materials

Article
The Influence of Manganese Slag on the Properties of
Ultra-High-Performance Concrete
Wenyu Xu 1 , Jia Yu 1 and Hui Wang 2, *

1 School of Intelligent Manufacturing, Nanjing University of Science and Technology Zijin College,
Nanjing 210023, China
2 School of Civil Engineering and Geographic Environment, Ningbo University, Ningbo 315000, China
* Correspondence: huiwang123@aliyun.com

Abstract: Manganese slag (MS) is a kind of chemical waste, which may pollute the environment if
conventional handling methods (stacking and landfill) are applied. Ultra-high-performance concrete
(UHPC)—with considerably high compactness and strength—can be used not only as a special
concrete material, but also to solidify the toxic substances in solid waste. This study proposes the
addition of MS to UHPC, where the mass ratio of MS varies from 0% to 40% in the total mass of
MS and silica fume. The effects of MS on the fluidity, plastic viscosity, and yield shear stress are
investigated, and the flexural strength, compressive strength, and dry shrinkage rate of UHPC with
MS are measured. X-ray diffraction (XRD) spectrum and energy spectrum analysis (EDS) diagrams
are obtained to analyze the performance mechanism of the UHPC. A rheological study confirms
that the slump flow increases with the increasing rate of 0–14.3%, while the yield shear stress and
plastic viscosity decrease with the rates of 0–29.6% and 0–22.2%, respectively. The initial setting time
increases with the mass ratio of MS by 0–14.3%, and MS has a positive effect on the flexural and
compressive strengths of UHPC. In the early curing stage (less than 14 days), the increasing rate
in the specimens increases with the curing age; meanwhile, when the curing age reaches 14 days
or higher, the increasing rate decreases with increasing curing age. The compactness of UHPC is
increased by adding MS. Furthermore, MS can increase the elements of Al and decrease crystals of
Ca(OH)2 and calcium silicate hydrate in UHPC.

Keywords: manganese slag; ultra-high-performance concrete; plastic viscosity; energy spectrum

Citation: Xu, W.; Yu, J.; Wang, H. The
analysis; X-ray diffraction
Influence of Manganese Slag on the
Properties of Ultra-High-Performance
Concrete. Materials 2024, 17, 497.
https://doi.org/10.3390/ma17020497
1. Introduction
Academic Editor: Miguel
Manganese slag (MS) is a strategic resource widely used in industries such as met-
Ángel Sanjuán
allurgy and the chemical industry [1,2]. According to statistics, the accumulation of elec-
Received: 20 November 2023 trolytic manganese slag due to historical and technical issues may have exceeded 100 million
Revised: 3 January 2024 tons, with an annual increase of 10 million tons [3–5]. At present, the resource utilization
Accepted: 16 January 2024 and comprehensive utilization methods for electrolytic MS are not mature, and there are few
Published: 20 January 2024 large-scale applications [6–9]. The new round of environmental policies has put forward
higher requirements for the comprehensive treatment of electrolytic MS, and the increase in
environmental investments has significantly increased production costs [10,11]. Therefore,
it is imperative to promote the comprehensive utilization and reduction of electrolytic
Copyright: © 2024 by the authors. MS, and research on environmentally friendly resource utilization technologies is urgently
Licensee MDPI, Basel, Switzerland.
needed. If MS is not treated in a timely and reasonable manner, it can pollute water sources.
This article is an open access article
At the same time, the metal elements in manganese slag will circulate to the human body,
distributed under the terms and
thereby endangering human health and safety [12,13].
conditions of the Creative Commons
At present, stacking and landfill methods are used for the treatment of MS [14,15].
Attribution (CC BY) license (https://
Direct landfilling of electrolytic MS is a simple and convenient method [16,17]; however,
creativecommons.org/licenses/by/
4.0/).
long-term open-air storage of electrolytic MS not only occupies a large amount of land, but

Materials 2024, 17, 497. https://doi.org/10.3390/ma17020497 https://www.mdpi.com/journal/materials

Materials 2024, 17, 497 2 of 17

also accumulates pollutants from the long-term storage of electrolytic MS in the landfill site
into leachate waste water under the action of rainfall [18]. High concentrations of pollutants
can accumulate in the leachate, posing a significant potential risk of pollution [19]. Based
on these reasons, MS needs to be permanently solidified.
MS has been shown to improve the mechanical strength of cement-based materials.
Due to the large amount of active substances in MS, crushed and ground MS not only
has a microaggregate filling effect on the cement but, also, can increase the hydration
process [20,21]. In this way, the pore structure inside the concrete is improved, thus
increasing the mechanical strength of cement concrete [22]. Maurilio et al. have reported
that the addition of MS decreased the porosity of cement concrete cured for 28 days, thus
increasing the corresponding compressive strength at a rate of 0–42.1%. Meanwhile, the
flexural strength was increased by the maximum rate of 41.7% [23]. Moreover, MS has
been proved to improve the chloride ion penetration resistance and frost resistance of
concrete [24]. However, ordinary concrete possesses a large number of pores; therefore, the
toxic substances may leach from the cement concrete.
Ultra-high-performance concrete (UHPC) is a cement concrete with excellent mechani-
cal strength and durability. As obtained from Zhang’s researches, UHPC with reinforced
fibers showing high toughness can strengthen RC beams in torsion [25]. However, UHPC
presents quite high drying shrinkage, leading to severe cracking [26]. As reported in prior
researches, the dry shrinkage rate of UHPC has been applied in characterizing its cracking
performance [27]. Yalçınkaya et al. have proved that the addition of fly ash, silica fume,
blast furnace slag powder, etc., can reduce the shrinkage and cracking of UHPC by the
dry shrinkage value testing method and the ultrasonic testing method [28,29]. Yoo et al.
have determined that UHPC with fibers can be used as twisted reinforced concrete beams.
Some chemical wastes (e.g., waste fly ash, secondary aluminum ash, and river silt) can be
used for the preparation of UHPC. Waste fly ash and secondary aluminum ash increased
the flexural strengths of UHPC by rates of 0–23.6% and 0–27.1%, respectively. Meanwhile,
the corresponding compressive strengths were improved by 0–18.6% and 0–21.7% [30].
Moreover, the recycled aggregate concrete and UHPC’s resistance to high temperature can
be improved by adding the waste rubber and the plant fibers. Furthermore, the natural
fibers with low cost can be used to prevent the reinforced concrete’s corrosion. However,
the effect of natural fibers on cement concrete’s mechanical strengths are limited [31–34].
Therefore, the natural fibers are not suitable as reinforcing materials for UHPC. At the
same time, the high compactness can prevent the toxic substances from leaching. Therefore,
UHPC with such excellent mechanical, durability, and compactness can be used to solidify
the MS. However, this issue has received little attention in the literature.
The principal aim of this study is to assess the influence of MS on the slump flow,
plastic viscosity, yield shear stress, and initial setting time of UHPC. The mechanical
strengths and the drying shrinkage rates of UHPC cured for 1 day, 3 days, 7 days, 14
days, and 28 days were measured, and scanning electron microscope imagery, energy
spectrum analysis results, and X-ray diffraction spectra were obtained to analyze the
inner performance mechanism of the UHPC. This study provides a new approach for the
treatment of MS.

2. Materials and Methods

2.1. Raw Materials
The Ordinary Portland cement (OPC) used in the current work was procured from
the Jiangsu Huaxi Cement Manufacturing Co., Ltd. in Wuxi, China. The cement has a
density of 3.2 g/cm3 , and the initial and final setting times were 121 min and 233 min,
respectively. Ultra-fine silica fume (SF) showing a density of 2.33 g/cm3 , specific surface
area of 14.82 m2 /g, and 98.1% SiO2 was applied in this study as a supplementary cementi-
tious material. Shandong Zhongfen Building Materials Technology Co., Ltd., Jinan, China,
provided the blast furnace slag powder (BFP), which has a density of 2.79 g/cm3 , specific
surface area of 433.7 m2 /g, and loss on ignition of 2.18%. Quartz sand (QS) with three
 Materials 2024, 17, x FOR PEER REVIEW 3 of 18

Materials 2024, 17, 497 mentitious material. Shandong Zhongfen Building Materials Technology Co., Ltd., 3Jinan, of 17
China, provided the blast furnace slag powder (BFP), which has a density of 2.79 g/cm3,
specific surface area of 433.7 m2/g, and loss on ignition of 2.18%. Quartz sand (QS) with
kinds
three ofkinds
particle size (1–0.5
of particle mm,
size 0.5–0.1
(1–0.5 mm,mm, and 0.1–0.01
0.5–0.1 mm, and mm), sourced
0.1–0.01 fromsourced
mm), Guangzhou
from
Yifeng Chemical
Guangzhou Technology
Yifeng ChemicalCo., Ltd. of Guangzhou,
Technology Co., Ltd. ofChina, was used
Guangzhou, as thewas
China, aggregate.
used as
The
the fluidity of the
aggregate. Thefresh UHPC
fluidity of was adjusted
the fresh UHPCusing anadjusted
was efficient using
polycarboxylic acid
an efficient water
polycar-
reducing
boxylic acid water reducing agent provided by Henan Jinrong Cement Co., Ltd. in The
agent provided by Henan Jinrong Cement Co., Ltd. in Sanmenxia, China. San-
manganese slag (MS)
menxia, China. shown in Figure
The manganese 1 wasshown
slag (MS) purchased from the
in Figure Hunan
1 was Daji Manganese
purchased from the
Industry
Hunan Daji Co., Manganese
Ltd., Hengyang, China,
Industry which
Co., Ltd.,was used for testing
Hengyang, China, and measurement
which was used forin
this study.
testing and measurement in this study.

Figure1.1.The
Figure Themanganese
manganeseslag
slagused
usedininthe
theUHPC.
UHPC.
Materials 2024, 17, x FOR PEER REVIEW 4 of 18
Tables11and
Tables and2 detail
2 detailthethe accumulated
accumulated pass
pass rates
rates andand chemical
chemical compositions
compositions of theofraw
the
raw materials.
materials. The particle
The particle size distribution
size distribution curves
curves of of the
the raw raw materials
materials are
are shown in shown in
Figure 2.
Figure 2.

100
Table 1. The accumulated pass rate (%).
The accumulated pass rate (%)

Particle Size/μm
80 Types
0.3 0.6 OPC1 4 8 64 360
OPC 0.12 0.37 BFP
3.09 14.77 29.14 92.61 100
60
SF 32.04 59.01 QS
82.99 99.8 99.9 100 100
BFP 0.03 0.11 SF3.4 19.3 35.1 98.3 100
40
QS 0 0 MS 0 0 0.036 23.95 100
20 MS 0.05 0.32 1.33 8.72 23.52 98.43 100

-50 0 50 100 150 200 250 300 350 400

Particle size (um)

Figure
Figure2.2.The
Theparticle
particlesize
sizedistribution
distributioncurves
curvesofofthe
theraw
rawmaterials.
materials.

Table
Table2.1.Chemical composition
The accumulated pass(%).
rate (%).
Types SiO2 Al2O3 FexOy MgO CaO SO3 K2O MnO2 Loss on Ignition
Particle Size/µm
OPC
Types 20.2 5.7 3.8 1.8 62.3 2.9 - - 3.0
0.3 0.6 1 4 8 64 360
SF 90.1 0.3 0.6 0.3 0.45 0.2 7.4 - -
BFPOPC 33.8 0.12
14.7 0.37
0.6 9.9 3.09 14.77
37.1 0.2 3.4 29.14
- 92.61 - 100
SF 32.04 59.01 82.99 99.8 99.9 100 100
QSBFP 98.4 0.03- 1.4
0.11 - 3.4 - - 19.3 - -
35.1 98.3 - 100
MSQS 34.22 07.32 12.03
0 1.91 013.92 0.08 0 30.52
0.036 23.95 - 100
MS 0.05 0.32 1.33 8.72 23.52 98.43 100
2.2. Preparation of the Specimens
Table 3 provides the UHPC mixing ratios. The UHPC specimens were fabricated by
the following steps. The powder binder materials were mixed in a JJ-5 planetary cement
mortar mixer from Wuxi Jianyi Instrument Machinery Co., LTD, Wuxi city, China with a
stirring speed of 140 rpm for 30 s. Then, the quartz sand was added with stirring at 285
Materials 2024, 17, 497 4 of 17

Table 2. Chemical composition (%).

Types SiO2 Al2 O3 Fex Oy MgO CaO SO3 K2 O MnO2 Loss on Ignition
OPC 20.2 5.7 3.8 1.8 62.3 2.9 - - 3.0
SF 90.1 0.3 0.6 0.3 0.45 0.2 7.4 - -
BFP 33.8 14.7 0.6 9.9 37.1 0.2 3.4 - -
QS 98.4 - 1.4 - - - - - -
MS 34.22 7.32 12.03 1.91 13.92 0.08 30.52 -

2.2. Preparation of the Specimens

Table 3 provides the UHPC mixing ratios. The UHPC specimens were fabricated by
the following steps. The powder binder materials were mixed in a JJ-5 planetary cement
mortar mixer from Wuxi Jianyi Instrument Machinery Co., Ltd., Wuxi city, China with a
stirring speed of 140 rpm for 30 s. Then, the quartz sand was added with stirring at 285 rpm
for 90 s. Finally, water mixed with the water reducing agent was added to the mixture and
stirred at a speed of 285 rpm for 120 s.

Table 3. The mixing proportions of UHPC (kg/m3 ).

Types Water OPC MS SF BFP QS WR

MS-1 240.2 839.9 0 910 111.1 961.5 16.0
MS-2 240.2 839.9 91 819 111.1 961.5 16.0
MS-3 240.2 839.9 182 728 111.1 961.5 16.0
MS-4 240.2 839.9 273 637 111.1 961.5 16.0
MS-5 240.2 839.9 364 546 111.1 961.5 16.0

2.3. Measuring Methods

2.3.1. The Measurement of Rheological Parameters
An NDJ-5S Rheometer with a mixing speed of 0–30 rpm was used for measurement of
the plastic viscosity and yield shear stress of fresh UHPC. The slump flow was tested using
the jumping table method. The study in [35] provides the detailed measuring process of
Materials 2024, 17, x FOR PEER REVIEW
the rheological parameters. Figure 3 shows the measurement of plastic viscosity and 5yield
of 18

shear stress.

Figure3.3.The
Figure Themeasurement
measurementof
ofplastic
plasticviscosity
viscosityand
andyield
yieldshear
shearstress.
stress.

2.3.2.
2.3.2.The
TheInitial
InitialSetting
SettingTime
Time
AAdigital
digitaldisplay
displaymortar
mortarsetting time
setting tester
time (Cangzhou
tester (Cangzhou Qiuzhen
QiuzhenInstrument Equipment
Instrument Equip-
Co., Ltd., Cangzhou, China) was used to measure the initial setting time of
ment Co., Ltd., Cangzhou, China) was used to measure the initial setting time of fresh fresh UHPC.
The measuring
UHPC. process for
The measuring the initial
process for setting timesetting
the initial of freshtime
UHPC is shown
of fresh UHPCin Figure 4. in
is shown
Figure 4.
 2.3.2.The
2.3.2. TheInitial
InitialSetting
SettingTime
Time

AAdigital
digitaldisplay
displaymortar
mortarsetting
settingtime
timetester
tester(Cangzhou
(CangzhouQiuzhen
QiuzhenInstrument
InstrumentEquip-
Equip-
ment Co., Ltd., Cangzhou, China) was used to measure the initial setting
ment Co., Ltd., Cangzhou, China) was used to measure the initial setting time of freshtime of fresh
Materials 2024, 17, 497 UHPC. The measuring process for the initial setting time of fresh UHPC
UHPC. The measuring process for the initial setting time of fresh UHPC is shown5 of is shown inin
17
Figure
Figure 4.4.

Figure
Figure4.4.
Figure The measurement
measurementofof
Themeasurement
4.The initial
ofinitial setting
initialsetting time.
settingtime.
time.

2.3.3. The
2.3.3. The Mechanical
Mechanical Strengths
Strengths
2.3.3. The Mechanical Strengths
The flexural
The and
andcompressive
flexuraland compressivestrengths were
strengths measured
were measuredusing a fully
using automatic bend-
The flexural compressive strengths were measured using aafully
fully automatic
automatic
ing integrated
bendingintegrated testing
integratedtesting machine.
testingmachine. The
machine.The mechanical strength
The mechanicalstrength tests
strengthtests were
testswere conducted using
were conductedusing
using
bending
40 ××4040××160160mm
mm 3 specimens loadingmechanical
atloading rates of
of 0.1
0.1 kN/s
kN/sandand 2.4 kN/s,conducted
2.4 kN/s, respectively. The
The
40
40mechanical
× 40 × 160 strength
3 specimens
mm3 specimens at
at loading rates
rates for
of 0.1 kN/sare
and 2.4 kN/s, respectively.
respectively. The
mechanicalstrength measurement
strengthmeasurement processes
measurementprocesses
processesfor UHPC
forUHPC
UHPCare shown
areshown in Figure
shownininFigure 5.
Figure5.5.
mechanical

Figure
Figure5.5.
Figure The measuring
Themeasuring
5.The process
processofof
measuringprocess UHPC’s
ofUHPC’s
UHPC’s mechanical
mechanical
mechanical strengths.
strengths.
strengths.

Samples
Samples wereutilized
Sampleswere utilizedto
utilized todetermine
to determinethe
determine thetoxic
the toxicheavy
toxic heavymetal
heavy metalsubstances
metal substances
substances released
released
released dur-
during
dur-
ing 6 months of immersion in deionized water. Monthly measurements of Crr and Zn nninin
ing
6 6 months
months of of immersion
immersion in in deionized
deionized water.
water. Monthly
Monthly measurements
measurements ofof CC r and
and ZZ in
immersion
immersion were carried out
out using
using an
an Inductively
Inductively Coupled
Coupled Plasma
Plasma
immersion were carried out using an Inductively Coupled Plasma Emission Spectrome- Emission
Emission Spectrome-
Spectrometer
ter
ter (Suzhou
(Suzhou
(Suzhou Huapu
Huapu
Huapu Scientific
Scientific
Scientific Instrument
Instrument
Instrument Co.,
Co., Ltd.,
Ltd.,
Co., Suzhou,
Suzhou,
Ltd., Suzhou, China).
China).
China).
AnAn
AnSU3800 scanningelectron
SU3800scanning
scanning electronmicroscope,
electron microscope,purchased
microscope, purchasedfrom
purchased from
from Hitachi
Hitachi
Hitachi Scientific
Scientific In-
Instru-
Scientific In-
struments
ments (Beijing)
(Beijing) Co., Co.,
Ltd.,Ltd., Beijing,
Beijing, ChinaChina
was was applied
applied to to acquire
acquire the
struments (Beijing) Co., Ltd., Beijing, China was applied to acquire the SEM images and the
SEM SEM images
images and and
the
the
EDS
the EDS
EDS results.
results. AtAt
results. Atfirst,
first,first,ofallthe
all all ofofthethesamples
samples
samples were were
removed
were removed
removed from
fromfrom thecore
the core
the core
of ofofspecimens.
the thespecimens.
the specimens.
Then,
they were dried in an oven at a temperature of 105 ◦ C for 2 days and coated by vacuum
gold spraying. Finally, the sprayed samples were transferred to the SU3800 for SEM and
EDS measurements.
The powdered samples were analyzed using a Bruker JV-DX X-ray diffractometer
from Shanghai Erdi Instrument Technology Co., Ltd. of Shanghai, China, and the resulting
X-ray diffraction curves were obtained. Additionally, a portion of the powder was analyzed
by thermogravimetric analysis utilizing a TGA thermogravimetric analyzer provided by
Estone Technology (Hong Kong) Co., Ltd., Hong Kong, China.

3. Results and Discussion

3.1. The Rheological Parameters of UHPC
Figure 6 displays the slump flow of the fresh UHPC. It was found that the slump flow
presents an upward trend with increasing MS dosage. The increasing rate of slump flow
with MS varied from 0% to 14.3%. The flowability of fresh UHPC is decided by its inner
free water and the shapes of the used materials [24]. MS has smaller specific surface area
than SF, leading to less adsorption of free water and higher slump flow. Furthermore, it
can be noted that MS has a more rounded micromorphology than cement and SF [36]. MS,
with its rounded shape, can reduce the flow resistance in fresh UHPC, thus increasing its
slump flow. The ball effect of MS can possibly increase the fluidity of fresh UHPC. The
 flow presents an upward trend with increasing MS dosage. The increasing rate of slump
flow with MS varied from 0% to 14.3%. The flowability of fresh UHPC is decided by its
inner free water and the shapes of the used materials [24]. MS has smaller specific sur-
face area than SF, leading to less adsorption of free water and higher slump flow. Fur-
Materials 2024, 17, 497 thermore, it can be noted that MS has a more rounded micromorphology than cement 6 of 17
and SF [36]. MS, with its rounded shape, can reduce the flow resistance in fresh UHPC,
thus increasing its slump flow. The ball effect of MS can possibly increase the fluidity of
fresh
error UHPC. Theoferror
bar values freshbar valuesslump
UHPC’s of fresh UHPC’s
flow slumpthan
were lower flow
8%were lower
of the than
slump 8%values,
flow of the
slump flow the
confirming values, confirming
accuracy the accuracy of the experiment.
of the experiment.

300 16
Slump flow

Increasing rate
14
250
12

Increasing rate (%)

Slump flow (mm)
200 10
8
150
6
100 4
2
50
0
0 -2
-10 0 10 20 30 40 50
MS (%)
Figure
Figure 6.
6. The
The slump
slump flow
flow of
of UHPC
UHPC with
with MS.
MS.

The
The plastic
plastic viscosity
viscosity ofof fresh UHPC is shown in Figure 7. Contrary Contrary to to the
the research
results on slump
slump flow,
flow, the
theplastic
plasticviscosity
viscositypresented
presenteda adownward
downwardtrend,trend, with decreas-
with decreasing
ing
rates of 0–29.6%, with the addition of MS. As has been pointed out in prior studiesstudies
rates of 0–29.6%, with the addition of MS. As has been pointed out in prior [37,38],
[37,38], the relationship
the relationship between between
the plasticthe plastic and
viscosity viscosity and the
the slump flowslump
showsflow showscorrela-
an inverse an in-
verse correlation.anTherefore,
tion. Therefore, increasedan increased
slump slump
flow leads toflow leads to the
the decreased decreased
plastic plastic
viscosity. On vis-
one
cosity. On MS
hand, the onecombines
hand, thelessMSfree
combines less freetowater,
water, leading leading fluidity
the increased to the increased fluidity
in fresh UHPC in
and,
fresh UHPC
thus, the and,viscosity
plastic thus, theis plastic
reducedviscosity
by adding is reduced by adding
MS. On the MS. the
other hand, On ball
the other
effect hand,
of MS
can ball
the increase
effectthe
of slump
MS canflow of fresh
increase theUHPC, as analyzed
slump flow of freshabove,
UHPC,thus decreasing
as analyzed its plastic
above, thus
Materials 2024, 17, x FOR PEER REVIEW 7 of 18
viscosity [39].
decreasing its The error
plastic bar values
viscosity [39].ofThe
plastic
errorviscosity for fresh
bar values UHPC
of plastic were lower
viscosity than
for fresh
7.6%, ensuring
UHPC were lowerthe than
experimental accuracy.
7.6%, ensuring the experimental accuracy.

18
Plastic viscosity 30
16 Decreasing rate

14 25
Plastic viscosity (Pa·s)

Decreasing rate (%)

12 20
10
15
8
10
6
4 5
2 0
0
-10 0 10 20 30 40 50
MS (%)

The plastic
Figure 7. The plastic viscosity
viscosity of
of UHPC
UHPC with MS.

The yield
The yield shear
shear stress
stress of
of fresh
fresh UHPC
UHPC withwith different
different dosages
dosages ofof MS
MS is is depicted
depicted in
in
Figure 8. As expected, the variation law of yield shear stress was the same as
Figure 8. As expected, the variation law of yield shear stress was the same as that for that for plastic
viscosity.
plastic Previous
viscosity. studiesstudies
Previous have pointed out that,
have pointed outatthat,
the at
same
the shear rate, the
same shear yield
rate, the shear
yield
stress of the fresh paste is positively correlated with the plastic viscosity [40].
shear stress of the fresh paste is positively correlated with the plastic viscosity [40]. Therefore, the
yield shear stress of fresh UHPC showed a similar trend as plastic viscosity. The
Therefore, the yield shear stress of fresh UHPC showed a similar trend as plastic viscos- decreasing
rates
ity. of decreasing
The the yield shear
ratesstress
of thewere
yield0–23.1%. The were
shear stress specific reasonsThe
0–23.1%. for specific
this variation
reasonswere
for
this variation were elaborated earlier. The corresponding error bar values were lower
than 7.3% of the yield shear stress values, guaranteeing the precision of the experimental
results.

160 25
 The yield shear stress of fresh UHPC with different dosages of MS is depicted in
Figure 8. As expected, the variation law of yield shear stress was the same as that for
plastic viscosity. Previous studies have pointed out that, at the same shear rate, the yield
shear stress of the fresh paste is positively correlated with the plastic viscosity [40].
Materials 2024, 17, 497 Therefore, the yield shear stress of fresh UHPC showed a similar trend as plastic viscos-
7 of 17
ity. The decreasing rates of the yield shear stress were 0–23.1%. The specific reasons for
this variation were elaborated earlier. The corresponding error bar values were lower
than 7.3% of
elaborated the yield
earlier. The shear stress values,
corresponding errorguaranteeing the precision
bar values were lower thanof 7.3%
the experimental
of the yield
results.
shear stress values, guaranteeing the precision of the experimental results.

160 25
Yield shear stress
140 Decreasing rate
20
Yield shear stress (Pa) 120

Decreasing rate (%)

100 15

80
10
60

40 5

20
0
0
-10 0 10 20 30 40 50
MS (%)

Figure8.8. The
Figure The yield
yield shear
shear stress
stressof
ofUHPC
UHPCwith
withMS.
MS.

3.2.
3.2. The
The Initial
Initial Setting
Setting Time
Time of
of UHPC
UHPC
The initial setting time of UHPC is shown in Figure 9. From Figure 9, the initial
The initial setting time of UHPC is shown in Figure 9. From Figure 9, the initial set-
setting time shows a reducing trend with the mass ratio of MS. As has been previously
ting time shows a reducing trend with the mass ratio of MS. As has been previously re-
reported, the hydration rate of hydraulic substances (e.g., Al2 O3 ) in MS is higher than that
ported, the hydration rate of hydraulic substances (e.g., Al2O3) in MS is higher than that
of hydraulic substances in cement [41–43]. Consequently, the addition of MS led to an
of hydraulic substances in cement [41–43]. Consequently, the addition of MS led to an
increase in the early hydration rate of cement and a reduction in the initial setting time. The
increase in the early hydration rate of cement and a reduction in the initial setting time.
decreasing rates of initial setting time with the addition of MS were 0–23.1%. The error
Materials 2024, 17, x FOR PEER REVIEW
bar
8 ofThe
18
The decreasing rates of initial setting time with the addition of MS were 0–23.1%.
values were lower than 8.1% with respect to the real initial setting time values, indicating
error bar values were lower than 8.1% with respect to the real initial setting time values,
the accuracy of experimental results.
indicating the accuracy of experimental results.
250 25
Initial setting time

Decreasing rate
200 20
Initial setting time (min)

Decreasing rate (%)

150 15

10
100

5
50

0
0
-10 0 10 20 30 40 50
MS (%)

Figure 9.
Figure Theinitial
9. The initialsetting
setting time
time of
of UHPC
UHPC with
with MS.
MS.

3.3. The DSR of UHPC

3.3. The DSR of UHPC
The results for the DSR are given in Figure 10, which indicates that the DSR of UHPC
The results
increases for manner
in a linear the DSRwith are the
given
massin ratio
Figure 10, and
of MS which indicatescuring
increasing that the
age.DSR
Tableof4
UHPC increases in a linear manner with the mass ratio of MS and increasing
shows the fitting results between the DSR and the mass ratio (M) of MS. The increasing curing age.
Table 4 shows the fitting results between the DSR and the mass ratio (M)
rates of DSR varied from 33.1% to 42.3% when adding MS. This is mainly due to the fact of MS. The in-
creasing rates of DSR varied from 33.1% to 42.3% when adding MS. This is
that the hydration activity of MS is higher than that of the cement, resulting in a fastermainly due to
the fact that
hydration theofhydration
rate MS [44,45]. activity of MS
Therefore, theisdrying
highershrinkage
than that rate
of the cement,with
increased resulting in a
increasing
faster hydration rate of MS [44,45]. Therefore, the drying shrinkage rate
MS content. The increasing rates of the DSR were 0–213.2% and 0–31.2% with the curing increased with
increasing MS content. The increasing rates of the DSR were 0–213.2% and 0–31.2% with
the curing age and the addition of MS. Evidently, the hydration degree increases with
the curing age, which leads to an increased drying shrinkage rate. It can be observed,
from Figure 10, that the error bar values were lower than 6.7% of the DSR values,
demonstrating the accuracy of the research results. The fitting degrees of the equations
 The results for the DSR are given in Figure 10, which indicates that the DSR of
UHPC increases in a linear manner with the mass ratio of MS and increasing curing age.
Table 4 shows the fitting results between the DSR and the mass ratio (M) of MS. The in-
creasing rates of DSR varied from 33.1% to 42.3% when adding MS. This is mainly due to
Materials 2024, 17, 497 the fact that the hydration activity of MS is higher than that of the cement, resulting8in a
of 17
faster hydration rate of MS [44,45]. Therefore, the drying shrinkage rate increased with
increasing MS content. The increasing rates of the DSR were 0–213.2% and 0–31.2% with
the
agecuring
and theage and the
addition addition
of MS. of MS.
Evidently, theEvidently,
hydrationthe hydration
degree degree
increases withincreases
the curingwith
age,
which
the leadsage,
curing to an increased
which leadsdrying shrinkage drying
to an increased rate. It can be observed,
shrinkage rate. Itfrom
can Figure 10, that
be observed,
the error
from bar 10,
Figure values
thatwere
the lower
error than 6.7% ofwere
bar values the DSR values,
lower thandemonstrating
6.7% of the DSR the accuracy
values,
of the research results.
demonstrating The fitting
the accuracy of thedegrees
research of results.
the equations were all
The fitting higherofthan
degrees the or equal to
equations
0.92, all
were ensuring
higherthe
thanrationality of 0.92,
or equal to the fitting results.
ensuring the rationality of the fitting results.

600
550 1d
3d
500 7d
14d
450 28d
DSR(10-6) (%)

400
350
300
250
200
150
100
0 10 20 30 40
MS (%)

Figure
Figure10.
10.The
TheDSR
DSRof
ofUHPC
UHPCwith
withMS.
MS.

Table
Table 4.
4. The
Thefitting
fittingresults
results between
between the
the DSR
DSR and
and the
the mass
mass ratio
ratio (M)
(M) of
of MS.
MS.
Equation
Equation
Types Types a a
b b
R2 R2
DSR(10 )(%)-1d−6
−6 116 1.93 0.97
DSR(10 )(%)-1d 116 1.93 0.97
DSR = a + bM DSR(10 )(%)-3d
−6 190.52 2.54 0.99
DSR(10−6 )(%)-3d 190.52 2.54 0.99
DSR(10−6)(%)-7d 265.7 3.06 0.99
DSR = a + bM DSR(10−6 )(%)-7d 265.7 3.06 0.99
DSR(10−6 )(%)-14d 312.2 3.24 0.99
DSR(10−6 )(%)-28d 389.14 3.43 0.92

3.4. The Mechanical Strength of UHPC

The flexural and compressive strengths of UHPC with MS are displayed in Figure 11,
from which it can be seen that the flexural strengths of UHPC increased, with increasing
rates of 0–28.3%, 0–48.2%, and 0–21.5%, when the curing age was 1 day, 3 days, and 7 days,
respectively. This can be explained by the substances having higher early hydration activity,
improving the flexural strength in the early curing stage (i.e., less than 14 days) [46,47].
However, when the curing age was 14 days and 28 days, the flexural strengths of UHPC
increased with the addition of MS, with the increasing rates of 0–2.8% and 0–2.1%, respec-
tively. This can be attributed to the fact that the MS can increase the early hydration rate
and hydration heat, thus increasing the cracks in UHPC and decreasing the increasing
rate of the flexural strength. Figure 11 indicates that the compressive strengths varied
with the same changing rules as the flexural strengths. In the early curing stage (lower
than 14 days, i.e., 1, 3, and 7 days), the increasing rates of compressive strengths with MS
were 0–26.1%, 0–42.5%, and 0–20.2%, respectively. When the curing ages were 14 days and
28 days, the increasing rates of compressive strengths with MS were 0–3.6% and 0–2.2%,
respectively. When compressive loading was applied to the specimens, the direction of
vertical compression caused tensile failure; thus, the essence of UHPC’s compression fail-
ure is tensile failure. Therefore, the mechanism of its compressive strength change is the
same as that of its flexural strength described above. Hence, the compressive strength
was improved obviously through the addition of MS, due to the obviously increased early
 the curing ages were 14 days and 28 days, the increasing rates of compressive strengths
with MS were 0–3.6% and 0–2.2%, respectively. When compressive loading was applied
to the specimens, the direction of vertical compression caused tensile failure; thus, the
essence of UHPC’s compression failure is tensile failure. Therefore, the mechanism of its
Materials 2024, 17, 497 compressive strength change is the same as that of its flexural strength described above. 9 of 17
Hence, the compressive strength was improved obviously through the addition of MS,
due to the obviously increased early hydration rate [48]. However, the compressive
strengths
hydrationincreased
rate [48].insignificantly, which can bestrengths
However, the compressive attributedincreased
to the increased cracks due
insignificantly, to
which
the
can increased early
be attributed hydration
to the heat
increased [49].due
cracks Apparently, the flexural
to the increased and compressive
early hydration heat [49].
strengths
Apparently,increased with and
the flexural the increasing
compressiverates of 0–316%
strengths and 0–223%
increased with thewith an increase
increasing ratesin
of
the curing
0–316% andage, ranging
0–223% withfrom 1 day to
an increase in 28
thedays.
curingThe
age,error barsfrom
ranging of mechanical
1 day to 28 strengths
days. The
error lower
were bars ofthan
mechanical
7.3% ofstrengths were lower
the mechanical than values,
strength 7.3% of indicating
the mechanical strength values,
the accuracy of the
indicating the accuracy
experimental results. of the experimental results.

40 200
Flexural strength-1 d Increasing rate-1 d Compressive strength-1 d Increasing rate-1 d 80
Flexural strength-3 d Increasing rate-3 d Compressive strength-3 d Increasing rate-3 d

Compressive strength (MPa)

Flexural strength-7 d Increasing rate-7 d 100 Compressive strength-7 d Increasing rate-7 d 60
Flexural strength (MPa)

Compressive strength-14 d Decreasing rate-14 d

Flexural strength-14 d Decreasing rate-14 d
30 150 Compressive strength-28 d Decreasing rate-28 d 40

Increasing rate (%)

Increasing rate (%)

Flexural strength-28 d Decreasing rate-28 d
50 20
0
20 0 100
-20

-50 -40
10 50 -60
-100 -80
-100
0 -150 0
0 10 20 30 40 0 10 20 30 40
MS (%) MS (%)

(a) (b)
Figure 11. The mechanical strengths of UHPC with MS. (a)The flexural strength; (b)The compres-
Figure 11. The mechanical strengths of UHPC with MS. (a) The flexural strength; (b) The compres-
sive strength.
sive strength.
3.5.
3.5.The
TheElectrical
ElectricalResistance
ResistanceofofUHPC
UHPC
The
Theelectrical
electricalresistance
resistanceof ofUHPC
UHPCisisillustrated
illustratedin
inFigure
Figure12,
12, which
whichshows
showsthat
thatthe
the
electrical
electricalresistance
resistanceincreased
increasedwith
withincreasing
increasingrates
ratesof
of0–138.6%,
0–138.6%,0–71.1%,
0–71.1%,and
and0–43.2%,
0–43.2%,
respectively,
respectively,with
withMSMSdosages
dosagesofof
0–40%
0–40% when
whenthethe
curing ageage
curing waswas
lower thanthan
lower 14 days. As
14 days.
As the hydration activity of UHPC with MS is higher than that of cement, the UHPC
with MS can consume more water, leading to a decrease in the concentration of the pore
solution [50]. Electrical conduction is mainly determined by the electrical resistance of the
pore solution [51]. As a result, the electrical conduction was decreased by MS. Hence, the
electrical resistance of the UHPC was increased. However, when the curing age reached
14 days, the electrical resistance was decreased by MS, with decreasing rates of 0–34.6% and
0–59.8%, due to the increased conductive effect of manganese [52]. Moreover, the electrical
resistance of UHPC increased with the curing age if the MS was maintained at the same
dosage. This can be explained by the decreased pore solution due to the effect of curing
age on the hydration rate [53].
The fitting equations between the mechanical strengths and the electrical resistance
are shown in Figure 13. It can be observed, from Figure 13, that the relationships between
the mechanical strengths and the electrical resistances coincided with power functions. The
fitting degrees of all fitting equations were no lower than 0.90, which confirms the accuracy
of the experimental results. This can be explained by the fact that the electrical resistance
depends on the pore solution of UHPC [54]. Meanwhile, the mechanical strengths of
UHPC were closely related to the electrical resistance. Therefore, the electrical resistance of
UHPC has a particular relationship to its mechanical strength. Consequently, the electrical
resistance of UHPC can be used to calculate its mechanical strength.
 electrical
4,000,000 resistance of the UHPC was increased. However,
50 when the curing age reached

Electrical resistanc

Increasing rate (
14 days, the electrical resistance was decreased by 0MS, with decreasing rates of 0–34.6%
and 0–59.8%, due to the increased conductive effect
3,000,000 -50 of manganese [52]. Moreover, the
electrical resistance of UHPC increased with the curing
-100 age if the MS was maintained at
Materials 2024, 17, 497 the same dosage. This can be explained by the decreased
2,000,000 -150 pore solution due to the10effect
of 17
of curing age on the hydration rate [53]. -200
1,000,000 -250
6,000,000 250
-300
Electrical resistance-1 d Increasing rate-1 d

0 Electrical resistance-3 d Increasing rate-3 d 200

-350
Electrical resistance-7 d Increasing rate-7 d
5,000,000 0 Electrical resistance-14
10 d 20 rate-14 d 30
Decreasing 40 150

Electrical resistance (Ω)

Electrical resistance-28 d MS (%)
Decreasing rate-28 d
100

Increasing rate (%)

4,000,000
Figure 12. The electrical resistance of UHPC with MS. 50
0
The fitting equations between the mechanical strengths
3,000,000 -50 and the electrical resistance
are shown in Figure 13. It can be observed, from Figure -100 13, that the relationships be-
tween the mechanical strengths and the electrical resistances
2,000,000 -150 coincided with power func-
tions. The fitting degrees of all fitting equations were -200 no lower than 0.90, which confirms
the 1,000,000
accuracy of the experimental results. This can be-250 explained by the fact that the elec-
trical resistance depends on the pore solution of UHPC -300[54]. Meanwhile, the mechanical
strengths of 0 UHPC were closely related to the electrical -350 resistance. Therefore, the elec-
trical resistance0 of UHPC 10 has a20particular 30 relationship
40 to its mechanical strength. Con-
MS (%)
sequently, the electrical resistance of UHPC can be used to calculate its mechanical
strength.
Figure12.
Figure 12.The
Theelectrical
electricalresistance
resistanceof
ofUHPC
UHPCwith
withMS.
MS.

26The fitting equations

Flexural strength-1 d
between the mechanical250
Compressive strength-1 d
strengths and the electrical resistance
are24shownFlexuralin Figure
strength-3 d
13. It can
Compressive be
strength-3 d observed, from Figure 13, that the relationships be-

22 Flexural strength-7 d Compressive strength-7 d

Compressive strength(MPa)
tween
20 the Flexural
mechanical
Flexural strength-14d
strengths and the electrical resistances coincided with power func-
Compressive strength-14d
Flexural strength(MPa)

strength-28d Compressive strength-28d

200
tions.
18 The fitting degrees of all fitting equations were no lower than 0.90, which confirms
the16accuracy
f =0.0021R of the experimental results.
t
0.75
This can be explained by the fact that the elec-
ft=0.72R0.22
14 R =0.92 2
R2=0.93
trical resistance depends ft=0.035R on the pore
0.44
solution of UHPC150 [54]. Meanwhile, the mechanical
12 R2=0.96
strengths
10 of UHPC were closely related to the electrical resistance. Therefore, the elec-
0.56
trical f =0.031R ft=0.0065R
8 resistance of UHPC t has a
0.49
particular relationship to its mechanical strength. Con-
6 R =0.96 R2=0.93 2

sequently, 100
the electrical resistance of UHPC can be used to calculate its mechanical
4 fcu=0.038R0.67 fcu=4.62R0.21 0.15
strength.
2 R 2
=1.00 2
f =11.66R
cu

R =0.91 R2=0.97
0 fcu=0.050R0.55
-2 0.31 50
26 f =1.70R R2=0.98
Flexural strength-1 d
cu
2
Compressive strength-1 d
250
-4
24 R =0.90Flexural strength-3 d Compressive strength-3 d

220 Flexural1000000
strength-7 d 2000000
Compressive strength-7 d 3000000
Compressive strength(MPa)

Flexural strength-14d Compressive strength-14d

20
Flexural strength(MPa)

Flexural strength-28d Compressive strength-28d

Electrical resistance (Ω) 200
18
16 ft=0.0021R0.75 f =0.72R0.22
Figure The fitting equations
1413.R2=0.92 between tthe electrical resistance and the mechanical strengths of
ft=0.035R0.44 R2=0.93
UHPC 12with MS. 2
150
R =0.96
10
0.49 f =0.0065R0.56
3.6. The
8 AC Impedance
ft=0.031R t Spectrum of UHPC
6 R 2
=0.96 R2=0.93
The 100
4 AC fcu=0.038Rimpedance
0.67 spectrum of UHPC is shown
fcu=4.62R0.21 f =11.66R 0.15
in Figure 14. In Figure 14, Zr and Zi
stand 2for the
R2=1.00 electrical resistance and electrical
cu
reactance, respectively. The fitting results are
R2=0.91 R2=0.97
shown0 in Table 5,fcufrom =0.050R which
0.55 it can be observed that the electrical reactance of the UHPC
-2in the
f =1.70R 0.31 50
varied form Rof2
a
=0.98 quadratic cu
function,
2 with respect to its electrical resistance. The fitting
-4 R =0.90
degrees0were all 1000000 1.0, demonstrating 2000000the accuracy 3000000of the fitting results. This can be explained
by the interfaces between different solids and the interfaces of solids and liquids [55]. The
Electrical resistance (Ω)
interfaces of different phases induce variation in the electrical reactance. As described
above, the electrical resistance of UHPC is dominated by the electrical conduction of the
inner pore solution. As a result, a specific relationship exists between the resistance and
capacitance of UHPC [56]. It can be observed, from Figure 14, that the electrical resistance
value corresponding to the extreme points increases with the curing age. This electrical
resistance value first increases with the addition of MS (curing age less than 14 days);
however, when the curing age reaches 14 days, the electrical resistance value is decreased
with the addition of MS. The variation was analyzed according to the results of the AC
electrical resistance above.
 tween the resistance and capacitance of UHPC [56]. It can be observed, from Figure 14,
that the electrical resistance value corresponding to the extreme points increases with
the curing age. This electrical resistance value first increases with the addition of MS
(curing age less than 14 days); however, when the curing age reaches 14 days, the elec-
Materials 2024, 17, 497 trical resistance value is decreased with the addition of MS. The variation was analyzed
11 of 17
according to the results of the AC electrical resistance above.

1,000,000
MS-0%
MS-10%
方程 y = Interce
800,000 MS-20%
B D
绘图
MS-30%
权重
MS-40%
600,000 截距 1.15946E6 ± 308054.56995 ±
B1 -123.33237 ± -75.2173 ± 15.

Zi(Ω)
B2 0.00295 ± 1. 0.00213 ± 2.22
400,000 残差平 1.93621E9 5.3957E9
R平方( 0.99834 0.99677
调整后 0.99825 0.9966
200,000

30,000 40,000 50,000 60,000 70,000 80,000

Zr(Ω)
(a)

(b)
Figure
Figure14.
14.The
TheAC
ACimpedance
impedance spectrum of of
spectrum UHPC with
UHPC MS.MS.
with (a) (a)
UHPC withwith
UHPC MS MS
cured for 3for
cured days; (b)
3 days;
UHPC with MS cured for 14 days.
(b) UHPC with MS cured for 14 days.

Table 5. The fitting results of the equations of the Zi and Zr .

Equation Types A B C R2
MS-0%-3 days 0.0030 −123.33 1.16 × 106 1.00
MS-10%-3 days 0.0021 −75.22 3.08 × 105 1.00
MS-20%-3 days 3.83 × 10−4 0.51 −5.79 × 105 1.00
MS-30%-3 days 8.19 × 10−4 −68.29 1.29 × 106 1.00
Zi = AZr 2 + MS-40%-3 days 4.84 × 10−4 −40.41 6.89 × 105 1.00
BZr + C MS-0%-14 days 3.70 × 10−6 −2.88 5.85 × 105 1.00
MS-10%-14 days 1.29 × 10−5 −9.95 1.98 × 106 1.00
MS-20%-14 days 8.31 × 10−6 −5.18 8.19 × 105 1.00
MS-30%-14 days 1.55 × 10−5 −8.34 1.15 × 106 1.00
MS-40%-14 days 2.23 × 10−5 −8.77 8.75 × 105 1.00

The equivalent circuits of UHPC are shown in Figure 15. It can be seen that the circuit
diagram for UHPC consists of four sets of electrical components. The three sets of electrical
components are introduced as follows. The parallel electrical resistances and reactances of
the pore solution and the UHPC matrix are connected in series, while the third electrical
component is the contact electrical resistance of the stainless steel electrode meshes between
 MS-40%-14 days 2.23 × 10−5 −8.77 8.75 × 105 1.00

The equivalent circuits of UHPC are shown in Figure 15. It can be seen that the cir-
cuit diagram for UHPC consists of four sets of electrical components. The three sets of
Materials 2024, 17, 497 electrical components are introduced as follows. The parallel electrical resistances12and of 17
reactances of the pore solution and the UHPC matrix are connected in series, while the
third electrical component is the contact electrical resistance of the stainless steel elec-
trode meshes
the UHPC between
matrix. Thethe
ChiUHPC matrix.
values of theThe Chiequivalent
UHPC values of the UHPCwere
circuits equivalent circuits
no higher than
were no higher than 0.026, indicating the accuracy of the equivalent
0.026, indicating the accuracy of the equivalent circuit diagrams. circuit diagrams.

Figure
Figure15.
15.The
Theequivalent
equivalentcircuit
circuitof
ofUHPC
UHPCwith
withMS.
MS.

3.7.The
3.7. TheLeached
LeachedToxic
ToxicSubstances
Substances
The leached
The leached Cr,Cr, Zn,
Zn, and
and Mn
Mn from
fromUHPC
UHPCare areshown
shownininFigure
Figure16,
16,from
fromwhich
whichit can
it canbe
seen that the leached Cr, Zn, and Mn increased with increasing immersion
be seen that the leached Cr, Zn, and Mn increased with increasing immersion time and time and the
dosage
the of MS.
dosage The increasing
of MS. rates of
The increasing Cr, of
rates Zn,Cr,
andZnMn leached from UHPC were 0–1218%,
, and Mn leached from UHPC were
0–1312.3%, and 0–406.8%, respectively, with respect to the immersion time. Meanwhile, the
0–1218%, 0–1312.3%, and 0–406.8%, respectively, with respect to the immersion time.
increasing amounts of Cr, Zn, and Mn in UHPC were 0–0.0361 mg/mL, 0–0.0353 mg/mL,
Meanwhile, the increasing amounts of Cr, Zn, and Mn in UHPC were 0–0.0361 mg/mL,
and 0–0.00317 mg/mL, respectively, with respect to the dosage of MS. MS, having a certain
0–0.0353 mg/mL, and 0–0.00317 mg/mL, respectively, with respect to the dosage of MS.
amount of toxicity, can cause some environmental pollution. Compared with other studies,
MS, having aCr,
the leached certain
Zn, andamount
Mn from of toxicity,
the UHPC cantested
causeinsome environmental
this study were much pollution.
lower thanCom-the
pared
Materials 2024, 17, x FOR PEER REVIEW with other studies, the leached Cr, Zn, and Mn from the UHPC tested in
toxic elements leached from ordinary cement concrete [57,58]. Therefore, the toxic elements this study
13 of 18
were much
seeping outlower
of UHPC thanhave
the toxic elements
minimized leached frompollution.
environmental ordinary cement concrete [57,58].
Therefore, the toxic elements seeping out of UHPC have minimized environmental pol-
lution.
0.003
MS‐0% MS‐0% 1200
MS‐10% MS‐10%
1000
Leaching amount (mg/ml)

MS‐20% MS‐20%
MS‐30% MS‐30%
800
Increasing rate (%)

MS‐40% MS‐40%
0.002
600
400
200
0.001
0
‐200
‐400
0.000
1 2 3 4 5 6
Immersing time (months)
(a)
0.003 16. Cont.
Figure 1400
MS‐0% MS‐0%
MS‐10% MS‐10% 1200
MS‐20% MS‐20%
Leaching amount (mg/ml)

MS‐30% MS‐30% 1000

Increasing rate (%)

MS‐40% MS‐40%
0.002 800
600
400
200
0.001
0
‐200
‐400
0.000
1 2 3 4 5 6
 0

Leac

I
‐200
‐400
0.000
Materials 2024, 17, 497 1 2 3 4 5 6 13 of 17
Immersing time (months)
(a)
0.003 1400
MS‐0% MS‐0%
MS‐10% MS‐10% 1200
MS‐20% MS‐20%

Leaching amount (mg/ml)

MS‐30% MS‐30% 1000

Increasing rate (%)

MS‐40% MS‐40%
0.002 800
600
400
200
0.001
0
‐200
‐400
0.000
1 2 3 4 5 6
Immersing time (months)

(b)
0.0020
MS‐0% MS‐0% 400
MS‐10% MS‐10%
MS‐20% MS‐20% 300
Leaching amount (mg/ml)

MS‐30% MS‐30%
0.0015

Increasing rate (%)

MS‐40% MS‐40% 200
100
0.0010 0
‐100

0.0005 ‐200
‐300
‐400
0.0000
1 2 3 4 5 6
Immersing time (months)

(c)
Figure
Figure16. Theleached
16.The leachedtoxic
toxic elements.
elements. (a)
(a)The
The leaching
leaching C
Crr of
ofUHPC
UHPCwith
with MS;
MS; (b)
(b) The
The leaching
leaching Z
Znnof
of
UHPC
UHPCwith
withMS;
MS;(c)
(c)The
Theleaching
leachingMMnnof
ofUHPC
UHPCwithwithMS.
MS.

3.8. The SEM-EDS of UHPC

The SEM-EDS of UHPC is depicted in Figure 17. It can be observed, from Figure 17,
that flocculent hydration and compact products were found in the UHPC. When the dosage
of MS increased, the compact hydration products also increased. The elements O, Mg, Al,
Si, K, Ca, and Fe were observed in every sample. When MS was added, the elements Na,
Ti, and Mn were additionally discovered. The element Mn increased with the addition of
MS. The addition of MS can improve the compactness of the UHPC, thus increasing the
mechanical strengths of UHPC.

3.9. The XRD of UHPC

XRD curves of the UHPC are exhibited in Figure 18. From Figure 18, the UHPC
consisted of Ca(OH)2 (CH), 3CaO·SiO2 , SiO2 , calcium silicate hydrate (C-S-H) crystals, and
MnO2 . When the amount of MS increased, the C-S-H crystals increased and the CH crystals
decreased. This can be explained by the increased pozzolanic effect of MS in UHPC [59]. It
can be observed, from the XRD curves, that the diffraction peak of MnO2 was not obvious,
confirming that the MnO2 had been solidified into a cement hydration substance in UHPC.
Hence, Mn can be effectively disposed through its addition into UHPC.
 that flocculent hydration and compact products were found in the UHPC. When the
dosage of MS increased, the compact hydration products also increased. The elements O,
Mg, Al, Si, K, Ca, and Fe were observed in every sample. When MS was added, the ele-
ments Na, Ti, and Mn were additionally discovered. The element Mn increased with the
Materials 2024, 17, 497 addition of MS. The addition of MS can improve the compactness of the UHPC, thus in-17
14 of
creasing the mechanical strengths of UHPC.

(a)

(b)

Materials 2024, 17, x FOR PEER REVIEW 15 of 18

(c)
Figure
Figure17.
17.The
TheEDS
EDSof
ofUHPC.
UHPC. (a)
(a) UHPC
UHPC with 0% MS;
with 0% MS; (b)
(b) UHPC
UHPCwith
with0%
0%MS;
MS;(c)
(c)UHPC
UHPCwith
with40%
40%MS.
MS.
C3S  C-S-H
▲

C2S ♦ SiO2
▲

ª of UHPC
●

3.9. The XRD★

♦ ▄ ª CH ★ MnO2
●

▲
●

XRD curves of the UHPC are exhibited in Figure 18. From Figure 18, the UHPC
MS-40%
consisted of Ca(OH)2 (CH), 3CaO·SiO2, SiO2, calcium silicate hydrate (C-S-H) crystals,
MS-30% the C-S-H crystals increased and the CH
and MnO2. When the amount of MS increased,
crystals decreased. This can be explained by the increased pozzolanic effect of MS in
UHPC [59]. It can be observed, from the XRD curves, that the diffraction peak of MnO2
MS-20%
was not obvious, confirming that the MnO2 had been solidified into a cement hydration
substance in UHPC. Hence, Mn can be effectively disposed through its addition into
UHPC. MS-10%

MS-0%

0 10 20 30 40 50 60 70 80 90 100
2θ(°)
Figure
Figure18.
18.The
TheXRD
XRDcurves
curvesofofUHPC.
UHPC.

4.4.Conclusions
Conclusions
Theconclusions
The conclusions of
of this
this research,
research, obtained
obtainedfrom
fromthe
theabove
aboveresults, cancan
results, be be
summarized
summa-
as follows.
rized as follows.
The addition of MS (0–40% in the mass ratio of the total binder materials) increased
the slump flow of fresh UHPC, with increasing rates of 0–14.3%. The corresponding
plastic viscosity and yield shear stress were decreased by 0–29.6% and 0–23.1%, respec-
tively, with the addition of MS.
The initial setting time of UHPC was increased by MS. The DSR of UHPC presented
Materials 2024, 17, 497 15 of 17

The addition of MS (0–40% in the mass ratio of the total binder materials) increased
the slump flow of fresh UHPC, with increasing rates of 0–14.3%. The corresponding plastic
viscosity and yield shear stress were decreased by 0–29.6% and 0–23.1%, respectively, with
the addition of MS.
The initial setting time of UHPC was increased by MS. The DSR of UHPC presented a
positive linear relationship with the mass ratio of MS. The increasing rates of DSR were
0–213.2% and 0–31.2% with respect to the curing age and the added MS, respectively.
The flexural and compressive strengths were increased by 0–48.2% and 0–22.5% with
the addition of MS when the curing age was lower than 14 days; however, the flexural and
compressive strengths were decreased by 0–2.8% and 0–3.6% after the curing age reached
14 days.
The electrical resistance of UHPC was first increased with the addition of MS and then
decreased in the curing stages of 1–7 days and 7–28 days, respectively. The electrical resis-
tance presented power function relationships with the flexural and compressive strengths
of the UHPC.
The Cr, Zn, and Mn leached from UHPC increased with increasing rates of 0–1218%,
0–1312.3%, and 0–406.8%, respectively, with the mass ratio of MS ranging from 0% to 40%
and the immersion time ranging from 1 to 6 months.
MS can increase the compactness of hydration products and increase the Mn elemental
composition in UHPC. Furthermore, the Ca(OH)2 crystals in the hydration products were
decreased with the addition of MS.

Author Contributions: Validation, W.X.; investigation, W.X.; resources, H.W.; data curation, H.W.;
writing—original draft, W.X.; writing—review and editing, H.W. and J.Y.; project administration,
H.W. All authors have read and agreed to the published version of the manuscript.
Funding: The Natural Science Foundation of Zhejiang Province, China (No. LY22E080005), and the
Ningbo Natural Science Foundation Project (2023J086).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data is unavailable due to privacy or ethical restrictions.
Conflicts of Interest: The authors declare no conflict of interest.

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