onsretion and Building Matrals 226 (2018) 72-82 Contents lists available at ScienceDirect Construction and Building Materials journal homepage: www. evier.com/locate/conbuildmat = Use of sugarcane bagasse ash sand (SBAS) as corrosion retardant for reinforced Portland slag cement concrete Seats it Fernando C.R. Almeida“, Almir Sales*", Juliana P. Moretti *““, Paulo C.D. Mendes * “Department of Ci Engineering Federal Univers of So Cars, ia Washington Las, kn 235, So Cn, SP 1356505, rai sta for Tecnologia! serch Av. Pf Amida Pade, 532, Cage Unies, Sto Pau, SP 05505501, Brac “Deparment of Meters Enginceing and Construction, Federal Universi of Minas Gerais fu esdente Ana Cals 6527, Blo Maron, MG 3127050, Bra “Sen ste, edo Uiersty of 00 Pu Carlo de Mendon 1, anos SP 1070-10, ach 0 Cals Instat of Chemisty, Unversity of Sao Pol, TrabolhadorSdo-cremse 40, So Cares, SP 13560-970, Bai + SAS increases the compressive etd 8 strength and chloride penetration resistance of concrete. + Hydration of slag cements can be activated by SBAS, «SUAS delays the depassvaton of Feinforcing steel (corosion Fetardan + Incorporation of SBAS up to 30% leads {oa corrosion propagation similar to that observed for the reference concrete ARTICLE INFO ABSTRACT ‘ace ony Despite their growing popularity in the construction industry, cement-based materials containing blast- Received 12 January 2019 furnace slag may be subject to various deterorative processes including corrosion susceptibility owing (0 Received in revised frm 4 jay 2018 ‘he reduced alkalinity of the cementitious matrix. Sugarcane bagasse ash sand (SBAS) he main agro melee Industrial waste in sugar and ethanol production, has the potential to enhance concrete durability. “Ths study aims to evaluate the effect of SUAS a8 2 fine agategate an the corrosion of reinforced sag cement conerete. Mixes with efferent proportions were analysed in terms of mechanical characteristics, ore hore penetration electrolytic conductivity of pore solution. corrosion potential (by open circuit Sorcerer cates) potential) and corrosion rate (by polarisation curves and Tafel plot technique) s well asthe analysis eae ofthe corroded ste! bars (by sang electron microscopy technique). This paper argues the efficiency Conon propaeation ff SBASimn retarding corrosion up to an optimal content of approximately 30%, SBAS can refine micropores and act as an alkaline activator of slag cements leading to increased compressive strength reduced chlo- ‘ide penetration depth, and delayed corrosion initiation, Above 30%, the corosion rate increases, which «ould be owing to the modified microstructure and higher electrolytic conductivity of SBAS-conctete pore solutions, that control the susceptibility of chloride atack on the steel bars. {© 2019 Elsevier Li, llrightsreserved eyo Introduction ‘The durability of reinforced concrete used in major infrastruc- Corresponding author ture suct as bridges, tunnels, ports, and offshore constructions can mal adres sminbutcarbe (R. Sas} be severely compromised by corrosion processes. Consequently, hups:ioiort0.1016i.conbuitimat 201907217 50-0518) 2019 Eee I A ght reserveECR, Aca eta Contraction an uling Materials 26 (2019) 72-82 n such damage reduces the service life ofthe overall structureand sig- nificantly increases maintenance and repair costs. In the United States, ti estimated that more than $500 billion (US) is necessary for rehabilitation of bridges and highway systems, in which the ‘majority of degradation problems are related to corrosion of rein- forced conerete (1.2) This problem refers not only to the corrosion of reinforcing steel but also tothe conditions of protection that the concrete itself cre- ates around a steel rebar [3.4]. According to Tuutt’s model [5], the corrosion process in concrete structures comprises two main stages: initiation and propagation. The first is determined by changes in the concrete cover asa result of chemical and physical actions. This cover is responsible for protecting the reinforcement against neutralising or activating substances with concentrations Tavourable for corrosion, Such corrosion begins when deleterious agents such as CO and chlorides penetrate the concrete, usually ‘through diffusion processes, until the passive environment closest to the steel is counteracted [6]. When this occurs, the corrosion :mechanisms of the reinforcing steel are initiated, and the propaga- ton stage begins. In turn the rate of attack is determined both by the rate of anode-cathode reactions and the physical contact between reaction areas |7.8|. As a result, corrosion-induced dam- ages (eg. concrete stain, cracking, spalling, delamination, and cross-section reduction ofthe reinforcement) may cause aesthetic deficiency or a decrease in the structural load-bearing capacity which can lead Co the collapse of the structute [1 ‘The durability of reinforced concrete can be optimized through adequate selection of sustainable materials [10). It is widely accepted that supplementary cementitious materials, such as blast-furnace slag reduce energetic costs and CO» emissions from cement production, improve concrete performance and reduce ‘wastes fom other industries 11,12). Beeause of the latent hydrat- lic property activated by alkaisjiime, slags can effectively replace up t0 95% of ordinary Portland cement [13,14]. However, slags gen- erally contain fewer alkali compounds and lower hydroxide con- centrations than pure clinker, leading to reduced pH in cementitious systems [15,16}. Thus, Portland slag cements can have a strong effect on the alkalinity of concrete, reducing the pro- tecting ability against corrosion initiation [17] In this context, incorporation of alternative materials as fine aggregates can lead to enhanced durability by means of pore ‘refinement and inereased resistance to the penetration of deleter ‘ous agents [18], Sugarcane bagasse ash sand (SBAS),a by-product of sugar and ethanol production, isa potential substitute for natu- ral sand in cementitious materials 19.20}. Brazil is the wore’ lar~ gest sugarcane producer and exporter with an estimated SBAS generation of 4 million tonjyear [21,22]. Previous studies have shown the potential benefits of SBAS in reducing macropores larger than 0.1 mand significantly increasing resistance to chloride pen- ettation in cementitious materials (20.23), Moreover, the carbona- tion depths of mortars with up to 30% of SBAS (with respect to the {otal sand content) were statistically equivalent to reference sam- piles [20], However, the influence of SBAS on concrete durability in {etms of corrosion development, particularly in combination with ipplementary cementitious materials is still unclear and defi- cent. Therefore, this study aims to evaluate the effect of SBAS as a fine aggregate inthe corrosion process of reinforced Portland slag, ‘cement concrete, Mixes with different SBAS contents were evalu- ated in terms of mechanical characteristics and electrochemical analysis such as corrosion potential and corrosion rate under an accelerated chloride attack, 2. Materials and methods In this study, SBAS was employed as a fine aggregate for partial replacement of natural quartz sand to produce slag cement con- crete. Three SBAS levels of substitution, in mass, were considered: 0% (reference), 30%, and 50%. SSBAS samples were collected from sugarcane plants in the state ‘of Sio Paulo, Brazil, and were submitted to a homogenisation treat- ‘ment by sieving with a #48 mm sieve and grinding for 3 min in a ‘mechanical mill [19.20]. The chemical compositions of SBAS sam- ples before and after homogenisation treatment are listed in Table 1 Although the equivalent alkali value (Na;0 +0.658 * K:0) for ‘SBAS (2.8%) is relatively high [24), this content is not harmful for deleterious expansions triggered by aggregate alkali reactions [25]. Cementitious matrices with 30% and 50% of SBAS had expan- sions in the same order of the reference samples, with values far below the limits required by the Brazilian standard 25,26]. Even after the homogenisation treatment, SBAS had a predom- {nantly crystalline structure of SiO, a-quartz, as shown by the X- ray diffraction (XRD) (Fig. 1), previously analysed in [19,20}. The XRD pattern presents the characteristic peaks of the crystalline phase and the absence of amorphous halo, justifying the technical motivation to replace quartz sand by SBAS. ‘The scanning election microscopy (SEM) micrographs (Fig. 2) illustrate the size difference between both aggregates studied. ‘Table 2 lists the physical characterisation of fine and coarse agare- gates used for concrete production, All samples were prepared using Portland composite cement, with 34%, in weight, of blast-furnace slag (CPI-E32 [28] similar 10 CEM I/8-S [13)). Physical and chemical characterisation of Port- land slag cement is listed in Table 3 (CA-60 steel bars (5mm diameter and 100mm length) were used as working electrodes for electrochemical analysis. For clean- ing purposes, the steel bars were immersed for 10 min in a 1:1 HCL aqueous solution with 3.5 g/l of hexamethylenetetramine t0 con- ‘ol the acid attack. Then, the bars were brushed, rinsed with deio- nised water and immersed in acetone for 2 min. immediately after drying under a heat gun, the bars were coated with galvanic tape to delimit the electrode-exposed area (40mm length cylinder side) {or chlotide corrosion (Fiz. 3) ‘The compositions of concrete mixtures are listed in Table 4 {rom which three series of concrete with different SBAS contents were produced [19], The water/cement ratio (w/c) was slightly adjusted for each composition to maintain the same consistency [29], because incorporation of SBAS requires more water in the mixture [18,30]. This procedure avoided the use of superplasi- cizer, which could interfere the electrochemical analysis consid- cred in this study, since techniques to evaluate corrosion may be very sensitive to different salts present in superplasticizer’s com- positions [31 Prismatic samples 50 x 70 x 100 mm?) were prepared for elec ‘trochemical analysis, considering two treated steel bars (Fig. 3) ‘embedded in each specimen (Fig. 4}, Also, cylindrical samples were “rable 1 Chemical composition of SAS samples in mass, Component S10; FO) KO ALD) GOO; THO; NNO Mn 50; Los on igition SHAS befowehomegensation 60258 40. 26° 18 1S tA 1a 02—~=~CC SHS ter omegensaion 808583925 BSA StECR Almeida ea Consracion nd Bling Materials 226 (2018) 72-42 ‘000 a Cua (154874) 800 s & B 600 3 & Bao z i @ a 220 3 aoe cc : ak . ok is 160 209 250 3009604060600 650600 260°) Fig 1. XRD of SAS used inthis sty (be) after homagenisation treatment (re, Q= quart) [9] (For interpretation af he references to olor this Higure legend he rede is efered to the web version ofthis ate) Fig 2. SEM micrographs of ie ageegates (a) quant sand (b) SBAS Table? Csractersation of ageezates wl for concrete production, Peper ‘SHAS Quan Base Sad gravel Specifie graviy 2s? 245255 iter absorption (2) os ass Maximum dimension (mm) iis 638 Finenese module 115 232 149 Quanity of powdery mater finerthan 75pm 162-035 (0 200 sieve) er washing (2) A (measured im aqueous solution Tel using 10462 tod A er, according (27 prepared for mechanical and chloride penetration tests, All con- ‘rete specimens were compacted by using a vibrating table, ‘demoulded after 24 h, and cured in climate chamber for 28 days at a temperature of 212°C and relative humidity of 955% [32,33], Each concrete composition was tested in triplicate forall tests, ‘The concrete samples were subjected to aging cycles for 22 weeks. Each cycle comprised a week which was divided into a ‘wetting semi-cycle in 3.5% NaCl solution for 2 days and a drying semi-cycle in an oven at 50 +5 °C for 5 days [33]. “Table 5 lists the adopted experimental programme according to specimen type, exposure conditions, and age of testing, Analysis of ‘able 9 anuicar, Proper CALE Componcat CPEB (inmas.%) Specie gravity 3az zat Bastturace slag content) 340 ADs 74 time (in) 197 Fey, a ime(min) 27a sui Myo 3a "reaed #200 360 50s, 2 Bane specie surface (mit) 4141 Na,0 a Compressive strength: Ko Mt Say rs) 185 Girone 3 nde, 7 days (a) 268 Insloble residue 25 aay (ha) 395 tone at ‘variance (ANOVA) and Student’ I-test at a significance level of 5% were considered for all testing results. ‘The compressive strength test was performed at 28 days (alter curing) and 182 days (after aging. cycles), and cartied out by a servo-mechanical press, at a loading rate of 0.45 + 0.15 MPajs, according to [34], The compressive strength was obtained from the average of the ratios between the maximum load of rupture and the cylindrical cross-sectional area of the specimen.ECR, Aca eta Constrction an ung Materials 26 (2018) 72-82 1% Fg. 3. Stel ba preparation: (a) immersion i hydrochloric acd and Hexamthyleettramine station: (Brushing in denied water: () immersion in aston) ng ith gaa ape ‘ables Mature composton of concrete samples. Saple SEAS conten) ‘Mure proportion tm mass) Samp ws am @ 7 1.00 2010 = 7850 0320 wes Go 30 1.00 1407 0503 2860 0330 s785 0 50 1.00 003 1005 260 0540 B85 Fig. 4. Prismatic mould of enforced concrete for electrochemical analyse (a) postionng of tel bars (b)conrete-flled mous with embedded te bac) open cult ‘rates Experimental programme for concrete samples Testing ‘Standard _Specinen oe pose conion ae of eating Compressive senate Tal Gjinact ‘ering ty 738 days Giindeal uring lowed by apg yeles At 1825s Teil stent 15] Ginger orig only 2898 Flatic mals ~ Method A ol curing os 2895 (hire penetraon by cooieticenthod with [27] Gyn Cun lowe by aging yetes AI 18238 'ARNO) and Mucrescis ectolyte conductivity of pore soliton [38] Aqueoussoluion exacted fom powder of Curing flowed by ying of AL 28 days once specimens concrete specimens Comovon pote by open cet potential [3] ‘Prisma Corin allowed by apg cycles using 22 weeks sir curing ‘omoson rate by polation curves (o) prismatic uring followed by aging yes 182days i depth by SEM anal [an] Beracted tee bars [mer aging ees cmbeed in For the tensile strength test, cylindrical specimens were sub- Jected to diametrical compression according to [35] at 28 days (afer curing). The test was performed using a servo-mechanical press at loading rate of 0.05 + 0.02 MPajs until the rupture. The tensile strength was determined by Eq, (1)- 2p fe o ‘where P is the maximum load of rupture (N), Dis the diameter of the cylindrical specimen (mm), and fis the height ofthe cylindrical specimen (mm). ‘The elastic modulus by compressive stress was determined according to [36] (Method A) at 28 days (after curing), Extensome- ters were positioned on cylindrical specimens for the strain mea- surement. The load was applied by a servo-mechanical press at a loading rate of 0.29 +005 MPa(s, until the stress corresponding,% CR Almeida a /Consracton an Bung Meter 226 (2019) 72-82 to 30% ofthe concrete compressive strength (6) and kept for 60s. ‘Aer that, the load was reduced to a stress of 0.5 MPa «,) and kept for 60 s-This process was repeated twice, and, in the last cyele, the strain was checked for 6, and «, resulting ¢, and &y. The elastic ‘modulus was determined by Eq. (2). oy -05 10? @ where of is the stress corresponding to 30% ofthe concrete com pressive strength (MPa), cis the strain at ©, = 0.5 MPa, and i the stain at 0, ‘The chloride penetration test was conducted using the ¢ol- ‘oximetry method by sprinkling silver nitrate and Nuoresceinsolu- tion [37], At 182 days after 28 days of curing followed by 22 aging «yces), concrete samples were dried at 105 25 °Cand then broken ‘The surface obtained by diamettcal rupture of the specimen was treated with 0.1 M silver nitrate (AgNOs) solution and fluorescein alcoholic solution (1% furescein salt, 29% distilled water, 70% ‘ethano)) A white precipitate (AgCl) was formed after the sprayed surface dried. This whitish region, in contrast to the darker area, indicates the presence of chloride ions. The depth ofthis whitish area was measured using.a digital pachymeter from the outer edge ‘ofthe specimen, which indicates the chloride penetration depth in the concrete specimen. Fleetrolytic conductivity was analysed for the pore solution ‘extracted ftom finely macerated concrete samples. The extractions ‘were prepared with a 1:1 proportion (in mas) between the solid samples and ultrapure water (2.37 jem), during 24h with occa- sional agitation, followed by vacuum filtration. The coarse aggre- gate was not included, since itis expected to release a negligible ‘quantity of ions [38]. A lab bench conductivity mete, with cell constant of 0.75¢m ', was used for the measurement at room temperature. “The corosion potential was estimated through the open circuit potential, which was measured in ipliate based on [33-39] Three Feinforced concrete (prismatic specimens with two embedded steel bars each) were continuously monitored by means of the ‘open circuit potential (Ex) using a high impedance input voltmeter (Minipa ET-2076). Measurements started at 28 days ater the cur- ing period and were conducted twice a week for both wetting and drying conditions at the end of each semi-cycle It was assumed that the standardisation of the testing condition was obtained ‘due tothe steel bars preparation (Fig. 3) [33]. At the end of 22 ‘ces, or 182 days after casting all working electrodes were in fan active state of cortosion, ie the Rye values were inferior (0 254 mV vs, the reference electrode of Ag/AgCKClax [39] ‘A tis stage, the polarisation curves were obtained by using a potentiostat/galvanostat PGSTAT mod. 20 Autolab, using the Aa ‘AGCIKClyg reference electrode and an auxiliary titanium electrode This technique is a perturbation method with linear scanning around Exc 350mV at 0.5 mV}s (4.40), The corrosion current Gensity (isin wAlcm’, whichis directly proportional tthe rate of corrosion, was calculated by Eq. (3) considering the corrosion potential (Ezy) and corrosion current (ky) obtained from Evans ‘iagrams and Tafel plots (42,43) Je in = @ Where Jory is the corrosion current intensity (jiA), and 5 is the ‘exposed surface area of the working electrode (15.83 cm?). After- Wards, the steel bars were extracted from the concrete specimens and were cleaned following the same procedure, as shown in Fig. 3. The pitting depths of extracted corroded bars were analysed through the Scanning Electron Microscopy (SEM) technique (EVO 50, Carl Zeiss AG, Oberkochen, German), according to [41], The sam- ples were not pre-coated, and abservations were cartied out in high ‘vacuum mode, accelerating voltage (EHT) of 19 KV, and working distance (WD) of 8 mm, The level of corrosion was characterised by measuring the deepest point of the pitting penetration of each working electrode [44 3, Results and discussion 2.1. Mechanical properties ‘The results of compressive strength at 28 and 182 days, before and after aging cycles, as well as those of tensile strength and elas- tic modulus at 28 days are listed in Table 6. ‘AL28 days, the incorporation of SBAS increased the compressive strength by around 8% and 11% for concretes with 30% and 50% of, ‘quartz sand replacement, respectively. At 182 days, the addition of 'SBAS resulted in increments of 4% and 14% (absolute values) for C30 and C50, respectively, relative to the reference concrete (CR). ‘The considerable increases in strength between both ages must be attributed to prolonged cement reaction owing to the blast- furnace slag in the cement composition in addition to the continu- ‘ous drying/wetting cycles in the saline solution. The differences between the compressive strength results at 28 days (no aging cycles) are statically significant. The SBAS incor- Poration indeed increased this property even with a higher wic ratio for concretes with SBAS. This increment can be attributed to the packing effect of SBAS in the mixture. According to previous studies 20.23], SBAS particles have filled pores in size ranges of 60-80 jum and 100-300 um, resulting in a denser microstructure ‘and hence increased compressive strength. The increased strength, ‘can also be related to the interaction of SBAS and Portland compos ite cement with blast-furnace slag [45]. ‘The reaction of slag itself with Portland cement and water is a ‘complex process. It is well known that the main constituents of ‘ordinary Portland cement (PC) are calcium silicates (CasSiO; and Ca,Si0,), aluminate (CasAlsO¢). and fertite (Cay(AInFey.)40so) which can be abbreviated to C;S, CS, GA, and C,AF. A number of ‘other minerals such as calcium sulphates (present as gypsum, anhydrite andjor hemilnydrate), calcite, calcium oxide, magnesium ‘oxide, Na- and K-sulphates are also usually present, These compo- nents react with water to form various hydration products such as calcium siticate hydrate (C-S-H), portlandite (CH), ettringte, cal~ ‘cium monosulphoaluminate or calcium monocarboaluminate (1446) ‘Slag. due to its high alumina and silica content, produces some- what more complex hydrates than PC. In hydrated PC-slag systems, the presence of C-5-H, CH, ettringite, AFm (monosulphate and ‘monocarbonate), and a hydrotaeite-ike phases is observed. How- ‘ever, hydration of PC-slag cements produces less portlandite (at Jong term), less ettringite (at high slag content) and less AFm and [APL phases (as more Al is bound in C-S-H) than in pure PC hydra- tion, Usually, the C-S-H formed in PC-slag blends has a lower CalSi ratio and a higher AI/Si ratio than pure PC [10], Introducing alu- ‘mina into the C-S-H phase, to form C-A-S-H, markedly increases its alkal-binding capacity and, hence, reduces alkalinity ofthe pore solution [47 ln the presence of water, slag hydrates to a limited degree. A protecting film deficient in calcium is quickly formed, which slows ‘down further reaction. If pH is kept sufficiently high in presence of activators, slag hydration can be accelerated and intensified. The ‘most common activator of slag is PC clinker, but also other alkaline ‘materials [48]. In this context, SBAS can act asan alkaline activator, considering its relatively high equivalent alkali value (Na;0 +0658 * K,0= 2.8%, from Table 1) and higher pH (Table 2) com- pared to quartz sand. Thus, secondary C-S-H phases can be formed {as hydration products of SBAS-PC-slag concrete, which are respon- ‘ible for lower permeability and higher strengthECR, Aca eta Constrction an ung Materials 26 (2018) 72-82 els of enechanicl tet of concrete n Sumple Compressive rent (at 28 dvs) Compressive stent at 182 days) Tensile stewth (at 2B days) lsc modus at 28 das) erage SDV Average SDV Average SDV verge SDV (Ques) (Pay) tayo) ay ra) ) a) @ wos on 3 aaa ANOVA and GC & CRCSOStaicaly——_GIEIESO ne Saisaty ICIESO nt Sasa jC) ne sais test Siena Sian sioifcant sie GT $b: andard deviation. Therefore, when slag is mixed with water, its hydration prod- ucts form a thin Si-tich layer on the surface of the slag grains, which stifles further hydration [49,50 In turn, together with port- Jandite (CH) and alkali hydroxides from Portland cement hydra- tion, SBAS can act as slag's activator. Owing to its higher alkalinity compared with quartz sand (Table 2), SBAS raises the pH in the vicinity of the slag and prevents the formation of the Sicrich layer, As a result, SBAS can improve the hydration degree ff Portland slag cement and increase the compressive strength of the concrete. However, according to ANOVA result, the null hypothesis can- ‘not be rejected for the results of compressive strength at 182 days (F-statistic< critical, Although C30 and C50 reached greater absolute values than CR, the specimens subjected to degradation ‘yeles had statistically equivalent compressive strength regardless of the SBAS content. NaCI salts were crystallised in the concrete pores, leading to increased compactness in all samples, as shown in Fig. 5, which led to an increase in the masses of specimens over the cycles. This effect was caused by the gradual accumulation of salts into the concrete microstructure in addition to the hyigro- scopic nature of NaCl, which led to increased water retention. However, the mass increment ceased, and the mass variation sta- bilised after approximately 16 weeks. This can indicate a ‘satura- tion’ of the salt crystallisation effect in which the microstructure clogging by NaCl potentially overcame the SBAS packing. Thus, the compressive strength values were statistically equivalent for coneretes with and without SBAS. ‘The results of tensile strength and elastic modulus at 28 days ‘were not affected by the SBAS incorporation with F-statistic 05). However, the evidence was insufficient {or rejecting the null hypothesis by ANOVA test. Thus, the concrete 45% 40% | 35% — 3.0% 25% 20% 15% 10% 05% 0.0% 05% “1.0% Mass variation (%) ‘with SBAS had similar performance for those properties when compared with the reference sample. ‘Therefore, SBAS enhanced the mechanical properties by increasing compressive strength at 28 days. Tensile strength and clastic modulus, as well as compressive strength after degradation ‘cles were not influenced by the SBAS incorporation, 3.2, Chloride penetration Fig. 6 shows the results of colorimetric testing of chloride pen- etration in concrete after 22 aging cycles of drying and wetting in [NaCI solution, This qualitative method indicates the presence of free chloride ions which indeed represent a risk for susceptibility of reinforcement corrosion ‘Analyses through ANOVA and Students t-test indicated that al, averages were statistically different. The incorporation of SBAS had 8 significant influence on the chloride penetration depth in con- Crete such that a higher SBAS level in the mixture corresponded to a lower chloride front depth. This result is attributed (0 the physical and chemical effects of SBAS. ‘The physical effect canbe related tothe filling of micropores with 'SBAS particles, particularly pores with dimensions smaller than 150 um, and the reduction of capillary interconnectivty by adding finer material in the mix [20,51]. Moreover, ionic diffusion can bbe considered as the main transport mechanism of chloride fons in concrete with SBAS, The presence of other fons in the pore solution, such as Na’, K', Ca? and OH affects the presence of CI, accelerat~ ing or slowing its penetration via mechanisms of repulsion or attrac- tion among the electrical charges [52,53]. Thus, incorporation of finer particles of SBAS affects the transport mechanisms and thus acts asa barter against chloride ion penetration. C50 -e-c00 +c 23 4 § 6 7 BO 1011 12 19 14 15 16 17 18 10 20.21 22 ‘Aging cycles (weoks) ig. 5. Variation in mass of concrete specimens during sping eyes. Higher (lower values eer saturated dee conditionsn CR Almeida a /Consracton an Bung Meter 226 (2019) 72-82 wCR C3050 @ ) Fig. 6. (2) Rests of nde ponetation depth and (b) olrmctctetment apple Lo cnctte specimens ‘The chemical effect, in turn, can be attributed to slag activation by SBAS. The higher pH of SBAS (compared to quartz sand, Table 2) contributes to activate hydration of Portland-slag cement, result= ing in the creation of secondary C-S-H. This leads to refinement of the pore structure and, hence, reduced permeability in the con- crete [53,54]. Chlorides bind to aluminate phases or are adsorbed ‘on C-S-H [6], Therefore, in comparison with the reference con- ‘rete, the incorporation of SBAS had a postive effect on the resis tance to chloride penetration. 33. Electrolytic conductivity of pore solution To improve the understanding of the solution that can be pre- sent in the pores of the concrete samples, the electrolytic conduc- tivities of solutions extracted from finely macerated samples (as an indirect approximation to the pore solution) were compared. The results are shown in Fig. 7 ‘There is positive correlation between the conductivity of the ‘extracted solution and the content of SBAS in the concrete; the ‘concictvity increased by 14% and 23% for a SBAS incorporation ‘of 30% and 50%, respectively, with respect to the reference without 'SBAS, The conductivity is a summation of contributions from all, ions (38|; however, the increase can be attributed mostly to the higher concentration of OH expected in the presence of SBAS. according to the higher associated pH compared with quartz sand (Table 2}-In fact, OH” are among the most conductive fons found in Concrete pore solutions [55,56], ‘The higher conductivity could be expected to facilitate corro- sion due to the increased mobility of reactive species, ie, allowing the flow of electrons and. hence corrosion of the reinforcement bars. However, it is not possible to ascertain the performance of these materials solely by this measurement, since many other fac- tors affect the permeability of species and corrosion, such as the ‘characteristics of the concrete (waterjcement ratio, type and pro- 5ca0—@CS0 10.00 9.00 8.00 700 6.00 5.00 400 3.00 2.00 1.00 0.00 Electrolytic conductivity {msiem) Fig 7. Rests forthe conductivity ofthe aqueous soltion extracted fom the ‘cestious mati silting pore elton portions of aggregates, cement consumption, the presence of ‘chemical admixtures, degree of hydration, microstructure and pore density, rebar passivity, alkalinity of the pore solution}: environ ‘mental characteristics (temperature and relative humidity) and the action of aggressive agents (chloride penetration and carbona- tion) [433]. Thus, all properties should be carefully evaluated in conjunction before reaching a reliable conclusion regarding the performance expected with SBAS incorporation. 3.4, Corrosion initiation ‘The results of open circuit potential (F<) measured during the degradation cycles in the saline solution are shown in Fis, 8. Because the system was allowed time to stabilise before each mea~ surement, the Eo. could be a satisfactory approximation to the cor- rosion potential for each condition of, specifically the anodic and ‘cathodic reactions should have the same rate. After 20 weeks, the probability of corrosion of all working electrodes was expected to be greater than 90% for all samples with Eye values below 254 mV versus AgiAgcl (saturated KCI) (29). The outliers observed during the first week can be attributed to the dramatic change in environment from a humidity chamber with curing at 95% relative humidity to aging cycles in a saline solution, However, during the following weeks, all measurements stabilised, indicating a trend related to the wetting and drying ‘eycles to which the concrete samples were subjected. The varia tions in the Eq. measurements for each semi-cycle were attributed to the moisture content of the specimens. directly affecting the ‘olimic drop in the concrete. Specifically, less negative Eye values were obtained after drying semi-cycles in which the electrical resistivity or the difficulty of ion movement was higher, whereas the Ey. was more negative when the samples were saturated with the solution. Ths is because the minimized ohmic drop under sat- uration condition led to lower electrical resistivity, resulting in ‘more negative E,. values [57] ‘Overall, during the passivation period, working electrodes pre- sented E values between 160 mV and 30 mV. At the time of ‘depassivation (Exc < ~254 mV), a sharp decline in Ege values was verified for all Samples, indicating the beginning of corrosion prop- _agation in the steel bars [23). The working electrodes in the refer- ‘ence concrete were the frst bars to begin corrosion propagation, at week 14, followed by concretes C50 and C30 at weeks 16 and 18, respectively. The delay in corrosion activation in the steel bars ‘may be related to the packing effect of SBAS. The substitution pro- portion of 30% must have contributed as an ideal condition to close ‘r interrupt the connectivity between pores [20,23]. This created a physical barrier against the attack of chloride ions [58]. Moreover, the increment of alkalinity inthe concrete by SBAS may have con tributed to delay corrosion initiation. Concrete samples CR, C30ECR, Aa eta Contraction an ung Materials 26 (2018) 72-82 ” 00 50.0 1500 2000 2500 000 3500 4000 ‘Open Circuit Potantial (mV vs Ag/AGCI- sat. KCI) ge 1234567 89 01 2 19 4 15 16 A 18 19 20-2 ‘Aging cycles (weeks) Fi. §. fvouton of the open i and C50 respectively had pH values of 11.93, 12.32 and 12.33, mea- ‘sured by this research group fom the solubilised extracts [1925] obtained according to the Brazilian standard [59]. The susceptiil- ity to pitting corrosion in an acid solution containing primarily chlorides increased with the decreased alkalinity provided by the passivation cover [650], ie. the balance between alkalinity and acidity, given by the activity of OH and Cl, respectively, is responsible for maintaining the passivation of the reinforced rebar. In summary, the beginning of the corrosion process in reinforced conerete was delayed by substituting 30% of the quartz sand with ‘SBAS, owing to its physical influence in refining micropores and its higher alkalinity 35, Corrosion propagation ‘The linear polarisation curves are shown in Fig. 9, where the ccurrent values (I) are plotted against the overpotential (m), obtained by sweeping at 0.5 mV/s, from the lower limit around the Exc following the relation 1) = Exc # 350 mV. Analogous to the interpretation of Ex. the Exc, indicates the electrochemical dynamic equilibrium, in which both the anodic and cathodic cur- rents have the same magnitude and thus the resultant total current is null. From this point, the anodic and cathodic terms are unbal- anced by the application of overpotentials. where the polarisation resistance and current propagation can be interpreted. Although ‘ohmic drop is one of the main error sources of this technique [4.57], it was minimised by employing samples which were already corroded after conditioning cycles (Fig. 8) and were fully saturated with NaCI solution electrolytes. Active dissolution of the working electrode was noted for all samples, as indicated by the upward sloping curve in relation 0 the overpotential axis, In particular, sample C50 presented the highest current values according to its highest slope, both in the anodic branch (positive values of n) and cathodic branch (negative values of 1) indicating greater dissolution of the metal. Specimens (CR and C30 had profiles similar to each other when compared with C50, although their current was significantly lower. Iris erucial to keep in mind that the current is proportional to the electrode area Although the exposed geometric area was the same fr all samples, the unique corrosion process that occurred on each material greatly affects this measurement, hence, a higher active area could be expected for C50 to explain the higher currents. The corrosion otal of working electrodes versus AlMGCIKC in conerete specimens 0.80 0.60 0.40 0.20 = 0.00 0.20 0.40 -0.60 -0.80 —— -400 -300 -200 -100 0 100 200 300 400 ‘Overpotential, n (mV) 1(mA) Currer —R = c30 + 50 Fg 8. Poaration curves of working letras concrete (ines se. rates are directly proportional to the corrosion current, i. higher values of electrical current passing through the system indicate that the corrosion is more severe. Thus, by a qualitative analysis, it can be inferred that the corrosion propagation was greater for C50 and was similar for CR and C30. ‘To determine the corrosion current, the polarisation curves were plotted in a fogarithm scale (Evans diagram. Fig. 10). From the intersection of the extended cathodic and anodic branches on the Tafel slope, the corrosion potential (Eaqx) and corrosion cur- rent, or more accurately, the logarithm of the corrosion current (log Heel) were found. This result, in turn, can be extrapolated 10 corrosion rate analysis by considering the following factors: (i) generalised corrosion, which is perfectly uniform along the sur- face; (ii) simple dissolution as the only anodic reaction, written as Fe? Fe" +2e ; and (iit) Faraday’s constant. The results of the corrosion current density (igyq) of each working electrode are listed in Table 7 ‘The results emphasise the similarities between CR and C30 samples, which had the same order of corrosion current density Because they were in the range of 0.5-1.0 wA/em, both rates could be classified as moderate levels but not severe [1]. However, C50 clearly had the greatest corrosion propagation compared with the20 20 | cates reactn: 4 09 08 97 0 |. cathode reactor: Eun “908 07 ao [ye etdeee S708 20 Fig 10. vans diagrams and Tf! pos polarisation curves of working letras Im coneret legaitin scale other two samples, with arate about 10 times greater than the rate of the reference sample. C50 can be characterised as have a high level of corrosion because its ig Value was greater than 1.0 Aj cm? [44 Ics worthwhile to note thatthe approximation ofthe corrosion, rate is affected by how localised the corrosion is. As mentioned above, this corrosion rate analysis is extrapolated by considering a generalised corrosion, which is perfectly uniform along the steel surface. However, the presence of pitting, cracks and other surface ‘able? ew CR Almeida a /Consracton an Bung Meter 226 (2019) 72-82 as 44 93 42 ari oa —cxo “5 a4 93 42 anode esto —cx Tl stone 05 04 03 02 sult of corosion parameters of working lectrodes in concrete samples. Fig. 11 SeM micrograph for epi iting depth measurements The inserts show the pointed caaies of each working eetrde [lenge ts) deta Sample Eun (a) tos al te ieee) iting pth by SEM om) asication ye eR 02 49 116 07 maa moderate Go 632 49 137, 09 nso moderate Go 68 29 ey fone iECR, Aca eta Contraction an uling Materials 26 (2019) 72-82 81 irregularities need to be evaluated carefully to further understand the results In this context, the typical pitting depths of corroded steel bars, ‘were characterised by the SEM micrography technique (Fig. 11. ‘The steel bars embedded in concrete C50 had the greatest surface irregularities (piting dept) in comparison with the other samples (Table 7) indicating a more localised corrosion. Ifthe remaining, areas of the steel bar are considered passive, a high corrosion cur- rent divided by a smaller area (more localised) results in a higher corrosion current density, This technique completes the under- standing of the corrosion profile, because the analysed working, electrodes did not incur uniform and generalised degradation. As expected, the corrosion was localised, which is characteristic of the chloride action and indicated by the cavities on the bar surface. Pitting corrosion can be more dangerous than uniform deteriora- tion because it progressively reduces the cross-sectional area of the rebar toa point at which it can no longer withstand the applied Toad, leading to severe structural failure [4], Increments of corrosion kinetics in concrete with SBAS, particu larly at contents above 30%, can be related to its increased elec- trolytic conductivity (Fig. 7). Moreover, the presence of some salts in the matrix, such as NaCI from saline solution during the aging cycles, accelerates the electrochemical reactions on the steel bars during corrosion progress. This is owing to their capacities for epolarising and, consequently, increasing the electrical charge passing through the concrete as an effect of dissolved salts. In this context, particularly C50 had the greatest mass variation on the wetting and drying cycles (Fig. 5), indicating a higher water absorption capacity (Including saline solutions) and, hence, a greater ability of NaCl crystallisation. Thus, incorporation of higher 'SBAS levels of more than 30% can contribute to faster propagation of the corrosive process, especially due to the modified microstruc- ture of the cementitious matrix and increased ionic mobility in the ‘mic which leads to greater electrolytic conductivity. Although SBAS may retard the beginning of the corrosive pro- ess, as indicated by Fy. measurements, this by-product con- tuibuted to accelerating the corrosion propagation as soon as it began. This negative effect was even more pronounced in concrete ‘with 50% SBAS. Therefore, incorporation of SBAS at levels up to 30% can reduce corrosion probability, asa retardant of corrosion initia- tion, and keep corrosion propagation atthe same rate asthe refer- tence sample. Moreover, i has been well identified that not only the corrosion rate is important but also how localised it is. Due to the limited number of samples to deduce a “Tuuttis prediction’ [5] and adverse conditions in field, the outcomes presented herein ‘may not occur in practice. However, this study is representative of general trends that can be expected and is important for basing the advances of the current knowledge on reinforcement corrosion ‘of SBAS concrete. 4. Conclusion (On the basis of the results obtained in this experimental study, the following conclusions were drawn: + The substitution of quartz sand by SBAS increases both the com- pressive strength and resistance to chloride penetration of con- crete. This positive outcome can be attributed mainly to a packing effect and the ability of SBAS to act as an alkaline acti~ vator to Portland-slag cement. The tensile strength and elastic ‘modulus are not significantly affected by the incorporation of SBAS. + The incorporation of SBAS leads to decreased probability of cor- rosion, owing to the delayed depassivation of the reinforcing steel. This effect is related to inereased concrete alkalinity and decteased pores connectivity promoted by SBAS. Concrete with approximately 30% of SBAS seems to indicate an appropriate ‘mixture for retarding the initiation of corrosive processes. Once corrosion began, the propagation rate is higher for con- crete with SBAS contents greater than 30%, due to the modified ‘microstructure and increased conductivity of its pore solution. It appears that a SBAS content of about 30% may result in a physical and electrochemical balance between closing microp- res (or interrupting pores connectivity) and satisfying an ade quate conductivity of the pore solution that controls the susceptibility of chloride attack on the steel bars. This equilib rium prevents the propagation of higher corrosion currents, and creates a propagation condition comparable to the beha- viour for a sample without SBAS, For future studies, evaluating different SBAS concentrations around 30% is recommended in, order to accurately identify the optimal content that leads to an enhaneed concrete performance. ‘Therefore, in addition to environmental benefits of reusing an agro-industrial by-product, the incorporation of SBAS at levels up to 30% can improve the mechanical properties and enhance the durability of reinforced concrete. The capacity of SBAS to retard corrosion initiation in an environment susceptible to chloride attack adds value to this new eco-friendly construction material Declaration of Competing Interest ‘There is no conflict of interest. Acknowledgments ‘The authors acknowledge CAPES 001 and CNPa (Grant numbers, 309892/2013-9 and 409685/2017-8) for financial support, Cosan {or SBAS supplies, and Prof Lucia H. 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