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Abstract: Recently, many efforts have been made to recycle waste of different nature as constituents of sustainable concrete. This practice produces large environmental benefits that can be further extended if deleterious chemical side-reactions, deriving from the use of some types of waste and/or raw materials, could be prevented and suppressed. This paper presents the combined action of different ceramic wastes partially replacing natural sand and cement, respectively. Alkali silica reaction (ASR) promoted by boron–silicate and lead–silicate glass used as fine aggregates (⩽4mm) is limited and controlled by using a new type of blended cement based on a siliceous residue coming from sludge produced by the polishing of porcelain stoneware tiles. The results of expansion tests carried out in accelerated conditions together with mechanical and microstructure characterisations of mortar samples highlight the combined action of the investigated wastes. Indeed, the blended cement containing porcelain stoneware polishing residue can be effectively exploited as valid alternative to pozzolan cement. [Copyright &y& Elsevier]

Abstract: The large amount of waste yearly disposed to landfill, the global impoverishing of natural resources and environment, the emergency of carbon dioxide emissions, are some of the motivations driving research institutes and industrial world to move towards sustainable solutions for civil engineering field. Accordingly, the use of sustainable materials for green buildings construction is an important goal that must be reached in short times. Sustainable cements can be designed by partially replacing clinker content with non hazardous waste. Indeed, recycling process can transform waste in secondary raw materials that work as new cement constituents usually leading to sustainable binders with peculiar environmental resistances. Details of cement manufacturing process and its effect on the environmental pollution as well as the route that can be carried out to tailor sustainable cements are reported and discussed. [Copyright &y& Elsevier]

Abstract: Blended cements are largely used for concrete: they are usually considered cements with a low environmental impact, as they require less clinker than ordinary Portland cement (OPC). Different constituents can be used as supplementary clinker component usually leading to cement with high resistance to outdoor environment. Polishing residue (PR), coming from porcelain stoneware tiles production, can be successfully used as new constituent for blended cement, however its action for enhancing the durability of cement matrix must be assessed. With this purpose, electrochemical tests (half cell potential, impressed voltage and linear polarization techniques) have been carried out on steel reinforced mortar samples, prepared using a 25% PR based cement and 100% OPC as binder and exposed to a 3.5% NaCl solution. The corrosion resistance results and microstructure analysis highlight better durability performances for PR based cement than those exhibited by OPC, mainly for curing time >28days. [Copyright &y& Elsevier]

Abstract: The alkali–silica-reaction (ASR) expanding behavior of different types of glass, all derived from cullet with different chemical composition, has been investigated. The glass reactivity was determined in different alkaline solutions based on sodium and/or calcium hydroxide to simulate concrete environment. The expansion of mortar containing different amounts of the investigated glass as fine aggregate has been carried out in different conditions: data collected underline a different response of glass towards the alkaline environment. Soda–lime glass shows negligible expansion, lead–silicate glass always generates expanding trends while boro–silicate glass has different behaviors depending on its colour. An attempt to link the behavior to the solubility and chemical reactivity of the glass is proposed. [Copyright &y& Elsevier]

While cast geopolymers are deeply investigated, geopolymers shaped by pressing are still rather unexplored. This work aims at developing one-part pressed geopolymers investigating the influence of parameters such as Na/Al molar ratio, water content and pressure load on the physical, microstructural and durability properties of the hardened geopolymers. Geopolymers were prepared by dry mixing and cured at 70 °C for 24 h and at room temperature for further 6 days. Density, water absorption, porosity features, microstructure and durability have been determined for all the samples. The results show that Na/Al molar ratio, water content and pressure load are key parameters to control the properties of one-part geopolymers. Their optimization can allow to obtain geopolymers suitable for microfiltration flat membrane support. Finally, the best performances in terms of durability are obtained when using the highest pressure load (20 MPa) and water content (15%). [ABSTRACT FROM AUTHOR]

This study investigated the potential application of geopolymeric material for the separation of oil-in-water emulsions in wastewater treatment. For the first time, an asymmetric membrane made of geopolymers was developed for this specific separation process. The performances of the geopolymeric membrane in oil separation were compared with those obtained by a commercial ceramic membrane. The study also aimed at exploring the effects of emulsion formulation and emulsion properties (surfactant type and concentration, pH, and zeta potential) and membrane parameters (surface charge and material) on permeate volumetric flux and chemical oxygen demand (COD) rejection. Emulsions were prepared using 3% (w/v) dodecane oil in distilled water, with surfactant concentrations of 1x and 10x critical micelle concentration (CMC) and three surfactants of different nature (Oleth-10, Brij 76, and CTAB) at pH values of 2, 5, and 8. Results showed that for the best operating conditions of the geopolymeric membrane, initial and final permeate flux values of 42 and 26 L h−1 m−2, respectively, were achieved. COD rejection values ranged from 95.0 to 99.4% using the geopolymeric membrane thus indicating a very similar behavior between geopolymeric and ceramic membranes. These findings suggest that geopolymers are promising to produce membranes for oil-in-water emulsion microfiltration, promoting an interesting alternative for the treatment of industrial wastewater more sustainable in terms of environmental effects and costs compared to ceramic membranes. • Novel geopolymeric asymmetric membrane was synthetized. • Geopolymer selective layer was successfully deposited on pressed geopolymer support. • The geopolymeric membrane showed excellent fluxes and removal efficiencies. • Flux and rejection properties vary with surfactant concentration and emulsion pH. • Geopolymer membrane performs similarly to a commercial microfiltration ceramic one. [ABSTRACT FROM AUTHOR]

This study reports on the possibility of applying one-part pressed geopolymers as a support for microfiltration membranes. The mineralogical, physical, mechanical, microstructural and hydraulic properties of the investigated materials are presented. Metakaolin-based geopolymeric membrane flat supports were synthesized by uniaxial pressing a dry-mixed powder (Si/Al = 1.45, Na/Al = 0.9, Na/Si = 0.62, H 2 O = 12%), with pressure between 2 and 20 MPa and a curing temperature of 70 °C. Mixing and pressing optimization resulted in samples with a total open porosity up to 39%, a modal pore diameter up to 23.5 μm and a flexural strength up to 20.4 MPa. Permeation measurement with demineralized water and ethanol-water solutions were carried out using a dead-end geometry membrane apparatus. A hydraulic permeability up to 31.3 · 103 L h−1 m−2 bar−1 has been obtained. Furthermore, permeation tests using water-ethanol solutions have demonstrated that the material is hydrophilic. These results highlighted the potential of geopolymers as microfiltration support. • Pressed one-part geopolymers are suitable to be used as membrane supports. • Geopolymer membrane supports possess a peculiar threshold pressure. • Geopolymer supports have similar characteristics to ceramic membrane supports. [ABSTRACT FROM AUTHOR]

This paper presents the comparative results obtained from X-ray and neutron pair distribution function (PDF) analysis aimed at determining the variability in aluminosilicate glass chemistry in five types of class F fly ash (FA). Results have been discussed in light of the complementary information provided by the two methods in order to give a comprehensive overview of FA structure at the nanoscale. The analysis of short range correlations reveals that the bulk glassy structure of FA sources differing in chemical composition are relatively similar, but some specific distinctions in atomic structure are visible in those containing high levels of amorphous VI-coordinated aluminum (e.g., amorphous mullite/alumina), iron and/or carbon (with similar local bonding environment to graphite). The obtained experimental results fill a deficit in literature in the atomic structure and associated variability for class F FA, which is extensively used in several industrial applications including as raw material in alkali-activated cements. [ABSTRACT FROM AUTHOR]

The addition of fibres to a brittle matrix is a well-known method to improve the flexural strength. However, the success of the reinforcements is dependent on the interaction between the fibre and the matrix. This paper presents the mechanical and microstructural properties of PVA and basalt fibre reinforced geopolymers. Moreover low density and thermal resistant materials used as insulating panels are known be susceptible to damage due to their poor flexural strength. As such the thermal and fire resistance properties of foamed geopolymers containing fibre reinforcement were also investigated. The results highlight that the presence of PVA fibres greatly increased the flexural strength and the toughness of the geopolymer composite, while the presence of basalt fibres improved the flexural behaviour of the composite after high temperature exposure. [ABSTRACT FROM AUTHOR]

• Protectiveness of fluoropolymer coating (FA-MS) on patinated bronze was assessed. • FA-MS coating covered the patinated bronze with a transparent layer few μm thick. • Good durability of FA-MS on bronze artwork was observed in real outdoor exposure. • Brushing was an efficient method for removing FA-MS without altering bronze patina. The application of protective coatings for the conservation of outdoor metallic artworks is currently considered the best approach actively employed. This paper focuses on the evaluation of the protectiveness of an optimised fluorosilane (FA-MS) coating with low occupational hazard impact and high inhibition efficiency. FA-MS coating was applied on a typical historical as-cast bronze (Cu-Sn-Zn-Pb), artificially patinated by synthetic acid rain dropping, to simulate natural unsheltered patinas. Subsequently, the patinated bronze was coated by brushing and then artificially aged by synthetic rain dropping. In order to investigate the coating-patina system, a multi-analytical approach was applied including scanning electron microscopy coupled with elemental analysis (FEG-SEM with EDS), microstructural analysis of cross-sections produced by Focused Ion Beam milling (FIB) and X-ray Photoelectron Spectroscopy (XPS). The coating homogenously covered the whole patinated surface producing a transparent layer few μms thick. The weathering solutions were also analysed for the assessment of metallic cations release. FA-MS showed excellent protective performances for the patinated bronze exposed to simulated outdoor conditions. Very high values of inhibiting efficiency in terms of metal release in the weathering solutions (up to 99%) were measured. In order to investigate all the necessary requirements for application in conservation field, the durability of FA-MS was also tested on a real bronze artistic casting, in terms of limiting the alloy composition changes (measured by in situ XRF) over time. A good durability of the coating was observed during the ongoing field exposure test. Lastly, reversibility of FA-MS was investigated by applying different mechanical cleaning methods, such as brushing and blasting. The reversibility was assessed by the evaluation of the morphology (colour change, surface roughness and optical microscopy) and the composition (SEM-EDS and Py-GC-MS chromatography) of the cleaned surfaces. Cleaning by brushing proved to be an efficient method for removing this coating without significantly altering the bronze patina. [ABSTRACT FROM AUTHOR]

Alkali-activated fly ashes have been proposed for various applications where resistance against high temperatures is required, yet several details regarding the response of these materials to heat-exposure need to be clarified. In the present study, heat-induced cracking in fly ash-based alkali-activated pastes and lightweight mortars was analyzed by in-situ acoustic emission (AE) detection during complete heating-cooling cycles (up to ∼1100 °C), augmented by thermogravimetry and ex-situ SEM and XRD analyses. The applicability of the lightweight mortars as passive fire protection coatings was assessed by recording temperature-time curves of mortar-coated steel plates. Cracking during heating was limited and associated exclusively with the dehydration of the materials in the temperature range ∼90–360 °C. However, samples heated to temperatures above ∼600 °C exhibited intense cracking on cooling. This was attributed to differential deformations caused by local sintering and partial melting at the glass transition temperature, and subsequent quenching on cooling. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Fly ash was successfully alkali activated at room temperature. • The use of expanded perlite and H 2 O 2 allowed obtaining lightweight mortars. • Numerical simulations predicted a satisfactory fire behaviour. • Alkali activated lightweight mortars were able to outperform cement-based ones. Abstract Alkali activated lightweight mortars, obtained by room temperature activation of coal fly ash, were studied as passive fire protection systems for steel elements. Physical, mechanical and thermal properties were investigated as a function of the compositional Si/Al molar ratio and of the amount of lightweight aggregate and foaming agent. Experimental findings were used as input data to assess their fire resistance by finite volume simulations. Results pointed out that the optimized alkali activated lightweight mortars are able to outperform alternative commercial cement-based mortars, thus representing a promising technology. [ABSTRACT FROM AUTHOR]

The compaction behavior of spray-dried powders has turned into concern in porcelain stoneware manufacturing due to the increasing diffusion of large slabs. It is necessary to fill a knowledge gap between the compaction behavior with conventional presses and novel technologies. For this purpose, eighteen industrially-manufactured spray dried bodies were characterized for specific properties connected to the compaction behavior (curves of bulk density, intergranular and intragranular porosity in function of applied load, apparent yield strength). In addition, the firing behavior was investigated in order to reveal any effect of dry bulk density on firing shrinkage and bulk density of fired samples. Powder compressibility is within 50% and 55% (Carr index) and is primarily controlled by moisture. Two regimes are found: low pressure (fast density increasing by granule cave in and closure of intergranular porosity) and high pressure (slow density gain by downsizing microporosity). A peculiar mechanism is unveiled: granules squeeze in the low-P regime and further densification is achieved through microfracture around individual agglomerate. A phenomenological model is illustrated for the compaction of spray-dried powders. In conclusion, the performance of spray dried bodies during compaction is crucial to control the uniformity, in terms of porosity and bulk density, which has important repercussions on the properties of final slabs, especially differential shrinkages and deformation during firing due to density gradients. [ABSTRACT FROM AUTHOR]

The technological behavior of porcelain stoneware bodies during deposition and pressing of large slabs depends on the rheological properties of spray-dried powders and the way they affect compaction. Although the literature offers some insights into the characteristics of spray-dried powders for ceramic tiles, no data are available on bodies utilized by novel technologies for large slabs (>4 m 2 ). In order to fill this gap, a systematic approach to properties and behavior of spray-dried powders for porcelain stoneware slabs was carried out. For this purpose, twenty industrially-manufactured spray-dried powders were characterized for intrinsic features (particle size and agglomerate size distribution; shape and moisture distribution in function of agglomerate size) and rheological properties (mass flow, static and dynamic angles of repose, poured and tap density, Hausner ratio). The effect of intrinsic characteristics on the flowability of powders was appraised, as the mutual relationships between the rheological parameters, in order to unveil the best parameters to be used in ceramic tile production. Two broad classes of spray-dried powders occur with a finer and a coarser agglomerate size distribution. Results reveal that ceramic powders are free-flowing, with rheological properties fluctuating in a rather narrow range of values, which makes hard to see significant relationships among the various methods (the only strict correlation is between mass flow rate and tap density). Flowability mainly depends on the occurrence of coarser aggregates, particularly those irregular in shape, stemming from coalescence of three or more individual agglomerates. A phenomenological description of how the spray-dried powders behave in the deposition on tape and the early stage of compaction is outlined. [ABSTRACT FROM AUTHOR]

Steel fiber reinforced geopolymer matrix (S-FRGM) composites are explored as a new tool in strengthening applications of reinforced concrete (RC) structures. The suitability of fly ash geopolymers as the matrix employed in S-FRGMs is investigated in this paper. Geopolymer matrix is used to embed galvanized steel fibers and bond the composite to a concrete substrate. By varying the molar concentration of the NaOH activating solution, three different geopolymer matrices are obtained and the influence of the alkaline environment on the bond behavior between fibers and matrix is examined. Physical, mechanical, and microstructural properties of the three matrices are measured and related to the interfacial bond behavior of S-FRGM-concrete joints. Results show that the decrease of the molar concentration of the NaOH activating solution leads to an increase of the interfacial bond behavior between matrix and fibers, which in turn improves the effectiveness of the composite action of the strengthening system. [ABSTRACT FROM AUTHOR]

Porcelain stoneware tiles are industrially processed by using high sintering temperatures and fast firing cycles that result in products characterized by an almost impervious surface layer surrounding a rather porous bulk material. Since mechanical properties are affected by porosity, the knowledge of the material stiffness is an important parameter to define the service behavior of tiles. In the present investigation, porcelain stoneware samples having different closed porosity were investigated in order to understand the influence of the porosity on the elastic constants of the materials. Based on the quantitative XRD phase composition, elastic constants have been calculated via Voigt-Reuss-Hill averaging, and the influence of porosity has been taken into account via power-law and exponential relations. It is shown that the effective elastic constants predicted by exponential and power-law relations are in agreement with experimental values. It may be concluded that for this class of materials, in the porosity range below 14–16%, both exponential and power-law relations are helpful tools to design tiles with controlled microstructure and tailored mechanical properties. [ABSTRACT FROM AUTHOR]

The response to thermal variations is the primary cause of marble deterioration in ancient and modern buildings. In this study, the thermal behavior of Carrara marble after consolidation by an innovative hydroxyapatite-based treatment was investigated in comparison with ammonium oxalate and ethyl silicate. Samples were subjected to heating-cooling cycles up to 80 °C. All the consolidating treatments were found to be fairly compatible, as in no case the residual strain after the thermal cycles was found to increase compared to the unweathered untreated marble. Anyway, the hydroxyapatite-treatment has the advantage of causing the highest increase in marble cohesion and the lowest residual strain, besides being more chromatically compatible and durable than the alternative commercial consolidants. [ABSTRACT FROM AUTHOR]

This paper aims at evaluating how the FRP/brick debonding force is influenced by brick mechanical properties (compressive, tensile and flexural strength) and physical-microstructural properties (surface roughness, porosity, pore size distribution, rate of water capillary suction). The depth of epoxy resin penetration into bricks and the thickness of brick layer detached at the end of bond test were also determined, in order to investigate the role of resin penetration into the brick on the FRP performance. All the tests were carried out on different brick surfaces (namely “bed” and “face”), to account for possible brick anisotropy. The results of the study point out that brick mechanical properties alone are not sufficient to accurately predict the maximum debonding force, but a better estimation can be achieved taking into account also brick surface roughness and resin penetration depth. If brick anisotropy is not considered, in some cases a remarkable overestimation of the maximum debonding force may be found. [ABSTRACT FROM AUTHOR]

Alkali-activation of brick waste has recently been proposed as a sustainable route to develop pastes/mortars with tailored mechanical properties and pore system. In this study, the suitability of using pastes from brick waste alkali-activation for repointing existing masonries (i.e., filling the most external part of mortar joints, lost due to deterioration processes) was investigated. Five different formulations (having SiO 2 /Al 2 O 3 molar ratio ranging from 1.4 to 0.4) and two different curing temperatures (room temperature and 50 °C) were investigated. Open porosity and efflorescence formation were found to decrease for decreasing SiO 2 /Al 2 O 3 ratio. Curing at high temperature generally favored geopolymerization and reduced efflorescence formation. Pastes with SiO 2 /Al 2 O 3 =0.8 and 0.9 exhibited open porosity and water vapor permeability fairly similar to those of historic lime-based mortars, thus proving to be potentially compatible with them. Further optimization of the mix design seems however necessary to reduce the formation of efflorescence. [ABSTRACT FROM AUTHOR]

[Display omitted] • Reclaimed asphalt pavement (RAP) was tested as aggregate replacement for concrete. • Five types of RAP sourced by different Italian collection sites were characterized. • RAP shows irregular porous surface due to bitumen covering the natural aggregate. • RAP shows hydrophobic behavior. • RAP exhibits dimensional stability and frost resistance. A study about the performances of reclaimed asphalt pavement (RAP) sourced from 5 different Italian collection sites is presented to evaluate RAP as aggregate for concrete. Several RAP properties were investigated: physical properties (particles size distribution, water absorption, porosity, wettability), microstructure by microscopy, dimensional stability (drying shrinkage of mortar and concrete with 100% of RAP as aggregates) and durability assessment by freezing-thawing cycles. Several differences between RAP and natural aggregates used for concrete were highlighted. The use of RAP as recycled aggregate for concrete is a promising route, but a complete characterization is needed to ensure concrete performance and durability. [ABSTRACT FROM AUTHOR]

Foaming to reduce the density of geopolymeric materials is increasingly being reported in the literature as it has been shown to be effective in improving their insulating properties. However, there is no consistency in foaming methods and as such this study was performed to compare methods in order to better understand their effect on the properties of geopolymers. A surfactant and two chemical foaming agents (hydrogen peroxide and aluminium powder) were added to a fly ash based geopolymer matrix. Surfactant was also combined with each of the chemical foaming agents in order to stabilise the foam in the geopolymer matrix and to reduce coarse pores. The physical, mechanical and microstructural properties of the low density geopolymers are presented and the effects of the foaming agents' characteristics on the hardened product is discussed, as well as the relative merits of the different procedures to synthesise the foamed geopolymer. It was found that homogeneous microstructures with small pores can be obtained by adding surfactant and hydrogen peroxide. The combination of hydrogen peroxide (0.1wt%) and surfactant (1.0wt%) produced geopolymer foams with density and compressive strength values of 0.94g/cm³ and 4.6MPa, respectively. [ABSTRACT FROM AUTHOR]

This paper examines the phase transformation, pore evolution, microstructural and mechanical changes that occur in inorganic polymer cement (IPC) in the presence of three different grade of fine aggregates (Φ<100μm) of ladle slag, nepheline syenite and quartz sand. Experimental results indicate that polycondensation was enhanced in nepheline syenite based specimens, compared to quartz sand, due to the increase in H M A S phases in relation to the dissolution and interaction of amorphous/disordered fraction of aggregates. H C S and H C A S with H M A S phases were identified in the ladle slag based specimens. The formation of these new phases reduced both the cumulative pore volume and pores size. The apparent increase in volume of capillary pores in ladle slag based specimens was explained by the residual bubbles from the carbonates included in raw slag. The flexural strength of the inorganic polymer cement increases from 4MPa to 4.2, 4.8 and 6.8MPa with the addition of 20wt% of quartz sand, nepheline syenite and ladle slag respectively. These values increase significantly between 28 and 180days of curing (9.1MPa for ladle slag and 10.0MPa for nepheline syenite). It was concluded that fines can be used to remove the HM and poorly bounded alumina oligomers in metakaolin based inorganic polymer matrices and improve the interfacial zone for the design of an optimum grade and high-performance composites. [ABSTRACT FROM AUTHOR]

Abstract: Old reinforced concrete (RC) structures often exhibit unsatisfactory performances in terms of both residual serviceability and seismic behavior. The durability requirements were not considered at all at the age of design and construction, exposing such structures to severe decay in aggressive urban and/or industrial environment; in the meantime, the use of plain steel bars (with poor bond strength) was common at the age of construction and this jeopardizes the RC performance under cyclic load reversals like those induced by earthquakes. In this paper, the deep impregnation of cement-based mortars and concrete with a solution of ethyl silicate and with electrochemical treatments by means of a solution of sodium carbonate was investigated, with a twofold aim: (1) increasing the bond strength of the embedded plain steel bars in existing structures without any need for demolition and (2) increasing the durability and safety of the reinforced concrete elements. Both the treatments are already exploited in other fields: ethyl silicate solutions are widely used for stone consolidation (and only recently proposed for concrete surface protection), while migration of sodium carbonate under DC voltage is used for RC realkalization. In the present study these treatments are expected to penetrate inside mortar and concrete and to modify their microstructure, hence improving their properties. The effects of the treatments are investigated by comparing the characteristics of treated and untreated mortar and concrete samples reinforced with plain bars, in terms of penetration inside the samples, pull-out strength, water absorption, pore size distribution, carbonation resistance and corrosion resistance. [Copyright &y& Elsevier]

• The fracture properties of three alkali-activated mortars are studied. • Low values of fracture energy might be associated with the presence of unreacted FA. • The fracture energy depends on the type of aggregate used. • Digital image correlation can be used to estimate the size of the FPZ. Results of three-point bending tests on notched beams cast with three alkali-activated mortars that differ by the type and size of the aggregates are presented. Digital image correlation is used to estimate the size of the fracture process zone. The fracture energy is computed by means of the work-of-fracture method and found to be strongly dependent on the type of aggregate used and does not differ whether the LDVT or DIC load-deflection curves are used. Finally, low values of the fracture energy in alkali-activated mortars might be associated with the presence of unreacted fly ash. [ABSTRACT FROM AUTHOR]