Journal of Physics: Conference Series

PAPER • OPEN ACCESS You may also like

- Research status and future trends on
Low Viscosity Polyurethane Modified Epoxy Resin surface pre-grouting technology in
reforming wall rock of vertical shafts in
Grouting for Steel Ring Reinforcement of Subway coal mines in China
Hua Wang

Tunnel - The differences between soil grouting with

cement slurry and cement-water glass
slurry
To cite this article: Liang Huang et al 2022 J. Phys.: Conf. Ser. 2329 012043 Mingting Zhu, Haitong Sui and Honglu
Yang

- Engineering practice of surface grouting

treatment through soft surrounding rock
stratum by TBM
View the article online for updates and enhancements. Wang Xiaochen, Guo Yanxv, Han Weiwei
et al.

This content was downloaded from IP address 190.237.27.203 on 06/11/2022 at 23:57

2022 2nd International Conference on Fluid and Chemical Engineering IOP Publishing
Journal of Physics: Conference Series 2329 (2022) 012043 doi:10.1088/1742-6596/2329/1/012043

Low Viscosity Polyurethane Modified Epoxy Resin Grouting

for Steel Ring Reinforcement of Subway Tunnel

Liang Huang1, Ming Xiao1, Weilong Li1, Shuguang Bi1,a*, Jiagong Tang2,
Xianmeng Luo2 and Jianhua Ran1,b*
1
Hubei Key Laboratory of Biomass Fibers and Eco-Dyeing & Finishing, State Key
Laboratory of New Textile Materials and Advanced Processing Technologies, College
of Chemistry and Chemical Engineering, Wuhan Textile University, Wuhan 430200,
China
2
Wuhan Rongshengjimei Technology Co., Ltd., Wuhan 430050, China
Email: a sgbi@wtu.edu.cn, b jhran@wtu.edu.cn

Abstract. Steel ring reinforcement technology is an effective method to eliminate the damage
of tunnel structure caused by ground load, surrounding foundation pit and underground water
source. The grouting material used to fill the gap between the tunnel segment and the steel ring
should have the characteristics of low viscosity, high strength, rapid curing at room
temperature and anti-subway vibration. In this work, a special polyurethane modified epoxy
resin grouting was fabricated to overcome the inherent brittleness of epoxy resin, and was
combined with the reactive diluent and the amine curing agent to suit the above applications.
The results showed that both tensile and impact strength of epoxy resin grouting modified by
polyurethane were improved obviously compared with those without modification, presenting
an obvious toughening effect. Although the viscosity increased slightly, it can still meet the
perfusion requirements of steel ring reinforcement of subway tunnels.
Keywords. Epoxy resin grouting, polyurethane prepolymer, low viscosity, high strength,
toughness.

1. Introduction
Epoxy resin adhesives are widely used in the fields of automotive [1-2], electronics [3], aircraft [4],
and construction engineering [5-6] due to their advantages of high strength, low curing shrinkage,
corrosion resistance, good thermal stability, and good electrical insulation performance. However,
epoxy resin chains contain multiple benzene or heterocyclic rings, resulting in the low elasticity of
molecular chains. Therefore, the cured epoxy resin adhesives have the disadvantages of high
crosslinking structure, easy cracking, low shear strength and poor impact resistance, and need to be
toughened [7]. Karthikeyan et al. [8] investigated the toughening effect of poly(etheretherketone)s
terminated with hydroxyl (PEEKTOH) on the room temperature curing epoxy resin. The results
showed that the shear strength and fracture toughness increased by 19% and 86% respectively when
the additive amount was 5wt%. However, the increase of PEEKTOH content in the epoxy matrix led
to the increase of viscosity, which reduced the wettability. Zeng et al. [9] used ethylene-glycidyl
methacrylate-vinyl acetate solid rubber (EGVA) modified with carboxyl groups (EGVA-COOH) and
amino groups (EGVA-NH2) as reactive tougheners to increase the compatibility between epoxy resin
matrix and rubbers. The results showed that the particle size of rubbers decreased by 71.4% and the
impact toughness of epoxy resin increased by 130% with the addition of 5 phr EGVA-NH2, while the

Content from this work may be used under the terms of the Creative Commons Attribution 3.0 licence. Any further distribution
of this work must maintain attribution to the author(s) and the title of the work, journal citation and DOI.
Published under licence by IOP Publishing Ltd 1
2022 2nd International Conference on Fluid and Chemical Engineering IOP Publishing
Journal of Physics: Conference Series 2329 (2022) 012043 doi:10.1088/1742-6596/2329/1/012043

tensile strength was not affected. However, the viscosity of epoxy precursors increased after adding
the EGVA. In addition, there have been many reports on the interpenetrating polymer networks (IPNs)
prepared by blending epoxy resin with polyurethane or hydroxyl-terminated polyurethane to improve
the toughness performance of epoxy resin [10]. In this work, the room-temperature cured epoxy resin
grouting with low viscosity, high strength and high toughness was prepared by using the active
isocyanate-terminated polyurethane prepolymer as the toughening agent for repairing cracks in the
subway tunnels.

2. Experimental

2.1. Materials
Toluene diisocyanate (TDI) was purchased from Aladdin. Polyethylene glycol (PEG200),
N-aminoethylpiperazine (AEP) and acetone were obtained from Sinopharm Chemical Reagent Co.,
Ltd. Benzyl glycidyl ether (BGE) was provided by Hubei Greenhome Materials Technology Co., Ltd.
Bisphenol F epoxy resin (BPF-170) was purchased from China Petrochemical Co. Ltd. Their chemical
structures and parameters were shown in table 1.

Table 1. Parameters of the epoxy resin, active diluent and curing agent.
Viscosity Epoxy equivalent weight
Molecular
Materials Molecular structure (25 ℃ (g/eq) or Amine equivalenta
weight
mPa·s) (g/mol)

BPF-170 312 3050 ±15 160-180

BGE 164 5-8 ≥0.43

AEP 129 12.0 ±2 43.0

a molecular weight of amine

Amine equivalent = number of active hydrogens in an amine

2.2. Preparation of Polyurethane Modified Epoxy Resin Grouting

Firstly, isocyanate-terminated polyurethane prepolymer were synthesized at 70 ℃ for 3 h in the
nitrogen atmosphere. The molar ratios of TDI and PEG200 were 1.5:1, 1.8:1 and 2:1, denoted as
PUR-1, PUR-2 and PUR-3, respectively. Then, the epoxy resin of BPF-170 was added to make the
account of polyurethane prepolymer for 10 wt%. Finally, 30 wt% of active diluent BGE and a certain
amount of curing agent AEP were added, following by mixing evenly and pouring into the mechanical
mold for vacuumization.

2.3. Characterization
Fourier transform infrared spectroscopy (FTIR) was taken on the BRUKER Tensor 27 using KBr
powder. Viscosity was measured using an NDJ-9S digital viscometer at 25 °C according to ASTM
D-1084. Tensile and shear properties were tested using GOTECH AI-7000M universal testing
machine according to ASTM D-638 and ISO 4587, respectively. Impact strength was tested by
GOTECH impact testing machine according to ASTM D-256. The microstructure of the tensile
section was observed by JSM IT500A scanning electron microscopy (SEM).

2
2022 2nd International Conference on Fluid and Chemical Engineering IOP Publishing
Journal of Physics: Conference Series 2329 (2022) 012043 doi:10.1088/1742-6596/2329/1/012043

3. Results and Discussion

3.1. FTIR Spectra

As shown in figure 1(a), the -OH vibration absorption peak of PEG200 and -NH- vibration absorption
peak of PUR-3 appeared at the wavenumber of 3300 cm-1. The -NCO vibration absorption peaks of
TDI and PUR-3 appeared at 2270 cm-1. The peak at 1720 cm-1 was the characteristic peak of the -C=O
group of PUR-3, indicating that the isocyanate-terminated polyurethane prepolymer was synthesized.
As shown in figure 1(b), compared with PUR-3, the polyurethane modified epoxy resin
(PUR-3/BPF-170) did not appear the vibration absorption peak of -NCO at 2270 cm-1, and the
vibration absorption peak of -NH- at 3300 cm-1 and the vibration absorption peak of -C=O at 1720
cm-1 were obviously weakened. This indicated that the polyurethane prepolymer was grafted onto the
epoxy resin by end-isocyanate.

Figure 1. FTIR spectra of polyurethane prepolymer (a) and polyurethane modified epoxy resin (b).

3.2. Viscosity of Polyurethane Modified Epoxy Resin Grouting

The viscosity of PUR-1/BPF-170/BGE/AEP, PUR-2/BPF-170/BGE/AEP, PUR-3/BPF-170/BGE/AEP
and BPF-170/BGE/AEP were 96.1, 142.9, 173.3 and 88.4 mPa·s at 25 °C, respectively. Although
polyurethane modification slightly increased the viscosity of epoxy resin grouting, the effect was small,
less than 200 mPa·s, presenting good fluidity, which can be used in the pouring technology.

3.3. Mechanical Properties of Polyurethane Modified Epoxy Resin Grouting

Compared with the unmodified epoxy resin grouting (BPF-170/BGE/AEP), the tensile strength of the
three polyurethane modified epoxy resin grouting increased, up to 49.8 MPa, and the elongation at
break increased 2-3 times, as shown in figure 2(a). Similarly, it can be seen from figure 2(b) and 2(c)
that the shear elongation at break and impact strength also increased and the maximum shear strength
and impact strength were 20.7 MPa and 3.18 kJ/m2, respectively. These results showed that
polyurethane modification increased the toughness of epoxy resin grouting.

Figure 2. (a) Tensile stress-strain curves, (b) steel-steel shear stress-strain curves and (c) impact
strength of polyurethane modified epoxy resin grouting.

3
2022 2nd International Conference on Fluid and Chemical Engineering IOP Publishing
Journal of Physics: Conference Series 2329 (2022) 012043 doi:10.1088/1742-6596/2329/1/012043

3.4. Morphology of Polyurethane Modified Epoxy Resin Grouting

As shown in figure 3, the tensile fracture section of the unmodified epoxy resin BPF-170/BGE/AEP
was smooth and the crack direction was consistent, presenting the characteristics of brittle fracture.
However, the tensile fracture section of polyurethane modified epoxy resins had more irregular and
disordered cracks in the growth direction, due to the absorption and dispersion of the corresponding
flexible chain segments in the polyurethane prepolymer, which further indicated that polyurethane had
the toughening effect on epoxy resin.

Figure 3. Microstructure of the tensile fracture section of (a) PUR-1/BPF-170/BGE/AEP, (b)

PUR-2/BPF-170/BGE/AEP, (c) PUR-3/BPF-170/BGE/AEP and (d) BPF-170/BGE/AEP.

4. Conclusion
In this work, epoxy resin was modified with different proportions of isocyanate-terminated
polyurethane prepolymer, and then prepared epoxy resin grouting with active diluent and amine curing
agent at room temperature. After modification, the viscosity of the three kinds of epoxy resin grouting
were all lower than 200 mPa·s, and the tensile strength and elongation at break were increased,
presenting high strength and high toughness, which can be used as the grouting materials for repairing
cracks in subway tunnels.

Acknowledgments
The authors would like to express the appreciation for the funding supported by Key Project of
"Science and Technology for Economy 2020" of National Key Research and Development Program,
Science and Technology Research Project of Hubei Province Education Department (B2020073),
Development of Science and Technology of Hubei Province (2021CFA034).

References
[1] Maggiore S, Pedemonte M, Bazurro A, Stagnaro P, Utzeri R and Luciano G 2020
Characterization of the effect of an epoxy adhesive in hybrid FSW-bonding aluminium-steel
joints for naval application International Journal of Adhesion and Adhesives 103 102702.
[2] Ocaña R, Arenas J M, Alía C and Narbón J J 2015 Evaluation of degradation of structural
adhesive jointsin functional automotive applications Procedia Engineering 132 716-723.
[3] Ranji S and CheonLee M 2022 Study on synthesizing new urethane epoxy adhesives and their
adhesive properties on different substrates International Journal of Adhesion and Adhesives
117 PartA 103174.
[4] Encinas N, Oakley B R, Belcher M A, Blohowiak K Y, Dillingham R G, Abenojar J and
Martínez M A 2014 Surface modification of aircraft used composites for adhesive bonding
International Journal of Adhesion and Adhesives 50 157-163.
[5] Balmori J A, Branco J M and Basterra L A 2021 Behaviour of the adhesive bond between
low-grade wood and GFRP reinforcements using epoxy resin Construction and Building
Materials 271 121516.
[6] Modesti L A, Vargas A S D and Schneider E L 2020 Repairing concrete with epoxy adhesives
International Journal of Adhesion and Adhesives 101 102645.

4
2022 2nd International Conference on Fluid and Chemical Engineering IOP Publishing
Journal of Physics: Conference Series 2329 (2022) 012043 doi:10.1088/1742-6596/2329/1/012043

[7] Cruz R, Correia L, Cabral-Fonseca S and Sena-Cruz J 2021 Effects of the preparation,curing
and hygrothermal conditions on the viscoelastic response of a structural epoxy adhesive
International Journal of Adhesion and Adhesives 110 102961.
[8] Karthikeyan L, Robert T M, Mathew D, DesakumaranSuma D and Thomas D 2021 Novel
epoxy resin adhesives toughened by functionalized poly(etheretherketone)s International
Journal of Adhesion and Adhesives 106 102816.
[9] Zeng Y, Wang Q, Xu P, Yang W, Hoch M and Ma P 2022 Toughening of epoxy resin with
balanced performance by in situ constructing interfacial bonding and elastic segments into
epoxynetwork Materials Chemistry and Physics 277 125529.
[10] Qu C B, Wu T, Huang G W, Li N, Li M, Ma J L, Liu Y and Xiao H M 2021 Improving
cryogenic mechanical properties of carbon fiber reinforced composites based on epoxy resin
toughened by hydroxyl-terminated polyurethane Composites Part B: Engineering 210
108569.