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LONG-TERM PERFORMANCE OF ZnO AS A REBAR CORROSION INHIBITOR

Oladis Troconis de Rincn, Orlando Prez, Edgar Paredes, Yaxcelys Caldera, Carolina Urdaneta and Isabel Sandoval Centro de Estudios de Corrosin, Facultad de IngenieraUniversidad del Zulia, Apdo. 10.482. Maracaibo, Venezuela

1. INTRODUCTION Proper design and preparation of concrete in accordance with ACI(1) standards and timely maintenance of the structures under those conditions would guarantee them a long and efficient life in aggressive media. However, these requirements are not always met and adhered to. It is therefore the case that, in civil construction, there have always been corrosion problems in reinforcements, both in structures erected near coasts, quays, ports, bridges, etc., and in structures in which the design and preparation of the concrete did not follow the appropriate standards and are exposed to aggressive conditions or lack of timely maintenance, reducing their useful life, generating high repair and/or rehabilitation costs; in some cases, even the loss of these structures, endangering the life and safety of persons using them. With current knowledge, the protection methods now available to neutralize the aggressive effects of chlorides introduced while mixing the concrete, are reduced to cathodic protection and the use of inhibitors, as galvanizing does not seem to offer sufficient guarantees for high chloride contamination. This situation arises in cases where it is necessary to carry out repairs on structures in the splash/wave zone, where appropriate water is not available to prepare the reinforced concrete, either because it is far away from these sources or roads are in bad condition, and/or because the water or aggregates available are contaminated by chlorides, scenarios that would bring about the use of these contaminated components, with the consequent deterioration of the reinforcing steel by corrosion. A viable alternative for controlling the corrosion phenomenon is the use of corrosion inhibitors when the concrete is prepared, so that they may reduce corrosion rates to technically tolerable levels. Corrosion inhibitors are compounds that, added or supplied to concrete in small proportions, must be compatible with it, not cause unwanted reactions nor negatively alter its physical properties; besides, they must compete economically with other control methods. From the action standpoint, inhibitors affect the rate of corrosion processes, since they influence the kinetics of the electrochemical reactions that cause these processes by simultaneously retarding either the anodic or cathodic reaction or both. Inhibitors are widely used in corrosion technology, but their use for controlling steel corrosion in concrete has been limited due to the different types of environments to which structures are exposed, and to their effect on the mechanical and physical-chemical properties produced by the inhibitor(2-4).

Corrosion inhibitors(2-21) are presented as an attractive option for preventing the corrosion of steel in concrete in the presence of chloride ions. The first patent was awarded to a company in 1977 for commercial application of nitrite-based inhibitors(16). Of the different inhibiting substances evaluated, appropriate for the alkaline medium in concrete, calcium nitrite has produced the best results, even for cracked concrete(10), so it has been used commercially with relative success. However, calcium nitrite is very costly and difficult to obtain in some countries, so studies of other additives have been undertaken in an effort to replace it, either partially or totally. It has been found that Ca(NO2)2 improves the corrosion resistance of steel to chloride-ion attacks for w/c ratios < 0.5(5,12), the w/c ratio being considered as the factor most affecting corrosion. On the contrary, other authors(20) found that corrosion rate varies significantly with the cement type, the minerals used and fine aggregate and, to a lesser degree, with the water/cement ratio. It has also been indicated, that if the durability of the structures is to be guaranteed, the inhibitor must be used in good quality concrete because the characteristics of the different components in the concrete influence durability(13). E. Ramirez(17) studied other inhibitors (gluconate, phosphate, urotropine, chromates, resorcinol, fluoroglucinol, and zinc oxide). He did not find any with efficiency comparable to that of the nitrites. He points out, however, that the protection afforded by nitrites is temporary when under immersion, requiring very good quality concrete and very thick covering. In the case of severely corroded reinforcements, nitrite fails to passivate them, so repeated spraying of pre-corroded structures with inhibiting solutions cannot be considered a method of protecting these reinforcements. It has also been shown(17) that NO2-/Cl- is ineffective when the ratio is < 1. As Ca(NO2)2 is an anodic inhibitor, it could become hazardous when its concentration is reduced to levels that would increase the corrosive attack. It has also been indicated that, with immersion, both Cl- and NO2- would also leach out of the concrete because they have similar diffusion coefficients, leaving the same relative proportion of both ions that were present before immersion. Other investigations(18) developed rehabilitation processes for reinforced concrete structures, using four inhibitor formulations: i) organic inhibitor, which is thought to form a protective film by transformation into a metallic soap; ii) a mixture of surfactant and amino salts in water, or volatile corrosion inhibitor; iii) alcanolamine, an additive that would function by migrating and inhibiting in the same way as iii); and iv) Ca(NO2)2. In field application to chloride-contaminated concrete and pre-corroded reinforcements, the results indicate that ii) and iii) showed a significant reduction in corrosion rate, and reduction in i) was lower than ii) and iii), whereas Ca(NO2)2 produced a substantial increase in corrosion rate. The latter result has been obtained in other investigations(17). On the basis of the foregoing discussion, a good case may be made for the use of Ca(NO2)2 as a corrosion inhibitor in reinforced concrete structures, given the series of advantages it presents, advantages that make it reliable within the initial and borderline conditions considered. However, for other conditions where nitrite performance is unsatisfactory, further evaluation and a more indepth study of other inhibitors and application methods are needed. Such is the case with ZnO(4,8,19-21), which has been under study to try and replace nitrite either partially or totally. These results(4) show that the best inhibiting effect is obtained by mixing them in equal concentrations. The behavior of these mixtures in chloride environments was evaluated electrochemically(19) and in concrete with w/c ratio = 0.6 (conventional concrete mixture used in Venezuela). Results show that the mixture of these inhibitors at 2% is effective during the evaluation period. It is important to point out that the use of inhibitors in concrete would be economically competitive with other corrosion-control techniques if they were effective in conventional concrete, this being

the reason why all the evaluations carried out in Centro de Estudios de Corrosin (CEC) used this type of mixture. In view of these results and of those obtained with Ca(NO2)2, field use of the latter is currently specified together with concrete of excellent quality (w/c = 0.4), it was decided to evaluate the effect of w/c ratio in the behavior of ZnO and its mixture with Ca(NO2)2. This work therefore presents a summary of the experimental procedure and the results obtained during the past two years evaluation. 2. EXPERIMENTAL PROCEDURE A total of 243 concrete probes with w/c ratios of 0.45, 0.5 and 0.6 were prepared, using Lake water to mix 27 pattern probes (probes with no inhibitor), 162 probes with inhibitor concentrations (ZnO or Ca(NO2)2) at 2, 3 and 4% on the basis of cement weight, mixture at 2% (on the same basis) of both inhibitors, and tap water in 27 pattern probes. The nomenclature is as follow:

Figure 1. Details of Probes for Electrochemical Tests

The pattern probes and those with nitrite were cured for 28 days, counted as of the date of preparation. The probes with inhibitors mixed in were cured for a longer period because zinc oxide retards setting, so they were taken out after several days, depending on the zinc oxide concentration. Curing was done in tap water. Compressive strength was determined for 81 of these probes and 27 were used to determine porosity. Figure 1 shows the arrangement of the probes used to evaluate the electrochemical properties (potentials, Rp and potentiodynamic cyclic polarization curves at 0.28 mV/s), of the different mixtures tested. In the polarized samples, chloride-ion content (ASTM D-512-65) at the reinforcement was also determined. Ohmic resistance was measured to determine whether it was necessary to correct Rp and cyclic curves for ohm reduction. The probes prepared with tap water were sprinkled periodically with tap water for 30 minutes during the evaluation period. The probes prepared with Lake water were sprinkled with salt water at 0.3% for 30 minutes per day for 115 days. Subsequently, in order to accelerate the process, they

were sprayed with salt water at 3.5% until the 147th day with respect to the preparation of the test probes and, finally, they were placed in a salt chamber with saline solution at 5%, 25C and 101,3 kPa. This exposure was done for 10.5 h/day, for 500 h. The data for corrosion potentials, corrosion rate, resistivity and ohmic drop were evaluated statistically by the Qi method in order to discard non-representative values in the calculation of the median. 3. DISCUSSION OF RESULTS 3.1 Physical Tests. After 28 days, the compressive strength test was applied to the test probes (with tap water and Lake water), the probes with calcium nitrite and those with the calcium nitrite and zinc oxide mixture at 2%; this test was carried out on the probes with zinc oxide at 3% after 73 days and 69 days in the case of the zinc oxide probes at 4%. This time difference with the zinc oxide probes was due to the retarding effect on setting exerted by zinc oxide, as indicated above2. Figure 2 shows that the results for all probes (with different w/c ratios and different inhibitor concentrations) were higher than the design strength, the best behavior being that of calcium nitrite at 4%. Resistance values grow as concentration of both inhibitors is increased. It should be noted that the zinc oxide probes have greater strength values than the calcium nitrite at w/c ratio = 0.6. This results has been observed in previous studies(2).
Strength at 28 days: P, L, M y N Strength at 73 days: Z Strength at 69 days: Z4

400 350 300 250 200 150 100 P L N2 50 N3 N4 0 Z3 Z4 M 0,45 0,5 0,6

15

Compressive Strength (Kg/cm2)

9 6 P L 3 N2 N3 N4 0 M Z2 Z3 0,5 0,6

Probe

Probe

w/c

Z4 0,45

w/c

Figure 2. Compressive Strength of Probes with different w/c ratios and different Inhibitor Concentrations

Figure 3. Porosity of Evaluated Probes

Porosity increases with w/c ratio (Figure 3), except for probes prepared with zinc oxide at 2% and w/c ratio of 0.6, where a decrease is observed when the w/c ratio increases from 0.45 to 0.5. Porosity decreases up to 3% for probes prepared with zinc oxide and a mixture of inhibitors. 3.1 Electrochemical Tests. Studies to date(25) indicate that, for a w/c ratio of 0.6, all potentials are active at the end of the evaluation period, except for the steel in the probes prepared with tap water. It is noted, however, that the time needed for activating the steel is greater in the probes prepared with ZnO than in the

Porosity(%)

12

ones prepared with Ca(NO2)2. The lower the w/c ratio, the better the inhibitor behavior, with ZnO being the best. After approximately 300 days exposure to the marine environment, (w/c = 0.5), the steel was still passive in all probes prepared with ZnO but not with Ca(NO2)2, where the steel had been activated, regardless of inhibitor content. This work presents the results for the probes prepared with the best mixture (w/c ratio = 0.45). Figure 4 shows the best behavior for ZnO and the mixtures, no difference being observed between the tap water and ZnO probes after more than 400 days exposure to the saline medium.
POTENTIAL vs. Cu/CuSO4 (mV)
0 L04 -100 -200 -300 -400 -500 -600 100 107 114 122 128 135 142 163 268 304 384 404 14 20 26 44 51 58 65 86 93 5 -700 -800 P04 M24 N24 N34 N44 Z24 Z34 Z44

Time (days)

Figure 4. Average Corrosion Potential of Reinforcing Steel in Concrete with w/c = 0.45, during the Evaluation Period. This behavior is also observed in Figure 5, which shows the variation in the corrosion current density during the evaluation period. However, greater steel-corrosion rates were always observed in the ZnO probes, even though they decreased drastically as time went on, especially for w/c = 0.45, where they have remained constant during the last days of evaluation (300 days).
1.4 1.2 1 L04 P04 M24 N24 N34 N44 0.6 0.4 0.2 0 40 90 140 190 240 Time (days) 290 340 390 Z24 Z34 Z44

Icorr ( A/cm2)

0.8

Figure 5. Variation of Average Steel Corrosion Rate of the different Inhibitors with w/c ratio= 0.45 during evaluation

Figures 610 show the cyclic curves for the different conditions under evaluation. They show inhibitor behavior under three different conditions: i) Post-cure (approximately 28 days), ii) after the steel in some probes started to become activated (approximately 172 days), and iii) after 407 days of evaluation. Only the curves for the w/c ratio = 0.45 and 4 % inhibitor concentration.

Figure 6. Potentiodynamic Cyclic Polarization Curves for Steel at 0.28 mV/s, at different evaluation times. Ca(NO2)2 at 4%, w/c ratio = 0.45. Note the behavior of Ca(NO2)2 (Figure 6), where loss of passivity is observed after 407 days. Figure 7 shows that the corrosion rate for the steel in the concrete with ZnO decreases, maintaining its passivity.

Figure 7. Potentiodynamic Cyclic Polarization Curves for Steel at 0.28 mV/s, at different evaluation times. ZnO at 4%, w/c ratio = 0.45.

Figures 8 and 9 show behavior, depending on inhibitor concentration for the same w/c ratio, after 407 days evaluation.

Figure 8. Potentiodynamic Cyclic Polarization Curves for Steel at 0.28 mV/s, in Ca(NO2)2 as F Inhibitor, w/c ratio = 0.45, after 407 days evaluation.

Figure 9. Potentiodynamic Cyclic Polarization Curves for Steel at 0.28 mV/s, in ZnO Inhibitor, w/c ratio = 0.45, after 407 days evaluation.

Note that the steel has lost its passivity for all Ca(NO2)2 inhibitor concentrations. This is not the case for ZnO, where passivity is lost only when concentration is at 2%. Note that there is very little difference between 3 and 4 %. Figure 10 compares inhibitors with the mixture and the test probe prepared with Lake water and exposed to the saline medium. The lowest corrosion rate is observed in the steel in the probes prepared with the mixture. Although the steel in the probes prepared with ZnO and Ca(NO2)2 shows the same corrosion rate, in the latter there is a hysteresis behavior in its inverse scan, indicating pitting in the sample. As already stated above, the potential is more negative.

Figure 10. Comparison between Potentiodynamic Cyclic Curves for Steel in different inhibitor mixtures used at w/c ratio = 0.45, after 407 days evaluation. 3.1 Chloride Content at Reinforcement Level in the Concrete Table 1 shows the results of the determination of free chloride ions at reinforcement level, after the periods indicated above. Note the effect of ZnO, where concentrations are very low, especially when the w/c ratio is 0.5 and 0.45; the same effect is observed in the mixtures. This may be due to a decrease in concrete porosity and, possibly, to ZnO reaction with the chloride ions. As is well known, ZnO acts as a cathodic inhibitor when used in water because it can precipitate compounds in the cathode because of its high alkalinity in comparison with the anode. However, concrete has high alkalinity, so it is therefore expected that ZnO precipitates compounds both from the cathodic and anodic areas, as well as within the concrete itself, which helps to reduce porosity and maintain the passivity of the steel in the concrete when it is exposed to a medium with high chloride-ion content. It is also possible that ZnO reacts with the chloride ions in the concrete, deactivating it.

4. CONCLUSIONS 1. Chloride diffusion and, therefore, corrosion rate, is controlled by reducing the w/c ratio to 0.4, regardless of calcium nitrite content. 2. Using ZnO reduces concrete porosity and chloride diffusion. 3. After the exposure period ( 500 days), the potential values (> -200 mV vs. Cu/CuSO4) and cyclic curves of the steel in the probes with ZnO as inhibitor show passivation, even though corrosion rates are high (> 0.1 A/cm2). 4. When ZnO is used, an appreciable change in corrosion rate is observed when the inhibitor concentration is changed from 2% to 3%. 5. After approximately 500 days exposure to the saline medium, all the probes prepared with Ca(NO2)2 showed breaks in the passive film on the reinforcement. 6. The ZnO/Ca(NO2)2 mixture at 2% showed the best results throughout the study period. Table 1. Chloride Concentration at Reinforcement Level (ppm for cement weight)
PROBE P04 P05 P06 M24 M25 M26 Z24 Z25 Z26 Z34 Z35 Z36 Z44 Z45 Z46 N24 N25 N26 N34 N35 N36 N44 N45 N46 L04 L05 L06 A 327 346 383 1571 2214 2759 2355 1938 1842 1571 1938 2148 1310 1386 2454 523 484 844 327 553 1764 720 484 690 589 346 537 B 261 207 194 1833 4419 14090 2612 3729 3683 1964 1522 4143 3273 12870 13964 523 4845 9348 1833 829 5062 654 691 613 3272 4148 3832 C 394 432 778 784 756 5186 2353 1081 63283 589 3677 18674 784 4543 15562 5887 11294 69505 7456 14059 46165 8240 18277 42359 18050 10813 51351

A: Concentration at end of curing period B: Concentration 170 days after probes were made C: Concentration 400 days after probes were made

REFERENCES 1. American Concrete Institute. Building Code Requirements for Reinforcements Concrete: reported by ACI Committe 318. Inc: ACI Manual of Concrete Practice. Detroit, v.3, (1992). 2. O. Trocnis de R., Uso de los Inhibidores para el Control de la Corrosin del Acero de Refuerzo del Concreto. Memorias VIII Reunin Latinoamericana de Electroqumica y Corrosin. (Argentina, 1988). p. 444-446. 3. R.J. Craig, L. Wood, "Effectiveness of Corrosion Inhibitors and their Influence on the Physical Properties of Portland Cement Mortars". Highway Research Record.N 328, Highway Res. Board, (1970), p 77/88 4. N. Martnez de F., O. Trocnis de R. "Efecto de los Inhibidores ZnO y Ca(NO2)2y del Agua del Lago en las Propiedades Fsico-qumicas del Concreto". Memorias del II Congreso Iberoamericano de Corrosin y Proteccin. Tomo I. (Maracaibo- Venezuela, 1986) p. 397-403. 5. N.S. Berke, W.R. Grace. Corrosion/85. Paper No. 273. (Houston, TX: NACE International, 1985) 6. A.M. Rosemberg, J.M. Gaydis, et al, "A Corrosion Inhibitor Formulated with Calcium Nitrite for used in Reinforced Concrete". ASTM-STP 629. (1977). 7. O. Trocnis de R., O. Prez, Y. Longa, J. Ludovic. Corrosion/93, paper no. 339. (Houston, TX: NACE International 1993) 8. A.M. Rosemberg, J.M. Gaidis, Materials Performance 18, 11(1979): p.45. 9. F. Alvarez, C. Surez, "Estudio de Inhibidores de Corrosin en Concreto Contaminado con Sal". Theses. LUZ. Facultad de Ingeniera. (Maracaibo-Venezuela, 1982). 10. N.S. Berke, M.P. Dallaire, M.C. Hicks Corrosion/91. paper No. 550. (Houston, TX: NACE International, 1991) 11. P. Tourney, N. Berke, A Call for Standardized Test for Corrosion-Inhibiting Admixtures. Concrete International. (April 1993), p. 57-62. 12. C.A. Loto, Corrosion 48, 9(1992): p. 759. 13. N.S. Berke, W.R. Grace. Corrosion/87. paper No. 132. (Houston, TX: NACE International, 1987) 14. O. Trocnis de R., A Survey on Research in Corrosion Control Systems for Reinforced Concrete Structures. Proceedings 1st Pan-American Corrosion and Protection Congress. (Argentina, 1992). 15. C. Locke, O. Rincn, Corrosion/87. paper No. 128. (Houston, TX: NACE International 1987). 16. M. Chiruzzi, N. Berke, Aplicacin de Inhibidores de Corrosin en el Hormign. Trabajo XII/B-3, Memorias del Congreso Iberoamericano del Hormign Premezclado, (Madrid, 1992).

17. N. Thompson, et. al., Effect of Concrete Mix Components on Corrosion of Steel in Concrete. Corrosion/96. Paper no. 334. (Houston, TX: NACE International, 1996) 18. E. Ramrez C., Corrosin de las Armaduras Embebidas en Hormign en Ambientes de Extrema Agresividad. Posibilidad de Proteccin Mediante Inhibidores. PhD. Theses Doctoral. Universidad Complutense de Madrid. Facultad de Ciencias Qumicas. Centro Nacional de Investigaciones Metalrgicas. (Madrid, 1994). 19. B.D.Prowell. valuation of Corrosion Inhibitors for the Repair and Rehabilitation of Reinforced Concrete Bridge Compoets. M.Sc. Theses. Virginia Polytechnic Institute and State University. Blacksburg. (VA. USA, 1992). 20. O. Prez, Estudio del ZnO, Ca(NO2)2 y del Ca5(PO4)3OH, como Inhibidores de Corrosin del Acero de Refuerzo en Concreto Preparado con Agua del Lago de Maracaibo. MSc. Theses Universidad del Zulia. (Maracaibo-Venezuela 1993). 21. Y. Caldera, E. Paredes, Estudio de la Calidad del Concreto sobre el Efecto Inhibidor del ZnO en el Acero de Refuerzo.Theses. Universidad del Zulia. Facultad de Ingeniera. (MaracaiboVenezuela. 1996). 22. I. Sandoval, C. Urdaneta, Estudio de la Relacin Agua/Cemento en el Comportamiento del ZnO y Ca(NO2)2 como Inhibidores de Armaduras Theses. Universidad del Zulia. Facultad de Ingeniera. (Maracaibo-Venezuela, 1997).

CURRICULUM VITAE OLADIS T. DE RINCON


Oladis Trocnis de Rincn is a Professor of Chemical Engineering at Universidad del Zulia (University of Zulia), where she graduated as a Chemical Engineer in 1972. She obtained her Master degree in Chemical Engineer from the University of Oklahoma at Norman in 1975. O.T. de Rincn is the founder and head of the Corrosion Research Center, of the Engineering Faculty. She has been leader of several projects which are supported by different local and national research fund agencies. She was awarded a Research Fellowship from the National Council of Scientific Research Venezuela (CONICIT). She has obtained various research awards, distinctions and plaques for her original research activities and her effort to form research groups in the University. She was awarded the JESUS ENRIQUE LOSSADA ORDER, in First Class in 1997. Professor Oladis is a prolific writer in her research field, having published 33 papers in International Journals. Professor Rincn was Director at Large of NACE International (1993-1995) and now is the Director of the Latin American Region (1996-1999). She was one of the founders of the Venezuelan Sections. In addition, she has been active in NACE committees for a number of years, serving as member of Group Committee 3T-K, International Relations (IRC), International Relations Management (IRMC), Award and Research Committees. At the present time, she is still a member of Education Committee. Oladis de Rincn is one of the Venezuelan representatives on the International Corrosion Council. She is the International Coordinator of DURAR (Durability of Rebars) and the Venezuelan Coordinator of PATINA (Anticorrosive Atmospheric Protection of Materials), the Iberoamerican Networks from CYTED (Science and Technology for Development Program). Professor Oladis de Rincn was the Editor-in-chief of a research journal Revista Tcnica de Ingeniera from 1984 to 1991. The Revista Tcnica is an International Journal, and was awarded as the best Venezuela Research in 1988 by the CONICIT. She has organized many research and technical seminars, conferences, symposia and congresses in the corrosion and other engineering fields. As one of her main research interest is corrosion in concrete reinforcement. She is brokering an agreement between the University of Zulia and the Venezuelan Government in connection with corrosion and rehabilitation of the Bridge on Lake Maracaibo (one of the longest concrete bridge in the world). She has published and served as adviser on several projects: Corrosion problems and rehabilitation of the University Hospital Maracaibo, Corrosion problems and rehabilitation of Buildings exposed to rural environments, Corrosion problems and rehabilitation of Docks located in a marine environment, Evaluation of mortars based on Acrylic and Epoxy Resins to Repair Reinforced Concrete Structures.

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