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Article
Properties of Cement Mortar Using Limestone Sludge
Powder Modified with Recycled Acetic Acid
Hwa-Sung Ryu 1 , Deuck-Mo Kim 1 , Sang-Heon Shin 1 , Wan-Ki Kim 2 , Seung-Min Lim 3 and
Won-Jun Park 4, *
1 Hanyang Experiment and Consulting Co., Hanyang University, Ansan 15588, South Korea;
rhsung73@hanyang.ac.kr (H.-S.R.); golanhae@naver.com (D.-M.K.); monanom80@gmail.com (S.-H.S.)
2 Department of Architectural Engineering, Hyupsung University, Hwaseong, 445-745, South Korea;
wankkim@uhs.ac.kr
3 Innovative Durable Building and Infrastructure Research Center, Hanyang University, Ansan 15588,
South Korea; smlim09@hanyang.ac.kr
4 Department of Architectural Engineering, Kangwon National University, Samcheok 25913, South Korea
* Correspondence: wjpark@kangwon.ac.kr; Tel.: +82-33-570-9529
Received: 19 November 2018; Accepted: 4 February 2019; Published: 8 February 2019
Abstract: One of the various methods of manufacturing low-carbon cement is substituting limestone
powder as a raw material or admixture. Limestone sludge powder (LSSP) has the same composition
as that of limestone powder. The surface characteristics of LSSP powder modified with recycled
acetic acid (RAA) and the characteristics of cement using this modified LSSP as a substitute were
investigated in this study. The surface of LSSP modified with RAA was converted into calcium acetate
and had a large grain size. When conventional LSSP was used as a substitute for cement, the initial
strength increased owing to improved pore filling; however, the strength after 28 days of aging was
lower than that of non-substituted cement. In the case of modified LSSP being replaced with cement
at up to 10% of the cement weight, however, the calcium acetate on its surface increased the amount
of hydration products in the cement, thereby increasing both the initial and the long-term strength.
Keywords: cement mortar; limestone sludge; recycled acetic acid; surface modification
1. Introduction
One of the major issues in the construction industry in recent years has been the demand for
cement materials that can reduce carbon emissions. The reality is that 1 t of CO2 is generated to
produce 1 t of cement, and most studies have focused on reducing cement usage or using cement
substitutes [1,2]. One of the most widely used materials in the cement production process is limestone
powder. In Europe, limestone powder may be used at up to 35% according to the EN 197-1 standard,
whereas in Canada and the United States, up to 5% Portland cement and 15% Portland limestone
cement may be used [3–5]. Limestone powder contains a large amount of calcium carbonate. Calcium
carbonate and silica or nanocarbon are used as fillers in organic and inorganic complexes. These
fillers serve to improve the viscosity or physical performance of polydimethylsiloxane (PDMS) [6–10],
which is used for penetrating water repellency and surface penetration coating. The functional groups
on the surfaces of these fillers may be changed to improve their reactivity with the polymer or to
optimize the dispersion ability. Compared with silica or nanocarbon, calcium carbonate is a less
expensive functional filler [8–15].
In the steel industry, burnt lime is produced by washing and burning limestone. The sludge
composed of powders washed from limestone is known as limestone sludge powder (LSSP). LSSP has
the same composition as limestone powder and can be used as a substitute for cement and, therefore,
as an admixture material of cement mortars. Limestone powder is a raw material of cement, and
the LSSP used in this study is an admixture for mixing with cement to reduce cement use. LSSP has
the same composition as that of limestone powder and can be replaced with cement as an admixture
material. The shape and particle size of limestone powder are relatively good compared to those of
cement particles. Replacing a portion of cement with limestone powder improves the fluidity of the
mortar [16,17]. It has been reported that it also contributes to quality enhancements such as improved
resistance to material separation and enhanced strength, owing to the pore-filling effect. Studies have
suggested that limestone powder accelerates the hydration of alite in cement. However, calcium
carbonate, which is a major component of limestone powder, is mostly non-hydrated and, thus, it is
possible that the initial strength can be lowered when a substantial amount of LSSP is used [16–21].
Similarly, using fly ash and blast furnace slag, which are mixed materials used to improve the
performance of cement, may delay the hydration of cement and lower its initial strength. To induce
initial hydration early, researchers have used strengthening agents such as compounds containing
carboxyl groups, lithium compounds, and calcium nitrate [22–29]. Waste acetic acid, a byproduct
of liquid crystal display (LCD) surface etching processes, has a low concentration and is restricted
to reuse in industry. The calcium acetate produced by the reaction of calcium salts with acetic acid
can promote the hydration of cement owing to the carboxyl groups of this acid. Calcium acetate
also improves the initial strength and reduces internal voids. Hence, modification of the surfaces of
limestone powders using acetic acid can improve the early strength properties of these powders when
they are used as admixtures for cement.
Therefore, in this study, an admixture material was developed by modifying LSSP using acetic
acid to form reactive limestone powders to enhance the performance of cement mortar. The properties
of the samples were investigated in terms of mortar setting time and compressive strength. They
were also analyzed using X-ray diffraction (XRD), thermogravimetric/differential thermal analysis
(TG-DTA), and scanning electron microscopy (SEM).
2.1. Materials
Table 1 shows the chemical properties of the binders used in the experiments. The cement used
was an ordinary type 1 Portland cement (OPC). Chemical analysis of LSSP showed that the CaO and
MgO contents were 51.5% and 1.60%, respectively. This corresponds to about 90% of CaCO3 , which
corresponds to high-grade limestone, and is similar in chemical properties to reagent-grade CaCO3 .
Recycled acetic acid (RAA) was obtained after being extracted from the separation process of acids
used in etching processes. For this study, RAA with 60% solid content was used. Figure 1 shows the
Fourier transform infrared (FT-IR) spectroscopy results for the RAA. Organic acids are denoted by the
peaks in the range of 3300–2500 cm−1 , where carboxylic groups are traditionally located. C=O groups
(1760–1690 cm−1 ) and C–O groups (1320–1210 cm−1 ) are also present in this spectrum. Some examples
of carboxylic acids are acetic acid, formic acid, glucosan, and propionic acid. The functional group of
the RAA used for this study was confirmed to be carboxylic acid.
Table 1. Chemical composition of the ordinary type 1 Portland cement (OPC), CaCO3 , and limestone
sludge powder (LSSP) (%).
Figure 1. Fourier transform infrared (FT-IR) spectrum of recycled acetic acid (RAA).
Figure
Figure 1.
1. Fourier
Fourier transform
transform infrared
infrared (FT-IR)
(FT-IR) spectrum
spectrum of
of recycled
recycled acetic
acetic acid
acid (RAA).
(RAA).
2.2. Methods
2.2.
2.2. Methods
Methods
Figure 2 shows the surface modification process of the LSS. A 10% aqueous solution was made
usingFigure
Figure 22 shows
RAA with 60%the
shows the surface
solid
surface modification
content; then, 1 kg of
modification process of
of the
the aqueous
process LSS.
LSS. A
thesolutionA 10%
wasaqueous
10% solution
mixed with
aqueous was
100 g of
solution wasLSSmade
and
made
using
the
using RAA
mixture with 60%
was kneaded
RAA with solid content;
60% solidfor then,
about 10
content; 1
min.
then, kg of the aqueous
Theofmodified
1 kg the aqueous solution
calcium was
carbonate
solution mixed with 100
was collected
was mixed g of
with 100throughLSS
g of LSS a
and
and the
filter. Themixture
the reactionwas
mixture withkneaded
was for
acetic acid
kneaded foronabout 10
10 min.
the surface
about min.of The
the
TheLSSmodified calcium
calcium carbonate
is as follows:
modified carbonate was
was collected
collected
through
through aa filter.
filter. The
The reaction
reaction with
with acetic
acetic acid
acid on
on the
the surface
surface of
of the
the LSS
LSS is
is as
as follows:
follows:
2CH3 COOH + CaCO3 = Ca (CH3 COO)2 + H2 O + CO2 (1)
2CH
2CH33COOH
COOH ++ CaCO
CaCO33 == Ca
Ca (CH
(CH33COO)
COO)22 ++ H
H22O
O ++ CO
CO22 (1)
(1)
Limestone
Limestone Sludge
Sludge Acetic
Acetic Acid
Acid
Reactor
Reactor
Filtration/Washing
Filtration/Washing
Modified
Modified Calcium
Calcium
Carbonate
Carbonate
Figure
Figure 2.
Figure 2. Flow
2. Flow diagram
Flow diagram for
diagram for the
for the modified
the modified calcium
modified calcium carbonate.
carbonate.
Table 222shows
Table showsthe
shows themixing
the mixingproportions
mixing proportions
proportions ofof
samples,
of samples,
samples, where
where
where OPCOPC
OPCwaswas substituted
was by conventional
substituted
substituted by
by conventional
conventional and
modified
and LSSP.
modified The
LSSP. specimens
The for
specimensevaluating
for the
evaluating characteristics
the of the
characteristics cement
and modified LSSP. The specimens for evaluating the characteristics of the cement mortar were of the mortar
cement were
mortarprepared
were
by mixingby themixing
mortartheand placing it into a beam-shaped mold with mold dimensions of 40 × 40 × 3
prepared
prepared by mixing the mortar
mortar and
and placing
placing it
it into
into aa beam-shaped
beam-shaped mold with
with dimensions
dimensions of160
of 40 ××mm
40 40 ××.
40
The
160 prepared
160 mm
mm
3. The specimens
3. The prepared were curedwere
prepared specimens
specimens for 18
were h at for
cured
cured room 18temperature
for 18 hh at
at room and demolded
room temperature
temperature andfor
and underwater
demolded
demolded for
for
curing.
underwater The compressive strength was then measured after different curing
underwater curing. The compressive strength was then measured after different curing times: 18 h,
curing. The compressive strength was then measured after times:
different 18 h,
curing1 day,
times: 3 days,
18 h,
171 days,
day, 3and 28
days, days,
7 according
days, and 28 to ISO
days, 679 [30].
according The
to mortar
ISO 679 fluidity
[30]. Thewas measured
mortar
day, 3 days, 7 days, and 28 days, according to ISO 679 [30]. The mortar fluidity was measured according
fluidity was to ASTM
measured
C 1437. The
according
according tomortar
to ASTMsetting
ASTM C 1437.time
C 1437. Thewas
The measured
mortar
mortar settingaccording
setting time
time was to the initial
was measured
measured and finalto
according
according setting
to the time and
the initial
initial specified
and final
final
in ASTM
setting timeC 191, and
specified the
in mortar
ASTM compressive
C 191, and thestrength
mortar was measured
compressive according
strength
setting time specified in ASTM C 191, and the mortar compressive strength was measured according was to ASTM
measured C 109.
according
toto ASTM
ASTM C C 109.
109.
The
The age of
age of the
the sample
sample for
for analysis
analysis isis 28
28 days,
days, and
and immersed
immersed in in acetone
acetone for
for 24
24 hours
hours to to stop
stop
hydration
hydration of of individual
individual samples.
samples. The
The water
water waswas then
then removed
removed in in aa 60
60 °C
°C dryer.
dryer. Sample
Sample preparation
preparation
Sustainability 2018, 10, x FOR PEER REVIEW 4 of 10
Sustainability 2019, 11, 879 4 of 10
for each analysis is as follows. SEM samples were made of flake samples with a width of 0.5 cm × 0.5
cm and a thickness of 5 mm or less. TGA and XRD analysis specimens were prepared with paste,
without aggregates, to suppress noise of Mixing
Table 2. sample. proportions (unit: g).
After grinding to below 100 microns at 28 days of
age, it was immersedOPC in an acetone solution
(Ordinary LSSP and dried usingModified
(Limestone a vacuum distillation apparatus.
Sample Silica sand Water
Portland Cement) Sludge Powder) LSSP
OPC 1000 - proportions (unit:
Table 2. Mixing - g).
OPC-L5 950 50
OPC-L10 900
OPC LSSP 100
OPC-L15 850 150
OPC-L20 (Ordinary
800(Limestone200 Modified
Sample
OPC-ML5 950
Silica2000
sand 340
Water
Portland Sludge LSSP 50
OPC-ML10 900 100
OPC-ML15 Cement)
850 Powder) 150
OPC 20
OPC-ML 1000
800 - - 200
OPC-L5 950 50
OPC-L10 900 100
The age of the sample for analysis is 28 days, and immersed in acetone for 24 hours to stop
OPC-L15 850 150
hydration of individual samples. The water was then removed in a 60 ◦ C dryer. Sample preparation for
OPC-L20 800 200 2000 340
eachOPC-ML5
analysis is as follows.
950SEM samples were made of flake 50 samples with a width of 0.5 cm × 0.5 cm
andOPC-ML10
a thickness of 5 mm900 or less. TGA and XRD analysis specimens
100 were prepared with paste, without
aggregates,
OPC-ML15 to suppress noise
850 of sample. After grinding to below
150 100 microns at 28 days of age, it was
immersed
OPC-MLin20an acetone 800
solution and dried using a vacuum 200distillation apparatus.
3. Results and
3. Results and Discussion
Discussion
(a) (b)
Figure 3.
Figure 3. Scanning
Scanningelectron
electronmicroscopy
microscopy(SEM) images
(SEM) of of
images limestone sludge
limestone powder
sludge (LSSP):
powder (a)
(LSSP):
conventional LSSP and (b) modified LSSP.
(a) conventional LSSP and (b) modified LSSP.
Sustainability 2019, 11, 879 5 of 10
Sustainability 2018, 10, x FOR PEER REVIEW 5 of 10
TGA (%)
DTA (um)
TGA (%)
DTA (um)
TGA (%)
DTA (um)
TGA (%)
DTA (um)
(a) (b)
Figure
Figure4.4.Results
Resultsof
ofthe
the thermogravimetric/differential
thermogravimetric/differentialthermal
thermalanalysis
analysis(TG-DTA):
(TG-DTA):(a)
(a)conventional
conventional
Temperature (℃) Temperature (℃)
LSSP
LSSPand
and(b)(b)modified
modifiedLSSP.
LSSP.
(a) (b)
3.2.Mortar
3.2. MortarApplication
Application
Figure Characteristics
4. Results of the thermogravimetric/differential thermal analysis (TG-DTA): (a) conventional
Characteristics
LSSP and (b) modified LSSP.
3.2.1.Setting
3.2.1. SettingTime
Time
3.2. Mortar Application Characteristics
Figure 55 shows
Figure shows the themeasured
measuredsetting settingtime
time of of
mortar
mortar mixed
mixed with conventional
with conventional and andmodified LSSP.
modified
The use 3.2.1.
ofuse Setting Time
conventional LSSP showed no noticeable difference in bothinthe initial
LSSP. The of conventional LSSP showed no noticeable difference both the and
initialtheand
final
thesetting
final
time. In the case
Figure of the
5 shows modified
the measuredLSSP, however,
setting time the initial
of mortar setting
mixed with
setting time. In the case of the modified LSSP, however, the initial setting time decreased as the time decreased
conventional as
and the substitution
modified
LSSP. The use
ratio increased. offinal
conventional LSSP decreased
showed no noticeable
up to difference in both the initial and the final above
substitution ratioTheincreased. setting time
The final setting time bydecreased 10%,by butupincreased
to 10%, but
setting time. In the case of the modified LSSP, however, the initial setting time decreased as the
for LSSP content
increased for LSSP
15%. It is possible
content substitution
above 15%.ratio that the initial
It isincreased.
possibleThe setting
thatfinal time
thesetting decreased
initialtime
setting owing
time decreased to hydration
owing reactions
to hydration induced
reactionsby
decreased by up to 10%, but increased for LSSP
calcium acetate
inducedcontent
by calcium on the surface
acetate
above 15%. It is on
of the modified
the surface
possible that the of
LSSP; however,
thesetting
initial modifiedtime LSSP;
the
decreased
presence
however, of
owing tothe
excessive
presence
hydration
organic calcium
of excessive
reactions
for higher
inducedcontents
by of
calcium LSSP caused
acetate on the
the increase
surface of in
the values
modified of the
LSSP;
organic calcium for higher contents of LSSP caused the increase in values of the final setting final
however,setting
the time.
presence Acetic
of acid,
excessive used for
time.
LSS modification,
organic has
calcium been
for reported
higher contents toofincrease
LSSP the
caused conductivity
the increase in in the
values
Acetic acid, used for LSS modification, has been reported to increase the conductivity in the initial initial
of the cement
final settingpaste,
time. thereby
Acetic acid, used for LSS modification, Ca2+ has beenAlreported − . increase
increasing
cement paste, the ionic
thereby concentration
increasing theof ionic and
concentration(OH)of 4 to
Ca However,
2+ and Al the an
conductivity
(OH) excessive in amount
the initialof acetic
4−. However, an excessive
acid maycement paste, thereby increasing the ionic concentration of Ca 2+ and Al (OH)4−. However, an excessive
amount of cause
amount acetic hydration
acid may
of acetic acid may
delay hydration
cause with increasing adsorption
cause hydrationdelay delay with increasing
with increasing
amount on the surface
adsorption
adsorption amount amount of cement
on theon
paste
the surface
surface
particles
of cement [31].
paste particles [31].[31].
of cement paste particles
500 500
500 500
400 400
400 400
Time (min)
(min)
300 300
Time (min)
(min)
TimeTime
300 300
200 200
Initial setting Initial setting
200 100 100
200
Initial setting
Final setting Initial
Final setting
setting
100 0 100
0
Final OPC
setting OPC-L5
OPC-L10 OPC-L15 OPC-L20 OPC Final settingOPC-ML10 OPC-ML15 OPC-ML20
OPC-ML5
0 (a) 0 (b)
OPC OPC-L5 OPC-L10 OPC-L15 OPC-L20 OPC OPC-ML5 OPC-ML10 OPC-ML15 OPC-ML20
Figure Figure 5. Setting
5. Setting time time of cement mortar: a) Mortar using conventional LSSP;LSSP;
(a) of cement mortar: (a) Mortar using conventional (b)
(b) Mortar using using
(b) Mortar
modified LSSP.
modified LSSP.
Figure 5. Setting time of cement mortar: a) Mortar using conventional LSSP; (b) Mortar using
3.2.2. Compressive Strength
3.2.2.modified
Compressive
LSSP. Strength
Figure 6a shows the compressive strength of the cement mortar according to the substitution
Figure
ratio of6aconventional
shows theLSSP compressive strength of the cement mortar according to the substitution
3.2.2. Compressive Strength for different curing times. Overall, the compressive strength of the mortar
ratio ofwas
conventional LSSP for different
not significantly different curing
from that times.
of OPC, evenOverall,
when thethe compressive
replacement ratio strength of the mortar
of conventional
was Figure
notLSSP 6a showsatthe
significantly
increased compressive
different
all curing from strength
that
ages. Figure of
6bOPC, of even
shows the cement
when
the graph mortar
the
of the according
replacement
compressive to the
ratio
strength substitution
of conventional
according
ratio to the substitution
LSSPofincreased
conventional ratiofor
at allLSSP
curing ofages.
the modified
different
Figure LSSP.
curing Substitution
times.
6b shows withthe
Overall,
the graph thethe
of modified LSSPstrength
compressive
compressive produced lower
of
strength the mortar
according
initial compressive strength than that of OPC for all specimens. After 1 day of aging,
was not significantly different from that of OPC, even when the replacement ratio of conventional
to the substitution ratio of the modified LSSP. Substitution with the modified the
LSSP substitution
produced lower
LSSP
initialincreased
compressive at allstrength
curing ages. Figure
than that 6b shows
of OPC for allthe graph of After
specimens. the compressive
1 day of aging,strength according
the substitution
to the substitution ratio of the modified LSSP. Substitution with the modified LSSP produced lower
initial compressive strength than that of OPC for all specimens. After 1 day of aging, the substitution
Sustainability 2018, 10, x FOR PEER REVIEW 6 of 10
proportions of 5% and 10% modified LSSP showed higher strength than that of OPC. After 28 days
of aging, the 5% substitution resulted in strength superior to that of OPC. We believe that the
introduction of modified LSSP into the space between cement particles improved pore filling and
Sustainability 11, 879
2019,hydration
induced reactions around the unreactive calcium carbonate particles, thereby increasing 6 of 10
the strength. At a replacement rate of up to 15%, the mortar using LSSP and modified LSSP showed
a performance equal to or higher than that of the mortar using OPC.
proportionsItofhas 5%beenand 10% modified LSSP showed higherare strength than thatlimestone
of OPC.powder
After 28 days of
Sustainability 2018, 10, xreported
FOR PEERthat the rheological
REVIEW properties improved when is 10
6 of
aging, the 5% substitution resulted in strength superior to that of OPC. We believe
replaced with cement. In addition, limestone powder is reported to be effective in reducing hydration that the introduction
of modified
heat and
proportions LSSPin into
5% andthe 10%
ofincreasing space between
the modified
initial cement
strength.
LSSP particles
However,
showed improved
it is expected
higher strengththatpore
both
than filling and induced
theoflong-term
that OPC. strength
After hydration
28 days
of and
reactionsaging,the the
chlorine
around 5% ion penetration
thesubstitution
unreactive resistance
resulted
calcium are decreased
incarbonate
strength [32]. When
superior
particles, theof
to thereby
that modified
OPC. LSSPbelieve
We
increasing was
thereplaced
that the At a
strength.
with cement
introduction
replacement rateofofatmodified
up to 10%
up to 15%, of the
LSSP cement
theinto weight,
the space
mortar using the initial
between
LSSP and (up toparticles
cement
modified3 days ofimproved
LSSPaging)
showed strength
pore was low.
filling
a performance and equal
On
induced the other
hydration hand, the compressive
reactions around strength
the of the
unreactive mortar
calcium was as good
carbonate as that of
particles, OPC after
thereby 28 days
increasing
to or higher than that ofsubstitution
the mortarshowed
using OPC. strength than those of OPC and conventional LSSP.
theofstrength.
aging, andAt aa 5%
replacement rate of uphigher
to 15%, the mortar using LSSP and modified LSSP showed
a performance
50 equal to or higher than that of the mortar50 using OPC.
OPC OPC
It has been reported that the rheological properties areOPC-ML5
improved when limestone powder is
Compressive strength (MPa)
OPC-L5
50 0 50
0
OPC OPC
1 day 3 days 7 days 28 days 18 hours
18 hours 1 day 3 days 7 days 28 days
Compressive strength (MPa)
0 10 20 30 40 50 60 0 1 0 2 0 3 0 4 0 5 0 6 0
0 10 20 30 40 50 C-S-H 60
2 Theta (degree)
C-S-H 2 Theta (degree) C-A-S-H
C-A-S-H Ca(OH)2
Ca(OH)2 Ettringite
OPC-L10 (a) Ettringite OPC-ML10 (b) CaCO3
CaCO3
OPC-L5 OPC-ML5
OPC OPC
0 1 0 2 0 3 0 4 0 5 0 6 0
0 10 20 30 40 50 60 0 1 0 2 0 3 0 4 0 5 0 6 0
0 10 20 30 40 50 60
2 Theta (degree)
2 Theta (degree)
(a) (b)
Figure 7. X-ray diffraction (XRD) patterns of samples with different contents: (a) conventional LSSP
and (b) modified LSSP.
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Figure 7. X-ray diffraction (XRD) patterns of samples with different contents: (a) conventional LSSP
and (b) modified LSSP.
Sustainability 2019, 11, 879 7 of 10
3.4. Thermogravimetric/Differential Thermal Analysis
95 95
200 200
DTA(uV) 90 90
TGA(%)
85 85
100 100 DTA(uV)
TGA
(um)
TGA
(um)
DTA(uV)
DTA(uV)
TGA(%)
TGA(%)
TGA(%)
80 80
(%)
(%)
DTA
DTA
0 0
75 75
70 70
-100 -100
65 65
-200 60 -200 60
0 200 400 600 800 1000 0 200 400 600 800 1000
Temperature
TTTTTTTTuTT((℃)
℃) TTTTTTTTuTT(℃
Temperature )
(℃)
(a) (b)
300 100
95
200
90
85
100
DTA(uV)
TGA
(um)
DTA(uV)
TGA(%)
TGA(%) 80
(%)
DTA
0
75
70
-100
65
-200 60
0 200 400 600 800 1000
Temperature
TTTTTTTTuTT((℃)
℃)
(c)
Figure
Figure8.8.TG-DTA
TG-DTAresults
resultsfor
forsamples
samplescured
curedfor
for2828days:
days:(a)(a)
OPC, (b)(b)
OPC, OPC with
OPC 5%5%
with conventional LSSP,
conventional LSSP,
and
and(c)
(c)OPC
OPCwith
with10%
10%conventional
conventionalLSSP.
LSSP.
TGA
DTA (um)
TGA (%)
DTA (um)
TGA(%)
TGA(%) 80
(%)
300 100 300 100
75
95 95
70
200 200
90 90
65
85 85
100 100 60
TGA
DTA(uV)
(um)
DTA(uV)
TGA
(um)
DTA(uV)
DTA(uV)
200 400 600 800
TGA(%)
000
TGA(%)
TGA(%) 80 TGA(%) 80
Temperature
TTTTTTTTuTT((℃)
℃) Temperature (℃)
(%)
(%)
DTA
DTA
0 0
75 75
(a) (b)
70 70
Figure 9. Results of the TG-DTA for samples cured for-100
-100 28 days: (a) OPC with 5% modified LSSP and
65 65
(b) OPC with 10% modified LSSP.
-200 60 -200 60
0 200 400 600 800 1000 0 200 400 600 800 1000
Table(℃)3.
Temperature(℃)
Temperature Quantification of the calcium hydroxide (28 days). (℃)
Temperature
Temperature(℃)
3.5. Scanning Electron Microscopy Analysis of the calcium hydroxide (28 days).
Table 3. Quantification
Sample
Figure OPC (Plain)
10 shows the SEM images of OPC-L5
samples withOPC-L10 OPC-ML5
5% substitution OPC-ML10
of conventional and modified
LSSP,
LSSP,Ca(OH) 2 Weight When reagent-grade calcium carbonate was mixed, it was observed that the
respectively.
respectively.
2.33 1.01 0.985 1.771 1.876
calciumcontent (%) was held between the hydrates. Hydrates, such as ettringite, were formed on the
carbonate
surface, which enabled compact filling through physical filling
filling and induced hydrate formation in the
3.5. Scanning
cement Electron Microscopy Analysis
mortar.
mortar.
Figure 10 shows the SEM images of samples with 5% substitution of conventional and modified
LSSP, respectively. When reagent-grade calcium carbonate was mixed, it was observed that the
calcium carbonate was held between the hydrates. Hydrates, such as ettringite, were formed on the
surface, which enabled compact filling through physical filling and induced hydrate formation in the
cement mortar.
Calcium Hydroxide
Calcium Hydroxide Calcium Hydroxide
Tobermorite
Calcium Carbonate
Ettringite
C-S-H
C-S-H
(a) (b)
C-S-H
Calcium Carbonate
10. SEM images
Figure 10. images of
of samples:
samples: (a)
(a)C-S-H
5% conventional
5% conventional LSSP
LSSP (10,000 ×) and
(10,000×) and (b) 5% modified LSSP
×).
(10,000×).
(10,000
4. Conclusions
4. Conclusion
The (a) study can be summarized as follows. (b)
The conclusions
conclusions of of this
this study can be summarized as follows.
Limestone
Figure 10. SEM
Limestone powder is used
imagesisofused
powder as
as aa(a)
samples:
raw material
5% material
raw or
or admixture
conventional
of
of cement.
LSSP (10,000×)
admixture In modified
and (b) 5%
cement. In this study,
this various
LSSP
study, various
properties of
(10,000×).
properties limestone sludge powder (LSSP) were evaluated by using recycled
of limestone sludge powder (LSSP) were evaluated by using recycled acetic acid (RAA), acetic acid (RAA),
which
which is one of the industrial byproducts, as a cement admixture after surface modification ofLSSP.
is one of the industrial byproducts, as a cement admixture after surface modification of LSSP.
4. Conclusion
The
The surface of LSSP modified with RAA was converted into calcium acetate and had a grain
surface of LSSP modified with RAA was converted into calcium acetate and had a large large
size.
grain Calcium
size. acetate has
Calcium effects
acetate has oneffects
mortaron properties.
mortar The settingThe
properties. timesetting
of mortars
time with
of conventional
mortars with
The conclusions of this study can be summarized as follows.
LSSP was independent
conventional ofindependent
the mixing ratios and was equal to that of ordinary type of
1 Portland cement
Limestone powder is used as a raw material or admixture of cement. In this study, various1
LSSP was of the mixing ratios and was equal to that ordinary type
(OPC), whereas the initial compressive strength slightly increased. When conventional LSSP is used as
properties of limestone sludge powder (LSSP) were evaluated by using recycled acetic acid (RAA),
a cement admixture material, it is possible that physical performance may deteriorate in the long term.
which is one of the industrial byproducts, as a cement admixture after surface modification of LSSP.
Nevertheless, the use of modified LSSP with RAA can promote and continuously induce hydration in
The surface of LSSP modified with RAA was converted into calcium acetate and had a large
the long term, thereby improving the performance of the cement mortar. When the modified LSSP
grain size. Calcium acetate has effects on mortar properties. The setting time of mortars with
conventional LSSP was independent of the mixing ratios and was equal to that of ordinary type 1
Sustainability 2019, 11, 879 9 of 10
was replaced with cement up to 10% of the cement weight, the initial (up to 3 days of aging) strength
was low. On the other hand, the compressive strength of mortar was as good as that of OPC after
28 days of aging, and 5% substitution showed higher strength than those of OPC and conventional
LSSP. Therefore, the use of cement admixture through modification of LSSP using RAA in this study is
expected to be useful as a sustainable construction material.
Author Contributions: For research articles, author contributions are as follows; conceptualization, H.-S.R.;
methodology and investigation, D.-M.K.; data curation, S.-H.S.; writing—original draft preparation, H.-S.R.;
writing and editing, W.-J.P.; review and editing, S.-M.L. and W.-K.K.
Acknowledgments: This work was supported by the National Research Foundation of Korea (NRF) grant funded
by the Korea government (no. NRF-2018R1D1A3B07045700).
Conflicts of Interest: The authors declare no conflict of interest. The founding sponsors had no role in the design
of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; and in the
decision to publish the results.
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