Reaction of Amino-Terminated PAMAM Dendrimers with Carbon Dioxide in Aqueous and Methanol Solutions

Polyamines have been used as active materials to capture carbon dioxide gas based on its well-known reaction with amines to form carbamates. This work investigates the reactions between three amino-terminated poly(amidoamine) (PAMAM) dendrimers (G1, G3 and G5) and CO2(g) in aqueous (D2O) and methanolic (CD3OD) solutions. The reactions were monitored using 1H NMR spectroscopy, and yielded dendrimers with a combination of terminal carbamate and terminal ammonium groups. In aqueous media the reaction was complicated by the generation of soluble carbonate and bicarbonate ions. The reaction was cleaner in CD3OD, where the larger G5 dendrimer solution formed a gel upon exposure to CO2(g). All reactions were reversible, and the trapped CO2 could be released by treatment with N2(g) and mild heating. These results highlight the importance of the polyamine dendrimer size in terms of driving changes to the solution’s physical properties (viscosity, gel formation) generated by exposure to CO2(g).

Curing Time and Temperature Effect on the Resistance to Wet-Dry Cycles of Fly Ash Added Pumice Based Geopolymer

The effects of curing regimes varying combinations of temperatures (ambient, 60 °C, 75 °C, 90 °C, 105 °C) and durations (4h, 8h, 24h, 48h, 96h, 168h) on the performance of fly ash added pumice based geopolymer pastes were investigated in this study. The precursor raw material consists of 70% pumice dust and 30% fly ash (FA). Alkali activator was prepared by mixing 10M sodium hydroxide (SH) solution and liquid sodium silicate (SS) in the ratio of SS/SH=2. Activator to precursor ratio was fixed as 0.45. Compressive strengths were determined at the 28 days of age as well as after exposure 5 wetting-drying (w-d) cycles. In addition, Fourier Transform Infrared Spectroscopy (FTIR) tests were conducted on the fresh and hardened geopolymer pastes in order to examine the effect of curing conditions to the structural changes and reaction products. The results show that in the case of 60 °C and 75 °C, the strength of the w-d conditioned samples increased steadily as the curing time increased. However, longer curing times of more than 24 hours are not beneficial for high curing temperatures (90 °C and 105 °C). The maximum strength after the w-d cycles is obtained for the curing conditions of 60°C/168h (74.4 MPa). Also, FTIR analysis confirmed that the hardened geopolymer paste transformed into a more coordinated structure and soluble carbonate compounds were reduced at 60 °C and 168 hours curing condition.

Influence of Various Carbonates on the Hydration of Portalnd Cement

Over the last 20 years, the effects of using limestone in Portland cement (PC) have been well studied. The benefits of limestone as a partial replacement for PC are well established. Its economic and environmental advantages of reducing CO2 emissions are well known. For a long time, the limestone has been considered as an inert filler. Recently it has been concluded that limestone serves both as an inert filler and also reacts to a limited extend. The reactivity depends on its fineness (specific surface)[1] and content [2,3]. The question arose, whether a) it is the availability of excess carbonate ion in the hydration system, which determines the degree of influence on the hydration process or b) does the system have its internal capacity to include carbonate ions and the increased availability (more carbonate ions in the solution, embedding the hydrating particles) would not have a significant effect. So the question was if the more soluble carbonates would have more pronounced effect on the hydration of the Portland cement than the limestone, which is only slightly soluble. The influence of slightly soluble (CaCO3, MgCO3, dolomite), medium soluble (Li2CO3) and highly soluble (K2CO3 and KHCO3) carbonates on the hydration of Portland cement was studied using Rietveld analysis. The results indicated that the amount of reacted carbonate in cement hydration at a 15% addition of slightly or medium soluble carbonates does not exceed 5% and is not affected by their solubility; at a 15% addition of the highly soluble carbonate K2CO3 the amount of reacted carbonate is around 6% leading to the conclusion that the system behaves according to the option b). The fugure presents the quantitative analysis of cement hydration at 3, 7, 28 and 90 days of hydration and temperatures of 25 and 400C.

14C Dating of Fire-Damaged Mortars from Medieval Finland

This study focuses on radiocarbon dating of mortars that have withstood city fires and display visible fire damage effects. Some fire-damaged and undamaged original Medieval mortars from the same site have also been tested. The mortars were heated at different temperatures and then analyzed using the same preparation procedures as in 14C dating of mortars to see what kind of changes the heating would introduce to the mineralogy, chemistry, and the carbon and oxygen isotope ratios. We found that decarbonation during heating starts at ∼600 ° and recarbonation starts as soon as the temperature drops. Already after a few days, most of the lost CO2 has been replaced with atmospheric CO2. The renewed carbonates are readily soluble in the acid hydrolysis process and their carbon and oxygen isotopes have a light signature. Fire-damaged historical mortars display the same features. If a long time has elapsed between hardening of the original mortar and the fire, the new carbonates have 14C concentrations that point to the fire event rather than to the building event. In several cases, the fire-damaged mortars have an easily soluble carbonate fraction with a 14C age that could be related to a major fire event, but still most of the soluble carbonate yields a 14C age that seems like a reasonable age for the original construction.