Study On Sustainable Application of Low-Carbon Sup

sustainability
Article
Study on Sustainable Application of Low-Carbon Supersulfated
Cement with Alkanolamines
Runduo Zhou 1 , Bingxin Jin 1 , Shuanglei Wu 1 , Shujing Fan 2 , Fafu Hang 2 and Huxing Chen 1, *
1 School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China
2 Linhai Zhongxin New Building Materials Co., Ltd., Taizhou 317000, China; liuluorenjiantree@163.com (S.F.)
* Correspondence: chenhx@zju.edu.cn
Abstract: As an environmentally friendly cement material in green buildings, due to its low con-
tribution to air pollution and its substantial use of solid waste, supersulfated cement (SSC) has
been extensively studied. However, the low early strength of sustainably utilized SSC needs to be
addressed. In order to use SSC to achieve great reductions in energy consumption during industrial
production, the effects of triethanolamine (TEA), diethanolisopropanolamine (DEIPA) and triiso-
propanolamine (TIPA) (with dosages ranging from 0.02% to 0.08%) on the strength and hydration
of SSC were studied, and the underlying mechanism was analyzed by TGA, XRD and SEM. The
results show that TEA and DEIPA significantly improve the 3-day and 28-day strength of SSC. The
former is better at low dosages, while the latter is more suitable for high dosages. TIPA also enhances
the 3-day strength of SSC, but it is not as good as the other two alkanolamines. The chelation of
alkanolamine with Al3+ ions plays an important role in the strength development of SSC, which accel-
erates the decomposition of slag and the formation of ettringite. In summary, adding alkanolamines
to low-carbon cement systems with a high proportion of industrial by-products such as SSC is a
potential and effective solution. In addition, alkanolamines can be used as a strength promoter for
most low-carbon blends, which fully utilize solid waste.
Keywords: low-carbon cement; solid waste; supersulfated cement; ground granulated blast furnace
slag; sustainable application; alkanolamine
Citation: Zhou, R.; Jin, B.; Wu, S.; Fan,
S.; Hang, F.; Chen, H. Study on
Sustainable Application of
Low-Carbon Supersulfated Cement 1. Introduction
with Alkanolamines. Sustainability
Cement production is the most energy-consuming and unsustainable process in
2024, 16, 3008. https://doi.org/
10.3390/su16073008
the building materials industry. For example, Chinese cement production has reached
2.4 billion tons, resulting in 1.23 billion tons of carbon emissions, which accounts for ap-
Academic Editor: José Ignacio proximately 13% of the country’s total carbon emissions. This phenomenon has caused the
Alvarez Chinese cement industry to face severe challenges in terms of air pollution and unsustain-
Received: 30 January 2024 able development.
Revised: 23 March 2024 In recent years, with the deepening of the concept of environmental protection [1–5],
Accepted: 2 April 2024 more attention has been paid to the use of solid waste like industrial by-products. Many
Published: 4 April 2024 studies have shown that alkanolamine better improves the mechanical properties of low-
carbon cement containing solid waste than ordinary Portland cement (OPC) [6,7]. Alka-
nolamines, including triethanolamine (TEA), triisopropanolamine (TIPA), diethanoliso-
propanolamine (DEIPA), and ethyldiisopropylamine (EDIPA), which are widely used in
Copyright: © 2024 by the authors. the cement industry as grinding aids, significantly influence the hydration and strength
Licensee MDPI, Basel, Switzerland. properties of cement. TEA promotes the early strength of OPC at low content but is
This article is an open access article
harmful to the strength of cement-based materials at high content, especially in terms of
distributed under the terms and
late strength [8–10]. The good early mechanical properties are because TEA promotes
conditions of the Creative Commons
the dissolution of C3 A and C4 AF and the hydration of C3 A+gypsum, which accelerates
Attribution (CC BY) license (https://
the formation of ettringite [11–13] and the secondary hydration of C3 A in OPC [8,9,14],
creativecommons.org/licenses/by/
related to the complexation of TEA with Ca2+ , Al3+ and Fe4+ ions in solution [9,15,16]. The
4.0/).
Sustainability 2024, 16, 3008. https://doi.org/10.3390/su16073008 https://www.mdpi.com/journal/sustainability

Sustainability 2024, 16, 3008 2 of 20
low late strength arises due to the inhibition of the hydration of C3 S by TEA [7,9,10,17].
In contrast to TEA, TIPA promotes the late strength of OPC, but its effect on the early
strength is slight [8,9,18,19]. The high late strength is because TIPA has a continuous
effect on the dissolution of ferrite, increasing the concentrations of Fe3+ and Al3+ ions in
pore solution, and this process accelerates the consumption of CH, thus promoting the
formation of AFt or AFm [20–22]. DEIPA and EDIPA are new alkanolamines similar to the
above two alkanolamines. Wang et al. [23] reported that alkanolamines with asymmetric
molecular structure have stronger solubilizing ability than alkanolamines with symmetric
molecular structure. DEIPA and EDIPA show better late strength than TEA and better early
strength than TIPA when used in OPC [9]. The addition of the two alkanolamines to OPC
promotes the initial dissolution of C3 A and C4 AF [24,25] and accelerates the secondary
hydration of C3 A and the conversion of AFt to AFm [8,26,27]. Both DEIPA and EDIPA
increase the hydration degree of C3 S at late stage [9,25,26]. Because alkanolamine acceler-
ates the dissolution of Al3+ and Fe4+ ions in supplementary cementitious materials (SCMs)
and enhances the pozzolanic reaction, its promotion on blended cements is better than its
promotion on OPC [6,20,28]. Different views on whether alkanolamines directly promote
SCMs have been discussed. Kong et al. [7] believed that the influence of TEA on the
pozzolanic reaction of FA can consume more CH, resulting in a lower CH content in FAC;
the reduction in actinomorphic CH is conducive to the refinement of pore structure [10].
Riding et al. [29] showed that DEIPA can directly act on slag by measuring the heat of
hydration of cement and cement-slag blend. However, Ma et al. [21] believed that the
addition of TIPA first accelerates the hydration of cement and generates more CH, which
further stimulates the pozzolanic reaction of FA and consumes more CH.
At present, alkanolamines have been extensively studied in many environmentally
friendly blended cement systems that replace approximately only 30 wt.% of clinker, but
few scholars have focused on systems with higher clinker replacement levels.
Supersulfated cement (SSC) is a low-carbon system with a small amount of clinker.
The proportion of clinker replacement is generally approximately 90 wt.%, of which the
proportion of granulated blast furnace slag (GBFS) is usually greater than 80 wt.%, and
the proportion of gypsum is approximately 10–20 wt.% [30–33]. Sometimes, a small
amount of alkali activator, such as KOH [34,35], is used instead of clinker to contribute
to the alkali excitation of slag. The main hydration products of SSC are ettringite and
C-S-H gel [36,37]. The clinker dissolves and generates CH at the beginning of hydration,
giving the environment a high alkalinity level to encourage the slag to dissolve [38].
The dissolved Al3+ , Ca2+ and Si4+ ions in GBFS react with calcium sulfate (CS) to form
ettringite (C6 AS3 H32 ) at early stage, and calcium silicate hydrate (C-S-H) phase in later
stages to support the increase in strength [32,39]. The simplified hydration process of SSC
is demonstrated in Equation (1) [38].
C5 S3 A + CH + 3CS + 34H → C6 AS3 H32 + 3CSH (1)
Although SSC has the advantages of good durability [39–42], low heat of hydra-
tion [36], good workability and rheology [43], it also has the disadvantages of low early
strength and weak carbonization resistance.
When used as a low-air-pollution material in construction engineering, SSC has the
shortcomings of low early strength. SSC is a hydration system dominated by aluminum
mineral phase at early stage. Moreover, most alkanolamines are early hydration promoters
of cement and can complex Ca2+ , Al3+ and Fe4+ ions in pore solution to accelerate the hy-
dration of aluminate and ferrite. Therefore, this study investigated whether alkanolamines
had a beneficial effect on SSC hydration. In addition, we evaluated whether alkanolamine
had a similar or more pronounced hydration mechanism in SSC than in OPC.
Therefore, this study attempted to add alkanolamine to SSC for the first time to explore
the effect of alkanolamine on the hydration and mechanical properties of such a low-early-
strength cement system with ettringite as the main mineral phase. A comparative study
on three alkanolamines (TEA, DEIPA and TIPA) was conducted. Due to its high toxicity,
early-strength cement system with ettringite as the main mineral phase. A comparative
study on three alkanolamines (TEA, DEIPA and TIPA) was conducted. Due to its high
toxicity, EDIPA was not considered. This not only has a guiding significance for the ex-
ploration of the general law of alkanolamine in the cement system containing SCMs, but
also provides a new reference and idea for the development of new low-carbon environ-
mental protection
EDIPA cement and
was not considered. the
This utilization
not of solidsignificance
only has a guiding waste suchforasthe
slag.
exploration of
the general law of alkanolamine in the cement system containing SCMs, but also provides
2. Materials and Methods
a new reference and idea for the development of new low-carbon environmental protection
cement and the utilization of solid waste such as slag.
2.1. Materials
2.Portland
Materialscement
and Methods
clinker, desulfurization gypsum, ground granulated blast furnace
2.1. Materials
slag (GGBS) and three kinds of alkanolamines were used in this experiment. The clinker
was obtainedPortland cement
from clinker,
South Cementdesulfurization
Co., Ltd.,gypsum,
Hangzhou,ground granulated
China. blast furnacegypsum
Desulfurization
slag (GGBS) and three kinds of alkanolamines were
was from Xindu Cement Co., Ltd., Hangzhou, China. GGBS (grade S95)used in this experiment. The clinker
was obtained
was obtained from South Cement Co., Ltd., Hangzhou, China. Desulfurization gypsum
fromwasDehang Mining Products Co., Ltd., Shijiazhuang, China. The density and specific
from Xindu Cement Co., Ltd., Hangzhou, China. GGBS (grade S95) was obtained from
surface areaMining
of GGBS wereCo.,
3.1 Ltd., 33 and 429 m22/kg, respectively. The chemical composi-
g/cmShijiazhuang,
Dehang Products China. The density and specific surface
tionsarea
of ofthese
GGBS materials
were 3.1 are
g/cm shown in Table
3 and 429 m2 /kg,1.respectively.
Figure 1 shows the SEM
The chemical morphologies of
compositions
GGBS and desulfurization
of these materials are shown gypsum.
in TableThe slag 1isshows
1. Figure angular
the and
SEM granular, while
morphologies the gypsum
of GGBS
and desulfurization gypsum. The slag is angular and granular,
has a parallelepiped shape. TEA (Yien Chemical Technology Co., Ltd., Shanghai, while the gypsum has a China,
China
parallelepiped shape. TEA (Yien Chemical Technology Co., Ltd., Shanghai, China, 98%
98% purity), TIPA (Yien Chemical Technology Co., Ltd., Shanghai, China, 95% purity) and
purity), TIPA (Yien Chemical Technology Co., Ltd., Shanghai, China, 95% purity) and
DEIPADEIPA(ShengHong
(ShengHongHolding
Holding Group
Group Co.,Co.,Ltd.,
Ltd., Suzhou,
Suzhou, China,
China, 85% 85% purity)
purity) wereand
were used, used, and
theirtheir
molecular
molecularformulas
formulasareare shown
shown ininFigure
Figure2. 2.
(a) (b)
Figure 1. SEM
Figure images
1. SEM ofofthe
images theraw
raw materials: (a)GGBS;
materials: (a) GGBS;(b)(b) Gypsum.
Gypsum.
TEA DEIPA TIPA

Figure 2. Molecular
Figure formulas
2. Molecular formulasof
of TEA, DEIPAand
TEA, DEIPA and TIPA.
TIPA.
Table 1. Chemical compositions of raw materials (wt.%).
SiO2 Al2 O3 Fe2 O3 CaO MgO SO3 Loss

Cement 22.16 5.18 3.95 66.25 1.26 0.36 0.09
GGBS 34.5 17.7 1.03 34 6.01 1.64 0.84
Desulfurization gypsum 2.18 0.91 0.49 30.07 0.25 42.38 22.71
2.2. Mix Proportion

The clinker was first ground with a 200-mesh sieve in a standard small mill of Φ500
until the residue content was less than 6.0%. Various SSC binders were prepared by
mixing clinker, desulfurization gypsum and GGBS. The basic ratio of SSC was 80 wt.%
slag, 15 wt.% desulfurization gypsum and 5 wt.% clinker. The proportions of alkanolamine
added to SSC were 0, 0.02%, 0.04%, 0.06% and 0.08%. Different mixtures are indicated by
corresponding symbols for the convenience of the discussion below, as shown in Table 2.
After proportional matching, the specimens were mixed uniformly by stirring.
Table 2. Mixture design of SSC cement (wt.%).
ID SSC TEA DEIPA TIPA

Blank 100 0 0 0
TEA0.02 100 0.02 0 0
TEA0.04 100 0.04 0 0
TEA0.06 100 0.06 0 0
TEA0.06 100 0.08 0 0
DEIPA0.02 100 0 0.02 0
DEIPA0.04 100 0 0.04 0
DEIPA0.06 100 0 0.06 0
DEIPA0.08 100 0 0.08 0
TIPA0.02 100 0 0 0.02
TIPA0.04 100 0 0 0.04
TIPA0.06 100 0 0 0.06
TIPA0.08 100 0 0 0.08
2.3. Methodology
2.3.1. Mechanical Strength
Alkanolamine was dissolved in water in advance and the solution was then mixed
with the binder to prepare the paste with a w/c of 0.4. The pastes were stirred in a
laboratory mixer at a speed of 140 r/min for 120 s, stopped mixing for 15 s, and then stirred
at a speed of 285 r/min for 120 s. The equipment used in this process was a NJ-160A
cement paste mixer from Luda Experiment Instrument Co., Ltd., Shanghai, China. The
fresh pastes were poured into 20 mm × 20 mm × 20 mm mold. All of mold were stored
in a curing box with a humidity of more than 95% and a temperature of (20 ± 1) ◦ C for
24 h. The equipment used was an HBY-40B cement (concrete) constant-temperature and
humidity cabinet from Luda Experiment Instrument Co., Ltd., Shanghai, China. Then,
the specimens were demoulded and further cured in water at (20 ± 1) ◦ C by using an
HBY-30 constant-temperature water cabinet from Luda Experiment Instrument Co., Ltd.,
Shanghai, China. The hardened pastes that were cured for 3 days and 28 days were tested
for compressive strength at a rate of 0.2 kN/s by using a YZH-300·10 constant load cement
flexural compression testing machine from Luda Machinery Instrument Co., Ltd., Shaoxing,
China. The average compressive strength of six specimens was adopted.
After the compressive strength test, the hydration was stopped by submerging small
pieces of samples in alcohol. The pieces were then dried in an oven at 40 ◦ C for 1 d and
grounded to pass through the sieve with 80 µm for XRD, TGA and SEM analysis.
2.3.2. Isothermal Calorimetry

The heat of hydration of the SSC pastes after the addition of TEA, DEIPA or TIPA was
measured by a TAM Air isothermal calorimeter from TA Company (New Castle, DE, USA)
at 20 ◦ C for 3 days using external stirring method [15]. An amount of 10 g of dry cement
was loaded in glass ampoules, and syringes were loaded with 5 g of alkanolamine–water
solution. After reaching a steady baseline, the solution was injected into the ampoule and
mixed with the cement. The dosages of alkanolamines were 0.08%.
2.3.3. XRD and QXRD

The phase composition was investigated using a Rigaku Ultimate IV powder X-ray
CuKα (λ = 1.5418 Å) radiation diffractometer operated at 40 kV and 40 mA. Data were
collected from 5◦ to 65◦ at 5◦ /min. Before testing, samples stored in ethanol were ground
and dried at 40 ◦ C for 24 h. Quantitative X-ray diffraction (QXRD) analysis utilized the
Rietveld method in X’Pert HighScore Plus (version 3.0e) using the external standard method,
with rutile as the standard reference. All structure models used for Rietveld refinement are
shown in Table 3.
Table 3. Structure models used for Rietveld refinement.
Phase Formula Crystal System ICSD Cods Reference

Ettringite 3CaO·Al2 O3 ·3CaSO4 ·32H2 O Trigonal 155395 [44]
Gypsum CaSO4 ·2H2 O Monoclinic 409581 [45]
Calcite CaCO3 Trigonal 40545 [46]
Rutile (standard) TiO2 Tetragonal 202241 [47]
2.3.4. TGA
TGA was conducted with a TGA/DSC3+ synchronous thermal analyzer from Mettler,
Zurich, Switzerland. The samples were heated from 50 to 1000 ◦ C at a rate of 10 ◦ C/min
under a 30 mL/min flow of N2 . The preparation process of powder samples used for
testing was consistent with that for XRD analysis.
2.3.5. Degree of Hydration

The selective dissolution of the hydrate phases in ethylenediaminetetraacetic acid
(EDTA) described by Kocaba et al. [48] was used to evaluate the reaction degree of slag.
This method is usually used for blended pastes. The preparation of powder samples used
for testing was consistent with that of XRD samples. The hydration degree of slag was
calculated by referring to Equation (2) recommended by Luke et al. [49]:
w2 + ( f SLAG (1 − RGGBS )w1 ) − ( f CEMENT Cr w1 )

αSLAG = 100 − ·100 (2)
f SLAG w1
where w1 is the weight of sample (ignited weight), w2 is the weight of residue (105 ◦ C dry
weight), Cr is the percentage of cement residue divided by 100, f SLAG is the percentage
of initial slag in the blended cement, f CEMENT is the percentage of initial cement in the
blended cement, and RGGBS is the percentage of unreacted slag that is insoluble in EDTA.
In addition, any method is subject to a certain amount of error. The EDTA selective
dissolution method is not an accurate method. However, it could still be used as a reference
to assist analysis.
2.3.6. SEM
The morphology of SSC pastes was observed by field emission environmental scanning
electron microscopy (SEM; FEG650, FEI, Shanghai, China). The acceleration voltage was
20 kV. Before the test, the sample was coated with a thin gold layer.
Sustainability 2024, 16, x FOR PEER REVIEW 6 of 21

3. Results
3.1. Mechanical Properties
3. The
Results
compressive strength of SSC specimens after the addition of different dosages of
alkanolamines isProperties
3.1. Mechanical shown in Figure 3. Detailed compressive strength data is listed in Tables
S1–S7 of The compressive strength
Supplementary of SSC
Materials. Atspecimens
3 days, TEAafterand
the addition of different dosages
DEIPA significantly improve the
of alkanolamines is shown in Figure 3. Detailed compressive
mechanical properties of SSC. Compared with that of DEIPA, the performance strength data is listedofinTEA is
Tables S1–S7 of Supplementary Materials. At 3 days, TEA and DEIPA significantly improve
superior at 3-day strength, while the improvement in SSC caused by TIPA is relatively
the mechanical properties of SSC. Compared with that of DEIPA, the performance of TEA is
slight. The at
superior strength of SSCwhile
3-day strength, increases obviously with
the improvement in SSCthe addition
caused by TIPA of TEA, especially
is relatively slight. at low
dosages. Whenof0.02%
The strength TEA isobviously
SSC increases added, the withstrength increases
the addition of TEA,by 4.1 MPa.
especially When
at low increasing
dosages.
theWhen
dosage to 0.06%
0.02% TEA isTEA,
added, the
thestrength
strength reaches
increasesabymaximum
4.1 MPa. Whenvalueincreasing
and increases by 8.3 MPa
the dosage
compared
to 0.06% with thatstrength
TEA, the of the reaches
blank sample.
a maximum Whenvalue0.02% DEIPA by
and increases is added,
8.3 MPa the strength in-
compared
with that
creases of the
by only 2.3blank
MPa,sample.
and when When 0.02%
0.04% DEIPAisisadded,
DEIPA added, thethe strength
strength increases
increasesbyby only
only 2.3 MPa, and when 0.04% DEIPA is added, the strength
4.4 MPa. However, at relatively high dosages, DEIPA is better than TEA. When increases by only 4.4 MPa.
the dosage
However, at relatively high dosages, DEIPA is better than TEA. When the dosage reaches
reaches 0.08%, the strength of SSC with DEIPA increases by 10.5 MPa, while the strength
0.08%, the strength of SSC with DEIPA increases by 10.5 MPa, while the strength of the SSC
of the
withSSCTEA with TEA increases
increases by only 7.9by onlyTIPA
MPa. 7.9 MPa. TIPA
slightly slightly
increases theincreases
strength of the strength
SSC only at of SSC
only at dosages,
high high dosages,
and theand the strength
strength increase isincrease
lower thanis that
lower than
of the thattwo
other of alkanolamines.
the other two alka-
nolamines.
At a dosageAtofa 0.02%,
dosageTIPA of 0.02%, TIPA
decreases thedecreases
strength bythe0.1 strength
MPa, and by 0.1 MPa,
it increases and
the it increases
strength
thebystrength
only 2.9byMPaonly
at a2.9 MPaofat0.08%.
dosage a dosage of 0.08%.
(a) (b)
(c)
Figure 3. Influences
Figure of of
3. Influences alkanolamines
alkanolamineson
onthe
thecompressive strengthofofSSC
compressive strength SSCpastes
pasteswith
with different dos-
different
ages: (a) TEA; (b) DEIPA; (c) TIPA.
dosages: (a) TEA; (b) DEIPA; (c) TIPA.
AtAt
28 28 days,
days, TEATEA andDEIPA
and DEIPAstill
stillincrease
increase the
the strength
strength of
ofSSC,
SSC,but
butthe
thetwotwoalka-
alkanola-
nolamines are different. The strength of SSC with TIPA generally decreases at all dosages.
mines are different. The strength of SSC with TIPA generally decreases at all dosages. TEA
TEA significantly enhances the strength of SSC at low dosages, but its strength fluctuates
significantly enhances the strength of SSC at low dosages, but its strength fluctuates and
even decreases with increasing dosage. The effect of TEA on the strength of SSC is differ-
ent from that of OPC. At a dosage of 0.04%, the strength with TEA is 33.1 MPa, and when
the dosage reaches 0.06%, the strength is 31.7 MPa, which is 1.4 MPa lower than the
and even decreases with increasing dosage. The effect of TEA on the strength of SSC is
previousfrom
different one. that
The ofstrength
OPC. At of aSSC is still
dosage ofenhanced
0.04%, thewith the increasing
strength with TEAdosage of DEIPA.
is 33.1 MPa, and
The strength
when the dosage after adding0.06%,
reaches 0.08%the DEIPA is 38.5
strength MPa,MPa,
is 31.7 whichwhichis 15.7 MPa
is 1.4 MPahigher
lowerthan that
than theof
the blankone.
previous sample; this result
The strength ofisSSC
similar to enhanced
is still that described
withbytheXu et al. [9]. dosage
increasing With the ofaddition
DEIPA.
of 0.08%
The TIPA,
strength afterthe strength
adding 0.08%of SSC
DEIPA is 21.0 MPa,
is 38.5 MPa,which
whichis is
1.415.7
MPa MPalower thanthan
higher thatthat
of the
of
blank
the sample;
blank sample; thisthis
result is also
result different
is similar from
to that OPC [9].by Xu et al. [9]. With the addition
described
of 0.08% TIPA, the strength of SSC is 21.0 MPa, which is 1.4 MPa lower than that of the
3.2. Degree
blank sample;of Slag
this Hydration
result is also different from OPC [9].
The selective dissolution method of EDTA described by Luke et al. [49] can be used
3.2. Degree ofthe
to measure Slaghydration
Hydrationdegree of slag. Prior to testing the SSC mixtures, it has shown
that The
96%selective dissolution
of unhydrated method
slag is insolubleof EDTA
during described by Luke et al. [49] can be used to
EDTA extraction.
measureThe hydration degree of slag with different dosagesSSC
the hydration degree of slag. Prior to testing the of mixtures,
TEA, DEIPA it has
andshown
TIPAthat
at 3
96% of unhydrated slag is insoluble during EDTA extraction.
days and 28 days is shown in Figure 4. Detailed hydration degree data is listed in Table
S8 ofThe hydration degree
Supplementary of slag At
Materials. with different
3 days, the dosages
hydrationof degree
TEA, DEIPA and TIPA
is improved withat 3the
daysin-
and 28 days is shown in Figure 4. Detailed hydration degree
creasing dosage of TEA and DEIPA. A high degree of hydration is achieved at a low dos- data is listed in Table S8 of
Supplementary Materials. At 3 days, the hydration degree is improved
age of TEA, which is in good agreement with strength. But at high dosages, the hydration with the increasing
dosage
degreeof TEA
with theand DEIPA.ofADEIPA
addition high degree of hydration
is greater than thatiswith
achieved TEA.atTIPA
a low dosageincreases
slightly of TEA,
which is in good agreement with strength. But at high dosages,
the hydration degree of slag at 3 days. At 28 days, the hydration degree after adding the hydration degree with
the addition of DEIPA is greater than that with TEA. TIPA slightly
DEIPA is better than that after adding TEA on the whole. Only at a dosage of 0.02% is the increases the hydration
degree
influenceof slag at 3 days.
of DEIPA At 28lower
slightly days,than
the hydration
that of TEA. degree after adding
However, DEIPA degree
the hydration is betterofthan
slag
that afterTIPA
adding adding TEA
is still on the
weak whole.
at 28 days. Only at a dosage of 0.02% is the influence of DEIPA
slightly lower than that of TEA. However, the hydration degree of slag adding TIPA is still
weak at 28 days.
Figure 4. Influence of alkanolamines with different dosages on the hydration degree of slag in SSC at
3Figure 4. Influence
days and 28 days. of alkanolamines with different dosages on the hydration degree of slag in SSC
at 3 days and 28 days.
3.3. Heat Evolution
3.3. Heat Evolution
Isothermal calorimetry was used to test the evolution curves for SSC after the ad-
ditionIsothermal
of TEA, DEIPA and TIPA
calorimetry for up
was used to 72
to test theh.evolution
The hydration rateSSC
curves for and cumulative
after the addi-
heat results are shown in Figure 5. Detailed hydration rate
tion of TEA, DEIPA and TIPA for up to 72 h. The hydration rate and cumulative data is listed in Tableheat
S9
of Supplementary Materials and high-resolution pictures are shown in Figures
results are shown in Figure 5. Detailed hydration rate data is listed in Table S9 of Supple- S1 and S2.
To clearlyMaterials
mentary quantify and
andhigh-resolution
compare the differences
pictures are between
shown intheFigures
hydration
S1 and curves
S2. Toofclearly
each
group,
quantifysome
andcharacteristic
compare theparameters
differenceson the heatthe
between evolution curve
hydration are extracted
curves and labeled
of each group, some
as and C, as shown in Table 4. t
characteristic parameters on the heat evolution curve are extracted and labeled as heat
A, B A and (dQ/dt) A represent the ending time and A, B
generation rate of in
and C, as shown induction
Table 4. period, respectively.
tA and (dQ/dt) kB represents
A represent
thetime
the ending secantand slope
heaton the heat
generation
evolution curve between
rate of induction period,Arespectively.
and C and itkBindicates
representsthethe
maximum acceleration
secant slope on the heatrate evolution
of hydra-
tion. t and (dQ/dt)
curveCbetween A and C represent the maximum heat generation rate time and
C and it indicates the maximum acceleration rate of hydration. tC the maximum
heat
and generation rate of the
(dQ/dt)C represent the main hydration
maximum heat peak, rate timeQand
respectively.
generation is thethecumulative
maximumheat heat
of hydration.
generation rate of the main hydration peak, respectively. Q is the cumulative heat of hy-
dration.
The general heat flow curve of OPC is divided into five stages: initial reaction, induc-
tion, acceleratory and deceleratory periods, and the final period of slow reaction. The
curve has four characteristic peaks [10,50]. However, in SSC, the curve is generally divided
Sustainability 2024, 16, 3008 into three stages: initial wetting and dissolution peak, dormant period with low heat re-
8 of 20
lease rate and wide exothermic peak [37,51].
(a) (b)
Figure
Figure5.5.Hydration
Hydrationheat
heatof
ofthe
the SSC
SSC pastes with or
pastes with or without
withoutalkanolamines:
alkanolamines: (a)(a) Hydration
Hydration rate; (b)
rate;
Cumulative
(b) Cumulative heat (A: Ending time of induction period. B: The maximum secant slope on the heat heat
heat (A: Ending time of induction period. B: The maximum secant slope on the
evolution
evolutioncurve
curvebetween
between AA and
andC.C.C:C:The
The maximum
maximum heat
heat generation
generation rate time).
rate time).
According
Table to of
4. The effects Figure 5a, withonthe
alkanolamines theaddition of alkanolamines,
characteristic thehydration.
parameters of cement main hydration peak
is more or less delayed to the right. By comparing the difference of tC in Table 4, the
tA (h) (dQ/dt)A (mW/g) tC (h) Q (J/g) kB
strength of the delaying effect of alkanolamine on(dQ/dt) C (mW/g)
the main hydration peak of SSC is com-
Blank 5.5 0.08119 23.18333 1.76642 139.89844 0.42955
pared as follows: TEA > DEIPA > TIPA. TEA and DEIPA significantly delay the hydration
TEA 7.56667 0.08109 28.66667 2.70791 196.85867 0.89248
peak of SSC,6.35833
DEIPA
while TIPA is0.07967
relatively weak. The regularities
26.49167 2.4025
satisfied by tA also indicate a
187.21136 0.68707
delay in hydration.
TIPA 5.96667 0.08271 24.71667 1.81567 152.32699 0.39886
Table 4. The effects of alkanolamines on the characteristic parameters of cement hydration.

The general heat flow curve of OPC is divided into five stages: initial reaction, induc-
tion, acceleratory
tA (h) and(dQ/dt)
deceleratory
A (mW/g)
periods, and the final
tC (h) periodC of
(dQ/dt) slow reaction.
(mW/g) The curve kB
Q (J/g)
has four characteristic peaks [10,50]. However, in SSC, the curve is generally divided into
Blank 5.5 0.08119 23.18333 1.76642 139.89844 0.42955
three stages: initial wetting and dissolution peak, dormant period with low heat release
TEA 7.56667 0.08109
rate and wide exothermic peak [37,51]. 28.66667 2.70791 196.85867 0.89248
DEIPA 6.35833
According 0.07967
to Figure 5a, 26.49167
with the addition of alkanolamines, 2.4025 187.21136
the main hydration peak0.68707
is
TIPA 5.96667
more or less delayed to 0.08271
the right. By 24.71667
comparing the difference1.81567
of t C in Table152.32699 0.39886
4, the strength
of the delaying effect of alkanolamine on the main hydration peak of SSC is compared as
follows:
However,TEA >the DEIPA > TIPA.ofTEA
addition andthree
these DEIPA significantly delay
alkanolamines the hydration
increases peak of heat
the maximum
SSC, while TIPA is relatively weak. The regularities satisfied by tA also indicate a delay
generation rate of the main hydration peak. For (dQ/dt)C: TEA > DEIPA > TIPA. TEA and
in hydration.
DEIPAHowever,
greatly promote the peak strength of the main hydration peak, while the maximum
the addition of these three alkanolamines increases the maximum heat
heat generation rate of TIPA
generation rate of the main hydration is closepeak.
to that
Forof the blank
(dQ/dt) sample. The law satisfied by kB
C : TEA > DEIPA > TIPA. TEA and
also indicates
DEIPA greatlythe increase
promote the in
peakpeak strength.
strength of theThe
main delay of thepeak,
hydration main hydration
while peak is con-
the maximum
sistent with the increase in the maximum heat generation rate. The cumulative
heat generation rate of TIPA is close to that of the blank sample. The law satisfied by kB also heat also
increases
indicateswith the delay
the increase of hydration
in peak peak
strength. The andofthe
delay theincrease in peakpeak
main hydration strength.
is consistent
with the increase
Because in the hydration
the main maximum heat peakgeneration rate. The
of SSC mainly cumulative heat
corresponds to thealso increases of hy-
formation
with the delay of hydration peak and the increase in peak strength.
dration products such as ettringite and C-S-H [52]. That is, the main hydration peak con-
Because the main hydration peak of SSC mainly corresponds to the formation of
tains both silicate reaction and aluminate reaction. Due to the retarding effect of TEA on
hydration products such as ettringite and C-S-H [52]. That is, the main hydration peak
silicate reaction, the hydration induction period is prolonged, but TEA accelerates alumi-
contains both silicate reaction and aluminate reaction. Due to the retarding effect of TEA on
nate reaction
silicate [9,15,17].
reaction, Therefore,
the hydration TEAperiod
induction delays the silicatebut
is prolonged, reaction of slag and
TEA accelerates accelerates
aluminate
the aluminate reaction of slag at early stage, resulting in the backward
reaction [9,15,17]. Therefore, TEA delays the silicate reaction of slag and accelerates the delay of the main
hydration
aluminatepeak of SSC
reaction andatthe
of slag increase
early stage, in peak strength.
resulting Similar delay
in the backward to TEA, DEIPA
of the maindelays
the hydration
hydration peakinduction
of SSC andperiod and activates
the increase in peakthe secondSimilar
strength. reaction of aluminate
to TEA, DEIPA delaysphase, but
the hydration induction period and activates the second reaction
its effect is relatively weaker than TEA [24,26]. Therefore, the main hydration peak of aluminate phase, butof SSC
its effect is relatively weaker than TEA [24,26]. Therefore, the main hydration peak of SSC
containing DEIPA appears earlier than that of SSC containing TEA. Because the impact
of TIPA on the hydration
containing induction
DEIPA appears period
earlier than is not
that ofapparent [9,20,21],
SSC containing TEA.curve
Becausecollected
the impactfrom
of
TIPA
isothermal on the hydration
calorimetry about SSC (b) period
induction
adding TIPAisshows
not apparent
a slight[9,20,21],
delay incurve collected peak.
its hydration from
isothermal
Furthermore, calorimetry
the strength about
of the SSC hydration
main adding TIPA shows
peak of aSSC
slight delay
with TIPAin its hydration
changes peak.
slightly.
Furthermore, the strength of the main hydration peak of SSC with TIPA
The weak effect on the main hydration peak is because TIPA does not greatly promote thechanges slightly.
The weak effect on the main hydration peak is because TIPA does not greatly promote the
hydration of the aluminate phase, which is similar to the results from [53].
hydration of the aluminate phase, which is similar to the results from [53].
3.4. Hydration Products
3.4. Hydration Products
3.4.1. XRD Analysis
3.4.1. XRD Analysis
The hydration products of SSC at 3 days and 28 days were analyzed qualitatively and quan-
The hydration products of SSC at 3 days and 28 days were analyzed qualitatively and
titatively by XRD and QXRD to further study the effect of alkanolamine on cement hydration.
quantitatively by XRD and QXRD to further study the effect of alkanolamine on cement
Figure 6 shows the 3-day
hydration. Figureand 28-day
6 shows XRD
the patterns
3-day of SSC
and 28-day withpatterns
XRD different
of dosages
SSC withofdifferent
TEA, DEIPA
dos-
and TIPA. Table
ages 5 shows
of TEA, DEIPA the phase
and TIPA.compositions
Table 5 showsofthehardened pastes obtained
phase compositions by Rietveld
of hardened pastes
quantitative analysis.
obtained Detailedquantitative
by Rietveld XRD data isanalysis.
listed in Detailed
Table S10XRDof Supplementary
data is listed inMaterials
Table S10and
of
high-resolution pictures Materials
Supplementary are shown in high-resolution
and Figures S3 and pictures
S4. are shown in Figures S3 and S4.
(a)
(b)
Figure 6. XRD pattern of SSC pastes containing different dosages of alkanolamines (E: Ettringite;
G: Gypsum; C: Calcite Ht: Hydrotalcite): (a) 3 d; (b) 28 d.
Table 5. Phase compositions of SSC pastes containing different dosages of alkanolamines as deter-
mined by Rietveld analysis.
3d Blank TEA0.04 TEA0.08 DEIPA0.04 DEIPA0.08 TIPA0.04 TIPA0.08

Ettringite 0.1118 0.1162 0.1226 0.1131 0.1343 0.1094 0.1061
Gypsum 0.1115 0.0611 0.0463 0.0529 0.0679 0.0729 0.0747
Calcite 0.0122 0.0075 0.0081 0.0089 0.0060 0.0148 0.0121
Amorphous 0.7644 0.8151 0.8230 0.8091 0.7918 0.8029 0.8071
28 d Blank TEA0.04 TEA0.08 DEIPA0.04 DEIPA0.08 TIPA0.04 TIPA0.08
Ettringite 0.1248 0.1259 0.1304 0.1320 0.1407 0.1152 0.1172
Gypsum 0.0700 0.0479 0.0349 0.0421 0.0359 0.0549 0.0477
Calcite 0.0107 0.0112 0.0070 0.0090 0.0089 0.0074 0.0104
Amorphous 0.7945 0.8150 0.8277 0.8170 0.8145 0.8225 0.8247
The main hydration phases of SSC are ettringite, gypsum, and a small amount of calcite
due to carbonization. The amorphous humps occurring between 25◦ and 35◦ are produced
by unhydrated slag [54], and the C-S-H phase cannot be detected by XRD. In addition,
as described in [37], because SSC pore solution is undersaturated in monosulphate, no
monosulphate is observed in the XRD patterns.
At 3 days, gypsum exists for all mixtures, and relatively obvious ettringite peaks also
exist. The strong ettringite peaks of SSC are due to the slag with high Al2 O3 content used in
this experiment. Gypsum content decreases significantly with the addition of alkanolamine,
and ettringite content increases correspondingly. The impacts of TEA and DEIPA on SSC are
the most significant, followed by TIPA, and the blank is the least significant. The hydration
rate of slag is related to the content of gypsum [54]. The greater the gypsum content in SSC,
the slower the hydration rate of slag. For TEA and DEIPA, the ettringite content increases
correspondingly with the increase in dosage. This agrees with the development of 3-day
strength, which also verifies the view that ettringite is responsible for the early strength
development of SSC [54].
The calcite content of almost all mixtures is maintained at a low level according
to QXRD. The amorphous phase content in the blank sample is lower than that in SSC
containing alkanolamines due to the presence of gypsum.
At 28 days, gypsum is further consumed for all mixtures, while the gypsum content in
SSC with alkanolamine is still lower than that in the blank sample. The consumption of
gypsum by TEA and DEIPA is the most obvious, followed by TIPA. Ettringite content also
increases correspondingly, and its enhancement in SSC with DEIPA is the most significant,
followed by SSC with TEA, and the worst in SSC with TIPA. Gypsum content decreases
and ettringite content increases with the increase in dosage, especially in SSC with DEIPA.
3.4.2. TGA
The TGA results for SSC with different dosages of TEA, DEIPA and TIPA at 3 days
and 28 days are shown in Figure 7. Detailed TGA data is listed in Tables S11 and S12 of
Supplementary Materials and high-resolution pictures are shown in Figures S5–S10. The
thermogravimetric curves shown in Figure 7 indicate the presence of ettringite, gypsum,
hydrotalcite and calcite, which agrees with the XRD results. The weight loss of gypsum
occurs at approximately 100–150 ◦ C [55,56]. The weight loss of about 100 ◦ C corresponds to
the loss of the bound water of ettringite [57–59]. Due to water loss present in the interlayer
and dihydroxylation, the C-S-H phase shows weight loss over a wide temperature range of
50–600 ◦ C [50] so that in TGA, it overlaps with ettringite and gypsum. The weight loss of
hydrotalcite is usually about 370–400 ◦ C [50,55,60] and overlaps with AFm in TGA [61],
but XRD analysis reveals the inadequacy of AFm. Generally speaking, the weight loss peak
of portlandite appears at about 400–500 ◦ C, but no corresponding peak can be observed for
any of the mixtures. The peak at 700 ◦ C is caused by the decarbonization of CaCO3 [62].
The weight loss peak of CaCO3 corresponding to all mixtures is not apparent, indicating
of 50–600 °C [50] so that in TGA, it overlaps with ettringite and gypsum. The weight loss
of hydrotalcite is usually about 370–400 °C [50,55,60] and overlaps with AFm in TGA [61],
but XRD analysis reveals the inadequacy of AFm. Generally speaking, the weight loss
peak of portlandite appears at about 400–500 °C, but no corresponding peak can be ob-
Sustainability 2024, 16, 3008 11 of 20 of
served for any of the mixtures. The peak at 700 °C is caused by the decarbonization
CaCO3 [62]. The weight loss peak of CaCO3 corresponding to all mixtures is not apparent,
indicating that the carbonization of the hardened pastes is not severe, which is also in
that the carbonization of the hardened pastes is not severe, which is also in good agreement
good agreement with the result obtained by QXRD. In addition, there is a relatively small
with the result obtained by QXRD. In addition, there is a relatively small weight loss peak
weight loss peak at approximately 800 °C, corresponding to the decomposition of C-S-H
at approximately 800 ◦ C, corresponding to the decomposition of C-S-H to wollastonite
to(CaSiO
wollastonite (CaSiO 3) [63]. By comparing the TGA curves at 3 days and 28 days, it can
3 ) [63]. By comparing the TGA curves at 3 days and 28 days, it can be seen that the
beweight
seen that
lossthe
peak weight loss800
at about peak at enhanced,
◦ C is about 800indicating
°C is enhanced, indicating
the formation theC-S-H
of the formation
phase of
theand
C-S-H phase and
its possible its possible
contribution contribution
to the to the later strength.
later strength.
(a) (b)
(c) (d)
(e) (f)
Figure 7. 7.
Figure TGATGAcurves of of
curves SSC pastes
SSC containing
pastes containingdifferent dosages
different dosagesofofalkanolamines:
alkanolamines:(a)
(a)TEA
TEA3 3d;d;(b)
TEA 28 d; (c) DEIPA 3 d; (d) DEIPA 28 d; (e) TIPA 3 d; (f) TIPA 28 d.
(b) TEA 28 d; (c) DEIPA 3 d; (d) DEIPA 28 d; (e) TIPA 3 d; (f) TIPA 28 d.
Strong weight loss peaks of ettringite and gypsum can be observed in the TGA curves
of all mixtures. Figure 7a,b show that at 3 days, as the dosage of TEA increases, the weight
loss peak of ettringite enhances, while the peak of gypsum decreases, which agrees with
the XRD results. The total weight loss increases when adding more TEA, which indicates
of all mixtures. Figure 7a,b show that at 3 days, as the dosage of TEA increases, the weight
loss peak of ettringite enhances, while the peak of gypsum decreases, which agrees with
the XRD results. The total weight loss increases when adding more TEA, which indicates
that TEA promotes the degree of hydration. At 28 days, the peak of ettringite at 0.08% is
close to that at 0.04%.
The TGA curve of SSC adding DEIPA is roughly similar to that of SSC adding TEA.
What is different is that at 28 days, the ettringite peak in SSC continues to increase when
that TEA promotes the degree of hydration. At 28 days, the peak of ettringite at 0.08% is
more DEIPA is added. This is because compared with DEIPA, TEA promotes the initial
close to that at 0.04%.
dissolution
The TGAof slag and
curve ofthe
SSCformation
adding DEIPAof ettringite
is roughlytosimilar
a greater extent
to that andadding
of SSC blocksTEA.
the path
of What
ionic isdissolution and diffusion at later stages [24]. Therefore, the addition
different is that at 28 days, the ettringite peak in SSC continues to increase when of DEIPA to
SSC stillDEIPA
more resultsis in the formation
added. of new
This is because ettringite
compared withphase
DEIPA, to TEA
fill the pore space,
promotes which is
the initial
why DEIPA continues to increase the mechanical properties of SSC in the later stages.
dissolution of slag and the formation of ettringite to a greater extent and blocks the path
of For
ionicTIPA,
dissolution and diffusion
the weight at later
loss peak of stages [24].does
ettringite Therefore, the addition
not increase at 3ofdays,
DEIPA and to even
SSC still results in the formation of new ettringite phase to fill the pore
when 0.08% TIPA is added, it is lower than that of the blank sample. Compared with the space, which is why
DEIPA continues to increase the mechanical properties of SSC in the later stages.
blank sample, the weight loss peak of gypsum also decreases slightly. At 28 days, TIPA
For TIPA, the weight loss peak of ettringite does not increase at 3 days, and even when
slightly affects ettringite and gypsum, and the total mass loss is not much different from
0.08% TIPA is added, it is lower than that of the blank sample. Compared with the blank
that of thethe
sample, blank sample.
weight loss peak of gypsum also decreases slightly. At 28 days, TIPA slightly
affects ettringite and gypsum, and the total mass loss is not much different from that of the
3.5.blank
Morphology
sample.
The dosage of each alkanolamine added to SSC samples observed in SEM is 0.08%.
3.5. Morphology
The SEM images of the blank sample at 3 days are shown in Figure 8a,b. More ettringite
The dosage of each alkanolamine added to SSC samples observed in SEM is 0.08%.
is formed, which agrees with the XRD patterns in Figure 6. This is because the slag with
The SEM images of the blank sample at 3 days are shown in Figure 8a,b. More ettringite
high Al2O3 content accelerates the formation of ettringite [54]. As shown in Figure 8a, the
is formed, which agrees with the XRD patterns in Figure 6. This is because the slag with
surface
high Al of Omost ettringite is covered with C-S-H gel, which has a high density. And some
2 3 content accelerates the formation of ettringite [54]. As shown in Figure 8a, the
newly formed
surface of mostettringite
ettringitehas not been
is covered covered
with C-S-H gel,withwhich
C-S-Hhasgel. Pore
a high space And
density. for the
somegrowth
of newly
this kind
formed ettringite has not been covered with C-S-H gel. Pore space for the growthis not
of ettringite is observed in the upper right corner of Figure 8a, but it
dense. The
of this more
kind newly formed
of ettringite ettringite,
is observed in thethe faster
upper thecorner
right formation rate 8a,
of Figure of ettringite and the
but it is not
dense. The more newly formed ettringite, the faster the formation rate
hydration rate of SSC. There are very few hydration products on the surface of gypsum. of ettringite and the
In hydration
contrast, the rate slag
of SSC. There are
particles very few
located near hydration
the gypsum products
haveonfaster
the surface of gypsum.
hydration rates, and
In contrast, the slag particles located near the gypsum have faster hydration rates, and
many hydration products, such as ettringite and C-S-H gel, form nearby. However, there
many hydration products, such as ettringite and C-S-H gel, form nearby. However, there
are more angular slag particles far away from the gypsum. Almost no hydration products
are more angular slag particles far away from the gypsum. Almost no hydration products
form
formonon thethesurface
surfaceofofthese
these slag particles,indicating
slag particles, indicating that
that many
many slagslag particles
particles do notdofully
not fully
participate
participate in the hydration reaction. The SEM images of the blank sample at 28 days days
in the hydration reaction. The SEM images of the blank sample at 28 are are
shown
shown ininFigure
Figure8c,d.
8c,d.The
The morphology
morphology ofofSSC SSCbecomes
becomes denser
denser thanthan
thatthat ofsample
of the the sample
at at
3 days.
3 days. InInaddition,
addition,almost
almost all slag
slagparticles
particlesare are coated
coated with
with a large
a large numbernumber of hydration
of hydration
products.Columnar
products. Columnar ettringite
ettringiteforms
forms and fillsfills
and porepore
space, and nearly
space, all ettringite
and nearly has C-S-Hhas C-
all ettringite
gel attached to its surface.
S-H gel attached to its surface.
(a) (b)
Figure 8. Cont.
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3008 13 of 13
20 of 21
(c) (d)
(e) (f)
(g) (h)
Figure 8. SEM
Figure images
8. SEM ofof
images the
theblank
blanksample
sampleand
and SSC addingTEA:
SSC adding TEA:(a)
(a)Blank
Blank3 3d d 20,000×;
20,000 (b)
×; (b) Blank 3 d
Blank
5000×;
3 d 5000×; (c) Blank 28 d 5000×; (d) Blank 28 d 20,000×; (e) TEA 3 d 20,000×; (f) TEA 3 d 5000(g)
(c) Blank 28 d 5000×; (d) Blank 28 d 20,000×; (e) TEA 3 d 20,000×; (f) TEA 3 d 5000×; ×; TEA
28 d 20,000×; (h) TEA 28 d 5000×.
(g) TEA 28 d 20,000×; (h) TEA 28 d 5000×.
The SEM images of SSC adding TEA at 3 days are shown in Figure 8e,f. A large num-
ber of dense columnar ettringite extending outward from the surface of slags is observed.
Compared with the blank sample, most of the ettringite is newly formed, and only a tiny
part of the ettringite close to slag particles is covered by C-S-H gel. The whole SSC mor-
phology is filled with the extended ettringite, which is denser than that of the blank sam-
ple, and particles connect with each other. The SEM images of SSC adding TEA at 28 days
The SEM images of SSC adding TEA at 3 days are shown in Figure 8e,f. A large number
of dense columnar ettringite extending outward from the surface of slags is observed.
Compared with the blank sample, most of the ettringite is newly formed, and only14a of 21
Sustainability 2024, 16, x FOR PEER REVIEW
tiny part of the ettringite close to slag particles is covered by C-S-H gel. The whole SSC
morphology is filled with the extended ettringite, which is denser than that of the blank
sample, and particles connect with each other. The SEM images of SSC adding TEA at
entire SSCare
28 days and the surface
shown in Figureof slagThe
8g,h. is network
basicallystructure
coveredofby hydration
ettringite products.
and C-S-H The mor-
gel covers
phology is denser, but some large pore space cannot be filled, as seen
the entire SSC and the surface of slag is basically covered by hydration products. The in Figure 8h.
The SEM isimages
morphology denser,ofbutSSC
somewith
largeDEIPA at 3cannot
pore space days are shown
be filled, in Figure
as seen 9a,b.
in Figure 8h.A large
amountThe of columnar
SEM images ettringite
of SSC extends
with DEIPA outward and part
at 3 days of the in
are shown ettringite formsAinlarge
Figure 9a,b. the pore
amount
space. Mostof columnar ettringitein
slags participate extends outward and
the hydration part ofand
reaction the ettringite forms in thehydration
the corresponding pore
space. Most
products slags participate
are formed in the hydration
on the surface. The SEMreaction
imagesand the corresponding
of SSC with DEIPA at hydration
28 days are
shown in Figure 9c,d. The development of 28-day strength caused by DEIPA days
products are formed on the surface. The SEM images of SSC with DEIPA at 28 are
is evidenced
shown in Figure 9c,d. The development of 28-day strength caused by DEIPA is evidenced
by the coating of hydration products on the surface of slags and the effective filling of pore
by the coating of hydration products on the surface of slags and the effective filling of pore
space crosslinked with ettringite and C-S-H. And large pore space rarely appears.
space crosslinked with ettringite and C-S-H. And large pore space rarely appears.
TheTheSEM
SEMimage
imageofof SSC
SSC with TIPAatat3 3days
with TIPA daysis is shown
shown in Figure
in Figure 9e. The
9e. The surface
surface of of
ettringite has been covered with C-S-H gel, indicating a slow reaction rate.
ettringite has been covered with C-S-H gel, indicating a slow reaction rate. The SEM image The SEM image
of of
SSCSSCwith
withTIPA
TIPAatat28
28days
days is shown
shownin inFigure
Figure9f.9f.AA dense
dense hydration
hydration microstructure
microstructure like like
SSCSSCwith TEA
with TEAororDEIPA
DEIPA is is not observed.
observed.
(a) (b)
(c) (d)
Figure 9. Cont.
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3008 15 of15
20 of 21
(e) (f)
Figure 9. SEM
(e)
Figure 9. SEMimages
imagesofofSSC
SSC adding DEIPAand
adding DEIPA andTIPA:
TIPA:
(f) (a)(a) DEIPA
DEIPA 3d3 d 5000×;
5000 (b) DEIPA
×; (b) DEIPA 3 d 20,000×;
3 d 20,000 ×;
(c) (c)
DEIPA 28 d 5000×; (d) DEIPA 28 d 20,000×; (e) TIPA 3 d 20,000×; (f) TIPA 28 d
DEIPA 28 d 5000×; (d) DEIPA 28 d 20,000×; (e) TIPA 3 d 20,000×; (f) TIPA 28 d 20,000×.20,000×.
Figure 9. SEM images of SSC adding DEIPA and TIPA: (a) DEIPA 3 d 5000×; (b) DEIPA 3 d 20,000×;
(c) DEIPA 28 d 5000×; (d) DEIPA 28 d 20,000×; (e) TIPA 3 d 20,000×; (f) TIPA 28 d 20,000×.
4. Discussion
4. Discussion
4. Discussion
Alkanolamines improve the mechanical properties of low-carbon SSC and increase
Alkanolamines improve the mechanical properties of low-carbon SSC and increase
the hydration
Alkanolamines degreeimprove of slagthe (as mentioned
mechanical in Sections
properties 3.1 andSSC
of low-carbon 3.2),and
and the increase in
increase
the hydration degree of slag (as mentioned in Sections 3.1 and 3.2), and the increase in
the hydration degree of slag (as mentioned in Sections 3.1
total weight loss also indicates the generation of more hydration products (Figure and 3.2), and the increase in 7). TEA
total weight
total weight loss
loss also
also indicates
indicates the the generation
generation of more of more
hydration hydration
enhances the early strength of SSC, while DEIPA increases its late strength. The role of products products
(Figure 7). TEA(Figure 7). TEA
enhances
enhances the
TIPA is weak early
the early
both strength
strength
on early of SSC,
of and
SSC, while
late while
DEIPADEIPA
strength. It onlyincreases
increases its lateThe
its late strength.
slightly increases strength.
the role
early The role of
of strength
TIPA
TIPA isisweak
weak both
both onon early
early and and
late late strength.
strength. It only It only
slightly slightly
increases
of SSC at high dosages. TEA plays an important role in SSC at low dosages, while DEIPA increases
the early the
strength early strength
of
of SSCSSC at high dosages. TEA plays an important role in SSC at low dosages, while DEIPA
tendsattoward
high dosages.
higher dosages. TEA plays Comparedan important
with OPCrole [9], in
SSC SSC at low
requires dosages,
more dosages while DEIPA
of TEA
tends toward higher dosages. Compared with OPC [9], SSC requires more dosages of TEA
tends
andtoward
DEIPA so higher
that itdosages.
can obtain Compared with
better mechanical OPC [9],
properties
and DEIPA so that it can obtain better mechanical properties than OPC, indicating that in
SSC requires
than more
OPC, indicating dosages
that inofa TEA
and system
DEIPA
a system
with
with
high
so high slag
that slag
it can content,
obtain
content,
the
thebetter
potential
potential
of alkanolamines
mechanical
of alkanolamines properties for
than
for promoting
promoting
OPC, hydration that
indicating
hydration
is in
considerable.
a system
is with high
considerable. The influence
slag content,
The influence ofofTIPA
TIPA onon
the SSC
potential
SSC is inferior
is inferior of to to that
alkanolamines
that on OPC.on OPC. for promoting hydration
According
According to to the
the results
results of this study, the corresponding
is considerable. The influence of TIPA on SSC is inferior to that onisOPC.
of this study, the corresponding mechanism
mechanism isdiscussed
discussed (taking
TEA asTEA
(taking an example
as an as shown
example as in Figure
shown in 10). The
Figure 10). type
The of slag
type of affects
slag affectsthe the
growthgrowth mechanism
According to the results of this study, the corresponding mechanism is discussed
of hydration
mechanism of products
hydrationand the mechanisms
products are divided
and the mechanisms areinto transport
divided controlled
into transport dissolution
con-
(taking TEA
and surface
as anand
controlled
example as shown
dissolution [36,64].
inSlag
Figure
with
10). The
Al2 OSlag
typebelowof slag affects the growth
trolled dissolution surface controlled dissolution [36,64]. 3 content
with Al 10 wt.%
2O3 content be-is defined
mechanism
low of hydration
10 wt.% is defined
as low-reactivity products
slagas(LR-slag).
low-reactivity and the mechanisms
slag (LR-slag).
Otherwise, Otherwise,
it is defined are divided into
it is defined as slag
as high-reactivity high-(HR-slag).con-
transport
trolled dissolution
reactivity
The Al and surface
slag (HR-slag). The Al2O3controlled
content of slag dissolution
used in this [36,64].
study isSlag
2 O3 content of slag used in this study is HR-slag, which contains 17.7 wt.% Al2 O3 .
withwhich
HR-slag, Al2O3 content be-
lowcontains
10 wt.%17.7 wt.%
is Al
defined 2O3. The
as surface of
low-reactivity slag has a
slag fast dissolution
(LR-slag).
The surface of slag has a fast dissolution reaction, so transport controlled dissolution reaction,
Otherwise, so transport
it is definedisas thehigh-
controlled dissolution is the main dissolution mechanism on slag surface. The dissolution
reactivity slag (HR-slag).
main dissolution mechanism TheonAlslag2O3surface.
contentThe of dissolution
slag used of in slag
thisisstudy
limited isbyHR-slag, which
the rate of
of slag is limited by the rate of diffusion of dissolved products and the formation of the
diffusion
contains 17.7of dissolved
wt.% Al2O products and the formation
3. The surface of slag has of the concentration
a fast dissolution gradient.
reaction, so transport
concentration gradient.
controlled dissolution is the main dissolution mechanism on slag surface. The dissolution
of slag is limited by the rate of diffusion of dissolved products and the formation of the
concentration gradient.
Figure 10. Hydration scheme for the hardening of SSC adding TEA.
Sustainability 2024, 16,16,
Sustainability x FOR PEER REVIEW 16 of 2120
2024, 16, 3008
Sustainability 2024, x FOR PEER REVIEW 1616of
of 21
Hydration
Hydration heat
heat analysis
analysis and and phase
phase analysis
analysis show show
that thatinclusion
the the inclusion
ofof
TEA ofdoes
TEApro-
does
Hydration heat analysis and phase analysis show that the inclusion TEA does pro-
promote
mote the the aluminate
aluminate reaction
reaction of SSCofand
SSCthe
andformation
the formation
of of ettringite,
ettringite, which which
is is related
related to theto
mote the aluminate reaction of SSC and the formation of ettringite, 3+ ions inwhich is related to the
the chelation
chelation of TEA with metal ions. TEA chelates with Al the cement hydration
chelationofofTEA
TEAwith
withmetal
metalions.
ions.TEA
TEAchelates
chelateswith AlAl3+ions
ionsininthe
thecement
cementhydration
3+
with hydration
process,
process, asasdemonstrated
demonstratedininEquation
Equation(3)(3)[11,65,66]:
[11,65,66]:
process, as demonstrated in Equation (3) [11,65,66]:
(3)(3)
(3)
TEATEA forms
forms TEA-Al
TEA-Al chelate
chelate compound
compound byby chelating
chelating withwith AlAl3+ ions, which accelerates
3+ ions, which accelerates
TEA forms TEA-Al chelate compound by chelating with Al 3+ ions, which accelerates
the
thedissolution
dissolution of Al
of
3+
Al ions. The chelate transports Al 3+ ions dissolved onon slag surface out-
the dissolution of Al
3+
3+ions.
ions. The The chelate
chelate transports
transports Al Alions
3+
3+ ionsdissolved
dissolved slag
on surface
slag out-
surface
side
side thetheslag
slagparticles,
particles, thereby
thereby improving
improving thethe diffusion
diffusion efficiency
efficiency of Al
of
3+
Al ions.
3+ ions.This
This
3+
process
process
hasoutside
two the slag
effects onon particles,
the hydration thereby ofof improving
SSC: (i)(i)
it it the diffusion
reduces the efficiency gradient
concentration of Al ions. onon This
slag
has
processtwo effects
has two the
effects hydration
on the hydration SSC: of SSC: reduces
(i) it the
reduces concentration
the concentration gradientgradient slag
on
surface,
surface, resulting
resulting ininthe the formation
formation ofofcolumnar
columnar ettringite
ettringite thatthatextends
extends outward
outward into
into thethe
slag
pore surface,
space; resulting
(ii)(ii)
the increase in the formation
inin diffusion of columnar
efficiency ettringite
also accelerates that extends
the outward
dissolution into
ofofslag the
pore
pore space;
space; the
(ii)inthe increase
increase diffusion
in diffusion efficiency
efficiency also
also accelerates
accelerates the
the dissolution
dissolution slag
of slag
itself,
itself,resulting
resulting inthe the improvement
improvement of the
of thehydration
hydration degree
degree of slag.
of slag. The
The greater
greater amount
amount
itself, resulting in the improvement of the hydration degree of slag. The greater amount
ofofnewly
newly formed
formed columnar ettringite in Figure 8e than in Figure 8a is isevidence that TEA
of newly formed columnarcolumnar ettringite ettringite3+in in Figure
Figure 8e 8e than
than in in Figure
Figure 8a evidence
8a is evidence that
that TEATEA
promotes
promotes the the outward
the outward diffusion
outward diffusion diffusion of of Al
of AlAl3+ions to reduce the ion concentration
3+ ions to reduce the ion concentration gradient gradient onon
promotes ions to reduce the ion concentration gradient on
slag
slag surface. The
surface. The columnar ettringite formed in the pore space is covered by C-S-H gel at
slag surface. The columnar
columnar ettringiteettringite formedformed in in the
the pore
pore spacespace is is covered
covered by by C-S-H
C-S-H gel gel atat
later
later stages,
stages, which
which plays
plays anan essential
essential role
role inin the thestrength
strength development
development ofof SSC.
SSC.
later stages, which plays an essential role in the strength development of SSC.
Figure
Figure 1111 shows the hydration scheme of alkanolamine added totoSSC. According toto
11 shows
shows the thehydration
hydrationscheme schemeofofalkanolamine
alkanolamineadded added SSC.
to SSC. According
According
the
the experimental
experimental analysis
analysis of [15],
of [15], TEA accelerates
TEATEA accelerates the initial
the initial dissolution
dissolution of gypsum
of gypsum andand
to the experimental analysis of [15], accelerates the initial dissolution of gypsum
aluminate
aluminate phase
phase andand promotes
promotes the theinitial
initial precipitation
precipitation ofofettringite.
ettringite. InIn other
other words,
words, TEATEA
and aluminate phase and promotes the initial precipitation of ettringite. In other words,
accelerates
accelerates thetheformation
formation ofofhydration
hydration products
products ononthe the surface ofofslag during initial hy-
TEA accelerates the formation of hydration products onsurface
the surfaceslag during
of slag during initial hy-
initial
dration.
dration. If If
thethe hydration
hydration product
product formed
formed atat thisthistime
time is istootoo dense,
dense, it it
will
will block
block the thepathpath ofof
hydration. If the hydration product formed at this time is too dense, it will block the path
further
further dissolution
of further dissolution
dissolution and andmigration
migration
and migration ofofions,
ions, affecting
of ions, affecting the
affecting thehydration
hydration
the ofofSSC.
hydration of Therefore,
SSC. Therefore,
SSC. ap-
Therefore, ap-
propriate
propriate
appropriate dosage
dosage is
dosage critical.
is critical. More
is critical. is
MoreMore not always
is notisalways better.
not always According
better.better.
According to the analysis
to the analysis
According of Figures
of Figures
to the analysis of
3 and
3Figures
and 4, 4,
when andthe
3when the
4, dosage
whendosage theofofTEA TEA
dosage reaches
reaches
of TEA 0.04–0.06%,
0.04–0.06%,
reaches the the
0.04–0.06%, mechanical
mechanical properties
properties
the mechanical andand hy-
properties hy-
dration
dration degree
and hydration
degree ofof SSC
degree
SSC reachof SSC
reach the themaximum
reach
maximum value.
the maximum value. The The morphology
value. ofof
The morphology
morphology Figure
Figure 8h8h
ofalso finds
Figure
also 8h
finds
unfilled
also finds
unfilled pore
pore space
unfilled at
spacepore high
at high content.
space The
at high
content. The first
content. peak
first peak of initial
Theoffirstinitial hydration
peak is lower
of initialishydration
hydration for
lower for thethe sam-
is lower
sam-
ple
plewith
for the
with the
sample
theadditionwithof
addition the DEIPA
of addition
DEIPA than
thanofthat
DEIPA
thatwithwith TEA
thanTEA [24].
that[24]. InIn
with this
TEA study,
this [24].the
study, In
the heat
this
heatofofhydration
study, the heat
hydration
ofofDEIPA
hydration
DEIPA atat3 days
3 ofdays is is
DEIPA alsoalso lower
at 3 days
lower than isthat
than also
that oflower
ofTEA.TEA. This
than This indicates
that of TEA.
indicates that
that the
Thisthepromoting
indicates
promoting effect
that the
effect
ofpromoting
DEIPA
of DEIPA on on initial
effect
initial hydration
of DEIPA
hydration of SSC
on initial is not
of SSChydration as strong
is not as strong of SSCas as that
is that of
not as TEA,
ofstrong
TEA, soso DEIPA
as DEIPA can
that of TEA,canstill so
still
improve
DEIPA the
can mechanical
still improve properties
the of
mechanical
improve the mechanical properties of SSC at high dosages. SSC at high
properties dosages.
of SSC at high dosages.
(a)(a) (b)(b) (c)(c)

Figure 11. Hydration scheme of SSC adding alkanolamines (light gray represents the hydration
Figure 11. Hydration
Hydrationscheme
schemeofof SSC
SSC adding
adding alkanolamines (light gray represents the hydration
Figure 11.
products extending outward, while dark grayalkanolamines
represents the(light gray
dense represents
hydration the hydration
products layer): prod-
(a)
products extending outward, while dark gray represents the dense hydration products layer): (a)
ucts extending
without outward,
alkanolamines while dark
(formation gray represents
of small amounts ofthe dense hydration
hydration products
products); layer): (a)dosage
(b) appropriate without
without alkanolamines (formation of small amounts of hydration products); (b) appropriate dosage
alkanolamines
(formation (formation
of a large amount ofof small amounts
hydration of hydration
products); products);
(c) excessive (b)(dense
dosage appropriate dosage
hydration (forma-
products
(formation of a large amount of hydration products); (c) excessive dosage (dense hydration products
layer
tioninhibiting
of a large further
amount hydration).
of hydration products); (c) excessive dosage (dense hydration products layer
layer inhibiting further hydration).
inhibiting further hydration).
Why TEA and DEIPA can still increase the 28-day strength of SSC is related to the
lack of adsorption effect of AFm on alkanolamine. In Portland cement, TEA is removed by
AFm after the sulfate exhaustion point due to low steric hindrance [15,19] and DEIPA also
has a similar effect [24]. However, at 28 days, although gypsum content greatly decreases
for all mixtures, the obvious gypsum peak still exists. When the content of gypsum is
sufficient, it is difficult to convert AFt to AFm so that AFm peaks in XRD or TGA cannot be
seen. Therefore, due to the lack of the adsorption effect of AFm on TEA and DEIPA, they
continue to increase the late strength of SSC.
The influence of TIPA on the mechanical properties of SSC is weak because compared
with its strong effect on the dissolution of Fe3+ , TIPA is not so good at accelerating the
dissolution of Al3+ and Si4+ ions [19,20]. And the Fe2 O3 content of slag used in SSC is
insufficient. This is disadvantageous to SSC, a system with ettringite responsible for the
early strength development. The hydration heat analysis in Figure 5 also proves this point.
In addition, due to the influence of air-entraining effect [9,21,67], TIPA cannot enhance the
early and late strength of SSC.
Three alkanolamines (TEA, DEIPA, and TIPA) have similar chemical formulas. Their
chelation with metal ions is mainly attributed to the coordination bond formed by -OH and
metal ions, and the coordination bond between N and metal ions is relatively weak [11,16,23].
The three alkanolamines in the order of left to right, the number of -CH3 groups in-
creases in order, and the relative molecular mass increases in order. The role of alka-
nolamines on improving the maximum heat generation rate of the main hydration peak:
TEA > DEIPA > TIPA (Figure 5). Therefore, -CH3 interferes with the coordination between
-OH and metal ions, affecting the chelation of alkanolamine with metal ions.
In short, alkanolamines such as TEA and DEIPA can effectively increase the strength of
low-carbon SSC by nearly 50% through the chelating effect, indicating the potential appli-
cation of SSC as a material with low environmental pollution in construction engineering.
5. Conclusions
In this work, the effects of three alkanolamines on cement hydration and strength de-
velopment in SSC system were investigated using the combined techniques of calorimetry,
XRD, TGA and SEM. The hydration mechanism of alkanolamines on SSC was demonstrated.
The following conclusions can be drawn.
TEA and DEIPA significantly increase the compressive strength of SSC. The two have
different preferences, with TEA tending towards earlier stages and DEIPA tending towards
later stages. TEA is better at low dosages, while DEIPA is more suitable at high dosages.
The influence of TIPA on the early strength of SSC is weak and TIPA is harmful to the late
strength of SSC. Compared with OPC, SSC needs to add more dosages of alkanolamine to
achieve better strength development. This is a potential and effective way to improve the
strength of SSC.
TEA and DEIPA accelerate the dissolution of slag at early stage, promote its alumi-
nate reaction, and consume a large amount of gypsum, which leads to the formation of
more hydration products such as ettringite, resulting in early strength improvement. The
acceleration of slag dissolution is attributed to the chelation of alkanolamine with Al3+ ions.
-CH3 in alkanolamine interferes with the coordination between -OH and metal ions. So
alkanolamine with more -CH3 has a weaker chelating effect with Al3+ ions, thus inhibiting
early hydration and strength development.
Above all, alkanolamine plays a more important role in SSC than OPC. And alka-
nolamines also differ from each other greatly due to different groups. This study did not
provide an in-depth experimental exploration of the ion chelating effect of alkanolamine
on SSC. The role of different groups in different molecules in hydration needs to be further
explained. This may require relevant experiments such as 1 H-NMR and FTIR. In addition,
SSC is a system very sensitive to alkalinity, and its mechanical properties are also related
to the complexity of the chemical composition of the slag influencing its solubility. There-
fore, more in-depth discussions of the effect of alkanolamine on SSC with different clinker
content and slag types are needed in the future.
Supplementary Materials: The following supporting information can be downloaded at: https://
www.mdpi.com/article/10.3390/su16073008/s1, Table S1: Compressive strength; Table S2: Detailed
compressive strength data of SSC adding TEA at 3 d; Table S3: Detailed compressive strength data
of SSC adding TEA at 28 d; Table S4: Detailed compressive strength data of SSC adding DEIPA at
3 d; Table S5: Detailed compressive strength data of SSC adding DEIPA at 28 d; Table S6: Detailed
compressive strength data of SSC adding TIPA at 3 d; Table S7: Detailed compressive strength data
of SSC adding TIPA at 28 d; Table S8: Hydration degree; Table S9: Hydration heat; Table S10: XRD;
Table S11: TGA (Differential); Table S12: TGA (integral); Figure S1: High-resolution pictures of
Figure 5a; Figure S2: High-resolution pictures of Figure 5b; Figure S3: High-resolution pictures of
Figure 7c; Figure S8: High-resolution pictures of Figure 7d; Figure S9: High-resolution pictures of
Figure 7e; Figure S10: High-resolution pictures of Figure 7f.
Author Contributions: Conceptualization, R.Z. and H.C. and B.J.; methodology, R.Z. and H.C. and
S.W.; software, R.Z.; validation, R.Z. and H.C.; formal analysis, R.Z.; investigation, R.Z.; resources,
R.Z.; data curation, R.Z.; writing—original draft preparation, R.Z.; writing—review and editing,
R.Z. and H.C. and S.F.; visualization, R.Z. and H.C.; supervision, H.C. and S.F. and F.H.; project
administration, H.C.; funding acquisition, H.C. All authors have read and agreed to the published
version of the manuscript.
Funding: This research was funded by Sichuan Province Science and Technology Plan Project, grant
number 2023YFSY0019.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are not available due to privacy.
Conflicts of Interest: Authors Shu-Jing Fan and Fa-Fu Hang were employed by Linhai Zhongxin
New Building Materials Co., Ltd. The remaining authors declare that the research was conducted
in the absence of any commercial or financial relationships that could be construed as a potential
conflict of interest.
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sustainability

Sustainability 2024, 16, 3008. https://doi.org/10.3390/su16073008 https://www.mdpi.com/journal/sustainability

C5 S3 A + CH + 3CS + 34H → C6 AS3 H32 + 3CSH (1)

TEA DEIPA TIPA

Table 1. Chemical compositions of raw materials (wt.%).

SiO2 Al2 O3 Fe2 O3 CaO MgO SO3 Loss

2.2. Mix Proportion

Table 2. Mixture design of SSC cement (wt.%).

ID SSC TEA DEIPA TIPA

2.3.2. Isothermal Calorimetry

2.3.3. XRD and QXRD

Table 3. Structure models used for Rietveld refinement.

Phase Formula Crystal System ICSD Cods Reference

2.3.5. Degree of Hydration

w2 + ( f SLAG (1 − RGGBS )w1 ) − ( f CEMENT Cr w1 )

Sustainability 2024, 16, 3008 6 of 20

Table 4. The eﬀects of alkanolamines on the characteristic parameters of cement hydration.

3d Blank TEA0.04 TEA0.08 DEIPA0.04 DEIPA0.08 TIPA0.04 TIPA0.08

Sustainability 2024, 16, x FOR PEER REVIEW 15 of 21

(a)(a) (b)(b) (c)(c)

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