Eggshell Pavilion: a reinforced concrete structure fabricated using robotically 3D printed formwork.

This paper discusses the design, fabrication, and assembly of the 'Eggshell Pavilion', a reinforced concrete structure fabricated using 3D printed thin shell formwork. Formworks for columns and slabs were printed from recycled plastic using a pellet extruder mounted to a robotic arm. The formworks were cast and demoulded, and the finished elements were assembled into a pavilion, showcasing the architectural potential of 3D printed formwork. The Eggshell Pavilion was designed and fabricated within the scope of a design studio at ETH Zurich. The structure was designed using a fully parametric design workflow that allowed for incorporating changes into the design until the fabrication. The pavilion consists of four columns and floor slabs. Each column and floor slab is reinforced with conventional reinforcing bars. Two different methods are used for casting the columns and floor slabs. The columns are cast using 'Digital casting systems', a method for the digitally controlled casting of fast-hardening concrete. Digital casting reduces the hydrostatic pressure exerted on the formwork to a minimum, thereby enabling the casting of tall structures with thin formwork. The floor slabs are cast with a commercially available concrete mix, as the pressure exerted on the formwork walls is lower than for the columns. In this research, 3D printed formwork is combined with traditional reinforcing, casting, and assembly methods, bringing the technology closer to an industrial application. Supplementary Information: The online version contains supplementary material available at 10.1007/s41693-023-00090-x.

Using micro-XRF to characterize chloride ingress through cold joints in 3D printed concrete.

Digital fabrication methods with concrete have been rapidly developing, with many problems related to component production and material control being solved in recent years. These processes produce inherently layered cementitious components that are anisotropic, and in many cases, produces a weak interface between layers, which are generally referred to as cold joints. While material strength at these interfaces has been well studied in recent years, durability has received less attention, even though cold joints can function as channels for aggressive agents, such as chlorides. This work presents a method using micro-X-ray fluorescence (µXRF) to image chloride ingress into layer interfaces of 3D printed fine-grained concrete specimens produced with varying layer deposition time intervals, and also compares it to neutron imaging of moisture uptake. The results show that cold joints formed after a 1 day time interval are highly susceptible to chloride ingress, and that curing conditions play a major role in how quickly interfacial transport can take place. The µXRF method is also shown to be useful for study of transport of chlorides in cold joints, due to its spatial resolution and direct analysis of an aggressive species of interest.

A method for the mix design of low carbon concrete towards industrial production.

The introduction of newly developed blended cements into the mass market is essential to ensure an effective reduction of the carbon footprint related to cement production. To facilitate this process, formulating mix proportions using pastes and/or mortars rather than concrete can be a great advantage. However, for the upscaling towards industrial concrete it is then essential to maintain the target rheological and mechanical properties, something that is all too often challenging. In this work, a procedure facilitating such an upscaling was illustrated in the form of a flow chart. Specifically, best practices to obtain a good correlation between concrete prepared in a laboratory and one prepared in a plant were presented. This includes new data showing how to accommodate for possible differences in temperature and/or water content between both situations. The dataset of state-of-the-art correlations between mechanical performance and heat of hydration, considering w/b ratios relevant to practice, were expanded. This greatly facilitates the mix design of concrete with particularly low clinker contents, which in this work were illustrated with a blended cement containing only 50% clinker. Supplementary Information: The online version contains supplementary material available at 10.1617/s11527-022-02040-5.

Additive Digital Casting: From Lab to Industry.

Concrete construction harms our environment, making it urgent to develop new methods for building with less materials. Structurally efficient shapes are, however, often expensive to produce, because they require non-standard formworks, thus, standard structures, which use more material than is often needed, remain cheaper. Digital fabrication has the potential to change this paradigm. One method is Digital Casting Systems (DCS), where the hydration of self-compacting concrete is controlled on the fly during production, shortening the required setting time and reducing hydrostatic pressure on the formwork to a minimum. This enables a productivity increase for standard concrete production. More importantly, though, it enables a rethinking of formworks, as the process requires only cheap thin formworks, thus, unlocking the possibility to produce optimised structural members with less bulk material and lower environmental cost. While DCS has already proven effective in building structural members, this process faces the challenge of moving into industry. This paper covers the next steps in doing so. First, we present the benchmark and expectations set by the industry. Second, we consider how we comply with these requirements and convert our fast-setting self-compacting mortar mix into a coarser one. Third, we present the next generation of our digital processing system, which moves closer to the industrial requirements in terms of size and the control system. Finally, two prototypes demonstrate how DSC: (a) increases standard bulk production by 50% and (b) can be cast into ultra-thin formworks. We discuss the results and the short-term industrial concerns for efficiency and robustness, which must be addressed for such a system to be fully implemented in industry.

Eco-Friendly, Set-on-Demand Digital Concrete.

Digital fabrication with concrete is considered to potentially revolutionize the construction sector and is often presented as a means to reduce its environmental footprint. However, at least in the case of concrete, it encounters significant challenges in terms of material design, since high paste volumes and Portland cement contents are normally used due to process requirements. In this article, the application to layered extrusion of a recently developed low clinker cement containing 50% Portland cement and 50% supplementary cementitious materials, such as limestone, burnt oil shale, and fly ash, is presented. It is found that an accelerator paste composed by Calcium Aluminate Cement (CAC) and anhydrite provides the required hydration and structural build-up for 3D printing, while not compromising the early and long-term compressive strength. Such a low clinker mortar can be successfully retarded, processed, pumped, and extruded just after mixing it in line with the accelerator paste. This accelerated mortar formulation contains only 303 kg/m3 of Portland cement, which is roughly half the amount used in current accelerated formulations used for digital fabrication with concrete.

A Method for Characterizing the Chemical Heterogeneity of Comb-Copolymers and Its Dependence on Synthesis Routes.

The heterogeneity in chemical structure of polymers is difficult to characterize and consequently remains an often-overlooked factor in mechanistic studies of functional polymers, as well as in their industrial scale optimization. In this study, we present a method to characterize chemical heterogeneity and apply it to illustrate how it can be affected differently in different synthesis routes. The polymers used are comb-copolymer dispersants used in particulate suspensions which are composed of a polycarboxylate backbone onto which PEG side chains are grafted. The largest use of these polymers concerns concrete, where they are referred to as poly(carboxylate ether) (PCE) superplasticizers and produced at a very large industrial scale. Apart from their practical relevance, PCEs provide a good test case for studying the means and benefits of characterizing chemical heterogeneity. Indeed, the simple addition of a UV detector to a traditional SEC setup with RI detection allowed us to monitor variations in the grafting ratio in dependence on the molecular size. We show that the synthesis pathway significantly impacts the chemical heterogeneity. The suggested method is versatile and can be adapted for a wide range of hydrophilic copolymers. Thus, we present a tool to comprehensively analyze the molecular heterogeneity of dispersants and give a deep insight into their chemical dispersity.

Mastering Yield Stress Evolution and Formwork Friction for Smart Dynamic Casting.

The construction industry is a slow adopter of new technologies and materials. However, interdisciplinary research efforts in digital fabrication methods with concrete aim to make a real impact on the way we build by showing faster production, higher quality and enlarged freedom of design. In this paper, the potential and constraints of a specific digital slip-forming process, smart dynamic casting (SDC), are investigated with a material-focused approach in the complex task of producing thin folded structures. Firstly, the workability and the strength evolution of different material compositions are studied to achieve the constant processing rate for SDC. Secondly, friction between the formwork walls and the concrete, a key aspect in slip-casting, is studied with a simplified experimental setup to identify if any of these mixes would provide an advantage for processing. Finally, a theoretical framework is constructed to link the material properties, the process conditions and the designed geometry. This framework introduces the 'SDC number' as a simplified approach to formulate the process window, the suitable conditions for slip-forming. The experimental results prove the assumption of the model that friction is proportional to yield stress for all base compositions and acceleration methods regardless of the filling history. The results are evaluated in the context of the narrow process window of thin folded structures as well as the wider process window of columns. The necessity of consistent strength evolution is underlined for narrow windows. Further, friction is shown to be the highest initially, thus with both narrow and wide process windows, after a successful start-up the continuation of slipping is less prone to failure. The proposed theoretical model could provide material and geometry-specific slipping strategy for start time and slipping rate during production.

Energy-effective Grinding of Inorganic Solids Using Organic Additives.

We present our research findings related to new formulations of the organic additives (grinding aids) needed for the efficient grinding of inorganic solids. Even though the size reduction phenomena of the inorganic solid particles in a ball mill is purely a physical process, the addition of grinding aids in milling media introduces a complex physicochemical process. In addition to further gain in productivity, the organic additive helps to reduce the energy needed for grinding, which in the case of cement clinker has major environmental implications worldwide. This is primarily due to the tremendous amounts of cement produced and almost 30% of the associated electrical energy is consumed for grinding. In this paper, we examine the question of how to optimize these grinding aids linking molecular insight into their working mechanisms, and also how to design chemical additives of improved performance for industrial comminution.

Characterization of Comb-Shaped Copolymers by Multidetection SEC, DLS and SANS.

PolyCarboxylate ether-based superplasticizers (PCEs) are a type of comb-shaped copolymers used as polymeric dispersants in cementitious materials. PCEs have a high degree of dispersity, which limits the suitability of conventional characterization techniques, such as Size Exclusion Chromatography (SEC). Properties of PCEs strongly depend on their molecular structure and a comprehensive characterization is needed to fully understand the structure⁻property relationships. PCEs with well-defined molecular structures were synthesized to study their solution conformation by SEC and scattering techniques. The combined use of SEC, dynamic light scattering and small-angle neutron scattering allowed us to demonstrate the validity of a scaling law describing the radius of gyration of comb-shaped copolymers as a function of their molecular structure. Moreover, we show that the use of SEC with standard calibration, although widely spread, is not adequate for PCEs.

Understanding silicate hydration from quantitative analyses of hydrating tricalcium silicates.

Silicate hydration is prevalent in natural and technological processes, such as, mineral weathering, glass alteration, zeolite syntheses and cement hydration. Tricalcium silicate (Ca3SiO5), the main constituent of Portland cement, is amongst the most reactive silicates in water. Despite its widespread industrial use, the reaction of Ca3SiO5 with water to form calcium-silicate-hydrates (C-S-H) still hosts many open questions. Here, we show that solid-state nuclear magnetic resonance measurements of (29)Si-enriched triclinic Ca3SiO5 enable the quantitative monitoring of the hydration process in terms of transient local molecular composition, extent of silicate hydration and polymerization. This provides insights on the relative influence of surface hydroxylation and hydrate precipitation on the hydration rate. When the rate drops, the amount of hydroxylated Ca3SiO5 decreases, thus demonstrating the partial passivation of the surface during the deceleration stage. Moreover, the relative quantities of monomers, dimers, pentamers and octamers in the C-S-H structure are measured.

Lime as an Anti-Plasticizer for Self-Compacting Clay Concrete.

This paper focuses on the modification of clay properties with inorganic additives to deflocculate and flocculate inorganic soil for the development of a material that would be as easy to use as the current concrete products, but with a much lower environmental impact. Considering that the rheological behaviour of clays is controlled by their surface charge, we first introduce potential determining ions to deflocculate the clay particles and to reduce the yield stress of the earth material. Their efficiency is characterized using zeta potential measurements and rheological tests. We then achieve the flocculation of clay particles by using natural minerals that slowly dissolve in the interstitial liquid and ultimately precipitate calcium silicate hydrate (C-S-H). The precipitation products are identified by X-ray diffraction and the consequences of this delayed precipitation are followed by oscillatory rheometric measurements. Finally, it is suggested that in this process, C-S-H precipitation is not used as a binding vector but as an anti-plasticizer that removes the inorganic dispersant additives.

Thermo-Mechanical Compatibility of Viscoelastic Mortars for Stone Repair.

The magnitude of the thermal stresses that originate in an acrylic-based repair material used for the reprofiling of natural sandstone is analyzed. This kind of artificial stone was developed in the late 1970s for its peculiar property of reversibility in an organic solvent. However, it displays a high thermal expansion coefficient, which can be a matter of concern for the durability either of the repair or of the underlying original stone. To evaluate this risk we propose an analytical solution that considers the viscoelasticity of the repair layer. The temperature profile used in the numerical evaluation has been measured in a church where artificial stone has been used in a recent restoration campaign. The viscoelasticity of the artificial stone has been characterized by stress relaxation experiments. The numerical analysis shows that the relaxation time of the repair mortar, originating from a low T g , allows relief of most of the thermal stresses. It explains the good durability of this particular repair material, as observed by the practitioners, and provides a solid scientific basis for considering that the problem of thermal expansion mismatch is not an issue for this type of stone under any possible conditions of natural exposure.

3D Microstructure Effects in Ni-YSZ Anodes: Prediction of Effective Transport Properties and Optimization of Redox Stability.

This study investigates the influence of microstructure on the effective ionic and electrical conductivities of Ni-YSZ (yttria-stabilized zirconia) anodes. Fine, medium, and coarse microstructures are exposed to redox cycling at 950 °C. FIB (focused ion beam)-tomography and image analysis are used to quantify the effective (connected) volume fraction (Φeff), constriction factor (ß), and tortuosity (τ). The effective conductivity (σeff) is described as the product of intrinsic conductivity (σ0) and the so-called microstructure-factor (M): σeff= σ0*M. Two different methods are used to evaluate the M-factor: (1) by prediction using a recently established relationship, Mpred= ε߰.36/τ5.17, and (2) by numerical simulation that provides conductivity, from which the simulated M-factor can be deduced (Msim). Both methods give complementary and consistent information about the effective transport properties and the redox degradation mechanism. The initial microstructure has a strong influence on effective conductivities and their degradation. Finer anodes have higher initial conductivities but undergo more intensive Ni coarsening. Coarser anodes have a more stable Ni phase but exhibit lower YSZ stability due to lower sintering activity. Consequently, in order to improve redox stability, it is proposed to use mixtures of fine and coarse powders in different proportions for functional anode and current collector layers.

3D Microstructure Effects in Ni-YSZ Anodes: Influence of TPB Lengths on the Electrochemical Performance.

3D microstructure-performance relationships in Ni-YSZ anodes for electrolyte-supported cells are investigated in terms of the correlation between the triple phase boundary (TPB) length and polarization resistance (Rpol). Three different Ni-YSZ anodes of varying microstructure are subjected to eight reduction-oxidation (redox) cycles at 950 °C. In general the TPB lengths correlate with anode performance. However, the quantitative results also show that there is no simplistic relationship between TPB and Rpol. The degradation mechanism strongly depends on the initial microstructure. Finer microstructures exhibit lower degradation rates of TPB and Rpol. In fine microstructures, TPB loss is found to be due to Ni coarsening, while in coarse microstructures reduction of active TPB results mainly from loss of YSZ percolation. The latter is attributed to weak bottlenecks associated with lower sintering activity of the coarse YSZ. The coarse anode suffers from complete loss of YSZ connectivity and associated drop of TPBactive by 93%. Surprisingly, this severe microstructure degradation did not lead to electrochemical failure. Mechanistic scenarios are discussed for different anode microstructures. These scenarios are based on a model for coupled charge transfer and transport, which allows using TPB and effective properties as input. The mechanistic scenarios describe the microstructure influence on current distributions, which explains the observed complex relationship between TPB lengths and anode performances. The observed loss of YSZ percolation in the coarse anode is not detrimental because the electrochemical activity is concentrated in a narrow active layer. The anode performance can be predicted reliably if the volume-averaged properties (TPBactive, effective ionic conductivity) are corrected for the so-called short-range effect, which is particularly important in cases with a narrow active layer.

Chemo-mechanics of salt damage in stone.

Many porous materials are damaged by pressure exerted by salt crystals growing in their pores. This is a serious issue in conservation science, geomorphology, geotechnical engineering and concrete materials science. In all cases, a central question is whether crystallization pressure will cause damage. Here we present an experiment in which the crystallization pressure and the pore saturation are varied in a controlled way. We demonstrate that a strain energy failure criterion can be used to predict when damage will occur. The experiment considered is the most widely used means to study the susceptibility to salt crystallization, so quantification of this test has far-reaching implications.

A force field for tricalcium aluminate to characterize surface properties, initial hydration, and organically modified interfaces in atomic resolution.

Tricalcium aluminate (C3A) is a major phase of Portland cement clinker and some dental root filling cements. An accurate all-atom force field is introduced to examine structural, surface, and hydration properties as well as organic interfaces to overcome challenges using current laboratory instrumentation. Molecular dynamics simulation demonstrates excellent agreement of computed structural, thermal, mechanical, and surface properties with available experimental data. The parameters are integrated into multiple potential energy expressions, including the PCFF, CVFF, CHARMM, AMBER, OPLS, and INTERFACE force fields. This choice enables the simulation of a wide range of inorganic-organic interfaces at the 1 to 100 nm scale at a million times lower computational cost than DFT methods. Molecular models of dry and partially hydrated surfaces are introduced to examine cleavage, agglomeration, and the role of adsorbed organic molecules. Cleavage of crystalline tricalcium aluminate requires approximately 1300 mJ m(-2) and superficial hydration introduces an amorphous calcium hydroxide surface layer that reduces the agglomeration energy from approximately 850 mJ m(-2) to 500 mJ m(-2), as well as to lower values upon surface displacement. The adsorption of several alcohols and amines was examined to understand their role as grinding aids and as hydration modifiers in cement. The molecules mitigate local electric fields through complexation of calcium ions, hydrogen bonds, and introduction of hydrophobicity upon binding. Molecularly thin layers of about 0.5 nm thickness reduce agglomeration energies to between 100 and 30 mJ m(-2). Molecule-specific trends were found to be similar for tricalcium aluminate and tricalcium silicate. The models allow quantitative predictions and are a starting point to provide fundamental understanding of the role of C3A and organic additives in cement. Extensions to impure phases and advanced hydration stages are feasible.

Conformation of adsorbed comb copolymer dispersants.

Comb copolymers with an adsorbing backbone and nonadsorbing side chains can be very effective dispersants, particularly when a high ionic strength strongly penalizes electrostatic stabilization. For this reason, they have become essential components of concrete over the past decade. This article examines the steric hindrance characteristics of such polymers through the use of atomic force microscopy (AFM) on calcium silicate hydrate, the main hydration product of Portland cement. It is found that solution and surface properties (hydrodynamic radius, radius of gyration, surface coverage, steric layer thickness) and force-distance curves obtained during AFM measurements can be well described by a scaling approach derived in this paper. This represents the first real quantitative step in relating these properties directly to the molecular structure of such comb copolymer dispersants.