addition of the
HTPU1: (a) 0 phr, (b) 5 phr, (c) 10 phr and (d) 20 phr
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Fig. 8. SEM images of the tensile fracture morphologies under RT tests with the addition of the HTPU1:
(a) 0 phr, (b) 5 phr, (c) 10 phr and (d) 20 phr
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Fig. 9. SEM images of the tensile fracture morphologies of EP/HTPU2: (a) 0 phr, (b) 5 phr, (c) 10 phr
and (d) 20 phr at RT; (e) 0 phr, (f) 5 phr, (g) 10 phr, (h) 20 phr at 77K
Comparing Fig.9(a)-(d) with Fig. 9(e)-(h), the distribution and the sizes of these
particles are identical at 77K and RT. In the process of crack advancement, it is
sometimes necessary to bypass the particles of the second phase. Because these
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second phase particles are more flexible than the matrix phase, particles deformation
is also observed. Shear bands formed by shear yield and multiple cracks can be seen
from where the edges are whitened [45]. This toughening mechanism is similar to
liquid rubber toughening epoxy resins such as CTBN [46]. Besides, as the content of
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the HTPU2 increases, the second phase precipitates more, the particles are larger, and
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the distribution is more density [47]. The size of the particles and the distribution can
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Fig. 10. Variation of impact strength of (a) EP/HTPU1 and (b) EP/HTPU2 at 77K and RT
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HTPU1 content increases almost 77% higher than control group at RT. However, the
EP
impact strength of the EP/HTPU1 does not increase significantly until the HTPU1
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content increases up to 20 phr at 77K. In general, the impact strength of the epoxy
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resin at 77K is lower than it at RT because of the freeze of the polymer chain.
content, the impact strength of EP/HTPU1 at 77K was slightly higher than at RT. This
may be due to the HTPU1 contains sufficient flexible groups to reduce the stiffness of
EP cross-linked network, further absorbing the fracture energy. And in Fig. 10(b), the
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trend of impact strength of the HTPU2 is similar with the HTPU1 at RT. The
EP/HTPU2 with the addition of 10 phr HTPU2 has the highest impact strength at RT
and 77K. In terms of the impact strength, HTPU1 and HTPU2 with the optimum
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Table 2
Tensile properties of unmodified and HTPU1-modified epoxy resins at RT and 77 K.
Tensile strength (MPa) Tensile modulus (GPa) Elongation at break (%)
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HTPU1 content (phr)
RT 77K RT 77K RT 77K
0 65.43 ± 5.23 111.71 ± 8.49 2.95 ± 0.17 6.90 ± 0.10 3.28 ± 0.42 1.62 ± 0.12
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5 71.59 ± 4.04 161.67 ± 5.09 3.05 ± 0.03 6.89 ± 0.19 3.33 ± 0.63 2.58 ± 0.17
10 81.97 ± 3.56 121.61 ± 8.50 3.07 ± 0.11 6.89 ± 0.60 3.40 ± 0.42 1.82 ± 0.17
20 50.70 ± 5.36 114.92 ± 4.27 2.49 ± 0.12 6.94 ± 0.64 5.32 ± 0.53 1.72 ± 0.49
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Table 3
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Tensile properties of unmodified and HTPU2-modified epoxy resins at RT and 77 K.
Tensile strength (MPa) Tensile modulus (GPa) Elongation at break (%)
HTPU2 content (phr)
RT 77K RT 77K RT 77K
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0 65.43 ± 5.23 111.71 ± 8.49 2.95 ± 0.17 6.90 ± 0.10 3.28 ± 0.42 1.62 ± 0.12
5 65.02 ± 5.33 92.33 ± 6.41 2.59 ± 0.10 6.52 ± 0.22 4.39 ± 1.01 1.43 ± 0.25
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10 60.97 ± 4.58 98.21 ± 11.73 2.58 ± 0.06 6.61 ± 0.23 4.12 ± 0.77 1.56 ± 0.27
20 45.31 ± 7.25 65.30 ± 2.23 2.11 ± 0.12 6.60 ± 0.08 3.22 ± 1.11 0.98 ± 0.07
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Fig. 11. Typical stress–strain cures of EP/HTPU1 at (a) RT and (b) 77 K and EP/HTPU2 at (c) RT and
(d) 77K.
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HTPU at RT and 77K has been shown in Fig. 11. Table 2 and Table 3 list the specific
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values of tensile properties of EP/HTPU1 and EP/HTPU2 at 77K and RT. With the
increase of the second phase rubberlike particles of HTPU2, the tensile modulus of
EP
groups of HTPU1 can form hydrogen bonds with epoxy and curing agent, the tensile
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modulus starts to gradually increase until the HTPU1 content is up to 20 phr. When
the HTPU1 content is 20 phr, the flexible chains in the system is sufficiently large, the
flexible chains provided by HTPU1 start to play a primary role rather than hydrogen
bonds result in tensile modulus decreasing. However, at 77K, variation trend of tensile
modulus is different to the RT. When the temperature decreases from RT to 77K, the
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molecule and the chemical bonds will shrink and freeze and the chemical bonds
between molecule will be stronger. Because of it, the tensile modulus of EP/HTPU1 is
unchanged and independent of the HTPU1 content and the tensile modulus of
EP/HTPU2 is only slightly reduced at 77K. Besides, comparing with same contents of
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HTPU1 and HTPU2 at 77K and RT, because of the enhancement of the chemical bond
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energy, the tensile modulus of EP/HTPU at 77K is twice than it at RT and the value of
tensile strength of EP/HTPU at 77K is much higher than it at RT. In addition, since
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the cross-linked network is frozen and difficult to stretch at 77 K, there is no yielding
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phenomenon of the epoxy resin. So the optimum tensile strength and elongation at
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break of EP/HTPU1 have the same appropriate content of HTPU1 at 77K. As shown
in Table 2, the tensile strength and elongation at break of EP/HTPU1 at 5 phr HTPU1
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content increase 45% and 59% at 77K. However, the tensile strength and elongation at
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break of EP/HTPU2 both show lower than the control group at 77K. It may due to the
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second phase rubberlike particle size is too large to benefit the toughness of EP at 77K
which is same like Chen et al. [49]. Besides, the tensile strength of EP/HTPU2
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continuously decreases with the increases of the HTPU2 content at RT. Fig. 9 shows
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that the particle size and distribution are positively related to the HTPU2 contents.
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When the HTPU2 content is higher than 5 phr, the particle size is too large and
becomes the point defect, leading to the decrease of the elongation at break of
EP/HTPU2 at RT. When the content of HTPU2 is 5 phr, the elongation at break of
network, the tensile strength of EP/HTPU1 increases initially and then decreases at RT.
When the content of HTPU1 is lower, HTPU1 is dispersed in the epoxy matrix and
forms hydrogen bonds with epoxy and curing agent, leading the increases of the
tensile strength of EP/HTPU1. When the HTPU1 content increases, more flexible
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chains of HTPU1 dissolve in epoxy matrix, reducing the rigidity of the entire network
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and the tensile strength of EP/HTPU1. Although the elongation at break of
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group at RT. Due to its Tg, tensile strength, and tensile modulus decreased
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significantly compared with the control group, it is not suitable for practical
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applications. Therefore, the optimum content of HTPU1 for EP/HTPU1 system is 10
phr, where the tensile strength and the elongation at break of EP/HTPU1 increase
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4. Conclusions
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In this study, two kinds of HTPU (HTPU1 and HTPU2) with same molecular
epoxy system, which forms homogeneous phase and sea-island structure in the
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two kinds of modified epoxy resins at RT and 77K were tested and compared. The
results of impact and tensile tests show that the introduction of HTPU1 with
appropriate contents into the epoxy matrix could effectively enhance the mechanical
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properties at both 77K and RT. This is because the formation of homogeneous phase
structure with HTPU1 could help the epoxy resin enlarge the dimples during the
fracture and further absorb more fracture energy. However, the tensile properties of
EP/HTPU2 at 77K and RT decrease with the increase of HTPU2 contents, which
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results from the large size of second phase rubberlike particle size. On the other hand,
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DMA results indicate that the Tg of the homogeneous phased composite significantly
reduces with the increase of the HTPU1 content. However, because of the phase
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separation, the Tg of EP/HTPU2 composite could be well maintained. The conclusions
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achieved in this work could be reference valuable for the design and apply of
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modified resins with difference phase structures at cryogenic temperature.
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Acknowledgements
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This work was supported by the National Natural Science Foundation of China
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ACCEPTED MANUSCRIPT
Highlights:
Homogeneous phase or sea-island structure of the modified epoxy resin can be
controllably obtained by regulating the molecular weight of the adding
hydroxyl-terminated polyurethane.
The modified epoxy resin with homogeneous phase exhibits greatly enhanced
cryogenic mechanical properties.
The glass transition temperature (Tg) of the modified epoxy resin with sea-island
structures can be well maintained.
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