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Building a greener future: Advancing concrete production sustainability and the thermal properties of 3D-printed mortars

Capêto, Ana Paula; Jesus, Manuel; Uribe, Braian Esneider Buitrago; Guimarães, Ana Sofia; Oliveira, Ana L. S.

Abstract

The integration of waste materials in extrudable cement mixtures has the potential to make the construction industry more sustainable by reducing carbon footprints and developing eco-friendly materials. This along with advancements in 3D concrete printing (3DCP) provides engineering and architectural benefits by reducing material waste and costs. In this paper, the impact of waste incorporation on properties of mortar and concrete is examined. The use of waste materials, such as pumice, coal slag, agricultural lignocellulosic residues, and recycled rubber tyres, to improve thermal insulation and durability of cementitious composites is discussed. In addition, the incorporation of air-entraining admixtures with surfactant activity is explored for their indirect effect on thermal behaviour, pore size reduction, and enhancement in concrete properties. This review includes important topics such as a strength resistance to freezing and thawing, fire resistance, plasticising effect, and delay in cement hydration. These findings highlight the benefits of using diverse waste materials in construction, providing a multidimensional approach to waste management, cost optimization, and enhanced construction materials in the context of 3DCP.

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Citation: Capêto, A.P.; Jesus, M.; Uribe, B.E.B.; Guimarães, A.S.; Oliveira, A.L.S. Building a Greener Future: Advancing Concrete Production Sustainability and the Thermal Properties of 3D-Printed Mortars. Buildings 2024,14, 1323. https://doi.org/10.3390/ buildings14051323 Academic Editors: Xiaoyong Wang and Binsheng (Ben) Zhang Received: 29 February 2024 Revised: 30 April 2024 Accepted: 30 April 2024 Published: 8 May 2024 Copyright: © 2024 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ 4.0/). buildings Review Building a Greener Future: Advancing Concrete Production Sustainability and the Thermal Properties of 3D-Printed Mortars Ana Paula Capêto 1, Manuel Jesus 2, Braian E. B. Uribe 3, Ana Sofia Guimarães 2and Ana L. S. Oliveira 1,* 1Centre for Biotechnology and Fine Chemistry (CBQF)—State Associated Laboratory, Faculty of Biotechnology (ESB), Portuguese Catholic University (UCP), 4169-005 Porto, Portugal 2CONSTRUCT, Faculty of Engineering, University of Porto (FEUP), 4200-465 Porto, Portugal; [email protected] (M.J.); [email protected] (A.S.G.) 3Institute for Polymers and Composites (IPC), Department of Polymer Engineering (DEP), University of Minho, Campus de Azurém, 4800-058 Guimarães, Portugal; [email protected] *Correspondence: [email protected] Abstract: The integration of waste materials in extrudable cement mixtures has the potential to make the construction industry more sustainable by reducing carbon footprints and developing eco-friendly materials. This along with advancements in 3D concrete printing (3DCP) provides engineering and architectural benefits by reducing material waste and costs. In this paper, the impact of waste incorporation on properties of mortar and concrete is examined. The use of waste materials, such as pumice, coal slag, agricultural lignocellulosic residues, and recycled rubber tyres, to improve thermal insulation and durability of cementitious composites is discussed. In addition, the incorporation of air-entraining admixtures with surfactant activity is explored for their indirect effect on thermal behaviour, pore size reduction, and enhancement in concrete properties. This review includes important topics such as a strength resistance to freezing and thawing, fire resistance, plasticising effect, and delay in cement hydration. These findings highlight the benefits of using diverse waste materials in construction, providing a multidimensional approach to waste management, cost optimization, and enhanced construction materials in the context of 3DCP. Keywords: 3D concrete printing; waste; mechanical properties; thermal insulation; admixtures 1. Introduction In the context of the application of circular economy (CE) principles [ 1 ], the European adoption of the Green Deal presents a joint effort in the implementation of strategies toward a competitive and efficient utilisation of resources’ economy that minimises environmental footprints, thus envisioning a carbon-neutral Europe in the near future [2]. The building and construction (B&C) sector is considered one of the key sectors for CE adoption due to its massive impact on resource consumption, waste generation, and environmental emissions [ 3 , 4 ]. As a result, this sector has become the focus of developing new policies and launching a new comprehensive strategy for a sustainable built environment [ 5 , 6 ]. Understanding the environmental impact of the B&C sector and cement manufacturing is becoming increasingly important since concrete production is responsible for 9% of total emissions of greenhouse gases (GHGs), known to exert an accentuated effect on climate change, with about 0.8 tons of CO 2 /ton of cement resulting from operations of transport, mixing, and application [ 7 ]. Improved production methods and formulations that reduce or eliminate CO 2 emissions from the cement manufacturing process are mandatory, as well as to counteract the impacts on the product cost of new regulations, green taxes, and escalating fuel prices [8]. A relevant perspective to consider is reducing the high amount of energy consumed by the cooling and heating of buildings, estimated to account for approximately 40% of primary energy and 36% of greenhouse emissions in European Union member states [ 9 ]. Buildings 2024,14, 1323. https://doi.org/10.3390/buildings14051323 https://www.mdpi.com/journal/buildings Buildings 2024,14, 1323 2 of 22 This fact, and the demand for housing due to the expected growth in the human population of about 10.9 billion in 2100 [ 10 ], is arousing many concerns about the negative impact on energy and climate goals [ 11 ]. One solution to increase sustainability and minimise the related environmental footprint of B&C is incorporating waste in concrete production as supplementary cementitious materials (SCMs) or fillers from several sources (construction and demolition, industrial, agricultural, etc.). This action will contribute to proper waste management and can fundamentally improve the thermal properties of cementitious composites, resulting in significant energy savings, correlated costs, and lower GHG emissions [12,13]. Since the beginning of this century, the application of additive manufacturing methods such as three-dimensional (3D) printing to concrete production and the fusion with the Contour Crafting technique [ 14 ] has gained ground over the established procedures of construction [ 15 ]. The computer-controlled deposition of extruded mortars layer-by-layer [ 16 ], also called 3DCP, coupled with Building Information Modelling (BIM), is already considered a practical tool mainly used for the fabrication of both structural and non-structural concrete elements [ 17 ]. While many advantages are already recognised, the complete adhesion of the sector to this technology depends on legislation that supports the pioneer companies since the investment has been focused mainly on the necessary automation and the demand for skilled labour, neglecting the sector’s economic, social, and environmental benefits [18]. This paper aims to summarise and discuss the strategies followed so far concerning the integration of wastes in the design stage of cementitious composites to enhance the mechanical and/or thermal performances in the building infrastructures, integrating digital construction as a new path to CE. The survey of the relevant literature was found within the article, title, abstract, and keywords. The keywords used for the systematic search are “cementitious mortars”, “waste integration”, “admixtures”, “additive manufacturing”, “3D concrete printing”, “mechanical properties”, and “thermal insulation”, and priority was given to scientific articles, also paying attention to their number of citations. Thus, a good majority of the articles collected are in journals indexed in ScienceDirect (such as Construction and Building Materials;Journal of Cleaner Production;Journal of Building Engineering;Cement and Concrete Composites;Automation in Construction; and Engineering Structures) and Scopus (such as Buildings;Materials;Applied Sciences; and Sustainability). 2. Three-Dimensional Concrete Printing Prerequisites The 3DCP technology allows rather complex and customised design, providing a quick construction method on and off site without precast, reducing the workforce, optimising material utilisation, and reducing materials waste, construction costs, and carbon footprints [ 11 , 19 ]. In opposition to conventional construction methods, 3D printing (3DP) is a highly customisable technology that allows the integration of nature-based infrastructures in the design stage, thus enabling the incorporation of secondary/recyclable materials with low environmental impact [ 20 , 21 ], providing a solid construction system based on robotic-assisted extrusion that is necessary to ensure the continuity of the printing process, a maximum extrusion rate, the consistency and quality of layers, freedom of movement, and reduction in human interaction [22]. Figure 1shows the equipment of a gantry system for 3DCP. Factors related to the mortar formulation and the printing process, such as the printing speed and mobility, flow rate, pump pressure, layer height and width, nozzle geometry, and environmental conditions, play crucial roles in affecting concrete performance in both fresh and hardened states [15,23]. Given its known properties, versatility, and ease of application, the choice for cementitious mortars on a global level is quite immediate. The formulation of cementitious mixtures proposed by different authors can vary considerably along with the printing system, the material supplier, and the equipment operator [ 24 ]. Table 1displays the charac- Buildings 2024,14, 1323 3 of 22 teristics that all designed mixtures must present [ 25 – 27 ] with some relevant references to experimental research. Figure 1. Gantry system constitution for 3DCP: (a) 3D printer; (b) mixer; (c) pumping system; (d) extruder with nozzle (from Be More 3D). Table 1. Printable mortar’s technical demands. Properties Description References Flowability Transportation of the paste from the mixer to the extruder [28,29] Pumpability The ability of the material to be extruded without phase separation under pressure [30,31] Open time Maintenance of the material’s consistency for good extrudability [32,33] Extrudability Extrusion of the material in continuous and uniform filaments Buildability Extrusion of the mortar in stacked layers and retention of the extruded shape [34,35] Mechanical strength Compressive and flexural strength [36,37] Mortar’s rheology and particle-size-dependent yield stress [ 38 , 39 ] are fundamental parameters that directly influence the mortar extrudability and the integrity of the bottom layers to meet stack layer-by-layer requirements and a large height-to-weight ratio typical of 3DCP of buildings [ 40 – 43 ]. Each layer must be able to support the weight of the subsequent ones so there are no cracks or collapse of the element. If the size of a mortar’s aggregate is incompatible with the nozzle diameter, it will lead to additional pressure, inducing clogging problems in the pumping system [ 44 ]. This will impact the extrusion rate, consistency, and printing velocity, leading to excessive layer porosity, poor interlayer bonding, and weak mechanical properties derived from geometrical imperfections and surface shrinking. This will culminate in failure due to elastic buckling and plastic collapse [ 45 , 46 ]. Therefore, to satisfy the required fresh properties of printable concrete, such as pumpability and extrudability, the content of a coarse aggregate needs to be significantly reduced, leading to a quantity of OPC in the mixture design typically 40% higher than the conventional concrete [ 47 , 48 ] and a higher cost of the concrete material [41]. Buildings 2024,14, 1323 4 of 22 To achieve economic and environmental sustainability, it is only logical to employ waste materials to replace OPC or as a part of a fine aggregate in mortar, solving two additional problems: the shortage of natural sand and the massive increase in waste disposal [49]. Chemical additives incorporated as admixtures in the mortar (e.g., superplasticisers, setting accelerators/retarders, and viscosity-modifying agents) will manipulate the mortar’s rheology, maintaining the workability and buildability over time, hence controlling the yield stress evolution [50,51]. A panoramic view of waste availability is essential to evaluate the feasibility of waste integration in concrete mortars. 3. Waste Availability Consulting the report provided by Eurostat [ 52 ], the production of waste generated by activities in 2018 for the 27 members of the European Union (EU27) shows that construction (35.9%), mining, and quarrying (26.6%) are the activities that produce the highest amounts of waste, followed by manufacturing (10.6%) and waste/water activities (9.8%) and Agriculture, Forestry, and Fishing (0.9%). In recent decades, the massive destruction of old structures has been the source of enormous construction and demolition waste (CDW). In Europe, the generation of this class of debris is estimated to be around 820 million tons/year, representing almost 50% of the total waste in the sector [ 52 , 53 ]. Moreover, EPA pointed out a CDW production of 600 million tons in 2018 in the USA, where concrete was the most significant portion at 67.5%, followed by asphalt concrete at 17.8%, more than twice the amount of generated municipal solid waste [54]. Several initiatives to promote circularity include CDW waste as a central aspect [ 55 ], and reusing them in concrete as a substitute for virgin aggregates is considered efficient [ 56 ]. Mining and processing industries are among the most intensive sources of environmental pollution, with wastes making up over 90% of raw materials extracted from minerals [ 57 ]. Managing such large quantities and the resulting long-term accumulation (estimative of 19 billion solid tailings until 2025) constitutes the most significant waste problem on the planet [ 58 ]. The waste generated by mineral extraction is waste rock, sludges, and nonmetallic (e.g., pumice, sand, quartz, phosphate, or forsterite) or metallic (copper, iron, zinc, lead, etc.) tailings. The vegetation and overburden may also be considered waste [ 59 ]. An estimated value for the worldwide production rate is 35 × 10 9 tons per year [ 60 ]. Slags are by-products of the metallurgical smelting of ores and used metals [61]. The pressure on natural sand extraction makes mine waste and metal tailings a potential replacement for natural fine aggregates [ 62 , 63 ] and a way of avoiding the major environmental problems due to soil contamination and the infiltration of surface and groundwater with heavy metals and processing chemicals. To address the sustainability concerns, a significant strategy is to mobilise those industrial by-products [ 64 , 65 ] to reduce the impact on carbon footprints. Manufacturing by-products is the most extensive category covering discarded material during or after processing. Some examples are waste from the processing of mine ores or wastewater treatment, oils and fatty acids from oil refining plants, sawdust produced by the furniture industry, cellulose from paper production, and plastics. More available leftovers from manufacturing processes or municipal solid wastes are artificial fibre wastes, glass fibre, polypropylene, and polyester, and rubbers are also available [ 66 , 67 ]. These materials have a high potential for environmental hazards due to their lower biodegradability and the probability of leaking into the ocean or other public spaces [ 68 ]. In 2015, the primary plastic production amounted to 407 million tons, with around 302 million tons (75%) ending as waste [ 69 ]. Despite ongoing management systems that lead to their growing recyclability, plastics must still be incinerated and landfilled [ 70 ]. Sludges from wastewater treatment plants containing heavy metals, like aluminium or other toxic residues [ 71 ], need previous solidification and stabilisation to be included in concrete [72]. Buildings 2024,14, 1323 5 of 22 Agro-wastes are generated mainly from forestry activities or the harvesting and processing of raw agricultural products, such as crops, fruits, poultry, dairy products, etc. [ 73 ]. The most produced agro-food wastes are rice/corn husk, sugarcane straw and bagasse, barley husk, eggshell, coconut, peanut shell, cotton stalks, and wheat straw residues. These wastes find direct uses in biofertilisers, mud houses, animal feed, biofuel, and heat generation in small-scale industries [74]. Eco-friendly materials designed for building applications seek to incorporate more agricultural waste and other cellulose-derived materials into mortars. This kind of waste usually offers a high availability, low cost, versatility, low weight, low energy consumption, and easy processability [75–77]. 3.1. Impact of Waste Addition on Concrete Performance—The Current Situation Driven by the increasing demand for sustainable construction solutions, the utilisation of waste materials in concrete production is a prominent focus in recent literature reviews. Various waste materials, including fly ash, silica fume, ground granular blast-furnace slag (GGBFS), and others, are being explored as partial replacements for traditional concrete ingredients. These materials contribute to enhanced mechanical performance, durability, and environmental sustainability of concrete structures. Additionally, waste materials such as clay brick powder, waste glass, ceramic powders, and tailings are being investigated for their potential to replace natural aggregates or cement in concrete mixes. Wastes derived from biomass such as wood, rice husks, bagasse, plant fibres, and leaves, among others, provide a structural advantage in cementitious mixtures due to increased specific properties (ratio of strength to density). In addition to their lightweight nature, recycled polymers incorporated into the mixtures offer advantages in terms of water absorption and corrosion resistance, and, in some cases, they improve the processability of the mortars. Incorporating these waste materials reduces environmental impact and addresses economic and availability concerns associated with traditional materials. Strategies such as fibre reinforcement further improve the mechanical properties of concrete, particularly in printable materials used in 3D concrete printing (3DCP). Ongoing research aims to optimise waste utilisation, improve concrete properties, and advance sustainable construction practices. The growing demand for concrete building blocks is satisfied with the partial replacement of waste materials from various industries. After consulting recent literature reviews regarding conservative formwork construction, it became apparent that most of the authors use a combination of cement, sand, fly ash, silica fumes, ground blasted-furnace slag (GGBFS or GGBS) and other slags (e.g., copper, lead–zinc slags), and micro-fibres [ 13 , 78 ]. The same strategy is still employed in mortar composition using the 3DP technology, and the experimental approach was the subject of a recent and detailed review by Dey et al. [79]. Fly ash (FA) is a by-product from coal production and combustion that usually replaces OPC in percentages between 15% and 30% [80]. Silica fume (SF) is the powdered by-product from producing elemental silicon or alloys containing silicon in electric arc furnaces with a high content of amorphous silicon dioxide [ 81 ]. In ultra-high-performance concretes, SF is usually present in elevated percentages (10 to 30%), inducing densely packed microstructures with reduced porosity [47,82–84]. GGBS is obtained by quenching molten iron slag and mainly consists of a silicate and aluminosilicate of calcium and can partially replace clinker in cement by up to 50% [85]. FA, SF, and GGBS additions in concrete lead to early heat production due to a slower hydration reaction preventing thermal cracking, increasing resistance to a chemical attack, and improving mechanical performance, abrasion resistance, and long-term durability of the built structures [ 86 – 90 ]. Excellent environmental performances are achieved with a multi-component binder mixture with FA, SF, or/and GGBS or FA and SF in the formulation of printable mortars [47,91]. Those by-products and natural pozzolanic materials, such as calcined clay or metakaolin, can partially replace the binder in concrete production. Although they do not display Buildings 2024,14, 1323 6 of 22 cementation properties on their own, when finely divided and in the presence of moisture, the silica and alumina contents react with the calcium oxide or calcium hydroxide present in the cement [ 92 ]. This reaction affects the mortar’s rheology and the cement hydration process, improving overall mechanical properties [39]. The economic viability of green concrete production depends highly on the waste accessibility/proximity, generated amount, and chemical and physical consistency [ 82 ]. Fly ash’s long-term global availability is compromised due to the increasing demand for concrete and the replacement of coal-based power plants with natural-gas-based power plants [79]. Several strategies have been employed to overcome this issue. Recovering ashes and other natural pozzolans in landfills and ponds presents a potential solution [ 86 ]. By-products such as biomass ashes (agro-waste and forestry) or ashes from other unconventional sources are good alternatives. Table 2references some examples, contemplating both the casting process and 3DCP. Figure 2shows an example of the use of sugarcane bagasse ash (SCBA) in 3D-printable mixtures. Table 2. Alternative sources of ashes (pozzolans). Source References Biomass-Based Casting Process 3DCP Wood (power plants) [93,94] - Rice husk [95,96] [97,98] Sugarcane bagasse [99] [100] Bamboo leaf [101] - Other Palm oil fuel (POFA) [102] - Municipal/industrial waste (solids and sludges) - [103] Buildings 2024, 14, x FOR PEER REVIEW 7 of 24 Figure 2. A 3D-printed element with a mixture based on SCBA. Since fillers and tailings are the waste categories with substantial representation [79], clay brick powder, waste glass, and ceramic powders (e.g., table and sanitary ware, electric insulators, floor, tiles, etc.) can replace natural coarse aggregates or cement, attaining suitable strength [104–106]. Glass powder, up to 15% in concentration, showed significant improvement in the properties of end-cast concrete [105,106]. Different gradations of recycled glass in printable mortars influence porosity, pore morphology, and related crack propagation while obtaining opposite effects on flexural properties in different loading directions [107]. The presence of granite, ceramic filler, or siliceous fillers with powder-size particles in cast concrete reduced the mechanical performance while increasing the absorption area, accelerating the hydration process, affecting the mortar’s drying shrinking performance, and improving adhesive strength [108]. Concerns due to higher water absorption raise problems that affect consistency and plasticity, leading to workability issues [109]. The size, content of particles, and percentage of waste replacement have some influence on the fresh and hardened properties of concrete. In addition, durability is one of the significant issues since recycled concrete structures are exposed to carbonation-induced corrosion. Carbonation depth in concretes with a 25 or 50% recycled aggregate was 1.07–1.20 times greater than in conventional concretes with a 100% natural aggregate [110]. Meanwhile, mixing fly ash (FA) and irregular limestone aggregate micro-fines (AMFs) with concentrations up to 12% in the mortar formulation displayed a synergistic effect. Despite reducing flowability and extrudability in the fresh state, AMFs improved the hydration reaction speed with increased shape stability and long-term strength [111]. The relation between printability and mechanical performance with size gradation and interlayer distribution was proved by incorporating recycled concrete, desert sand, and river sediment [112] and preserving buildability with up to 50% replacement of sand with spent garnet [113]. Tailings consisting mainly of silica, aluminium, calcium, and iron oxides are used in cement clinker production to increase mechanical performance [114]. Casting concretes with tailings added as fine aggregates from lead–zinc [115] and gold [116] ores led to increased strength in compression. Printable mortars incorporating copper and iron tailings revealed a close relationship between fluidity and setting time and material concentration and the relation of particle size with water absorption [24,117]. Figure 2. A 3D-printed element with a mixture based on SCBA. Since fillers and tailings are the waste categories with substantial representation [ 79 ], clay brick powder, waste glass, and ceramic powders (e.g., table and sanitary ware, electric Buildings 2024,14, 1323 7 of 22 insulators, floor, tiles, etc.) can replace natural coarse aggregates or cement, attaining suitable strength [104–106]. Glass powder, up to 15% in concentration, showed significant improvement in the properties of end-cast concrete [ 105 , 106 ]. Different gradations of recycled glass in printable mortars influence porosity, pore morphology, and related crack propagation while obtaining opposite effects on flexural properties in different loading directions [107]. The presence of granite, ceramic filler, or siliceous fillers with powder-size particles in cast concrete reduced the mechanical performance while increasing the absorption area, accelerating the hydration process, affecting the mortar’s drying shrinking performance, and improving adhesive strength [108]. Concerns due to higher water absorption raise problems that affect consistency and plasticity, leading to workability issues [ 109 ]. The size, content of particles, and percentage of waste replacement have some influence on the fresh and hardened properties of concrete. In addition, durability is one of the significant issues since recycled concrete structures are exposed to carbonation-induced corrosion. Carbonation depth in concretes with a 25 or 50% recycled aggregate was 1.07–1.20 times greater than in conventional concretes with a 100% natural aggregate [110]. Meanwhile, mixing fly ash (FA) and irregular limestone aggregate micro-fines (AMFs) with concentrations up to 12% in the mortar formulation displayed a synergistic effect. Despite reducing flowability and extrudability in the fresh state, AMFs improved the hydration reaction speed with increased shape stability and long-term strength [ 111 ]. The relation between printability and mechanical performance with size gradation and interlayer distribution was proved by incorporating recycled concrete, desert sand, and river sediment [ 112 ] and preserving buildability with up to 50% replacement of sand with spent garnet [113]. Tailings consisting mainly of silica, aluminium, calcium, and iron oxides are used in cement clinker production to increase mechanical performance [ 114 ]. Casting concretes with tailings added as fine aggregates from lead–zinc [ 115 ] and gold [ 116 ] ores led to increased strength in compression. Printable mortars incorporating copper and iron tailings revealed a close relationship between fluidity and setting time and material concentration and the relation of particle size with water absorption [24,117]. Concrete with iron and aluminium fillings and GGBS exhibited better mechanical performance (compressive, tensile, and flexural strengths) and durability properties, creating bonds between fibres and cement mortar across the cracks that promoted a superior resistance to crack propagation [118,119]. Two detailed reviews concerning slag valorisation concluded that copper slag improves the concrete chemical resistance to corrosion and carbonation/freezing–thawing resistance with an optimum mechanical performance obtained with 40% replacement and particle sizes below 10 mm [ 120 ] from the mechanical properties’ perspective; lead and zinc slags could be used in mortar and concrete mixes for up to 50% replacement [ 121 ]. A study concluded that the water absorption rate and mechanical and durability characteristics of a concrete mixture incorporating fly ash (15%), aluminium dross (10%), and quarry dust (20%) are better than those of standard concrete [122]. Printable materials like in conventional concrete casting processes require reinforcement to counteract their low tensile strength [ 123 ]. The addition of fibres such as polypropylene, nylon, steel, copper, basalt, and glass fibres improves resistance to cracking and tensile strength and flexural capacity [ 24 ] and is efficacious in improving the explosive spalling resistance and residual mechanical properties in the case of fire [ 123 – 127 ], positively impacting printing speed, setting time, and yield stress [103]. Table 3summarises the waste utilisation regarding 3DCP with referenced articles and assesses the impact on specific fundamental properties, such as the pumpability, flowability, buildability, viscosity, interlayer bond, shrinkage, and more. Buildings 2024,14, 1323 8 of 22 Table 3. Examples of the impact of waste additives in 3DCP mixture properties (summary). Waste Optimum Replacement Material Replaced or Reinforced Concrete Properties Reference Magnesium oxide from waste brine 3% Cement Good extrudability, flowability, and buildability, ↓sorptivity [128] Fly ash (FA) and silica fume (SF) 60:10% Magnesium potassium phosphate cement Variations on setting time, with good extrudability and buildability [39] Fly ash (FA) and granulated blast-furnace slag (S) 0:60% PC The superior material efficiency index [47] Rice husk ash 20% PC ↑Workability than control [97] Municipal sludge waste ashes (fly and bottom) and nylon fibres (NF) 7.5–10% FA 0.14% binder weight PC ↑Buildability and yield stress ↓Setting time, flowability, and interlayer bond [103] Recycled concrete (RA), ceramsite particles (CPs), and desert sand (DS) Depending on particle size and distribution Aggregates Adequate flowability and extrudability ↑Interlayer bond and can ↑ shrinkage [112] Wood chips from spruce with different binders Chips/cement = 0.15 Water/cement = 0.80 Aggregates Density = 0.7 to 0.8 g/cm3 Mechanical strength is enough for non-structural applications [129] Stone sludge + Al-polishing waste + cork + eucalyptus ash + superplasticiser SIKA 2:1 cement/stone sludge with superplasticiser Sika control 40 Composite with concrete Good flowability, extrudability, shape retention, buildability, and open time Conventional mortar ↑ early age strength development properties [130] Nano-attapulgite clay 0.5% Plasticizer Compared with the control mixture ↑Viscosity recovery and structural build-up [131] Cellulose fibre (CS) and limestone, silica fume (SF) Ratio—0.15 HB-CSA: 0.85 OPC: 0.15 SF Filler for application between layers ↑Printing interval, interlayer strength, and durability ↓Voids and longitudinal flaws [132] Copper tailings 30% Sand Favourable buildability and high mechanical strength [24] Copper and iron tailings Mass ratio—1:4 Water treated ↑Mechanical properties [117] Recycled glass 10% Sand ↓Mechanical properties ↑Flowability [133] Thermally treated peat-based admixture (MT-600) 0.5% of cement fraction [0.08–0.125] mm Cement ↑Strength of hardened cement pastes at an early age (3 days) than reference composition [134] Polypropylene fibres Lengths 3 (M3) and 6 mm (M6), 0.1 to 0.3% v/v Aggregates ↑Workability ↑Porosity (in the hardened state) ↑Flexural strength (M6) ↓Total free shrinkage (M3) [123] FA, SF, and ground granulated blast-furnace slag (GGBS) 20 wt.% (FA), 15 wt.% (SF), and 10 wt.% (GGBS) Cement ↑Compressive strength ↓Flexural strength [91] Limestone aggregate micro-fines (AMFs) 3% < AMF < 12% FA ↓Flowability ↓Extrudability ↑Shape stability ↑Green strength ↑Compressive strength ↑Flexural strength (after 60 days) [111] Spent garnet (SP) SP ≤50% Natural sand ↓Green strength ↓Young’s modulus –Buildability [113] Recycled sand (RS) (crushed from waste concrete) 25 and 50% (only tested values) Natural sand Change from plastic to solid material It affects early-age behaviour ↑Buildability ↓Open time [135] ↓decreased; ↑increased; – same. Buildings 2024,14, 1323 9 of 22 3.2. Alternative Binders—A More Sustainable Approach Despite the use of supplementary cementitious materials (SCMs) like fly ash and slag in concrete production, cement manufacturing remains a significant contributor to global CO 2 emissions. To mitigate this issue, alternative binders such as calcium sulphoaluminate (CSA) cement, limestone calcined clay cement (LC3), and geopolymer cement are discussed in this subsection. For 3DCP, the challenge is the excess surface water that leads to shrinkage, but solutions involving intermediate layers and additives have shown promise. Furthermore, replacing ordinary Portland cement (OPC) with calcined magnesium oxide (MgO) offers sustainability benefits. The subsection highlights the importance of optimising particle pack density and adding viscosity-modifying agents to enhance printability. Furthermore, it discusses the mechanical properties and durability of cementitious materials, emphasising the potential of geopolymer cement. Despite these advancements, the slow development of 3DCP technologies raises challenges in achieving robust and versatile extrusion systems. Consequently, ongoing research involves a trial-and-error process to balance material properties and advancements in printing technology. The polemic involving the mitigation of cement production’s environmental impact is far from ending. About 800 MT per year of the most common SCMs used in concrete production (e.g., fly ash, silica fume, limestone, and slags) are used, but the cement industry still accounts for 5–8% of global CO 2 emissions [ 136 ]. Limitations regarding performance and the scarcity associated with SCMs [ 48 , 137 ] lead to the exploration of globally available materials to formulate new and more sustainable binders to replace OPC, exemplified by CSA cement, LC3, geopolymer cement, and reactive magnesium oxide systems [138]. A significant problem of 3DCP is that excessive surface water expedites shrinkage in the extrusion process, resulting in a weak interlayer bond adhesion. It was found that this deficiency can be overcome by incorporating an intermediate layer of CSA cement, limestone filler, and cellulose fibres that retained excessive water, allowing internal curing, minimising shrinking, and providing mechanical cohesion [132]. Replacing OPC with calcined magnesium oxide (MgO) is an attractive option mainly due to the overall sustainability benefits derived from a greater capacity for CO 2 mineralisation [ 139 ] and lower temperatures necessary for clinker production while decreasing the concrete shrinkage strain, upholding good mechanical properties and long-term durability within certain limits [ 140 , 141 ]. Adding suitable additives to printed mortars improves overall performance compared to cast samples [128]. The synergistic effect of calcined clays exemplified by kaoliIite, illite, montmorillonite, and limonite (sedimentary rock based on calcite and dolomite) allows the replacement of more than 50% of clinker while retaining mechanical performance and durability [ 137 , 142 ]. The particle pack density can be optimised to improve printability and the increased amount of metakaolin in the calcined clay can overcome problems with extrusion pressure, initial setting time, and compressive strength of the concrete [ 48 ]. Furthermore, the addition of suitable amounts of viscosity-modifying agents can reduce the negative impact on the mortar’s extrudability of these materials, stabilising the shape of the extruded filaments [143]. The hydration process of OPC results mainly in a calcium silicate hydrate gel (C-S-H) responsible for the time-dependent viscoelastic response to applied deformation [ 144 ], impacting the mechanical properties and durability of cement-based materials [ 145 ]. On the other hand, geopolymer cement is a binder produced by the alkali-activation of aluminosilicates such as fly ash/rice husk ash, silica fume, clay, metakaolin, GGBS, etc. [ 146 ]. Relying on aluminosilicate bonds, this binder is more resistant to acid attacks, with added qualities of high early strength and low shrinkage degrees [ 147 ]. Critical reviews of the experimental studies made so far have been recently published regarding the mixture design, printability, and fresh and hardened properties of 3D-printed geopolymers, considering different factors and economic and environmental benefits [ 148 , 149 ]. Further investigation is necessary to eliminate the constraints found [148,150]. Buildings 2024,14, 1323 16 of 22 10. Szmigiera, M. Total Global Research and Development (R&D) Spending on Automotive from 2017 to 2019. Available online: https: //www.statista.com/statistics/1102932/global-research-and-development-spending-automotive (accessed on 28 February 2024). 11. Pessoa, S.; Guimarães, A.S.; Lucas, S.S.; Simões, N. 3D printing in the construction industry—A systematic review of the thermal performance in buildings. Renew. Sustain. 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