Construction and Building Materials 216 (2019) 128–136

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Construction and Building Materials

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

Dispersion of triethanolamine-functionalized graphene oxide (TEA-GO)

in pore solution and its influence on hydration, mechanical behavior of
cement composite
Miaomiao Hu, Jintang Guo ⇑, Jinjie Fan, Pengpeng li, Di Chen
Department of Polymer Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin, China

h i g h l i g h t s

 Chemically functionalized GO was synthesized.

 The growth of TEA-GO aggregates was restricted in pore solution.
 TEA-GO leads to the increment in hydration degree of oil well cement (OWC).
 The mechanical properties of TEA-GO/OWC composites were enhanced.
 TEA-GO are tough enough to hinder the crack propagation due to energy dissipation.

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

Article history: Re-aggregation of graphene oxide (GO) in cementitious solutions compromises the mechanical enhance-
Received 4 September 2018 ment of cement composite. We chemically functionalized GO via triethanolamine (TEA), the removal of
Received in revised form 20 April 2019 ACAOACA groups on basal planes and the attachment of extra AOH groups on edges promoted its dis-
Accepted 23 April 2019
persibility during hydration and in cement paste. When incorporated into cement, TEA-GO provides more
Available online 6 May 2019
nucleation sites due to the better dispersion, further promoting the hydration degree. TEA-GO enhanced
the compressive strength and flexural strength by 9.4–31% and 8.1–36.7% respectively, which was signif-
Keywords:
icantly higher than that of GO(4.1–17.2%; 7.8–20%).
Triethanolamine
Graphene oxide
Ó 2019 Elsevier Ltd. All rights reserved.
Dispersion
Mechanical behavior
Pore solution
Crack propagation

1. Introduction the plentiful oxygen functional groups and the matrix. The mech-
anisms proposed so far to explain this enhancement generally
Graphene oxide (GO) is composed of a mono-layer of sp 2 and assume that GO is well dispersed [8,9].
sp 3 hybridised carbon atoms covalently bonded to various func- Paste studies have realized that the dispersion state of GO was
tional groups, such as carboxyl, hydroxyl, and epoxy [1,2], which affected by the pH and ionic composition during hydration by
alter the van der Waals interactions between the GO sheets, experiments and modelling studies [9,10]. Park [10] found that
thereby improve its dispersion in water. Considering the outstand- the addition of alkaline-earth salts immediately led to agglomera-
ing tensile strength of 130 GPa, large specific surface area of 2630 tion and uncontrollable precipitation, presumably due to the
(m2 /g) and amazing dispersion in water, GO is an ideal reinforce- crosslinking of the graphene oxide sheets by the divalent cations.
ment material for cement composites [3,4]. Summarized from Shih et al. [11] showed the pH-dependent behavior of GO.
reported studies [5–7], the enhanced mechanical properties of Some attempts have been made to prevent GO from agglomer-
cement composites by GO are generally attributed to the proper- ation [12–15]. For instance, Li et al. [16] found that GO dispersion
ties of GO nanosheets such as plentiful nucleation sites, interlock- in the cement paste was highly improved, with the assistance of
ing achieved by the wrinkled morphology, bonding force between silica fume mechanically separating the GO sheets and preventing
aggregation. However, the incorporation of second materials may
⇑ Corresponding author. results in many uncertainties and uncontrolled variables in the
E-mail address: [email protected] (J. Guo). complex cement system.

https://doi.org/10.1016/j.conbuildmat.2019.04.180
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
 M. Hu et al. / Construction and Building Materials 216 (2019) 128–136 129

Thus, we functionalized the GO sheets by TEA via reaction with preparation of saturated Ca(OH)2 solution refers to Ref. [19]. TEA-
ACOOH and ACAOACA groups. Various approaches, including GO or GO (2 mg/ml) was added into the saturated Ca(OH)2 via
UV–vis, optical images, SEM-EDS, were applied to observe its dis- ultrasonication for 1 h, then the mixture was shaken continuously
persion in cementitious solutions and cement matrix. The com- for 12 h to reach equilibration. The obtained suspension was then
plexation with Ca was firstly directly observed and quantitatively filtered, washed and freeze-dried for characterization. The GO dis-
measured by SEM-EDS. Moreover, the properties of cement com- persion in the cement matrix was observed using SEM-EDS.
posites with added GO/TEA-GO, including isothermal calorimetry,
composition and mechanical properties, were investigated. We 2.4. Sample preparation
believed that modification based on functional groups holds more
significance in the creative utilization of graphene oxide. TEA-GO and GO were added at 0.03 wt% and the water-to-
cement ratio was fixed at 0.44. Three different types of samples
2. Experimental program were prepared, noted as OWC, GO/OWC and TEA-GO/OWC, respec-
tively. First, disperse GO/TEA-GO powder into mixing water. Then
2.1. Materials the cement was added within 15 s and was placed in the Waring
blender’s cup at 4000 rpm and then blended for 35 s at
The cement used in our research is Class G high sulfur-resistant 12,000 rpm. The cement pastes were cured in a moist storage room
oil well cement (OWC) purchased from Jiahua Special Cement Co., at 60 °C for 1 day, 3 days, 7 days and 28 days for compressive
Ltd., China. Different from the Portland cement, OWC is composed strength and flexural strength evaluation. The curing temperature
of ordinary Portland cement, limestone and clay and its composi- of oil well cement is higher than Portland cement, which is chose
tions were determined by X ray fluorescence spectrometer (XRF, according to the properties and the working environment of oil
S4 Pioneer, Bruker AXS) and are given in Table 1. Triethanolamine cement sheath.
(TEA, AR), Ca(OH)2 were provided by Yuan Li Chemical Co., Ltd.,
(Tianjin China). Multilayer Graphene oxide (GO, purity: >80 wt%; 2.5. OWC composites measurement
thickness: 3.4–7 nm; diameter: 50-100 um; number of floors: 6–
10; specific surface area: 150–200 m2/g) was obtained from Tan- The hydration heat flow of the cement at 30 was recorded via
feng Tech. IN. C., (Su Zhou). isothermal calorimeter (YT-5855-T, China) with 6 channels. It
worth noting that external stirring of the cement pastes when
2.2. Functionalization of GO placing inside the calorimeter after a few minutes will lead to
meaningless heat signal recorded during the very initial period.
A GO dispersion was firstly prepared by dispersing 150 mg GO Therefore, the data within 20 min were not recorded to minimize
into 75 ml deionized water and then stirred at 80 °C for 2 h at the error in the initial period [20,21].
the presence of 3% TEA. The black solution was filtered, washed The compositions of hydrated cement at 28 days were evalu-
and freeze-dried for further characterization and utilization. Simi- ated using X-ray diffraction (XRD) with CuKa (k = 1.54 nm) radia-
lar method has been discussed by Liu [17]. tion (X’Pert Pro, Holland) at the step size of 0.0167°. To prepare
The freeze-dried powder was directly characterized by Raman samples for XRD measurement, all cement samples were ground
microscope (excitation wavelength 532 nm, DXR Microscope, and sieved through 70 mesh.
USA) and XPS (Kratos XSAM-800) with Al Ka (ht 1486.6 eV) to To examine the influence of GO/TEA-GO incorporation on the
study its structure. The morphology of TEA-GO can be confirmed mechanical properties of cement paste, compressive and flexural
by SEM image and the samples for SEM observation were prepared strength measurement were conducted using mechanical hydrau-
by dropping GO/TEA-GO solutions on copper foil, where the sol- lic pressure testing machine (model 4207 from Chandler Engineer-
vent was evaporated at room temperature. ing, Tulsa). The compressive strength measurements of TEA-GO
reinforced specimens (50.8  50.8  50.8 mm) were conducted at
2.3. Agglomeration state of GO and TEA-GO a loading rate of 1.2KN/s. The flexural properties for the specimen
with dimensions 160  40  40 mm were characterized at a load-
The dispersion homogeneity of TEA-GO (2 mg/ml) in deionized ing rate of 0.2 KN/s. At least six samples were repeated for each test
water and pore solutions were assessed by optical microscope to obtain the mean mechanical strength value, together with the
(CX31, Olympus, Japan) and UV–vis. The pore solution standard deviation.
(pH = 13.27; Ca2+=20.32 mmol/L) representing the hydration envi- The microstructure of the 28-day-cured cement paste after
ronment of cement pastes was extracted from the not yet hard- compressive strength measurement was observed by SEM (Hitachi,
ened pastes at 2 h using pressure filtration, as reported in Ref. [18]. S-4800, Japan) and central parts were collected.
For UV–vis investigation, GO/TEA-GO (2 mg/ml) was dispersed
via ultrasonication and the suspensions were measured after 3. Results and discussion
5 min. The solutions after UV–vis measurement were dropped on
a glass slide and covered with a cover glass for microscope 3.1. Functionalization of GO with TEA
observation.
Interaction between the Ca ions with GO and TEA-GO was stud- Scheme 1 shows the possible mechanism of the TEA-GO synthe-
ied using scanning electron microscope (SEM) equipped with thin- sis. TEA is prone to hydrolyze and then forms N+ to react with plen-
window energy dispersive spectrometer (EDS) and the elemental tiful epoxy and carboxyl groups on GO [22]. The O atoms in epoxy
mapping was collected on the surface of these samples [16]. The are attacked by N+ groups, which results in the ring opening [22].

Table 1
Chemical composition of OWC cement by XRF.

Composite CaO SiO2 Fe2O3 SO3 Al2O3 K2O MgO P2O5 loss
Content (%) 71.25 15.04 6.23 2.8 2.16 0.74 0.88 0.53 0.37
130 M. Hu et al. / Construction and Building Materials 216 (2019) 128–136

Scheme 1. Illustration of reaction between TEA and GO.

While the grafted hydrolyzed amino groups on the GO surface are (284.61 ev) and CAC (284.4 ev) peaks, there is another peak cen-
unstable at 80 °C, thus this kind of transient adhesion is replaced tering at 285.6 ev, corresponding to CAN, which suggests the
by C@C bonds, where TEA molecules are oxidized to nitroso chemical bonding between nitrogen and GO. After functionaliza-
groups, as shown in Scheme 1. Besides the ring opening, the N+ tion with TEA, the intensity of CAOAC decreased while that of
groups can easily react with carboxyl groups to form quaternary CAOH increased as compared to GO. The new CAN peak suggests
nitrogen, and in this way, a large number of hydroxyl groups are the chemical bonding between TEA and GO. This observation
introduced at the edge of the GO sheets [17]. Compared with the shows the removal of epoxy groups and the attachment of TEA
totally reduced GO, the increased hydrophilic AOH groups at edge during the functionalization process of GO, which provides direct
enhance the hydrophilicity of partially reduced GO sheets. evidence for Scheme 1.
To evaluate the microstructure of GO and TEA-GO, Raman spec-
troscopy and SEM are present in Fig. 1. It is well recognized that 3.2. Agglomeration state and distribution of GO and TEA-GO in
the structural and electronic properties of graphene oxide includ- hydration and cement matrix
ing disorder and defect structures, defect density and doping levels
can be characterized by Raman spectral. As shown in Fig. 1a and b, 3.2.1. Effects of Ca2+ on dispersion of GO
both GO and TEA-GO present the D band at 1358 cm 1 and the G In current studies, the influence of Ca2+ on the stability of GO
band at 1589 cm 1. To evaluate the defect in graphene sheets, the and TEA-GO was examined by introducing a small amount of GO
intensity ratio of D and G band (ID/IG) was applied [23,24]. After the or TEA-GO into saturated Ca(OH)2 solution [25,26]. As shown in
functionalization with TEA, the ID/IG value increased from 0.99 to Fig. 3(a), GO aggregates with larger size were found, which was
1.49 owing to the enhanced defects, which indicates increasing much greater than that of original GO before complexation. The
amount of sp3 hybridized C atoms in the structure of TEA-GO. elemental maps of carbon (C), oxygen (O), calcium (Ca) were taken
In SEM images (Fig. 1c and d), it is obvious that the layers of mul- by the SEM-EDS elemental mapping, and the results are shown in
tiple GO surface are expanded after modification with TEA, thus Fig. 3(c). The distribution of Ca and O on nanosheets of GO indi-
more active sites due to larger surface area are exposure to act. cates that complex groups provided by GO are sufficient, confirm-
As shown in Fig. 2a, the element composition of GO changes ing that GO surface were cross-linked by calcium ions. The crystals
from C/O/N = 67.3:32.7:0 to 72.8:25.2:2 (C/O/N) after modification deposited on the surface demonstrated the non-unifrom distribu-
with TEA. The N 1 s peak, which originates from TEA, appears and tion of Ca ions. In comparison with GO, the TEA-GO exhibits smal-
the decreased amount of O suggests the deoxygenation of GO, thus ler size, which indicates its better dispersion than GO in pore
GO was partially reduced by TEA. To quantitatively confirm the solution. The crystals deposited at the edge of monolayer TEA-GO
chemical bonding formed between TEA and GO, the composition (Fig. 3b) indicates that the edge-to-edge bridge mode is dominant
of the C 1s XPS spectra are fitted with Gaussian curves [22]. As pre- in complexation with Ca2+. As suggested by Cui [27], the crystals
sented in Fig. 2b, there exists four distinct Gaussian peaks in GO may be calcium carbonate. The decreased Ca content in TEA-GO
centering at 286.7 ev, 286.4 ev, 285.5 ev, 284.5 ev, corresponding sample may result from the decreased complexation degree due
to C@O, CAOAC, CAOH, and CAC, respectively. While for TEA-GO to the removal of functional groups on sheets and the steric hin-
(Fig. 2c), in addition to C@O (286.9 ev), CAOAC (286.89 ev), CAOH drance generated by the TEA structure at edge. The complexation
 M. Hu et al. / Construction and Building Materials 216 (2019) 128–136 131

Fig. 1. Raman spectral of GO (a) and TEA-GO (b). SEM image of GO (a) and TEA-GO (b).

Fig. 2. XPS survey spectra (a) of GO and TEA-GO, C1s XPS spectra (b) of GO and (c) TEA-GO.
132 M. Hu et al. / Construction and Building Materials 216 (2019) 128–136

Fig. 3. SEM image of GO (a) and TEA-GO (b) after complexed with Ca, corresponding elemental maps (Ca, O, C) of GO (c) and TEA-GO (d) at higher magnification.

with Ca was firstly directly observed and quantitatively measured TEA-GO. This is because the edge-bridging complexation mode
by SEM-EDS. and steric hindrance, as shown in Scheme 2.

3.2.2. Dispersibility in mixing water and pore solution 3.2.3. Distribution of GO and TEA-GO in cement paste
The relative agglomeration state of GO and TEA-GO was As shown in Fig. 5, the dispersion state of GO in cement matrix
revealed from optical microscope as shown in Fig. 4. Both GO was demonstrated by the distribution of C elements via SEM-EDS
and TEA-GO disperse well in water, where TEA-GO with smaller [14,28]. Cement composite with the addition of TEA serves as blank
size presents better uniformity. The UV–vis absorbance of TEA- reference. In Fig. 5a, small amount of C from TEA/cement compos-
GO water suspension was higher than that of GO suspension. The ite is negligible. For GO/cement composite, a number of blank
reaction between ACOOH and TEA increases the amount of AOH spaces and aggregates were observed, indicating that GO tends to
groups at the edge, therefore the difference in hydrophilicity agglomerate in the hardened cement paste. For TEA-GO/cement
between the edge and the basal plane is more obvious, which composite, the uniform distribution of C in TEA-GO/cement com-
makes TEA-GO behaves like a surfactant in aqueous media posite in Fig. 5c was found, which confirms that the TEA-GO is well
[10,11]. The strong hydrophilicity of the edge pulls the GO sheets dispersed in the hardened cement matrix, since the serious aggre-
into bulk water, and the hydrophobic sheets tends to shrink and gation in pore solution was avoided to some extent.
avoids exposure in water [11].
The unexpected aggregation exists in both GO and TEA-GO and 3.3. Influence of GO and TEA-GO on cement hydration
the absorbance of both two suspension were decreased, when dis-
persed in pore solutions. The heavy aggregation of GO suggests the The influence of nanosheets on the heat evolution of cement
stacking and bridging behavior of GO sheets under sufficient Ca2+ hydration is presented in Fig. 6. Fig. 6a illustrates the cumulative
in pore solution, as reported by Park S [10]. While the TEA-GO alle- heat release of cement with GO and TEA-GO. It was evident that
viates this state, as shown in Fig. 3d, the aggregation of TEA-GO is the cumulative hydration heats of cement with GO and TEA-GO
smaller and the inset image shows the single layer structure of nanosheets for 45 h were 318 J/g and 346 J/g, which were 2.25%
 M. Hu et al. / Construction and Building Materials 216 (2019) 128–136 133

Fig. 4. Optical micrographs of GO powder in water (a) and in pore solution (b), TEA-GO in water (c) and in pore solution (d).

Scheme 2. Interaction of TEA-GO and GO with Ca2+.

and 11.2% higher than that of the control sample (311 J/g). This As shown in Fig. 6b, The time of induction and acceleration per-
result indicated that both GO and TEA-GO accelerated cement iod remains almost unchanged for all samples. However, it should
hydration. Moreover, the effect of the TEA-GO seemed more dra- be noted that both GO and TEA-GO cement composites have higher
matic than that of GO. heat flow of hydration than that of plain cement, especially for
134 M. Hu et al. / Construction and Building Materials 216 (2019) 128–136

Fig. 5. EDS results of the cement matrix with (a) TEA, (b) GO and (c) TEA-GO.

Fig. 6. Cumulative heats (a) and hydration heat flows of OWC hydration with the addition of GO and TEA-GO.

TEA-GO/OWC composite. This is because that TEA-GO provides highlights the occurrence of Calcium hydroxide (CH 2h{18.05,
more nucleation sites due to better dispersion during hydration, 34.2, 50.9}), ettringite (AFt), monosulphoaluminate (AFm) and alite
which is positive to the formation hydration products. (C3S) for all samples [29]. CH is mainly used as an indicator to
demonstrate the degree of hydration. The incorporated GO and
TEA-GO significantly increased the intensities of the signals related
3.4. Effects of GO or TEA-GO on hydration products to CH crystals, especially for TEA-GO/OWC, which is in agreement
with the results of hydration heat flow. The highest CH intensity in
The typical XRD patterns of the hydrated cement samples are TEA-GO/cement composite attributes to the seeding effects of well
shown in Fig. 7. The XRD profile after 28 days of curing clearly dispersed TEA-GO in hydration and cement matrix, which acceler-
ates the hydration process and promotes the formation of hydra-
tion products.

3.5. Influence of GO and TEA-GO on mechanical properties

Average flexural and compressive strengths of OWC composites

as a function of curing time (i.e., 3, 7, 14, and 28 days) with the
added GO and TEA-GO are shown in Fig. 8. The corresponding
increments compared to OWC were exhibited in Table 2. Fig. 8a
shows the compressive strength test results of GO and TEA-GO
reinforced cement composites, which indicates that the compres-
sive strength of cement incorporating GO and TEA-GO is enhanced
after curing various days in comparison to blank cement. The
increment of compressive strength for TEA-GO are 9.4%-31% and
was higher than that of GO reinforced cement (4.1%-17.2) due to
the higher maturity of hydration products [30,31]. The well-
dispersed GO can provide more active surface area, accelerating
the nucleation and growth of hydration products. As proved in
Fig. 9, the crystal in TEA-GO/ cement composite are more mature
and fewer cracks and pores were observed when compared to
blank cement and GO/cement composite. Thus, TEA-GO greatly
refined the microstructure of cement composite.
Fig. 7. XRD patterns of samples OWC, GO/OWC and TEA-GO/OWC at 28 days of Fig. 8b and Table 2 show that GO and TEA-GO enhance the flex-
curing. ural strength of cement pastes. The flexural increment of cement
 M. Hu et al. / Construction and Building Materials 216 (2019) 128–136 135

Fig. 8. Compressive (a) and flexural strength (b) of cement composites.

Table 2
Increment in compressive strength and flexural strength.

Samples 1d 3d 7d 28d
Compressive strength GO 4.1% 5.46% 12.8% 17.2%
TEA-GO 9.4% 11.3% 22% 31%
Flexural strength GO 20% 12% 10% 7.8%
TEA-GO 36.7% 30.7% 11% 8.1%

Fig. 9. SEM images of blank OWC (a) and modified OWC paste with GO (b) and TEA-GO (c) after compressive strength measurement at 28 days.

composite with TEA-GO is 8.1–36.7%, which is higher than that of flexural strength. For blank cement (Fig. 10a), the cracks usually
GO reinforced cement (7.8–20%). According to hydration kinetics, penetrate the dense hydration products in a straight-through man-
the flexural enhancement of GO/OWC and TEA-GO/OWC can be ner. In Fig. 10b, a number of fine cracks with random branches, and
attributed to the acceleration in hydration. considerable discontinuity in GO/cement composite can be used to
In current research, the effects of GO and TEA-GO on cracks explain this effect [32]. For TEA-GO/OWC sample (Fig. 10c), fewer
were also observed, which can also explain the enhancement in cracks with finer size are observed in TEA-GO cement samples. This

Fig. 10. (a) SEM image of plain OWC matrix showing a straight-through type crack. (b) SEM image of GO/OWC composite showing a number of fine cracks with few branches.
(c) SEM image of TEA-GO/OWC.
136 M. Hu et al. / Construction and Building Materials 216 (2019) 128–136

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