Ancient Roman syntheses of Al-tobermorite in a 2000-year-old concrete block submerged in the Bay of Pozzuoli (Baianus Sinus), near Naples, have unique aluminum-rich and silica-poor compositions relative to hydrothermal geological occurrences. In relict lime clasts, the crystals have calcium contents that are similar to ideal tobermorite, 33 to 35 wt%, but the low-silica contents, 39 to 40 wt%, reflect Al 3+ substitution for Si 4+ in Q 2 (1Al), Q 3 (1Al), and Q 3 (2 Al) tetrahedral chain and branching sites. The Al-tobermorite has a double silicate chain structure with long chain lengths in the b [020] crystallographic direction, and wide interlayer spacing, 11.49 Å. Na + and K + partially balance Al 3+ substitution for Si 4+ . Poorly crystalline calcium-aluminum-silicate-hydrate (C-A-S-H) cementitious binder in the dissolved perimeter of relict lime clasts has Ca/(Si+Al) = 0.79, nearly identical to the Al-tobermorite, but nanoscale heterogeneities with aluminum in both tetrahedral and octahedral coordination. The concrete is about 45 vol% glassy zeolitic tuff and 55 vol% hydrated lime-volcanic ash mortar; lime formed <10 wt% of the mix. Trace element studies confirm that the pyroclastic rock comes from Flegrean Fields volcanic district, as described in ancient Roman texts. An adiabatic thermal model of the 10 m 2 by 5.7 m thick Baianus Sinus breakwater from heat evolved through hydration of lime and formation of C-A-S-H suggests maximum temperatures of 85 to 97 °C. Cooling to seawater temperatures occurred in two years. These elevated temperatures and the mineralizing effects of seawater and alkali-and alumina-rich volcanic ash appear to be critical to Al-tobermorite crystallization. The long-term stability of the Al-tobermorite provides a valuable context to improve future syntheses in innovative concretes with advanced properties using volcanic pozzolans.

An ultra-thin and large-area skin-compatible heterogeneous organic/metal-oxide photosensor array is demonstrated which is capable of sensing and boosting signals with high detectivity and signal-to-noise ratio. For the realization of ultra-flexible and high-sensitive heterogeneous photosensor arrays on a polyimide substrate having organic sensor arrays and metal-oxide boosting circuitry, solution-processing and room-temperature alternating photochemical conversion routes are applied.

This article presents the results of a round-robin test performed by 13 international research groups in the framework of the activities of the RILEM Technical Committee 260 RSC "Recommendations for use of superabsorbent polymers in concrete construction". Two commercially available superabsorbent polymers (SAP) with different chemical compositions and gradings were tested in terms of their kinetics of absorption in different media; demineralized water, cement filtrate solution with particular cement distributed to every participant and local cement chosen by the participant. Two absorption test methods were 2 considered; the tea-bag method and the filtration method. The absorption capacity was evaluated as a function of time. The results showed correspondence in behaviour of the SAPs among all participants, but also between the two test methods, even though high scatter was observed at early minutes of testing after immersion. The tea-bag method proved to be more practical in terms of time dependent study, whereby the filtration method showed less variation in the absorption capacity after 24 hours. However, absorption followed by intrinsic, ion-mediated desorption of a respective SAP sample in the course of time was not found by the filtration method. This SAP-specific characteristic was only displayed by the teabag method. This demonstrates the practical applicability of both test methods, each one having their own strengths and weaknesses at distinct testing times.

The material characteristics and elastic properties of aluminumsubstituted 11 A tobermorite in the relict lime clasts of 2000year-old Roman seawater harbor concrete are described with TG-DSC and 29 Si MAS NMR studies, along with nanoscale tomography, X-ray microdiffraction, and high-pressure X-ray diffraction synchrotron radiation applications. The crystals have aluminum substitution for silicon in tetrahedral bridging and branching sites and 11.49(3) A interlayer (002) spacing. With prolonged heating to 350°C, the crystals exhibit normal behavior. The experimentally measured isothermal bulk modulus at zero pressure, K 0 , 55 ±5 GPa, is less than ab initio and molecular dynamics models for ideal tobermorite with a double-silicate chain structure. Even so, K 0 , is substantially higher than calcium-aluminum-silicate-hydrate binder (C-A-S-H) in slag concrete. Based on nanoscale tomographic study, the crystal clusters form a well connected solid, despite having about 52% porosity. In the pumiceous cementitious matrix, Al-tobermorite with 11.27 A interlayer spacing is locally associated with phillipsite, similar to geologic occurrences in basaltic tephra. The ancient concretes provide a sustainable prototype for producing Al-tobermorite in high-performance concretes with natural volcanic pozzolans.

No abstract

No abstract

No abstract

No abstract