scholarly journals The Stability and Chloride Entrapping Capacity of ZnAl-NO2 LDH in High-Alkaline/Cementitious Environment

2021 ◽  
Vol 2 (1) ◽  
pp. 78-99
Author(s):  
Zahid M. Mir ◽  
Celestino Gomes ◽  
Alexandre C. Bastos ◽  
Rui Sampaio ◽  
Frederico Maia ◽  
...  

In this work, the ZnAl-NO2 LDH (layered double hydroxide) is investigated as a possible additive for mitigating the chloride-induced corrosion of steel in reinforced concrete. The investigation focused on the stability and chloride binding capacity of this LDH in the pH range typical of cementitious materials. Until pH = 12.5 the material was stable and effective in capturing chloride ions from the surrounding aqueous environment. For higher pH, precisely that of hydrated cement, the LDH was partially dissolved and OH− preferentially entrapped instead of Cl−. These results suggested that ZnAl-NO2 has excellent chloride entrapping capability at neutral pH, but this is reduced with increasing pH. However, when the LDH was incorporated into mortars, the chloride ingress was delayed, signifying that the dissolution of LDH leads to a secondary mechanism responsible for chloride capture.


Materials ◽  
2020 ◽  
Vol 13 (7) ◽  
pp. 1769 ◽  
Author(s):  
Celestino Gomes ◽  
Zahid Mir ◽  
Rui Sampaio ◽  
Alexandre Bastos ◽  
João Tedim ◽  
...  

This work investigated the use of ZnAl-layered double hydroxide (LDH) intercalated with nitrate or nitrite ions for controlling the corrosion of steel in reinforced concrete. The work started by analyzing the stability of the powder in the 1–14 pH range and the capacity for capturing chloride ions in aqueous solutions of different pH. The effect of the ZnAl-LDH on the corrosion of steel was studied in aqueous 0.05 M NaCl solution and in mortars immersed in 3.5% NaCl. It was found that the LDH powders dissolved partially at pH > 12. The LDH was able to capture chloride ions from the external solution, but the process was pH-dependent and stopped at high pH due to the partial dissolution of LDH and the preferential exchange of OH– ions. These results seemed to imply that ZnAl-LDH would not work in the alkaline environment inside the concrete. Nonetheless, preliminary results with mortars containing ZnAl-LDH showed lower penetration of chloride ions and higher corrosion resistance of the steel rebars.



Materials ◽  
2018 ◽  
Vol 11 (12) ◽  
pp. 2537 ◽  
Author(s):  
Lin Chi ◽  
Zheng Wang ◽  
Youfang Zhou ◽  
Shuang Lu ◽  
Yan Yao

In this study, the chloride adsorption behaviors of CaAl-Cl LDH precursors with various Ca:Al ratios were investigated. The optimal chloride ion removal rate was 87.06% due to the formation of hydrocalumite. The chloride adsorption products of CaAl-Cl LDH precursors were further characterized by X-ray diffraction analysis and atomic structure analysis, the adsorption mechanism was considered to be co-precipitate process. The chloride adsorption behaviors of cementitious materials blended with CaAl-Cl LDH precursors were further investigated. Leaching test according to Test Code for Hydraulic Concrete (SL352-2006) was performed to testify the stability of chloride ions in the mortar. The results show that more than 98.3% chloride ions were immobilized in cement mortar blended with CaAl-Cl LDH precursor and cannot be easily released again. The inhibition performance of steel in the electrolytes with/without CaAl LDH precursor was investigated by using electrochemical measurements. The results indicate that CaAl LDH precursor can effectively protect the passive film on steel surface by chloride adsorption. Considering the high anion exchange capacities of the LDHs, synthesized chloride adsorbent precursor can be applied as new inhibitors blended in cementitious materials to prevent the chloride-induced deterioration. Moreover, the application of chloride adsorption on CaAl-Cl LDH could also be of interest for the application of seawater blended concrete.



2018 ◽  
Vol 6 (11) ◽  
pp. 153-162
Author(s):  
Rajesh V. ◽  
E. U. B. Reddi ◽  
T. Byragi Reddy ◽  
Ch. Durga Prasad ◽  
B. Prasanna Kumar

The present study was initiated with an objective of investigating a plant extract as an effective corrosion inhibitor useful for protection of carbon steel in aqueous environment containing chloride ions. For this purpose, the leaf extract of the plant ‘Aerva lanata’ belonging to Amaranthaceae family of genus Aerva was chosen. The required optimum concentration of the extract for an effective inhibition was found to be 5 %, resulting in the inhibition efficiency of 95 % against corrosion of carbon steel in 200 ppm of NaCl solution. The extract introduced as a corrosion inhibitor was found to be effective in the pH range from 4.0 to 9.0. The extract could retain its inhibition efficiency for about an immersion period of 60 days and also up to a temperature of 333 K. The 5 % extract was found to control corrosion of carbon steel in highly aggressive medium containing 300 ppm of NaCl also. In order to maintain the protective nature, the required concentration of the extract was 2 %. From these studies, it was inferred that the Aerva lanata leaf extract exhibits good inhibitive properties for carbon steel in aqueous environment in wide ranges of pH, temperature and aggressiveness of medium.



1980 ◽  
Vol 43 (331) ◽  
pp. 901-904 ◽  
Author(s):  
D. Alun Humphreys ◽  
John H. Thomas ◽  
Peter A. Williams ◽  
Robert F. Symes

SummaryThe chemical stabilities of mendipite, Pb3O2Cl2, diaboleïte, Pb2CuCl2(OH)4, chloroxiphite, Pb3CuCl2O2(OH)2, and cumengéite, Pb19Cu24Cl42 (OH)44, have been determined in aqueous solution at 298.2 K. Values of standard Gibbs free energy of formation, ΔGf°, for the four minerals are −740, −1160, −1129, and −15163±20 kJ mol−1 respectively. These values have been used to construct the stability diagram shown in fig. I which illustrates their relationships to each other and to the minerals cotunnite, PbCl2, paralaurionite, PbOHCl, and litharge, PbO. This diagram shows that mendipite occupies a large stability field and should readily form from cold, aqueous, mineralizing solutions containing variable amounts of lead and chloride ions, and over a broad pH range. The formation of paralaurionite and of cotunnite requires a considerable increase in chloride ion concentration, although paralaurionite can crystallize under much less extreme conditions than cotunnite. The encroachment of the copper minerals on to the stability fields of those mineral phases containing lead(II) only is significant even at very low relative activities of cupric ion. Chloroxiphite has a large stability field, and at given concentrations of cupric ion, diaboleïte is stable at relatively high aCl−. Cumengéite will only form at high concentrations of chloride ion.



2016 ◽  
Vol 711 ◽  
pp. 241-248 ◽  
Author(s):  
Mickael Saillio ◽  
Véronique Baroghel-Bouny ◽  
Sylvain Pradelle

The main cause of premature deterioration of reinforced concrete structures is the corrosion of steel bars, induced by chloride ions (for example in marine environment) and/or by carbonation (atmospheric CO2). At the same time, environmental-induced degradations of concrete can also affect the structure, such as sulphate attack. This can lead to the formation of ettringite, inducing expansion inside the materials and finally degradation. Carbonation, chloride and sulphate ingress are usually studied separately in the literature. This is not representative of in-situ conditions since they can occur at the same time and can have an influence on each other. In this paper, chloride ingress are studied for concretes and cement pastes partially carbonated or/and in presence of sulphate in chloride contact solution. The mixtures contain OPC alone or with supplementary cementitious materials (SCM). SCMs are here pozzolanic materials (Fly Ash or Metakaolin) or alkali-activated materials such as ground granulated blast furnace slag (GGBS). The materials, partially carbonated (2 months in chamber at 1.5 % of CO2) or not, are put in contact with chloride solutions in presence of sulphate. This study focuses on the apparent chloride diffusion coefficients, as well as chloride binding isotherms which are obtained by the profile method. In addition, some aspects of the microstructure and of the pore structure are investigated, by using Mercury Intrusion Porosimetry and 27Al NMR, in order to better understand the results obtained relatively to the apparent chloride diffusion coefficients and to the chloride binding. Chloride ingress increases when sulphates are present in the contact solution for all cement materials tested (partially carbonated or not). In addition, chloride ingress is faster when the material is partially carbonated before contact with chloride solution. It appears that both carbonation or presence of sulphate decrease chloride binding, thus explaining the results. The results show an evolution of the properties as a function of the cement replacement ratio by SCMs.



1986 ◽  
Vol 51 (6) ◽  
pp. 1340-1351 ◽  
Author(s):  
Rudolf Kohn ◽  
Karol Tihlárik

The binding of calcium and lead ions to carboxy derivatives of starch prepared by allowing nitrogen dioxide to act on native maize starch (procedure A) and on starch 2,3-dialdehyde derivatives of degrees of oxidation DO(d.a.) ≥ 0.94 (procedure B) was studied. The carboxy group content of the samples in the H+ form was 4.6 - 12.1 mmol g-1. The effect of alkaline medium on the stability of the carboxy derivatives and on their ability to bind and exchange cations was examined. The Ca2+ → 2K+ exchange was evaluated in terms of the decrease in the electrostatic free enthalpy Δ(Gel/N)KCa, determined by alkalimetric potentiometric titrations, and the binding of Pb2+ ions was evaluated in terms of the activity of the Pb2+ counter-ions determined in suspensions of Pb salts of the carboxy derivatives by means of an ion specific electrode. The IR and CD spectra revealed that the carboxystarch preparations obtained by procedure A contained, in addition to free carboxy groups, a considerable amount of carbonyl groups. During the conversion of the latter groups to the former, even in a weakly alkaline medium, the carboxy derivatives undergo an appreciable degradation and lose, to a great extent, their ability to bind and exchange cations. Procedure B, on the other hand, leads to highly selective starch and amylose carboxy derivatives, exhibiting a small amount of carbonyl groups and featuring a relative stability towards alkaline medium; their binding capacity is as high as 12 milliequivalents of cations per g of sample.



2021 ◽  
Vol 11 (12) ◽  
pp. 5322
Author(s):  
Yang Ding ◽  
Tong-Lin Yang ◽  
Hui Liu ◽  
Zhen Han ◽  
Shuang-Xi Zhou ◽  
...  

Cement is widely used in marine concrete, and its resistance to chloride ion corrosion has been widely considered. In this paper, based on a laboratory test, the influence of different hydrostatic pressures, coarse aggregate contents and w/c ratios on the chloride resistance performance is analyzed. Based on COMSOL finite element software, a two-dimensional cementitious materials model is established, and the simulation results are compared with the experimental results. The results show that the penetration depth of chloride ions in cement increases with the increase of the w/c ratio. Under the hydrostatic pressure of 0 MPa, when the w/c ratio is 0.35, the penetration depth of chloride ions is 7.4 mm, and the simulation result is 8.0 mm. When the w/c ratio is 0.45, the penetration depth of chloride ions is 9.3 mm, and the simulation result is 9.9 mm. When the w/c ratio is 0.55, the penetration depth of chloride ions is 12.9 mm, and the simulation result is 12.1 mm. Under different hydrostatic pressures, the penetration depth of chloride ions obviously changes, and with the increase in hydrostatic pressure, the penetration depth of chloride ions deepens. Under the w/c ratio of 0.35, when the hydrostatic pressure is 0.5 MPa, the penetration depth of chloride ions is 11.3 mm, and the simulation result is 12.1 mm. When the hydrostatic pressure is 1.0 MPa, the penetration depth of chloride ions is 16.2 mm, and the simulation result is 17.5 mm.



Antioxidants ◽  
2021 ◽  
Vol 10 (2) ◽  
pp. 208
Author(s):  
Guillermo García-Díez ◽  
Roger Monreal-Corona ◽  
Nelaine Mora-Diez

The thermodynamic stability of 11 complexes of Cu(II) and 26 complexes of Fe(III) is studied, comprising the ligands pyridoxamine (PM), ascorbic acid (ASC), and a model Amadori compound (AMD). In addition, the secondary antioxidant activity of PM is analyzed when chelating both Cu(II) and Fe(III), relative to the rate constant of the first step of the Haber-Weiss cycle, in the presence of the superoxide radical anion (O2•−) or ascorbate (ASC−). Calculations are performed at the M05(SMD)/6-311+G(d,p) level of theory. The aqueous environment is modeled by making use of the SMD solvation method in all calculations. This level of theory accurately reproduces the experimental data available. When put in perspective with the stability of various complexes of aminoguanidine (AG) (which we have previously studied), the following stability trends can be found for the Cu(II) and Fe(III) complexes, respectively: ASC < AG < AMD < PM and AG < ASC < AMD < PM. The most stable complex of Cu(II) with PM (with two bidentate ligands) presents a ΔGf0 value of −35.8 kcal/mol, whereas the Fe(III) complex with the highest stability (with three bidentate ligands) possesses a ΔGf0 of −58.9 kcal/mol. These complexes can significantly reduce the rate constant of the first step of the Haber-Weiss cycle with both O2•− and ASC−. In the case of the copper-containing reaction, the rates are reduced up to 9.70 × 103 and 4.09 × 1013 times, respectively. With iron, the rates become 1.78 × 103 and 4.45 × 1015 times smaller, respectively. Thus, PM presents significant secondary antioxidant activity since it is able to inhibit the production of ·OH radicals. This work concludes a series of studies on secondary antioxidant activity and allows potentially new glycation inhibitors to be investigated and compared relative to both PM and AG.



2021 ◽  
Vol 13 (8) ◽  
pp. 4169
Author(s):  
Congtao Sun ◽  
Ming Sun ◽  
Tao Tao ◽  
Feng Qu ◽  
Gongxun Wang ◽  
...  

Chloride binding capacity and its effect on the microstructure of mortar made with marine sand (MS), washed MS (WMS) and river sand (RS) were investigated in this study. The chloride contents, hydration products, micromorphology and pore structures of mortars were analyzed. The results showed that there was a diffusion trend for chloride ions from the surface of fine aggregate to cement hydrated products. During the whole curing period, the free chloride content in the mortars made by MS and WMS increased firstly, then decreased and stabilized finally with time. However, the total chloride content of three types of mortar hardly changed. The bound chloride content in the mortars made by MS and WMS slightly increased with time, and the bound chloride content included the MS, the WMS and the RS arranged from high to low. C3A·CaCl2·10H2O (Friedel’s salt) was formed at the early age and existed throughout the curing period. Moreover, the volume of fine capillary pore with a size of 10–100 nm increased in the MS and WMS mortar.



2020 ◽  
Vol 9 (1) ◽  
pp. 93-104
Author(s):  
Mingrui Du ◽  
Yuan Gao ◽  
Guansheng Han ◽  
Luan Li ◽  
Hongwen Jing

AbstractMulti-walled carbon nanotubes (MWCNTs) have been added in the plain cementitious materials to manufacture composites with the higher mechanical properties and smart behavior. The uniform distributions of MWCNTs is critical to obtain the desired enhancing effect, which, however, is challenged by the high ionic strength of the cement pore solution. Here, the effects of methylcellulose (MC) on stabilizing the dispersion of MWCNTs in the simulated cement pore solution and the viscosity of MWCNT suspensions werestudied. Further observations on the distributions of MWCNTs in the ternary cementitious composites were conducted. The results showed that MC forms a membranous envelope surrounding MWCNTs, which inhibits the adsorption of cations and maintains the steric repulsion between MWCNTs; thus, the stability of MWCNT dispersion in cement-based composites is improved. MC can also work as a viscosity adjuster that retards the Brownian mobility of MWCNTs, reducing their re-agglomerate within a period. MC with an addition ratio of 0.018 wt.% is suggested to achieve the optimum dispersion stabilizing effect. The findings here provide a way for stabilizing the other dispersed nano-additives in the cementitious composites.



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