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Superhydrophobic surfaces present promising applications in the protection of building materials, such as the self-cleaning effect promoted by their high water-repellent properties. However, these surfaces easily lose their properties when exposed to oil contaminants. This is a critical weak point for their application in building facades, which are exposed to environmental pollutants such as hydrocarbons and vandalism (e.g., grafitti). A viable strategy to remove oils is to produce superhydrophilic surfaces, which present underwater superoleophobic behavior. In the case of buildings, the use of this strategy can be considered counterproductive because it promotes their interaction with water, the main vehicle of most decay agents. In this work, we have successfully combined the advantages of a superhydrophilic coating with a hydrophobic impregnation treatment, which prevents water ingress into the porous structure of the substrate. Specifically, a photoinduced superhydrophilic surface was produced on concrete by simple spraying of a starting sol containing TiO2NPs, which create a Cassie-Baxter state, a silica oligomer, producing a compatible matrix promoting good adhesion to the substrate and polydimethylsiloxane as a hydrophobic agent. After being exposed to sunlight, the treated surfaces switched from superhydrophobic (SCA 160°) to superhydrophilic (SCA 85% reduction). The treatment showed suitable adhesion to the substrate and good resistance to rainfall and outdoor exposure due to the presence of the hydrophobic silica matrix in the concrete pore structure.

The composition and structure of Calcium-Silicate-Hydrate (C-S-H) phases depends on various reaction parameters leading to its formation. Molecular Dynamic simulation studies probing the formation and structure of C-S-H are generally computationally expensive and can reach only very short time scales. Herein, we propose a coarse graining approach to model the formation of C-S-H, using patchy particles and a modified Patchy Brownian Cluster Dynamics algorithm. The simulations show that patchy particle systems can recover the qualitative kinetic evolution of C-S-H formation, and the obtained final structures were comparable to previously reported molecular dynamics studies and experiments. The model was extended to study the effect of water in the polymerization of tetraethoxysilane oligomers, the principal component of an impregnation treatment for deteriorated concrete surfaces. The intermediate system properties predicted by the simulations, such as viscosity and gel time, and structure were found to be well in accordance with the tailored experiments., The work described in this manuscript has been performed under InnovaConcrete EC project, supported by funding from the European Union's Horizon 2020 Research and Innovation Programme under Grant Agreement N° 760858. AP and JSD also acknowledge the support received from the BASKRETE initiative and the Joint Transborder Laboratory (LTC) “Aquitaine-Euskadi Network in Green Concrete and Cement-based Materials”.

As a consequence of human activities, today, we are exposed to high pollution levels that cause building materials damage and many diseases. The application of TiO2 as coating on building materials has proven the efficiency of self-cleaning and air de-pollution. However, its performance is limited due to its absorption being exclusively located at UV light. In this study, Cu-TiO2 photocatalysts were integrated into silica sol-gel synthesis to manufacture new long-lasting term coatings with self-cleaning and air purification properties for concretebased building materials. The enhancement of TiO2 photoactivity by incorporating Cu into its network has been clearly demonstrated. The self-cleaning and air de-polluting efficiency were assessed using methylene blue (MB), soot and NO, respectively, indicating that the presence of Cu promotes the TiO2 performance. For low doping levels, by increasing the copper loading, the TiO2 photoactivity increased. The highest efficiency was obtained by the photocatalyst containing 5% copper, which shows maximum destruction of methylene blue and soot of 95% and 50% within 60 min and 168 h of irradiation, respectively. However, higher copper loading led to a decrease in its performance, reaching a total degradation of MB and soot of 90% and 45% after 60 min and 168 h of irradiation, respectively, for the sample containing 15% of copper loading., This work has been supported by the Spanish Government/FEDEREUMAT2017-84228-R, MINECO/AEI/FEDER/UE) and PID2020115843RB-I00/AEI/10.13039/501100011033. This work has been cofinanced by the European Union under the 2014-2020 ERDF Operational Programme and by the Department of Economic Transformation, Industry, Knowledge, and Universities of the Regional Government of Andalusia. Project reference: FEDER-UCA18-106613. We want to thank Margarita Carballido, Mercedes Marquez and Sergio Moreno to facilitate the real exposure of the samples.

The air pollution is becoming one of most important health problems around the world. Thus, the development of depolluting building materials is a crucial challenge. TiO2 is a photocatalyst with demonstrated performance for degradation of NOx and other typical pollutants. However, its limited absorption of solar light reduces its performance. In this study, Au-TiO2NPs are integrated into a silica matrix in order to produce long-lasting coatings with de-pollutant performance and applicability in building. The interaction between Au and TiO2 improves the photoactivity of TiO2 and it promotes a considerably increase in visible light absorption. A significant role of the AuNPs size and their loading on the material photoactivity has been also demonstrated. The lowest AuNPs size enhances the activity due to their better dispersion and subsequently, the higher Au-TiO2 interaction observed. Regarding the Au loading, the maximum photoactivity, in terms of NO conversion and dye degradation, was reached for the intermedium Au loading. It can be mainly associated to the abrupt increase of Au-TiO2 agglomeration for the highest loading evaluated. Finally, it has been stablished that AuNPs also increased the selectivity of the NO oxidation to nitrates and nitrites, reducing the amount of NO2 released.

Alkoxysilane-based consolidation treatment are commonly employed in restoration and conservation works of Cultural Heritage buildings. However, their poor affinity to carbonate stones is well-known. In this paper, we evaluate three consolidant treatments (two of them modified to incorporate hydrophobic or photocatalytic properties), formulated to circumvent this drawback and their cracking during drying, through a surfactant-assisted synthesis. The consolidants were applied on Noto stone, a biocalcarenite (~95% CaCO3 ) employed in numerous Cultural Heritage buildings of Southern Italy. A comprehensive validation of the three consolidants, compared to a commercial TEOS based consolidant, was performed regarding their compatibility, effectiveness and susceptibility to degradation. The obtained results show that all consolidants improved the mechanical resistance of the stone, up to 6 mm for the commercial consolidant and up to 9 mm in depth for the surfactant-synthetized ones, though over-consolidation on the surface is a factor to watch for on the latter. Moreover, the treated stones exhibited a greater resistance to salts ingress respect to untreated ones related to the reduction in the smaller pores (0.1–2 μm range). In addition, all tested consolidants can be considered within the low and moderate incompatibility degree, though this factor is slightly higher than for the commercial one. Regarding the susceptibility to degradation, the surfactant-synthetized products experienced lower loss of consolidating effect, compared to the commercial one, after prolonged immersion in water and salts (sulphate) crystallization tests. However, the modification of the consolidant to obtain photocatalytic properties has a significant impact on its susceptibility against the latter.

Water and waterborne decay agents (e.g. salts, microorganisms) are commonly associated with undesired alterations and damages on concrete elements. A strategy to mitigate their impact is to decrease water retention in the material either by surface treatments or admixtures. In this work, hydrophobic concretes were developed by the addition of a hydrophobic sol containing TEOS and PDMS oligomers, synthetized by a surfactant-assisted sol-gel route, either as an admixture or as a surface treatment. The hydrophobic performance was similar for both application modes (>70% capillary absorption reduction) and higher than concrete containing a commercial (calcium stearate) admixture or a nanosilica-based hydrophobic coating. Addition as an admixture led to a higher durability in the rain and abrasion tests. The hydrophobic sol as an admixture promotes an increase of surface roughness and porosity, as well as the formation of C–S–H like reaction products with the cement matrix components, as evidenced by AFM, MIP, SEM and FTIR. Despite the higher porosity, impact resistance and material cohesion were not negatively affected respect to the plain concrete. Application as a surface treatment decreased porosity and led to a higher amorphous SiO2 content. The material cohesion and impact resistance was increased by this application, although penetration was limited to the first 4 mm and the hydrophobic properties were more susceptible to mechanical damages to the surface. © 2021 The Authors, This project has received funding from the European Union's Horizon 2020 - Research and Innovation Framework Programme under grant agreement No 760858; This work has been financed by the Spanish State Research Agency R&D program 2020 (Project reference: PID2020-115843RB-I00); This work has been co-financed by the European Union under the 2014-2020 ERDF Operational Programme and by the Department of Economic Transformation, Industry, Knowledge, and Universities of the Regional Government of Andalusia (Project reference: FEDER- UCA18-106613).

The performance of impregnation treatments used for protection and remediation of porous building materials relies on sufficient penetration depth. The penetration of sol–gel impregnation products into partially saturated porous material is driven by capillary suction and depends on material properties, such as pore size distribution on one hand, and on the other hand on sol physical properties, viscosity, density, surface tension and contact angle, along with the time in which the sol gels. In this work we analyse, by the way of modelling and experiments, the penetration depth of a sol–gel impregnation product as the function of pore size distribution and sol properties. The main goal is to determine the importance of sol’s physical properties for the penetration depth for a specific pore size, which will serve as a basis of the optimization of impregnation products to maximize their penetration depth. The model is first calibrated in terms of penetration depth and sol uptake by the experimental data obtained from mortar samples each with a specific pore-size distribution. The correlation between penetration depth and physical parameters is then established by the use of Monte-Carlo method. The results show that the most important parameters for the optimization are surface tension, whose influence increases for larger pores, and gelation time, which with decreasing importance for larger pores., The work described in this manuscript has been performed under InnovaConcrete EC project, supported by funding from the European Union’s Horizon 2020 Research and Innovation Programme under Grant Agreement N° 760858.

Following treatment with androgen receptor (AR) pathway inhibitors, ∼20% of prostate cancer patients progress by shedding their AR dependence. These tumors undergo epigenetic reprogramming turning castration-resistant prostate cancer adenocarcinoma (CRPC-Adeno) into neuroendocrine prostate cancer (CRPC-NEPC). Currently, no targeted therapies are available for CRPC-NEPCs, and there are minimal organoid models to discover new therapeutic targets against these aggressive tumors. Here, using a combination of patient tumor proteomics, RNA sequencing, spatial omics, immunohistochemistry, and a synthetic hydrogel-based organoid, we define putative extracellular matrix (ECM) cues that regulate the phenotypic, transcriptomic, and epigenetic underpinnings of CRPC-NEPCs. Short-term culture in tumor-expressed ECM differentially regulated DNA methylation and mobilized genes in CRPC-NEPC tumors. The ECM type distinctly regulated the response to small molecule inhibitors of epigenetic repressor EZH2 and Dopamine Receptor D2 (DRD2), the latter being an understudied target in neuroendocrine tumors. In vivo patient-derived xenograft studies in immunocompromised mice showed a robust anti-tumor response when treated with a DRD2 inhibitor. Finally, we demonstrate that therapeutic response in CRPC-NEPCs under drug-resistant ECM conditions can be overcome by first cellular reprogramming with EZH2 inhibitors, followed by DRD2 treatment. The synthetic hydrogel-based organoids suggest the regulatory role ECM may play in therapeutic response to targeted therapies in CRPC-NEPCs and enable the discovery of single drugs and combination therapies to overcome resistance. This article is protected by copyright. All rights reserved.

Building materials decay is caused by the combination of chemical, physical and biological aspects. Therefore, the development of innovative multifunctional building materials is an alternative to reduce their impact. This can be achieved by post-treatments or by direct changes in the fabrication of synthetic materials, such as engineered stone. The aim of this work is to develop a new type of engineered stone by using a CuO/SiO2 nanocomposite matrix, synthetized via sol–gel, as a binder and quartz particles of different grain size as aggregate. The use of a sol–gel route allows creating an amorphous SiO2 structure chemically compatible with the quartz aggregates, while CuO nanoparticles are added for their biocidal properties. The new materials present anti-fungal properties against yeast and Aspergillus carbonarius spores, a high surface hardness, thermal resistance and an appropriate impact resistance for their use in flooring and claddings, although their mechanical strength is overall lower than a resin-matrix engineered stone. The proportion of CuO in the matrix and water content modify the sol–gel kinetics and quartz sedimentation, which have an impact on the structure and mechanical properties.

Microbial fouling on the surface and water retention are common problems affecting porous ceramic materials (stone, concrete…) that can alter their properties, shorten their service life and even pose a health risk. Though proper maintenance (disinfection, drainage…) can mitigate these issues, it is a time and resource intensive process and preventive measurements are desired, such as hydrophobic or anti-fouling coatings. In this work, we report a simple sol-gel route to obtain a multifunctional coating combining superhydrophobic, biocide and photoactive properties, by incorporating TiO2 nanoparticles (NPs), functionalized with –SH or –NH terminated alkoxysilanes, and AgNPs into an organically modified silica matrix (ormosil). The low surface energy of the ormosil, combined with the nano-roughness created by the accumulation of Ag-TiO2NPs on the surface promotes a Cassie-Baxter wetting state, leading to water repellence and a lower bioreceptivity of the coatings due to a decreased cell attachment. The influence of this factor was evidenced by the comparatively higher cell attachment on the smoother surface of xerogels samples prepared from the ormosils, where TiO2 surface charge plays a major role. The incorporation of AgNPs increases the photocatalytic effectiveness of the TiO2 and effectively inhibits the growth of the tested microorganisms (Escherichia coli and Saccharomyces cerevisiae), even in the absence of light. Surface functionalization of the TiO2NPs affects the distribution, size and stability of the AgNPs, and thus, the biocide and photocatalytic effectiveness of the treatments.

A well-known drawback of sol–gel materials is their tendency to crack because of the high capillary pressure supported during drying. We have pioneered a facile and low-cost route to obtain monolithic xerogels, from a silica precursor and a surfactant, mixed under ultrasonic agitation. This route presents a clear interest for practical application at industrial scale. In this paper, a model to explain the formation of silica monoliths in the presence of the surfactant is presented. It is demonstrated that a stable microemulsion of water in the silica oligomer media is produced due to the combined effect of surfactant, producing inverse micelles, and ultrasonic agitation. The model proposed, suggests that the water is encapsulated in the surfactant micelles that act as nanoreactors, producing silica primary particles. The growth of these silica seeds continues outside the micelles until the formation of the constituent particles of the xerogel. Next, the particles are packed, and mesopores are produced from the interparticle spaces. This mesoporosity prevents xerogel cracking because it reduces capillary pressure during gel drying. An in-depth investigation of the structure of the xerogels revealed that they are effectively composed of silica nanoparticles of nearly uniform size values that could match with the size of the surfactant inverse micelles. Finally, it was demonstrated that surfactant and water content present a significant effect on the final structure of the xerogels. An increase of surfactant content produces a reduction in particle size, whereas an increase of water produces an opposite effect.

The decay of building materials is generally caused by the combination of chemical, physical and biological agents. Therefore, the development of products that combine multiple protection mechanisms is desirable. We have developed, via a sol-gel route, CuO/SiO2 nanocomposites with application as a multifunctional protective treatment for building stones. In this work, we demonstrate that CuONPs act as a catalyst of the sol-gel process and promote the formation of nucleation centers, affecting the final structure of the nanocomposites. We also conclude that the nanocomposites increase mechanical resistance and decrease microbial growth of two reference laboratory microorganisms (bacteria and yeast) on a typical building limestone. Moreover, the release of Cu2+ ions is the most likely mechanism for the biocidal effect. Finally, we find that the highest concentration of CuONPs, in the studied range (0.00–0.35% w/v), was not the most effective because it causes a NPs precipitation, decreasing the biocidal effect, and the resulting material is heterogeneous and fragile. An intermediate proportion of CuONPs provides a suitable consolidant and biocide performance. Keywords: Biocide, Biofouling, Building stone, Copper oxide, Silica nanocomposite, Consolidant

Gut microbiome and metabolic syndrome regulate nanovaccine response and can be immunomodulated using advanced nanomaterials., Biomaterials-based nanovaccines, such as those made of poly(lactic-co-glycolic acid) (PLGA), can induce stronger immunity than soluble antigens in healthy wild-type mouse models. However, whether metabolic syndrome can influence the immunological responses of nanovaccines remains poorly understood. Here, we first show that alteration in the sensing of the gut microbiome through Toll-like receptor 5 (TLR5) and the resulting metabolic syndrome in TLR5−/− mice diminish the germinal center immune response induced by PLGA nanovaccines. The PLGA nanovaccines, unexpectedly, further changed gut microbiota. By chronically treating mice with antibiotics, we show that disrupting gut microbiome leads to poor vaccine response in an obesity-independent manner. We next demonstrate that the low immune response can be rescued by an immunomodulatory Pyr-pHEMA nanogel vaccine, which functions through TLR2 stimulation, enhanced trafficking, and induced stronger germinal center response than alum-supplemented PLGA nanovaccines. The study highlights the potential for immunomodulation under gut-mediated metabolic syndrome conditions using advanced nanomaterials.

Although silicon alkoxides (especially ethylsilicates) have long been used as consolidants of weathered stone monuments, their physical properties are not ideal. In this study, an innovative procedure for the consolidation of sedimentary rocks was developed that combines the use of organometallic and alkylamine catalysts with the addition of well-defined nanoparticles exhibiting a narrow size distribution centered at ca. 10 nm. As a suitable test material, Pietra di Lecce limestone was selected because of its color and problematic physico-chemical properties, such as rather low hardness. Using the developed procedure, the mechanical and surface properties of the limestone were improved without the unwanted over-consolidation of the surface layers of the stone, and any significant deterioration in the pore size distribution, water vapor permeability, or the stone&rsquo, s appearance. The developed modified ethylsilicates penetrated deeper into the pore structure of the stone than the unmodified ones and increased the hardness of the treated material. The formed xerogels within the stone pores did not crack. Importantly, they did not significantly alter the natural characteristics of the stone.

Protective coatings with hydrophobic or biocide properties are commonly employed to prevent biofouling of building materials exposed to the environment. Although the factors affecting bioreceptivity of the base materials are well known, the influence of the coating and/or biocide agent surface properties on the interaction with the cell surface is often overlooked. As such, a proper understanding of these interfacial interactions can help improve their anti-fouling effectiveness. This work studies a multifunctional superhydrophobic/biocide treatment, containing surface engineered Ag/SiO2 nanoparticles embedded in an organically modified silica matrix, focusing on determining the effect of the cell-nanoparticle interactions and surface properties on its effectiveness against algal fouling. The modification of SiO2 with positively charged groups increased the interaction of the biocide with the cell walls through electrostatic forces, while at the same time it promotes cell aggregation. The hydrophobic matrix decreases initial colonization due to its lower roughness and water absorption, although surface free energy measurements indicated an increase of the cell-surface adhesion force as polarity of the cell wall decreased. A Cassie-Baxter wetting regime on the superhydrophobic surfaces decreased effective contact area and adhesion force, though this state was quickly lost under exposure to the cultures

Nowadays, PLA is one of the most promising alternatives to the petroleum-based polymers, since it can be obtained from renewable sources. An innovative application of PLA is to protect the exterior of buildings. PLA compounds meet an important requirement of products for conservation, which is their reversibility. This paper describes a simple procedure to create highly hydrophobic and reversible coatings. We demonstrate that water droplets produces contact angles of about 140° on a typical building marble by the combined action of roughness created by silica particles and low surface energy due to fluorine integrated in the PLA. Finally, we also demonstrate that the coatings under study preserve the esthetic properties of the stone substrate and that they do not significantly alter stone breathability. In addition, we confirm the reversibility of the coatings by using a simple procedure (removal by an organic solvent) that can be employed in a real-life situation.

Two factors are key in the design of a TiO2 photocatalyst for building materials that meets the requirements for environmental applications: the TiO2 light absorption restricted to UV and its poor adhesion to the substrates. In this work, two strategies of TiO2 modification, nitrogen doping and AuNPs deposition, were combined in order to promote the TiO2 photoactivity under solar radiation. By the other hand, the Au/N–TiO2 photocatalysts were incorporated in a silica sol allowing their application by spray on three different building material substrates (limestone, granite and concrete), where the sol spontaneously produced Au/N–TiO2/SiO2 well-adhered coatings. The samples photoactivity was evaluated by dye degradation tests and NO abatement measurements. The obtained results demonstrated that the AuNPs considerably enhanced the photoactivity of N–TiO2, doubling the amount of NOx removed under UV–visible light. In addition, the role of the substrate and the TiO2/SiO2 ratio of the coating were also investigated. The coatings practically triplicated their depolluting effectiveness on concrete in comparison with their application on limestone. A direct correlation between the TiO2 loading and the photoactivity was observed, increasing NOx abatement by a factor of 1.3 when the Au/N–TiO2 loading of the coating was raised from 10 to 25%. However, the Au presence can induce evident colour modifications of the treated substrates that can limit the product application on certain substrates.

The high pollution levels in urban areas is producing a significant damage on buildings. The use of photoactive coatings on building materials can produce building surfaces with self-cleaning and de-pollutant properties. We have developed a simple sol-gel route for producing Au-TiO2/SiO2 photocatalysts which were applied on common cultural heritage stones. We studied the photoactivity efficiency of the photocatalysts under study against methylene blue, soot and NOx.

In this work, the self-cleaning and photocatalytic properties of mesoporous TiO2/AuNRs-SiO2 composites (namely UCA&ndash, TiO2Au) prepared by a simple and low-cost technique were investigated toward application in building materials. Mesoporous photocatalytic nanocomposites coating the surface of stone and other building materials are a very promising approach to address relevant questions connected with the increasing atmospheric pollution. We tested three types of preformed TiO2/AuNRs nanostructures in order to evaluate the effect of AuNRs on the photocatalytic activity of resulting coatings deposited on the surface of a popular building limestone. The resulting nanocomposites provide crack-free surface coatings on limestone, effective adhesion, improve the stone mechanical properties and impart hydrophobic and self-cleaning properties. Photocatalytic characterization involved the degradation of a target compound (Methylene blue, MB) under direct exposure to simulated solar light using TiO2 P25 Evonik (TiO2 P25) as a reference material. Moreover, these coatings upon irradiation by simulated solar light were successfully employed for the photocatalytic oxidation of carbon soot. The experimental results revealed that UCA&ndash, TiO2Au samples are the best performing coating in both MB bleaching and soot degradation.

An effective procedure has been developed to consolidate and hydrophobize decayed monumental stones by a simple sol-gel process. The sol contains silica oligomer, silica nanoparticles and a surfactant, preventing gel cracking. The effectiveness of the process on biocalcareous stone samples from an 18th century cathedral has been evaluated, and it was found that the gel creates effective linking bridges between mineral grains of the stone. Silica nanoparticles produced a significant increase in the mechanical resistance and cohesion of the stone. The application of an additional fluorinated oligomer onto the consolidated stone gave rise to a surface with lasting hydrophobicity, preventing water absorption.

The high pollution levels in our cities are producing a significant increase of dust on buildings. An application of photoactive coatings on building materials can produce buildings with self-cleaning surfaces. In this study, we have developed a simple sol-gel route for producing Au-TiO2/SiO2 photocatalysts with application on buildings. The gold nanoparticles (AuNPs) improved the TiO2 photoactivity under solar radiation because they promoted absorption in the visible range. We varied the content of AuNPs in the sols under study, in order to investigate their effect on self-cleaning properties. The sols obtained were sprayed on a common building stone, producing coatings which adhere firmly to the stone and preserve their aesthetic qualities. We studied the decolourization efficiency of the photocatalysts under study against methylene blue and against soot (a real staining agent for buildings). Finally, we established that the coating with an intermediate Au content presented the best self-cleaning performance, due to the role played by its structure and texture on its photoactivity.

The synthesis of improved photocatalysts capable of removing pollutants deposited on building surfaces is an important challenge for researchers nowadays. By using a simple and low-cost process we have synthesized mesoporous Ag–TiO 2 –SiO 2 photocatalytic coatings that meet the requirements of outdoor application. These are new materials designed to give to the building material improved self-cleaning properties. We have varied the loading of TiO 2 and Ag nanoparticles in order to investigate their effect on the photocatalytic activity of our nanocomposites. We find that the integration of higher Ag loadings in a TiO 2 –SiO 2 network (10% w/w) significantly increase the photoactivity of the coating containing 1% (w/v) TiO 2 due to the improved absorption of visible light and higher surface area of the photocatalyst. For higher TiO 2 contents (4%) there is an increase in photoactivity for 1% (w/v) Ag loading. Higher amounts of Ag loadings (5% w/w) generate an undesired color change on stone or inhibit the sol–gel transition of the coatings (10% w/w).

In this article, the protocol to identify the most suitable consolidant to be applied in a granitic Romanesque church form Galicia is presented. The study consisted in two phases: an initial laboratory evaluation during which the treatment with a nanoconsolidant never applied on granite is compared with the treatment with two commercial consolidants (an acrylic resin and ethyl silicate), evaluating several properties in order to determine the effectiveness and harmful effects on the stone. In this phase, the new nanomaterial was identified as the most suitable product in order to slow down the specific deterioration processes which affect the building. In a second phase, the evaluation of the effectiveness and harmful effects of the application of the nanoconsolidant in the building is presented. This article also provides new data about two procedures to asses effectiveness never applied in granites.

TiO2 is a photocatalytic material that has proven to have the ability to produce self-cleaning and de-polluting building materials, which can be a valuable alternative to mitigate the pollution consequences. However, the TiO2 performance is limited in outdoor conditions due to its exclusive UV absorption. In this work, Au-TiO2 photocatalysts were integrated into a silica sol-gel synthesis in order to produce long-lasting coatings with self-cleaning and de-polluting properties on building materials. This simple synthesis allows the in situ application on buildings. The enhancement of TiO2 photoactivity by AuNPs was clearly demonstrated. The self-cleaning and de-polluting properties were evaluated using soot and NO, respectively, showing that AuNPs promote the TiO2 performance. In addition, the role of AuNPs size and their loading on TiO2 performance were investigated. It was demonstrated that the smallest AuNPs size (13 nm) and the intermedium gold content (0.5% w/w Au/TiO2) show the highest photoactivity.

The alarming increase of pollution has significantly increased buildings maintenance. Nowadays, the economic figures associated to repairing activities are even more relevant than those corresponding to new construction works, especially on heritage buildings. Since the degradation of building materials is the result of a complex combination of physical, chemical and biological agents, the development of multifunctional protective treatments remains a significant challenge. We report a simple strategy to produce a versatile biocidal/superhydrophobic/consolidant treatment by incorporating biocidal Ag nanoparticles (AgNPs) grafted to functionalized SiO2NPs into a silica sol, which can be applied by simple procedures such as spraying. The use of an Ag-SiO2 coupling agent increases biocidal effectiveness up to >90% values due to: (1) an increase of the AgNPs stability; (2) a hierarchical roughness due to the formation of Ag/SiO2NPs clusters; and (3) an enhanced contact with the cell walls. In addition, the synergistic effect allows for an easier removal of the dead cells, increasing the durability of the treatment.

Numerous superhydrophobic materials have been developed in recent years by using a combination of two strategies: reducing the surface free energy and roughening the surface. Most of these procedures have the serious drawback of involving tedious multistage processes, which prevent their large-scale application, such as on the external stone and similar material surfaces of buildings exposed to the weather. This paper describes an innovative synthesis route for producing superhydrophobic surface coatings. The coating can even be produced, outdoors, on the building by a low-cost process. We demonstrate that the addition of silica nanoparticles to a mixture of organic and inorganic silica oligomers in the presence of a surfactant produces a coating of closely packed particles. The effect of this is to trap air beneath the water droplets, thus significantly minimizing the contact area between droplet and surface. The organic component reduces the surface free energy of the material, resulting in a high static contact angle. This has the effect of repelling water because the water droplets that form simply roll rapidly down the coated surface. The surfactant plays a valuable role, acting as a sol-gel transition catalyst and, by coarsening the pore structure of the gel network, prevents the coating material from cracking.

A TiO2–SiO2 nanocomposite material was formed inside the pore structure of a very friable carbonate stone by simple spraying of a sol containing silica oligomers, titania particles and a non-ionic surfactant (n-octylamine). The resulting nanomaterial provides an effective adhesive and crack-free surface layer to the stone, and gives it self-cleaning properties. In addition, it efficiently penetrates into the pores of the stone, significantly improving its mechanical resistance, and is thus capable of converting an extremely friable stone into a building material with self-cleaning properties. Another important advantage of the nanocomposite is that it substantially improves protection against salt crystallization degradation mechanisms. In the trial described, the untreated stone is reduced to a completely powdered material after 3 cycles of NaSO4 crystallization degradation, whereas stone treated with this novel product remains practically unaltered after 30 cycles. For comparison purposes, two commercial products (with consolidant and photocatalytic properties) were also tested, and both alternative materials produced coatings that crack and provide less mechanical resistance to the stone than this product. These results also confirm the valuable role played by n-octylamine in reducing the capillary pressure responsible for consolidant cracking, and in promoting silica polymerization inside the pores of the non-reactive pure carbonate stone.

Atmospheric pollution has an evidently adverse impact on the esthetics of urban buildings and structures. Thus, the synthesis of photocatalysts capable of removing pollutants deposited on the surface of stone and other building materials is a challenge to researchers. By a simple and low cost process we have synthesized mesoporous TiO2–SiO2 photocatalytic coatings that meet the requirements of outdoor application. These are new materials designed to give to the building material long-term self-cleaning and strengthening properties. We have varied the loading and size of TiO2 nanoparticles in order to investigate their effect on the photocatalytic activity. We find that the integration of larger and sharper titania particles in a silica network with a titania content of around 4% (w/v) significantly improves self-cleaning effectiveness, due to the enhanced availability of surface photoactive sites. For a higher TiO2 content (10%, w/v), photocatalytic action decreases because the porous volume is drastically reduced and consequently, access to photoactive sites is more difficult.

Three innovative strengthening, protective and self-cleaning agents for marble and calcareous stones were synthesized by using a simple sol–gel route at ambient conditions. TiO2 nanoparticles and hydroxyl-terminated polydimethylsiloxane (PDMS) were incorporated in a tetraethoxysilane (TEOS) matrix in the presence of oxalic acid (Ox). Both the Ox concentration and the addition sequence of the reagent agents were assessed through the evaluation of the microstructure and of the physicochemical and self-cleaning properties of all the synthesized nanocomposites. The presence of Ox contributed to the production of both homogeneous materials and photoactive independent domains of anatase TiO2 crystals at ambient conditions. In addition, the role played by Ox as a hole-scavenger increased the photocatalytic activity of the nanocomposites. The synthesized crack-free, homogeneous, transparent and photoactive nanocomposites provide self-cleaning, water repellency and consolidation properties to building substrates, while respecting their aesthetic qualities.

Mesoporous titania-silica composites that have photocatalytic activity have been synthesized by mixing ethoxysilane oligomers and titanium dioxide nanoparticles in the presence of a nonionic surfac...

We have developed a simple sol–gel treatment procedure that enhances the properties of pure limestones to make them more suitable for commercial use; in particular, we have improved the mechanical robustness of the stone. When treated, the stone also has enhanced hydrophobic, water-repellent, and stain-resistant properties, which have been evaluated. We have demonstrated that the addition of poly(dimethylsiloxane) (PDMS) to a silica oligomer associated with a neutral catalyst, in the presence of a surfactant, accelerates the gelling process; this reduction of the time needed for the product to gel in carbonate stones helps to achieve effective stone consolidation. The addition of PDMS to the starting sol has been shown to produce a combined effect: it reduces surface energy and creates a dual scale of roughness that is responsible for the improvement of its water-repellent properties. Increasing the PDMS content thus improves the mechanical properties, hydrophobic behavior, and stain-repellent quality of ...

A challenging objective in monumental stone restoration is to synthesize crack-free silica materials for application as consolidants. Hydrophobicity is also a valuable property for such products; it is important to prevent the penetration of water because water is the main vehicle by which the agents of decay enter the pore structure of the stone. We report the development of a hydrophobic crack-free nanomaterial with application to stone restoration. Specifically, organically modified silicate (ormosil) has been synthesized by the co-condensation of tetraethoxysilane (TEOS) and hydroxyl-terminated polydimethylsiloxane (PDMS) in the presence of a nonionic surfactant (n-octylamine). The role played by the surfactant in the assembly of the organic-inorganic hybrid silica gel was investigated. We also prepared a crack-free material using the same synthesis but without adding PDMS to the starting sol. Finally, the effectiveness of the nanomaterials synthesized as a consolidant and hydrophobic protective treatment was evaluated on a particular widely used monumental stone. The high hydrophobicity of the organic-inorganic hybrid product synthesized in our laboratory is discussed as a function of the surface roughness of the material.

Monolithic gels, prepared from different mixtures of colloidal silica in a sol solution containing tetraethoxysilane under powerful ultrasonic agitation (sonosols), were compacted at an isostatic pressure of 390 MPa. Then N2 adsorption-desorption data were used to construct structural models of the gels using Monte-Carlo calculations on the basis of random close-packing (RCP) premises. Structural information on these composites obtained before compaction indicates that the characteristic uniform structure of silica colloid gel undergoes profound modification when it is mixed with silica sonogel. From a structural point of view, the behaviour under compaction of the sonogel phase, which exhibits a significant degree of microporosity, depends on the relative concentration of the colloidal phase. Two hierarchic levels of micropores were discerned. After compression, the size of the elementary particles—and their aggregates—of the sonogel phase increases from 1.6 to 2.1 nm radius when the colloidal phase content is increased from 30 to 82% by weight. For an intermediate content, 50% of the volume reduction is caused by compression of the sonogel phase at the micropore level.

We propose an innovative strategy to obtain crack-free gels by using a surfactant as a template for the silica pores. We use a neutral surfactant – n-octylamine – which weakly interacts by hydrogen bonding with the silica precursor. This allows it to be removed by simple drying in ambient air. We investigate the effect of the surfactant in simple inorganic silica obtained from tetraethoxysilane (TEOS) and an organic–inorganic hybrid xerogel, containing TEOS and polydimethylsiloxane (PDMS), as precursors. Although both the syntheses promote the formation of a crack-free uniform mesoporous silica gel, the hybrid gel network exhibits a larger pore size than the gel containing exclusively the silica from TEOS.

The main focus of this work is to determine the effect of cement addition, a common practice in many restorations, on the pore structure of lime-based mortars. A second target is to establish correlations between microstructure and water vapor transport across the mortar, which is a key characteristic of building decay. In order to achieve these objectives, we prepared a set of mortars consisting of air-hardening lime with a progressively increasing cement content, as well as a mortar containing hydraulic lime. Several different techniques, most notably mercury intrusion porosimetry and scanning electron microscopy in the backscatter mode, were used to investigate the pore structure. The results from these procedures led to the conclusion that porosity and pore size are progressively reduced as cement content increases. Moreover, an excellent correlation between pore radius parameter and the vapor diffusion coefficient was established. Hydraulic lime mortar exhibited textural parameters and diffusivity values halfway between those of the different lime/cement mixes studied.

A liquid isooctane (C$_{8}$H$_{18}$) filled ionization linear array for radiotherapy quality assurance has been designed, built and tested. The detector consists of 128 pixels, each of them with an area of 1.7 mm $\times$ 1.7 mm and a gap of 0.5 mm. The small pixel size makes the detector ideal for high gradient beam profiles like those present in Intensity Modulated Radiation Therapy (IMRT) and radiosurgery. As read-out electronics we use the X-Ray Data Acquisition System (XDAS) with the Xchip developed by the CCLRC. Studies concerning the collection efficiency dependence on the polarization voltage and on the dose rate have been made in order to optimize the device operation. In the first tests we have studied dose rate and energy dependences, and signal reproducibility. Dose rate dependence was found lower than 2.5 % up to 5 Gy min$^{-1}$, and energy dependence lower than 2.1 % up to 20 cm depth in solid water. Output factors and penumbras for several rectangular fields have been measured with the linear array and were compared with the results obtained with a 0.125 cm$^{3}$ air ionization chamber and radiographic film, respectively. Finally, we have acquired profiles for an IMRT field and for a virtual wedge. These profiles have also been compared with radiographic film measurements. All the comparisons show a good correspondence. Signal reproducibility was within a 2% during the test period (around three months). The device has proved its capability to verify on-line therapy beams with good spatial resolution and signal to noise ratio., 16 pages, 12 figures Submitted to Phys. Med. Biol

Crack-free monolithic gels were prepared from different mixtures of colloidal silica with a sol solution containing tetraethoxysilane, under powerful ultrasonic agitation (sonosol). Recently, information on the structure of these gels, inferred from N2 adsorption and mercury intrusion porosimetry, was presented. In the present paper, these data were used to construct structural models of the gels using Monte Carlo calculations on the basis of random close packing (RPC) premises. In addition, the structure of gels under study was investigated by transmission and scanning electron microscopy. The material can be described as a composite in which the sonogel is the matrix and the colloid particles the reinforcing phase. For low colloid content, the colloid forms discrete clusters, and the main structural characteristic of sonogels, i.e., a network of uniformly sized particles of ∼3−4-nm radius, remains unmodified. However, for high colloid silica content, a multimode distribution appears, the structure is di...

We have constructed and tested a 2d position sensitive parallel-plate gas ionization chamber with scanned charge transfer readout. The scan readout method described here is based on the development of a new position dependent charge transfer technique. It has been implemented by using gate strips perpendicularly oriented to the collector strips. This solution reduces considerably the number of electronic readout channels needed to cover large detector areas. The use of a 25 micron thick kapton etched circuit allows high charge transfer efficiency with a low gating voltage, consequently needing a very simple commutating circuit. The present prototype covers 8 x 8 cm^2 with a pixel size of 1.27 x 1.27 mm^2. Depending on the intended use and beam characteristics a smaller effective pixel is feasible and larger active areas are possible. This detector can be used for X-ray or other continuous beam intensity profile monitoring.

The object of this paper is to evaluate behaviour during drying of two stone consolidants: Wacker OH and Tegovakon V, containing tetraethoxysilane. During drying, the gel network contracts due to capillary pressure generated by solvent evaporation. When the consolidant dries inside the stone porous structure, the shrinkage is constrained in all three dimensions. In these conditions, the dried gel suffers a high stress that could cause it to crack. When there is a free surface, as for a consolidant layer on the surface of a pore, the stress can relax in the direction normal to the surface. In this case, the stress is controlled by network rigidity. The rigidity of the gel network has been evaluated by mercury porosimetry, while pore size, which controls capillary pressure, has been determined by nitrogen adsorption. The shrinkage of gels under mercury pressure is characterised by high moduli. This fact suggests a high rigidity of the networks. The small pore radii found in the network (

Several mixtures obtained by ultrasonic agitation of colloidal silica with a sol solution containing tetraethoxysilane (TEOS) were used to form crack-free monoliths. The dry gels that were submitted to mercury porosimetry showed differences in behavior according to the proportion of silica colloid in the gel. For low proportions, the mercury isostatic pressure exclusively induced an irreversible compaction of material, but intrusion occurred in gels with a high proportion of colloid. This permitted the evaluation of the textural properties of intruded gels, whereas the pressurization−depressurization paths, where intrusion was prevented, provided information about their compression behavior. Specimens exhibited elastic strain, followed by yield and plastic hardening. Bulk modulus was significantly reduced as the content of silica particles in the gel was increased. This was related to the increase in free volume of the network. The yield point, which characterizes the limit of the elastic region, was take...

Since mortars play a key role in buildings decay, their suitable choice is critical to the success of restoration projects. The focus of this paper is to characterise the pore structures of a set of mortars and correlate them with mechanical properties and vapour permeability, which are relevant to the decay of granite buildings. Water vapour transport was tested by means of a simple set-up developed in our laboratory. A good correlation was found between total porosity and the two parameters tested: strength and vapour diffusivity. Pore size distribution also showed a strong influence on diffusivity. A mix based on cement with a high sand proportion was considered as the most suitable for granite building restoration because it showed good mechanical properties and low free calcium content. A negative aspect was that this mix exhibited significantly lower vapour permeability than mortar containing lime; this could be explained by the smaller radius of its pores.

Alkoxysilanes, low-viscosity monomers that polymerize into the porous network of stone by a sol–gel process, are widely used in the restoration of stone buildings. We have used the mercury porosimetry technique to characterize changes in microstructure of three granites following their consolidation with two popular commercial products (Wacker OH and Tegovakon V). The suitability of this technique is questioned because a surprising increase of stone porosity is observed. In order to investigate the feasibility of porosimetry, we analyze the behavior of xerogels prepared from the two commercial products, under mercury pressure. Gels are basically compacted and not intruded by mercury. Thus, the increase of stone porosity after consolidation can actually be associated with gel shrinkage. Mercury porosimetry, therefore, has been found unsuitable for characterizing the microstructure of consolidated rocks. However, it can be employed usefully to evaluate shrinkage of gels under mercury pressure, which permits the behavior of a consolidant during the process of drying in stone to be predicted. It is a key factor because many problems of consolidants are related to their drying process within the stone. Gels under study exhibit a high rigidity and an elastic behavior, as consequence of their microporous structure. Finally, the reduction in the porous volume of gels after the porosimetry test demonstrates that the shrinkage mechanism is based on pore collapse.

Solar thermal receivers absorb concentrated sunlight and can operate at high temperatures exceeding 600°C for production of heat and electricity. New fractal-like designs employing light-trapping structures and geometries at multiple length scales are proposed to increase the effective solar absorptance and efficiency of these receivers. Radial and linear structures at the micro (surface coatings and depositions), meso (tube shape and geometry), and macro (total receiver geometry and configuration) scales redirect reflected solar radiation toward the interior of the receiver for increased absorptance. Hotter regions within the interior of the receiver also reduce thermal emittance due to reduced local view factors in the interior regions, and higher concentration ratios can be employed with similar surface irradiances to reduce the effective optical aperture and thermal losses. Coupled optical/fluid/thermal models have been developed to evaluate the performance of these designs relative to conventional designs. Results show that fractal-like structures and geometries can reduce total radiative losses by up to 50% and increase the thermal efficiency by up to 10%. The impact was more pronounced for materials with lower inherent solar absorptances (< 0.9). Meso-scale tests were conducted and confirmed model results that showed increased light-trapping from corrugated surfaces relative to flat surfaces.

Superhydrophobic materials can find promising applications in the field of building. However, their application has been very limited because the synthesis routes involve tedious processes, preventing large-scale application. A second drawback is related to their short-term life under outdoor conditions. A simple and low-cost synthesis route for producing superhydrophobic surfaces on building materials is developed and their effectiveness and their durability on clay roof tiles are evaluated. Specifically, an organic-inorganic hybrid gel containing silica nanoparticles is produced. The nanoparticles create a densely packed coating on the roof tile surface in which air is trapped. This roughness produces a Cassie-Baxter regime, promoting superhydrophobicity. A surfactant, n-octylamine, was also added to the starting sol to catalyze the sol-gel process and to coarsen the pore structure of the gel network, preventing cracking. The application of ultrasound obviates the need to use volatile organic compounds in the synthesis, thereby making a 'green' product. It was also demonstrated that a co-condensation process effective between the organic and inorganic species is crucial to obtain durable and effective coatings. After an aging test, high hydrophobicity was maintained and water absorption was completely prevented for the roof tile samples under study. However, a transition from a Cassie-Baxter to a Wenzel state regime was observed as a consequence of the increase in the distance between the roughness pitches produced by the aging of the coating.

A novel sol-gel synthesis, in which a surfactant acts to make the pore size of the gel network more coarse and uniform, is shown to provide an effective alternative for the consolidation of stone. The new mesoporous silica avoids the main inconvenience of current commercial consolidants, which is their tendency to crack inside the pores of the stone. Since the cracking of xerogels is a well-known drawback of the sol-gel process, the synthesis presented here can be extended to other applications. Finally, preliminary studies of the effectiveness of the novel surfactant-templated sol in consolidating a typical biocalcareous stone are also discussed.

A customary procedure in the protection of monumental buildings is the consolidation of decaying stone by the application of commercial products containing tetraethoxysilane (TEOS). These products polymerize within the porous structure of the decaying stone, significantly increasing the cohesion of the material. However, TEOS-based consolidants suffer practical drawbacks, such as cracking of the network during the drying phase, and significant blocking of the rock pores. These limitations are related to the growth of a dense microporous network of the xerogel inside the stone material, which is typical from TEOS sols. Therefore, the purpose of this work is to increase porosity of the product by including colloidal particles in the starting sol.We prepared a colloid-polymer composite gel using TEOS and a commercial silica colloid. The percentage by weight of silica colloid particles to total silica was 54%. Ethanol and dibutyltindilaurate (DBLT) were chosen as solvent and catalyst, respectively. This catalyst promotes the gelation at a neutral pH, preventing stone decay related to acid or basic catalysis. We characterized the properties playing a key role in consolidation. Data were compared with those obtained using a popular commercial product: Tegovakon V 100 produced by Goldsmith.In spite of the colloidal particle addition, sols exhibited viscosity values close to those of the commercial products, as a consequence of their dispersion in ethanol. A gelation time similar to that of commercial consolidants was maintained, whereas the contained sol was stable over a period of up to six months. Concerning textural parameters, the addition of colloid permitted to obtain a crack-free, mesoporous material structure. This generated a crack-free material whereas the gel from Tegovakon V 100 exhibited cracking.We also evaluated the consolidant efficacy on a biocalcareous stone, one of the most common monumental building stone employed in the southwest of Spain. Three key parameters -penetration depth in the rock, mechanical properties and water vapour diffusivity- were measured. Stone permeation was similar to that from the commercial product. Notably, a significant improvement of compression strength of the stone was observed. Reduction in vapour diffusivity of the treated stone was slightly lower for our gel than for the commercial consolidant.

The capillary transport of water into granitic rocks has been interpreted on the basis of the structure of its porous network. An effective pore radius has been calculated from a three-sized single-pore model proposed by F. A. L. Dullien, El-Sayed, and V. K. Batra (J. Colloid Interface Sci. 60, 497, 1977) Considering the porous network of granites as consisting of fissures grouped in two size types, macro- and microfissures, an effective radius was found from the characteristic radii for each type and the average of these two values. Good agreement between the effective radius calculated and the radius estimated using a capillary rate value measured experimentally provides a suitable basis for identifying interrelationships between the pore structure and moisture capillary rise. In fact, it is possible to predict the process rate from only two characteristic pore sizes, corresponding to the radii of macrofissures and microfissures. The abnormally low rate of capillary rise observed in one of the granites studied could be easily interpreted as due to the involvement exclusively of the macrofissures of its porous network in capillary transport. Copyright 2000 Academic Press.

A mesoporous TiO(2)-SiO(2) nanocomposite photocatalyst has been prepared from TiO(2) nanoparticles and ethoxysilane oligomers in the presence of a non-ionic surfactant (n-octylamine). The 2D and 3D structure properties of the resulting nanomaterial are described. The use of 3D techniques, particularly HAADF-STEM electron tomography, together with 3D reconstructions and atomic force microscopy, provides insight into the fine structure of these materials. We find that n-octylamine creates a mesoporous silica structure in which titania nanoparticles are embedded, and that some of the titania is retained on the outer surface of the material. Rapid photodegradation of methylene blue dye is facilitated, due to the synergistic effect of: (1) its adsorption into the composite mesoporous structure, and (2) its photodegradation by the superficial TiO(2).