Research, Development, and Technology

Turner-Fairbank Highway Research Center

6300 Georgetown Pike

McLean, VA 22101-2296

The Use of Lithium to Prevent or

Mitigate Alkali-Silica Reaction in

Concrete Pavements and Structures

Publication No. FHWA-HRT-06-133 March 2007
Foreword 

Progress is being made in efforts to combat alkali-silica reaction in portland cement concrete 

structures—both new and existing. This facts book provides a brief overview of laboratory and 

field research performed that focuses on the use of lithium compounds as either an admixture in 

new concrete or as a treatment of existing structures. 

This document is intended to provide practitioners with the necessary information and guidance 

to test, specify, and use lithium compounds in new concrete construction, as well as in repair and 

service life extension applications. This report will be of interest to engineers, contractors, and 

others involved in the design and specification of new concrete, as well as those involved in 

mitigation of the damaging effects of alkali-silica reaction in existing concrete structures. 

Gary L. Henderson, P.E. 

Director, Office of Infrastructure 

 Research and Development 

Notice 

This document is disseminated under the sponsorship of the U.S. Department of Transportation 

in the interest of information exchange. The U.S. Government assumes no liability for its 

contents or use thereof. This report does not constitute a standard, specification, or regulation. 

The U.S. Government does not endorse products or manufacturers. Trade or manufacturers’ 

names appear herein only because they are considered essential to the objective of this manual. 

Quality Assurance Statement 

The Federal Highway Administration (FHWA) provides high-quality information to serve 

Government, industry, and the public in a manner that promotes public understanding. Standards 

and policies are used to ensure and maximize the quality, objectivity, utility, and integrity of its 

information. FHWA periodically reviews quality issues and adjusts its programs and processes to 

ensure continuous quality improvement. 
Technical Report Documentation Page 

1. Report No. 

FHWA-HRT-06-133 

2. Government Accession 

No. 

3. Recipient’s Catalog No. 

5. Report Date 

March 2007 

4. Title and Subtitle 

The Use of Lithium To Prevent or Mitigate Alkali-Silica Reaction 

in Concrete Pavements and Structures 

6. Performing Organization Code 

7. Author(s) 

Michael D.A. Thomas, Benoit Fournier, Kevin J. Folliard, Jason 

H. Ideker, and Yadhira Resendez 

8. Performing Organization Report No. 

9. Performing Organization Name and Address 10. Work Unit No. 

The Transtec Group, Inc. 

6111 Balcones Drive 

Austin, TX 78731 11. Contract or Grant No. 

DTFH61-02-C-00097 

13. Type of Report and Period Covered 

Final Report 

12. Sponsoring Agency Name and Address 

Office of Infrastructure R&D 

Turner-Fairbank Highway Research Center, HRDI-11 

6300 Georgetown Pike, Room F-209 

McLean, VA 22101

14. Sponsoring Agency Code 

15. Supplementary Notes 

Contracting Officer’s Technical Representative: Fred Faridazar, HRDI-12 

16. Abstract 

Alkali-silica reaction (ASR) was first identified as a form of concrete deterioration in the late 1930s 

(Stanton 1940). Approximately 10 years later, it was discovered that lithium compounds can be used to 

control expansion due to ASR. There has recently been increased interest in using lithium technologies to 

both control ASR in new concrete and to retard the reaction in existing ASR-affected structures. 

This facts book provides information on lithium, its origin and properties, and on its applications. The 

mechanism of alkali-silica reaction is discussed together with methods of testing to identify potentially 

alkali-silica reactive aggregates. Traditional methods for minimizing the risk of damaging ASR are 

presented; these include the avoidance of reactive aggregates, controlling the levels of alkali in concrete 

and using supplementary cementing materials such as fly ash, slag and silica fume. The final two sections 

of the facts book discuss the use of lithium, first as an admixture for new concrete construction and second 

as a treatment for existing concrete structures affected by ASR.

17. Key Words 

alkali-silica reaction, lithium, concrete durability, mitigation, 

fresh concrete, hardened concrete, case studies, laboratory 

testing, field investigation, existing structures 

18. Distribution Statement 

No Restrictions. This document is 

available to the public through the 

National Technical Information 

Service; Springfield, VA 22161 

19. Security Classif. (of this report) 

Unclassified 

20. Security Classif. (of this 

page) 

Unclassified 

21. No. of Pages 

47 

22. Price 

Form DOT F 1700.7 (8-72 Reproduction of completed page authorized. 
ii 

SI* (MODERN METRIC) CONVERSION FACTORS 

APPROXIMATE CONVERSIONS TO SI UNITS

Symbol When You Know Multiply By To Find Symbol 

LENGTH 

in inches 25.4 millimeters mm 

ft feet 0.305 meters m 

yd yards 0.914 meters m 

mi miles 1.61 kilometers km 

AREA 

in2 square inches 645.2 square millimeters mm2

ft2 square feet 0.093 square meters m2

yd2 square yard 0.836 square meters m2

ac acres 0.405 hectares ha 

mi2 square miles 2.59 square kilometers km2

VOLUME 

fl oz fluid ounces 29.57 milliliters mL 

gal gallons 3.785 liters L 

ft3 cubic feet 0.028 cubic meters m3 

yd3 cubic yards 0.765 cubic meters m3 

NOTE: volumes greater than 1000 L shall be shown in m3

MASS 

oz ounces 28.35 grams g

lb pounds 0.454 kilograms kg

T short tons (2000 lb) 0.907 megagrams (or "metric ton") Mg (or "t") 

TEMPERATURE (exact degrees) o

F Fahrenheit 5 (F-32)/9 Celsius oC 

or (F-32)/1.8 

ILLUMINATION 

fc foot-candles 10.76 lux lx 

fl foot-Lamberts 3.426 candela/m2 cd/m2

FORCE and PRESSURE or STRESS 

lbf poundforce 4.45 newtons N 

lbf/in2 poundforce per square inch 6.89 kilopascals kPa 

APPROXIMATE CONVERSIONS FROM SI UNITS 

Symbol When You Know Multiply By To Find Symbol 

LENGTH

mm millimeters 0.039 inches in 

m meters 3.28 feet ft 

m meters 1.09 yards yd 

km kilometers 0.621 miles mi 

AREA mm2

 square millimeters 0.0016 square inches in2 

m2 square meters 10.764 square feet ft2 

m2 square meters 1.195 square yards yd2 

ha hectares 2.47 acres ac 

km2 square kilometers 0.386 square miles mi2 

VOLUME 

mL milliliters 0.034 fluid ounces fl oz 

L liters 0.264 gallons gal 

m3 cubic meters 35.314 cubic feet ft3 

m3 cubic meters 1.307 cubic yards yd3 

MASS 

g grams 0.035 ounces oz

kg kilograms 2.202 pounds lb

Mg (or "t") megagrams (or "metric ton") 1.103 short tons (2000 lb) T 

TEMPERATURE (exact degrees) o

C Celsius 1.8C+32 Fahrenheit oF 

ILLUMINATION 

lx lux 0.0929 foot-candles fc 

cd/m2 candela/m2 0.2919 foot-Lamberts fl

FORCE and PRESSURE or STRESS 

N newtons 0.225 poundforce lbf 

kPa kilopascals 0.145 poundforce per square inch lbf/in2

*SI is the symbol for th International System of Units. Appropr e iate rounding should be made to comply with Section 4 of ASTM E380. 

(Revised March 2003)
iii 

TABLE OF CONTENTS 

CHAPTER 1. INTRODUCTION..................................................................................... 1

CHAPTER 2. LITHIUM—PROPERTIES AND PRODUCTION...............................3

CHAPTER 3. ALKALI-AGGREGATE REACTION...................................................7

3.1 Terminology----------------------------------------------------------------------------------------------------7

3.2 Mechanisms of ASR ------------------------------------------------------------------------------------------7

3.3 Symptoms of ASR------------------------------------------------------------------------------------------- 10

3.4 Methods of Evaluating Potential Reactivity of Aggregates----------------------------------------- 11

3.4.1 Field Performance................................................................................................................. 11

3.4.2 ASR Testing in the Laboratory ............................................................................................. 11

3.5 Measures To Prevent ASR -------------------------------------------------------------------------------- 14

3.6 Treating Existing ASR-Affected Pavements and Structures--------------------------------------- 18

CHAPTER 4. USING LITHIUM TO PREVENT ASR IN NEW CONCRETE.......21

4.1 Laboratory Studies ----------------------------------------------------------------------------------------- 21

4.2 Field Applications ------------------------------------------------------------------------------------------- 23

4.3 Laboratory Testing To Determine the Amount of Lithium Required --------------------------- 25

4.4 Effect of Lithium on the Properties of Concrete------------------------------------------------------ 26

CHAPTER 5. USE OF LITHIUM TO TREAT EXISTING ASR-AFFECTED 

STRUCTURES ................................................................................................................27

5.1 Laboratory Studies ----------------------------------------------------------------------------------------- 27

5.2 Field Applications ------------------------------------------------------------------------------------------- 27

5.2.1 Topical Treatment with Lithium........................................................................................... 27

5.2.2 Electrochemical Lithium Impregnation ................................................................................ 29

5.2.3 Vacuum Impregnation With Lithium.................................................................................... 31

5.3 Recommendations for Treating ASR-Affected Structures with Lithium------------------------ 32

CHAPTER 6. SUMMARY .............................................................................................35

ACKNOWLEDGEMENTS ............................................................................................ 37

REFERENCES ................................................................................................................39
iv 

LIST OF FIGURES 

Figure 1. Periodic table showing the position of lithium. .......................................................................... 3

Figure 2. Photograph of lithium metal. ...................................................................................................... 3

Figure 3. Photograph of the lithium- bearing mineral spodumene............................................................. 3

Figure 4. Aerial view of lithium-bearing brines in Argentina (Salar del Hombre Muerto). ...................... 4

Figure 5. Aerial view of lithium-bearing brines in Chile (Salar de Atacama). .......................................... 4

Figure 6. Sequence of alkali-silica reaction (ASR) in concrete. ................................................................ 8

Figure 7. Schematic showing difference in crystal structure of quartz (left) and opal (right).................... 9

Figure 8. Three essential requirements for deleterious ASR...................................................................... 9

Figure 9. Typical symptoms of ASR........................................................................................................ 10

Figure 10. Concrete prism test—prisms stored over water in sealed containers. ....................................... 13

Figure 11. Concrete prism test—length change measurements (ASTM C1293)........................................ 13

Figure 12. Accelerated mortar bar test (ASTM C1260): (a) view from the top of four rectangular 

concrete samples, under water in a blue rectangular container; (b) measuring a 

concrete sample for length change using a digital comparator. ................................................ 14

Figure 13. Effect of the alkali content of concrete on the expansion of prisms.......................................... 15

Figure 14. Effect of SCM on the expansion of concrete (using concrete prism test). ................................ 17

Figure 15. Barrier wall in Quebec—the section of the wall to the right of the picture has been 

treated with a silane sealer. ....................................................................................................... 19

Figure 16. Relative expansion of concrete prisms (ASTM C1293) containing lithium compounds 

and reactive siltstone aggregate (Thomas et al., 2000). ............................................................ 23

Figure 17. Photographs of 12-year-old pavement sections reactive aggregate from Shakespeare 

pit in Albuquerque, NM (photos taken in 2004)....................................................................... 24

Figure 18. Photographs of 12-year-old pavement sections reactive aggregate from Placitas pit in 

Albuquerque, NM. .................................................................................................................... 25

Figure 19. Expansion of concrete prisms after treatment with lithium at 10 weeks 

(expansion = 0.061 percent) and 16 weeks (expansion = 0.107 percent) (Thomas 

and Stokes, 2004)...................................................................................................................... 27

Figure 20. Spraying 30 percent LiNO3 solution with a tanker truck on a concrete pavement near 

Mountain Home, ID. ................................................................................................................. 28

Figure 21. Spraying 30-percent LiNO3 solution with handheld spray applicator on barrier wall near 

Leominster, MA........................................................................................................................ 28

Figure 22. Lithium concentration profiles for concrete pavement after six treatments (at 

approximately 6-month intervals) of 0.24 L/m2

 (6 gal/1000 ft2) (Stokes et al., 2002). ............ 29

Figure 23. Electrochemical lithium impregnation. ..................................................................................... 30

Figure 24. Electrochemical lithium treatment process. (a) irrigation tubes, wood splices, and 

metal strips are placed on the column. The metal strips are attached to titanium mesh 

that runs inside holes drilled into the sides of the column. (b) A cellulose layer is 

applied to the side of the column, and (c) plastic sheeting is placed on all sides of the 

column. The gutters under the sheeting collect excess lithium for reuse.................................. 31

Figure 25. Typical vacuum impregnation setup.......................................................................................... 32

Figure 26. Precipitation of LiNO3 from solution (a) on barrier wall and (b) on pavement........................ 33

Figure 27. Monitoring techniques—(a) crack mapping of a barrier wall and (b) measuring length 

changes on concrete pavement with a DEMEC gauge. ............................................................ 34
v 

LIST OF TABLES 

Table 1. Principal lithium minerals and their sources (after Lumley, 1997)............................................... 4 

Table 2. List of lithium compounds and applications for lithium............................................................... 5 

Table 3. Terminology for alkali-aggregate reactions (CSA A23.1-04). ..................................................... 7 

Table 4. Typical chemical analysis for portland cement............................................................................. 7 

Table 5. Table of alkali-silica reactive minerals and possible rock types in which they may be found. .... 9 

Table 6. ASTM test methods related to alkali-aggregate reaction............................................................ 12 

Table 7. Calculation for alkali content of portland cement concrete. ....................................................... 15 

Table 8. Range of alkali limits (CSA A23.1-27A).................................................................................... 16 

Table 9. Example showing calculation of [Li]/[Na + K] molar ratio........................................................ 22 

Table 10. Proportioning mixtures with lithium for the concrete prism test. ............................................... 26 

Table 11. Penetration of lithium after electrochemical treatment of bridge deck....................................... 30 

Table 12. General guidelines for topical lithium treatment. ....................................................................... 33 

Table 13. Suggestions for monitoring lithium-treated structures................................................................ 33 
vi 

LIST OF ACRONYMS AND ABBREVIATIONS 

Terms 

AAR alkali-aggregate reaction 

ACR alkali-carbonate reaction 

ASR alkali-silica reaction 

ASTM American Society for Testing and Materials 

CSA Canadian Standards Association 

DEMEC demountable mechanical 

FHWA Federal Highway Administration 

ppm parts per million 

SASW spectral analysis of surface waves 

SCM supplementary cementitious material 

w/cm water-cementitious material ratio 

Chemical Notations 

C-S-H Calcium silicate hydrate 

Ca Calcium 

CaCO3 Calcium carbonate 

Ca(NO3)2 Calcium nitrate 

Ca(OH)2 Calcium hydroxide 

OH-

 Hydroxyl ion 

K Potassium 

K2O Potassium oxide 

KCl Potassium chloride 

[Li]/[Na+K] Molar ratio of lithium ions to the sum of sodium and potassium ions 

LiCl Lithium chloride 

LiF Lithium fluoride 

LiNO3 Lithium nitrate 

LiOH Lithium hydroxide 

LiOH•H2O Lithium hydroxide monohydrate 

Li2CO3 Lithium carbonate 

Li2SiO3 Lithium silicate 

Li2SO4 Lithium sulfate 

M molar 

N normal 

Na Sodium 

Na2O Sodium oxide 

Na2Oe Total sodium oxide equivalent 

NaCl Sodium chloride 

NaOH Sodium hydroxide 

Si Silicon 

SiO2 Silicon dioxide
1 

CHAPTER 1. INTRODUCTION 

Alkali-silica reaction (ASR) was first identified as a form of concrete deterioration in the late 1930s 

(Stanton 1940). About 10 years later, it was discovered that lithium compounds could be used to control 

expansion due to ASR. Recently there has been increased interest in using lithium technologies both to 

control ASR in new concrete and to retard the reaction in existing ASR-affected structures. 

This book provides information on lithium, its origin and properties, and its applications. The mechanism 

of alkali-silica reaction is discussed together with methods of testing to identify potential alkali-silica 

reactive aggregates. Traditional methods for minimizing the risk of damaging ASR are presented; these 

include the avoidance of reactive aggregates, controlling the levels of alkali in concrete, and using 

supplementary cementing materials such as fly ash, slag, and silica fume. 

The final two sections of the book discuss the use of lithium, first as an admixture for new concrete 

construction, and second as a treatment for existing concrete structures affected by ASR. 

The information in this document was obtained primarily from the FHWA publication Interim 

Recommendations for the Use of Lithium to Mitigate or Prevent Alkali-Silica Reaction (ASR) (Publication 

No. FHWA-HRT-06-073). For further information, the reader should refer to the above publication. 

3 

CHAPTER 2. LITHIUM—PROPERTIES AND PRODUCTION 

Lithium is the third element in the periodic table (see figure 1) and is denoted by the chemical symbol 

“Li.” Its atomic number is 3 and its atomic mass is 6.941 grams (g), making it the third lightest element 

on earth after hydrogen (H) and helium (He). 

Figure 1. Periodic table showing the position of lithium. 

As a pure element, lithium is a soft, silver-white metal and belongs in the Alkali Metal Group together 

with sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr). 

Lithium has only one electron in its outer shell (i.e., valence = +1) which makes the pure metal very 

unstable and reactive to moisture. Stable lithium compounds can be manufactured for commercial use; 

examples are lithium carbonate (Li2CO3), lithium chloride (LiCl), lithium sulfate (Li2SO4), and lithium 

nitrate (LiNO3). 

Lithium metal does not occur naturally in the environment, and lithium is most commonly found in 

lithium-bearing minerals such as spodumene (LiAlSi2O6) in pegmatite rocks or as dissolved salt such as 

lithium chloride (LiCl) in brines (see figures 2 and 3). Table 1 provides a list of common lithiumcontaining minerals. 

Figure 2. Photograph of lithium metal. Figure 3. Photograph of the lithiumbearing mineral spodumene. 
4 

Table 1. Principal lithium minerals and their sources (after Lumley, 1997). 

Mineral Formula Locations of Deposits (in 

Alphabetical Order) 

Spodumene LiAlSi2O6 Australia, Brazil, Canada, 

China, Russia, United States 

Petalite LiAlSi4O10 Australia, Brazil, Namibia, 

Russia, Sweden, Zimbabwe 

Amblygonite (Li,Na)Al(PO4)(F,OH) Brazil, Canada, Mozambique, 

Namibia, Rwanda, South 

Africa, Suriname, Zimbabwe 

Lepidolite K(Li,Al)3(Si,Al)4O10(F,OH)2 Brazil, Canada, Namibia, 

Zimbabwe 

Eucryptite LiAlSiO4 Zimbabwe 

Spodumene is the most abundant of the lithium-containing minerals from which lithium is extracted. To 

extract lithium in this process, spodumene ore concentrate is first heated in a rotary kiln at about 

1,000 °Celsius (C) (1,832 °Fahrenheit (F)) to decrepitate the spodumene. This clinker is then roasted with 

sulfuric acid at about 250 °C (482 °F) to leach out an aqueous extract of lithium sulfate. This lithium 

sulfate is then converted to lithium carbonate, the primary compound from which other lithium 

compounds are manufactured. 

Processing ore deposits is energy-intensive, but less expensive lithium extraction methods exist. For 

instance, much of the lithium produced today is extracted from subsurface salt brine deposits. The largest 

deposits of lithium-containing brines are found in Argentina and Chile. Solar evaporation is used to 

precipitate the salts, which are then processed chemically to separate the lithium (as Li2CO3) from the 

other compounds; figures 4 and 5 show aerial views of these deposits. 

Figure 4. Aerial view of lithium-bearing 

brines in Argentina (Salar del Hombre 

Muerto). 

Figure 5. Aerial view of lithium-bearing 

brines in Chile (Salar de Atacama). 

Lithium carbonate (Li2CO3) is used as a feedstock for other processes to produce a variety of lithium 

compounds which are then used in a wide range of applications. Table 2 provides a list of common 

lithium compounds and different applications. 

The main application for lithium in the construction industry is in the formulation of chemical admixtures 

for concrete. Various lithium compounds (Li2CO3, LiOH, Li2SO4) are used in the formulation of set 

accelerators for calcium-aluminate-cement concrete and both lithium hydroxide monohydrate 

(LiOH•H2O) and lithium nitrate (LiNO3) have been used to control ASR in portland cement concrete. 
5 

Table 2. List of lithium compounds and applications for lithium. 

Forms of Lithium Common Applications 

Lithium metal (Li) 

Lithium carbonate (Li2CO3) 

Lithium nitrate (LiNO3) 

Lithium hydroxide (LiOH) 

Lithium hydroxide monohydrate (LiOH•H2O) 

Lithium chloride (LiCl) 

Lithium fluoride (LiF) 

Lithium sulfate (Li2SO4) 

Air treatment 

Alloys 

Batteries 

Construction (e.g., chemical admixtures or 

 treatment of ASR-affected structures) 

Fine chemicals 

Glass and ceramics 

Greases and lubricants 

Pharmaceuticals 

Polymers 

Pool water treatment 

Other specialty applications 

7 

CHAPTER 3. ALKALI-AGGREGATE REACTION 

3.1 Terminology 

Alkali-aggregate reaction (AAR) is a reaction in concrete between the alkali hydroxides, which originate 

mainly from the portland cement, and certain types of aggregate. Two types of AAR are currently 

recognized; these are alkali-silica reaction (ASR) and alkali-carbonate reaction (ACR). As the names 

imply, these types of reaction differ in that they involve reactions with either siliceous or carbonate 

phases in the aggregates (table 3). ASR is far more widespread than ACR and is the focus of this 

document. ACR will not be discussed further, however, it should be noted that the measures used to 

control ASR have generally shown limited effectiveness in controlling ACR. 

Table 3. Terminology for alkali-aggregate reactions (CSA A23.1-04). 

Alkali-Aggregate 

Reaction (AAR) 

Chemical reaction in either concrete or mortar between hydroxyl ions (OH−

) of the 

alkalies (sodium and potassium) from hydraulic cement or other sources and 

certain constituents of some aggregates; under certain conditions deleterious 

expansion of concrete or mortar may result. 

Alkali-Carbonate 

Reaction (ACR) 

Chemical reaction in either concrete or mortar between hydroxyl ions (OH−

) of the 

alkalies (sodium and potassium) from hydraulic cement or other sources and 

certain carbonate rocks, particularly calcitic dolostone and dolomitic limestones, 

present in some aggregates; the reaction causes dedolomitization and expansion of 

the affected aggregate particles, leading to abnormal expansion and cracking of 

concrete in service. 

Alkali-Silica 

Reaction (ASR) 

Chemical reaction in either concrete or mortar between hydroxyl ions (OH−

) of the 

alkalies (sodium and potassium) from hydraulic cement or other sources and 

certain siliceous rocks and minerals, such as opal, chert, microcrystalline quartz, 

and acidic volcanic glass, present in some aggregates. This reaction and the 

development of the alkali-silica gel reaction product can, under certain 

circumstances, lead to abnormal expansion and cracking of the concrete. 

3.2 Mechanisms of ASR 

Concrete is a porous material (typically about 10 percent of the volume of concrete is occupied (by pores) 

and, in saturated concrete, the pores contain a solution composed of alkali hydroxides (NaOH and KOH). 

The origin of the sodium (Na) and potassium (K) is, principally, the portland cement. Table 4 shows an 

oxide analysis of a typical portland cement. 

Table 4. Typical chemical analysis for portland cement. 

Oxide SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O SO3 LOI 

Percent 20.55 5.07 3.10 64.51 1.53 0.15 0.73 2.53 1.58 

It is convenient to convert the potassium oxide to an equivalent amount of sodium oxide using a molar 

ratio and to express the alkalies in terms of the equivalent alkali content of the cement; which is defined 

as: 

O2 O 0.658 x K 2 Oe Na 2 Equivalent Alkalies, Na = +

(1) 

For the analysis given in table 4, the equivalent alkali content is calculated as follows: 

Na 2Oe = 0.15 + 0.658 x 0.73 = 0.63%

(2) 
8 

The equivalent alkali content of portland cements produced in or imported into North America typically 

ranges from 0.20 to 1.20 percent Na2Oe. 

Although the alkalies represent a small fraction of the portland cement, they dominate the pore solution of 

the concrete, which, as a result, is highly alkaline with a pH in the range of 13.2 to 13.8. Diamond (1989) 

indeed found a direct correlation between the cement alkali content and the pH of the pore solution. 

Figure 6 summarizes the sequence of ASR in concrete. Some forms of silica (SiO2) found in some 

aggregates are unstable at high pH and react with the alkali hydroxides to form an alkali-silica gel. This 

gel has the propensity to absorb large quantities of water and swell. Under certain conditions, the swelling 

pressures can cause expansion and, eventually, cracking of the concrete.

Figure 6 demonstrates the sequence of alkali-silica reaction (ASR) in concrete. 

Concrete pore solution is 

dominated by Na, K & OH 

(with minor amounts of Ca).

If the silica in the aggregate is 

reactive – the OH and then the 

Na & K will react with the SiO2

The product of the reaction is in 

alkali-silica gel composed of 

Na, K, Ca & Si

The gel forms around and 

within the aggregate

The gel imbibes water from the 

surrounding cement paste

The gel expands

Eventually the swelling 

pressures may exceed the tensile 

strength of the surrounding 

paste and cause expansion & 

cracking of the concrete

(Na,K,Ca)Si gel

(Na,K,Ca)Si gel

(a)

(b)

(c)

Concrete pore solution is 

dominated by Na, K & OH 

(with minor amounts of Ca).

If the silica in the aggregate is 

reactive – the OH and then the 

Na & K will react with the SiO2

The product of the reaction is in 

alkali-silica gel composed of 

Na, K, Ca & Si

The gel forms around and 

within the aggregate

The gel imbibes water from the 

surrounding cement paste

The gel expands

Eventually the swelling 

pressures may exceed the tensile 

strength of the surrounding 

paste and cause expansion & 

cracking of the concrete

(Na,K,Ca)Si gel

(Na,K,Ca)Si gel

(a)

(b)

(c)

Figure 6. Sequence of alkali-silica reaction (ASR) in concrete. 

Not all forms of silica are reactive in concrete. The reactivity depends on the crystal structure of the silica 

rather than its chemical composition. For example both quartz and opal are silica minerals and are 

predominantly composed of silica (SiO2); i.e., they are of similar composition (although opal has varying 

proportion of water, usually 3 to 9 percent). Quartz has a well-ordered crystal structure (figure 7) and is 

very stable in concrete at normal temperatures. Opal, on the other hand, has an internal structure 

consisting of more-or-less densely packed aggregate of spheres of silica (cristobalite and/or tridymite) and 

is highly reactive in concrete. 
9 

Figure 7. Schematic showing difference in crystal structure of quartz (left) and opal (right). 

Table 5 contains a list of reactive silica forms and the rock types in which they may be found. Not all 

sources of these rock types are reactive in concrete. Damaging reaction will only occur if these rock types 

contain sufficient quantities of the reactive silica. For example, many granites are not deleterious reactive 

in concrete and make excellent concrete aggregates. However, if the granite contains a sufficient quantity 

of strained or microcrystalline quartz, the use of the rock may result in ASR when used in concrete, unless 

appropriate precautions are taken to control the reaction (sufficient alkali and moisture are also required 

to sustain the reaction—see figure 8 below). 

Table 5. Table of alkali-silica reactive minerals and possible rock types in which they may be found. 

Rock Types Reactive Minerals and Glass 

Andesite 

Arenite 

Argillite 

Arkose 

Basalt 

Chert 

Flint 

Gneiss 

Granite 

Greywacke 

Hornfels 

Quartz-arenite 

Quartzite 

Rhyolite 

Sandstone 

Shale 

Silicified carbonate 

Siltstone 

Tuff 

Cristobalite 

Cryptocrystalline (or microcrystalline) quartz 

Opal 

Strained quartz 

Tridymite 

Volcanic glass 

Figure 8. Three essential requirements for deleterious ASR. 
10 

3.3 Symptoms of ASR 

Common symptoms of ASR in affected structures include (figure 9): 

• Cracking which may be random in direction (i.e., map or pattern cracking) or may show preferred 

orientation if expansion is restrained in one direction. 

• Discoloration around cracks. 

• Gel exudation from cracks. 

• Misalignment of adjacent sections. 

• Closing of joints, extrusion of joint sealant and crushing/spalling of concrete around joints. 

• Pop-outs over reactive aggregate particles. 

• Operation difficulties (e.g., jamming of sluice gates in dams). 

Field symptoms of ASR in concrete structures have been described and illustrated in a number of 

documents, including SHRP 315 (1995), CSA A864 (1992), and BCA 1992. 

Figure 9. Typical symptoms of ASR. 

(a) (b) 

(c) (d) 

(e) (f) 
11 

3.4 Methods of Evaluating Potential Reactivity of Aggregates 

3.4.1 Field Performance 

Field performance survey of concrete structures can be used to determine the potential alkali-reactivity of 

concrete aggregates (CSA A23.1). When field performance is used for that purpose (CSA A23.1): 

• The structure examined should have similar or higher cement/alkali contents compared to the new 

structure to be built. 

• The concrete examined should be at least 10 years old. 

• The exposure conditions of the structure examined should be at least as severe as those likely to 

affect the new structure to be built. 

• In the absence of documentation, a petrographic report should confirm that the aggregates used 

(existing structure) and for use (new structure) are identical. 

• The possibility that supplementary cementitious materials (SCMs) have been used should be 

considered / investigated so that if present SCMs for use (new structure) are as close to identical as 

possible in the structure under investigation. 

Evaluating potential alkali-reactivity from field performance requires the involvement of an engineer 

and/or scientist with experience of assessing ASR in concrete structures. 

3.4.2 ASR Testing in the Laboratory 

A wide variety of standard test methods is available for identifying potentially reactive aggregates. Table 

6 lists the tests that have been standardized by ASTM. Only the concrete prism test (ASTM C1293) and 

the accelerated mortar bar test (ASTM C1260) are currently recommended for use in identifying reactive 

aggregates. Petrographic examination of aggregates (ASTM C295) is often seen as the essential first step 

of an ASR testing program; however, it should not be used to accept an aggregate source without 

expansion testing in concrete or mortar. (ASTM C1105 is recommended for evaluating alkali-carbonate 

reactive rocks). ASTM C 1567 is used to test the efficacy of pozzolans and slags for controlling concrete 

expansion due to ASR rather than to identify reactive aggregates. 
12 

Table 6. ASTM test methods related to alkali-aggregate reaction. 

 

C1293-05 Standard Test Method for Concrete Aggregates by Determination of Length Change of 

Concrete Due to Alkali-Silica Reaction1,3

C1260-05a Standard Test Method for Potential Alkali Reactivity of Aggregates (Mortar Bar Method)1

C227-03 Standard Test Method for Potential Alkali Reactivity of Cement Aggregate Combinations (Mortar 

Bar Method) 

C289-03 Standard Test Method for Potential Alkali-Silica Reactivity of Aggregates (Chemical Method) 

C1105-05 Standard Test Method for Length Change of Concrete Due to Alkali-Carbonate Rock Reaction 

C295-03 Standard Guide for Petrographic Examination of Aggregates for Concrete2

C1567-04 Standard Test Method for Determining the Potential Alkali-Silica Reactivity of 

Combinations of Cementitious Materials and Aggregate (Accelerated Mortar-Bar Method)3

C441-05 Standard Test Method for Effectiveness of Mineral Admixtures or Ground Blast Furnace Slag in 

Preventing Excessive Expansion of Concrete Due to the Alkali-Silica Reaction 

1

Only the concrete prism test (ASTM C1293) and the accelerated mortar bar test (ASTM C1260) are currently recommended for 

use in identifying reactive aggregates. 

2

Often seen as the essential first step of an ASR testing program; however, it should not be used to accept an aggregate source 

without expansion testing in concrete or mortar. 

3

Only the modified version of the concrete prism test (ASTM C 1293) and the ASTM C 1567 are recommended for evaluating 

the efficacy of pozzolans and slag for controlling expansion due to ASR.

The concrete prism test is generally considered to be the most reliable laboratory test in its ability to 

predict field performance. In this test, concrete prisms are stored in sealed containers over water at 38 °C 

(100 °F). Figure 10 shows the test setup, and figure 11 provides the length change measurements. The test 

uses the following parameters: 

• Aggregate is tested in a concrete mixture containing 420 kilograms per cubic meter (kg/m3) (705 

pounds per cubic yard (lb/yd3

)) of cement. 

• Cement alkalies are raised to 1.25 percent Na2Oe from a cement with an alkali content of 

0.9 ± 0.1 percent Na2Oe. 

• Concrete is molded into prisms measuring 75 millimeters (mm) by 75 mm by minimum 250 mm 

gauge length (3 inches by 3 inches by minimum 10 inches). 

• Concrete prisms are stored over water in sealed containers at 38 °C (100 °F). 

• Length change is measured for 12 months to determine aggregate reactivity and 24 months to 

determine efficacy of preventive measures (CSA A23.2-27A). 

The appendices to ASTM C1293 (the standard test method) and ASTM C33 (the specification for 

aggregates) consider aggregates that produce expansions greater than or equal to 0.04 percent at 1 year to 

be potentially deleteriously reactive. In Canada, in a test almost identical to ASTM C1293 

(CSA A23.2-27A), the expansion after 12 months is used to classify the aggregate as (i) nonreactive 

(expansion < 0.04 percent), (ii) moderately reactive (expansion between 0.04 and 0.12 percent) or 

(iii) highly reactive (expansion > 0.12 percent). This test method can also be used to evaluate preventive 

measures (see section 3. 5). 
13 

Figure 10. Concrete prism test—prisms stored over 

water in sealed containers. 

0.00

0.05

0.10

0.15

0.20

0.25

0 3 6 9 12

Age (months)

Expansion (%) .

Highly-reactive

Moderately-reactive

Non-reactive

0.00

0.05

0.10

0.15

0.20

0.25

0 3 6 9 12

Age (months)

Expansion (%) .

Highly-reactive

Moderately-reactive

Non-reactive

Figure 11. Concrete prism test—length change measurements (ASTM C1293)1

. 

The accelerated mortar bar test yields results in as little as 16 days. In this test, mortar bars containing the 

aggregate under test are immersed in an alkaline solution at elevated temperature (1 N NaOH at 80 °C 

(176 °F)) and the length change of the bars is monitored. The test uses the following parameters: 

• Aggregate is tested in mortar mixture. 

• Coarse aggregates must be crushed to pass 5-mm (number 4) sieve, washed, dried and combined in 

the proper gradation to meet the requirements of the test. 

• Mortar is molded into prisms measuring 25 mm by 25 mm by minimum 250 mm gauge length (1 inch 

by 1 inch by minimum 10 inches). 

• Mortar bars are stored at laboratory temperature for 1 day and then demolded and immersed in tap 

water and raised to 80 °C (176 °F) for 1 day. 

• After the second day, mortar bars are removed from water and the initial length reading is taken. 

 

1

 Note that the expansion limits shown in the graph are based on CSA recommendations. 
14 

• Mortar bars are then immersed in 1 N NaOH already at 80 °C (176 °F), and length change is 

monitored periodically. 

• If expansion is greater than 0.10 percent after 14 days in the alkaline solution, the aggregate is 

considered to be potentially reactive, and the reactivity should be confirmed by testing in concrete 

(i.e., ASTM C1293). 

• If expansion is less than or equal to 0.10 percent after 14 days in the alkaline solution, the aggregate is 

considered to be innocuous. 

ASTM suggests the following interpretation of expansion results: 

• Expansions of less than 0.10 percent at 16 days after casting are indicative of innocuous behavior in 

most cases. 

• Expansions of more than 0.20 percent at 16 days after casting are indicative of potentially deleterious 

expansion. 

• Expansions between 0.10 percent and 0.20 percent at 16 days after casting include both aggregates 

that are known to be innocuous and deleterious in field performance. For these aggregates, it is 

particularly important to develop supplemental information as described in Section 3.3. In such a 

situation, it may also be useful to take comparator readings up to 28 days. 

However, other parties have suggested extending the immersion period to 28 days and using the same or a 

lower expansion limit (i.e., 0.08 percent). Details of the test are shown in figure 12. The accelerated 

mortar bar test can also be used to evaluate preventive measures in accordance with ASTM C1567 (see 

section 3.5). ASTM C1567 follows identical procedures in terms of storage conditions and measurements 

as ASTM C1260; the only difference is the incorporation of SCMs in the mortar mixture. 

Figure 12. Accelerated mortar bar test (ASTM C1260): (a) view from the top of four rectangular 

concrete samples, under water in a blue rectangular container; (b) measuring a concrete sample for 

length change using a digital comparator. 

3.5 Measures To Prevent ASR 

The risk of damage due to ASR in new concrete can be minimized by following one or more of the 

following strategies: 

• Avoid the use of reactive aggregates. 

• Limit the alkali content of the concrete mixture. 

• Use a sufficient quantity of effective SCM(s). 

• Use of lithium-based compounds—see chapter 4. 

(a) (b) 
15 

(3) (4)

The use of nonreactive aggregate is the most obvious measure for preventing damaging alkali-silica 

reaction. Aggregates that do not cause deleterious expansion when tested in accordance with ASTM 

C1293 and ASTM C1260 are unlikely to cause damage due to ASR when used in the field. However, 

because there is a small risk of ASR even when aggregate sources have been shown to be “nonreactive” 

by testing, some agencies still specify that additional precautions be taken (e.g., use of SCM or limiting 

the alkali content of the concrete). Furthermore, in some locations “nonreactive” aggregates may be 

scarce and potentially reactive aggregates can be used safely when appropriate preventive measures are 

taken. 

The risk of damage due to ASR when potentially reactive aggregate is used increases as the alkali content 

of the concrete increases. Figure 13 shows the relationship between expansion of concrete prisms and the 

alkali content of concrete containing a reactive siliceous limestone. It can be seen that, in laboratory 

specimens, deleterious expansion only occurs with this aggregate when the alkali content exceeds 

3.0 kg/m3 (5 lb/yd3) Na2Oe. The alkali content of portland cement concrete is calculated by multiplying 

the cement content by the alkali content of the cement, as shown in table 7.

Figure 13. Effect of the alkali content of concrete on the expansion of prisms. 

Table 7. Calculation for alkali content of portland cement concrete. 

For example, the alkali content of a concrete mixture containing 350 kg/m3

of Portland cement which has an alkali content of 0.91 percent Na2Oe is: 

350 kg/ m 3 ×0.91 % Na2Oe / 100 = 3.19 kg/m3 Na2Oe 

 

Alkali content of concrete (kg/m3Na2

Oe) 

= Cement content of concrete (kg/m3) 

× alkali content of cement (percent Na 2Oe)/100

588 lb/yd3 × 0.91 % Na 2Oe / 100 = 5.35 lb/yd3 Na2Oe

(3) 

(4) 

(5) 
16 

It should be noted that expansion may occur in the field at lower alkali contents than that found necessary 

to cause expansion in the laboratory. The reason for this is that a portion of the alkalies may be lost 

through leaching under the conditions of the concrete prism test (Thomas et al., 2005). For example, the 

aggregate for which expansion data are presented in section 3.4.2 caused expansion and cracking of fieldexposed concrete blocks (approximately 0.6 by 0.6 by 2.0 m (2 by 2 by 6 ft.)) with an alkali content of 

just 1.9 kg/m3 (3.2 lb/yd3) Na2Oe (Rogers et al., 2004). 

Limits on alkali contents in national specifications vary between different countries with values in the 

range of 2.5 to 4.5 kg of Na2Oe per cubic meter (4.2 to 7.6 lb of Na2Oe per cubic yard) being used (Nixon 

and Sims 1992). In Canada (CSA A23.1-27A), a range of alkali limits are specified depending on the 

level of prevention required; these are presented in table 8. 

Table 8. Range of alkali limits (CSA A23.1-27A). 

Level of Prevention Alkali Limit (Na2Oe) 

Required kg/m3 lb/yd3 

Mild 3.0 5.0 

Moderate 2.4 4.0 

Strong 1.8 3.0 

Exceptional 1.8 + SCM 3.0 + SCM 

In Standard Practice CSA A23.2-27A, the level of prevention required is determined by considering the 

reactivity of the aggregate proposed for use, the exposure condition, the size of the element and the design 

life of the structure to be built. As indicated in table 8, the required levels of prevention vary from “mild” 

to “exceptional” as a function of the above factors, with corresponding alkali limits for prevention 

purposes. For example, “mild” preventions (e.g., maximum total concrete alkali content of 3 kg/m3

 

(5 lb/yd3

)) are required for massive concrete elements incorporating a moderately reactive aggregate (i.e., 

inducing a concrete prism expansion greater than 0.04 percent but less than 0.12 percent) in a dry 

environment (e.g., interior elements of buildings). The level of prevention would increase to “moderate” 

(maximum total concrete alkali content of 2.4 kg/m3

 (4 lb/yd3)) if such a moderately reactive aggregate 

were used in an exposed structure with a design life of less than 75 years (e.g., sidewalk or pavement), or 

“strong” (maximum total concrete alkali content of 1.8 kg/m3

 (3 lb/yd3)) if used in an exposed structure 

with a design life of greater than 75 years (e.g., a bridge or a dam). An “exceptional” level of prevention 

would be required when a highly reactive rock is used in the same type of structure. For the latter, it is 

recommended not only to limit the total concrete alkali content at less 1.8 kg/m3

 (3 lb/yd3), but also to use 

a sufficient amount of SCM. 

Specifying the use of low-alkali cement (< 0.60 percent Na2Oe) or limiting the total alkali content in 

concrete under a certain level, as a means for preventing ASR when reactive aggregates are used, may 

however not be sufficient / effective in all cases. There have been a number of cases of ASR in concrete 

structures built with low-alkali cement. For example, a concrete with 400 kg/m3 (~670 lb/yd3

) of cement 

with an alkali content of 0.55 percent Na2Oe will have a total alkali content of 2.2 kg/m3 (3.7 lb/yd3

) 

Na2Oe, which is sufficient to produce ASR damage with some aggregates. Also, limiting the alkali 

content in concrete may not provide sufficient protection if the concrete is exposed to external sources of 

alkalies (e.g., deicing chemicals, seawater, etc.) 

One of the most efficient means of controlling ASR in concrete containing reactive aggregates is the 

appropriate use of supplementary cementing materials (SCM). Such materials include pozzolans (e.g., fly 

ash, silica fume, calcined clay, or shale) and ground-granulated blast furnace slag. Almost any SCM can 
17 

be used for this purpose provided it is used in sufficient quantity (figure 14). The amount of SCM 

required generally increases as: 

• Reactivity of the aggregate increases. 

• Alkali content of the concrete increases. 

• Available alkali content of the SCM increases. 

• Calcium-to-silica ratio (CaO/SiO2) of the SCM increases. 

Pozzolans, such as silica fume, which have a high content of reactive silica and low levels of calcium and 

alkali tend to be very efficient in controlling ASR and can be used at relatively low levels of replacement 

(typically 7 to 15 percent2

) for this purpose. On the other hand, SCM with relatively high levels of 

calcium and lower amounts of silica, such as Class C fly ash or slag, generally need to be used at 

replacement levels of 35 percent or more. Low-calcium Class F fly ash is relatively more efficient (i.e., 

can be used at lower replacement levels) than Class C fly ash or slag, but has to be used at higher 

replacement levels than silica fume. Figure 14 shows typical expansion behavior of concrete containing 

high-alkali cement (see note below), reactive aggregate, and different types of SCM. 

8

10

12

15

20

25

30

45

60

30

40

50

SCM %

0

0.1

0.2

0.3

Control Silica

Fume

Class F

Fly Ash

Class C

Fly Ash

Slag

Expansion (%)

8

10

12

15

20

25

30

45

60

30

40

50

SCM %

0

0.1

0.2

0.3

Control Silica

Fume

Class F

Fly Ash

Class C

Fly Ash

Slag

Expansion (%)

0

0.1

0.2

0.3

Control Silica

Fume

Class F

Fly Ash

Class C

Fly Ash

Slag

Expansion (%)

Figure 14. Effect of SCM on the expansion of concrete (using concrete prism test). 

Ternary cement blends, which contain three different cementing materials (portland cement plus two 

SCMs) have been found to be very effective in controlling ASR, especially blends containing silica fume 

plus either Class F fly ash or slag. Relatively low levels of silica fume (3 to 5 percent) together with 

moderate levels of Class F fly ash (15 to 20 percent) or slag (25 to 35 percent) have been shown to be 

effective (Shehata and Thomas, 2002; Bleszynski et al., 2002). 

The concrete prism test (ASTM C1293) can be modified to determine the amount of SCM required to 

control expansion with a particular reactive aggregate. The method is described in CSA A23.2-28A-04. 

When testing SCM, the portland cement component of the mixture is partially replaced with the SCM. 

Various replacement levels can be used to determine the minimum level required to suppress expansion. 

The alkali content of the portland cement component of the mixture should be maintained at 1.25 percent 

Na2Oe (by adding NaOH, usually in liquid form, to the mixing water) to a cement with 0.90 ± 0.10 

 

2

 Note that SCM replacement levels are expressed as the mass percentage of the total cementitious material content 

of the concrete. For example, 10-percent silica fume means that 10 percent of the total mass of cementitious material 

is comprised of silica fume, the remaining 90 percent being portland cement. 
18 

percent Na2Oe). When evaluating preventive measures, the test period should be extended to 2 years and 

the measure shall be considered effective if the expansion at this age is not greater than 0.04 percent. 

The accelerated mortar bar test (ASTM C1567) can also be used to determine the amount of SCM 

required to control expansion with a particular aggregate. The portland cement component of the mix is 

partially replaced with the SCM under test; different replacement levels can be used to determine the 

minimum level of SCM required to control expansion. The preventive measure is considered effective if 

the expansion after 2 weeks immersion in the alkaline solution is not greater than 0.10 percent (Thomas et 

al., 2005). This test is generally not considered to be as reliable as the concrete prism test for evaluating 

SCM, and it is recommended that the results of the accelerated test be confirmed by the longer-term 

concrete test. 

3.6 Treating Existing ASR-Affected Pavements and Structures 

Methods for mitigating the effects of ASR can be divided into two categories: (1) mitigating the 

symptoms of distress and (2) addressing the cause of distress. 

Methods for mitigating the symptoms include filling cracks; cutting joints to allow further expansion to 

take place, thereby relieving internal stresses within the concrete or pressures on adjacent members or 

structures; and providing restraint to further expansion. 

Caulking cracks with an epoxy grout (or similar compound) can help protect embedded reinforcement and 

reinstate the integrity of the cracked concrete. However, it will not significantly retard the rate of reaction 

and expansion, and new cracks will inevitably form with time if the reaction is allowed to proceed. 

Cutting joints to allow for expansion to take place has been used in a number of hydraulic structures, with 

the principal aim in these cases being to relieve stresses on embedded mechanical equipment such as 

sluice gates or turbines. Joints can also be cut to isolate expanding structures from adjacent structures or 

to relieve internal stresses in pavements. Providing space for expansion does not deal with the reaction, 

and it is likely that the expansion and cracking will continue. 

Providing restraint in the form or rock anchors or post-tensioned tendons also has been used in hydraulic 

structures to prevent unwanted expansion and distortion of the structure. Fiber-reinforced polymers 

(FRPs) have been used to wrap elements such as columns. 

The only two practical means for addressing the cause of damage (i.e., to retard or prevent further 

reaction), are to either dry the concrete to eliminate the moisture required to sustain ASR or to change the 

nature of the reaction by introducing lithium compounds. 

Silane sealers have been used successfully to reduce the relative humidity in ASR-affected concrete piers 

(Kojima et al., 1992), railway sleepers (Oberholster et al., 1992) and median barriers (Bérubé et al., 1998). 

Silanes applied to concrete render the surface of the concrete hydrophobic and prevent the ingress of 

liquid water into the concrete. However, water vapor can still exit through the layer, reducing the 

moisture content, and hence reducing the relative humidity, with time. Figure 15 shows a photograph of 

silane-treated and untreated sections of a barrier wall in Quebec. 

The use of lithium compounds to treat ASR-affected concrete structures is discussed in chapter 5. 
19 

Figure 15. Barrier wall in Quebec—the section of the wall to 

the right of the picture has been treated with a silane sealer. 

21 

CHAPTER 4. USING LITHIUM TO PREVENT ASR IN NEW CONCRETE 

4.1 Laboratory Studies 

In 1951, McCoy and Caldwell published data showing that the incorporation of various lithium 

compounds (LiCl, Li2CO3, LiF, Li2SiO3, LiNO3, and Li2SO4) in mortars (ASTM C227) containing highly 

reactive Pyrex® glass could control damaging alkali-silica reaction provided the lithium was present in 

sufficient quantity. Although little work was conducted in the 40 years that followed the publication of 

this paper, there has been renewed interest in the use of lithium as an admixture, starting with the work 

conducted under the SHRP program (SHRP-C-343), and the last 15 years has seen the publication of 

numerous papers on the subject. Detailed reviews of the literature have been published elsewhere 

(Folliard et al., 2005; Feng et al., 2005). 

The amount of lithium required to suppress expansion depends upon the form of lithium, the nature of the 

reactive aggregate, and the amount of alkali in the concrete. Many studies have shown that the expansion 

of concrete for a given aggregate depends on the amount of lithium relative to the amount of sodium plus 

potassium in the mortar or concrete mixture. This has led to the use of the molar ratio [Li]/[Na+K] for 

expressing the lithium dose in mortar and concrete mixtures, where [Li] is the number of moles of lithium 

and [Na+K] is the sum of the moles of sodium plus the moles of potassium present in the mixture. 

McCoy and Caldwell’s (1951) data showed that expansion was largely eliminated if the lithium-tosodium-plus-potassium ratio was equal to or greater than 0.74; i.e., [Li]/[Na+K] ≥ 0.74. A number of 

recent laboratory studies have confirmed this finding, and [Li]/[Na+K] = 0.74 has become the “standard 

dose” for controlling ASR in concrete containing reactive aggregate. 

At the time of writing this guideline, the only commercially available lithium compound for use as a 

concrete admixture is a solution containing 30 percent lithium nitrate (LiNO3). To achieve a molar ratio 

of [Li]/[Na+K] = 0.74 requires the addition of 4.6 L of 30-percent LiNO3 solution for every 1.0 kg of 

Na2Oe in the mixture (0.55 gal of solution for every 1.0 lb of Na2Oe), as shown in table 9. 
22 

Table 9. Example showing calculation of [Li]/[Na + K] molar ratio. 

Alkali Molecular 

Weight Compound Molecular Weight 

Li 7 LiNO3 69 

Na 23 LiOH·H2O 42 

K 39 Na2Oe 62 

Moles of lithium in 1 L of 30 % LiNO3 solution 

Moles of sodium + potassium in 1 kg of Na2Oe 

Volume of 30 % LiNO3 solution required for [Li]/[Na+K] = 0.74 

1 g = 0.035 ounce 

1 Liter (L) = 0.26 gallon 

1 kilogram (kg) = 2.20 lbs 

Prior to the use of lithium nitrate, lithium hydroxide monohydrate (LiOH•H2O) was used in both 

laboratory testing and in a number of concrete structures (see section 4.3). To achieve a molar ratio of 

[Li]/[Na+K] = 0.74 requires the addition of 1 kg of LiOH•H2O for every 1 kg of Na2Oe in the mixture (1 

lb LiOH•H2O for every 1 lb of Na2Oe). 

LiOH•H2O is somewhat less effective than LiNO3 (see figure 16) as it introduces additional hydroxyl ions 

into the concrete. Furthermore, LiOH•H2O may exhibit a pessimum behavior with some aggregates, with 

low doses actually increasing expansion. Other lithium compounds such as Li2CO3 and LiCl may also 

increase the concentration of hydroxyl ions because of reaction with Ca(OH)2 in the paste as follows: 

3 2LiOH CaCO 2 Ca(OH) 3 CO 2 Li + → +

(14) 

Lithium nitrate does not produce this effect because of the high solubility of Ca(NO3)2. 

Specific gravity of 30% LiNO3 solution = 1.2 

Mass of 1 L of 30% LiNO3 = 1,200 g 

Mass of LiNO3 in 1 L = 30/100 x (1,200) = 360g 

Number of moles of LiNO3 = 360/69 = 5.217 moles 

Number of moles of Na2Oe in 1 kg of Na2Oe = 1,000/62 = 16.13 moles 

Number of moles of Na = 2 x 16.13 = 32.26

Molar ratio for 1 L of 30% LiNO3 solution per 1 kg of Na2Oe = 5.217/32.26 = 0.162 

Volume of 30% LiNO3 solution for molar ration of 0.74 = 0.740/0.162 

 = 4.6 L per 1 kg of Na2Oe 
23 

Figure 16. Relative expansion of concrete prisms (ASTM C1293) containing 

lithium compounds and reactive siltstone aggregate (Thomas et al., 2000). 

Although the “standard dose” of [Li]/[Na+K] = 0.74 appears to be sufficient to control expansion with a 

great many aggregates, it is not sufficient for all aggregate types (Lane, 2000; 2002; Durand, 2000; 

Tremblay, 2004), and higher doses are required. With some aggregates, a dose of 1.5 times the standard 

dose, i.e., [Li]/[Na+K] = 1.11, may still not be sufficient to suppress damaging ASR (Tremblay, 2004). 

It would appear that lithium is more effective with rapidly reacting aggregates where the reactive phase is 

opal, chert, or volcanic glass, and less effective with slowly reacting aggregates which contain 

microcrystalline or strained quartz as the reactive phase. However, it is difficult to assess whether lithium 

will be effective or to determine the appropriate dose based purely on the mineralogy of the aggregates. 

At this time, it is recommended that amount of lithium required to control expansion with a particular 

aggregate is determined by appropriate testing methods (see section 4.3). 

4.2 Field Applications 

The first field application of lithium as an admixture in concrete containing reactive aggregate was in the 

construction of an experimental pavement in Albuquerque, NM, in 1992. Two local sources of highly 

reactive sand and gravel were used together with low-alkali cement (0.55 percent Na2Oe) and a range of 

preventive measures, which included lithium hydroxide monohydrate. Two doses of lithium were used; 

these were 0.5 percent and 1.0 percent LiOH•H2O by mass of cement, which yielded lithium-to-sodiumplus- potassium molar ratios of [Li]/[Na+K] = 0.67 and 1.34 (i.e., 91 percent and 182 percent of the 

standard dose), respectively. Figures 17 and 18 show selected sections of this pavement after 12 years of 

service. As shown in figure 17, cracking has occurred in the control section, the section with 20 percent 

Class C fly ash, the section with 20 percent of the blended Class F plus Class C fly ash, and in the section 

with 0.5 percent LiOH•H2O (lower dose lithium: [Li]/[Na+K] = 0.67). The section with the higher lithium 

dose ([Li]/[Na+K] = 1.34) is still performing well. These sections were constructed with the aggregate 

from the Shakespeare pit that contained mixed volcanic aggregates. Figure 18 shows the section with the 

higher dose of lithium and the aggregate from the Placitas pit, in Albuquerque that also contained mixed 
24 

volcanics and is also in good condition after 12 years. There is no formal monitoring program tracking the 

long-term behavior of these pavements, and the only evaluation has been periodic visual inspections 

conducted by members of the research team or others. 

Since the early 1990s, lithium compounds have been used in a variety of concrete structures across the 

United States, and some of these have been described in detail by Folliard et al., 2003. There have been 

no reports of ASR in these structures at the time of writing this report. 

a. Control b. 20% Class C Fly Ash

c. 20% Class F Fly Ash d. 20% Class F/C Fly Ash

e. 1.0% LiOH·H2O f. 0.5% LiOH·H2O

a. Control b. 20% Class C Fly Ash

c. 20% Class F Fly Ash d. 20% Class F/C Fly Ash

e. 1.0% LiOH·H2O f. 0.5% LiOH·H2O

Figure 17. Photographs of 12-year-old pavement sections reactive aggregate 

from Shakespeare pit in Albuquerque, NM (photos taken in 2004). 
25 

Figure 18. Photographs of 12-year-old pavement sections 

reactive aggregate from Placitas pit in Albuquerque, NM. 

4.3 Laboratory Testing To Determine the Amount of Lithium Required 

To determine the amount of lithium required to control ASR with a specific aggregate, it is recommended 

that the combination of materials be tested using a modification of the concrete prism test (ASTM C1293). 

The only modifications necessary are to add the required amount of lithium nitrate solution to the mix 

water and to correct the total water content for the water contained in the lithium nitrate solution. The test 

should be conducted at a range of different lithium doses to determine the minimum amount required to 

control expansion (< 0.040 percent at 2 years) with the aggregate under consideration. Table 10 provides 

an example of calculation for concrete prism testing using a standard dose (i.e., [Li]/[Na+K] of 0.74) of 

LiNO3.
26 

Table 10. Proportioning mixtures with lithium for the concrete prism test. 

Control Mixture 

420 kg/m3

 portland cement, NaOH added to mix water to raise 

cement alkalies to 1.25 percent: 

Water-to-cement ratio, 

Mixture with [Li] / Na + K] = 0.74 

420 kg/m3

 portland cement, NaOH added to mix water to raise 

cement alkalies to 1.25 percent: 

Add: 

Water-to-cement ratio, 

include water in 30-percent LiNO3 solution. 

Calculate as follows: 

This water should be included in the calculation of W/CM (i.e., it 

should be subtracted from the water content used in the control 

mixture). 

The accelerated mortar bar test (ASTM C1260) cannot be used to evaluate lithium without significant 

modification. Immersion of the mortar bars in the high temperature alkaline solution overwhelms the 

mortar bar with alkali and changes the [Li]/[Na+K]. Proposed modifications have included adding lithium 

to both the mortar mixture and the soak solution using the same [Li]/[Na+K] ratio. However, there is 

currently little information available to confirm whether the lithium dose determined using a modified 

version of the accelerated mortar bar test is similar to that determined using the longer-term concrete 

prism test and field experience. 

4.4 Effect of Lithium on the Properties of Concrete 

The use of lithium nitrate solution, at the levels of addition necessary to effectively control expansion due 

to ASR, has no adverse effect on the properties of fresh and hardened concrete, even at dosages in excess 

of 10 liters per cubic meter. The use of lithium nitrate may slightly enhance the workability of concrete 

(i.e., there is a small water-reducing effect) and lead to small decreases in the setting time (i.e., slight setaccelerating effect). 

Water present in solution = 70-percent of mass = 70/100 x 28.98 = 20.29 kg

Mass of solution = volume x density = 24.15 L x 1.2 kg/L = 28.98 kg/m3

W/CM = 0.42 to 0.45 

30-percent LiNO3 solution at 4.6L per kg of Na2Oe = 4.6 x 5.25 = 24.15L 

Total alkalis in concrete = 420 x 1.25/100 = 5.25 kg/m3 Na2Oe 

W/CM = 0.42 to 0.45 

Total alkalis in concrete = 420 x 1.25/100 = 5.25 kg/m3 Na2Oe (15) 

(16) 

(17) 

(18) 

(19) 

(20) 

(21) 
27 

CHAPTER 5. USE OF LITHIUM TO TREAT EXISTING ASR-AFFECTED 

STRUCTURES 

5.1 Laboratory Studies 

A number of laboratory studies (Stark et al., 1993; Stokes et al., 2000) have demonstrated that treating 

ASR-affected concrete with lithium compounds can reduce or eliminate future expansion due to ASR 

(e.g., figure 19). Typically, such studies have used laboratory-sized specimens with relatively small crosssections and it has not yet been demonstrated that lithium treatment is effective with larger specimens that 

are more representative of elements of concrete structures.

Figure 19. Expansion of concrete prisms after treatment with 

lithium at 10 weeks (expansion = 0.061 percent) and 16 weeks 

(expansion = 0.107 percent) (Thomas and Stokes, 2004). 

5.2 Field Applications 

5.2.1 Topical Treatment with Lithium 

Numerous structures have been treated by spraying the surface of the structure with a solution of lithium 

(both LiNO3 and LiOH have been used). These structures have included pavements, bridge decks and 

other bridge components, and median barriers. The solution has been applied by either truck-mounted 

spraying systems (figure 20) or hand-held pressurized spray bottles (figure 21). 
28 

Figure 20. Spraying 30 percent LiNO3 solution with a tanker 

truck on a concrete pavement near Mountain Home, ID. 

Figure 21. Spraying 30-percent LiNO3 solution with handheld 

spray applicator on barrier wall near Leominster, MA. 

Typical application rates have been in the range of 0.12 to 0.24 liters per square meter (L/m2) 

(3 to 6 gallons per square feet (gal /1000 ft2)). The most commonly used lithium compound for this 

purpose is a 30 percent LiNO3 solution. Commercially available solutions contain a proprietary surfactant 

to enhance penetration. 

There are few data available regarding the depth of lithium penetration following lithium treatment. 

Figure 22 shows lithium concentration profiles in concrete cores cut from a pavement after six treatments 
29 

(one treatment in each of spring and fall for 3 consecutive years) of 0.24 L/m2 (6 gal/1000 ft2). The depth 

of lithium penetration is clearly dependent on the extent of cracking. 

1 mm = 0.039 inch 

Figure 22. Lithium concentration profiles for concrete pavement after six treatments 

(at approximately 6-month intervals) of 0.24 L/m2

 (6 gal/1000 ft2) (Stokes et al., 2002). 

Figure 22 indicates that very little lithium penetrates below 25 to 50 mm (1 to 2 inches) unless the 

concrete is heavily cracked. Even in heavily cracked concrete, the lithium concentration at this depth is 

low, and its ability to suppress ASR is questionable3

. 

Most of the structures that have been treated topically with lithium have not been monitored properly (i.e., 

other than by simple visual inspection) to confirm whether the treatment has been effective in terms of 

suppressing ASR expansion.

5.2.2 Electrochemical Lithium Impregnation 

Electrochemical impregnation techniques have been used to increase lithium penetration on a number of 

structures (Whitmore and Abbot, 2000). A typical setup (i.e., for a bridge deck) is shown in figure 24 and 

includes the following parameters: 

• Technique is based on electrochemical chloride extraction technique. 

• Electrode (anode) applied to concrete surface. 

• Lithium-bearing electrolyte ponded at surface. 

• D.C. voltage (~40 volts) applied between surface anode and embedded steel (cathode). 

 

3 If lithium were added to concrete containing 4 kg/m3 (6.7 lb/yd3

) Na2Oe at the standard dose of 4.6 Liters of 30 

percentLiNO3 solution per 1 kg Na2Oe (0.55 gal of solution for every 1.0 lb of Na2Oe), the lithium concentration in 

the concrete would be approximately 280 ppm. 
30 

• Positively charged lithium ions are repelled by the positively charged anode and are drawn towards 

the negatively charged cathode (steel reinforcement). 

• Duration of treatment is typically 4 to 8 weeks. 

Figure 23. Electrochemical lithium impregnation. 

Two such cases of using this electrochemical technology have been documented in the literature; these 

are two bridge decks, one in Arlington, VA, the other in Seaford, DE. In both cases, lithium borate was 

used as the electrolyte. Cores were taken from the deck in Virginia after 8 weeks of electrochemical 

treatment. Slices taken from the cores and subjected to chemical analysis revealed the data shown in 

table 11. 

Table 11. Penetration of lithium after electrochemical 

treatment of bridge deck. 

Depth of slice (mm) Lithium (ppm) 

6–19 315–343 

19–32 203–265 

1 mm = 0.039 inch 

The data indicate that significant lithium penetrates to a depth of at least 19 to 32 mm (0.75 to 1.25 

inches), and these dosages are theoretically high enough to have a beneficial effect on reducing ASRinduced expansion (see footnote 2 in chapter 3). 

In March 2006, two columns in Houston, TX, were selected for electrochemical treatment as part of the 

Federal Highway Association Lithium Implementation Technology Program. Figure 24 shows the process 

of the treatment for one of the columns. The entire treatment was completed mid-May of 2006. 
31 

 (a) (b) (c) 

Figure 24. Electrochemical lithium treatment process. (a) irrigation tubes, wood splices, and metal 

strips are placed on the column. The metal strips are attached to titanium mesh that runs inside 

holes drilled into the sides of the column. (b) A cellulose layer is applied to the side of the column, 

and (c) plastic sheeting is placed on all sides of the column. The gutters under the sheeting collect 

excess lithium for reuse. 

5.2.3 Vacuum Impregnation With Lithium 

Vacuum impregnation is an alternative to pressure injection and has been used to increase grout 

penetration into cracked concrete. A number of structures have been treated with lithium using this 

technique; these include several substructure elements (beams and columns) of the New Jersey Turnpike, 

a number of elements on the Prospect Avenue Viaduct in Johnstown, PA, a trapezoidal prestressed bridge 

girder (treated by vacuum impregnation as part of a study of ASR-mitigation methods on 5 girders in 

Corpus Christi, TX), and sections of a barrier wall on Highway 2 near Leominster, MA (figure 26). 

At the time of writing, no data were available concerning the depth of lithium penetration as a result of 

vacuum impregnation. 
32 

Figure 25. Typical vacuum impregnation setup. 

5.3 Recommendations for Treating ASR-Affected Structures with Lithium 

Before treating a structure with lithium-based compounds, an investigation should be conducted to ensure 

that the structure meets the following criteria: 

• The main cause of damage is alkali-silica reaction. Lithium treatment is unlikely to “cure” any other 

deterioration processes such as freeze-thaw damage, corrosion of embedded steel or even alkalicarbonate reaction. Proper diagnosis involves extracting samples for petrographic analysis and other 

testing in the laboratory. 

• There remains potential for further expansion and damage due to ASR. 

Lithium treatment will not “repair” any damage that has already occurred. A protocol for selecting 

structures that may be suitable for lithium-treatment is available from FHWA (FHWA-RD-04-113). 

Treating structures with lithium is a technology that is still under development and, at this time, 

recommended protocols for selecting the type of treatment (e.g., topical, electrochemical, or vacuum 

impregnation) or methodologies for performing the treatment do not exist. Electrochemical and vacuum 

impregnation require specialized knowledge and equipment, and should be conducted only by an 

experienced contractor. Topical applications are relatively simple to perform, and a few general 

guidelines are provided in table 12. Figure 26 shows examples of LiNO3 precipitation after application. 

(a) 

(b) 

(c) 
33 

Table 12. General guidelines for topical lithium treatment. 

Treatment Procedure 

• Clean surface (e.g., road sweeper) prior to treatment. 

• Do not treat if rain is forecast within 6 hours. 

• Keep single application rate ≤ 0.12 L/m2 (3 gal /1,000 ft2). 

• Minimum two applications. 

• Applications at least 30 minutes apart. 

• Ensure uniform surface coverage and no runoff. 

• If precipitate forms over > 5 percent of surface, re-wet the surface to dissolve the precipitate. If surface 

becomes slippery, applications of water should continue until the surface is safe for vehicular traffic. 

The number of individual treatments that can be applied to a structure will be governed by economics and 

other aspects of the repair strategy. For example, if the structure is being treated prior to the application of a 

concrete or asphalt overlay, there may only be time for a single treatment. For pavements or bridge decks 

that remain exposed after treatment, additional treatments may be considered at appropriate intervals. For 

example, the treatment of State Route 1 in Delaware involved a total of 6 individual treatments over a 3-

year period. 

As the efficacy of lithium treatment has yet to be established, it is recommended that treated structures are 

tested and monitored properly. Some suggestions for monitoring are provided in table 13. Figure 27 

shows crack mapping and length change monitoring. 

The authors are not aware of any studies aimed at evaluating the effect of lithium nitrate on the 

environment. 

Figure 26. Precipitation of LiNO3 from solution (a) on barrier wall and (b) on pavement. 

Table 13. Suggestions for monitoring lithium-treated structures. 

Monitoring Guidelines 

• Take core samples to determine depth of lithium penetration. 

• If possible, maintain untreated control section to compare performance with treated section. 

• Monitor length change of concrete. There are a wide variety of techniques available; one of the 

simplest being to embed stainless steel reference pins and monitor the change in length between the 

pins using a demountable mechanical (DEMEC) strain gauge (see figure 27b). 

• Crack mapping techniques can be used to follow damage accumulation. 

• Consider use of non-destructive techniques such as spectral analysis of surface waves (SASW). 

• There are a number of technologies available for performing condition surveys of roads and bridges. 

Some of these have been employed to follow the progress of damage due to ASR. 

(a) (b) 
34 

Figure 27. Monitoring techniques—(a) crack mapping of a 

barrier wall and (b) measuring length changes on 

concrete pavement with a DEMEC gauge. 

(a) (b)
35 

CHAPTER 6. SUMMARY 

1. Lithium-based admixtures can be used to control expansion due to ASR provided they are used in 

sufficient quantity. The amount of lithium required increases as the amount of alkali in the concrete 

increases. LiNO3 is more efficient (i.e., can be used in lesser amounts) than other lithium compounds. 

2. Some aggregates require higher doses of lithium than others for efficiently controlling deleterious 

expansion due to ASR. It would appear that lithium is more effective with rapidly reactive aggregates 

containing opaline silica, chert, or volcanic glass as the reactive component, and that lithium is 

relatively less efficient (at similar dosages) with more moderately reactive aggregates that contain 

microcrystalline or strained quartz as the reactive phase. 

3. At this time, it is recommended that the lithium dose required to control ASR with a specific 

aggregate be determined by testing using the concrete prism test, with an expansion limit of 

0.04 percent at 2 years. 

4. Laboratory testing has shown that ASR-affected concrete specimens can be treated topically using 

lithium-based compounds to slow down the rate of expansion. 

5. Many structures have been treated with lithium using either a simple topical application or 

electrochemical or vacuum impregnation techniques to increase lithium penetration. 

6. The extent to which lithium penetrates hardened concrete or controls expansion in the field structures 

has not been unequivocally established. 

7. It is recommended that treated structures be monitored and tested to provide information on the 

efficacy of lithium treatment. 

37 

ACKNOWLEDGEMENTS 

A special thank you goes to the FHWA Expert Panel for their assistance reviewing this document and 

providing useful feedback that was integrated into the final printed version of this facts book. 

39 

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Recycled

Recyclable HRDI-11/03-07(3M)E