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Article

Durability Improvement of Cement Using Amphiphilic Calcium Carbonate Nanoparticles

by
Han Yan
1,
Xin Shu
1,
Dongliang Zhou
1,2,
Yong Yang
1,*,
Lu Chen
1 and
Qianping Ran
1,2,*
1
State Key Laboratory of High Performance Civil Engineering Materials, Nanjing 211103, China
2
School of Material Science and Engineering, Southeast University, Nanjing 211189, China
*
Authors to whom correspondence should be addressed.
Coatings 2022, 12(10), 1431; https://doi.org/10.3390/coatings12101431
Submission received: 17 July 2022 / Revised: 20 September 2022 / Accepted: 22 September 2022 / Published: 29 September 2022
(This article belongs to the Section Functional Polymer Coatings and Films)
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Abstract

:
The durability of cementitious materials is significant concerning long-term performance. Nanomaterials are promising candidates for deep refinement of cement durability. Hydrophobic calcium carbonate is a widely applied and easily accessible nanomaterial. However, its hydrophobicity and poor dispersity in water prohibit its direct application in cementitious materials. In this study, hydrophobic calcium carbonate nanoparticles (HbCC) were modified using a novel amphiphilic comb-shaped dispersant that is capable of laurinol release. The modification was conducted to improve the dispersity of HbCC and their compatibility with hydration products. The dispersion-improved calcium carbonate particles (AmphCC) were characterized and tested for cement durability improvement performance. According to the results, the AmphCC particles showed a pronounced effect on improving permeation resistance of cement mortars, with water absorption and chloride penetration considerably lowered. Moreover, the introduction of AmphCC in cement did not show significant adverse effects on strength development. Compared with AmphCC, a single addition of the unmodified HbCC and the dispersant cannot achieve equivalent effects. The superior effect of AmphCC is due to the synergistic effect of good particle dispersion and controlled release of the hydrophobic molecules, which is achieved by dispersion of HbCC with binding of the dispersant.

1. Introduction

The durability of cement is a key factor concerning long-term performance and economical cost, as well as the environmental effect of cementitious materials [1,2,3]. Building structures with high environmental endurance and long life is becoming the trend in the construction industry.
In application, durability consists of many aspects, such as permeability [4], freeze-thaw resistance [5], alkali–silica reaction regulation [6,7], soundness [8,9] and tolerance to harsh environments [10]. Durability can be improved via multiple ways, such as mix design [7,11], curing [12], coating [4,13,14] and additives [3,15,16,17,18,19,20,21]. Despite the essential role of mix design, the conduction of proper curing and the introduction of proper coatings and additives can offer further and synergistic enhancement to the durability of concrete structures [20,21].
Among the novel additives for cement durability enhancement, nanotechnology is a promising one with much research concern. In recent years, many studies about durability improvement of cementitious materials using nanotechnology have been carried out [1,2,3,15,16,17,18,19,20,21,22,23,24]. Numerous nanomaterials, such as nano silica [1,17], nano clay [19], graphene [2,19] and nano calcium carbonate [21,22,23,24] have shown a prominent effect on durability enhancement.
In the many nanomaterials that were put into application trials, nanocomposites that are capable of hydrophobic content release have attracted great research appeal due to their simultaneous and synergistic refinement on both pore and microstructure [17,25,26]. Extensive studies were conducted by researchers in recent years. Hou et al. [17] used aliphatic silane modified nano silica as additives for permeation resistance; Gu et al. [26] experimented a silane-containing comb-polymer as a strong dispersant for nano silica dispersion.
Among these nanocomposites, hydrophobic nano calcium carbonate (HbCC) with oleic acid treatment is of great application potential [21]. As a versatile and easily accessible nanomaterial, it has already enjoyed wide application in multiple fields such as printing, paints and polymer fillers, and was produced in large quantities annually [21,27].
Still, some problems lie before further application of HbCC on cementitious materials, the toughest one being dispersion in water [28,29]. Due to their high surface activity, nanomaterials are prone to agglomerate, and hydrophobic treatment makes the situation worse, making them nearly unwettable by water. Therefore most researchers laid focus on HbCC coatings, while experiments concerning the use of HbCC as an additive were seldom conducted.
In this work, calcium carbonate dispersion in cementitious media was achieved with aid from an amphiphilic dispersant; its effect on durability of cementitious material was investigated via mortar tests and relevant characterizations.

2. Materials and Methods

2.1. Materials

The materials for dispersant preparation, including lauric methacrylate (A.R.), methyl polyethylene glycol methacrylate (95%, Mw = 500), 1-dodecanethiol (A.R.), ethyl acetate (A.R.), azo-bis-isobutyronitrile (AIBN, C.P., recrystallized before use) and methacrylic acid (A.R.) were purchased from Aladdin chemical reagents Co., Ltd. (Shanghai, China) Dispersants that were used for comparison, namely, Sodium dodecyl sulfonate (A.R.) and nonyl phenyl polyethylene oxide (98%, 10EO units), were purchased from Sinopharm Co., Ltd. (Beijing, China) Hydrophobic calcium carbonate (HbCC, containing 2% oleic acid, other impurities < 0.5%) was purchased from Changzhou Calcium Carbonate Co., Ltd. (Changzhou, China).
A P I 42.5 Portland cement was used in paste and mortar preparation; its composition is available in Table 1. The water used in this study was deionized. A polycarboxylate superplasticizer (PCA-I, Jiangsu sobute Co., Ltd., Nanjing, China) was used for fluidity adjustments.

2.2. Preparation of the Dispersant and the Amphiphilic Material

The comb-shaped amphiphilic dispersant (AmphD), which is inspired by polycarboxylate dispersants, was prepared by free-radical polymerization of the aforementioned monomers in ethyl acetate. Its chemical structure is demonstrated in Figure 1. The preparation method is available in Supplementary Information Text S1.
The hydrophobic long-chain aliphatic acrylate backbone and the polyethylene glycol (PEG) side chain make it a non-ionic and amphiphilic dispersant. The PEG side chain offers a strong steric effect to ensure its fine dispersity in aqueous media. The polymeric and non-ionic nature of the dispersant largely avoided undesired air entrainment in cement pastes, as small-molecule ionic surfactants (e.g., sodium dodecyl sulfonate) do. The dispersant is also hydrolysable with laurinol as the product; the release of laurinol, if controlled, can hydrophobify the hydration product surface and further improve the resistance to permeation.
The hydrophobic calcium carbonate was first mixed with the dispersant (HbCC/AmphD = 2/1 w/w), the mix was conducted by shear mixing at 600 rpm for 15 min at room temperature, and the resultant slurry (noted as amphiphilic calcium carbonate/AmphCC) was kept for further use. The mechanism of dispersion is shown in Figure 2.
A comparison between this dispersant and other common dispersants was also carried out. The dispersants that were involved are listed in Table 2. The referential dispersants (10% aqueous solution, since PC and SDS are solid at r.t.) were mixed with HbCC (HbCC/dispersant = 2/1 w/w), respectively. The mixtures were also mixed at 600 rpm for 15 min at room temperature. The resultant mixtures were kept for further use.

2.3. Characterization of the Dispersant and Amphiphilic Calcium Carbonate

The amphiphilic dispersant was characterized by gel permeation chromatography (Type LC-20, Shimazu Co., Ltd. Kyoto, Japan), AmphCC was characterized by X-ray diffraction(XRD, Type D8 Advance, Brucker Co., Ltd., Billerica, MA, USA), with a step of 0.02° and a dwell time of 1 s), particle size analysis (Type Helos-Sucell Sympatec Co., Ltd., Clausthal-Zellerfeld, Germany) and scanning electron microscope (SEM, Type FEI Quanta 250, FEI Co., Waltham, MA, USA, at 15 kV acceleration voltage). The dispersing effect of the dispersant and dispersion stability were tested by dispersing AmphCC and other dispersant-modified HbCC in a saturate Ca(OH)2 solution (200 mL) at a concentration of 5%(w/w) under N2 atmosphere. The dispersions were then sealed with N2 and placed. The concentration change was monitored by sampling (10 mL) and measuring concentrations at 12, 24 and 72 h. The results were indexed by relative concentration decline (concentration decline/total initial concentration × 100%)

2.4. Mortar Tests

2.4.1. Mortar Preparation

The mortars were mixed based on GB/T-17671-1999 [31]. Detailed procedures were described below. The flow of the mortar was adjusted to 160 ± 5 mm by altering SP amount. After mixing, the mortar samples were cast into 40 × 40 × 160 mm3 molds and cured at 20 ± 1 °C and 95% relative humidity (RH). The water/binder ratio of the mortars was 0.5 and the dosage of AmphCC was 0.3%, 0.8% and 1.5%, respectively. Additionally, HbCC (0.8%) and the dispersant (0.27%) were introduced as references. Due to its extremely poor dispersity in water, the mixing time of HbCC-added samples was doubled.

2.4.2. Water Permeation Tests

In the permeation tests, mortar samples (three blocks for each sample) were prepared and cured for 28 d. After 28 d, the samples were first dried at 65 °C to constant weight and then coated with epoxy resin on the four lateral surfaces. After setting of the resin coating, the samples were horizontally put in the testing tank with a water depth of 6 cm. After the desired time intervals, the sample was shortly taken out, removed of surface water, and weighed.

2.4.3. Chlorine Permeation Tests

In the tests, the mortar samples (four blocks for each sample) were prepared and treated with the procedures described in Section 2.4.1 and Section 2.4.2. The samples were horizontally put in the testing tank with the NaCl solution (3.5%). The depth of the NaCl solution was also 6 cm. After 28 d and 56 d, each sample was evenly divided into two groups, one was split axially and sprayed with a coloring agent to reveal penetration depth, the other was sliced every 2 mm from the uncoated surface until 5 mm beyond the penetration depth. The slices were ground and tested for chlorine content via titration method.

2.4.4. Strength Tests

Strength tests were conducted for samples in ages of 1 d and 28 d. The samples were prepared via the as-described method. The flexural and compressive strength of the mortar samples were tested also according to GB/T17671-1999 [31]. The strength tests were run on an Aelikon AEC-201 testing machine. The test was run in 6 parallels (3 mortar columns, each split and tested 2 times).

2.5. Paste Characterizations

The w/b of the pastes was 0.40, and the flow was adjusted to 180 ± 5 mm. The samples were processed according to GB/T-8077-2012 [32]. The samples with the AmphCC dosage of 0.3%, 0.8% and 1.5% were prepared, as well as the HbCC (0.8%) and dispersant (0.27%) references; the HbCC reference was also mixed for double the time. After curing at 293 K and 95% RH for the desired time, the hardened paste samples were used for the following characterizations.
In the XRD and SEM characterizations, the outer layer (1 mm) of the samples was polished off with a Buehler Phoenix 4000 polisher.
X-Ray diffraction scans for hardened pastes (28 d) were also run on a Bruker D8 Advance diffractometer, with a step of 0.02° and a dwell time of 1 s. Corundum (33% sample mass) was used as an internal standard. The samples were polished, ground, and hydration was stopped by soaking in isopropanol at a solid/liquid ratio of 1/50 (w/v) for 24 h with isopropanol refreshed every 8 h. Then, the treated paste powders were separated and dried under vacuum at 50 °C and sieved through 180-mesh. The test was conducted in 3 parallels; only results with standard deviation below 0.35 were accepted, or the sample was re-tested.
The pastes in SEM observations were prepared with 0.8% calcium carbonate substitution. After preparation and curing for the target time (12 h and 28 d), the samples were demolded and removed off the outer layer. Then, the samples were rapidly crushed into flakes of 3–5 mm and soaked in isopropanol at a solid/liquid ratio of 1/50 (w/v) for 72 h, with refreshment at every 24 h. Samples were then separated and dried in a vacuum at 40 °C. The tests were also conducted on a FEI Quanta 250 scanning electron microscope (FEI Co., Waltham, MA, USA) in a vacuum condition with a voltage of 15 kV.
The contact angle of the samples was tested on a Krüss DSA30E drop shape analyzer (Krüss Co., Hamburg, Germany). In the test, hardened paste cubes (40 × 40 × 40 mm3) of 14 d and 28 d were surface-polished (top, bottom and one of the side faces) and tested. The test was conducted on 4 evenly distributed points (at diagonals 14 mm to the center) on each face for data reliability.

3. Results

3.1. Preparation and Characterizations of AmphCC

XRD spectra of the samples are shown in Figure 3a. According to Figure 3a, the spectra of both HbCC and AmphCC showed typical peaks of calcite, indicating that treatment from the dispersant did not change the structure and composition of the calcium carbonate particle.
The calcium carbonate particles were then subjected to size analysis to evaluate the effect of dispersion. According to the results, the apparent size of HbCC in ethanol is about 4 μm, while in water it is barely dispersible, as can be seen in Figure 3c. Compared with HbCC, the degree of dispersion of AmphCC (Q50 = 4.8 μm) in water was improved to HbCC’s extent of dispersion in ethanol, as its apparent size in water dispersion reached the same level as HbCC. Additionally, in the Ca(OH)2 (CH) solution, the effectiveness did not seem to deteriorate, as size only increased slightly to 5.02 μm, offering a firm basis for application in cementitious materials. SEM images of the samples are shown in Figure 3d; as can be observed, the overall shape of the particles was similar, with AmphCC being slightly larger than HbCC, which is due to coating of the dispersant.
The time-lapse stability variation of AmphCC in the CH solution and comparison with other dispersants is demonstrated in Figure 4. As demonstrated, AmphCC showed the best resistance against sedimentation, with a 72 h relative concentration decline of less than 8%. In contrast, ionic-backboned PC showed little effect in HbCC dispersion, with a 12 h decline of over 85%. The poor performance is due to its highly hydrophilic structure. The dispersion effect of SDS and NPEO-10 was moderate, but still did not match AmphD. Between the two small-molecule dispersants, SDS’s performance was inferior due to side interaction with calcium ions in the solution, while NPEO-10 was limited by its size, making its binding force to HbCC particles less than AmphD and, thus, prone to desorb and destabilize. Additionally, the excessive air entraining effect of small-molecule surfactants may further impede the application potential of SDS and NPEO-10. The results from comparison tests confirmed the superior dispersion effect of AmphCC.

3.2. Effect of AmphCC on Durability

The impact of calcium carbonate particles on the durability of cement was investigated in the aspects of water adsorption and chloride permeation.
Water absorption of the mortar samples with a calcium carbonate addition is demonstrated in Figure 5. As can be seen from Figure 5, the long-term development on the amount of water adsorption was clearly affected by the addition of AmphCC, with long-term adsorption in samples with AmphCC addition considerably lower than the reference. Additionally, the effect of water resistance went up with AmphCC dosage, from 0%–0.8%, the water absorption lowered greatly, but from 0.8% to 1.5%, the effect was not as high.
Compared with AmphCC, the addition of unmodified HbCC did not improve the water penetration resistance of the mortar sample, and its water absorption was even higher than those of the blank reference, which was likely caused by its high hydrophobicity and poor dispersion. Additionally, the sample with the mere dispersant addition only showed a slight decrease in water absorption, which may be due to the lack of synergistic effect from the calcium carbonate particles.
To further investigate the effect of AmphCC on water adsorption, the water adsorption data was subjected to simulation via the following equations [33]:
ΔW = a [1 − exp (−bt0.5)]
Ai = ab
where ΔW is the water adsorption amount (m2/kg) at a certain time interval. a is a constant indicating saturation water adsorption and b is a constant indicating water absorption rate. t is the water-treating time, and Ai is an empirical coefficient indicating the overall water absorption affinity of the mortar sample.
The results are shown in Table 3. According to the results, the water absorption data is well described by the model, with correlation coefficients all above 0.99. Additionally, constants from the simulation are mainly consistent with the apparent observation of the data. The saturation absorption constant a in samples with the AmphCC addition was much lower than that of the reference and the sample with HbCC. The drop is probably due to the synergistic effect of pore-filling and microstructure hydrophobification. However, the absorption rate b was higher in those samples with AmphCC, but the overall water absorption coefficient Ai in AmphCC-modded samples was still lower than those without AmphCC.
The depth of Chloride permeation, as well as chloride concentration in the hardened mortars, was demonstrated in Table 4. As shown in Table 4, the penetration depth was greatly lowered by the addition of AmphCC. and the effect grew considerably from 0.3% to 0.8% dosage, but from 0.8% to 1.5%, the fall of the penetration depth was not as great, which is consistent with the water absorption data.
In contrast, the penetration depth of the sample with HbCC enjoyed no improvement but rather slight worsening. The poor effect was due to the aggregating status of HbCC in aqueous media. Also, the addition of the dispersant only slightly improved the chloride permeation resistance.
The free chloride content beneath the surface was also measured using titration. The results are shown in Figure 6. According to Figure 6, the chloride content declined slowly from the surface and diminished approximately at the edge of apparent penetration depth. Among the sample, samples with the AmphCC addition showed a decrease in both free chloride content and the diminishing point, further confirming its effectiveness. Additionally, the performance of HbCC and the dispersant was in agreement with the penetration depth experiments. The analysis result of the free chloride content was consistent with penetration depth.
The results from water absorption and chloride penetration clearly demonstrated the significance of better dispersion of AmphCC than the single addition of HbCC or the dispersant.
The contact angles of 14d and 28 d samples are shown in Figure 7. As Figure 7 suggests, the contact angles of AmphCC-added samples showed an evident increase at 14 d, and the increase was further enhanced at 28 d, while the contact angle of the reference only showed a slight elevation. Compared with AmphCC, HbCC did not show a comparable effect, and the variation of test parallels (as the error bar indicates) in the HbCC-added sample was greater, which is likely due to its poor dispersity in water. The poor dispersity caused effect loss and paste inhomogeneity. The dispersant, despite displaying a very high contact angle at 14 d, showed little further increase at 28 d. The data trend of the sample with only dispersant is due to its relatively fast hydrolyzation, as it is in free form instead of being adsorbed in CC particles. The fast hydrolyzation and resultant hydration inhibition can also explain the poor strength and unsatisfactory penetration resistance in previous results.

3.3. Impact on Strength

The impact of the calcium carbonate particles on mortar strength was assessed to evaluate its effect on macroscopic performance. According to the results that were listed in Table 4, the introduction of AmphCC did not affect the development of early strength, while samples with HbCC and the dispersant experienced a considerable 1 d strength loss. As for 28 d strength, the AmphCC addition also had little adverse effect on the mortar samples, as the strength drop in all AmphCC modded samples was below 10%. While HbCC and mere introduction of the dispersant caused a notable drop of later-age strength, which was 22% and 17%, respectively. The drop may be due to the poor dispersion of the former and inhibition of the hydration process of the latter [34,35].
Overall, according to strength test results, the introduction of AmphCC had little negative impact on later age strength, which is very beneficial for its application potential.

3.4. Impact on Microstructure and Phase Composition

Hardened paste samples were subjected to XRD and SEM characterizations for further information on the mechanism. The XRD spectra and relevant phase analysis are shown in Figure 8a and Table 5; standard deviations of the phase analysis results are below 0.35. According to the results, the calcium hydroxide (CH) content of the AmphCC-added samples showed a slight decreasing trend. The lowered CH content is likely due to the reaction with hydrolysable contents at the highest dosage. The tricalcium silicate (C3S) content of AmphCC-added samples showed a mild increasing trend, indicating mild inhibition of hydration, which corresponds to the slight strength decrease. As for HbCC and the dispersant, a clear drop in CH content and a rise in C3S content could be observed, which is evidently due to hydration inhibition. The indifference in the hydration product content in the AmphCC-added samples is consistent with what strength tests found.
SEM images of the samples are shown in Figure 8b; the microstructure morphology of the samples can be observed in the images. As can be observed, the introduction of AmphCC evidently densified the microstructure of the paste sample, especially in the sample with 1.5% AmphCC addition. Whereas in samples with HbCC and the dispersant, no densification was observed but rather more cracks and voids.

4. Discussion

According to the above results, AmphCC exhibited a fine effect on water and chloride permeability decrease; it also had little adverse effect on strength development. Whereas the unmodified HbCC and a simple addition of the dispersant could not achieve equivalent performances. The reason for the superior performance of AmphCC on durability enhancement may arise from its synergistic effect from both the dispersant and calcium carbonate particles.
As demonstrated in Figure 9, due to its surface oleic acid coating, HbCC is hydrophobic and barely dispersible in water. The higher agglomeration tendency and poor dispersion of HbCC in aqueous media cause it to appear as large agglomerates in cement paste; the agglomerates are unable to enter capillary pores in hardened structures. Additionally, the loose assembly of the HbCC agglomerate would further deteriorate strength. As for the dispersant, without proper binding to particles, it would present as free molecules in a cement pore solution, leading to quick hydrolysis and early release of laurinols, which can hamper early hydration and, thus, strength development. Additionally, excessive air entrainment brought about by the large number of free molecules is also undesired.
Compared with the single components, The calcium carbonate particles in AmphCC are well dispersed by the amphiphilic dispersant; the small apparent size allowed it to enter capillary pores and exert a filling effect. Additionally, since most of the dispersant is bound to calcium carbonate particles, free molecules are few, and the hydrolysis of the molecules is more controlled, and undesired air entraining is also reduced. Therefore, the combination of HbCC and the dispersant avoided the adverse aspects of each other and showed a synergistic effect on cement durability improvement.

5. Conclusions and Research Perspective

In this work, hydrophobic calcium carbonate nanoparticles (HbCC) were dispersed with the help of a novel amphiphilic dispersant. The degree of dispersion of the resultant calcium carbonate particle (AmphCC) was greatly improved, and its dispersion showed little impact in the saturate Ca(OH)2 solution.
According to the results from durability tests, the AmphCC particles showed a pronounced effect on improving permeation resistance of cement mortars. The water absorption of samples with the AmphCC addition was lowered and the process was also slowed down. The absorption behavior fitted well to the exponential model. Furthermore, the addition of AmphCC enhanced the cement mortar’s resistance to chloride penetration, with the penetration depth and chloride content both decreasing and contact angle of AmphCC samples evidently increasing.
Moreover, the introduction of AmphCC in cement did not show a significant adverse effect on strength development. Compared with AmphCC, a single addition of the unmodified HbCC and the dispersant cannot achieve equivalent effects, as control experiments suggest. The superior effect of AmphCC is due to the synergistic effect of good particle dispersion and controlled release of the hydrophobic molecules, which are achieve by dispersion of HbCC with binding of the dispersant.
In summary, this study provides a perspective for cement durability improvement by synergistic microstructure modification from amphiphilic nanocomposites. Compared with other nanomaterials such as nano silica, the amphiphilic nano calcium carbonate and the modification method in this study are more convenient to conduct on an industrial scale, since nano silica is prone to agglomeration and gelation (water dispersion) and its modification process is usually more complicated.
Still, there are some aspects that need further study and improvement, such as a full mitigation of the hydration inhibition effect. Despite being much milder than the unmodified reference in hydration inhibition, the AmphCC modified samples still experienced a slight strength loss. Maintaining strength in the application of microstructure hydrophobicizing agents is significant for future researches.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/coatings12101431/s1, Text S1: Preparation of the dispersant.

Author Contributions

Conceptualization, H.Y., X.S. and Q.R.; methodology, H.Y., Y.Y., D.Z., L.C. and X.S.; investigation, H.Y., D.Z. and Y.Y.; writing—original draft preparation, H.Y.; writing—review and editing, H.Y. and X.S.; supervision, Q.R.; All authors have read and agreed to the published version of the manuscript.

Funding

This research was supported by Natural Science Foundation of China (Grant No. 51902142), and National Science Fund for Distinguished Young Scholars (51825203).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Conflicts of Interest

The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or in the decision to publish the results.

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Coatings 12 01431 g001 550
Figure 1. Molecular structure of the dispersant, m/n = 2/1, p = ~12, Mw = 8 × 103 g/mol, PDI = 1.43, conversion = 92.1%.
Figure 1. Molecular structure of the dispersant, m/n = 2/1, p = ~12, Mw = 8 × 103 g/mol, PDI = 1.43, conversion = 92.1%.
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Coatings 12 01431 g002 550
Figure 2. Mechanism of the dispersion process of AmphCC.
Figure 2. Mechanism of the dispersion process of AmphCC.
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Coatings 12 01431 g003 550
Figure 3. Characterization of the calcium carbonate samples, XRD spectra (a), particle size distribution (b), macroscopic view in Ca(OH)2 solution (c) and SEM images (d).
Figure 3. Characterization of the calcium carbonate samples, XRD spectra (a), particle size distribution (b), macroscopic view in Ca(OH)2 solution (c) and SEM images (d).
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Figure 4. Relative concentration decline of HbCC dispersions with different dispersants.
Figure 4. Relative concentration decline of HbCC dispersions with different dispersants.
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Figure 5. Water absorption of hardened mortar samples with AmphCC addition.
Figure 5. Water absorption of hardened mortar samples with AmphCC addition.
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Figure 6. Free chloride content distribution from the surface of samples with the AmphCC addition after 56 d chloride treatment.
Figure 6. Free chloride content distribution from the surface of samples with the AmphCC addition after 56 d chloride treatment.
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Figure 7. Contact angles of the hardened paste samples.
Figure 7. Contact angles of the hardened paste samples.
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Coatings 12 01431 g008a 550Coatings 12 01431 g008b 550
Figure 8. XRD spectra (a) and SEM images (b) of the hardened paste samples, the scale bar in subfigure b applies to all the sub-images.
Figure 8. XRD spectra (a) and SEM images (b) of the hardened paste samples, the scale bar in subfigure b applies to all the sub-images.
Coatings 12 01431 g008aCoatings 12 01431 g008b
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Figure 9. Mechanism illustration of the effect of AmphCC.
Figure 9. Mechanism illustration of the effect of AmphCC.
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Table
Table 1. Composition of the P I 42.5 cement used in this study.
Table 1. Composition of the P I 42.5 cement used in this study.
CompoundContent (m%)
SiO220.90
Al2O34.65
CaO61.73
MgO2.20
Fe2O32.85
SO33.03
K2O0.73
Na2O0.13
Total96.22
Surface Area325 m2/kg
Table
Table 2. Dispersants that were used in CC dispersion comparison tests.
Table 2. Dispersants that were used in CC dispersion comparison tests.
DispersantStructure/FormulaNote
The Amphiphilic dispersant (AmphD)Coatings 12 01431 i001The dispersant that is used in this study
Polycarboxylate (PC)Coatings 12 01431 i002Ionic comb dispersant, m, n and p are the same as the amphiphilic one, preparation based on [30].
Sodium dodecyl sulfonate (SDS)C12H25SO3NaTypical ionic small-molecule dispersant
Nonyl phenyl polyoxy ethylene ether (NPEO-10)C9H19C6H5O(CH2CH2O)10HTypical non-ionic small-molecule dispersant
Table
Table 3. Simulation results of water adsorption of mortar samples with the AmphCC addition.
Table 3. Simulation results of water adsorption of mortar samples with the AmphCC addition.
SampleDosage (%)abAiR2
Ref.--28.680.160.470.9989
AmphCC0.318.410.230.420.9976
0.812.210.350.420.9974
1.510.320.410.420.9979
HbCC0.827.230.180.480.9991
Dispersant0.2724.300.180.450.9987
Table
Table 4. Penetration depth of chloride and strength results of the mortar samples.
Table 4. Penetration depth of chloride and strength results of the mortar samples.
SampleDosage (%)Penetration Depth (mm)Strength (MPa)
28 d56 d1 d28 d
Ref.--16.3 ± 0.119.7 ± 0.113.72 ± 0.4046.08 ± 1.00
AmphCC0.312.6 ± 0.114.3 ± 0.112.76 ± 0.4044.67 ± 1.00
0.811.0 ± 0.112.3 ± 0.113.23 ± 0.4043.72 ± 1.00
1.510.5 ± 0.111.7 ± 0.113.25 ± 0.4042.57 ± 1.00
HbCC0.817.1 ± 0.121.1 ± 0.110.78 ± 0.4036.02 ± 1.00
Dispersant0.2714.7 ± 0.117.6 ± 0.111.52 ± 0.4038.30 ± 1.00
Table
Table 5. Phase content of the paste samples from XRD calculation.
Table 5. Phase content of the paste samples from XRD calculation.
SampleDosage (%)CH%C3S%
Ref.--15.266.30
AmphCC0.315.226.22
0.815.056.81
1.514.826.92
HbCC0.814.707.55
Dispersant0.2714.178.10
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Yan, H.; Shu, X.; Zhou, D.; Yang, Y.; Chen, L.; Ran, Q. Durability Improvement of Cement Using Amphiphilic Calcium Carbonate Nanoparticles. Coatings 2022, 12, 1431. https://doi.org/10.3390/coatings12101431

AMA Style

Yan H, Shu X, Zhou D, Yang Y, Chen L, Ran Q. Durability Improvement of Cement Using Amphiphilic Calcium Carbonate Nanoparticles. Coatings. 2022; 12(10):1431. https://doi.org/10.3390/coatings12101431

Chicago/Turabian Style

Yan, Han, Xin Shu, Dongliang Zhou, Yong Yang, Lu Chen, and Qianping Ran. 2022. "Durability Improvement of Cement Using Amphiphilic Calcium Carbonate Nanoparticles" Coatings 12, no. 10: 1431. https://doi.org/10.3390/coatings12101431

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