EFFECT OF LITHIUM BASED ADMIXTURE ON ALKALI AGGREGATE REACTION IN CONCRETE - A STATE OF ART REPORT

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1 International Journal of Civil Engineering and Technology (IJCIET) Volume 8, Issue 9, September 2017, pp , Article ID: IJCIET_08_09_035 Available online at ISSN Print: and ISSN Online: IAEME Publication Scopus Indexed EFFECT OF LITHIUM BASED ADMIXTURE ON ALKALI AGGREGATE REACTION IN CONCRETE - A STATE OF ART REPORT Manju R Assistant Professor (SRG), Department of Civil Engineering, Kumaraguru College of Technology, Coimbatore, India Sathya S PG student, Department of Civil Engineering, Kumaraguru College of Technology, Coimbatore, India ABSTRACT Alkali aggregate reaction continues to be a very severe problem in term of concrete durability many despite physical and chemical mitigation techniques which successfully prevent it. For a long time aggregates have been considered as inert materials but later on, particularly, after1940 sitwasclearlybrought out that the aggregates are not fully inert. Structures which fails due alkali silica reaction rate is high. In this paper, a critical review of the research work done so far on the suppression of alkali aggregate reaction in the presence of lithium compounds is provided. The existing literature has been thoroughly studied and the summary of the research findings are provided. It shows that, the lithium based admixtures are effective in suppression of alkali silica reaction and delayed ettringite formation., if the dosage added are appropriate. The lithium compounds which can be used in concrete for the suppression of alkali silica reaction are LiF, LiCl, LiBr, LiOH, LiOH.2H₂O, LiHNO₃, LiNO₃, LiCO₃, Li₂SO₄, Li₂HPO₄. Among all the lithium compounds, LiNO₃ is very much effective and a promising one. Keywords: Alkali aggregate reaction, cracks, Lithium admixtures, optimum dosage Cite this Article: Manju R and Sathya S, Effect of Lithium Based Admixture on Alkali Aggregate Reaction in Concrete - A State of Art Report, International Journal of Civil Engineering and Technology, 8(9), 2017, pp INTRODUCTION Concrete is a composite material composed of cement, fine and coarse aggregate bonded together in the presence of water which hardens over time. Cracks in concrete are irregular and cannot be prevented. If causes were better understood, the elimination of cracks would be less difficult. Cracks in concrete is mainly due to in adequate investigation of all the editor@iaeme.com

2 Manju R and Sathya S ingredients involved.cracking can be the result of one or a combination of factors such as chemical reaction, drying, creep &shrinkage, thermal cracking, moisture movement, elastic deformation, foundation movements and settlement of soil, manufacturing defects. The cracks due to chemical reaction is mainly due to alkali aggregate reaction.aggregates contain reactive silica, which reacts with alkali present in the cement. Certain types of reactive aggregates are responsible for alkali aggregate reaction. The reaction starts with the attack of reactive siliceous minerals in the aggregate by hydroxyl ions derived from alkalis in the cement, resulting in the unlimited swelling of alkali silicate gel, which leads to disruption of concrete, with the spreading of cracks and it may eventually leads to failure of concrete structures. There are three types of alkali aggregate reaction, in which, the alkali silica reaction commonly known as "concrete cancer". it is the swelling of concrete due to the reaction between high alkaline cement paste and reactive silica in the aggregate in the presence of sufficient moisture. this reaction causes expansion of aggregate by forming soluble viscous gel sodium silicate Na 2 SiO 3 n H 2 O. On absorbing water, this gel swells and increases in its volume. It exerts pressure inside the siliceous aggregate, causes spalling of concrete and results in the reduction of strength. ASR leads to severe cracks, leads to severe structural problem, which finally leads to destruction of the structure. If lithium based admixture is used in concrete, it reacts with silica before the hydroxyl ions, forming Li₂SO₃, which serves as a diffusion barrier and protective layer to prevent alkali silica reaction, which in turn leads to prevention of cracks. 2. LITERATURE REVIEW M. J. Millard (2008) investigated the early age hydration of cement fly ash blend with six different compositions of cement. The dosage of lithium added was 0-400%. It was observed that higher dosages increased the autogeneous shrinkage after 40 days. Lithium Nitrate accelerated the early hydration. The 100% dosage means the 0.74 lithium to alkali molar ratio. The reaction between the fly ash and Lithium Nitrate decreases the early heat and mitigates Alkali Silica Reaction.[1] Bashar Taha (2008) studied the suppression of alkali silica reaction with two different mineral admixtures nitrate and pozzolanic glass powder. Four prisms was examined for three different mix using Scanning Electron Microscope. The pozzolanic glass powder as a cement replacement leads to change in concentration of hydroxyl ion in the pore solution which is the direct reason for the reduction in ASR expansion. Lithium nitrate as a chemical admixture contributes to reduction in ASR expansion.[2] Xiangyin Mo, (2005) made an investigation on alkali aggregate reaction by using Lithium based admixtures at 80⁰c with relative humidity of 95%. LiOH showed better results in the control of expansion of mortar bars and concrete with high alkali content of %. Four types of aggregates were used for testing. The inhibition of Alkali aggregate reaction by LiOH in reactive type of aggregates is better than non- reactive type of aggregates.[3] Ekolu, S. O, (2007), the investigation on delayed ettringite formation and alkali-silica reaction due to the influence of lithium nitrate has been done. The above stated damage mechanisms were examined using heat-cured mortars and concrete containing lithium nitrate. The optimum dosage of lithium nitrate was molar ratio of 0.72.[4] Andreas Leemann (2014),The addition of lithium nitrate decreased the dissolution rate and solubility of silica. In mortar, addition of lithium nitrate, decreases the calcium, sodium and potassium content and changes the reaction product from porous plate like configuration to a dense one without texture. The suppression of alkali silica gel is due to the lower potential of the reaction product to swell. The dissolution rate of silica slows down when lithium nitrate combines with caustic soda and reduces its solubility.[5] editor@iaeme.com

3 Effect of Lithium Based Admixture on Alkali Aggregate Reaction in Concrete - A State of Art Report Deng, (2014),The alkali aggregate reaction can be restrained by lithium salts but its influence on initial setting time and strength is uncertain. The lithium sulphate accelerates the cement hydration and shortens the setting time and improves the early strength but it does not have any reverse effect on ultimate strength. The lithium sulphate decrease the initial and final setting time by 4-20%, such that it accelerates the setting. Lithium sulphate increases the rate of early strength development. Lithium ion decreases the calcium ion stability and reduces the nucleation barrier of ettringite, such that growth of hydration products takes place. Sulphate ion accelerates the formation hydration products.[6] Craig W. Hargis, deals with the aggregate passivation- a new method of study. Use of 4M LiOH is superior to 2M LiOH in producing aggregate passivation layer and it reduces the expansion due to alkali silica reaction.[7] FarshadRajabipour(2015),investigated the mechanism of alkali silica reaction, especially molecular to micro scale levels is not clearly understood and it resulted in inability to assess its risk. This study states that aggregate reactivity depends on the size and distribution of minerals in addition to that of silica content. The presence of calcium is required for the ASR formation. Among the lithium based admixtures use in the study, the lithium nitrate efficiently controls ASR.[8] Mohammad S. Islam, (2016) Expansion of mortar bars with 6 dosage of lithium to alkali molar ratio 0.59, 0.74, 0.89, 1.04, 1.19 & 1.33 with six reactive type aggregates were studied. As a result, the amount of lithium salt needed to suppress ASR induced mortar expansion values depends on the extent of reactivity of aggregate mineralogy and the duration of the test. Lithium nitrate found to be more effective for reactive type of aggregates.[9] Kawamura (2003), The influence of lithium on composition of alkali silica reaction gel was studied. The average of CaO/SiO₂ ratio decreases with the increae in amount of lithium Salts added. The optimum dosage level of LiOH and LiNO₃ in reduction of ASR gel was 0.75M with the high alkali cement of 1.1% NaOₑ. ASR gel becomes a homogeneous compound at high dosage levels of CaO.[10] Feng, X(2010)In the presence of lithium in concrete, there is a formation of two products, viz.,crystalline lithium silicate and lithium bearing, which serves as a diffusion barrier and as a protective layer to prevent alkali silica reaction. The studies include, expansion testing and silica dissolution measurements, from which its proved that lithium reacts easily with the reactive type of aggregates than non-reactive type of aggregates.[11] Feng, X(2005), Alkali silica reaction in concrete was examined using LiF, LiCl, LiBr, LiOH, LiOH.2H₂O, LiHNO₃, LiNO₃, LiCO₃, Li₂SO₄, Li₂HPO₄ and these compounds are sffective in suppressing ASR. LiNO₃ shows better efficiency in mitigating alkali silica reaction. The lithium alkali molar ratio which efficiently inhibits alkali silica reaction lies between 0.67 and 1.2 for other lithium salts and for lithium nitrate, it lies between 0.72 and 0.93[12] Collins, C. L, (2004), The effects of lithium additives - LiOH, LiCl, and LiNO₃ on alkali silica reaction were examined at various dosages. The expansion was below the acceptable limit of 0.05% at 56 days. The optimum dosage of Li₂O/Na₂Oₑ to control alkali silica reaction was approximately 0.6 for LiOH, 0.8 & 0.9 for LiNO₃ and LiCl respectively, and the mechanism behind the alkali silica suppression due to addition lithium salts was not clear. Lithium salts either decrease the silica dissolution or the precipitation of silica rich products because, the dissolved silica concentration decreased with increase in dosage of lithium salts[13] Lyndon D. Mitchell (2004) The reaction of opal with calcium hydroxide, KOH, LiOH, was investigated. The reaction was examined using XRD, SEM and NMR. In the presence of editor@iaeme.com

4 Manju R and Sathya S Li, there is a change in the structure of the silicate. A protective barrier exists when the opal reacts with the ion. This layer prevents the ASR expansion[14] AndreasLeemann(2015)The mechanism of aluminium containing metakaolin and LiNO₃ against alkali silica reaction was investigated. The addition of metakaolin slows down the silica dissolution rate but there is no effect on final product, i.e the aluminium ions only influences the kinetics of the reaction but not on the product. Metakaolin and LiNO₃ has an ability to reduce the ASR expansion. LiNO₃ can suppress the ASR by forming dense product i.e. the reactive minerals are protected by the formation of layer around the aggregates. [15] Zapała-Sławeta J(2016), The mortars containing gravel as aggregate with LiNO₃ has been tested. The lithium ion decreases the expansion of mortar than standard specifications and also there is reduction in micro cracks due to the lower swelling capacity of the gels. Alkali aggregate reaction causes internal corrosion which leads to damage of the structure. The optimum Li/ Na₂Oₑ was found to be 0.74.[16] Kim Taehwan(2016),The physical and chemical changes on account alkali silica reaction were studied in the presence of lithium ions. The pore solution of the mortar with different dosage(0%, 35%, 100%) was studied. Lithium ion prevents the dissolution of silica and a physical barrier was formed on the surface of reactive silica, which is facilitated by lithium ions and thus prevents ASR gel formation.[17] Bérubé, M. A, (2016), Tests are done on low and high alkali cement paste with and without the addition of LiNO₃ and lithium bearing glass. The Li/ Na₂Oₑ molar ratio was kept constant The pore solution of three types of specimen were tested which has been subjected to 23, 38 & 60⁰C in sealed container at 3, 7, 28& 91 days. It has been stated that LiNO₃ decreases ph by 0.1 and lithium glass increases the ph by 0.2. In mixtures which were made with lithium glass, lithium ion was not rapidly released by Li-glass under normal conditions, temperature and ph. The temperature between 23 & 60⁰C has no significant influence on the density of the pore solution.[18] E.Saouma (2015),An attempt has been made to develop a mathematical framework through which the reaction kinetics can be better understood. Temporal evolution of the expansive gel formation is contrasted with both macro-kinetics model and diffusion based meta-model. three mathematical conservative laws are derived. Concentration of gel and the expansion of concrete under alkali silica reaction shows qualitative similarities.[19] Asghar (2016), investigated about the major challenge to the durability of the concrete, which is due to alkali silica reaction. this is because, the relationship between the composition, properties and behavior of alkali silica reaction is not clearly understood. the effects of composition of synthetic alkali silica reaction gel on pore solution, ph, osmotic pressure, rheological and swelling properties are investigated and the regression analyses have been done. in gels with low calcium and low sodium composition, highest yield stresses were observed and they showed negligible osmotic and swelling pressure. [20] 3. CONCLUSION From the above review, the some of the findings from the above literature were, The addition of LiNO₃ decreased the dissolution rate and solubility of silica The optimum Li/ Na₂Oₑ molar ratio for suppression of alkali silica reaction lies between 0.72 and 0.93 Comparatively, with lithium based admixtures, LiNO₃ shows remarkable effects to restrain alkali aggregate reaction editor@iaeme.com

5 Effect of Lithium Based Admixture on Alkali Aggregate Reaction in Concrete - A State of Art Report The mechanical and durable properties of lithium based admixture concrete are uncertain. The aluminium containing metakaolin has no significant effect on the alkali silica reaction, but it affects the kinetics of the reaction. In concrete, in the presence of lithium, lithium ions attacks the silica present in the aggregate before Na/K hydroxyl ions, forming Li₂SO₃, which serves as a diffusion barrier and protective layer to prevent alkali silica reaction. Lithium easily reacts with reactive type of aggregate than non- reactive type of aggregates. Lithium ions helps in delayed ettringite formation i.e. lithium ions decreases the calcium ion solubility and reduces the nucleation barrier of ettringite and accelerates the growth of hydration products. The lithium based admixtures is very costly. The lithium can be extracted from the lithium ion batteries and so it can be used in concrete as a preventive measure for alkali silica reaction. Still, the durability properties and mechanical properties can also be studied. REFERENCES [1] Effects of Lithium Nitrate admixture on early-age cement hydration, M. J. Millard, K.E.Kurtis Cement and Concrete Research, Volume- 38, Issue 4, (2008) pg [2] Using lithium nitrate and pozzolanic glass powder in concrete as ASR suppressors, Bashar Taha, GhassanNounu Cement and Concrete Composites, Volume 30 Issue 6(2008) [3] Alkali-aggregate reaction suppressed by chemical admixture at 80⁰c, Xiangyin Mo, TongshunJin, Gang Li, Keyu Wang, Zhongzi Xu, Mingshu Tang - Construction and Building Materials, Volume 19 Issue 6(2005) Pp [4] Dual effectiveness of lithium salt in controlling both delayed ettringite formation and ASR in concretes, Ekolu, S. O, Thomas. M. D A, Hooton. R. D. - Cement and Concrete Research, Volume 37 Issue 6 (2007) Pp [5] Mitigation of ASR by the use of LiNO3 - Characterization of the reaction products, Leemann, Andreas, LörtscherLuzia Bernard, Laetitia Le Saout, Gwenn Lothenbach, Barbara Espinosa-Marzal, Rosa M.- Cement and Concrete Research Volume 59 (2014) Pp [6] Influence of lithium sulfate addition on the properties of Portland cement paste - Deng, Yuhai Zhang, Changqing Wei, Xiaosheng - Construction and Building Materials,Volume 50, (2014) Pp [7] Aggregate passivation: Lithium hydroxide aggregate treatment to suppress alkali-silica reaction, Craig W. Hargis, Maria C. G. Juenger, and Paulo J. M. Monteiro - ACI Materials Journal, Issue 5 volume [8] Alkali silica reaction : Current understanding of the reaction mechanisms and the knowledge gaps, FarshadRajabipour, Eric Giannini, Cyrille Dunant, Jason H. Ideker Michael D.A. Thomas Cement and Concrete Research, Volume -76, Pp [9] Experimental study and empirical modeling of lithium nitrate for alkali-silica reactivity - Mohammad S. Islam, Nader Ghafoori - Construction and Building Materials, Volume 121(2016) Pp [10] The effects of lithium hydroxide solution on alkali silica reaction gels created with opal, Lyndon D. Mitchell - Cement and Concrete Research, Volume 34, Issue- 4 (2004) Pp editor@iaeme.com

6 Manju R and Sathya S [11] Summary of research on the effect of LiNO3 on alkali-silica reaction in new concrete, Feng, X., Thomas M. D A, Bremner T. W., Folliard K. J., Fournier B. - Cement and Concrete Research, Volume- 40(2010), Issue 4, Pp [12] Studies on lithium salts to mitigate ASR-induced expansion in new concrete: A critical review, Feng, X., Thomas M. D A, Bremner T. W., Balcom, B. J, Fournier B. - Cement and Concrete Research, Volume- 35(2005), Issue 9, Pp [13] Examination of the effects of LiOH, LiCl, and LiNO₃ on alkali-silica reaction, Collins, C. L, Ideker, J. H., Willis, G. S., Kurtis, K. E. - Cement and Concrete Research, Volume- 34(2004), Issue 8, Pp [14] Effects of lithium salts on ASR gel composition and expansion of mortars, Kawamura,Mitsunori, Fuwa Hirohito - Cement and Concrete Research, Volume- 33(2003), Issue 6, Pp [15] ASR prevention Effect of aluminum and lithium ions on the reaction products, Leemann Andreas, Bernard Laetitia, AlahracheSalaheddine, Winnefeld Frank - Cement and Concrete Research, Volume- 76(2015), Pp [16] The role of lithium compounds in mitigating alkali-gravel aggregate reaction, Zapała- Sławeta J., Owsiak, Z. - Construction and Building Materials, Volume- 115(2016), Pp [17] The effects of lithium ions on chemical sequence of alkali-silica reaction, Kim Taehwan, Olek Jan - Cement and Concrete Research, Volume- 79(2016), Pp [18] Influence of lithium-based products proposed for counteracting ASR on the chemistry of pore solution and cement hydrates, Bérubé, M. A, Tremblay, C, Fournier, B, Thomas, M. D, Stokes, D. B. - Cement and Concrete Research, Volume- 79(2016), Pp [19] 19. Composition rheology relationships in alkali silica reaction gels and theimpact on the gel's deleterious behavior, AsgharGholizadehVayghan, FarshadRajabipour, James L. Rosenberger - Cement and Concrete Research, Volume- 83(2016), Pp [20] A mathematical model for the kinetics of the alkali silica chemical reaction, Victor E. SaoumaRuth A. Martin, Mohammad A. Hariri-Ardebili, Tetsuya Katayama - Cement and Concrete Research, Volume-68(2015), Pp [21] G. Adisekhar and B. Sarath Chandra Kumar Effect on Flexural Strength of Reinforced Geopolymer Concrete Beams by Using GGBS, Metakaolin and Alkaline Solution. International Jour 8(5), 2017, pp [22] Sonu Pal, M. K. Mishra and V. Pandey, Effects of Alkaline Curing on The Properties of Polyester Fibre Reinforced Concrete. International Journal of Civil Engineering and Technology, 7(4), 2016, pp [23] M. Vijaya Bhargav and B. Sarath Chandra Kumar, Strength and Durability Study of Geopolymer Concrete Incorporating Metakaolin and Ggbs with 10m Alkali Activator Solution. International Journal of Civil Engineering and Technology, 8(1), 2017, pp editor@iaeme.com