Startseite Effect of graphene oxide on the properties of ternary limestone clay cement paste
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Effect of graphene oxide on the properties of ternary limestone clay cement paste

  • Jing Gong , Yi Qian , Ziyang Xu EMAIL logo , Chaoqian Chen , Yijing Jin , Junze Zhang , Zhipeng Li EMAIL logo und Xianming Shi
Veröffentlicht/Copyright: 4. Juli 2024
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Nanotechnology Reviews
Aus der Zeitschrift Nanotechnology Reviews Band 13 Heft 1

Abstract

Given the pressing threat of global warming, it is imperative to promote CO2 emission reduction within the cement industry which is widely recognized as a major contributor to the overall carbon footprint. Limestone clay cement (LCC) emerges as a promising alternative to Portland cement. However, to facilitate the implementation of LCC technology, it is urgent to address the low early-age compressive strength issue. Inspired by the successful implementation of nano-engineered cementitious material, we hereby introduce a novel nanomaterial, graphene oxide (GO), into unconventional LCC paste (cement:clay:limestone = 65%:20%:15%, water/binder ratio: 0.45). Experimental results revealed that the 0.09% GO by weight of the LCC binder was the optimal dosage in this work, which improved the compressive strength of the LCC paste at 7, 14, and 28 days by 25.6, 21.6, and 20.3%, respectively. Advanced characterizations were then conducted, suggesting that the admixed GO not only enabled a higher polymerization degree of binder hydrates (which benefited the development of compressive strengths) but also improved the carbonation resistance of LCC paste. These findings not only offer valuable insights for researchers but also provide practical guidance for engineers in the field. Notably, the admixed GO converted the unstable orthorhombic crystal systemic aragonite to the stable trigonal crystal systemic calcite, which offers insights into the technology of carbon sequestration in concrete.

Keywords: limestone clay cement; graphene oxide; compressive strength; degree of polymerization; carbonation resistance; Fourier-transform infrared spectroscopy analysis

1 Introduction

Recent years have seen increasing concerns over the environmental footprint of the concrete industry, especially its considerable CO2 emission and energy consumption [1], largely associated with the production of ordinary Portland cement (OPC). According to the global carbon emission report, the CO2 emission from the concrete industry is estimated to be about 8% of the total CO2 emission [1]. The emitted CO2 will result in an irreversible greenhouse effect and ultimately pose a significant risk to the ecosystem. Therefore, there is an urgent need to reduce the carbon emissions from the cement and concrete industries.

Limestone calcined clay cement (LC3) has emerged as a promising candidate to reduce the environmental footprint of the cement and concrete industries [2,3]. LC3 is a ternary blended cement consisting of calcined clay, limestone, and OPC, and saves up to 40% of CO2 and 20% of energy consumption as compared with conventional OPC [2]. In this ternary system, the limestone (carbonate phase) reacts with alkali and alumina derived from the hydration of OPC to generate hard and crystalline carboaluminate phases which significantly contribute to the development of the microstructure [4]. Additionally, the calcined clay displays promising pozzolanic reactivity, actively promoting the hydration process. Moreover, some of the limestone effectively fills the hydrate pores, contributing to the densification of the microstructure [3]. The synergistic effects of these three components make it possible to decrease the cement content while retaining the satisfactory performance of the hardened LC3 binder [2]. In addition, both clay and limestone are affordable and locally available, making the widespread application of LC3 much more feasible than many other types of alternative cementitious binders (e.g., supplementary cementitious material [SCM] cement and SCM-based geopolymer) [5,6]. Nevertheless, the utilization of LC3 requires the grinding of clinker with calcined clay and limestone, a process that may face limitations due to the limited availability of local cement plants with the necessary infrastructure for such grinding. Therefore, we introduced calcined clay and limestone in combination as a mineral additive and investigated the performance of this limestone clay cement (LCC) ternary composite, differentiated from the aforementioned LC3 composite.

LCC binders have been previously explored and have demonstrated significant potential for local construction. For example, Antoni et al. [7] employed a ternary binder consisting of 30% metakaolin, 15% limestone, and 55% OPC, which exhibited promising mechanical properties suitable for construction applications. Additionally, Drissi et al. [8] investigated the relationship between the composition of ternary OPC–metakaolin–limestone composites and their hydration, microstructure, and mechanical properties, contributing significantly to both scientific understanding and engineering practice. However, the relatively low early-age compressive strengths of LCC composites hinder the widespread application of this sustainable technology [9]. Therefore, finding an alternative method to improve their mechanical strength while maintaining a lower OPC dosage is of paramount importance to ensure their sustainability.

Cumulative studies have demonstrated the feasibility of admixing a trace amount of novel graphene oxide (GO) to greatly enhance various cementitious materials [10–12]. As a nascent nano-sized material, GO is originally derived from graphite through a strong oxidization process (e.g., Hammer’s method) [13]. The oxidization process not only exfoliates the layers of graphite but also grafts functional groups onto the surface of GO nanosheets, and these include, but are not limited to, carboxyl, hydroxyl, epoxide, and carboxylic groups [14]. The functional groups endow the GO with an electronegative surface charge, which plays a crucial role in the hydration process of cementitious materials. Generally, the electronegative GO serves to fill nanoscale pores, bridge and deflect microcracks, attract electropositive ions (e.g., Ca2+, Na+, and K+), and regulate the process of binder hydration to form better products [15,16]. More importantly, these functional groups endow GO with a higher level of hydrophilicity than other nanomaterials. In other words, GO can be dispersed more easily without requiring significant additional effort, making it a promising candidate among the various nanomaterials reported in previous studies aimed at enhancing cementitious composites. Furthermore, recent advances in large-scale manufacturing of GO have led to the exponential decline of the cost of GO, making it greatly more affordable than before. Our previous research has demonstrated the benefits of admixing 0.02 wt% GO in the OPC binder [17] and a fly ash-based geopolymer binder [11], respectively, inspiring the beneficial use of GO in this unconventional LCC binder.

Up to now, limited studies have investigated the effect of admixing GO on the LCC composites, yet we hypothesized that GO plays similar roles in LCC binder as it works in OPC and geopolymer binders and thus benefits the early-age compressive strengths of LCC paste. In this context, this work aimed to enhance the early-age compressive strengths of LCC paste specimens by incorporating GO. To test the aforementioned hypothesis, we employed scanning electron microscopy (SEM), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) to shed light on the influence of GO on the microscale characteristics of the LCC paste. The following sections detail the experimental design, sample preparation, performance testing, and advanced characterizations of the GO-LCC paste. This innovative composite material holds promise for a wide range of engineering applications (e.g., low-carbon concrete pavement) and the fundamental understanding from this research helps inform future research and application.

2 Experimental study

2.1 Materials

This study used P.O.42.5 OPC as purchased from Foshan Runhe Building Materials Co., Ltd. The limestone (calcite) and calcined clay (98 wt% metakaolin) were produced by Henan Borun Casting Materials Co., Ltd. The chemical composition of cement and metakaolin was examined by X-ray fluorescence, the chemical composition of limestone was provided by the producer, and all results are provided in Table 1. XRD analysis was also performed on the cement and metakaolin to reveal their crystalline mineral phases (Figure 1). As seen in Figure 1, the main crystalline phases in the cement were C3S, C2S, C3A, and C4AF, while kaolinite was dominant in the calcined clay. In addition, the specific surface area of cement, limestone, and metakaolin was 363, 475, and 17,000 m2/kg, respectively. The naphthalene superplasticizer provided by Shunxin Huagong (Jinan, China) was employed in this study to guarantee the flowability of LCC paste. The water reduction rate of this superplasticizer was 18–28% and its recommended dosage for OPC was 0.5–1%, as provided by the manufacturer.

Table 1

Chemical composition (wt%) content of materials

Chemical composition Cement Limestone Calcined clay
Al2O3 4.12 — 37.18
SiO2 20.50 0.40 57.81
Fe2O3 3.40 — 1.19
CaO 65.54 0.66 0.88
MgO 2.61 1.12 —
SO3 0.52 0.18 0.58
K2O + Na2O 0.78 0.43 0.72
TiO2 — — 1.39
CaCO3 — 97.21 —
LOI* 2.53 — 0.25

*The loss on ignition was determined by TGA.

Figure 1 XRD patterns of (a) OPC and (b) metakaolin.
Figure 1

XRD patterns of (a) OPC and (b) metakaolin.

Based on previous exploration, the LCC binder investigated in this study consists of 65 wt% cement, 20 wt% metakaolin, and 15 wt% limestone. The GO employed in this study was fabricated using a modified Hammer’s method in the laboratory [13], featuring a specific surface area of about 2,600 m2/g and no more than five layers of nanosheet (Figure 2a). This GO contained about 71 wt% carbon, 26 wt% oxygen, and some other elements from the oxidation process [18,19], and its main functional groups/chemical bonds were C–OH, C–C, and C═O bonds (Figure 2b).

Figure 2 (a) Micromorphology of GO nanosheet and (b) X-ray photoelectron spectroscopy analysis of GO [18,19].
Figure 2

(a) Micromorphology of GO nanosheet and (b) X-ray photoelectron spectroscopy analysis of GO [18,19].

2.2 Specimen preparation

The GO-LCC paste samples were fabricated in the laboratory as follows. The dosage of admixed GO was designed as 0, 0.045, 0.09, 0.135, and 0.18% by the weight of the LCC binder, respectively (Table 2). The water-to-LCC mass ratio was fixed at 0.45. First, the laboratory-fabricated GO and naphthalene superplasticizer (1 wt% to LCC) were ultrasonically dispersed in deionized water, with the ultrasonicator power of 40 W for 30 min to obtain desirable dispersion. Then, the fabricated GO solution (or aqueous suspension when exceeding 5 g/L) was poured into a 2.5 L mixer, followed by blending with limestone (15 wt%), metakaolin (20 wt%), and cement (65 wt%) in sequence with 1 min intervals. During the intervals and the mixing process, the mixer was kept at a slow but constant blending rate (i.e., 60 rpm). After mixing the LCC cement for another 1 min, the fresh paste was cast into cubic molds (70.7 mm × 70.7 mm × 70.7 mm) and then cured in a standard environment (temperature of 18–22°C, relative humidity of 95–98%). After 24 h of curing, these paste samples were demolded and then cured in the same condition for 6, 13, and 27 days in order to evaluate the compressive strength of the hardened LCC paste at 7, 14, and 28 days, respectively. The fabrication of A0 followed the same procedure but without GO.

Table 2

Mixture design of GO-LCC paste samples (g)

No. Cement Limestone Metakaolin Water GO Superplasticizer
A0 845 195 260 585 0 13
A1 0.585 13
A2 1.17 13
A3 1.755 13
A4 2.34 13

2.3 Macroscopic testing

The macroscopic testing included compressive strength and flowability tests, aimed at assessing the impact of GO on general practical engineering performance. By following the ASTM C109, the compressive strength of cubic specimens (50 cm × 50 cm × 50 cm) was conducted using an electro-hydraulic servo compression test machine with a loading speed of 0.1 MPa/s. The peak load was recorded to calculate the compressive strength, and the final result was reported as the average value of three measurements. Flowability assessment utilized a 50 mL beaker to simulate the mini-slump test, following the methodology outlined in Li and Shi’s study [11]. In this procedure, the fresh paste was poured into the beaker, then covered and inverted with a wet plastic plate. The beaker was subsequently raised vertically, allowing measurement of the diffused diameter, which was used to evaluate the flowability among distinct paste samples. Four pairs of perpendicular diameters were gauged, and their average was employed for comparative analysis, as detailed in Figure 3.

Figure 3 (a) 50 mL beaker filled with fresh paste and (b) demonstration of one pair of perpendicular diameter measurements of the diffused fresh paste.
Figure 3

(a) 50 mL beaker filled with fresh paste and (b) demonstration of one pair of perpendicular diameter measurements of the diffused fresh paste.

2.4 Microscopic investigations

This study entailed microscopic investigations designed to unravel the mechanistic roles of the admixed GO on the hydration of LCC paste. Before the analysis, the selected paste samples were dried at 50°C to remove the remaining moisture. The XRD analysis was performed using a D/max-2500 facility (Rigaku company, Japan) to investigate the effect of GO on the crystalline phases in the LCC hydration system. For the XRD analysis, the tube voltage was set at 40 kV, the tube current was set at 200 mA, the scanning range was set between 10° and 80°, and the scanning speed was set at 10°/min. The SEM analysis was conducted using a Hitachi S-4800 facility (HITACHI Company, Japan) to investigate the effect of GO on the microstructure and micromorphology of LCC hydration products. For the SEM, the selected samples were pre-coated with gold before analysis, the accelerating voltage was set as 15 kV and the probe current was set as 22 nA. The FTIR analysis was conducted using a Nicolet iS5 facility (Jingong Instrument Technology (Suzhou) Co., Ltd, China) to investigate the effect of GO on the chemical groups or bonds of LCC hydration products. For the FTIR, powdered paste samples were well-mixed with KBr in the mass ratio of 1:100 and then fabricated plates for analysis, the scanning range was between 400 and 4,000 cm−1 with a resolution of 4 cm−1. The TGA and corresponding differential thermogravimetry (DTG) study were performed by a Q2000 facility (TA Instrument, USA) to investigate the effect of GO on the chemical composition of LCC hydration products. For the TGA, the powdered paste samples were pre-heated at 50°C for 10 min to remove the remaining moisture and then heated up for analysis, the initial and ending temperature was set as 50 and 800°C, respectively, at a heating rate of 10°C/min.

3 Results and discussion

3.1 Compressive strength

The admixed GO significantly improved the compressive strength of LCC paste (as shown in Figure 4); in particular, the 0.09 wt% GO improved the compressive strength of the LCC paste at 7, 14, and 28 days by 25.6, 21.6, and 20.3%, respectively, working as the optimum dosage among all designed dosages. Our previous work reported similar results, in which the 0.02% GO (by weight of cementitious binder) improved the 7-day and 28-day compressive strength of a fly ash-based geopolymer paste by 6 and 9% [11], and improved the 7-day, 14-day, and 28-day compressive strength of a cement paste by 34, 27, and 29% [17], respectively. Other researchers have also reported similar trends. Pan et al. [18] reported that admixing 0.05 wt% GO increased the compressive strength and flexural strength of cement paste at 28 days by 15–33% and by 41–59%, respectively. Lv et al. [20] reported that admixing 0.05 wt% GO led to the highest 28-day compressive strength of an OPC mortar, featuring an increase of 48%. The different levels of strength improvement observed across these studies are due to the differences in the cementitious binder matrix. Furthermore, Lin et al. reported the 12.5 and 28.2% increase in the 28-day compressive strength by incorporating 1 and 2 wt% nano-silica to enhance the LC3 binder [21], respectively. This finding not only underscores the advantages of utilizing nanomaterials but also serves as an inspiration for enhancing unconventional limestone–cement–clay binders.

Figure 4 Effect of admixed GO on the compressive strength of LCC paste.
Figure 4

Effect of admixed GO on the compressive strength of LCC paste.

When the dosage of GO exceeded 0.09 wt%, however, the benefits of admixed GO to the compressive strength of the LCC paste declined, as illustrated in Figure 4. This is likely due to poor dispersion and thus undesirable agglomeration of GO that undermines the homogeneity of the LCC paste matrix. Although GO is hydrophilic, the GO nanosheets feature a considerably high specific surface area; as such, a high concentration of GO nanosheets in the concrete pore solution tends to agglomerate with each other, because of the presence of Van der Waals force [5,22] and possibly hydrogen bonding. Additionally, the accelerated hydration induced by GO, as explained in later sections, in the LCC binder results in reduced flowability, consequently exerting a detrimental impact on the consolidation of fresh paste. In other words, it introduces pores into the hardened paste and reduces its compressive strength. Similar mechanisms have been widely reported in nano-modified cementitious materials [23,24].

The beneficial effects of GO on the compressive performance of non-LCC cementitious composites have been widely discussed and accepted in the last few years [22,25]. The admixed GO works against crack propagation in the cementitious composite, due to the GO’s sheet-like structure (Figure 2a) and excellent mechanical property (290–430 GPa of the elastic modulus). Furthermore, the admixed GO benefits the hydration of cementitious binders through several mechanisms. The known mechanisms of this improvement include the nano-filling, microcrack bridging and deflecting, hydrates growth template, hydration acceleration, and hydration regulation roles played by GO. The following sections will focus on the microstructural morphology, chemical composition, and crystalline phases of selected GO-LCC paste samples to confirm the aforementioned roles played in GO in the LCC matrix.

3.2 Flowability

The admixed GO resulted in decreased flowability of fresh LCC paste, particularly noticeable when the GO dosage exceeded 0.135 wt% (as shown in Table 3). Despite metakaolin’s recognized high water absorptivity, the relatively increased amount of water-reducing agent and elevated water-to-binder ratio offset the metakaolin-induced decline in flowability. Furthermore, the addition of GO caused a reduction in flowability, consistent with the findings from previous researchers. For instance, Lu et al. demonstrated a 24% decrease in fluidity with 0.08 wt% admixed GO [25], while Li and Shi reported a reduction in diffused area from 161.4 mm × 156.76 mm to 139.8 mm × 136.6 mm with 0.02 wt% admixed GO [11]. This reduction is often attributed to GO’s extensive specific surface area and high surface reactivity, leading to boosted water absorption and subsequently diminished flowability. The same principle can explain the flowability reduction observed in this study. The GO-accelerated hydration process is another crucial factor contributing to the decreased fluidity. Due to limitations in the laboratory conditions, the hydration heat of each binder was not evaluated in this study. Nevertheless, findings from other studies support this perspective. For example, in Lin et al.’s research, the addition of nano-silica resulted in a significantly higher cumulative hydration heat in the first 15 h than the original LC3 and OPC binders, indicating the accelerated hydration induced by nanomaterials. An et al. [26] also reported that GO-modified OPC released more cumulative hydration heat in the first 20 h, further demonstrating GO’s role as a hydration accelerator in cementitious binders.

Table 3

Mean and standard deviation of flowability for each fresh LCC paste (mm)

Sample A0 A1 A2 A3 A4
Flowability 181(10) 163(8) 129(9) 73(8) 53(7)

Comparing the A1 and A2 specimens with paste A0 (without GO), although their flowability decreased but remained within acceptable limits; as such, they still could be easily compacted through vibration during practical applications. Conversely, the A3 and A4 specimens experienced substantial flowability losses, rendering them difficult to compact. The compromised flowability facilitated the formation of entrapped air voids, contributing to a porous macrostructure in A3 and A4, which is a contributing factor to the slightly reduced compressive strength.

3.3 FTIR and XRD analyses of hydrates

FTIR analysis was conducted to illustrate the influence of GO on the phase change, product formation, and chemical arrangement in the hydrated LCC paste. As shown in Figure 5a. The −OH bond detected at around 3,640 cm−1 could be attributed to the presence of portlandite, derived from the hydration of cement [27]. The H–O–H broad band centered at around 3,400 and 1,640 cm−1 can be ascribed to the presence of bound water in hydration products [28]. The C═O stretching detected at around 1,410 cm−1 (asymmetric C═O stretching) in Figure 5a, 875 cm−1 (out-of-plane bending), and 713 cm−1 (in-plane vibration) in Figure 5b could be ascribed to the presence of both carbonated hydrates and mixed limestone [29]. These chemical compositions were also confirmed by TGA/DTG analysis in a later section.

Figure 5 FTIR patterns of selected GO-LCC paste samples from (a) 1,200–4,000 cm−1 and (b) 600–1,300 cm−1 wavenumber length.
Figure 5

FTIR patterns of selected GO-LCC paste samples from (a) 1,200–4,000 cm−1 and (b) 600–1,300 cm−1 wavenumber length.

The in-depth analysis of FTIR data suggests that the admixed GO improved the polymerization degree of binder hydrates, which is consistent with the compressive strength results and the later SEM analysis of the LCC paste. Figure 6 depicts the deconvolution analysis of FTIR from 750 to 1,250 cm−1, and Figure 7 summarizes the relative area of these deconvoluted sub-peaks. The deconvolution of FTIR sub-peaks in Figure 6 followed the methodology detailed by Zhang et al. [30], and the results illustrate the influence of GO on the critical hydrates (e.g., C–(A)–S–H and C–Na–(A)–S–H) in the hydrated LCC paste. In general, Q0 represents the cement monomer, Q1 represents the Si–O tetrahedron located at the end of the C–S–H chain, Q2 represents the Si–O tetrahedron located in the middle of the C–S–H chain, Q3 represents the Si–O tetrahedron in the C–S–H network, and Q4 represents the Si–O tetrahedron in the quartz structure [23]. In this study, the sub-peak located at around 865 cm−1 was assigned to Si–O terminal vibrations in C–S–H/C–A–S–H gel (a.k.a., Q1 tetrahedron), the sub-peak at around 962 cm−1 was assigned to Q2 tetrahedron, the sub-peak at around 1,026 cm−1 was assigned to Si–O stretching in C–Na–(A)–S–H gel which was ascribed to the binding of Na onto C–(A)–S–H gel, the sub-peak at 1,097 cm−1 was assigned to Q3 tetrahedron, and 1,175 cm−1 was assigned to typical bands of Q4 tetrahedron, respectively [31,32]. It is worth noting that these sub-peaks shifted and varied slightly in other samples, likely due to the fitting error and the potential chemical reaction/change during the hydration process of LCC samples. The intensity (proportion of relative area) of the Si–O (Q3) bond in all GO-LCC paste decreased along with the increase of GO (Figure 7b), whereas the intensity of Q4 increased (Figure 7c), indicating that GO converted more Q3 into Q4 [33]. The transformation from Q3 to Q4 corresponds to the generation of more complex hydrates.

Figure 6 Deconvoluted FTIR patterns of selected GO-LCC paste samples from 750 to 1,250 cm−1 wavenumber length: (a) no-GO, (b) 0.045% GO, (c) 0.090% GO, (d) 0.135% GO, and (e) 0.180% GO. Note: due to the potential chemical reaction and fitting error, the center location for each sub-peak was slightly different.
Figure 6

Deconvoluted FTIR patterns of selected GO-LCC paste samples from 750 to 1,250 cm−1 wavenumber length: (a) no-GO, (b) 0.045% GO, (c) 0.090% GO, (d) 0.135% GO, and (e) 0.180% GO. Note: due to the potential chemical reaction and fitting error, the center location for each sub-peak was slightly different.

Figure 7 (a) Relative area of deconvoluted sub-peaks from 750 to 1,250 cm−1 wavenumber length, (b) the relative area of Q3 (1,097 cm−1), and (c) the relative area of Q4 (1,175 cm−1). Note: due to the bond shift and fitting error, the center location for each sub-peak was slightly different.
Figure 7

(a) Relative area of deconvoluted sub-peaks from 750 to 1,250 cm−1 wavenumber length, (b) the relative area of Q3 (1,097 cm−1), and (c) the relative area of Q4 (1,175 cm−1). Note: due to the bond shift and fitting error, the center location for each sub-peak was slightly different.

Yang et al. [34] reached a similar conclusion in their study on GO-OPC binders from a nuclear magnetic resonance (NMR) perspective. Their findings provide additional evidence to support the deconvolved FTIR analysis conducted in this study. After 28 days of curing, it was observed that in the OPC binder, more Q0 structures were transformed into higher-polymerized Si–O tetrahedra (Q1 and Q2) in the presence of GO. Specifically, the inclusion of 0.15 and 0.2 wt% of GO led to an increase in the mean chain length by 3.5 and 1.9%, respectively, suggesting the generation of more complex hydration products.

Figure 8 reveals the various carbonated phases in the hydrated LCC paste, demonstrating the influence of GO on the carbonation behavior of LCC paste samples. Generally, Ca-based carbonate could be divided into calcite, aragonite, and vaterite, which are characteristic of different FTIR patterns (Figure 8a), as verified by Chakrabarty and Mahapatra [35]. In this study, the calcite mainly came from the admixed limestone and the carbonated portlandite [31], whereas the aragonite and vaterite mainly came from the carbonated C–S–H/C–A–S–H. The unique two peaks (700 and 712 cm−1) of aragonite were not observed after admixing GO (Figure 8b), suggesting that during the carbonation of LCC paste in the air, the presence of GO mitigated the formation of unstable orthorhombic crystal systemic aragonite but facilitated the formation of stable trigonal crystal systemic calcite. This result was also confirmed by XRD analysis (Figure 8c) in which the intensity of aragonite in 0.09% GO-LCC was weaker than its counterpart without the admixed GO. The quantification of carbonate phases will be discussed in the TGA/DTG section later.

Figure 8 (a) FTIR patterns of calcite, aragonite, and vaterite [35], (b) the weak two-peak (700 and 712 cm−1) verified the presence of aragonite, and (c) the XRD patterns of original LCC paste and 0.09% GO LCC paste.
Figure 8

(a) FTIR patterns of calcite, aragonite, and vaterite [35], (b) the weak two-peak (700 and 712 cm−1) verified the presence of aragonite, and (c) the XRD patterns of original LCC paste and 0.09% GO LCC paste.

The XRD analysis also sheds light on the hydration process of selected LCC binders. Compared with the original no-GO LCC paste, the intensity of peaks in 0.09%-GO LCC paste at about 18° (Ca(OH)2), 34°(Ca(OH)2), 36°(CaCO3), 39°(Quartz), and 48°(kaolinite) decreased [32,36,37], suggesting that these components were consumed due to participation in the binder hydration process. In other words, the admixed GO accelerated the hydration process of LCC paste. This conclusion is consistent with our previous work that GO accelerated the hydration process of both OPC and geopolymer binder [11,17]. Furthermore, Lin et al. reported enhanced carbonation resistance of the LC3 binder by introducing nano-silica, as observed in a laboratory accelerated carbonation test. Their research primarily focuses on the denser microstructure induced by nano-silica.

3.4 SEM analysis

Figure 9 illustrates the microstructure of 0.09 wt% GO-LCC paste and its control sample (no-GO) at 28-day curing age, aimed to evaluate the influence of GO on the morphology of hydrates of LCC paste. As shown in Figure 9a and b, the microstructure of 0.09 wt% GO-LCC paste is denser than the control sample and seems to have fewer defects, suggesting the beneficial effects of GO on the microstructure of LCC paste. Note that denser microstructure tends to translate to higher compressive performance as well as better durability performance (through lower water absorption, lower gas permeability, and lower diffusivity of detrimental ions). Our previous research also demonstrated similar results; specifically, the admixed GO facilitated more homogenous layer-by-layer hydrates in a fly ash-based geopolymer paste while the unmodified geopolymer featured loose and disordered hydrates [11]. This phenomenon was also known as the “hydrate growth template effect.” This effect primarily stemmed from the interaction between chemical functional groups (such as C–OH) present on the surface of GO and the chemical constituents of hydrates. This interaction facilitated the generation of a layered structure through a sequential process. A comparable outcome has been observed in the current study as well (Figure 9c).

Figure 9 SEM results of (a) 0.09 wt% GO-LCC paste and (b) control sample at the magnification of 5k times; and (c) 0.09 wt% GO-LCC paste and (d) control sample at the magnification of 20k times.
Figure 9

SEM results of (a) 0.09 wt% GO-LCC paste and (b) control sample at the magnification of 5k times; and (c) 0.09 wt% GO-LCC paste and (d) control sample at the magnification of 20k times.

More obvious differences were detected in SEM at the magnification of 20,000 times (Figure 9c and d), where the 0.09 wt% GO-LCC paste exhibits a more homogenous and denser microstructure. It is well known that the morphology of cementitious hydrates (e.g., C–S–H and C–A–S–H) mainly depends on the molar ratio of key elements (especially Ca/Si, S/Al, and Ca/(Si + Al)). The more uniform the molar ratio of key elements, the more consistent the polymerization degree of binder hydrates, and the more homogenous the hydration products [5]. Therefore, the homogeneous hydrates in this study indicate that the admixed GO facilitated a more uniform distribution of key elements. In other words, the presence of GO reduced the variability in the polymerization degree of the LCC binder, as suggested by the positive correlation between Ca/Si (or Ca/(Si + Al)) and hydration polymerization degree [38].

The aforementioned advantages of GO likely resulted from the functional groups on the surface of GO, which provide the GO nanosheets with a significant negative charge. The GO nanosheets thus serve as templates to attract cations (e.g., Ca2+, Na+, and K+). The cations can then react with Si, Al, and S species to form hydration products (such as C–S–H, C–A–S–H, AFt, and AFm). In summary, the GO guided the hydration of the cementitious binder and led to a more integrated microstructure and better compressive strengths. Lv et al. [20] reported similar results that the admixed GO induced homogeneous flower-like hydrates in an OPC paste matrix. In addition, Lv et al. detailed the template mechanism of GO, which is also responsible for the homogenous hydrates observed in this study.

3.5 Thermogravimetric and differential thermal analysis

Figure 10 illustrates the thermogravimetric-differential thermal analysis results of selected GO-LCC paste samples, which help elucidate the influence of GO on the hydration products of LCC paste. As shown in Figure 10, this first mass loss was detected between 50 and 150°C, corresponding to the escape of the residual water, the decomposition of AFt (Ettringite) and AFm, and the dehydration of partial C–S–H/C–A–S–H. It was clear that the admixed GO mitigated the generation of AFt, inspiring the potential use of GO to mitigate the risk of delayed ettringite formation in heat-cured concrete [39] or mass concrete. Xu et al. also demonstrated a similar result by analyzing the key elemental information obtained by electron probe microanalysis; specifically, they reported that 0.02 wt% GO facilitated the transformation from AFt to other Al-rich phases [17].

Figure 10 (a) TGA and (b) DTG analysis of selected GO-LCC paste.
Figure 10

(a) TGA and (b) DTG analysis of selected GO-LCC paste.

The second mass loss in Figure 10 was detected between 350 and 450°C, corresponding to the decomposition of portlandite. The DTG peak of portlandite in the curve of 0.09 wt% GO-LCC paste was sharper than in other samples, suggesting that the admixed GO induced the formation of more and better crystallized portlandite. This result agrees with the study by Mokhtar et al. [40] in which GO induced a higher content of portlandite in OPC binder and they attributed this higher content of portlandite to the GO-accelerated hydration process of OPC. Yang et al. also reported that the content of portlandite was slightly increased along with the increment of GO dosage in OPC binder [34].

The last mass loss in Figure 10 was detected between 450 and 750°C, corresponding to the decomposition of carbonate. It was clear that the admixed GO mitigated the carbonation of the LCC paste, because 0.045, 0.090, 0.135, and 0.180% GO decreased the relative amount of total carbonate by about 19.7, 25.1, 17.5, and 23.6%, respectively. This result agreed well with our previous work that the admixed GO improved the carbonation resistance of an OPC paste [17].

It is noteworthy that the third main mass loss consists of multiple peaks, suggesting that multiple decompositions or transformations occurred simultaneously. As confirmed by FTIR, two other types of Ca-carbonates: vaterite and aragonite, were also detected in the carbonated LCC paste. Both of them not only decomposed in the temperature range Ⅰ (Figure 10b) but also transformed into calcite and then decomposed in the temperature range Ⅱ [41], which made the quantification of each component much more complex.

4 Concluding remarks

This work proposed an innovative strategy to employ GO to enhance unconventional LCC paste. To elucidate the mechanistic roles played by GO in the LCC paste system, this laboratory study explored the influence of GO on the compressive strength and flowability of the designed paste, and the microscopic investigation further shed light on the microscopic change of LCC paste induced by GO. The main conclusions are drawn as follows:

  1. GO effectively improved the compressive strength of LCC paste samples. The optimal dosage of GO in this study was 0.09% by weight of the LCC paste, which improved the compressive strength at 7, 14, and 28 s by 25.6, 21.6, and 20.3%, respectively. However, when the dosage of GO exceeded 0.09 wt%, the benefit to the compressive strength of the LCC paste declined, likely due to undesirable agglomeration of GO and pores resulted from GO-accelerated hydration of LCC. In addition, the admixed GO reduced the flowability of fresh LCC paste, due to the accelerated hydration of LCC induced by GO. These results provide a promising strategy for engineers to enhance the performance of LCC paste in the field while balancing the constructability of the fresh concrete and the mechanical properties of the hardened concrete.

  2. GO played several critical roles in the LCC paste. It served as the hydration growth templates and regulated the hydrates, as evidenced by the layer-by-layer hydrate structures observed in SEM. GO also accelerated the hydration process, as indicated by the presence of more crystalline portlandite phases, as shown by TGA, and the consumption of more mineral phases, as demonstrated by XRD. GO improved the polymerization degree of hydrates, as evidenced by a higher content of complex hydrates observed in FTIR. Moreover, GO enhanced the carbonation resistance of hydrates, as supported by the various carbon-related peaks observed in FTIR and TGA. In addition, GO converted the unstable orthorhombic crystal systemic aragonite to the stable trigonal crystal systemic calcite. All these roles are similar to the roles played by GO in cement and geopolymer binders.

Future work should further investigate the fundamentals underlying the mechanical properties and durability performance of GO-modified LCC composites, using advanced tools (e.g., nanoindentation and NMR spectroscopy), to offer in-depth insights and fundamental understanding. Additional research may also explore the use of higher content of calcined clay and limestone (i.e., lower content of cement) to further greening the LCC technology with the aid of nanotechnology. While this study did not directly assess the durability performance, the results suggest that the admixed GO is beneficial to the durability of LCC composites, including slowing down the ingress of moisture, gases, and detrimental ions (in light of the denser microstructure), and improving chemical resistances (in light of the higher polymerization degree of hydrates).

  1. Funding information: This work was financially supported by the Key Laboratory of Catalysis and Energy Materials Chemistry of Ministry of Education & Hubei Key Laboratory of Catalysis and Materials Science (Project # CHCL19001), Hubei Provincial Department of Construction (Construction Science and Technology Plan Project 2019-672-3-3), and Hubei Provincial Department of Construction (Construction Science and Technology Plan Project 2021-28-56).

  2. Author contributions: Jing Gong: writing – original draft, funding acquisition, validation, methodology, data collection, data curation, conceptualization; Yi Qian: writing – original draft, data curation; Ziyang Xu: validation, methodology, data collection, data curation; Chaoqian Chen: data curation; Yijing Jin: data curation; Junze Zhang: data curation; Zhipeng Li: writing – review and editing, validation, methodology, conceptualization; Xianming Shi: writing – review and editing, supervision, conceptualization. All authors have accepted the responsibility for the entire content of this manuscript and approved its submission.

  3. Conflict of interest: The authors state no conflict of interest.

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Received: 2023-06-14
Revised: 2023-11-09
Accepted: 2024-02-22
Published Online: 2024-07-04

© 2024 the author(s), published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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  140. Special Issue on Advanced Nanomaterials for Carbon Capture, Environment and Utilization for Energy Sustainability - Part II
  141. Calcium-, magnesium-, and yttrium-doped lithium nickel phosphate nanomaterials as high-performance catalysts for electrochemical water oxidation reaction
  142. Low alkaline vegetation concrete with silica fume and nano-fly ash composites to improve the planting properties and soil ecology
  143. Mesoporous silica-grafted deep eutectic solvent-based mixed matrix membranes for wastewater treatment: Synthesis and emerging pollutant removal performance
  144. Electrochemically prepared ultrathin two-dimensional graphitic nanosheets as cathodes for advanced Zn-based energy storage devices
  145. Enhanced catalytic degradation of amoxicillin by phyto-mediated synthesised ZnO NPs and ZnO-rGO hybrid nanocomposite: Assessment of antioxidant activity, adsorption, and thermodynamic analysis
  146. Incorporating GO in PI matrix to advance nanocomposite coating: An enhancing strategy to prevent corrosion
  147. Synthesis, characterization, thermal stability, and application of microporous hyper cross-linked polyphosphazenes with naphthylamine group for CO2 uptake
  148. Engineering in ceramic albite morphology by the addition of additives: Carbon nanotubes and graphene oxide for energy applications
  149. Nanoscale synergy: Optimizing energy storage with SnO2 quantum dots on ZnO hexagonal prisms for advanced supercapacitors
  150. Aging assessment of silicone rubber materials under corona discharge accompanied by humidity and UV radiation
  151. Tuning structural and electrical properties of Co-precipitated and Cu-incorporated nickel ferrite for energy applications
  152. Sodium alginate-supported AgSr nanoparticles for catalytic degradation of malachite green and methyl orange in aqueous medium
  153. An environmentally greener and reusability approach for bioenergy production using Mallotus philippensis (Kamala) seed oil feedstock via phytonanotechnology
  154. Micro-/nano-alumina trihydrate and -magnesium hydroxide fillers in RTV-SR composites under electrical and environmental stresses
  155. Mechanism exploration of ion-implanted epoxy on surface trap distribution: An approach to augment the vacuum flashover voltages
  156. Nanoscale engineering of semiconductor photocatalysts boosting charge separation for solar-driven H2 production: Recent advances and future perspective
  157. Excellent catalytic performance over reduced graphene-boosted novel nanoparticles for oxidative desulfurization of fuel oil
  158. Special Issue on Advances in Nanotechnology for Agriculture
  159. Deciphering the synergistic potential of mycogenic zinc oxide nanoparticles and bio-slurry formulation on phenology and physiology of Vigna radiata
  160. Nanomaterials: Cross-disciplinary applications in ornamental plants
  161. Special Issue on Catechol Based Nano and Microstructures
  162. Polydopamine films: Versatile but interface-dependent coatings
  163. In vitro anticancer activity of melanin-like nanoparticles for multimodal therapy of glioblastoma
  164. Poly-3,4-dihydroxybenzylidenhydrazine, a different analogue of polydopamine
  165. Chirality and self-assembly of structures derived from optically active 1,2-diaminocyclohexane and catecholamines
  166. Advancing resource sustainability with green photothermal materials: Insights from organic waste-derived and bioderived sources
  167. Bioinspired neuromelanin-like Pt(iv) polymeric nanoparticles for cancer treatment
  168. Special Issue on Implementing Nanotechnology for Smart Healthcare System
  169. Intelligent explainable optical sensing on Internet of nanorobots for disease detection
  170. Special Issue on Green Mono, Bi and Tri Metallic Nanoparticles for Biological and Environmental Applications
  171. Tracking success of interaction of green-synthesized Carbopol nanoemulgel (neomycin-decorated Ag/ZnO nanocomposite) with wound-based MDR bacteria
  172. Green synthesis of copper oxide nanoparticles using genus Inula and evaluation of biological therapeutics and environmental applications
  173. Biogenic fabrication and multifunctional therapeutic applications of silver nanoparticles synthesized from rose petal extract
  174. Metal oxides on the frontlines: Antimicrobial activity in plant-derived biometallic nanoparticles
  175. Controlling pore size during the synthesis of hydroxyapatite nanoparticles using CTAB by the sol–gel hydrothermal method and their biological activities
  176. Special Issue on State-of-Art Advanced Nanotechnology for Healthcare
  177. Applications of nanomedicine-integrated phototherapeutic agents in cancer theranostics: A comprehensive review of the current state of research
  178. Smart bionanomaterials for treatment and diagnosis of inflammatory bowel disease
  179. Beyond conventional therapy: Synthesis of multifunctional nanoparticles for rheumatoid arthritis therapy
https://doi.org/10.1515/ntrev-2023-0222
Schlagwörter für diesen Artikel
limestone clay cement; graphene oxide; compressive strength; degree of polymerization; carbonation resistance; Fourier-transform infrared spectroscopy analysis
Creative Commons
BY 4.0

Artikel in diesem Heft

  1. Research Articles
  2. Tension buckling and postbuckling of nanocomposite laminated plates with in-plane negative Poisson’s ratio
  3. Polyvinylpyrrolidone-stabilised gold nanoparticle coatings inhibit blood protein adsorption
  4. Energy and mass transmission through hybrid nanofluid flow passing over a spinning sphere with magnetic effect and heat source/sink
  5. Surface treatment with nano-silica and magnesium potassium phosphate cement co-action for enhancing recycled aggregate concrete
  6. Numerical investigation of thermal radiation with entropy generation effects in hybrid nanofluid flow over a shrinking/stretching sheet
  7. Enhancing the performance of thermal energy storage by adding nano-particles with paraffin phase change materials
  8. Using nano-CaCO3 and ceramic tile waste to design low-carbon ultra high performance concrete
  9. Numerical analysis of thermophoretic particle deposition in a magneto-Marangoni convective dusty tangent hyperbolic nanofluid flow – Thermal and magnetic features
  10. Dual numerical solutions of Casson SA–hybrid nanofluid toward a stagnation point flow over stretching/shrinking cylinder
  11. Single flake homo p–n diode of MoTe2 enabled by oxygen plasma doping
  12. Electrostatic self-assembly effect of Fe3O4 nanoparticles on performance of carbon nanotubes in cement-based materials
  13. Multi-scale alignment to buried atom-scale devices using Kelvin probe force microscopy
  14. Antibacterial, mechanical, and dielectric properties of hydroxyapatite cordierite/zirconia porous nanocomposites for use in bone tissue engineering applications
  15. Time-dependent Darcy–Forchheimer flow of Casson hybrid nanofluid comprising the CNTs through a Riga plate with nonlinear thermal radiation and viscous dissipation
  16. Durability prediction of geopolymer mortar reinforced with nanoparticles and PVA fiber using particle swarm optimized BP neural network
  17. Utilization of zein nano-based system for promoting antibiofilm and anti-virulence activities of curcumin against Pseudomonas aeruginosa
  18. Antibacterial effect of novel dental resin composites containing rod-like zinc oxide
  19. An extended model to assess Jeffery–Hamel blood flow through arteries with iron-oxide (Fe2O3) nanoparticles and melting effects: Entropy optimization analysis
  20. Comparative study of copper nanoparticles over radially stretching sheet with water and silicone oil
  21. Cementitious composites modified by nanocarbon fillers with cooperation effect possessing excellent self-sensing properties
  22. Confinement size effect on dielectric properties, antimicrobial activity, and recycling of TiO2 quantum dots via photodegradation processes of Congo red dye and real industrial textile wastewater
  23. Biogenic silver nanoparticles of Moringa oleifera leaf extract: Characterization and photocatalytic application
  24. Novel integrated structure and function of Mg–Gd neutron shielding materials
  25. Impact of multiple slips on thermally radiative peristaltic transport of Sisko nanofluid with double diffusion convection, viscous dissipation, and induced magnetic field
  26. Magnetized water-based hybrid nanofluid flow over an exponentially stretching sheet with thermal convective and mass flux conditions: HAM solution
  27. A numerical investigation of the two-dimensional magnetohydrodynamic water-based hybrid nanofluid flow composed of Fe3O4 and Au nanoparticles over a heated surface
  28. Development and modeling of an ultra-robust TPU-MWCNT foam with high flexibility and compressibility
  29. Effects of nanofillers on the physical, mechanical, and tribological behavior of carbon/kenaf fiber–reinforced phenolic composites
  30. Polymer nanocomposite for protecting photovoltaic cells from solar ultraviolet in space
  31. Study on the mechanical properties and microstructure of recycled concrete reinforced with basalt fibers and nano-silica in early low-temperature environments
  32. Synergistic effect of carbon nanotubes and polyvinyl alcohol on the mechanical performance and microstructure of cement mortar
  33. CFD analysis of paraffin-based hybrid (Co–Au) and trihybrid (Co–Au–ZrO2) nanofluid flow through a porous medium
  34. Forced convective tangent hyperbolic nanofluid flow subject to heat source/sink and Lorentz force over a permeable wedge: Numerical exploration
  35. Physiochemical and electrical activities of nano copper oxides synthesised via hydrothermal method utilising natural reduction agents for solar cell application
  36. A homotopic analysis of the blood-based bioconvection Carreau–Yasuda hybrid nanofluid flow over a stretching sheet with convective conditions
  37. In situ synthesis of reduced graphene oxide/SnIn4S8 nanocomposites with enhanced photocatalytic performance for pollutant degradation
  38. A coarse-grained Poisson–Nernst–Planck model for polyelectrolyte-modified nanofluidic diodes
  39. A numerical investigation of the magnetized water-based hybrid nanofluid flow over an extending sheet with a convective condition: Active and passive controls of nanoparticles
  40. The LyP-1 cyclic peptide modified mesoporous polydopamine nanospheres for targeted delivery of triptolide regulate the macrophage repolarization in atherosclerosis
  41. Synergistic effect of hydroxyapatite-magnetite nanocomposites in magnetic hyperthermia for bone cancer treatment
  42. The significance of quadratic thermal radiative scrutinization of a nanofluid flow across a microchannel with thermophoretic particle deposition effects
  43. Ferromagnetic effect on Casson nanofluid flow and transport phenomena across a bi-directional Riga sensor device: Darcy–Forchheimer model
  44. Performance of carbon nanomaterials incorporated with concrete exposed to high temperature
  45. Multicriteria-based optimization of roller compacted concrete pavement containing crumb rubber and nano-silica
  46. Revisiting hydrotalcite synthesis: Efficient combined mechanochemical/coprecipitation synthesis to design advanced tunable basic catalysts
  47. Exploration of irreversibility process and thermal energy of a tetra hybrid radiative binary nanofluid focusing on solar implementations
  48. Effect of graphene oxide on the properties of ternary limestone clay cement paste
  49. Improved mechanical properties of graphene-modified basalt fibre–epoxy composites
  50. Sodium titanate nanostructured modified by green synthesis of iron oxide for highly efficient photodegradation of dye contaminants
  51. Green synthesis of Vitis vinifera extract-appended magnesium oxide NPs for biomedical applications
  52. Differential study on the thermal–physical properties of metal and its oxide nanoparticle-formed nanofluids: Molecular dynamics simulation investigation of argon-based nanofluids
  53. Heat convection and irreversibility of magneto-micropolar hybrid nanofluids within a porous hexagonal-shaped enclosure having heated obstacle
  54. Numerical simulation and optimization of biological nanocomposite system for enhanced oil recovery
  55. Laser ablation and chemical vapor deposition to prepare a nanostructured PPy layer on the Ti surface
  56. Cilostazol niosomes-loaded transdermal gels: An in vitro and in vivo anti-aggregant and skin permeation activity investigations towards preparing an efficient nanoscale formulation
  57. Linear and nonlinear optical studies on successfully mixed vanadium oxide and zinc oxide nanoparticles synthesized by sol–gel technique
  58. Analytical investigation of convective phenomena with nonlinearity characteristics in nanostratified liquid film above an inclined extended sheet
  59. Optimization method for low-velocity impact identification in nanocomposite using genetic algorithm
  60. Analyzing the 3D-MHD flow of a sodium alginate-based nanofluid flow containing alumina nanoparticles over a bi-directional extending sheet using variable porous medium and slip conditions
  61. A comprehensive study of laser irradiated hydrothermally synthesized 2D layered heterostructure V2O5(1−x)MoS2(x) (X = 1–5%) nanocomposites for photocatalytic application
  62. Computational analysis of water-based silver, copper, and alumina hybrid nanoparticles over a stretchable sheet embedded in a porous medium with thermophoretic particle deposition effects
  63. A deep dive into AI integration and advanced nanobiosensor technologies for enhanced bacterial infection monitoring
  64. Effects of normal strain on pyramidal I and II 〈c + a〉 screw dislocation mobility and structure in single-crystal magnesium
  65. Computational study of cross-flow in entropy-optimized nanofluids
  66. Significance of nanoparticle aggregation for thermal transport over magnetized sensor surface
  67. A green and facile synthesis route of nanosize cupric oxide at room temperature
  68. Effect of annealing time on bending performance and microstructure of C19400 alloy strip
  69. Chitosan-based Mupirocin and Alkanna tinctoria extract nanoparticles for the management of burn wound: In vitro and in vivo characterization
  70. Electrospinning of MNZ/PLGA/SF nanofibers for periodontitis
  71. Photocatalytic degradation of methylene blue by Nd-doped titanium dioxide thin films
  72. Shell-core-structured electrospinning film with sequential anti-inflammatory and pro-neurogenic effects for peripheral nerve repairment
  73. Flow and heat transfer insights into a chemically reactive micropolar Williamson ternary hybrid nanofluid with cross-diffusion theory
  74. One-pot fabrication of open-spherical shapes based on the decoration of copper sulfide/poly-O-amino benzenethiol on copper oxide as a promising photocathode for hydrogen generation from the natural source of Red Sea water
  75. A penta-hybrid approach for modeling the nanofluid flow in a spatially dependent magnetic field
  76. Advancing sustainable agriculture: Metal-doped urea–hydroxyapatite hybrid nanofertilizer for agro-industry
  77. Utilizing Ziziphus spina-christi for eco-friendly synthesis of silver nanoparticles: Antimicrobial activity and promising application in wound healing
  78. Plant-mediated synthesis, characterization, and evaluation of a copper oxide/silicon dioxide nanocomposite by an antimicrobial study
  79. Effects of PVA fibers and nano-SiO2 on rheological properties of geopolymer mortar
  80. Investigating silver and alumina nanoparticles’ impact on fluid behavior over porous stretching surface
  81. Potential pharmaceutical applications and molecular docking study for green fabricated ZnO nanoparticles mediated Raphanus sativus: In vitro and in vivo study
  82. Effect of temperature and nanoparticle size on the interfacial layer thickness of TiO2–water nanofluids using molecular dynamics
  83. Characteristics of induced magnetic field on the time-dependent MHD nanofluid flow through parallel plates
  84. Flexural and vibration behaviours of novel covered CFRP composite joints with an MWCNT-modified adhesive
  85. Experimental research on mechanically and thermally activation of nano-kaolin to improve the properties of ultra-high-performance fiber-reinforced concrete
  86. Analysis of variable fluid properties for three-dimensional flow of ternary hybrid nanofluid on a stretching sheet with MHD effects
  87. Biodegradability of corn starch films containing nanocellulose fiber and thymol
  88. Toxicity assessment of copper oxide nanoparticles: In vivo study
  89. Some measures to enhance the energy output performances of triboelectric nanogenerators
  90. Reinforcement of graphene nanoplatelets on water uptake and thermomechanical behaviour of epoxy adhesive subjected to water ageing conditions
  91. Optimization of preparation parameters and testing verification of carbon nanotube suspensions used in concrete
  92. Max-phase Ti3SiC2 and diverse nanoparticle reinforcements for enhancement of the mechanical, dynamic, and microstructural properties of AA5083 aluminum alloy via FSP
  93. Advancing drug delivery: Neural network perspectives on nanoparticle-mediated treatments for cancerous tissues
  94. PEG-PLGA core–shell nanoparticles for the controlled delivery of picoplatin–hydroxypropyl β-cyclodextrin inclusion complex in triple-negative breast cancer: In vitro and in vivo study
  95. Conduction transportation from graphene to an insulative polymer medium: A novel approach for the conductivity of nanocomposites
  96. Review Articles
  97. Developments of terahertz metasurface biosensors: A literature review
  98. Overview of amorphous carbon memristor device, modeling, and applications for neuromorphic computing
  99. Advances in the synthesis of gold nanoclusters (AuNCs) of proteins extracted from nature
  100. A review of ternary polymer nanocomposites containing clay and calcium carbonate and their biomedical applications
  101. Recent advancements in polyoxometalate-functionalized fiber materials: A review
  102. Special contribution of atomic force microscopy in cell death research
  103. A comprehensive review of oral chitosan drug delivery systems: Applications for oral insulin delivery
  104. Cellular senescence and nanoparticle-based therapies: Current developments and perspectives
  105. Cyclodextrins-block copolymer drug delivery systems: From design and development to preclinical studies
  106. Micelle-based nanoparticles with stimuli-responsive properties for drug delivery
  107. Critical assessment of the thermal stability and degradation of chemically functionalized nanocellulose-based polymer nanocomposites
  108. Research progress in preparation technology of micro and nano titanium alloy powder
  109. Nanoformulations for lysozyme-based additives in animal feed: An alternative to fight antibiotic resistance spread
  110. Incorporation of organic photochromic molecules in mesoporous silica materials: Synthesis and applications
  111. A review on modeling of graphene and associated nanostructures reinforced concrete
  112. A review on strengthening mechanisms of carbon quantum dots-reinforced Cu-matrix nanocomposites
  113. Review on nanocellulose composites and CNFs assembled microfiber toward automotive applications
  114. Nanomaterial coating for layered lithium rich transition metal oxide cathode for lithium-ion battery
  115. Application of AgNPs in biomedicine: An overview and current trends
  116. Nanobiotechnology and microbial influence on cold adaptation in plants
  117. Hepatotoxicity of nanomaterials: From mechanism to therapeutic strategy
  118. Applications of micro-nanobubble and its influence on concrete properties: An in-depth review
  119. A comprehensive systematic literature review of ML in nanotechnology for sustainable development
  120. Exploiting the nanotechnological approaches for traditional Chinese medicine in childhood rhinitis: A review of future perspectives
  121. Twisto-photonics in two-dimensional materials: A comprehensive review
  122. Current advances of anticancer drugs based on solubilization technology
  123. Recent process of using nanoparticles in the T cell-based immunometabolic therapy
  124. Future prospects of gold nanoclusters in hydrogen storage systems and sustainable environmental treatment applications
  125. Preparation, types, and applications of one- and two-dimensional nanochannels and their transport properties for water and ions
  126. Microstructural, mechanical, and corrosion characteristics of Mg–Gd–x systems: A review of recent advancements
  127. Functionalized nanostructures and targeted delivery systems with a focus on plant-derived natural agents for COVID-19 therapy: A review and outlook
  128. Mapping evolution and trends of cell membrane-coated nanoparticles: A bibliometric analysis and scoping review
  129. Nanoparticles and their application in the diagnosis of hepatocellular carcinoma
  130. In situ growth of carbon nanotubes on fly ash substrates
  131. Structural performance of boards through nanoparticle reinforcement: An advance review
  132. Reinforcing mechanisms review of the graphene oxide on cement composites
  133. Seed regeneration aided by nanomaterials in a climate change scenario: A comprehensive review
  134. Surface-engineered quantum dot nanocomposites for neurodegenerative disorder remediation and avenue for neuroimaging
  135. Graphitic carbon nitride hybrid thin films for energy conversion: A mini-review on defect activation with different materials
  136. Nanoparticles and the treatment of hepatocellular carcinoma
  137. Special Issue on Advanced Nanomaterials and Composites for Energy Conversion and Storage - Part II
  138. Highly safe lithium vanadium oxide anode for fast-charging dendrite-free lithium-ion batteries
  139. Recent progress in nanomaterials of battery energy storage: A patent landscape analysis, technology updates, and future prospects
  140. Special Issue on Advanced Nanomaterials for Carbon Capture, Environment and Utilization for Energy Sustainability - Part II
  141. Calcium-, magnesium-, and yttrium-doped lithium nickel phosphate nanomaterials as high-performance catalysts for electrochemical water oxidation reaction
  142. Low alkaline vegetation concrete with silica fume and nano-fly ash composites to improve the planting properties and soil ecology
  143. Mesoporous silica-grafted deep eutectic solvent-based mixed matrix membranes for wastewater treatment: Synthesis and emerging pollutant removal performance
  144. Electrochemically prepared ultrathin two-dimensional graphitic nanosheets as cathodes for advanced Zn-based energy storage devices
  145. Enhanced catalytic degradation of amoxicillin by phyto-mediated synthesised ZnO NPs and ZnO-rGO hybrid nanocomposite: Assessment of antioxidant activity, adsorption, and thermodynamic analysis
  146. Incorporating GO in PI matrix to advance nanocomposite coating: An enhancing strategy to prevent corrosion
  147. Synthesis, characterization, thermal stability, and application of microporous hyper cross-linked polyphosphazenes with naphthylamine group for CO2 uptake
  148. Engineering in ceramic albite morphology by the addition of additives: Carbon nanotubes and graphene oxide for energy applications
  149. Nanoscale synergy: Optimizing energy storage with SnO2 quantum dots on ZnO hexagonal prisms for advanced supercapacitors
  150. Aging assessment of silicone rubber materials under corona discharge accompanied by humidity and UV radiation
  151. Tuning structural and electrical properties of Co-precipitated and Cu-incorporated nickel ferrite for energy applications
  152. Sodium alginate-supported AgSr nanoparticles for catalytic degradation of malachite green and methyl orange in aqueous medium
  153. An environmentally greener and reusability approach for bioenergy production using Mallotus philippensis (Kamala) seed oil feedstock via phytonanotechnology
  154. Micro-/nano-alumina trihydrate and -magnesium hydroxide fillers in RTV-SR composites under electrical and environmental stresses
  155. Mechanism exploration of ion-implanted epoxy on surface trap distribution: An approach to augment the vacuum flashover voltages
  156. Nanoscale engineering of semiconductor photocatalysts boosting charge separation for solar-driven H2 production: Recent advances and future perspective
  157. Excellent catalytic performance over reduced graphene-boosted novel nanoparticles for oxidative desulfurization of fuel oil
  158. Special Issue on Advances in Nanotechnology for Agriculture
  159. Deciphering the synergistic potential of mycogenic zinc oxide nanoparticles and bio-slurry formulation on phenology and physiology of Vigna radiata
  160. Nanomaterials: Cross-disciplinary applications in ornamental plants
  161. Special Issue on Catechol Based Nano and Microstructures
  162. Polydopamine films: Versatile but interface-dependent coatings
  163. In vitro anticancer activity of melanin-like nanoparticles for multimodal therapy of glioblastoma
  164. Poly-3,4-dihydroxybenzylidenhydrazine, a different analogue of polydopamine
  165. Chirality and self-assembly of structures derived from optically active 1,2-diaminocyclohexane and catecholamines
  166. Advancing resource sustainability with green photothermal materials: Insights from organic waste-derived and bioderived sources
  167. Bioinspired neuromelanin-like Pt(iv) polymeric nanoparticles for cancer treatment
  168. Special Issue on Implementing Nanotechnology for Smart Healthcare System
  169. Intelligent explainable optical sensing on Internet of nanorobots for disease detection
  170. Special Issue on Green Mono, Bi and Tri Metallic Nanoparticles for Biological and Environmental Applications
  171. Tracking success of interaction of green-synthesized Carbopol nanoemulgel (neomycin-decorated Ag/ZnO nanocomposite) with wound-based MDR bacteria
  172. Green synthesis of copper oxide nanoparticles using genus Inula and evaluation of biological therapeutics and environmental applications
  173. Biogenic fabrication and multifunctional therapeutic applications of silver nanoparticles synthesized from rose petal extract
  174. Metal oxides on the frontlines: Antimicrobial activity in plant-derived biometallic nanoparticles
  175. Controlling pore size during the synthesis of hydroxyapatite nanoparticles using CTAB by the sol–gel hydrothermal method and their biological activities
  176. Special Issue on State-of-Art Advanced Nanotechnology for Healthcare
  177. Applications of nanomedicine-integrated phototherapeutic agents in cancer theranostics: A comprehensive review of the current state of research
  178. Smart bionanomaterials for treatment and diagnosis of inflammatory bowel disease
  179. Beyond conventional therapy: Synthesis of multifunctional nanoparticles for rheumatoid arthritis therapy
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