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Construction and Building Materials 187 (2018) 884–891

Contents lists available at ScienceDirect

Construction and Building Materials


journal homepage: www.elsevier.com/locate/conbuildmat

Study on flexural properties of active magnesia carbonation concrete


with fly ash content
Henian Zhang a, Chen Shen a,⇑, Peisheng Xi a, Kaixiang Chen b, Fang Zhang a, Shaohan Wang a
a
Anhui Key Laboratory of Building Structures and Underground Engineering, Anhui Jianzhu University, Hefei 230022, China
b
The Key Laboratory of Road and Traffic Engineering, Ministry of Education, Tongji University, Shanghai 230000, China

h i g h l i g h t s

 Appropriate amount of fly ash can increase the flexural and ductile properties of concrete test blocks.
 Nesquehonite, Dypingite and Hydromagnesite are the major products of carbonation of active gamma magnesia.
 The combination of fly ash and the carbonation products of magnesium oxide improves the internal structure of concrete.
 It is an environmentally friendly material.

a r t i c l e i n f o a b s t r a c t

Article history: The fly ash activated magnesia carbonized concrete developed based on cement carbonization technology
Received 23 May 2018 is a new type of cement-based composite material, the effects of four different proportions of fly ash and
Received in revised form 23 July 2018 active magnesium oxide on the flexural and ductile failure of carbonized concrete were studied. The
Accepted 3 August 2018
results show that the early flexural strength of magnesia carbonized concrete decreases with the increase
of fly ash content, the flexural strength increases obviously during 0–7 days of carbonation curing.
Afterwards, there is a flat growth, then increases significantly after 21–28 days of curing. The increase
Keywords:
of fly ash content has a high stimulatory effect on ductility, which slows down the brittle failure of the
Fly ash
Carbonization block
test block. However, excessive fly ash content will also have a negative impact on the strength and per-
Magnesia concrete formance. The optimum value is verified by the relationship between strain-time curve, the optimum
Flexural strength mixing amount of fly ash is 0.3, and the ratio of water to glue is 1:1. Microscopic test results verify the
Destructive damage magnesium carbonized products of Nesquehonite, Dypingite and Hydromagnesite are the main reasons
for improving the flexural properties.
Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction effect of fly ash on compressive strength by replacing cement with


different proportions of fly ash. The results show that with the
Concrete is a quasi-brittle material [1]. With the strength grad- increase of fly ash, the early strength of coagulation gradually
ually improving, the increase of its brittleness may lead that its decreases, and the later strength has Increased, but gradually
structure is destroyed suddenly. It is no doubt that the safety haz- decreased when it exceeds 20%. Therefore, it is one of the effective
ards of the complex large scale concrete structures will be ways to improve the flexural strength and toughness of concrete
increased. Meanwhile it does not meet the requirements of the by adding fly ash and active magnesium oxide into the matrix as
structural design safety and limits the scope of application of curing agent, which can effectively solve the difficult problems of
high-strength concrete. Portland cement, the main raw material high energy consumption and high carbon emission, etc. caused
for ordinary concrete, has high CO2 emissions, high energy con- by PC curing agent.
sumption, slow strength growth and serious environmental pollu- Vandeperre et al. (2008) [3,4] conducted carbonization tests on
tion. Incorporating fly ash can reduce hydration heat, reduce cracks magnesium oxide cement and PC paste samples. It was found that
and improve concrete performance, Harison [2] et al. studied the the fly ash- magnesium oxide slurry could provide the same
mechanical properties as the fly ash-Portland cement paste under
20% CO2. The strength of PC block with only active magnesium
⇑ Corresponding author.
oxide as curing agent could reach 2–3 times under forced
E-mail address: ivans_shen@126.com (C. Shen).

https://doi.org/10.1016/j.conbuildmat.2018.08.017
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
H. Zhang et al. / Construction and Building Materials 187 (2018) 884–891 885

carbonization, and the CO2 of the same quality as magnesium Table 1


oxide could be absorbed; Goswami & Mahanta [5] cured residual Chemical composition of reactive magnesium oxide (%).

red soil with a mixture of fly ash and slaked lime. Formosaa [6] MgO Hydrochloric acid CaO Fe2O3 chloride (cl) others
indicated that cement mortar formulate with a low-cost magne- insoluble matter
sium oxide by-product could be an interesting alternative to other 93% 0.2% 1.5% 0.08% 0.1% 5.12%
repair mortars; Afshin [7] researched the stabilization of soil using
olivine and the application of novel techniques utilizing alkaline
activation and carbonation. Dung [8] studied enhance the
Table 2
microstructure and performance of magnesium oxide concrete Strain gauge parameters.
mixes by increasing hydration and lowering water demand via
Type Tipo BX120-50AA Precision Grade A
the introduction of hydration and dispersion agents. Pu [9] investi-
gated the carbonation potential, strength gain and microstructural Gage Resistance 119.9 ± 0.1 Fence Long 50 * 3 mm
Gage Factor 2.08 ± 1% Thermal Output 100 lm/m °C1
development of magnesium oxide blocks and provides a compar-
ison with Portland cement blocks. In addition, many foreign schol-
ars have studied the application effect of granulated blast furnace
slag and waste gypsum in soil reinforcement. Prof. Huang con- 2.2. Sample preparation
ducted a long-term research on the use of industrial waste solidi-
fied soft soil and achieved rich results; Fang [10] et al. put According to the study by Al-Tabbaa and Yi [17–19] et al., and
forward a GT-type soil curing agent based on high-calcium ash studies carried out by Mo and Panesar [20,21] et al., the strength
and desulfurized gypsum, supplemented with quicklime, cement, of the test block containing 40% magnesium oxide is approximately
calcined gypsum, aluminum sulfate, and alumite; Liu and Li [11] the same as the strength of the test block of 20% magnesium oxide,
found that magnesium oxide activity had a significant effect on and the amount of magnesia should not exceed 40%. Therefore,
carbonization and solidification. Zhang et al. [12] concluded that four different ratios (mass ratio) are used when fly ash is added.
carbonized products of reactive magnesium oxide are mainly Fly ash in the curing agent doping as: 10%, 20%, 30%, 40%, the
Hydromagnesite and Nesquehonite/Dypingite, with the higher water-binder ratio of each dosage is 1:1. The specific process is
amount of reactive magnesium oxide, the more carbonized prod- as follows:
ucts. Ye [13] found that in the early stage, with the increase of
fly ash content, the strength of magnesia cement was obviously (1) Weigh a certain amount of raw materials, stir for five min-
decreased. However, with the passage of time, the influence of utes in a small blender in the room, and then add weigh
fly ash content on the strength became smaller and smaller. When water and water reducer, then stir for five minutes to ensure
curing to the 90th day, the strength of the fly ash test piece was uniform mixing.
almost equivalent to that of the ordinary test piece, and even (2) Weigh a sample of the required sample quality, the stirred
slightly increased. Zhang [14] concluded that under the low fly sample is divided into two rounds and poured into a non-
ash replacement rate, the reduction of the flexural strength is standard rectangular mold (400 mm  100 mm  100 mm).
lower than the reduction of the high fly ash replacement rate. Yang Tamp with the rod evenly, the upper mouth with the lack
[15] conducted a bending test on the trabecular beam with a of follow-up until the test die level after scraping.
replacement rate of fly ash of 0%, 15% and 25%. Rahul et al. [16] (3) The sample is first moved into a carbonization box for curing
studied the effect of different proportions of fly ash on the flexural for 24 h and demolded, then the curing is continued. Car-
strength of coagulation. They concluded that with the increase of bonization conditions were 20 °C of ambient temperature,
the proportion of fly ash, the late flexural strength will increase, 98 ± 2% of relative humidity and 20% CO2 concentration.
and the proportion of fly ash will decrease when it exceeds 20%.
At present, there are few studies on fly ash-magnesium oxide car- 2.3. Flexural performance test
bonized concrete by domestic and foreign scholars. There are many
aspects that need to be further studied and analyzed. (1) Two specimens per group. When the test block was cured to
This study provides a new method to improve the flexural per- the 3rd, 7th, 14th, 21st, 28th day removed respectively from
formance of fly ash concrete, and through the combination of the- the curing room and was wiped cleanly, then attach the
ory and experiment, it gives the best fly ash content of active strain gauge, they were counted as YB-1 and YB-2 layers
magnesium oxide carbonation concrete block, reduces the waste respectively. The position of the strain gauge is shown in
gas produced by the cement industry and resources and energy Fig. 1:
consumption caused by the development of limestone. Designed (2) Loading the test block. The universal testing machine is used
to increase the flexural properties of concrete as much as possible to load the specimen at the middle three points of the test
with large amounts of fly ash. block. The bearing surface of the test piece is two relatively
flat sides when the test block is formed, and the test block
shall ensure that the test block is in close contact with a sup-
2. Materials and methods port and a roller, a cover plate is in close contact with the
roller and a press on the testing machine. The loading device
2.1. Experiment materials is shown in Fig. 2:
(3) The applied load should be uniform and continuous, the
The cement used in this experiment is 32.5 grade ordinary loading speed should be 0.5 mm per minute until the test
Portland cement. Its various technical indicators meet the block is damaged or the universal testing machine automat-
corresponding provisions of the Ordinary Portland Cement ically stops working.
(GB175-2007). The chemical composition of high activity magne- (4) Record the damage load and the fracture location of the test
sium oxide is shown in Table 1. The resistance strain gauge param- piece. According to ‘‘Ordinary Concrete Mechanical Proper-
eters are shown in Table 2. According to the size of the mold, two ties Test Method Standard” [22], samples can be used in
test blocks are a group, the test material composition ratios are non-standard sizes. The flexural strength of the concrete test
shown in Table 3. block is calculated according to the following formula:
886 H. Zhang et al. / Construction and Building Materials 187 (2018) 884–891

Table 3
Material usage.

Fly ash (kg/m3) Cement (kg/m3) MgO (kg/m3) H2O (kg/m3) Sand (kg/m3) Gravel (kg/m3)
0.075 0.3375 0.3375 0.75 5.5 8.0
0.15 0.3 0.3 0.75 5.5 8.0
0.225 0.2625 0.2625 0.75 5.5 8.0
0.3 0.225 0.225 0.75 5.5 8.0

Fl
ff ¼ 2
bh

ff – Flexural strength of concrete test block (MPa),


F – Failure load of test block (KN),
l – Span between supports (mm),
h – Specimen section height (mm),
b – Specimen section width (mm)

Fig. 1. Strain gauge pasting position.


Su [23] et al. conducted an experimental study on the size effect
of the flexural strength of concrete. Since the carbonization test
block uses a non-standard test block, according to the ‘‘Standard
test method for mechanical properties of ordinary concrete regula-
tion” [24], the ultimate flexural strength of concrete specimen
should be obtained by multiplying the size conversion coefficient
of 0.85 after obtaining the flexural strength.

3. Analysis of test results

3.1. Failure form

According to the cracking trend of the specimen, the fracture


mode of the bending specimen is defined as the four modes shown
in Fig. 3: Type I is a vertical fracture in the middle of 0.1 fly ash con-
crete sample; Type II is the concrete fracture surface curved, failed
and damaged; Type III is a straight slope of the fracture surface of
the concrete; Type IV is a fractured surface with an oblique linear
fracture, and cracking extends to the fulcrum. Under the ideal
bonding condition, the flexural strength of the I–IV type members
will increase in turn, the lowest in type I and the highest in type IV.
The results of four-point bending test show that the fracture of
Fig. 2. Loading device. the test block with 0.1 and 0.2 content of fly ash is type I and II

Fig. 3. Effect of fly ash content on failure mode.


H. Zhang et al. / Construction and Building Materials 187 (2018) 884–891 887

respectively. When the dosage is 0.3, The crack is significantly clo- composite material has not fully activated the activity of fly ash,
ser to the fulcrum, so the loading capacity of the sample is the best and the hydration rate is relatively slow. No matter how much
when the content of fly ash is 0.3, and the fracture is type IV, which the fly ash content, the flexural strength of the test piece increases
is better than the mode III fracture with 0.4 content of fly ash. rapidly with time in 0–21 days. The growth rate is the largest when
the fly ash content is 0.3, and there is a continuous growth process
3.2. Flexural strength within 21–28 days. In general, the flexural strength of concrete
block increases with the increase of fly ash content, but when
Fig. 4 shows the flexural strength values of different fly ash con- the fly ash content is higher than a certain critical value, the flex-
tents. FCF-Flexural strength. ural strength decreases obviously. The higher the content of fly
Three specimens are grouped, and the flexural strength of all ash is, the more the later strength increases.
specimens is average. It can be seen from Fig. 3 that the early
strength of concrete specimens is low due to the increase of fly
ash content, because that the polymer on the surface of fly ash 3.3. Strain-time curve

Figs. 5 and 6 shows the strain-time curve of YB-1/YB-2 position


at different pulverized coal content for 7 days and 14 days and 21
days and 28 days.
From Fig. 5, it can be seen that when carbonization is cured to 7
d, the strain of YB-1 at the tensile part increases with time. At the
inflection point of the curve, the strain caused by the fracture
increases rapidly, the strain gauges are broken after reaching the
limit, showing brittle failure. After curing to the 14th day, the fly
ash content was 0.1 and the strain was rapid. It showed obvious
brittle failure. 0.3 addition was better than 0.2, and the addition
was better than 0.4 and apparently showed the characteristics of
ductile failure. After curing to the 21st day, the strain of 0.3, 0.4
fly ash concrete test blocks were significantly bigger than that of
0.1 and 0.2. After 28 days of curing, the strain of all the specimens
increased to reach their maximum value, and 0.3 additions were
Fig.4. Influence of fly ash content on rupture strength. better than other content.

Fig. 5. Strain-time pictures of different fly ash content (YB-1).


888 H. Zhang et al. / Construction and Building Materials 187 (2018) 884–891

Fig. 6. Strain-time pictures of different fly ash content (YB-2).

According to the Fig. 6, the regularity of YB-2 in the compres- seen from the figure: (1) There are MgO and Mg(OH)2 peaks in
sion zone is slightly different from the regularity of the stretch XRD, and the higher the content of fly ash is, the weaker the peak
zone. The greater the strain, the better the ductility. On the 7th value is, which indicates that fly ash can promote the hydration of
day, the concrete specimens with 0.3 and 0.4 content have larger MgO and form carbonized Mg(OH)2. (2) The calcite peak and quartz
strain, and on the 14th day, the concrete specimens with 0.4 con- peak reflect the main crystal composition of fly ash, which indi-
tent show obvious ductility characteristics. However, the ductility cates that the more fly ash content, the more dense aggregate pore
failure of 0.3 content is better than the ductility failure of 0.2 con- filling. (3) The higher the content of fly ash, the more obvious the
tent and it is also better than the ductility failure of 0.1 content and peak of magnesite (MgCO33H2O), and the improvement of the
0.4 content at the 21st day of curing. After 28 days of curing, all flexural strength and ductility of the carbonized sample is mainly
specimens reached the maximum strain, and the 0.2 content is bet- due to the formation of a dense microstructure of the aggregate.
ter than 0.3 and 0.4 content. The 0.1 content of concrete specimens
showed obvious brittle failure. The concrete’s compressive ability 4.2. Scanning electron microscope (SEM)
is superior to its tensile strength, and the hydration reaction and
carbonization reaction of fly ash and active magnesium oxide Fig. 8 is a different amount of fly ash scanning electron micro-
occurred completely after curing to 7 d, leading to early brittle scopy (SEM) picture. It can be seen from the figure that Hydromag-
fracture characteristics of concrete test blocks. With the increase nesite, Dypingite and Nesquehonite is in the four kinds of different
of fly ash content over time, the amount of carbonized product pro- fly ash content samples. When the fly ash content increases the
duced by the reaction increases. The carbonate compound can fill pore gradually decreases. This is because the higher the content
the pores in the sample and the product has strong cementation of fly ash is, the more effectively the aggregate is filled, and the
ability. Therefore, the strength and compactness of the concrete more complete the carbonation reaction of magnesium is. The den-
increase, and the ductility performance also increases. The strain sely packed aggregates of these cohesive carbonized products
in the compression zone is smaller than that in the tension zone. reduce the internal porosity of the test block to form a dense
microstructure, which greatly improves the flexural strength and
ductility of the concrete.
4. Micro test
4.3. Thermogravimetric analysis (TGA)
4.1. X-ray diffraction (XRD)
DSC – Temperature difference between sample and reference
Fig. 7 is the XRD spectrum of the blocks with different fly ash during program warming; DTG – The rate of change of weight as
content carbonized for 28 d in the carbonization tank. As can be a function of time/temperature.
H. Zhang et al. / Construction and Building Materials 187 (2018) 884–891 889

Fig. 7. XRD patterns of different fly ash contents Note: Symbol meaning in the figure: N-Magnesite MgCO33H2O, D/H-Dypingite/Hydromagnesite, B-Magnesium hydroxide
Mg(OH)2, Q – Quartz SiO2, C – Calcite CaCO3, M – Magnesium oxide MgO.

Fig. 8. SEM pictures of different fly ash content.


890 H. Zhang et al. / Construction and Building Materials 187 (2018) 884–891

Thermogravimetric analysis (TGA) can solve the problem that it 400 °C of fly ash being called N1 and N2 peak respectively. With the
is difficult for conventional to accurately and quantitatively ana- increase of active MgO content, the N1 and N2 peaks are also more
lyze the carbonized products of active magnesium oxide. From obvious, and N1 is more obvious than N2. N1 shows that nesque-
the thermogravimetric analysis of the four kinds of fly ash in Figs. 9 honite absorbs heat and loses adsorption water, 2 units of crystal
and 10, it can be seen that there are obvious peak near 100 °C and water and part of the constitution water at near 100 °C, and N2

Fig. 9. Thermogravimetric analysis of different fly ash contents. Note: Symbol meaning in the figure: N1, N2 – Magnesite, DSC – Temperature difference between sample and
reference during program warming; DTG – The rate of change of weight as a function of time/temperature.

Fig. 10. DTG patterns of different fly ash contents.


H. Zhang et al. / Construction and Building Materials 187 (2018) 884–891 891

shows that nesquehonite absorbs heat and loses the remaining thank Professor Fusheng Zha at HeFei University of Technology,
constitution water and CO2 at near 400 °C, which verifies the infer- China, for theirvaluable comments.
ence of the magnesium carbide product.
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The authors greatly appreciate the funding provided by Natural Ordinary Concrete Regulation, China Planning Press, Beijing, 2011.

Science Foundation of Jiangsu Province (BY2014120). The authors

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