Portland Cement Association

Volume 18/Number 3 December 1997 5420 Old Orchard Road Skokie, Illinois 60077-1083 Phone: (847) 966-6200 Fax: (847) 966-8389 Web Site: www.portcement.org

Effect of Ettringite on Frost Resistance

by Rachel J. Detwiler and Laura J. Powers-Couche*
In investigations of frost damaged concrete, white deposits are commonly found in air voids. These deposits are often identified as ettringite. Questions arise as to what role ettringite has on freezethaw deterioration of concrete. A laboratory study was developed to examine this issue. The following hypotheses were suggested: 1. Gypsum-bearing deicing salt diffuses into the concrete. Gypsum, a common component of deicing salts, reacts with the hydration products of tricalcium aluminate (C3A) in the cement paste to form ettringite that fills the air voids until they are unable to protect the concrete from frost damage. 2. Excess gypsum already present in the cement reacts with the C3A hydration products, filling the air voids with ettringite and compromising the air-void system as described above. 3. Deterioration is due to frost damage of inadequately air-entrained concrete. As the paste breaks up microscopically, ions go into solution and recrystallize as ettringite in voids or cracks. The ettringite seen in the air voids is thus a consequence, not a cause, of frost damage.

Contents
Effect of Ettringite on Frost Resistance

Origins of Chloride Limits for Reinforced Concrete

Ettringite Formation
The mineral ettringite has limited natural occurrence in rocks; however, ettringite has widespread occurrence as a primary mineral in fresh concrete and as a secondary mineral in mature concrete exposed to moisture. Mineralogists define primary minerals as the minerals or phases initially formed in a system. Secondary minerals are deposited or formed at a later time, usually as a result of alteration of existing minerals. As a secondary mineral, ettringite is generally deposited in open spaces such as air voids and cracks (Fig. 1). When it appears in

New Literature

Figure 1. White ettringite deposits in voids of field concrete (20x). (S67533)

Principal Engineer and Senior Microscopist, respectively, Construction Technology Laboratories, Skokie, Illinois 60077, USA.

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Concrete Technology Today hardened concrete, its presence may or may not indicate distress. Gypsum is added to portland cement clinker during finish grinding to provide sulfate to react with C3A during hydration in order to control setting. This reaction forms ettringite. If the supply of sulfate ions is not adequate to maintain the stability of the ettringite as the C3A continues to hydrate, the ettringite converts to monosulfoaluminate. The initial formation of primary ettringite is innocuous because it takes place while the cement paste is still plastic. Monosulfoaluminate takes up less space than ettringite. Provided no additional sulfate becomes available, it is stable. Secondary ettringite crystals are needle-like and are usually less than 0.1 mm long. Masses of needles appear as white deposits. Secondary deposits such as ettringite require a hand lens or stereomicroscope to be seen. Ettringite can be confused with other minerals, such as thaumasite, that have a tendency to needle-like growth. Confirmation of ettringite requires expertise with mineralogy, the petrographic microscope, scanning electron microscope, or X-ray diffraction analysis. It is generally agreed that the morphology (size and shape of grains or crystals), associations (the minerals typically found together), amount, and location of deposits within a mass of concrete distinguish the ettringite as harmful or harmless. Table 1. Concrete Mix Design Three different cements, made from the same raw materials, were Cement 314 kg/m3 (530 lb/yd3) used for the concretes: two verFine agg. 873 kg/m3 (1472 lb/yd3) sions of a Type I cement with 12% C3A, one having 2.03% sulfate and Coarse agg. 1067 kg/m3 (1798 lb/yd3) the other having 3.14% sulfate, and Water Not to exceed 154 kg/m3 a Type II cement with 5% C3A and (259 lb/yd3) 2.72% sulfate. The higher sulfate, Slump 50 12 mm (2 1/2 in.) higher C3A cements would be expected to create more ettringite Water reducer Not to exceed 1 L/m3 than the lower sulfate, lower C3A (5 oz/cwt) cement. A 3-day moist cure followed by 25 days in laboratory air (23C [73F], 50% RH) was used to reflect field curing. also to establish the failure mechanism (that is, to determine whether Exposure Conditions ettringite deposition or frost damThe 76x76x286 mm (3x3x11-1/4 in.) age comes first), it was necessary to prism specimens were tested according monitor the changes in the specito ASTM C 666, Procedure A, Freezmens in several ways through the ing and Thawing in Water, with the course of the program. Before the following modifications: specimens were returned to their respective solutions at the beginning 1. Instead of water, one of two salt so- of each week, the mass, length, and lutions was used. One consisted of fundamental transverse frequency 3% sodium chloride (NaCl) by were measured and recorded. Sacmass, the other, a 3% NaCl with rificial companion specimens were added gypsum. The level of gypperiodically sampled for petrosum added was 5% by mass of graphic examination. NaCl to simulate the worst case This test program demonstrated that would still meet ASTM D 632, the need to monitor freeze-thaw which states that road salt must be samples for changes in at least at least 95% NaCl. three properties: relative dynamic 2. At the end of each week, the speci- modulus (RDM), mass, and length mens were removed from the solu- because each property reflects a tions and allowed to dry over the different mechanism of frost damweekend in laboratory air (simuage and they do not necessarily lated field exposure conditions). correlate with each other. For example a concrete may have no Since the purpose of the test program change in length or RDM, but may was not only to determine whether the have severe mass loss (scaling). Pepresence of ettringite in the entrained trography is also helpful when corair voids accelerates frost damage, but related with these properties.

Materials and Mix Designs

The basic mix design and air-void characteristics are shown in Tables 1 and 2. Three target air contents for the fresh concretes were initially used: 2 0.5%, 4 0.5%, and 6 0.5%. The low air contents were intended to represent cases of deteriorated pavements that are often found to have air contents of 1% to 4% with air-void spacing factors exceeding the recommended maximum of 0.20 mm (0.008 in.). After approximately 300 cycles of testing with no apparent signs of deterioration, the 6% air specimens were found to be too durable and tests of these samples were discontinued. The aggregates were siliceous sand and gravel (19 mm max. size). 2

Table 2. Air Void Characteristics for Laboratory Concrete Specimens

Specimen Type I Target air content, % 2 4 6 2 4 2 4 Air content, fresh, %* 2.1 4.0 6.0 2.0 3.8 2.5 4.5 Air content, hard, %** 2.4 3.9 8.2 1.8 3.8 3.2 3.5 Spacing factor, mm (in.)** 0.38 (0.015) 0.23 (0.009) 0.07 (0.003) 0.99 (0.039) 0.36 (0.014) 0.56 (0.022) 0.20 (0.008)

Type I with added gypsum Type II

* ASTM C 231, "Standard Test Method for Air Content of Freshly Mixed Concrete by the Pressure Method" ** ASTM C 457, "Standard Test Method for Microscopical Determination of Parameters of the AirVoid System in Hardened Concrete"

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Microscopy
Proper specimen preparation techniques are essential in order to obtain valid microscopic observations. The specimens were stabilized with epoxy before drying in order to prevent further cracking from taking place during preparation for microscopic examination. Thus any cracks observed were generated by the durability testing, not by the specimen preparation techniques. Some of the solid materials in cement paste and concrete, particularly calcium hydroxide, ettringite, gypsum, and salts, are at least somewhat soluble in water. For this reason only nonaqueous lubricants were used for cutting and polishing of the specimens to a uniform thickness before identifying crystal phases using optical properties. Specimens for air-void system analysis (ASTM C 457) and microscopical examination were cut transversely from the sacrificial specimens using an oil-lubricated saw. One side of each transverse slice was lapped for modified point-count linear traverse analysis. Microscopical examination (ASTM C 856) of each specimen was performed using a polarized-light microscope. Observations were made at four magnifications, 100x, 200x, 400x, and 1000x. Selected thin sections were later examined by scanning electron microscopy using backscattered electron imaging and X-ray microanalysis to supplement the information obtained by optical microscopy.

subparallel to the surface and passing around aggregates. No secondary deposits were observed in the microcracks. Scattered air voids with diameters up to 1 mm were present. The air voids were empty; the walls were smooth, shiny, and free of deposits. Thus the concrete had suffered severe damage without the formation of secondary ettringite deposits.

Concretes with 4% Air

The concretes with 4% air performed much better than the concretes with 2% air, as shown in Figures 2 through 4. In the Type I cement specimens with a nominal 4.0% air content exposed to the salt + gypsum solution, a small amount of ettringite was observed in the air voids located within approximately 1 mm of the exposed surfaces of the test specimens after 500 freeze/thaw cycles. Ettringite occurred as clusters or rosettes of small needles, or as poorly-defined small masses projecting into the air voids. Generally, only one small cluster or rosette was present in an air void and not every void contained ettringite. The majority of air voids remained empty. At the same time the specimens exposed to NaCl solution did not have any detectable ettringite in the voids and no microcracking was present. After 616 to 740 cycles, both sets of specimens from all the 4% air concretes had some ettringite and calcium hydroxide deposits in the voids within 3 mm of the surface (voids below 3 mm were clean). The specimens exposed to salt + gypsum had greater deposition of both ettringite and calcium hydroxide. After 1033 cycles, the amount of material deposited in the voids of both sets (both solutions) of Type I specimens appeared to be about the same. Voids containing deposits occurred within 3 mm of the exposed surface. A few short surface-parallel microcracks were observed at maximum depths of 0.5 mm below the exposed surface. No secondary deposits were observed in the microcracks. At this stage these specimens were subjected to continuous freeze/thaw cycling without the weekend drying period. After a total of 1291 cycles, the Type I cement specimens showed no sig-

nificant length change or loss of modulus. However, they did show some surface scaling and shallow surface-parallel microcracks. Portions of these microcracks contained loose masses of long ettringite needles. Many air voids within 5 mm of the scaled surface contained ettringite or calcium hydroxide, or both. Air voids with diameters less than 25 m typically appeared to be filled with secondary deposits. Individual ettringite needles were approximately 1 to 2 m wide and 5 to 7 m long. All three measures of deterioration show the effect of the deicer solution composition to be insignificant. The 4% air concretes made with Type I cement with added gypsum deteriorated faster than the other specimens with a nominal 4% air content because the spacing factor was significantly higher at 0.36 mm (0.014 in.) versus 0.20 to 0.23 mm (0.008 to 0.009 in.) for the other 4% air concretes. As with the 2% air concretes, the 4% air concretes with better air void systems performed better, as would be expected. As in the other 4% air concretes, secondary deposits in air voids were rare below the deteriorated surface layer, and cracks or microcracks with orientations other than roughly parallel to the surface were not present.

Conclusions
1. With 2% air contents (no entrained air), frost damage occurs without the formation of ettringite deposits. Without air entrainment the deterioration process is too rapid to allow time for ettringite deposition to take place in the voids before the concrete disintegrates. 2. The failure process was much more gradual for the 4% air concretes. Deposition of ettringite appeared to follow, rather than cause, the formation of cracks. Cracks did not emanate from ettringite-filled air voids and ettringite deposits did not span the cracks, but lined them. The orientation of the ettringite needles perpendicular to the walls of the cracks indicates that they grew into open (water-filled) space. All of these observations suggest that the ettringite deposition was neither a primary nor a contributing cause of the cracks. 3

Concretes with 2% Air

All 2% air specimens were destroyed or had significant deterioration within 360 cycles, exhibiting similar performance in salt solutions with or without gypsum. Figures 2, 3, and 4 show the length change, mass change, and relative dynamic modulus for the specimens. Non-air-entrained concretes used in the normal ASTM C 666 Method A test would have failed much sooner; however, these specimens lasted longer because of the weekend drying period. The concrete was severely scaled, exposing the coarse aggregate. Below the scaled surface were a few short microcracks oriented

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Concrete Technology Today

0.70
B

0.70 2% air, NaCl Solution 2% air, NaCl+Gypsum Soln. 4% air, NaCl Soln. 4% air, NaCl+Gypsum Soln.
E 2 C B C 1291 C C C C C C B C CB E B E 2 E 2 2 2 E 2 E 2 2 E 2 B C 2 2 E B2 C E E 2 E E E 2 2 2 E 2 E 2 2 E 2 2 E 2 E 2 E 2 E BC C B EC 2 B E2 2 E E2 E E 2 E 2 E 2 2 E 2 2 2 E 2 E E 2 E 2 E E 2 E E 2 E E E E B B B B B B B

0.70 2% air, NaCl Soln.

Length change, %
B

360
Length change, %

2% air, NaCl Soln. 2% air, NaCl+Gypsum Soln. 4% air, NaCl Soln. 4% air, NaCl+Gypsum Soln. 315 616

Length change, %

0.50 0.30

C E 2

0.50
E

4% air, NaCl Soln. 172 616

B BB BEEE BE B E E EE EE E

0.50 0.30

C E 2

0.30 0.10
B E B

0.10
C E 2

0.10
C 2 B B C

E E E E E

C B BC BC 2 C B C B C E 2 B C 2 C B B B C 2 E E 2 E 2 E E 2 2 E C B2 E B 2 E 2 E 2 E2 2 EC EC E2 2 E

-0.10

-0.10

-0.10

10
E 2 0C 2 E B C E E 2 2 2 E2 E2 E E 22 E 2 E E 2 E 2 E 2 E 2 E 2 E 2 E 2 E 2 E 2 E E E E B E 2 2 2 2 E 2 2 E 2 E E 2 C E 2 E 2 2 E 2 E 2 2 E 2 2 2 BB E E E 2 2 E 2 E E C C BB CCB C BB CB 1291 C B C C B C B B B C C C

10
B 0E B E E E B B E E E E B E EE BB E

10
B C 02 B C B2 B C B C B BC C B E C 2 2C B C 2 BC C E E BC 2 BC E2 B EE22 2 2 2 EE C 2 B 2 E 2 2 E E 2 E E E E E

Mass change, %

Mass change, %

-10 -20 -30 -40

-10 -20 -30 -40

616

Mass change, %

-10 -20 -30 -40

B B

E E E E E

315 616

360

172

Relative dynamic modulus, %

Relative dynamic modulus, %

120
E 2 100 C E 2 C B 2 2 E 2 2 2 E 2 2 E 2 E 2 E 2 E 2 E 2 2 E E 2 E E E E 2 E E 2 2 E E 2 2 E E E 2 2 2 2 2 2 2 E E E 2 2 E 2 E E E E E 2E 2E 2 E E E E E 2E 2E 2 2 2 2 2 E E E 2 2 2 E B C C BB C BB CC B C BB CB C

120
B 100 E B E B BB E E E E EE E EEB

Relative dynamic modulus, %

120
C E B 100 2 C B

315
CCCC C C C B C B BBBB CC B BB C B 2 2 2 2 2222 2 2 EB 2 E E E E EEEE E E 2 2 2 2 E 2 E E E E

80 60 40 1 10 100 Number of cycles

360 1291

80 60
B

616 172

80 60

40 1 10 100 Number of cycles 1000 2000

616 40 1 10 100 Number of cycles 1000 2000

1000 2000

Figure 2. Length change, mass change, and relative dynamic modulus for the Type I cement concretes with 2% and 4% air and exposed to 3% NaCl solution or salt-gypsum solution.

Figure 3. Length change, mass change, and relative dynamic modulus for the Type I+gypsum cement concretes with 2% and 4% air and exposed to 3% NaCl solution.

Figure 4. Length change, mass change, and relative dynamic modulus for the Type II cement concretes with 2% and 4% air and exposed to 3% NaCl solution or salt-gypsum solution.

3. The presence of gypsum in the salt solution had no significant effect on the durability of the concretes. Those with poor air void systems (nominal 2% air) performed poorly. Those with marginal air void systems (nominal 4% air) performed remarkably well. The best protection against frost damage is a proper air void system. 4. From the above observations, it is clear that the ettringite in these specimens did not cause the cracking, nor did it contribute to the propagation of existing cracks. Rather, it appears to have been opportunistic. That is, cracks due to frost damage cre-

ated space for the crystals to grow. Water entered the cracks and dissolved ettringite from the hydrated cement paste. On drying of the concrete, the ettringite precipitated in the open space left by the cracks. Damage progressed through repeated cycles of freezing and thawing, with progressive formation of ettringite deposits during the drying periods. 5. The air void system played a far more important role in frost resistance than the chemistry of cement and deicer solutions or the presence of ettringite and other secondary deposits.

Acknowledgment
The research reported in this paper (PCA R&D Serial No. 2128c) was conducted at Construction Technology Laboratories, Inc. with the sponsorship of the Portland Cement Association (PCA Project Index No. 9305). The contents of this paper reflect the views of the authors, who are responsible for the facts and accuracy of the data presented. The contents do not necessarily reflect the views of the Portland Cement Association.

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December 1997

Origins of Chloride Limits for Reinforced Concrete

by David Whiting*
The subject of chloride limits in concrete is currently being debated within the concrete industry. The purpose of chloride limits is control of steel corrosion in reinforced and prestressed concrete (see Fig. 1). The origins of these limits provide an appreciation of the need for limits, and the potential need for changes. Currently, the American Concrete Institute (ACI) committees most involved with chloride limits are: ACI 318, Standard Building Code; ACI 222, Corrosion of Metals in Concrete; and ACI 201, Durability of Concrete. A distinction should be made between the limit, which refers to the amount of chloride permitted in new concrete by code authorities (a criterion set by man) and the so-called threshold limit for corrosion, which is the actual amount of chloride needed to initiate corrosion under a given set of conditions (determined by nature). The two are not necessarily equal. The limit must be set; the threshold must be investigated. Rational limits should reflect thresholds. Significant research into the threshold for chloride-induced corrosion has been carried out over the past few decades. Throughout this document, the commonly accepted reference for chloride limits, percent of chloride ion by mass of cement, will be used unless noted otherwise.

The 1977 ACI 201 Limits

In 1977, ACI Committee 201 published limits on chloride content in concrete (see Table 1). The first limit shown in the table, 0.06%, is for prestressed concrete, and was justified because of concern that only a small amount of corrosion on highly stressed strands might potentially lead to fracture of tendons. Some studies showed that as little as 0.15% water-soluble chloride by weight of cement could trigger corrosion in reinforced concrete that is moist and where oxygen is abundant.** The limit of 0.10% for concrete that may eventually be exposed to external chloride appears to be an arbitrary reduction factor to the 0.15% limit, recognizing that if chlorides will eventually penetrate into the concrete, it is better to have less chloride in the concrete initially. Note that the chloride equivalent of 2% calcium chloride is approximately 1% chloride ion by mass of cement, significantly above the 0.15% limit originally published by ACI 201.

Figure 1. Steel corrosion induced by chlorides. (S67482)

given in Table 1. The only significant change from the ACI 201 Task Groups recommendations was for concrete that will remain dry in service, where the no limit of ACI 201-77 and the 1982 Task Group has been replaced by a limit of 1.00%. This allows the use of up to 2.0% flake calcium chloride as an accelerator assuming chloride is not present in other concrete ingredients. Two years later (1985), the British code stated calcium chloride and chloride-based admixtures should never be added to reinforced concrete, prestressed concrete, and concrete containing embedded metal, thus formally banning the use of calcium chloride accelerators in the United Kingdom. At this point, the rationale for the limit on concrete exposed to chloride was again questioned, the argument being that one has no control over how much chloride will eventually
* Senior Principal Engineer, Materials Research and Consulting, Construction Technology Laboratories, Inc., Skokie, Illinois. ** Where did 0.15% water-soluble chloride come from? Apparently, it is from FHWA studies by Clear (1973) showing that a threshold limit of 0.20% total chloride could induce corrosion of reinforcing steel in bridge decks. Watersoluble chlorides are only a portion of the total: work at the FHWA demonstrated that the conversion factor could range from 0.35 to 0.90 depending upon the particular constituents and history of the concrete. Arbitrarily, 0.75 was chosen: 0.75 x 0.20% total chlorides = 0.15% water-soluble chlorides.

Deliberations Prior to ACI 318-83

Until 1982, little documentation was available regarding the adoption of the ACI 201-77 limits into the Building Code. A modified set of limits was developed by a task group of ACI 201 and forwarded to ACI 318 (see Table 1). The most significant change is the relaxation of the limit for concrete not exposed to external sources of chlorideincreased to 0.30%because the original intent of ACI 201 appeared to be to limit the chloride to no more than the threshold amount for concrete that may be exposed to moisture in service. In December 1982, ACI 318 published limits and encouraged formal discussion.

A Historical Perspective
Early studies (from 1923) indicated little progressive corrosion when calcium chloride was added to reinforced concrete. By the late 1950s and 1960s, reports of corrosion of prestressing steel in concrete containing chloride salts were published. In 1972, the British banned the use of calcium chloride in all prestressed concrete and in certain reinforced concrete. In 1974, the ACI Building Code Commentary suggested a limit of 400 to 500 ppm for prestressed concrete, but did not include this limit in the code body. At the same time, ACI Committee 201 began a series of discussions on chloride limits.

ACI 318-83 Limits

The ACI 318 limits, adopted in 1983 and currently still in force, are also

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Concrete Technology Today New ACI 222 limits (Table 2) ACI 201.2R-77 ACI 201 Task Group ACI 318-83 and were approved recommendations (1982) ACI 318-95 and published. Guide to Durable Concrete Durability of Concrete Building Code Requirements for The old ACI 222 Structural Concrete R-89 limits for preMaximum water-soluble chloride ion content in concrete, percent by weight of cement stressed and reinforced concrete Type of member Limit Type of member Limit Type of member Limit were 0.08% and 0.20% acid-soluble Prestressed concrete 0.06 Prestressed concrete 0.06 Prestressed concrete 0.06 chloride, respecConventionally rein0.10 Reinforced concrete 0.15 Reinforced concrete 0.15 tively (irrespective forced concrete in that will be exposed exposed to chloride of concrete expoa moist environment to chlorides in in service sure conditions). and exposed to service The new limits alchloride low one to Conventionally 0.15 Reinforced concrete 0.30 Other reinforced concrete 0.30 progress from reinforced concrete that will not be construction more severe to less in a moist environexposed to chloride severe test condiment but not but may be wet in tions when atexposed to chloride* service tempting to have Above ground building No Reinforced concrete No Reinforced concrete 1.00 concrete apconstruction where limit that will be completely limit that will be dry or proved. The acidthe concrete will stay for dry, or suitably for protected from soluble test can be dry corroprotected, in service corromoisture in service run first; this is the sion** sion simplest test for chloride in con* Includes locations where the concrete will be occasionally wetted such as kitchens, parking garages, waterfront crete. Using the structures, and areas with potential moisture condensation. ** If calcium chloride is used as an admixture, a limit of 2% is generally recommended for reasons other than widely accepted corrosion. Using 2% of the usual form (the dihydrate, CaCl2 . 2H2O) results in approximately 1% chloride ion. 0.75 conversion Includes bridge decks, parking garages, marine construction, and certain industrial plants. factor, the limit on Tested on hardened concrete at an age of 28 days: includes chlorides from water, aggregates, cementitious prestressed conmaterials, and admixtures. crete (0.08% total Note: ASTM did not develop a water-soluble chloride content test method until 1992. or acid-soluble chloride) is effectively the same as ACI 318-95 (0.06% penetrate into concrete, so its initial normal water-soluble procedures. water-soluble). The limit for reinchloride content should not matter. This equates to 0.18% chloride ions forced concrete in wet conditions is The ACI Committee 318 0.15 % limit by mass of cement in a typical con0.10% acid-soluble, vs 0.30% wateron concrete exposed to chloride was crete mix (about 356 kg of cement soluble for 318-95, a considerable difa consensus value, and was to be per cubic meter [600 lb per cubic used for the most severe conditions yard]), well above the accepted limit ference. The 0.10% limit apparently to prolong the life of the structure. for prestressed concrete and for rein- derives from a paper published in forced concrete exposed to chlorides. 1987. There is no separate category Recent Developments and the However, no chloride problems can for concrete exposed to chloride in service, as there is in ACI 318, bebe attributed to these aggregates ACI 222 Limits cause the new ACI 222 limit of 0.10% during their many years of use. is stringent enough for both expoSimilar situations have been reIn the early 1990s, an entirely differsures (chloride and non-chloride). ent concern about chloride limits ported for aggregates in Eastern Table 2 shows the ACI 222R-96 Canada. was raised, which led to reexaminalimit on reinforced concrete in dry ACI 222 was presented with a test tion of the limits. procedure utilizing a Soxhlet extrac- conditions to be less than the ACI The new concern is the naturally occurring presence of chloride in tion method (ACI 222.1-96) to leach 318-95 limit for concrete in wet conwater-soluble chloride out of concertain limestone-based aggregates. ditions. Corrosion does not occur in Evidence suggests that this chloride crete specimens. It did not, appardry concrete, but the committees poently, extract the chloride present in is part of the crystal structure of sition is that one cannot ensure that the limestone aggregates, so it was these aggregates and cannot become concrete will stay dry throughout the proposed as a test method for acsoluble under normal conditions of service life of the structure. Concrete service. As an example, a high-qualcepting these materials. At the same members that have been dry for time, dissatisfaction with the ACI ity limestone aggregate used in many years may begin to corrode if many structures in the Chicago area, 318 limits led to a proposal for a new sufficient chlorides are present and has been found to contain up to set of limits from ACI 222, with sub- they are suddenly exposed to mois0.06% chloride ions when tested by sequent submittal to ACI 318. ture (like wet laundry areas). Table 1. ACI Chloride Limits 6

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December 1997 The remaining columns in Table 2 allow a producer to resort to other test procedures if concrete does not meet the acid-soluble test limits. The water-soluble or Soxhlet procedures could also be used when borderline amounts of chloride are present. Table 2. New Chloride Limits in ACI 222R-96
Category Test method Prestressed concrete Reinforced concrete in wet conditions Reinforced concrete in dry conditions Chloride limit for new construction Acid-soluble ASTM C 1152 0.08 0.10 0.20 Water-soluble ASTM C 1218 0.06 0.08 0.15 Soxhlet * 0.06 0.08 0.15

Canadian Limits
Canadian limits (see Table 3) are very similar to the ACI 318-95 limits. For prestressed concrete, both codes limit chloride ion to 0.06%; for dry reinforced concrete, 1.00% chloride ion is allowed. The Canadian Standards Association (CSA) limit of 0.15% applies to concrete exposed to a moist environment or chlorides or both, whereas ACI is more lenient (0.30 %) for concrete in a moist environment that is not exposed to chlorides. In addition, CSA A23.2-4B, Sampling and Determination of WaterSoluble Chloride Ion Content in Hardened Grout or Concrete, acknowledges that the test method includes chloride ions in the aggregate that may unduly influence the test results. The method suggests determining the chloride content of the aggregate separately and adjusting the watersoluble chloride ion content of the concrete accordingly.

* ACI 222.1-96 Note: Normally concrete materials will be tested for chloride content using either the acidsoluble test described in ASTM C 1152 or water-soluble test described in ASTM C 1218. If the materials meet either of these limits given in the above table, they are acceptable. If neither limit is met, then materials may be tested using the Soxhlet test method, which appears to measure only those chlorides that contribute to corrosion. This permits the use of some aggregates that would not be allowed by ASTM C 1152 or ASTM C 1218. If the materials fail the Soxhlet test, then they are not suitable.

Table 3. Chloride Limits in Canada

Application Maximum watersoluble chloride ion, percent by mass of cement* 0.06 0.15 1.00

Prestressed concrete Reinforced concrete exposed to a moist environment or chlorides or both Reinforced concrete exposed to neither moist environment nor chlorides

Summary
In the United States the chloride limits in ACI 318 are referenced as they are the limits used in building codes. ACI 222 has developed options for cases where significant quantities of chloride in aggregates are encountered. Canadian standards directly address the issue of chlorides in aggregates. Changes to U.S. standards are currently being evaluated.

* These limits may be exceeded if the Owner is satisfied that no corrosion problems have occurred in other concrete structures made with similar materials and exposed to similar conditions. Note: Quarried carbonate coarse aggregates from the Niagara Escarpment of Southern Ontario contain sufficient chloride ions to cause concrete to exceed the above values, but experience shows this chloride to remain within the aggregate (unavailable to participate in corrosion). Concrete made with these aggregates may be safely used, provided chloride ion contributed by other concrete components does not cause the concrete to exceed the above limits. Reference: 1994 edition of CSA A23.1 Concrete Materials and Methods of Concrete Construction, Section 15.1.6.1.

References
1. American Concrete Institute, Corrosion of Metals in Concrete, ACI 222R-96, Farmington Hills, Michigan, March 1997. 2. American Concrete Institute, Provisional Standard Test Method for Water-Soluble Chloride Available for Corrosion of Embedded Steel in Mortar and Concrete Using the Soxhlet Extractor, ACI 222.1-96, Farmington Hills, Michigan, 1997. 3. Clear, K. C., and Hay, R. E., Time-to-Corrosion of Reinforcing Steel in Concrete Slabs, V. 1: Effect of Mix Design and Construction Parameters, Report No. FHWARD-73-32, Federal Highway

Administration, Washington, DC, April 1973, 103 pages. 4. Hope, B. B., and Ip, A. K. C., Chloride Corrosion Threshold in Concrete, ACI Materials Journal, Vol. 84, No. 4, July-August 1987, pages 306-314. 5. National Bureau of Standards, Effect of Calcium Chloride on Corrosion of Steel in Concrete, Engineering and Contracting, Vol. 60, July 1923, page 202. 6. Reading T. J., Chloride Content Limits Recommended by ACI Committee 201, Concrete Construction, Vol. 27, No. 10, October 1982, page 777.

Acknowledgment
The above article (PCA R&D Serial No. 2153a) is an excerpt taken from a research report (Serial No. 2153) conducted for PCA by Construction Technology Laboratories, Inc. The full report, of the same title, covers the development of foreign chloride limits in more detail. The contents of this paper reflect the views of the author, who is responsible for the facts and accuracy of the data presented. The contents do not necessarily reflect the views of the Portland Cement Association.

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The following publications are now available. In Canada please direct requests to the nearest regional office of the Canadian Portland Cement Association (Halifax, Montreal, Toronto, and Vancouver).

Concrete Slab Surface Defects: Causes, Prevention, Repair, IS177

Defects that can occur on concrete flatwork include: blisters, cracking, crazing, curling, efflorescence, delaminations, discoloration, dusting, low spots, popouts, scaling, and spalls. Common causes and suggestions for avoiding each type of defect are given.

1996/1997 PCA Research Reports Summary, MS375

This 6-page document provides a list of PCA research reports from 1996 and 1997. The 59 reports are categorized by research projects with respect to their market or technical area. Categories include: Engineered Structures, Residential, Public Works, Product Standards and Technology, Energy and Environment, and Manufacturing Technology.

Effects of Substances on Concrete and Guide to Protective Treatments, IS001

Substances that attack concrete include: salts and alkalies, oils and fats, coal tar distillates, and solvents and alcohols. Durable concrete mixtures and proper design are emphasized cover over reinforcement, drainage, surface preparation and cleaning, and coatings. Sources of products are also included.

Working Safely with Concrete, MS271

Safety on the job continues to be an important topic, especially for construction workers who are at risk from numerous hazards. Protection for head and eyes, back, and skin are handled with common sense suggestions and a knowledge of basic precautions regarding cement and concrete.

Insulating Concrete Forms for Residential Design and Construction, SP208

This book is the most comprehensive resource for designing and building concrete homes with Insulating Concrete Forms (ICFs). Written to meet the needs of architects, engineers, and building officials, it focuses on the technical aspects of ICF home design including design principles, details, formulas, and performance.

This publication is intended SOLELY for use by PROFESSIONAL PERSONNEL who are competent to evaluate the significance and limitations of the information provided herein, and who will accept total responsibility for the application of this information. The Portland Cement Association DISCLAIMS any and all RESPONSIBILITY and LIABILITY for the accuracy of and the application of the information contained in this publication to the full extent permitted by law.
Our purpose is to show various ways of using concrete technology to your Intended for decision makers associadvantage and avoiding problems. If ated with design, management, and there are problems or ideas readers construction of building projects, would like discussed in future issues, Concrete Technology Today is published please let us know. Items from this triannually by the Construction Infor- newsletter may be reprinted in other mation Services Department of the publications subject to prior permisPortland Cement Association. sion from the Association.

PUBLISHER'S NOTE:

Direct all correspondence to Steve Kosmatka, Editor Jamie Farny, Assistant Editor Concrete Technology Today Portland Cement Association 5420 Old Orchard Road Skokie, Illinois 60077-1083 Phone: 847/966-6200 Fax: 847/966-8389 E-mail: steve_kosmatka@portcement.org E-mail: jamie_farny@portcement.org

Printed in U.S.A. 8

PL973.01B

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