1. Introduction
Environmental concerns regarding the cement and concrete contribution to CO
2 emissions in the atmosphere have captured the attention of researchers, who have recently turned the focus onto reducing cement content in concrete without compromising strength, if possible. In conventional concrete mixtures, cement is partially replaced by industrial byproducts such as fly ash (FA), silica fume (SF), metakaolin (MK) and ground granulated blast-furnace slag (GGBS). Furthermore, aiming to reduce the use of cement use in construction, the development of eco-friendly, cementless alternatives to concrete has been rising, leading to significant advancements in geopolymer research [
1].
Geopolymer research and development provides the revolutionary opportunity to reuse waste into novel building material mixtures, while concurrently contributing to decreasing the detrimental environmental impact imposed by the construction industry mainly due to the extremely high temperatures required for cement manufacturing. Cement accounts for roughly 8% of anthropogenic CO
2 emissions [
2,
3] and is the principal constituent of concrete, which is currently the most widely used construction material [
4,
5] as well as the highest consumed substance in the world after water [
4,
6].
Following the circular economy principles [
7], which entail extending the life cycle of products and reducing waste to a minimum, locally available waste is exploited for inclusion in novel construction material mixtures [
6]. Moreover, byproducts of the quarry industries, which constitute a major environmental and health threat globally due to exponentially increasing accumulation, could be effectively reused in construction materials [
8]. The new circular economy action plan (CEAP) adopted by the European Commission in March 2020 [
9] includes targets for landfill reuse to create further value, in line with the European Green Deal [
10] goals for sustainable economic growth.
Geopolymers are alkali-activated aluminosilicates, integrating silica-rich industrial byproducts and wastes that are activated using alkaline solutions such as NaOH, potassium hydroxide and calcium hydroxide among others [
1,
11]. In addition to industrial byproducts such as fly ash (FA), metakaolin (MK), silica fume (SF) and ground granulated blast-furnace slag (GGBS), which have been most commonly used as partial cement replacement in concrete technology, geopolymer mixtures can incorporate additional types of wastes such as waste clay brick powder [
1,
12], glass polishing waste [
1,
13], palm oil fuel ash (POFA) [
14] and even rice husk [
1], a silica-rich waste material, abundantly available in all rice producing countries [
15,
16]. Previous research studies have denoted the potential of geopolymer mixtures to reach higher compressive strengths than conventional concrete [
17] and possess fracture energy comparable to cement concrete [
14,
18] as well as superior durability [
19]. Therefore, a silica-rich waste mud, produced in abundance by the quarry industry on the island of Cyprus, was investigated for geopolymerization.
During the last 10 years, various studies [
19,
20] in Cyprus have attempted to develop a cost-effective way to valorize the particular hazardous DM waste. Even though several cases have been investigated, none of them were successful. In the meantime, accumulation of DM has increased, and certain quarries are presented with the challenge of DM storage, with their production exceeding 25,000 tons yearly. Bearing in mind the availability and environmental issues pertaining to DM accumulation, research continues to investigate effective reuse of the waste DM in construction materials [
6].
Previous research revealed the significant SiO
2 content (nearly 41%) of the local quarry waste “Diabase Mud” (DM), deeming it worthy of geopolymerization, but dissolution test results indicated limited reactivity potential denoting that the DM alone is not capable of producing chemically stable alkali activated binders. Alkali-activation was therefore implemented in combination with CEM I cement, Gypsum and Metakaolin (MK), but none of the mixtures were able to reach compressive strengths higher than 10 MPa [
19]. To further explore valorization of the local waste DM in geopolymer development, this research study focused on alkali-activating the DM along with the industrial byproduct GGBS.
A byproduct of the iron manufacturing industry blast furnaces, GGBS is rich in calcium oxide and silica, and of similar density to ordinary cement. It is commonly used as cement replacement at ready mix concrete plants for sustainability. In geopolymers the use of GGBS allows for ambient curing conditions [
21,
22], whereas under other circumstances high temperature curing is necessary for alkali activation. In addition, GGBS has indicated an ability to significantly accelerate reactivity of activator solutions, therefore geopolymer mortars that incorporate high GGBS percentages are expected to attain reduced workability [
21]. Although researchers were able to alleviate workability issues by incorporating metakaolin (MK) instead of GGBS [
14], this study aims to provide a cementless binder for large-scale manufacturing of precast construction products, thus availability and cost of materials were considered and therefore the use of GGBS was largely favorable to Metakaolin (MK) due to cost-effectiveness.
Mechanical properties of three mixtures with varying DM/GGBS content combinations were examined. In addition, full scale pavement tiles were manufactured and tested according to standard procedures, as a first attempt in the development of a novel cementless binder, capable of being produced on a larger scale and intended for the industrial manufacturing of precast products (e.g., pavement tiles) for the local and international market that will not only be more sustainable and cost effective, but will possess equivalent or even superior properties compared to conventional market products.
2. Materials and Methods
This study investigates the development of high compressive strength cementless binder mixtures incorporating local waste DM and GGBS. The DM is a byproduct of local diabase quarries, specifically the sludge derived from the remainders of aggregate production processes of crushing and washing. The DM consists mostly of silicon and alumina oxides and its original sludge form contains about 25–30% water. At nearly 41% quartz or silicon dioxide, the crystalline composition of the waste DM revealed significant potential for geopolymerization. The detailed oxide composition of the DM, as obtained through Energy Dispersive X-Ray Fluorescence (ED-XRF) analysis [
19], is presented in
Table 1.
The DM average density was measured after oven drying the as-received sludge at 105 °C until mass stability was reached and subsequently grinding to particle sizes smaller than 63 microns. The results indicated a 2362 kg/m
3 average density, with a standard deviation of 25.2 kg/m
3. The experimentally obtained material density was slightly lower than the reported average density of crushed diabase aggregates produced by the specific quarry that supplied the DM [
19].
To determine the reactivity potential of the DM, dissolution testing was conducted using NaOH and KOH at different molarities, up to 16M [
19]. The low amount of either Al or Si leaching indicated that the DM alone may not be dissolved sufficiently in any one of the two alkaline activators used, even at high molarities. To enable successful activation of a single raw material, leading to stable geopolymer development, a minimum 10% dissolution is required while as reported by various studies, higher raw material dissolution percentages lead to superior geopolymer mechanical properties. The DM investigated in this study had a maximum dissolution of 2.54% at 12M NaOH and is therefore considered unreactive and unable to be alkali-activated alone [
19].
Since the DM reactivity is not sufficient for geopolymerization unless combined with other raw materials, and previous attempts to activate it with CEM I, gypsum and MK did not yield binders of adequate compressive strength, incorporation of GGBS is investigated in this study. GGBS mainly consisting of CaO (43.8%), SiO2 (37.7%), Al
2O
3 (10.2%) and MgO (6.4%) was used to assist in DM activation [
23]. The GGBS technical data [
23] conveyed by the GGBS provider are summarized in
Table 2. In addition to the properties reported in
Table 2, indicative compressive strengths and setting times were given by the GGBS provider, namely compressive strength and setting time results for a 50% GGBS-50% Cement paste and a control 100% Cement paste, for comparison purposes. Therefore, according to the values provided [
23], replacing 50% of the Cement included in a 100% Cement control mixture by the GGBS utilized in this study led to slight reduction in both the 7- and 28-day compressive strengths but did not affect the 90-day compressive strength, while it also delayed setting by 35 minutes, or increased setting time by 20% [
23].
In this study, 3 mixtures were developed and assessed experimentally. The 3 mix-tures incorporated DM and GGBS at varying contents, mixed with equal amounts of liquid Na
3SiO
2 and 8M NaOH. To reduce the cost of processing, the DM was used in the sludge form received, but to keep the moisture content consistent throughout the study the DM was allowed to release part of its moisture content (while being monitored) and was used in mixture development while at a moisture content of 22% in all cases. The mixtures are labeled according to their DM and GGBS content; 70%DM-30%GGBS, 50%DM-50%GGBS, and 30%DM-70%GGBS. The mix constituents per 1 m
3 are shown in
Table 3. It should be noted that even though a consistent S/L ratio of 5 was planned and used during the preliminary study, the S/L ratio of the 30%DM-70%GGBS mix had to be modified to 3.75 to enable casting of specimens within the workable time window. Higher GGBS content led to higher temperatures and quicker setting. This issue is further discussed in
Section 3.1.
A standard mortar mixer was used for the mixture preparation, following standard mortar preparation procedures, but to accommodate for the fact that GGBS is known to react quickly with alkaline solutions leading to accelerated mix setting, the liquids Na3SiO2 and 8M NaOH were initially mixed together before the DM and finally the GGBS were added to the mixer. To examine the hardened mechanical properties of the 3 mixtures, 100 × 100 × 100 mm cubic, 40 × 40 × 160 mm prismatic and 200 × 100 mm cylindric specimens were cast in metal forms, while 400 × 400 × 40 mm pavement tiles were cast in wooden forms. The setting time, 7- and 28-day compressive strengths, modulus of elasticity, splitting tensile strength and flexural strength of flags as well as sorptivity were determined for the 3 DM–GGBS mixtures by experimentally evaluating that the 3 specimens were per mixture for all experimental testing procedures.
The setting time for the 3 geopolymer mixtures developed in this study was assessed following the guidelines for testing cement for determination of setting times [
24]. The 3 geopolymer mixtures developed were also tested for the Rate of Absorption of Water (Sorptivity) following standard guidelines by Hydraulic Cement Concretes [
25], with the only deviation from the standard being the fact that 100% concentrate Isopropyl alcohol (C
3H
8O) [
26] was used instead of water.
The compressive strength of standard 100 × 100 × 100 mm cubes was determined at 7-days and 28-days maturity. Cubic specimens were cast following preparation guidelines for hardened concrete specimens intended for strength testing [
27], but instead of following standard curing procedures for concrete the geopolymer cubes were cured in a controlled indoor environment at 30 °C while sealed in plastic bags to avoid sudden loss of moisture. The particular curing regime was selected based on preliminary studies on a variety of alternative curing options. Subsequently, the geopolymer cubes were tested for compressive strength following the hardened concrete testing guideline [
28].
Similarly, splitting tensile strength of the 3 mixtures developed was evaluated following the Standard Test Method for Splitting Tensile Strength of Cylindrical Concrete Specimens [
29]. In addition, the flexural strength of prismatic specimens was experimentally evaluated following the standard procedure for concrete [
30], while likewise the modulus of elasticity values for each mixture were determined following standard guidelines for concrete specimens [
31]. Finally, the flexural strength of paving flag specimens was examined following the standard guidelines for equivalent concrete products [
32]. The results are presented and discussed in
Section 3. Testing geopolymer mixtures using the conventional cementitious mixture standards is common practice [
33], while Rilem Technical Committee 224-AAM is working on providing performance-based specifications and recommendations for the development of standards that will specifically apply to alkali-activated materials [
34].
4. Discussion and Conclusions
Successful geopolymerization of local quarry waste DM was accomplished, following a ten-year course of attempts to valorize a waste material that is continuously produced in large quantities at diabase quarries in Cyprus. Adequate DM activation was achieved in combination with GGBS, using 8M NaOH and Na3SiO2 at a S/L ratio of five and curing under ambient conditions. The results highlight the potential of waste DM in the development of high performance cementless precast products to be used in construction. Even though difficulties were encountered during casting, especially when larger volume mixtures were produced and mostly when the mixture with the highest GGBS content was utilized, adequate mechanical properties were achieved by all three mixtures developed.
Specifically, the 70%DM-30%GGBS mixture reached an average compressive strength of 69.38 MPa, the 50%DM-50%GGBS mixture reached an average of 85.58 MPa, and the 30%DM-70%GGBS mixture reached an average of 98.05 MPa at 28 days. The elastic moduli of the geopolymer mixtures are lower than expected based on compressive strength values. As the GGBS content increased, both the compressive strength and Modulus of Elasticity increased. The three mixtures had similar splitting tensile strength and flexural bending performance. Due to excessive drying shrinkage cracking present on the surfaces of pavement tile specimens cast in this study, the flexural strengths of paving flags obtained are not considered indicative of the developed mixtures. Considering capillary absorption, the three DM/GGBS combination geopolymers outperform conventional concrete in terms of susceptibility to liquid ingression.
To enable efficient large-scale production of sustainable and cost-effective construction products, further mixture optimization and most importantly optimization of curing procedure is required to reduce shrinkage. Utilizing the 70%DM-30%GGBS mixture for the development of industrial products is suggested. Not only did the 70%DM-30%GGBS mix experience the least porosity and least shrinkage cracking out of the three mixtures developed, but most importantly, it is the most sustainable and widely effective of the three since it is comprised of DM to a larger extent. Further research on the developed geopolymer mixture is suggested, as follows:
Investigating the reaction mechanism and microstructure evolution of alkali activated DM/GGBS combination mixtures would lead to optimizing the fresh properties of the developed geopolymers, thus eliminating specimen surface imperfections and pre-existing cracking, and therefore leading to enhanced hardened geopolymer mechanical properties;
Optimizing the curing conditions to specifically suit DM/GGBS combination geopolymer mixtures is required, to tackle shrinkage cracking issues caused due to premature drying.