Materiales de Construcción 74 (355)
ISSN-L: 0465-2746, eISSN: 1988-3226
https://doi.org/10.3989/mc.2024.371123

Effect of pre-wetting treatment for waste waterglass foundry sand on the properties of alkali-activated slag

Efecto del pretratamiento de humectación del residuo de arena procedente de la fundición de vidrio en las propiedades de la escoria activada alcalinamente

 

1. INTRODUCTION

 

With the increasing demand for machines and equipment around the world, the foundry industry is in a flourishing period. About 112.7 million tons of metal castings were produced worldwide in 2018 (1AshishDK, VermaSK. 2021. Robustness of self-compacting concrete containing waste foundry sand and metakaolin: A sustainable approach. J. Hazard Mater.401: 123329. 10.1016/j.jhazmat.2020.123329), and this figure will exceed 120 million tons in the next decade. Casting production generates a large amount of waste foundry sand (WFS), even if recycled in the production process, it still yields 600 kg of WFS per ton of casting produced (2DyerPPOL, de LimaMG, KlinskyLMG, SilvaSA, CoppioGJL. 2018. Environmental characterization of Foundry Waste Sand (WFS). in hot mix asphalt (HMA. mixtures. Constr. Build. Mater. 171:474-484. 10.1016/j.conbuildmat.2018.03.151). Normally, WFS is classified into green sand and chemically bonded foundry sand, the latter is quartz sand bound together by chemical binders such as waterglass, phenolic-urethanes, epoxy-resins and furfur alcohol (3ParasharA, AggarwalP, SainiB, AggarwalY, BishnoiS. 2020. Study on performance enhancement of self-compacting concrete incorporating waste foundry sand. Constr. Build. Mater.251:118875. 10.1016/j.conbuildmat.2020.118875-5SiddiqueR, SchutterGd, NoumoweA. 2009. Effect of used-foundry sand on the mechanical properties of concrete. Constr. Build. Mater.23(2):976-980. 10.1016/j.conbuildmat.2008.05.005). Over the years, WFS has been dumped in landfills (6MashifanaT, SitholeT. 2020. Recovery of silicon dioxide from waste foundry sand and alkaline activation of desilicated foundry sand. J. Sustainable Metall. 6(4):700-714. 10.1007/s40831-020-00303-5-8MavroulidouM, LawrenceD. 2018. Can waste foundry sand fully replace structural concrete sand?. J. Mater. Cycles Waste Manage. 21(3):594-605. 10.1007/s10163-018-00821-1) due to its high alkaline and toxic compounds (9SitholeNT, TsotetsiNT, MashifanaT, SillanpääM. 2022. Alternative cleaner production of sustainable concrete from waste foundry sand and slag. J. Cleaner Prod.336:130399. 10.1016/j.jclepro.2022.130399-11ParkCL, KimBG, YuY. 2012. The regeneration of waste foundry sand and residue stabilization using coal refuse. J. Hazard. Mater.203-204:176-182. 10.1016/j.jhazmat.2011.11.100) that bring high treatment cost, which further contributes to soil and groundwater pollutions (12AhmadJ, AslamF, ZaidO, AlyousefR, AlabduljabbarH. 2021. Mechanical and durability characteristics of sustainable concrete modified with partial substitution of waste foundry sand. Struct. Concr.22(5):2775-2790. 10.1002/suco.202000830, 13IlohP, FanourakisG, OgraA. 2019. Evaluation of physical and chemical properties of South African Waste Foundry Sand (WFS). for Concrete Use, Sustainability. 11(1):193. 10.3390/su11010193).

Therefore, the question of how to dispose of and utilize these hard-to-handle WFS, while minimizing their impact on the environment and the economy, has attracted considerable attention. Considering that WFS is harmful to mechanical properties and durability when used as a fine aggregate in cement systems (14ManoharanT, LaksmananD, MylsamyK, SivakumarP, SircarA. 2018. Engineering properties of concrete with partial utilization of used foundry sand. Waste Manage. (Oxford). 71:454-460. 10.1016/j.wasman.2017.10.022-16GuneyY, SariYD, YalcinM, TuncanA, DonmezS. 2010. Re-usage of waste foundry sand in high-strength concrete. Waste Manage. (Oxford). 30(8-9):1705-1713. 10.1016/j.wasman.2010.02.018), and that low utilization (10-30%) is an obstacle to the effective use of WFS in concrete (17MynuddinS, MohanM, ReddyTI, Pratik ReddyN. 2018. Strength behavior of concrete produced with foundry sand as fine aggregate replacement. Int. J. Mod. Trends Eng. Sci.5(8):3476-3480. 10.13140/RG.2.2.29829.91367/1, 18MartinsMA, BarrosRM, da SilvaLRR, dos SantosVC, LintzRC, GachetLA, de Lourdes MeloM, MartinezCB. 2022. Durability indicators of high-strength self-compacting concrete with marble and granite wastes and waste foundry exhaust sand using electrochemical tests. Constr. Build. Mater.317:125907. 10.1016/j.conbuildmat.2021.125907), several researchers chose to use WFS in alkali-activated slag mortars (AASM). For example, Ferrazzo et al. (7FerrazzoST, AraújoMTd, BruschiGJ, ChavesHM, KorfEP, ConsoliNC. 2023. Mechanical and environmental behavior of waste foundry sand stabilized with alkali-activated sugar cane bagasse ash-eggshell lime binder. Constr. Build. Mater.383:131313. 10.1016/j.conbuildmat.2023.131313) found that substituting some of the sand with WFS, with sugar cane bagasse ash and hydrated eggshell lime as raw materials, AASMs were produced with higher strength, stiffness, and durability than ordinary Portland cement (OPC). Sabour et al. (19SabourMR, DerhamjaniG, AkbariM. 2022. Mechanical, durability properties, and environmental assessment of geopolymer mortars containing waste foundry sand. Environ. Sci. Pollut. Res. Int.29(16):24322-24333. 10.1007/s11356-021-17692-z) demonstrated that, compared to cement-based mortar, AASM containing treated WFS exhibited a 158% increase in compressive strength at 91 d. In addition, consistent with the trend of WFS in OPC, high substitution rates of WFS may not be beneficial to the development of compressive strength in AASM. Sithole et al. (9SitholeNT, TsotetsiNT, MashifanaT, SillanpääM. 2022. Alternative cleaner production of sustainable concrete from waste foundry sand and slag. J. Cleaner Prod.336:130399. 10.1016/j.jclepro.2022.130399) reported that concrete specimens with 40% slag binder, 30% WFS, and 30% crushed stones in the mixture had the highest unconfined compressive strength at 90 d, i.e., replacement of fine aggregates with more than 30% WFS impaired the unconfined compressive strength of concrete specimens. Bhardwaj et al. (20BhardwajB, KumarP. 2019. Comparative study of geopolymer and alkali activated slag concrete comprising waste foundry sand. Constr. Build. Mater.209:555-565. 10.1016/j.conbuildmat.2019.03.107) also found that in AASM, the mixture with a WFS replacement level of 20% exhibited the highest compressive strength. When the fine aggregate was completely substituted by WFS, the compressive strength was only 45% of the control group. Although the high substitution rate of WFS has a slight deficiency in mechanical properties, it is still implied that WFS shows great potential for application.

For waste waterglass foundry sand (WwFS), a type of WFS bonded by waterglass and hardened by carbon dioxide, the quantity of WwFS awaiting disposal is huge because of its simple preparation procedures. Recently, Fang et al. (21WangC, ChenP, XuY, ZhangL, LuoY, LiJ, WangY. 2022. Investigation on the utilization of spent waterglass foundry sand into Ca(OH)2-activated slag materials considering the coating layer of dried waterglass. Constr. Build. Mater.329:127180. 10.1016/j.conbuildmat.2022.127180, 22FangJ, XieJ, WangY, TanW, GeW. 2023. Alkali-activated slag materials for bulk disposal of waste waterglass foundry sand: A promising approach. J. Build. Eng.63(Part A):105422. 10.1016/j.jobe.2022.105422) discovered that one of the essential defects for the decreasing of compressive strength is a poor interface known as sandwich-like interface structure (WwFS-dried waterglass coating-pastes) between WwFS and the surrounding pastes. Although the WwFS interface has an important effect on the performance of concrete containing WwFS, it occupies only a small portion of the entire AASM system, and the dissolution and migration distance of SO32- in the dried waterglass layer is quite limited. Therefore, just focusing on improving the bonding of the interface of WwFS is far from sufficient to achieve the goal of enhancing the performance of AASM. In AASM, the formation of binding capacity is dependent on the temperature of WwFS treatment and the type of alkaline activator (23Fernández JiménezA, PalomoJG, PuertasF. 1999. Alkali-activated slag mortars: Mechanical strength behaviour. Cem. Concr. Res.29(8):1313-1321. 10.1016/S0008-8846(99)00154-4-25BakharevT, SanjayanJG, ChengY. 1999. Alkali activation of Australian slag cements. Cem. Concr. Res.29(1):113-120. 10.1016/S0008-8846(98)00170-7). Common alkaline activators such as NaOH, KOH, Na2SiO3 and K2SiO3 are used to activate slag. Under these highly alkaline conditions, alkaline activators facilitate the dissolution of slag and the reorganization of units such as (SiO4)- and (AlO4)-, which is the process of binder formation in AASM (26AbubakrAE, SolimanAM, DiabSH. 2020. Effect of activator nature on the impact behaviour of Alkali-Activated slag mortar. Constr. Build. Mater.257:119531. 10.1016/j.conbuildmat.2020.119531, 27KaiMF, LiG, YinBB, AkbarA. 2023. Aluminum-induced structure evolution and mechanical strengthening of calcium silicate hydrates: an atomistic insight. Constr. Build. Mater.393:132120. 10.1016/j.conbuildmat.2023.132120). Among them, the combination of NaOH and waterglass works effectively because of their synergistic coupling effect (28ZhangZ, JiaY, LiuJ. 2022. Influence of different parameters on the performance of alkali-activated slag/fly ash composite system. Materials. 15(8):2714. 10.3390/ma15082714, 29JinL, HuangG, LiY, ZhangX, JiY, XuZ. 2021. Positive influence of liquid sodium silicate on the setting time, polymerization, and strength development mechanism of MSWI bottom ash alkali-activated mortars. Materials. 14(8):1927. 10.3390/ma14081927). Huang et al. (29JinL, HuangG, LiY, ZhangX, JiY, XuZ. 2021. Positive influence of liquid sodium silicate on the setting time, polymerization, and strength development mechanism of MSWI bottom ash alkali-activated mortars. Materials. 14(8):1927. 10.3390/ma14081927) studied that when using both NaOH and liquid waterglass as activators, AASM showed rapid coagulation and high strength. And he also pointed out that the combination of NaOH and waterglass would not affect their respective excitation effects, but rather be mutually reinforcing. Compared to activating the slag with NaOH alone, the addition of waterglass could be beneficial in providing extra SiO32- to the pore solution, which reacts with the dissolved ions from slag to form C-(A)-S-H gels with high hydration level (22FangJ, XieJ, WangY, TanW, GeW. 2023. Alkali-activated slag materials for bulk disposal of waste waterglass foundry sand: A promising approach. J. Build. Eng.63(Part A):105422. 10.1016/j.jobe.2022.105422).

Considering the additional alkaline environment provided by the dried waterglass coating, and its great limitation on the development of strength, this paper proposes utilizing different times and temperatures of the pre-wetted WwFS for preparing AASM. During the hydration process of AAS, the dried waterglass layer needs to absorb water from the pore solution before releasing it as needed to facilitate the transfer of ions such as Al and Si and the polycondensation of oligomers (30LiW, LemougnaPN, WangK, HeY, TongZ, CuiX. 2017. Effect of vacuum dehydration on gel structure and properties of metakaolin-based geopolymers. Ceram. Int.43(16):14340-14346. 10.1016/j.ceramint.2017.07.190). The addition of pre-wetted WwFS allows the water absorption step to be skipped, providing water more directly and efficiently for the hydration of slag. Subsequently, the solubility of waterglass increased with the rise in pre-wetting temperature, leading to the dissolution and release of more SiO32- from the wetted waterglass layer into the mixing water, activating the bonding potential of the paste matrix in a broader and more homogeneous manner. The dissolved waterglass layer became thinner, weakening the defects of the sandwich structure, and the residual waterglass layer could still play a role in improving the interface. In addition, the waterglass coating of WwFS works as a necessary co-activator to activate slag together with NaOH, resulting in strength enhancement. In this paper, the effect of wet WwFS on the performances of AAS, such as fluidity, compressive strength, flexural strength, scanning electron microscopy (SEM), pore structure and micromechanical properties, was investigated. The significant contribution of this paper is the direct use of wet WwFS as a raw material for the preparation of AAS, unlike other studies focusing on dry WwFS, with a special focus on the interfacial properties between WwFS and paste as well as the waterglass coating in the sandwich-like microstructures. Meanwhile, the effect of the interfacial properties of wet WwFS on the micromechanical properties of AAS was investigated, and the nanoindentation test provided more accurate information for the study of the different phase regions in the microstructure of AAS, which has not yet been addressed in previous studies on dry WwFS. The findings of this research can offer a theoretical foundation for the disposal and utilization of WwFS for application in construction materials, thus contributing to the sustainable development of the city.

2. MATERIALS AND METHODS

 

2.1. Materials

 

Shandong Kang Crystal New Material Co., Ltd. provided ground granulated blast slag (GGBS) that met S105 grade standards. The chemical composition, density and BET area of GGBS are shown in Table 1 and the particle size distribution of GGBS is presented in Figure 1. Both the aggregates for AASM and the raw materials for WwFS use quartz sand with a particle size of 380-830 μm and a chemical composition of 99% SiO2, which is milky white or colourless and translucent. The waterglass, model SP38, has a modulus of about 3.3 and was bought from Jiashan Yourui Refractory Co., LTD. Analytically pure KOH and NaOH were supplied from Tianjin Hengxing Chemical Reagent Manufacturing, Co., Ltd.

Table1 The density, BET area, and chemical composition of GGBS / %. 
Density (kg/m3)BET area (m2/g)Chemical composition / %
CaOSiO2Al2O3MgOFe2O3TiO2K2OOther
2800153543.826.418.34.81.10.90.83.9
media/0673faf8e574476692eed61e8528b273_charts_001.png
  
Figure 1 Particle size of GGBS. 

2.2. Preparation of WwFS

 

The production of WwFS is usually higher in industrial production because the use of waterglass in the foundry process is more common. Waterglass is an inorganic cementitious material commonly used as a binder to bind sand grains during the casting process to form the casting model. WwFS are usually subjected to a high temperature thermal field during the casting process, and the shells are heated differently due to the location of the casting, creating a temperature gradient. Using a typical WwFS treated at 100°C guarantees consistency in the treatment temperature of the waterglass layer. According to Fang (22FangJ, XieJ, WangY, TanW, GeW. 2023. Alkali-activated slag materials for bulk disposal of waste waterglass foundry sand: A promising approach. J. Build. Eng.63(Part A):105422. 10.1016/j.jobe.2022.105422) et al. that real WwFS usually contain more impurities, such as metallic elements and organic matter, which may affect the hydration process of AAS pastes. To ensure that the experiments were controlled, reproducible, and to avoid the influence of impurities such as metallic elements and organics, this study chose not to use actual waste samples, but to use laboratory-prepared WwFS samples and apply them to the AAS system.

In a Harbor mixer, quartz sand, waterglass, and KOH were mixed together for three minutes at a mass ratio of 100: 5: 2, as per Ref (21WangC, ChenP, XuY, ZhangL, LuoY, LiJ, WangY. 2022. Investigation on the utilization of spent waterglass foundry sand into Ca(OH)2-activated slag materials considering the coating layer of dried waterglass. Constr. Build. Mater.329:127180. 10.1016/j.conbuildmat.2022.127180). Then, pure CO2 was injected into the mixture for 10 mins at 5 L/min. After hardening, the mixture was cracked and dried at 100°C for 24 h to prepare WwFS, which was synthesized as shown in Figure 2. Also, WwFS with a particle size of 380-830 μm was selected to keep the same particle size as that of the quartz sand.

media/0673faf8e574476692eed61e8528b273_002.png
  
Figure 2 WwFS preparation process. 

As shown in Figure 3b, compared with the sharp-edged and smooth-surfaced quartz sand (Figure 3a), the surface of WwFS is encapsulated with a thicker layer of dry waterglass, which is mainly composed of Na2CO3, sodium silicate gel, and a small amount of KOH (31QiuY, PanH, ZhaoQ, ZhangJ, ZhangY, GuoW. 2022. Carbon dioxide-hardened sodium silicate-bonded sand regeneration using calcium carbide slag: The design and feasibility study. J. Environ. Chem. Eng.10(3):107872. 10.1016/j.jece.2022.107872). The width of the waterglass layer is about 1-5 μm. WwFS is composed of quartz sand and the waterglass layer on the surface, so its chemical composition is mainly SiO2, Na2SiO3, Na2CO3 and a small amount of KOH. Figure 4 displays the particle size distribution of quartz sand and WwFS analyzed with the Malvern Mastersizer 2000 particle size analyzer. Obviously, the volume of WwFS is higher in the range of 760-1450 μm, while the volume of small (380-760 μm) and large (1450-2000 μm) particle sizes decreases. This may be explained by the mixing, hardening and crushing processes that increase the grain size of small particles and the damage to large sand sizes.

media/0673faf8e574476692eed61e8528b273_003.png
  
Figure 3 SEM images of (a) quartz sand and (b) WwFS. 
media/0673faf8e574476692eed61e8528b273_004.png
  
Figure 4 Particle size distribution of quartz sand and WwFS. 

The SiO32- released from the waterglass coating of WwFS has an important effect on the hydration of AASM. To evaluate the dissolution characteristics of WwFS, the absorbance of Si at 648 nm (32JiangZ, LiJ, LiW. 2019. Preparation and characterization of autolytic mineral microsphere for self-healing cementitious materials. Cem. Concr. Compos.103:112-120. 10.1016/j.cemconcomp.2019.04.004) was tested according to the method of Wang et al (21WangC, ChenP, XuY, ZhangL, LuoY, LiJ, WangY. 2022. Investigation on the utilization of spent waterglass foundry sand into Ca(OH)2-activated slag materials considering the coating layer of dried waterglass. Constr. Build. Mater.329:127180. 10.1016/j.conbuildmat.2022.127180). Silicate standard solutions of 0, 2, 4, 8, 12, 16 and 20 mg/L were made up using Na2SiO3·9H2O and deionized water. Using a 752UV-VIS spectrophotometer, the absorbance of the standard solution was measured. The final standard curve is shown in Equation (1AshishDK, VermaSK. 2021. Robustness of self-compacting concrete containing waste foundry sand and metakaolin: A sustainable approach. J. Hazard Mater.401: 123329. 10.1016/j.jhazmat.2020.123329) and presented in Figure 5.

A=0.0313C0.0007 [1]  

Where, C is the concentration of Si and A is the absorbance of the solution.

media/0673faf8e574476692eed61e8528b273_005.png
  
Figure 5 Fitting chart of absorbance of silica at different concentrations. 

Testing solutions were collected at 1, 3, 6, and 24 hours by adding 500 g of WwFS20 or WwSF70 to 500 mL of deionized water, respectively. The absorbance and silicate concentration of each solution are shown in Table 2. This suggested that the dissolution rate of WwFS70 is obviously higher than that of WwSF20, which may influence the hydration and mechanical properties of AASM.

Table 2 Absorbance and concentration of silicate of WwFS solution. 
TimeWwFS20WwFS70
AbsorbanceConcentration of silicate (mg/L)AbsorbanceConcentration of silicate (mg/L)
1h0.1605.130.38612.36
3h0.2728.720.89328.54
6h0.32510.411.23939.62
24h0.47115.081.31942.17

2.3. Mix proportion and sample preparation

 

Six mixtures were designed to explore the influence of the pre-wetting methods of WwFS on AASM performance, 0.55 was the ratio of activator to binder. As shown in Table 3, dried WwFS was used to replace all of the quartz sand in WwFS1. WwFS20 and WwFS70 represent WwFS immersed in water at 20°C and 70°C, respectively. The last number in the designation denotes the time that WwFS was immersed in water. Also, WwFS701, WwFS703 and WwFS706 can be considered as the experimental groups, and the other three groups as the control groups.

Fresh AAS mortars were prepared by the following process. Initially, NaOH was weighed and added into the water and mixed to exotherm it to room temperature, then WwFS was added and soaked for different times at two temperatures. Dry materials were mixed for three minutes using a Harbor mixer, and then wet materials (water for soaking WwFS and wet WwFS) were added and mixed for 3 mins. Two groups, WwFS0 and WwFS1, directly mixed slag, NaOH solution and sand for three minutes.

Table 3 Mixing proportions of mortars / kg/m3
MixturesGGBSWaterNaOHWwFSQuartz Sand
WwFS0322.6177.416.640500
WwFS1322.6177.416.645000
WwFS2024322.6177.416.645000
WwFS701322.6177.416.645000
WwFS703322.6177.416.645000
WwFS706322.6177.416.645000

2.4. Test methods

 
2.4.1. Fluidity
 

A STNLD-3 fluidity tester was used to measure the fluidity of AASM in compliance with ASTM C1437 (33ASTM C1437. 2020. Standard test mrthod for flow of hydraulic cement mortar. ASTM International, West Conshohocken, PA. Retrieved fromhttps://www.astm.org/.). Three samples of each mixture were tested and averages were given.

2.4.2. Compressive strength
 

According to ASTM C192 (34Burciaga DíazO, Betancourt CastilloI. 2018. Characterization of novel blast-furnace slag cement pastes and mortars activated with a reactive mixture of MgO-NaOH. Cem. Concr. Res.105:54-63. 10.1016/j.cemconres.2018.01.002), fresh mortar was formed in cubic molds of 50 mm size and after vibration the specimens were continuously cured for 3d, 7d and 28d. Finally, three specimens of above age were selected for compressive strength testing.

2.4.3. Flexural strength
 

The flexural strength of AASM was measured according to ASTM C348 (35ASTM C348-18. 2018. Standard test method for flexural strength of hydraulic-cement mortars. ASTM International, West Conshohocken, PA. Retrieved fromhttps://www.astm.org.). In addition, three samples were selected at each age, and the test ages were 3, 7, and 28 days, respectively.

2.4.4. Mercury intrusion porosimetry
 

The pore structure of AASM was analyzed at 28 days using an AutoPore IV 9510 mercury intrusion porosimetry (MIP) analyzer. Test samples were collected from flexural strength testing.

2.4.5. Microstructure analysis
 

Using a Flex1000 scanning electron microscopy (SEM), the effect of different pre-wetting methods upon the microstructure of AASM was investigated.

2.4.6. Grid nanoindentation
 

Nanoindentation testing was used to examine the mechanical property of ITZ in the microstructure between WWFS and pastes. First, the samples were cut after testing for flexural strength at 28d and cast into a capsule of 30 mm diameter epoxy resin. The specimens were smoothed with 400, 800 and 1200 grit SiC sandpaper by using a Buehler AutoMet250 Pro polisher, followed by polishing of the specimens with 6 µm, 3 µm and 1 µm diamond suspensions on felt. The KLA-iMicro nanoindenter was used to make 121 indentations in an 11 × 11 grid with a spacing of 10 µm and 231 indentations in an 11 × 21 grid with a spacing of 10 µm. Figure 6 shows the region of 231 indentations covering the aggregate (quartz sand or WwFS) at the bottom of the figure and AAS paste at the top.

media/0673faf8e574476692eed61e8528b273_006.png
  
Figure 6 Nanoindentation region of AASM. 

The indentation process involved a linear increase in load to 1 mN, achieved through multiple partial unloading steps, followed by a 2 s period of load stability, and eventually a linear decrease to zero over 5 seconds. It was assumed that the Poisson ratio of the prepared specimens was 0.18. To address concerns related to creep, surface roughness, and size effects, each indentation underwent multiple cycles of partial loading and unloading, as recommended in the literature (36MondalP. 2008. Nanomechanical properties of cementitious materials. Northwestern UniversityProQuest Dissertations Publishing.). For every indentation, the stiffness was calculated using a specific unloading phase that varied from 95% to 50% of the maximum load. The method for calculating the elastic modulus of the indentation was in accordance with the approach detailed in the literature (37XieJ, ChenP, LiJ, XuY, FangY, WangA, WangJ. 2022. Directly upcycling copper mining wastewater into a source of mixing water for the preparation of alkali-activated slag materials. Process Saf. Environ. Prot.168:362-371. 10.1016/j.psep.2022.10.011).

3. RESULTS AND DISCUSSION

 

3.1. Fluidity of mortars

 

The fluidity of AAS mortars is shown in Figure 7. It is clear that the use of dried WwFS to replace quartz sand reduces the flow of the mortar by 12.7% compared to WwFS0. WwFS is fine and porous and has a larger specific area than quartz sand (12AhmadJ, AslamF, ZaidO, AlyousefR, AlabduljabbarH. 2021. Mechanical and durability characteristics of sustainable concrete modified with partial substitution of waste foundry sand. Struct. Concr.22(5):2775-2790. 10.1002/suco.202000830, 38MartinsMAB, da SilvaLRR, RanieriMGA, BarrosRM, Dos SantosVC, GoncalvesPC, RodriguesMRB, LintzRCC, GachetLA, MartinezCB, MeloM. 2021. Physical and chemical properties of waste foundry exhaust sand for use in self-compacting concrete. Materials. 14(19):5629. 10.3390/ma14195629), which increases the water required for particle lubrication and, thus, reduces the fluidity of the mortar. When WwFS2024 was added, the fluidity of the AAS mortar increased by 10.4%, in comparison to WwFS1. Since the water absorbed by WwFS can participate in the lubrication between particles (39AshishDK, VermaSK, JuM, SharmaH. 2023. High volume waste foundry sand self-compacting concrete – Transitioning industrial symbiosis. Process Saf. Environ. Prot.173:666-692. 10.1016/j.psep.2023.03.028), the fluidity of the mortar increases. Furthermore, the fluidities of all WwFS70-added AAS mortars were lower than that of WwFS1, and the longer the pre-wetting time, the lower the fluidity. Specifically, with increasing the pre-wetting time from 1 h to 6 h, the fluidity decreased by 2.1% to 29.2% compared to WwFS1. The decrease in the fluidity of WwFS70-incorporated mortars may indicate that the presence of WwFS accelerated the early hydration of AASM. It could be attributed to the properties of WwFS, as WwFS70 is not only rich in hydrophilic silica (40ŞahmaranM, LachemiM, ErdemTK, YücelHE. 2010. Use of spent foundry sand and fly ash for the development of green self-consolidating concrete. Mater. Struct.44(7):1193-1204. 10.1617/s11527-010-9692-7), but also WwFS70 is coated with high silica modulus waterglass and KOH, which may release OH- during the process of hot-water immersion to increase the pH conditions of pore solutions (41LiuQ, ZhangJ, SuY, LüX. 2021. Variation in polymerization degree of C-A-S-H gels and its role in strength development of alkali-activated slag binders. Journal of Wuhan University of Technology-Mater. Sci. Ed.36(6):871-879. 10.1007/s11595-021-2281-z). The increased alkalinity in AAS system may accelerate the dissolution process of GGBS and promote the polycondensation of flocculated products (42CihangirF, ErcikdiB, KesimalA, DeveciH, ErdemirF. 2015. Paste backfill of high-sulphide mill tailings using alkali-activated blast furnace slag: Effect of activator nature, concentration and slag properties. Miner. Eng.83:117-127. 10.1016/j.mineng.2015.08.022). Consequently, higher alkaline conditions result in a faster rate of generation of hydration products, which decreases the fluidity of AASM (43ZhuZ, XuX, LiuR, LiuP, TangH, GongY, ZhangC, LiX, LiuY, BaiJ, ChenM. 2023. Feasibility study of highly alkaline biomass ash to activate alkali-activated grouts. Constr. Build. Mater.393:132067. 10.1016/j.conbuildmat.2023.132067).

media/0673faf8e574476692eed61e8528b273_charts_007.png
  
Figure 7 Fluidity of AASM. 

3.2. Compressive strength

 

The compressive strength of AAS mortars is depicted in Figure 8. When WwFS was used to replace all quartz sand, the compressive strength of AASM at all ages increased significantly by 22.1% to 30.8% compared to WwFS0. This may be attributed to the dried waterglass layer that can release a small amount of SiO32- into AAS paste, providing an additional source of Si for the formation of hydration products (44KaiMF, SanchezF, HouDS, DaiJG. 2023. Nanoscale insights into the interfacial characteristics between calcium silicate hydrate and silica. Appl. Surf. Sci.616:156478. 10.1016/j.apsusc.2023.156478). The compressive strength of WwFS2024 was reduced at all ages compared to WwFS1. This suggests that the water absorbed by wet WwFS increased the local w/b ratio of AASM (45LiuK, YuR, ShuiZ, YiS, LiX, LingG, HeY. 2020. Influence of external water introduced by coral sand on autogenous shrinkage and microstructure development of Ultra-High Strength Concrete (UHSC). Constr. Build. Mater.252:119111. 10.1016/j.conbuildmat.2020.119111), although the water released from pre-wetted WwFS may have contributed to the hydration of the slag, but high w/b dominated the negative effect on compressive strength. When incorporating WwFS70 into AASM, the compressive strength of AAS mortars was higher than that of WwFS1 and WwFS0 at all ages. As the pre-wetting time increased from 1 h to 6 h, the compressive strength of WwFS70 increased by 4.5~10.7% at 3d, 3.7~14.2% at 7d, and 1.3~10.0% at 28d, in comparison with WwFS1. This finding is associated with the dissolution of the waterglass coating with high solubility and the release of ions. Pre-wetting WwFS in hot water dissolved and released more SiO32- from the wetted waterglass layer into the mixing water, not just confined around the WwFS, but in a broader and more homogeneous way activating the binding potential of the paste matrix. Moreover, WwFS70 could release SiO32- and some KOH from the WwFS coating on the quartz particles into the pore solution, working as an auxiliary activator and forming a synergistic activating effect with NaOH on GGBS. Based on previous research by Wang et al. (21WangC, ChenP, XuY, ZhangL, LuoY, LiJ, WangY. 2022. Investigation on the utilization of spent waterglass foundry sand into Ca(OH)2-activated slag materials considering the coating layer of dried waterglass. Constr. Build. Mater.329:127180. 10.1016/j.conbuildmat.2022.127180), the dried waterglass coating of WwFS could be a primary limiting factor in AASM compressive strength development. However, the waterglass layer of WwFS dissolved in hot water became thinner, weakening the defects of the sandwich structure, while the residual waterglass layer still played a role in improving the bonding between aggregate and paste (46BasarHM, Deveci AksoyN. 2012). The effect of waste foundry sand (WFS. as partial replacement of sand on the mechanical, leaching and micro-structural characteristics of ready-mixed concrete. Constr. Build. Mater.35:508-515. 10.1016/j.conbuildmat.2012.04.078, 47Ganesh PrabhuG, HyunJH, KimYY. 2014. Effects of foundry sand as a fine aggregate in concrete production. Constr. Build. Mater.70:514-521. 10.1016/j.conbuildmat.2014.07.070). Hence, more hydration products could be generated in the interfacial transition zone (ITZ), resulting in a denser ITZ between WwFS and the surrounding paste, thus increasing the compressive strength of AASM.

media/0673faf8e574476692eed61e8528b273_charts_008.png
  
Figure 8 Compressive strength of AASM. 

3.3. Flexural strength

 

The flexural strength of AAS mortars is presented in Figure 9. It is clear that the development trend of flexural strength is similar to that of compressive strength of AAS mortars with different pre-wetted WwFS treatment methods. The flexural strength of WwFS1 is higher than that of WwFS0 by approximately 16.2~20.0% at all ages. Although the flexural strength of WwFS2024 is lower than that of WwFS1 due to its high w/b, it is still higher than the flexural strength of WwFS0. In addition, the flexural strength of mortar at all ages increases with the increase of soaking time when the pre-wetting temperature of treated WwFS is kept at 70°C. At 28d, the flexural strength of WwFS70 is increased by 3.1~18.3% compared to WwFS0, where WwFS706 possesses the highest flexural strength. The increase in flexural strength is attributed to the waterglass coating on WwFS70, which is highly soluble as shown in Table 2. WwFS can release SiO32- into the pore solution around the paste, providing additional Si species for the generation of hydration products (48PuertasF, PalaciosM, ManzanoH, DoladoJ, RicoA, RodríguezJ. 2011. A model for the CASH gel formed in alkali-activated slag cements. J. Eur. Ceram. Soc.31(12):2043-2056. 10.1016/j.jeurceramsoc.2011.04.036). As a result, more stress-bearing hydration products can be produced and the microstructure of AAS can be densified, resulting in higher flexural strength.

media/0673faf8e574476692eed61e8528b273_charts_009.png
  
Figure 9 Flexural strength of AASM. 

3.4. Pore structure

 

Figure 10a presents the pore structure of AAS mortars. The pore size distributions are very similar for all groups, with a distinct single peak around 10 nm and a flat profile after 100 nm. After adding WwFS1, the peak increased obviously compared to WwFS0. This may be associated with the inherent sandwich-like structure of WwFS, where the interface between the paste and aggregate changes from dual to ternary, leading to additional pores in the microstructure system (21WangC, ChenP, XuY, ZhangL, LuoY, LiJ, WangY. 2022. Investigation on the utilization of spent waterglass foundry sand into Ca(OH)2-activated slag materials considering the coating layer of dried waterglass. Constr. Build. Mater.329:127180. 10.1016/j.conbuildmat.2022.127180). The mortar with the addition of WwFS2024 was similar to that of WwFS1, which suggests that room temperature pre-wetting for 24 h did not improve the pore structure. The free water and waterglass released by WwFS2024 could probably produce a denser ITZ, but the effect is rather weakened by the locally high w/b. By contrast, with the increase of hot water pre-wetting time, the peak of WwFS70 exhibited a tendency to gradually decrease and move to the left, indicating that WwFS70 refined the pore structure of AASM. Generally, pores smaller than 10 nm mainly consist of gel pores and pores between gel units, the lowest peak of WwFS706 means that soaking WwFS in hot water results in tighter connection between generated gel (49ChenP, WangJ, WangL, XuY. 2019. Perforated cenospheres: A reactive internal curing agent for alkali activated slag mortars. Cem. Concr. Compos.104:103351. 10.1016/j.cemconcomp.2019.103351-52RanB, Omikrine MetalssiO, Fen ChongT, DanglaP, LiK. 2023. Pore crystallization and expansion of cement pastes in sulfate solutions with and without chlorides. Cem. Concr. Res.166:107099. 10.1016/j.cemconres.2023.107099). Moreover, it is also possible that waterglass has entered the paste, generating extra hydration products that fill the pores and cracks, further densifying the ITZ.

media/0673faf8e574476692eed61e8528b273_010.png
  
Figure 10 Pore structure of 28d AASM: (a) pore sizes distribution; (b) cumulative pore volume. 

Figure 10b further shows the cumulative volume of pores in the three zones. It is evident that replacing quartz sand with WwFS increased the total pore volume of the mortar by 3.3%, indicating that the sandwich structure introduced more pores into AASM. Incorporating pre-wetted WwFS not only reduced the total porosity and macro pores volume, but also optimized the gel pores and capillary pores volume. However, the improvement in the pore structure of mortars by pre-wetting WwFS at 20°C was limited, with a slight reduction in the total porosity of mortars containing WwFS2024 compared to WwFS1. With the addition of WwFS70, the volumes of all three pore size zones decreased, especially the total porosity of WwFS706 decreased by 30.4% compared to that of WwFS1. Therefore, since the refined pore structure could be produced in AASM using WwFS70, the hypothesis about the auxiliary activation of slag by WwFS70 is further substantiated.

3.5. Microstructure analysis

 

The typical SEM images of 28d AASM are shown in Figure 11. From Figure 11(a), cracks with a width as high as 20 μm were found between the quartz sand and the surrounding paste, which indicates that the interface is a typical physical interface with poor bonding. After substituting quartz sand with WwFS, the cracks between WwFS1 and AAS paste were clearly narrowed. Since the layer of dried waterglass on the surface of WwFS1 may dissolve into the surrounding paste in small amounts, it promoted the hydration of slag, leading to an enhanced bonding effect between WwFS1 and AAS paste. The paste around WwFS2024 is loose and porous, as shown in Figure 11(c), attributed to a significant local increase in w/b near WwFS. This results in the deterioration of the microstructure (53HuX, ShiC, LiJ, WuZ. 2021. Chloride migration in cement mortars with ultra-low water to binder ratio. Cem. Concr. Compos.118:103974. 10.1016/j.cemconcomp.2021.103974), consistent with the decrease in compressive strength of WwFS2024 in Figure 8. In contrast, AASM with the addition of WwFS701 exhibited a large number of hydration products in the microstructure, such as C-(A)-S-H gels. Dissolved SiO32- and KOH from the hot water-soaked waterglass layer could be released into the mixing water as a source of coactivator in addition to NaOH. Moreover, the pre-wetted waterglass coating could function as reactive aggregates, with the dissolution and permeation of SiO32- and some KOH facilitating the hydration of the surrounding slag particles, producing additional hydration products. The enhanced dense ITZ structural layer was observed in WwFS706 with tight interfaces and no cracks generated, as shown in Figure 11(e). In conclusion, the improved bonding between WwFS and surrounding paste by hot water pre-wetting of WwFS can be confirmed, consequently influencing the compressive strength and pore structure of AAS mortar.

media/0673faf8e574476692eed61e8528b273_011.png
  
Figure 11 SEM images of 28d AASM: (a) WwFS0; (b) WwFS1; (c) WwFS2024; (d) WwFS701; (e) WwFS706. 

3.6. Nanoindentation analysis (interface and paste around WwFS)

 

Figure 12 shows the contour mapping of the elastic modulus of AAS mixtures determined by nano-indentation method, respectively. The average elastic modulus of AASM along the Y axis in Figure 12 was calculated to investigate the variations in ITZ properties after incorporating pre-wetted WwFS, as shown in Figure 13. There is no weak zone between the quartz sand and paste, and the elastic modulus is approximately 30~50 GPa. Since the dried waterglass layer may cause the discontinuity of the interface structure, a weak transition zone was found in WwFS1. The ITZ thickness of AAS mortar with the addition of WwFS is about 60 μm. For WwFS2024, ITZ has the lowest elastic modulus. However, the ITZ with the addition of WwFS70 was enhanced with an increase in elastic modulus, and in particular, the elastic modulus of ITZ with WwFS706 tended to be closer to that of WwFS0. This implies that hot water immersion treatment of WwFS did promote slag hydration, generating more hydration products in the interface. Meanwhile, these results further proved that WwFS706 can achieve better bonding between AASM matrix and aggregate, and also contribute to the strength of mortars.

media/0673faf8e574476692eed61e8528b273_012.png
  
Figure 12 Contour mappings of the elastic modulus in AAS interface: (a) WwFS0; (b) WwFS1; (c) WwFS2024; (d) WwFS701; (e) WwFS706. 
media/0673faf8e574476692eed61e8528b273_charts_013.png
  
Figure 13 Distributions of averaged elastic modulus in ITZ. 

Figure 14 presents the contour mapping of elastic modulus of pastes around AAS aggregates. The red areas represent unhydrated GGBS or aggregates with an elastic modulus more than 60 GPa (54AhmadMR, QianL, FangY, WangA, DaiJ. 2023. A multiscale study on gel composition of hybrid alkali-activated materials partially utilizing air pollution control residue as an activator. Cem. Concr. Compos.136:104856. 10.1016/j.cemconcomp.2022.104856), while the areas less than 60 GPa are considered to be hydration products. In Figs. 14d and 14e, the red (>60 GPa) areas are significantly decreased and the cyan (20~30 GPa) and green (30~40 GPa) areas are increased, which suggests that WwFS706-added mortars had a higher degree of hydration with less unhydrated GGBS.

media/0673faf8e574476692eed61e8528b273_014.png
  
Figure 14 Nanoindentation results of AASM pastes around WwFS: (a), (b), (c) elastic modulus mapping for WwFS0, WwFS1, WwFS2024, WwFS701 and WwFS706. 

Figure 15 illustrates the deconvolution results of elastic modulus and volume fraction of pastes around AAS aggregates. According to previous studies, the elastic modulus was divided into four stages in order from low to high, i.e., porous phase (PP), low-density C-A-S-H (LD), high-density C-A-S-H (HD) and unreacted GGBS (UG). The average elastic modulus of C-A-S-H for each mixture is presented in the inset table in Figure 15a. After replacing quartz sand with WwFS, the average elastic modulus of both LD and HD was higher than that of WwFS0. Compared to WwFS1, the C-A-S-H average elastic modulus is increased for all of WwFS70, although WwFS2024 is slightly lower. The average elastic modulus of C-A-S-H increased from 32.66 GPa for WwFS1 to 37.88 GPa for WwFS706, indicating that the addition of WwFS706 densified the microstructure of the hydration products. In Figure 15b, the hydration products with the largest volume fraction in WwFS701 and WwFS706 are both HD. WwFS706 shows a decrease in PP volume fraction from 26% to 19% and an increase in HD volume fraction from 26% to 37% compared to WwFS1, suggesting that WwFS706 promotes the formation of more HD in AAS. The above findings further demonstrate the synergistic effect on activating the slag between NaOH and sodium silicate dissolved into the mixing water, which contributes to improving the compressive strength of AAS mortars, consistent with the results of MIP.

media/0673faf8e574476692eed61e8528b273_015.png
  
Figure 15 Comparison of indentation properties of four different phases of hydrates for AASM: (a) Elastic modulus; and (b) Volume fraction. 

4. CONCLUSIONS

 

This study investigates the replacement of quartz sand by WwFS at two different pre-wetting methods (24 h pre-wetting at 20°C and 1~6 h pre-wetting at 70°C) and compares their performances with those of added quartz sand and dried WwFS mortars. The experimental results demonstrated that the addition of dried WwFS resulted in lower fluidity and higher compressive strength than WwFS0 due to the dried waterglass layer that can release a small amount of SiO32- into AAS paste. Although the pre-wetted WwFS improved fluidity, the increase in local w/b led to a decrease in the compressive strength of WwFS2024. In contrast, the addition of WwFS70 achieved higher compressive and flexural strengths and denser pore structure than WwFS1. On the one hand, the solubility of waterglass increased with increasing pre-wetting temperature, leading to the dissolution and release of more SiO32- from the wetted waterglass layer into the mixing water, which activated the bonding potential of the paste matrix in a broader and more homogeneous manner and promoted the generation of additional hydration products. As the pre-wetting time increased from 1 h to 6 h, the compressive strength of WwFS70 increased by 4.5~10.7% at 3d, 3.7~14.2% at 7d, and 1.3~10.0% at 28d, in comparison with WwFS1. On the other hand, the dissolved waterglass layer becomes thinner, weakening the defects of the sandwich structure, while the residual waterglass layer still plays a role in improving the interface. The hydration of the slag was improved in WwFS706-added mortars, with fewer and smaller unhydrated slag particles around WwFS, and no obvious ITZ in the microstructure.

Funding Sources

 

This work was funded by the National Natural Science Foundation of China (52008003), Outstanding Youth Project of Natural Science Research in Universities of Anhui Province (23AH030043), National Key Research and Development Plan (2021YFB3401504).

Authorship contribution statement

 

Xin Shen: Investigation, Methodology, Writing-original draft.

Peiyuan Chen: Conceptualization, Supervision, Writing – review & editing.

Shangkun Li: Investigation.

Yonghui Wang: Investigation.

Shuimu Hu: Investigation.

Chunning Pei: Investigation.

Jiankai Xie: Investigation.

Declaration of competing interest

 

The authors of this article declare that they have no financial, professional or personal conflicts of in-terest that could have inappropriately influenced this work.

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