Journal Pre-proof

Experimental study on the mechanical properties of

cement-based grouting materials after exposed to
high temperatures

Yunxing Wang, Chuanguo Fu, Huashuo Kuang,

Hailiang Qin, Tengfei Xu, Weihao Meng

PII: S2214-5095(24)00219-5
DOI: https://doi.org/10.1016/j.cscm.2024.e03068
Reference: CSCM3068

To appear in: Case Studies in Construction Materials

Received date: 7 January 2024
Revised date: 29 February 2024
Accepted date: 19 March 2024
Please cite this article as: Yunxing Wang, Chuanguo Fu, Huashuo Kuang,
Hailiang Qin, Tengfei Xu and Weihao Meng, Experimental study on the
mechanical properties of cement-based grouting materials after exposed to high
temperatures, Case Studies in Construction Materials, (2024)
doi:https://doi.org/10.1016/j.cscm.2024.e03068
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 (8564 words)
Experimental study on the mechanical properties of
cement-based grouting materials after exposed to high
temperatures
Yunxing Wanga,b, Chuanguo Fua,, Huashuo Kuanga, Hailiang Qina, Tengfei Xua,
Weihao Menga
a
Shandong Jianzhu University, Jinan 250101, PR China
b
Shandong Agriculture and Engineering University, Jinan 251100, PR China

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Keywords:

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Prefabricated structures; Residual strength; Grouted sleeve connections; Cement-based grouting materials; Microstructure

ABSTRACT
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This paper experimentally investigates the compressive and flexural strengths of cement-based grouting materials
used in grouted sleeve connections at both room temperature and after exposure to high temperatures. The tests
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were conducted at three different temperatures (200°C, 400°C, and 600°C) using two cooling methods
(natural-cooled and water-cooled), and various durations of constant temperature and dwell times after
high-temperature exposure were considered. The mechanical properties of the grout after high temperature were
comparatively analyzed, and the changes in the microstructure were observed and analyzed using a scanning
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electron microscope. The experimental results demonstrate a linear decrease in the dynamic elastic modulus as the
temperature rises. Moreover, the sample tested at 200°C exhibits an upward trend in its mechanical properties due
to the development of stable phases of calcium silicate hydrate (C-S-H) and the additional effects of secondary
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hydration. However, beyond 400°C, a substantial decomposition of C-S-H occurs, leading to severe internal
structural damage and a sharp decline in mechanical performance.Furthermore, the cooling method employed also
influences the mechanical properties of the grouting material after exposure to high temperatures. The sample
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cooled by water displays a slight increase (up to 10%) in the dynamic elastic modulus, attributed to the secondary
hydration of surface hydration products, compared to the naturally cooled sample. Nevertheless, the water-cooled
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sample experiences an uneven temperature distribution caused by the temperature disparity between its interior
and exterior, exacerbating internal damage. As a result, their flexural strength and compressive strength exhibited
varying degrees of decline, up to 43.9% and 27.9%, respectively, compared to natural-cooled specimens.
Microscopic observations revealed that exposure to high temperature induced significant physical and chemical
changes in the cement-based grouting materials, which were closely correlated with their macro mechanical
properties. Based on the experimental study, a calculation formula for the discount coefficient of flexural and
compressive strengths of the cement-based grouting materials after exposure to high temperatures was established
through data analysis. The computational results demonstrated good agreement with the experimental findings.
Finally this study provides reliable and valuable test data for investigating the bonding properties between
reinforcement and grouting materials in grouted sleeve connections.

1. Introduction

*Corresponding author at: Shandong Jianzhu University, Jinan 250101, China. E-mail address:
fcguo@sdjzu.edu.cn.

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 Grouted sleeve connection is a widely used method for joining reinforcing bars in
prefabricated reinforced concrete structures. In recent years, the fire resistance of grouted
sleeves has received significant attention due to the increasing occurrence of building fires.
The mechanical properties of grouting materials, as the main components of grouted sleeves,
have also been extensively studied in relation to their behavior after exposed to fire.
After the hydration reaction of cement-based grout, a non-homogeneous multi-phase
system is formed, comprising C-S-H gel, CH crystals, ettringite crystals, unhydrated cement
particles, silica, water, and pores. Cement-based materials undergo significant degradation
and loss of mechanical properties during fire exposure due to chemical reactions and phase
transformations. The exposure of cement materials to temperatures ranging from 100°C to 250°C
primarily leads to dehydration reactions involving both free and chemically bound water [1-2]. At

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approximately 500°C, calcium hydroxide (C-H) dissociates into calcium oxide (CaO) and water
(H2O), while calcium silicate hydrate (C-S-H) can decompose at temperatures above 600°C [2].
This high-temperature exposure results in the destruction of cement hydration products, with

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significant implications for the macroscopic and microscopic characteristics of the materials.

Taylor[3] systematically introduced the process of cement hydration reaction and its effects on

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the mechanical properties, durability, and microstructure of cement materials. Alonso et al. [4]
further investigated the chemical changes in cement paste after exposure to different high
temperatures, as well as the processes of dehydration and rehydration. They also provided relevant
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descriptions of the microstructural changes in hydration products following high-temperature
exposure. Meanwhile, Mindess S [5] focused on the constituents of the gel structure and the
typical morphology and physical properties of the major hydrates. Additionally, studies on the
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microscopic morphology of ettringite have been investigated by Yang et al. [6] and Wu [7].
Currently, a number of researchers have conducted extensive studies on the mechanical
strength of cement-based grouting materials after exposed to high temperatures. Li [8]
investigated the residual compressive strength and elastic modulus of cement-based grouting
a

materials through experimental means, and observed that the reduction of the residual
compressive strength and elastic modulus of the material increases with an increase in water
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mixing ratio [9-10]. Yan et al. [11] highlighted that the fire resistance of cement-based
grouting materials is superior to that of normal concrete. Yuan et al. [10] investigated the
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degradation of compressive strength in high-performance cement-based grouting materials

subjected to elevated temperatures. The study revealed that the compressive strength tends to
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decrease with increasing temperature, but stabilizes over time. Additionally, it was found that
cooling through water spray can partially restore the compressive strength. Jin et al. [12]
conducted a study on the mechanical properties of cement-based grouting materials for
grouted sleeve connections after exposed to high temperatures. The study revealed that the
compressive strength and flexural strength of the materials decreased to varying extents as the
temperature increased, with the decrease in flexural strength being greater than that in
compression. Xue [13] investigated the thermal and mechanical properties of grouting
materials at elevated temperatures up to 900°C and found that as the temperature increased,
the thermal conductivity and compressive strength of the materials decreased, while the heat
capacity and thermal strain increased.
Certain scholars have indicated that the post-fire performance of cement-based materials
can be recovered by the post-fire curing process (re-curing) due to a possible C-S-H
rehydration [14-16]. Henry et al. [17] observed that air re-curing resulted in the development
of surface cracks due to thermal shrinkage and an increase in carbonation and porosity.

2
Karahan [18] investigated the effects of cooling method and air curing after fire on mortar's
compressive strength, noting that specimens cooled in air or oven exhibited varying degrees
of strength reduction, while those cooled in water and air cured showed a noteworthy increase
in strength [17-19]. Furthermore, elastic modulus was more significantly affected by cooling
conditions compared to compressive strength [20].
Additionally, researchers have successfully improved the crack resistance, durability, and
expansibility of grouting materials by incorporating various fibers, polymers and compound,
while also enhancing the mechanical properties of these materials, such as flexural strength
and compressive strength [21-29].Zang et al. [30] studied the influence of lithium sulfate on
the performance of high-water grouting materials, noting that an increase in lithium carbonate
content resulted in a gradual reduction in bleeding capacity, continuous shortening of setting
time, and higher compressive strength.Wang et al. [31] discovered that sodium sulfate and
potassium sulfate significantly enhance the compressive strength of calcium sulfoaluminate

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(CSA) cement based grouting materials.Wang et al. [32] enhanced the expansibility and
strength of aluminum powder blended grouting materials by incorporating sodium sulfate or
gypsum.Wang et al. [33] pointed out that sodium aluminate can shorten the setting time of

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CSA and rapidly increase its early compressive strength.
Moreover, elevated temperatures induced intricate physical and chemical alterations in
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cement-based materials, resulting in a decrease in the bonding capability of grouted sleeves
[34-36]. Nevertheless, augmenting the thickness of the concrete cover layer can substantially
enhance the aforementioned properties [37]. Liu et al. [38] investigated the bonding behavior
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between grouting materials and rebar after fire and established an equation for the bond
strength between grouting materials and rebar.
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In conclusion, there is currently a lack of research data regarding the mechanical properties
of grouting materials for reinforcing bar connections after exposure to high temperatures.
With the increasing frequency of building fires, there is a growing concern about the
degradation of the mechanical properties of grouting materials used in prefabricated buildings
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after high-temperature conditions. This study aims to investigate the macroscopic mechanical
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properties of grouting materials after exposure to different high temperatures and analyze
their degradation patterns. Additionally, scanning electron microscopy is utilized to observe
the microscopic phenomena of grouting materials after high-temperature exposure and
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analyze the mechanisms leading to their deterioration. These research findings have
significant theoretical and practical implications for the safety analysis of concrete structures
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utilizing grouted sleeve connections after fire incidents.

2. Experimental overview

2.1 Experimental design

The cement-based grouting materials (CGM) used specifically for assembly building were
supplied by Beijing Zhongde Xinya Construction Technology Co., Ltd. The CGM exhibited a
compressive strength of 94.8 MPa after 28 days, meeting the requirements outlined in the
current industry standard "Cementitious grout for coupler of rebar splicing"
(JG/T408-2019)[39]. Comprising plain 525 or 425 cement, superfine mineral powder, 95%
silica powder, gypsum, 30-40 mesh sand, 40-70 mesh sand, and various admixtures, these

3
components form the essential composition of the grouting material, ensuring its effectiveness
and compliance with industry standards.
To facilitate the research, the experiment was divided into two phases. In the first stage, an
orthogonal test was conducted in accordance with engineering practice and theoretical
considerations. The selected factors for this orthogonal experiment were the water mixing rate,
elevated temperature, constant temperature duration, cooling method, and dwell time. The
specific levels for each of the five factors are presented in Table 1. A total of 16 groups of
specimens were set up in this stage, with each group consisting of 3 specimens. Through
variance analysis, significant factors that influence the mechanical properties of grouting
materials after high temperature exposure will be determined. Considering the previous
research findings [40-41], which demonstrated a significant decrease in compressive strength
of cement-based materials when exposed to temperatures up to 600 °C, a maximum heating
temperature of 600 °C was selected for this research.

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Table 1

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Level table of orthogonal experiment factors.
Factors
Levels Water mixing
rate/%
-p
Temperature/°C Thermostatic time/h Cooling method Dwell time/d
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1 12 200 0.5 N 1
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2 14 400 1 W 7

3 16 600 2 - 14
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Note:N-natural-cooled, W-water-cooled;
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The experimental design resulted in the creation of Table 2, which displays an orthogonal
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test table composed of predetermined factors and their corresponding levels.

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Table 2
Orthogonal test table L16.
Water mixing
Sample ID Temperature/°C Thermostatic time/h Cooling method Dwell time/d
rate/%

P12T2H0.5ND1 12 200 0.5 N 1

P12T4H1WD7 12 400 1 W 7

P12T6H2ND14 12 600 2 N 14

P12T4H2WD1 12 400 2 W 1

P14T2H1ND7 14 200 1 N 7

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 Water mixing
Sample ID Temperature/°C Thermostatic time/h Cooling method Dwell time/d
rate/%

P14T4H0.5WD14 14 400 0.5 W 14

P14T6H1ND7 14 600 1 N 7

P14T2H2WD1 14 200 2 W 1

P16T2H2WD7 16 200 2 W 7

P16T4H0.5ND1 16 400 0.5 N 1

P16T6H0.5WD14 16 600 0.5 W 14

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P16T6H1ND14 16 600 1 N 14

P16T2H1WD14 16 200 1 W 14

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P14T4H2ND1 14 400 2 N 1

P12T6H1WD1

P14T4H0.5ND7
12

14
600

400
-p 1

0.5
W

N
1

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Note:
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P-water admixture rate(% ), 12, 14, 16-12% , 14% , 16% ;

T-temperature rise(℃ ), 2, 4, 6-200℃, 400℃, 600℃ ;

H-thermostatic time(h), 0.5, 1, 2-0.5h, 1h, 2h;

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N-natural-cooled, W-water-cooled; D-dwell time(d), 1, 7, 14, 28-1d, 7d, 14d, 28d.

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In the subsequent phase of experimentation, 24 groups of specimens (Table 3) were

prepared, each comprising 3 specimens, to investigate the variation law in residual
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compressive strength, flexural strength, and dynamic elastic modulus of grouting materials
after exposed to high temperatures under different factors.

Table 3
Design of grouting materials in the second phase.
Water mixing Dwell
Sample ID Temperature/°C Thermostatic time/h Cooling method
rate/% time/d

T0H0ND1 14 25 - - 1d

T0H0ND3 14 25 - - 3d

T0H0ND28 14 25 - - 28d

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 Water mixing Dwell
Sample ID Temperature/°C Thermostatic time/h Cooling method
rate/% time/d

T2H1ND1 14 200 1 N 1d

T4H1ND1 14 400 1 N 1d

T6H1ND1 14 600 1 N 1d

T2H1WD1 14 200 1 W 1d

T4H1WD1 14 400 1 W 1d

T6H1WD1 14 600 1 W 1d

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T2H0.5ND1 14 200 0.5 N 1d

T2H2ND1 14 200 2 N 1d

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T4H0.5ND1 14 400 0.5 N 1d

T4H2ND1

T6H0.5ND1
14

14
600

600
-p 2

0.5
N

N
1d

1d
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T6H2ND1 14 600 2 N 1d
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T2H1ND7 14 200 1 N 7d

T2H1ND14 14 200 1 N 14d

a

T4H1ND7 14 400 1 N 7d
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T4H1ND14 14 400 1 N 14d

T6H1ND7 14 600 1 N 7d
u

T6H1ND14 14 600 1 N 14d

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T2H1ND28 14 200 1 N 28d

T4H1ND28 14 400 1 N 28d

T6H1ND28 14 600 1 N 28d

Note:The naming convention follows the same rules as Table 2.

The preparation of the specimens followed the "Test method of cement mortar strength
(ISO method)" (GB/T17671-2021) [42]. The specimens were standardized as 40 mm × 40
mm × 160 mm prismatic cement-based grouting specimens. After fabrication, the specimens
underwent standard curing for 28 days in a thermostatically controlled curing chamber.
To prevent the occurrence of specimen bursting during the high temperature test [6], the

6
specimens were initially dried for 24 hours in a drying chamber at 105°C prior to the high
temperature exposure. The manufacturing process of the specimens are illustrated in Fig. 1.

(a)Fabricating test specimens (b)Standard curing (c) Drying treatment

Fig. 1 Fabrication of specimens

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2.2 High temperature exposure test and main testing equipment

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To conduct high temperature tests on the specimens, an SX2-12-10 box-type resistance
furnace manufactured by Shanghai Yiheng Technology Co., Ltd. was used at the Materials
Testing Laboratory of Shandong Jianzhu University. The furnace temperature was
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automatically controlled using a controller. Heating of the specimens in the furnace took
place at an approximate rate of 10°C/min until reaching the target temperature. They were
then maintained at a constant temperature for 0.5 hours, 1 hour, or 2 hours. Afterward, the
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heating was stopped, and the specimens were removed from the furnace and allowed to
naturally cool to room temperature or cooled using water spray. To determine their
mechanical properties, the specimens were left to stand for 1 day, 7 days, 14 days, or 28 days
a

before undergoing flexural strength, compressive strength, and dynamic modulus tests at the
Materials Testing Laboratory. The flexural and compressive strength tests were conducted
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using a YAW-300E fully automatic compression and flexure testing machine produced by
Jinan Kaide Instrument Co., Ltd. The dynamic modulus measurement equipment used was the
NELD-DTV dynamic modulus measurement instrument produced by Beijing Neird
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Technology Co., Ltd. Scanning electron microscopy (SEM) was conducted using the
GeminiSEM 300 scanning electron microscope in the Electron Microscopy Room. The
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testing equipments are shown in Fig. 2.

(a)High temperature testing (b)Flexural strength testing (c) Compressive strength testing

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 (f) Electron microscopic observa
(d)Dynamic modulus measuring (e)Gold-sprayed treating
ting

Fig. 2 Testing equipments

3. Text results

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3.1 High-temperature impact test and primary testing equipment

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The specimen was exposed to high temperatures and then promptly transferred and
positioned on the work platform for natural-cooled or water-cooled until it reached room
temperature (refer to Fig.s 3 and 4). Upon drying after water-cooled, the appearance and color
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of the specimen resembled those after natural-cooled. However, both the width and length of
surface cracks exhibited a slight increase due to the rapid temperature drop (further specific
details are provided in Table 4). In the case of the 400°C specimen, the water-cooled sample
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demonstrated a 10% increment in crack width on its lateral side as compared to the naturally
cooled counterpart. Additionally, the water-cooled sample exhibited a significant 33%
increase in the maximum crack length.
a
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(a) Exposed to 200°C

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 (b) Exposed to 400°C

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(c) Exposed to 600°C

a

Fig. 3 Surface characteristics of specimens after natural-cooled

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(d) Exposed to 200°C

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 (e) Exposed to 400°C

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(f) Exposed to 600°C

Fig. 4 Surface characteristics of specimens after water-cooled

a
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Table 4
Appearance characteristics of specimens after exposure to high temperature.
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Temperature Cooling No. of Maximum length of Maximum width

External color
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/°C method cracks(top/side) cracks (top/side)/mm of cracks/mm

200 natural-cooled gray 7 10 3 15 0.5

400 natural-cooled light gray cracked pattern 10 cracked pattern 15 1

600 natural-cooled grayish-white cracked pattern 12 cracked pattern 40 1.2

200 water-cooled gray 8 11 4 16 0.55

400 water-cooled light gray cracked pattern 11 cracked pattern 20 1.1

600 water-cooled grayish-white cracked pattern 12 cracked pattern 40 1.3

Based on the findings from Figure 3 and Table 4, it is evident that the specimens, following
exposure to a high temperature of 200°C and subsequent natural cooling, presented an overall
gray surface. Notably, the upper surface exhibited 6-7 cracks, measuring 2-3 cm in length,

10
predominantly concentrated along the edges. Approximately 9-10 cracks were observed at the
top of the side surface, with the largest crack measuring about 0.5mm in width, extending
towards the center and occupying roughly one-third of the specimen's height. Signs of
increased crack width and number on the side surface were evident during the natural cooling
process, although no obvious cracks were observed at the bottom. Following exposure to a
temperature of 400°C, the specimen's surface turned light gray overall, with local areas
exhibiting a pale yellow coloration. A cracked pattern emerged across the entire top surface,
with the largest crack width ranging from 0.5-1mm. On the top of the side surface, 9-10
vertical cracks extended towards the center, measuring 0.5-1mm in width and 1-1.5cm in
length. Additionally, irregular fine cracks with a width of 0.2mm were occasionally observed
in the middle part of the side surface. After being subjected to a temperature of 600°C, the
specimen's surface assumed an overall grayish-white appearance, with a cracked pattern
covering the entire surface and the largest crack width measuring 1.2mm. The side surface
featured 10-12 vertical cracks, with the longest crack penetrating the entire side surface and

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reaching a maximum width of 1.2mm. With the aid of SEM analysis, it is revealed that as the
temperature increases, the internal C-S-H gel, C-H crystals, and ettringite (AFt) crystals

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within the specimen gradually decompose. This transformation leads to a change in surface
color and is the primary cause for varying degrees of increase in both the number and length
of cracks.

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3.2 Results of flexural, compressive, and dynamic-elastic mode tests
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Mass loss can indirectly indicate the extent of damage to grout specimens after undergoing
different high-temperature processes. The mass loss rate ( I ) can be determined by the
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following Eq. 1:

m0 − mf
I=  100% （1）
a

m0
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Note: I represents the mass loss rate (%), m0 represents the mass of the test specimen
before high temperature (g), and m represents the mass of the test specimen after high
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temperature (g).
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Following flexural and compressive strength testing, the specimens' characteristic failure
modes are depicted in Fig. 5. Under ambient conditions and subsequent water cooling, the
specimens demonstrated negligible brittleness during the testing process, showcasing a
relatively intact structural integrity after failure. Conversely, upon exposure to elevated
temperatures, the specimens exhibited a notable transition towards brittle failure, exhibiting
an escalated severity proportional to the temperature rise. Noteworthy manifestations included
fragmented debris ejection and resonant acoustic emissions.

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 Fig. 5 Typical failure modes of flexural and compressive strength tests

Test measurements encompassing mass loss, dynamic elastic modulus, flexural strength,
and compressive strength of cement-based grouting specimens were conducted under diverse
operational conditions and are tabulated in Tables 5 and 6.

Table 5
Experimental results of grout specimens in the first stage after exposure to high temperature.
Sample ID Number of specimens fcf,Avg/MPa fc,Avg/MPa

P12T2H0.5ND1 3 10.9 94.1

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P12T4H1WD7 3 7.1 81.7

P12T6H2ND14 3 4 60.3

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P12T4H2WD1 3 6.6 73.8

P14T2H1ND7 3 12.8 86.5

P14T4H0.5WD14 3
-p 5.5 78.5
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P14T6H1ND7 3 3.2 54.7

P14T2H2WD1 3 7.5 82.9

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P16T2H2WD7 3 9.4 83.7

P16T4H0.5ND1 3 9.3 82.8

P16T6H0.5WD14 3 3.5 58.8

a

P16T6H1ND14 3 2 53.6
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P16T2H1WD14 3 6.1 78.6

P14T4H2ND1 3 5.7 61.3

u

P12T6H1WD1 3 6 57.9
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P14T4H0.5ND7 3 8.1 78.8

Note:fcf,Avg-Average of Flexural Strength, fc,Avg-Average of Compressive Strength,

P-water admixture rate(% ), 12, 14, 16-12% , 14% , 16% ;

T-temperature rise(℃ ), 2, 4, 6-200℃, 400℃, 600℃ ;

H-thermostatic time(h), 0.5, 1, 2-0.5h, 1h, 2h;

N-natural-cooled, W-water-cooled; D-dwell time(d), 1, 7, 14, 28-1d, 7d, 14d, 28d.

Table 6

12
Experimental results of grout specimens in the second stage after exposure to high temperature.
Number of
Sample ID Mass loss/% EAvg/GPa fcf,Avg/MPa fc,Avg/MPa
specimens

T0H0ND1 3 - - 3.4 38.5

T0H0ND3 3 - - 6.1 62.5

T0H0ND28 3 - 40.7 9.0 86.4

T2H1ND1 3 1.5 29.1 9.6 90.4

T4H1ND1 3 6.3 18.0 8.2 88.4

T6H1ND1 3 6.5 5.0 3.4 60.1

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T2H1WD1 3 - 31.3 8.7 81.0

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T4H1WD1 3 - 19.8 4.6 63.4

T6H1WD1

T2H0.5ND1
3

3
-

0.57
-p 5.5

30.8
2.2

9.4
51.2

86.5
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T2H2ND1 3 3.2 27.3 9.9 100.0

T4H0.5ND1 3 5.8 18.3 8.9 93.8

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T4H2ND1 3 6.8 14.0 7.6 77.6

T6H0.5ND1 3 6.5 6.2 4.8 68.1

a
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T6H2ND1 3 6.9 3.3 3.3 57.1

T2H1ND7 3 - 28.5 10.8 95.0

u

T2H1ND14 3 - 29.2 10.9 98.4

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T4H1ND7 3 - 13.4 6.0 72.7

T4H1ND14 3 - 14.0 6.5 74.0

T6H1ND7 3 - 3.0 3.1 55.2

T6H1ND14 3 - 3.2 2.4 50.2

T2H1ND28 3 - 29.3 11.7 90.8

T4H1ND28 3 - 12.9 5.9 72.3

T6H1ND28 3 - 3.5 2.9 55.6

Note:The numbering rules are the same as Table 5, EAvg-Average of Dynamic Elastic Modulus,
T0-room temperature 25℃, H0-no high temperature action.

13
4. Analysis of experimental results

4.1 Variance analysis on factors affecting mechanical properties of specimens after high temperature
exposure

Controllable factors exerting influence and random factors, etc., play a major role in the
fluctuations of the test data. By utilizing variance analysis, researchers can overcome the
limitations of range analysis, minimize the impact of random errors during the experimental
process, and enhance the precision of their experiments. Originating from the pioneering
work of British statistician R.A. Fisher, variance analysis, commonly known as the F test,
serves as a statistical tool for assessing the significance of mean differences among multiple

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samples [43]. In this context, the influencing factors A, B, C, D, and E correspond to the
water mixing rate, temperature elevation, constant temperature duration, cooling method, and

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settling time, respectively. The interactions between these factors are not considered in the
variance analysis. The mathematical model for conducting the variance analysis can be
expressed as Eq. 2.
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 X ijklm =  +  i +  j +  k +  l +  m +  ijklm (i = 1,2,  , r;
 j = 1,2,  , s; k = 1,2,  , t ; l = 1,2,  , u; m = 1,2,  , v; )
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 r s t u v



 i =1
ai = 0;   j = 0;  
 k = 0; 
 l = 0;  m = 0;
a

j =1 k =1 l =1 m =1

 ijklm ~ N (0, );  ijklm Independent of each other
2
rn


（2）
u
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In this Eq.2, Xijklm represents the experimental result, μ denotes the weighted average value
of the experimental results under each factor, α signifies the effect of the ith level of factor A,
β corresponds to the effect of the jth level of factor B, γ describes the effect of the kth level of
factor C, δ depicts the effect of the lth level of factor D, φ captures the effect of the mth level
of factor E, and εijklml accounts for the random error, following a normal distribution denoted
by N.
By conducting variance analysis on the experimentally measured data using SPSS software,
the results obtained can be presented in Table 7-8.

Table 7

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Flexural strength - multi-factor analysis of variance.

Itemperature SS df MS F p

Intercept distance 699.609 1 699.609 236.613 0.000**

Water admixture rate 4.655 2 2.328 0.787 0.497

temperature 52.648 2 26.324 8.903 0.016*

thermostatic time 7.557 2 3.778 1.278 0.345

Cooling method 2.417 1 2.417 0.818 0.401

Dwell time 12.329 2 6.165 2.085 0.205

of
Residual 17.741 6 2.957

ro
Note: (1) SS - Square Sum, MS - Mean Square, df - degree of freedom, F - statistic, and p -
significance level. (2) Table 7 R2=0.860; R-Correlation coefficient. (3) * indicates p<0.05, **i
ndicates p<0.01.
-p
re
Table 8
Compressivel strength - multi-factor analysis of variance.
lP

Itemperature SS df MS F p

Intercept distance 81927.003 1 81927.003 4301.858 0.000**

a

Water admixture rate 151.300 2 75.650 3.972 0.080

rn

temperature 1560.901 2 780.451 40.980 0.000**

u

thermostatic time 232.627 2 116.314 6.107 0.036*

Jo

Cooling method 0.038 1 0.038 0.002 0.966

Dwell time 47.132 2 23.566 1.237 0.355

Residual 114.267 6 19.045

Note:(1)Table 8 R2=0.955. R-Correlation coefficient

The significance level for the test was set at α=0.05. According to Table 5, the p-value of
the temperature test is found to be less than 0.05, indicating a significant influence of
temperature on the flexural strength. Likewise, Table 6 reveals that both the temperature and
constant temperature duration tests yielded p-values below 0.01 and 0.05, respectively. This
suggests that both temperature and constant temperature duration have a significant impact on
compressive strength, with temperature exhibiting an extremely pronounced effect. Therefore,
it can be concluded that temperature significantly affects both flexural and compressive
strengths, whereas constant temperature duration also has a notable influence on compressive

15
strength. Other factors, however, lack statistically meaningful implications.

4.2 Analysis of the variation in mass loss of specimens after high temperature exposure

Fig.s 6 shows the variation in mass loss of grout specimens after exposed to high
temperatures at different heating temperatures and constant temperature duration.

8 8

6 6

of
Maa loss / %

Maa loss / %
4 4

ro
T
em
p
erature/℃
2 2
0.5h 200
1h 400

0
200 400 600
2h

-p 0
0.5 1.0 1.5
Constant temperature duration / h
600

2.0
re
(b) Mass loss with constant temperature
(a) Mass loss with temperature.
duration
lP

Fig. 6 Mass loss of grout specimens

a

As demonstrated in Fig. 6a, the mass loss of grout specimens after exposed to high
temperatures increases as the temperature rises. The most significant mass loss rate is
rn

observed in the temperature range of 200°C to 400°C, while the rate decreases in the range of
400°C to 600°C. This can be attributed to the evaporation of free water on the outer surface of
u

the specimens after drying at 105°C, followed by the loss of bound water. When the
temperature reaches 400°C, a significant portion of the C-S-H gel, which is the primary
Jo

component of the grout, has already decomposed, leading to the most severe mass loss below
400°C. The slow growth rate of mass loss in the temperature range of 400°C to 600°C is
primarily due to the decomposition of a small amount of C-S-H gel and CH crystals.
As depicted in Fig. 6b, it is evident that at a temperature of 200°C, the mass loss exhibits a
linear increase with respect to the constant temperature exposure time. This phenomenon can
be attributed to the evaporation of interlayer water, adsorbed water, as well as the significant
decomposition of ettringite and C-S-H gel within the grout specimens. Conversely, at
temperatures of 400°C and 600°C, the rate of mass loss demonstrates minimal variation as the
exposure time increases. This observation suggests that above 400°C, there is a persistent,
albeit gradual, decomposition of the remaining C-S-H gel, accompanied by a lesser
decomposition of CH crystals. Consequently, the temperature range spanning from 105°C to
400°C emerges as the primary interval associated with the release of internal free water and
the decomposition of hydration products within the grout specimens. Notably, this conclusion
aligns harmoniously with the findings derived from meticulous microscopic structural

16
analysis.

4.3 Analysis of mechanical property variations of specimens after exposure to high-temperature

4.3.1 Dynamic elasticity modulus

The variations of dynamic elastic modulus of grout specimens after high-temperature

exposure with respect to temperature, constant temperature exposure time, and dwell time are
illustrated in Fig. 7.

of
0.5 N
40 40
1 W
2

ro
30 30
DEM / GPa

DEM / GPa
20 20

-p
T
em
p
erature/℃ T
em
p
erature/℃
10 10
re
0
0 200 400 600 200 400 600
lP

(b) Variation of DEM with different cooling me

(a) Variation of DEM with different temperature

2
0℃
thods

4
6
0℃
a

200
40 40
400
rn

600

30 30
DEM / GPa

DEM / GPa
u

20 20
Jo

10 10

0
0.5 1.0 1.5 2.0 0 10 20 30
Constant temperature duration / h Dwell time / d

(c) Variation of DEM with constant temperature

(d) Variation of DEM with dwell time
duration

Fig. 7 Variation of dynamic elastic modulus (DEM)

Based on Fig. 7a, it is evident that the dynamic elastic modulus exhibits a linear decrease
with increasing temperature. Moreover, the decay rate of the dynamic elastic modulus is
similar for specimens subjected to different constant temperature exposure times. For instance,
the measured dynamic elastic modulus of the specimen exposed to a constant temperature of
200°C for 2 hours is only 67% of that of the specimen at room temperature. Similarly, under

17
constant temperatures of 400°C and 600°C for 2 hours, the dynamic elastic modulus
decreases to 34.4% and 8.1% of the room temperature value, respectively. Hence, it is
apparent that the dynamic elastic modulus of the grout is significantly affected by elevated
temperatures.
Taking the specimen with a constant temperature exposure time of 1 hour as an example,
the cooling method has little influence on the trend of dynamic elastic modulus attenuation, as
depicted in Fig. 7b. However, specimens cooled by water-cooling exhibited relatively higher
values of the measured dynamic elastic modulus, with an increase of approximately 7.6% at
200°C. This increase may be attributed to the rehydration reaction [44] of some decomposed
materials inside the specimen, leading to the formation of AFt and C-S-H gel. From Fig. 7c, a
significant decrease in the measured dynamic elastic modulus of specimens with an increase
in constant temperature exposure time is observed. Specifically, the measured dynamic elastic
modulus of specimens subjected to constant temperatures of 200°C, 400°C, and 600°C for 2

of
hours are 88.6%, 76.5%, and 53.2% of that of the specimen exposed to a constant temperature
of 0.5 hours, respectively.

ro
Regarding the influence of dwell time, Fig. 7d reveals that the dynamic elastic modulus is
relatively unaffected. There is a slight fluctuation within 1 day to 14 days of dwell time, with
a maximum fluctuation of 7%. After dwelling for 14 days, the dynamic elastic modulus tends
-p
to stabilize. The experimental results show a slight increase in the measured dynamic elastic
modulus with an increase in dwell time for specimens exposed to 200°C. This may be due to
the formation of secondary ettringite after cooling, which compensates for some of the
re
internal structural damage caused by high temperatures.
lP

4.3.2 Flexural strength

a

Fig. 8 illustrates the variations in the measured flexural strength of grout specimens after
exposure to high temperatures, as influenced by temperature, constant temperature duration,
rn

and dwell time.

u
Jo

12 12
0.5h N
1h W
10 10
2h
Flexural strength / MPa

Flexural strength / MPa

8
8

6
6

T
em
p
erature/℃ T
em
p
erature/℃
4
4

2
200 400 600 200 400 600

(a) Variation of flexural strength with different (b) Variation of flexural strength with different

temperature cooling methods

18
 Flexural strength / MPa
12

10
200
400
600
12

10
2
0
4
6℃
0℃

Flexural strength / MPa

8 8

6 6

4 4

2 2

0.5 1.0 1.5 2.0 0 10 20 30

Constant temperature duration / h Dwell time / d

(c)Variation of flexural strength with (d) Variation of flexural strength with dwell tim
constant temperature duration e

of
Fig. 8 Flexural strength of grout specimens

ro
The overall trend of the measured flexural strength of grout specimens after
high-temperature exposure is depicted in Fig. 8a, showing an initial increase followed by a
subsequent decrease. When exposed to a constant temperature of 200°C for durations of 0.5h,
1h, and 2h, the measured flexural strength of the specimens is 104.4%, 106.6%, and 110% of
-p
re
that of the specimens at room temperature, respectively. The observed phenomenon can
potentially be attributed to the liberation of internal bound water from the grouting specimen
at the given temperature, resulting in an increase in free water. This free water then undergoes
lP

secondary hydration reactions with unhydrated cement particles and decomposed products [4],
facilitating the formation of new hydration products that repair the crack damage caused by
the initial high temperature. Moreover, the development of C-S-H towards a steady-state
a

phase [45-47] at 200°C, along with the superimposition of secondary hydration effects, is
likely another factor contributing to the increase in flexural strength observed in the
rn

specimens.
The rate of flexural strength decrease is relatively gradual in the temperature range of
u

200°C to 400°C. However, in the temperature range of 400°C to 600°C, the flexural strength
experiences a significant decrease due to the extensive decomposition of C-S-H [48]. For
Jo

instance, when exposed to a constant temperature of 600°C for durations of 0.5h, 1h, and 2h,
the measured flexural strength is only 53.3%, 37.8%, and 36.7% of that at room temperature,
respectively. This significant decrease in flexural strength can be attributed to the
decomposition of most of the C-S-H gel in the grout material, resulting in severe internal
shrinkage, increased cracks, pores, and voids. Additionally, it leaded to a porous internal
structure, which ultimately causes a substantial reduction in flexural strength. Fig. 8b presents
the variations in the measured flexural strength of specimens after a constant temperature
duration of 1h. It can be observed that the cooling method of water-cooling exhibits a similar
trend to the natural cooling method, but with significantly lower flexural strength. Among
them, the cooling method has the most pronounced effect on the flexural strength at 400°C,
with a decrease of 43.9% compared to the natural-cooling method. This is due to the
formation of an uneven temperature field inside and outside the specimens as a result of water
cooling [44][49], exacerbating internal damage, known as the thermal gradient effect. Fig. 8c
illustrates that the flexural strength of specimens at 200°C increases linearly with the constant
temperature duration. Specifically, the flexural strength of specimens exposed for 1h and 2h is

19
2.1% and 5.3% higher, respectively, than that of specimens exposed for 0.5h. Conversely, at
temperatures of 400°C and 600°C, the flexural strength shows a decreasing trend with
increasing constant temperature duration. The most significant decrease occurs during the
0.5h-1h duration, with a maximum decrease of 29%, while the decrease is relatively gradual
during the 1h-2h duration, with a maximum decrease of 8.8%. According to Fig. 8d, it is
evident that the flexural strength of specimens at 200°C gradually increases as the dwell time
extends. Specifically, the flexural strength of specimens after a 14-day dwell period is 118.2%
of that after a 1-day dwell period. On the other hand, for specimens exposed to 400°C, the
flexural strength exhibits a noticeable decrease within the initial 7 days of dwelling, with a
decrease of 21.1%. However, it stabilizes after 7 days. Similarly, for specimens subjected to
600°C, the flexural strength experiences a significant decrease within the first 14 days of
dwelling, with a decrease of 21.3%. Subsequently, it stabilizes after 14 days.

of
4.3.3 Compressive Strength

ro
Fig. 9 illustrate the trends in the measured compressive strength of grout specimens after
exposed to high temperatures, considering variations in temperature, duration of constant
temperature, and dwell time.
-p
re
100 0.5h 100 N
1h W
lP
Compressive strength / MPa

Compressive strength / MPa

2h
90 90

80 80

70 70
a

T
em
p
erature/℃ T
em
p
erature/℃
60 60
rn

50 50

0 200 400 600 200 400 600

u

(b) Variation of compressive strength with

Jo

(a) Variation of compressive strength with differ

2
0℃
ent temperature different cooling methods

100
200
100
4
6
0℃
Compressive strength / MPa

Compressive strength / MPa

400 90
90
600

80 80

70 70

60
60

50
50

0.5 1.0 1.5 2.0 0 10 20 30

Constant temperature duration / h Dwell time / d

20
 (c) Variation of compressive strength with (d) Variation of compressive strength with dwell
constant temperature duration time

Fig. 9 Compressive strength of grout specimens

Fig. 9a illustrates the temperature sensitivity of grout specimens, as evidenced by the

variation in both flexural and compressive strength. The compressive strength follows a
similar trend, initially increasing and then decreasing with temperature. Notably, specimens
tested after 2 hours of constant temperature maintenance exhibit the most pronounced effect.
At 200°C, 400°C, and 600°C, the compressive strengths are 116%, 89.8%, and 66.1% of the
ambient temperature specimens, respectively, indicating a significant deterioration as
temperature rises.

of
In Fig. 9b, the impact of different cooling methods on compressive strength is evident. Due

ro
to the temperature gradient effect [44] [49], specimens cooled by water-cooling show a
notable decrease compared to those cooled naturally, with the 400°C specimens experiencing
the largest reduction at 27.9%. Examining the duration of constant temperature exposure, Fig.
-p
9c reveals interesting patterns. For specimens maintained at 200°C, the compressive strength
steadily increases over time, with the 1-hour and 2-hour specimens exhibiting gains of 4.5%
and 15.6%, respectively, compared to the 0.5-hour specimens. Conversely, the compressive
re
strength of the 400°C specimens diminishes linearly with longer durations of constant
temperature, with reductions of 5.8% and 17.3% for the 1-hour and 2-hour specimens,
lP

respectively. Similar trends are observed for the 600°C specimens, with a significant overall
decline and a more gradual decrease between the 1-hour and 2-hour periods. Fig. 9d provides
insights into the compressive strength behavior during extended dwell periods. Both the
200°C and 400°C specimens exhibit decreasing trends within the first 7 days, stabilizing
a

thereafter with fluctuations ranging from 2.4% to 8.4%. The 600°C specimens, however,
experience a substantial decrease within the initial 14 days before reaching stability.
rn

4.4 Calculation of residual flexural and compressive strength of cementitious grout materials naturally
u

cooled after high-temperature exposure

Jo

According to the analysis results mentioned above, it is evident that the residual flexural
strength of grout materials after high-temperature exposure is significantly affected by two
factors: temperature and the duration of constant temperature maintenance. Therefore, based
on the measured data of the residual flexural strength, a fitting relationship between the
reduction coefficient α1 of flexural strength and temperature can be established (as shown in
Eq. 3 and Fig. 10a), as well as a fitting relationship between the reduction coefficient α2 of
flexural strength and the duration of constant temperature maintenance after high-temperature
exposure (as shown in Eq. 4 and Fig. 10b).

f T T T
1 = cf = f (T ) = 0.965 + 0.131 ( ) - 0.037 ( )2 （25℃ ≤ T ≤ 600℃）
f cf 100 100

21
 (3)


0.985 + 0.033 t （0.5h ≤ t ≤ 2h,25℃ < T ≤ 200℃）
f cf T ,t 
2 = = f (t ) = 1.035 - 0.096 t （0.5h ≤ t ≤ 2h,200℃ < T ≤ 400℃
f cf T 
 -0.296 (4)
0.788t （0.5h ≤ t ≤ 2h,400℃ < T ≤ 600℃)

The coefficient of determination R2 in Eq. 3 is 0.971, and in Eq. 4 the coefficient of

determination R2 is 0.84. This indicates a strong agreement between the experimental values

of
and the fitted values, demonstrating a high level of correlation in the results.

ro
Test value
1
1.0

0.8
-p 1.0

0.9
Test value
2(25℃≦T≦200℃)
1（%）

re 2(%)

0.6 2(400℃<T≦600℃)
0.8
2(400℃<T≦600℃)
lP

0.4 0.7

0.2
0 2 4 6 0.6
0.5 1.0 1.5 2.0
T(℃) t(h)
a

(a) Fitted curves of reduction coefficient α1 (b) Fitted curves of reduction coefficient α2
rn

Figure 10 Fitted curves of reduction coefficient α

u
Jo

From Eqs. 3 and 4, a modified formula can be established to calculate the reduction
coefficient α of the flexural strength for grouting materials considering the coupling effect of
temperature and constant temperature maintenance after high-temperature exposure. The
revised formula is as follows:
 T T 2 T T 2
0.95 + 0.129( 100 )-0.036( 100 ) + 0.003t + 0.004( 100 )t − 0.001( 100 ) t
 （0.5h ≤ t ≤ 2h,25℃ ≤ T ≤ 200℃）



f T,t  T T 2 T T 2
α = cf = f( T,t) = 0.999 + 0.136( 100 )-0.038( 100 ) - 0.093t - 0.013( 100 )t + 0.004( 100 ) t
f cf  （0.5h ≤ t ≤ 2h,200℃ < T ≤ 400℃）


 − 0.296 T
)t − 0.296 − 0.027(
T 2 − 0.296 (5)
0.76t + 0.103( ) t
 100 100
 （0.5h ≤ t ≤ 2h,400℃ < T ≤ 600℃）

22
 In Eqs. 3, 4, and 5, the variables are defined as follows:
Fcf - Flexural strength of grout specimens at room temperature (MPa).
fcfT - Flexural strength of grout specimens after undergoing high-temperature exposure at
temperature T, followed by natural-cooling (MPa).
fcfT,T - Flexural strength of grout specimens after undergoing high-temperature exposure at
temperature T and constant temperature maintenance for a duration of t, followed by
natural-cooling (MPa).

of
The comparison between the calculated results from Eq. 5 and the experimental
measurements is presented in Table 9. It can be observed that the calculated results are in
good agreement with the experimental results.

ro
Table 9
-p
Comparison of reduction coefficient α calculation results and experimental measurements.
re
Sample ID Test value α Fitted value α Eα /%
lP

T0H0ND28 1 - -

T2H0.5ND1 1.04 1.07 2.88

a

T2H1ND1 1.07 1.07 0

rn

T2H2ND1 1.1 1.08 -1.82

T4H0.5ND1 0.99 0.89 -10.1

u

T4H1ND1 0.91 0.85 -6.59

Jo

T4H2ND1 0.84 0.77 -8.33

T6H0.5ND1 0.53 0.5 -5.66

T6H1ND1 0.38 0.41 -7.89

T6H2ND1 0.37 0.38 -10.8

Note:Eα - Error α in Reduction Coefficient

Similarly, the relationship between the reduction coefficient β1 of compressive strength of

grouting material after natural-cooling and temperature (as described by Eq. 6 and illustrated
in Fig. 11a), as well as the relationship between the reduction coefficient β2 of compressive

23
strength of grouting material after natural cooling and constant temperature duration (as
expressed by Eq. 7 and depicted in Fig. 11b), can be determined.

fcT T T
1 = = f (T ) = 0.973 + 0.1 ( ) - 0.024 ( )2 （25 ℃ ≤ T ≤ 600 ℃） (6)
fc 100 100

0.945 + 0.107 t （0.5h ≤ t ≤ 2h,25 ℃ < T ≤ 200 ℃）


f cT ,t 
2 = = f (t ) = 1.055 - 0.113 t （0.5h ≤ t ≤ 2h,25 ℃ < T ≤ 200 ℃）
T
fc 
 -0.129 （0.5h ≤ t ≤ 2h,25 ℃< T ≤ 200 ℃） (7)
0.904t

of
ro
In Eq. 6, the coefficient of determination R2=0. 84; in Eq. 7, the coefficient of
determination R2≧0. 94.
-p
re
Test value
1
lP

1.15

1.10
1.0
Test value
1.05
2(25℃≦T≦200℃)
1(%)

2(200℃<T≦400℃)
2(%)
a

1.00
2(700℃<T≦600℃)
0.8 0.95
rn

0.90

0.85
u

0.6
0 2 4 6 0.5 1.0 1.5 2.0
T(℃)
T(℃)
Jo

(a) Fitted curve of reduction coefficient β1 (b) Fitted curves of reduction coefficient β2

Fig. 11 Fitted curve of reduction coefficient β

The expression for the reduction coefficient β of compressive strength of grouting

materials after natural-cooling, considering the coupled effect of temperature and constant
temperature duration, can be obtained from Eqs. 6 and 7. The modified formula is as follows:

 T T 2 T T 2
0.919 + 0.095 ( 100 )-0.023 ( 100 ) + 0.104 t + 0.011 ( 100 )t − 0.003 ( 100 ) t
 （0.5h ≤ t ≤ 2h,25 ℃ ≤ T ≤ 200 ℃）



f cf T,t  T T 2 T T 2
 = = f(T,t) = 1.026 + 0.105 ( 100 )-0.025 ( 100 ) - 0.11 t - 0.011 ( 100 )t + 0.003 ( 100 ) t
f cf  （0.5h ≤ t ≤ 2h,200 ℃ < T ≤ 400 ℃）

 24
 − 0.129 T − 0.129 T 2 − 0.129
0 .88 t + 0 .091 ( )t − 0.02 ( )t
 100 100
 （0.5h ≤ t ≤ 2h,400 ℃ < T ≤ 600 ℃）
 (8)

In Eqs. 6, 7, and 8, the variables are defined as follows:

of
Fc - Compressive strength of grout specimens at room temperature (MPa).
fcT - Compressive strength of grout specimens after undergoing high-temperature exposure at

ro
temperature T, followed by natural-cooling (MPa).
fcT,T - Compressive strength of grout specimens after undergoing high-temperature exposure at
temperature T and constant temperature maintenance for a duration of t, followed by
natural-cooling (MPa). -p
re
Table 10 presents a comparison of the experimental measurements and the calculated results
obtained from Eq. 8 and the findings demonstrate a high level of agreement between the two
datasets.
lP

Table 10

Comparison of reduction coefficient β calculation results and experimental measurements.

a

Sample ID Test value β Fitted value β Eβ /%

rn

T0H0ND28 1 - -
u

T2H0.5ND1 1 1.07 6.54

Jo

T2H1ND1 1.05 1.13 7.62

T2H2ND1 1.16 1.25 7.76

T4H0.5ND1 1.09 0.99 -9.17

T4H1ND1 1.02 0.94 -7.84

T4H2ND1 0.9 0.83 -7.78

T6H0.5ND1 0.79 0.77 -2.53

T6H1ND1 0.7 0.71 1.43

T6H2ND1 0.66 0.65 -1.51

25
Note:Eβ - Error β in Reduction Coefficient

4.5 Microstructural analysis of cement-based grouting materials after high-temperature exposure

To investigate the microstructural changes inside grout specimens after exposure to

different high-temperature conditions, samples were taken from typical locations within the
test pieces following the compression test and analyzed using a GeminiSEM300 scanning
electron microscope (SEM).

Examination of SEM images of the sample at room temperature (Fig. 12) revealed a dense

of
and intact surface of the grout material without prominent voids. The surface exhibited rich
hydration products, including fibrous and reticular C-S-H gel, as well as widely and evenly
distributed needle-like and rod-like ettringite (AFt) and plate-like C-H crystals [50-51].

ro
Moreover, numerous capillary pores were found throughout the C-S-H gel.

-p
re
a lP
rn

(a) (b)
u
Jo

(c) (d)

Fig. 12 SEM images of specimens at room temperature

26
 In Fig. 12a, a significant amount of fibrous Type I [52] C-S-H gel was observed, while Fig.
12b showed the presence of interlaced reticular Type II [52] C-S-H gel. Fig. 12c displayed
numerous interlocking needle-like and rod-like AFt crystals, and Fig. 12d revealed abundant
rod-like AFt crystals, well-developed plate-like CH crystals, and a small amount of thin
sheet-like Monosulphate (AFm) crystals embedded in C-S-H.
Comparing to the room temperature sample, the sample subjected to a constant temperature
of 200°C for 2 hours (Fig. 13) exhibited internal cracks, but the increased density of the
C-S-H structure was due to secondary hydration reactions [4]. Notably, there were no
prominent aggregation areas of needle-like or rod-like AFt, indicating decomposition of most
AFt crystals and a noticeable increase in thin-sheet AFm.

of
ro
-p
re
lP

(a) (b)
a
u rn
Jo

(c) (d)

Fig. 13 SEM images of specimens exposed to 200℃ constant temperature for 2 hours

Fig. 13a showcased the microstructural appearance of the C-S-H gel in the grout sample
exposed to a constant temperature of 200°C for 2 hours. At this temperature, exudation of free
water and bound water from the interior of the gel resulted in shrinkage compared to the room
temperature C-S-H, but an overall increase in density. Most AFt crystals had decomposed,

27
making it challenging to detect the presence of AFt. Additionally, a large number of newly
formed AFm crystals and a small amount of unhydrated cement particles were observed, as
depicted in Fig. 13b, 13c, and 13d.
The sample exposed to a constant temperature of 400°C for 2 hours exhibited a notable
increase in surface voids, indicating an overall loosening of the structure. The gel structure
suffered severe damage, with other crystalline substances showing a high degree of
decomposition, leading to significant material deterioration, as illustrated in Fig. 14.

of
ro
-p
re
(a) (b)
a lP
u rn
Jo

(c) (d)

Fig. 14 SEM images of specimens exposed to 400℃ constant temperature for 2 hours

Fig. 14a portrayed the surface of the grout sample exposed to a constant temperature of
400°C for 2 hours, showing a plethora of pore-like voids. The C-S-H gel in Fig. 14b exhibited
a deteriorated structural appearance due to the high temperature, with the original fibrous and
reticular structures disappearing and presenting a fibrous appearance overall. Fig. 14c
displayed the AFm crystals embedded in the C-S-H, appearing thin-sheeted and curved.
Moreover, Fig. 14d depicted a cluster-like distribution of the C-S-H gel, with an overall loose
structure.
Following exposure to a constant temperature of 600°C for 2 hours, the sample displayed
numerous cracks and voids on the surface, along with a significantly loose structure and

28
severe overall material deterioration (Fig. 15). The hydration products exhibited severe
degradation, with the original structures vanishing, replaced by a large amount of disordered
decomposition products and an increased proportion of fibrous structures. Additionally, a
small amount of AFt and CH crystals were still visible in certain areas.

of
ro
(a) (b)

-p
re
a lP
rn

(c) (d)
u

Fig. 15 SEM images of specimens exposed to 600℃ constant temperature for 2 hours
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Fig. 15a demonstrated that most of the crystalline water had escaped from the grout sample
subjected to a constant temperature of 600°C for 2 hours, leading to severe damage to the
structure's density and an overall loose appearance. Scattered gel tissue was depicted in Fig.
15b, occasionally showing a very small amount of AFt, C-H crystals, and a small amount of
unhydrated cement particles. Fig. 15c illustrated the disintegration of the original fibrous gel
structure into a large amount of fibrous products, resulting in an overall loose structure.
Furthermore, Fig. 15d displayed severe damage to the reticular gel structure, with evident
signs of sintering.
Overall, SEM observations revealed that the microstructure and composition of the
cement-based grout used for steel bar connection sleeves are highly sensitive to temperature
variations. The grout material exhibited varying degrees of structural looseness after
experiencing different high-temperature effects. Decomposition reactions affected most of the

29
C-S-H gel and other crystal substances, with the decomposition temperatures varying, such as
AFt decomposing at a relatively low temperature [3], a large amount of C-S-H gel
decomposition around 400°C [48], and significant C-H crystal decomposition mainly starting
at around 600°C [3], [4], [53]. These compositional changes further exacerbated the overall
microstructural variations of the grout material, thereby exerting different degrees of
influence on its macroscopic mechanical properties.

5. Conclusions

1) Based on orthogonal experimental analysis, it was determined that the residual flexural
strength and compressive strength of grout after exposure to high temperatures were
significantly affected by the temperature experienced. Additionally, the residual flexural

of
strength was also noticeably influenced by the duration of constant temperature exposure.
2) The dynamic modulus, flexural strength, and compressive strength of grout showed a

ro
distinct decrease after exposure to high temperatures, indicating a marked temperature
sensitivity.

-p
3) At 200°C, the development of C-S-H towards a steady-state phase, coupled with
secondary hydration effects, leads to an increasing trend in both flexural and compressive
strength of the specimens.
re
4) Water-cooling method resulted in the generation of a temperature gradient effect,
exacerbating internal damage to the specimens. Compared to the specimens natural-cooled,
lP

the flexural and compressive strength of the specimens showed varying degrees of decline,
with the most significant decrease observed in the specimens subjected to 400°C high
temperature.
a

5) By employing numerical fitting and derivation of experimental data, expressions for the
reduction coefficients of flexural strength and compressive strength, incorporating the
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coupled effects of temperature and constant temperature duration, were established for grout.
The calculated values for residual compressive and flexural strength aligned well with the
u

corresponding experimental results.

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6) Further examination of the grout microstructure using SEM revealed an increasing level
of degradation as the temperature rose. At 200°C, AFt decomposed initially, resulting in some
portions of the C-S-H gel absorbing water and precipitating crystalline water. However, due
to the secondary hydration effect, the compactness of the colloidal structure was enhanced to
a certain extent. At 400°C, most of the C-S-H gel decomposed, while at 600°C, C-H crystals
were difficult to identify, indicating the most severe level of structural degradation.
Experimental findings demonstrated significant correlation between the changes in the
microstructure of grout materials and their macroscopic mechanical properties.

Declaration of Competing Interest

No conflict of interest exits in the submission of this manuscript, and all authors for
publication approve manuscript. This work described was original research that has not been

30
published previously, and not under consideration for publication elsewhere, in whole or in
part. All the authors listed have approved the manuscript that is enclosed.

Data Availability

The data that has been used is confidential.

Acknowledgements

of
This research was financially supported by the National Natural Science Foundation of
China (Project No. 51478254) and the Open Project of Shanghai Key Laboratory for
Engineering Structural Safety (Project No. 2021-KF03).

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References
-p
re
[1] P. Bamonte, P.G. Gambarova, F. Sciarretta, Thermo-mechanical properties and stress-strain curves
of ordinary cementitious mortars at elevated temperatures, Constr. Build. Mater. 267 (2021)
lP

121027, https://doi.org/10.1016/j.conbuildmat.2020.121027.

[2] J. Ollivier, A. Vichot, La durabilité des bétons: bases scientifiques pour la formulation de bétons
durables dans leur environnement, Presses de l'ecole nationale des ponts et chaussees, 2008.
a

[3] H.F. Taylor, Cement chemistry, Thomas Telford London, 1997.

rn

[4] C. Alonso, L. Fernandez, Dehydration and rehydration processes of cement paste exposed to high
u

temperature environments, J. Mater. Sci. 39 (9) (2004) 3015-3024, https://doi.org/10.1023/B:JMS

C.0000025827.65956.18.
Jo

[5] S. Mindess, F. Young, D. Darwin, Concrete 2nd editio, Technical Documents. 585 (2003).

[6] J. Yang, Z. Guan, H. Yu, Y. Zhou, The structure variance of ettringite in different hydrothermal co
nditions, J. Chin. Ceram. Soc. (04) (1997) 101-105, 10.14062 /j .issn.0454 -5648.1997.04.017.

[7] Z. Wu, Microorphologyofttringite, Chin. Build. Mater. Sci. Technol. (04) (1995) 9-14.

[8] Q. Li, L. Liu, Z. Huang, G. Yuan, Residual compressive strength of cement-based grouting material
with early ages after fire, Constr. Build. Mater. 138 (2017) 316-325,
https://doi.org/10.1016/j.conbuildmat.2017.02.025.

[9] Q. Li, L. Liu, Z. Huang, G. Yuan, Degradation of the elastic modulus of cement-based grouting
material with early ages after fire, Constr. Build. Mater. 187 (2018) 510-518,

31
 https://doi.org/10.1016/j.conbuildmat.2018.07.232.

[10] G. Yuan, Q. Li, Q. Li, Q. Zhang, Degradation of Compressive strength of high-performance c

ementitious g routing m aterial after e xposure to h igh t emperature , J. Build. Mater.
17 (03) (2014) 470-474, 10.3969/j.issn.1007-9629.2014.03.018.

[11] H. Yan, X. Gu, Z. Tan, X. Jin, F. Peng, Performance study and application of RGM grouting m
aterial (strengthening type), Constr. Technol. (05) (2007) 47-49.

[12] Q. Jin, B. Sun, J. Zhang, W. Wang, Y. Zhao, Experimental study on fire resistance of grouti
ng material for sleeve of rebar splicing, Build. Struct. 50 (22) (2020) 62-66, 10.19701/j.jzjg.2
020.22.011.

of
[13] C. Xue, C. Su, M. Yu, H. Xu, J. Ye, Experimental study on the thermal-mechanical properties and
degradation of sleeve grouting material at elevated temperatures, J. Mater. Civ. Eng. 33 (2) (2021
) 4020453, https://doi.org/10.1061/（ASCE）MT.1943-5533.0003493.

ro
[14] C. Poon, S. Azhar, M. Anson, Y. Wong, Strength and durability recovery of fire-damaged concret

-p
e after post-fire-curing, Cem. Concr. Res. 31 (9) (2001) 1307-1318, https://doi.org/10.1016/s0008-
8846(01)00582-8.
re
[15] M. Chromá, D. Vo, P. Bayer, Concrete rehydration after heating to temperatures of up to 1200°C,
in: Int. Conf. Durab. Build. Mater. Components, 2011, pp. 1633-1639.
lP

[16] L. Li, L. Shi, Q. Wang, Y. Liu, J. Dong, H. Zhang, G. Zhang, A review on the recovery of fire-da
maged concrete with post-fire-curing, Constr. Build. Mater. 237 (2020) 117564, https://doi.org/10.
1016/j.conbuildmat.2019.117564.
a

[17] M. Henry, M. Suzuki, Y. Kato, Behavior of fire-damaged mortar under variable re-curing conditio
rn

ns., Aci Mater. J. 108 (3) (2011), https://doi.org/10.14359/51682493.

u

[18] O. Karahan, Residual compressive strength of fire‐damaged mortar after post‐fire‐air‐

curing, Fire Mater. 35 (8) (2011) 561-567, https://doi.org/10.1002/fam. v35.810.1002/fam.1074.
Jo

[19] J.A.D.F. Neto, T.N. Sombra, V.G. Haach, M.R.S. Correa, Effects of post-fire curing on the residu
al mechanical behavior of cement-lime masonry mortars, Constr. Build. Mater. 327 (2022) 126613,
https://doi.org/10.1016/j.conbuildmat.2022.126613.

[20] K. Yu, J. Dai, Z. Lu, C.K. Leung, Mechanical properties of engineered cementitious composites s
ubjected to elevated temperatures, J. Mater. Civ. Eng. 27 (10) (2015) 4014268, https://doi.org/10.
1061/(ASCE)MT.1943-5533.0001241.

[21] J. Chen, A. Kwan, Superfine cement for improving packing density, rheology and strength of cem
ent paste, Cement and Concrete Composites. 34 (1) (2012) 1-10, https://doi.org/10.1016/j.cemcon
comp.2011.09.006.

[22] H. Huang, L. Zhu, M. Huang, Y.H. Wang, Z.K. Ding, Research and analysis on the performance of

32
 modified concrete with different materials, Bull. Chin. Ceram. Soc. 37 (06) (2018) 1887-1896,
10.16552/j.cnki.issn.1001-1625.2018.06.014.

[23] X. Cong, X. Cong, F. Zhao, Q. Bai, Effect of different fibers on crack resistance of cement-based
materials, J. Hebei Inst. Archit. Civ. Eng. 36 (04) (2018) 55-57, 10.3969/j.issn.1008-4185.2018.04.
011.

[24] C. Shi, X. Zou, L. Yang, P. Wang, M. Niu, Influence of humidity on the mechanical properties of
polymer-modified cement-based repair materials, Constr. Build. Mater. 261 (2020) 119928, https:/
/doi.org/10.1016/j.conbuildmat.2020.119928.

[25] W. Mahmood, A. Mohammed, K. Ghafor, Viscosity, yield stress and compressive strength of cem
ent-based grout modified with polymers, Results in Materials. 4 (2019) 100043 ，

of
https://doi.org/10.1016/j.rinma.2019.100043

[26] X. Shu, Y. Zhao, Z. Liu, C. Zhao, A study on the mix proportion of fiber-polymer composite reinf

ro
orced cement-based grouting material, Constr. Build. Mater. 328 (2022) 127025, https://doi.org/10.
1016/j.conbuildmat.2022.127025.
-p
[27] T. Nishimura, Y. Shinonaga, C. Nagaishi, R. Imataki, M. Takemura, K. Kagami, Y. Abe, K. Harad
a, K. Arita, Effects of powdery cellulose nanofiber addition on the properties of glass ionomer ce
re
ment, Materials. 12 (19) (2019) 3077, https://doi.org/10.3390/ma12193077.
lP

[28] Q . Wa n g , Q . Z h u , T. Shao, X. Yu , S . Xu, J. Zhang, Q. Kon

g, The rheological test and application research of glass fiber cement slurry based on plugging me
chanism of dynamic water grouting, Constr. Build. Mater. 189 (2018) 119-130, https://doi.org/10.
a

1016/j.conbuildmat.2018.08.081.
rn

[29] Z. Shi, Q. Wang, L. Xu, Experimental study of cement alkali-resistant glass fiber (c-argf) groutin
g material, Materials. 13 (3) (2020) 605, https://doi.org/10.3390/ma13030605.
u

[30] Y. Zhang, Y. Wang, T. Li, Z. Xiong, Y. Sun, Effects of lithium carbonate on performances o
Jo

f sulphoaluminate cement-based dual liquid high water material and its mechanisms, Constr.
Build. Mater. 161 (2018) 374-380, https://doi.org/10.1016/j.conbuildmat.2017.11.130.

[31] J. Wang, Y. Wang, J. Yu, L. Xu, M. Li, J. Cheng, Z. Li, Effects of sodium sulfate and pota
ssium sulfate on the properties of calcium sulfoaluminate (csa) cement based grouting materi
als, Constr. Build. Mater. 353 (2022) 129045, https://doi.org/10.1016/j.conbuildmat.2022.1290
45.

[32] Y. Wang, H. Tang, J. Su, H. He, Y. Zhao, J. Wang, Effect of sodium sulfate and gypsum on
performances of expansive grouting material with aluminum as expansion agent, Constr. Bui
ld. Mater. 394 (2023) 132212, https://doi.org/10.1016/j.conbuildmat.2023.132212.

[33] Y. Wang, J. Yu, J. Wang, D. Xiang, H. Gu, J. Cheng, Effects of sodium aluminate and quic
klime on the properties of csa grouting materials, J. Build. Eng. 58 (2022) 105060, https://do

33
 i.org/10.1016/j.jobe.2022.105060.

[34] J. Outinen, P. Mäkeläinen, Mechanical properties of structural steel at elevated temperatures and
after cooling down, Fire Mater. 28 (2‐4) (2004) 237-251, https://doi. org/10.1002/fam.849.

[35] A. Mendes, J.G. Sanjayan, F. Collins, Effects of slag and cooling method on the progressive
deterioration of concrete after exposure to elevated temperatures as in a fire event, Mater. Struct. 44
(2011) 709-718, https://doi.org/10.1617/s11527- 010-9660-2.

[ 3
6] R.H. Haddad, L.G. Shannis, Post-fire behavior of bond between high strength pozzolanic concr
ete and reinforcing steel, Constr. Build. Mater. 18 (6) (2004) 425-435, https://doi.org/10.1016/j.co
nbuildmat.2004.03.006.

of
[37] Y. Li, L. Cheng, W. Lei, Y. Su, T. Huang, Y. Zhu, C. Mei, X. He, Microstructures and mechanical
property of post-fire grouting sleeve connections considering concrete cover, Constr. Build. Mater.

ro
403 (2023) 132578, https://doi.org/10.1016/j.conbuildmat.2023.132578.

[
-p
8] L. Liu, C. Luo, L. Ouyang, Z. Xia, W. Li, Post-fire bond behaviors between grout and steel reb
ar, Int. J. Concr. Struct. Mater. 16 (1) (2022) 1-14, https://doi.org/10.1186/s40069-022-00527-7.
3
re
[39] Ministry of housing and urban-rural development: cement-based grout for coupler of rebar s
lP

plicing (JG/T 408-2019), Standards Press of China,Beijing, 2019

[ 4
0] Y. Niu, C. Tu, R.Y. Liang, S. Zhang, Modeling of thermomechanical damage of early-age concr
a

ete, J. Struct. Eng. 121 (4) (1995) 717-726 ，

rn

https://doi.org/10.1061/（ASCE）0733-9445（1995）121：4（717）.

[41] SAC (Standardization Administration of the People's Republic of China): "Test method of ce
u

ment mortar strength (ISO method)" (GB/T17671-2021), Standards Press of China, Beijing, 2
Jo

021.

[42] N. Li, X. Shi, M. Xiao, Experimental investigation on compressive strength decaying behaviors o
f concrete after elevated temperature, Build. Sci. 23 (9) (2007) 5, 10.13614/j.cnki.11-1962/tu.
2007.09.016.

[43] K. Yi, X. Cheng, A frequently mistaken concept in hypothesis test - a dispute triggered by
china undergraduate mathematical contest in modeling, J. Chongqing Univ. Technol. (Nat. Sc
i.) 27 (04) (2013) 106-109, 10.3969/j. issn. 1674-8425 (z) .2013.04.022.

[44] S. Feng, Study on bond behavior between steel bar and cementitious grouting material after
high temperature, Master's thesis, in: China University of Mining and Technology, 2015, P.

[45] E.R. Buckle, H. Taylor, The hydration of tricalcium and β‐dicalcium silicates in pastes unde

34
 r normal and steam curing conditions, Journal of Applied Chemistry. 9 (3) (1959) 163-172.

[46] S.L. Colston, P. Barnes, A.C. Jupe, S.D. Jacques, C. Hall, P. Livesey, J. Dransfield, N. Mell
er, G.C. Maitland, An in situ synchrotron energy-dispersive diffraction study of the hydration
of oilwell cement systems under high temperature/autoclave conditions up to 130 c, Cem. C
oncr. Res. 35 (12) (2005) 2223-2232.

[47] B. Bresson, F. Meducin, H. Zanni, C. Noik, Hydration of tricalcium silicate (c 3 s) at high t

emperature and high pressure, J. Mater. Sci. 37 (2002) 5355-5365.

[48] Y. Chan, G. Peng, M. Anson, Residual strength and pore structure of high-strength concrete
and normal strength concrete after exposure to high temperatures, Cement and Concrete Com
posites. 21 (1) (1999) 23-27, https://doi.org/10.1016/S0958-9465(98)00034-1.

of
[49] Y. Guo, G. Xu, W. Zhang, S. Chen, Study on mechanical properties of cement-based groutin
g material after high temperature spray cooling, J. North China Univ. Sci. Technol.

ro
(Natural Science Edition) (2021).

-p
[50] Q. Li, Research on the thermal expansion performance of cement-based materials, Doctoral
dissertation, in: China Building Materials Academy, 2007, p.
re
[51] K. Zhao, Water state evolution and pore structure development during hydration of cement-b
ased materials, Doctoral dissertation, in: Qingdao University of Technology, 2022, p.
lP

[52] W. Kurdowski, Cement and concrete chemistry, Springer Science & Business, 2014.

[53] J. Wang, Effect of chemical additives on formation and structures of synthetic ettringite, por
a

tlandite and C-S-H, Doctoral dissertation, in: Tsinghua University, 2021, p.

u rn

Declaration of Competing Interest

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The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests. Chuanguo Fu reports financial support was provided by
National Natural Science Foundation of China. Chuanguo Fu reports financial support was
provided by Open Project of Shanghai Key Laboratory for Engineering Structural Safety. If there
are other authors, they declare that they have no known competing financial interests or
personal relationships that could have appeared to influence the work reported in this paper

35