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Chemistry for Everyone

edited by

George B. Kauffman

California State University Fresno, CA 93740

Cement: Its Chemistry and Properties

Douglas C. MacLaren and Mary Anne White* Department of Chemistry and Institute for Research in Materials, Dalhousie University, Halifax, Nova Scotia B3H 4J3, Canada; *Mary.Anne.White@DAL.ca

One of the most active areas in scientific research is the development of new and exciting materials for a wide vari- ety of applications. In this context, it could be easy to lose sight of the importance of more common materials that are vitally important in many areas of our lives. Cement is one such material, and its rich chemistry links well with a num- ber of concepts in most undergraduate chemistry curricula. This paper addresses several important questions con- cerning cement, including: What is its optimal composition and why? Why do cement truck barrels roll? What are the processes involved in cement setting, and how long does it take? How does cement break down?

A Brief History of Cement

Cements and cement-containing materials comprised some of the first structural materials exploited by humanity (1), as cement’s components are common materials: sand, lime, and water. On a molecular level, cement is a paste of calcium silicate hydrates polymerized into a densely cross- linked matrix (2). Its most important property is called hydraulicity—the ability to set and remain insoluble under water (3, 4). Cement can be used as a mortar to bind large stones or bricks. When sand and stones are added to cement, the aggregate is called concrete. The word cement comes from the Latin phrase, opus caementum, or chip work, in reference to the aggregate often used in applications (3). Cement production dates back to the ancient Romans, who produced mortars using a mixture of lime, volcanic ash, and crushed clay. These cements are referred to as Pozzolanic cements after the Pozzulana region of Italy, which contained Italy’s chief supply of ash (1, 5 ). Pozzolanic cements derive their strength from rich aluminate phases present in the vol- canic ash that promote efficient hydration of the final ce- ment powders (6). Fine grinding and attention to consistency are also fundamental to the success of Roman cement, much of which is still in existence today in structures such as the Pantheon, the Pont du Gard, and the Basilica of Constantinople (2, 5). An example of a structure made with Roman cement is shown in Figure 1. The art of cement production was lost in Europe after the fall of the Roman Empire (2, 5). At that time, the access to volcanic ash was limited and the grinding and heating tech- niques required for cement precursor production were lost. Cements of this period, if still in existence, are inconsistent in composition and are composed almost exclusively of un- reacted starting materials (1, 2, 5). There was no significant breakthrough in the development of cement chemistry until 1756, when Smeaton was commissioned to rebuild the Eddystone lighthouse in Cornwall, England. In contrast to

the methods of his contemporaries, Smeaton found superior results through experimentation by using an impure lime- stone with noticeable clay deposits. This produced extremely strong cement “that would equal the best merchantable Port- land stone in solidity and durability”(5). 1 Another major advance came in the early 19th century when the French engineer Vicat performed the first empiri- cal study on the composition of cements. Although crude and incomplete, it was one of the most comprehensive ex- aminations of cement chemistry for the next 80 years (3, 4,

8–10).

The term Portland cement did not become officially rec- ognized until 1824 when Aspidin filed the first patent for its production (2, 5). Cement compositions at this time were poorly understood but closely guarded secrets. Portland ce- ment was introduced into the United States by Saylor in 1871 (3, 4). By the start of the 20th century, cement manufacture was common but was still regarded as more of an art than a science. Emphasis was placed on bulk manufacture, not qual- ity control or consistency (10, 11). Early in the 20th cen- tury, cement research became more scientific, incorporating the relatively new Gibbs phase rule and Le Châtelier equi- librium principles (3). In 1904 the first set of ASTM stan- dards 2 for cement were presented and in 1906 the geophysical laboratory of the Carnegie Institution began an extensive in- vestigation of cement chemistry. These advances resulted in the development of uniformity in the cement industry, al- lowing a rapid expansion in the application of cement to large construction projects such as skyscrapers, roads, and dams (2, 3, 8, 11).

such as skyscrapers, roads, and dams (2, 3, 8, 11). Figure 1. Roman aqueduct in Segovia,

Figure 1. Roman aqueduct in Segovia, Spain, from the first cen- tury C.E. Courtesy Stephen L. Sass. Reproduced, with permission, from ref 1.

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More recent advances in materials-characterization tech- niques, such as X-ray crystallography, electron microscopy, nuclear magnetic resonance spectroscopy, Mössbauer spec- troscopy, infrared spectroscopy, and thermal analysis, have allowed the systematic examination of cement’s chemistry and the complex processes surrounding its production and hy- dration (2, 12). Scientific research has led to a better under- standing of the properties of cement, cement production, and cement corrosion. In fact, breakthroughs in cement research have provided us with cements of increasing quality and strength. Cement is prepared in a two-step process. The first step is the high-temperature mixing and processing of limestone, sand, and clay starting materials to produce a cement pow- der. The second step involves the hydration, mixing, and set- ting of the cement powder into a final cement product (2, 6, 13). The dry portion of Portland cement is composed of about 63% calcium oxide, 20% silica, 6% alumina, 3% iron(III) oxide, and small amounts of other matter includ- ing possibly impurities (7). Calcium silicates and calcium alu- minates dominate the structure. The cement literature uses abbreviations for the many calcium oxide, silicate, aluminate, and ferrate compounds important to cement. We have used the same abbreviations here and present the correspondence between the chemical formulas and abbreviations in Table 1 (14).

Cement Formation

Preparation of Cement Precursors: Clinkers The raw materials for cement production are blended in the required proportions, ground, and heated to high tem- peratures, usually with rotation. Heating first releases H 2 O and CO 2 and then causes other reactions between the solids, including partial melting. Cooling results in clinkers, a term from the coal industry in the 19th century to describe stony, heavily burnt materials that were left after the burning of coal (7). Ironically, Aspiden and Vicat both dismissed the hard glassy clinker material (which was expensive to grind) as be- ing useless to cement manufacture (8, 11), although we now know that clinkers are essential for good cement production. After heating, cement clinkers are reground for use in the production of cement. Commercial cement manufacture in- corporates a wide variety of minerals, including: calcium ox- ide, silica, alumina, iron oxide, magnesium oxide, titanium dioxide, and many others (5, 14). Of these, three are most important to the final cement product: calcium oxide, silica, and alumina. Consideration of all the possible phases pro- duced by these multicomponent systems is simplified by con- sidering a ternary system of primary importance—the calcium oxide silica alumina system (14). High-quality cement powders require the presence of two major components, tricalcium silicate, ‘C 3 S’, and dicalcium

Table 1. Common Cement Component Names, Compositions, Formulae, and Abbreviations

Component Name

Composition

 

Empirical Formula

Abbreviation

Calcium oxide (lime)

CaO

CaO

C

Silicon dioxide (silica)

SiO 2

SiO 2

S

Aluminum oxide (alumina)

Al 2 O

3

Al 2 O 3

A

Iron(III) oxide

Fe 2 O 3

 

Fe 2 O 3

F

Dicalcium silicate

2CaO SiO

2

Ca 2 SiO

4

C 2 S

Tricalcium silicate

3CaO SiO

2

Ca 3 SiO

5

C 3 S

Tricalcium aluminate

3CaO Al 2 O 3

 

Ca 3 Al 2 O 6

 

C 3 A

Tetracalcium aluminoferrate (Brownmillerite)

4CaO Al 2 O 3 Fe 2 O 3

Ca 4 Al 2 Fe 2 O 10

C 4 AF

Calcium silicate hydrate gel

(CaO) x SiO 2 yH 2 O with x < 1.5 in solid solution with Ca(OH) 2

(variable)

 

CSH

Calcium silicate

(Wollastonite)

CaO SiO 2

 

CaSiO 3

CS

Calcium silicate

(Rankinite)

3CaO 2SiO 2

 

Ca 3 Si 2 O 7

 

C 3 S 2

Calcium aluminum silicate (Gehlenite)

2CaO Al 2 O 3 SiO

2

Ca 2 Al 2 SiO

7

C 2 AS

Aluminium silicate

(Mullite)

3Al 2 O 3 2SiO 2

Al 6 Si 2 O 13

A 3 S 2

Calcium aluminum silicate (Anorthite)

CaO Al 2 O 3 2SiO

2

CaAl 2 Si 2 O

8

CAS 2

Aluminium silicate

2Al 2 O 3 2SiO 2

Al 4 Si 2 O

10

A 2 S 2

Calcium aluminate

CaO Al 2 O 3

 

CaAl 2 O

4

CA

Calcium

dialuminate

CaO 2Al 2 O 3

 

CaAl 4 O

7

CA 2

Dodecacalcium septaluminate

12CaO 7Al 2 O 3

Ca 12 Al

14

O

33

C 12 A 7

Calcium hexaluminate

CaO 6Al 2 O 3

CaAl 12

O

19

CA 6

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For this discussion, the important region of the CaO SiO 2 Al 2 O 3
For this discussion, the important region of the
CaO SiO 2 Al 2 O 3 phase diagram is the ‘C 3 S’ ‘C 2 S’ ‘C 3 A’
phase field, the region close to the CaO vertex in Figure 4. A
three-dimensional view of the ternary phase diagram in this
region is shown in Figure 5. As the temperature of the sys-
Mullite (
‘A S ’
)
3
2
SiO
2
1723
1698
1598
x
x
Gehlenite
Two
AS’)
liquids
1470
(‘C
x
2
silicate, ‘C 2 S’, in the clinkers. These materials react vigorously
with water to produce the cement paste formed in the final
product. Of the two, tricalcium silicate is the more desirable
clinker material because it hydrates and sets much faster than
dicalcium silicate (hours for ‘C 3 S’, days for ‘C 2 S’) (2, 15).
The binary phase diagram of SiO 2 and CaO is shown
in Figure 2 (16, 17). Most important is the 0–30 mass %
SiO 2 region. ‘C 3 S’ is formed at less than 30 mass % SiO 2
but is not stable below about 1250 C or above about 2200
C. In the low end of this temperature range ‘C 3 S’ will form,
but extremely slowly because it involves a reaction between
two solid phases. For example, forming ‘C 3 S’ at temperatures
of 1200–1400 C would require heating for days and is not
economical. At the other end, production from the melt at
2200 C is also impractical because of the very high tempera-
ture.
x
1698
1368
x
1345 x
1470
1436
1170
x
x
-‘CS’
Anorthite
‘CS’
Therefore, the temperature of the ‘C 3 S’ production for
the clinker is lowered by fluxing 3 the reaction mixture with a
third component, alumina (7, 14, 15). The binary phase dia-
gram of CaO and Al 2 O 3 is shown in Figure 3 (16). Com-
parison with the ternary CaO SiO 2 Al 2 O 3 phase diagram (7,
14, 16), Figure 4, shows that the addition of Al 2 O 3 lowers
the preparation temperature of ‘C 3 S’.
1544 x
(‘CAS
2 ’)
x
1512
1460
‘C S
2 1307
3
1464
1310
‘C S
1265 ‘CAS
2
3
2 x
1553 1547
x
1318
‘C S’
1315
2
2130
‘A S
1385
2
2
2050 x
1405
1380
x 1850
2150
-‘C S’
Corundum
‘C S’
2
3
1840
1475
1545
( -Al
O )
2
3
x
‘C AS’
x ‘C S’
2
3
1590 1552
x Lime
1380
1512 1500
x
1455
(CaO)
1350
1335 ‘CA
2
1470
‘CA
1335
6
‘CA’
‘C A’
2500
2570 x
3
x x
x
x
x x
x
x
‘C
S’ + L
1542
1415 1605
1789 1860
3
CaO + L
α-‘C
S’ + L
‘C A’
2
Cristabolite
+ L
CaO
‘C
‘CA’
‘CA
‘CA
Al
O
3
12
A 7
2
6
2
3
‘C
S’ +
3
α-‘C
S’
2000
Two
2
Figure 4. The ternary phase diagram of calcium oxide, silica, and
CaO + ‘C
S’
Liquids
3
‘C
S ’ + L
3
2
α-‘CS’+L
C S +
3
2
Cristabolite + L
α-‘C
S’
alumina. The region nearest the CaO vertex represents the primary
phase field for the formation of tricalcium silicate. Temperatures
are presented in C (13, 16).
2
1500
Tridymite
+ L
‘C
S’ +
3
β-‘C
S’
‘C
S ’+
2
3
2
β
-‘CS’
α
-‘CS’ +
Tridymite
CaO + β-‘C
S’
2
β-‘CS’ +
Tridymite
1000
‘C
3 S’ ‘C
2 S’
‘C
2 ‘CS’
3 S
0 20
40
60 80
100
Tridymite
(CaO)
( SiO
2 )
mass % SiO 2
‘CA
’ +
Al
O
6
2
3
Figure 2. The binary phase diagram of calcium oxide and silicon
dioxide. The region of interest is 0–30 mass % SiO 2 where
tricalcium silicate (‘C 3 S’) is formed (14).
2200
Al
O
‘CA
’+ L
2
3
6
+ L
‘CA
’+ L
CaO + L
2
1800
‘CA’
+ L
‘C
A’ + L
‘C
A
’ + L
3
12
7
‘C
S ’+
3
2
‘CA
α
-‘CS’
2
+
1400
‘CA’ +
‘C
S ’+
‘CA
3
2
6
‘CA
β-‘C
S’
CaO + ‘C
A’
2
‘C
A’
‘C
A
2
3
3
12
7
+ ‘C
A
+ ‘CA’
12
7
1000
‘C
A’
‘C
A
‘CA’
‘CA
‘CA
3
12
7
2
6
0
20
40
60 80
100 Figure 5. Three-dimensional view of the CaO-rich portion of the
(CaO)
( Al
O
3 )
2
mass % Al 2 O 3
Figure 3. The binary phase diagram of calcium oxide and alumina
(Al 2 O 3 ). The temperature of the liquidus of the binary system de-
creases significantly as Al 2 O 3 is added to the mixture (13).
ternary phase diagram of calcium oxide, silica, and alumina em-
phasizing the tricalcium silicate primary phase field. The composi-
tion of the liquid will follow the minimum path along the liquidus,
which deeply slopes into the tricalcium silicate phase field as the
temperature of the system is lowered from 2150 C to 1450 C (5).
Temperature / °C
Temperature / °C
Cristabolite

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tem decreases from about 2100 C, the composition of the liquid goes into the ‘C 3 S’ ‘C 2 S’ ‘C 3 A’ phase field (5). Add- ing 20 mass % alumina to a silica lime system lowers the liquidus into the region of stable ‘C 3 S’ formation, from the reaction of ‘C 2 S’ and CaO in the liquid phase. This, of course, is much faster than the solid–solid reaction (5, 7, 15, 18). Therefore, heating a composition in the ‘C 3 S’ phase field to 1450–1500 C results in a liquid phase that can be quenched to form the final ‘C 3 S’-rich cement clinker. Although nei- ther Smeaton nor the Romans fully realized the chemistry, it was the addition of rich aluminate matter in the form of vol- canic ash or clay impurities that allowed their production of strong cement precursors (5). The total process of cement-clinker formation is sum- marized in Figure 6, which shows the main components as a function of temperature (18). Calcium carbonate (limestone), quartz, clay (primarily Al 2 O 3 ), and water are combined and heated. (Iron oxide, clay, and other minor components are neglected in this discussion.) As the temperature rises, first water is lost, and then above 700 C, the limestone decom- poses forming CaO and carbon dioxide. CaO reacts with silica to form ‘C 2 S’ and with the aluminate phases to form a calcium aluminate phase (an Ettringite phase 4 ), which melts at about 1450 C (18). The formation of this liquid phase is associated with the rapid production of tricalcium silicate. The final mixture at 1500 C is primarily tricalcium silicate with smaller portions of dicalcium silicate, aluminate, and aluminoferrate phases. The minor components present in cement paste (e.g., iron oxide) have only subtle effects on the properties of the final cement properties (5, 14). One of the reasons for using them is that they also help to flux the system to a lower tem-

perature. Table 2 lists a group of multicomponent clinker ma- terials in the ‘C 3 S’ phase field. It is apparent that adding small amounts of other minerals can lower the temperature at which

a liquid phase is formed (5). After quenching, the resulting clinker is milled and ground into a fine powder. At this stage various other mate- rials can be added to the cement powder prior to packaging.

Cement Hydration

Cement hydration is a familiar process. The cement pow- der is mixed with water and then is poured for the desired application. The final cement product generally contains

about 30–40 mass % water after hydration, and this value varies little with the composition of the cement clinker. Al- though it might appear simple, cement hydration consists of

a complex series of chemical reactions, which are still not

completely understood (13). Cement hydration rates can be affected by a variety of factors, including: the phase compo- sition of the clinker, the presence of foreign ions, the spe- cific surface of the mixture, the initial water:cement ratio, the curing temperature, and the presence of additives (13,

18).

The rate of hydration of ‘C 3 S’ in a Portland cement clin- ker is shown in Figure 7. Immediately upon contact with water ‘C 3 S’ undergoes an intense, short-lived reaction, the pre-induction period (I). The rate (dα/dt, where α is the de- gree of hydration or the fraction of cement precursor mate- rial that has been hydrated) is as high as 5 day 1 . This process begins with the dissolution of ‘C 3 S’. Oxygen ions on the sur-

face of the ‘C 3 S’ lattice react with protons in the water and form hydroxide ions, which in turn combine with Ca 2 to form Ca(OH) 2 (13):

O

2 (lattice) + H (aq)

2OH

(aq) + Ca 2 (aq)

2 (lattice) + H (aq) 2OH (aq) + Ca 2 (aq) OH (aq) Ca(OH) 2 (aq)

OH

(aq)

Ca(OH)

2

(aq)

(1)

(2)

2OH (aq) + Ca 2 (aq) OH (aq) Ca(OH) 2 (aq) (1) (2) Figure 6. A

Figure 6. A schematic view of the components of cement-clinker formation, their reactions, and the products formed as the tempera- ture of the mixture is raised. Calcium carbonate decomposes to form calcium oxide and carbon dioxide. Calcium oxide reacts with silica to form dicalcium silicate at temperatures below 1250 C, which converts to tricalcium silicate at temperatures above 1250 C. Formation of a liquid aluminate, Ettringite, phase at about 1450 C facilitates the conversion of dicalcium silicate to tricalcium sili- cate (18).

Table 2. Clinker Components in the ‘C 3 S’ Cement Phase Field and Their Temperatures of Liquid Formation (5)

Components

Temperature of Liquid Formation / C

CaOSiO 2

2065

CaOSiO 2 Al 2 O 3

1455

CaOSiO 2 Al 2 O 3 Na 2 O

1430

CaOSiO 2 Al 2 O 3 MgO 1375

CaOSiO 2 Al 2 O 3 Fe 2 O 3

1340

CaOSiO 2 Al 2 O 3 Na 2 OMgO

1365

CaOSiO 2 Al 2 O 3 Na 2 OFe 2 O 3

1315

CaOSiO 2 Al 2 O 3 MgOFe 2 O 3

1300

CaOSiO 2 Al 2 O 3 Na 2 OMgOFe 2 O 3

1280

At the same time, silicate material from the C 3 Slattice sur- face enters the liquid phase (13):

(3)

SiO

4 4 (lattice) + nH (aq)

phase (13) : (3) SiO 4 4 (lattice) + n H (aq) H SiO n (4-

H SiO

n

(4-n)
4

(aq)

The dissolved components combine to form the calcium silicate hydrate CSHgel, an amorphous two-component solid solution composed of Ca(OH) 2 and a calcium silicate hydrate of low Ca:Si ratio, hydrated as in this example (13, 19, 20):

2(3CaO SiO 2 )(s) + 6H 2 O(l) 3CaO 2SiO 2 3H 2 O(s) + 3Ca(OH) 2 (aq)

(4)

2SiO 2 3 H 2 O (s) + 3Ca(OH) 2 (aq) (4) However, the reaction would

However, the reaction would not likely be of this exact sto- ichiometry. Most cement powders have gypsum (CaSO 4 ) added prior to packaging. Gypsum acts to slow down the pre-induction period to avoid rapid setting of the cement (3, 8). It reacts with tricalcium aluminate (C 3 A) to form various aluminate and sulfoaluminate phases, collectively referred to as Ettringite phases (7, 13, 15, 19). Some examples are:

3CaO Al 2 O 3 (s) + 3CaSO 4 (s) + 32H 2 O(l) 3CaO Al 2 O 3 3CaSO 4 32H 2 O(s)

3CaO Al 2 O 3 3CaSO 4 32H 2 O(s) A (5) 0.25 IV 0.20 III

A

(5)

0.25 IV 0.20 III 0.15 0.10 II I 0.05 0.00 0 5 10 15 'CofFraction
0.25
IV
0.20
III
0.15
0.10
II
I
0.05
0.00
0
5 10
15
'CofFraction
3 S'
Hydrated

B

Hydration Time / h

1.0 0.8 0.6 IV 0.4 0.2 0.0 0 50 100 150 'CofFraction 3 S' Hydrated
1.0
0.8
0.6
IV
0.4
0.2
0.0
0 50
100 150
'CofFraction
3 S'
Hydrated

Hydration Time / days

Figure 7. A graphic representation of the rate of consumption of tricalcium silicate (C 3 S) as a function of hydration time: (A) changes in hydration rates in the first few hours as a result of (I) pre-induc- tion, (II) induction, (III) acceleration, and (IV) deceleration processes. (B) an expanded view showing the length of time required for com- plete cement hydration (13).

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3CaO Al 2 O 3 (s) + 3CaSO 4 (s) + 12H 2 O(s)

Al 2 O 3 (s) + 3CaSO 4 (s) + 12H 2 O(s) 3CaO Al 2

3CaO Al 2 O 3 3CaSO 3 12H 2 O(s)

(6)

C 3 Aand C 4 AFcan also hydrate independently of calcium sulfate:

3CaO Al

(7)

2 O 3 (s) + 6H 2 O(l)

sulfate: 3CaO Al (7) 2 O 3 (s) + 6H 2 O(l) 3CaO Al 2 O

3CaO Al

2

O

3

6H

2 O(s)

4CaO Al 2 O 3 Fe 2 O 3 (s) + 2Ca(OH) 2 (aq) + 10 H 2 O(l) 3CaO Al 2 O 3 6H 2 O(s) + 3CaO Fe 2 O 3 6H 2 O(s)

H 2 O (s) + 3CaO Fe 2 O 3 6 H 2 O (s) (8)

(8)

During the pre-induction period about 525% of the C 3 Aand C 4 AFundergoes hydration, causing a saturation of Ettringite in the solution (13). After a few minutes of hydration an induction period (II in Figure 7) begins where the reaction slows signifi- cantly, dα/dt = 0.01 day 1 . The exact reason for this in- duction period is not known. Several theories have been proposed that involve some sort of mixture saturation from the intense burst of hydration in the pre-induction period (13). One theory states that the CSHlayer quickly cov- ers the surface of dissolving C 3 S, slowing the reaction. As time passes, the CSHbecomes more permeable and the reaction accelerates. Another theory states that the so- lution may become supersaturated with Ca(OH) 2 because the surfaces of Ca(OH) 2 crystal nuclei are poisoned by sili- cate ions. The high concentration of aqueous Ca(OH) 2 limits the rate of dissolution of the silicate species to neg- ligible rates. Eventually the level of aqueous Ca(OH) 2 be- comes too high and calcium hydroxide crystallizes, allowing the hydration reactions to continue. Another

theory speculates that two types of CSHare formed. The rate of first-stage” ‘CSHis dependent on the concentra-

tion of aqueous Ca(OH) 2 . As the concentration of aque- ous Ca(OH) 2 decreases, the production of first-stage

CSHstops, causing induction. Hydration resumes later when the thermodynamic barrier for the nucleation of second-stage” ‘CSHis overcome (13). At any rate, an induction period occurs and varies in

time depending on the type of cement and the desired application, usually lasting several hours. This property of ce- ment hydration is what makes it easy to use as a construc- tion materialit is a semi-solid that can be easily poured into desired shapes for application. Aqueous gels are often semi- solid owing to interaction between water molecules and the

surfaces of the particles. Mixing of the system provides energy

to overcome these interactions and allows the gel to become more fluid. In the case of cement mixtures, constant mixing is required to keep the material in a fluid state (15). This is why wet cement is often stored in large rotating drums until it is poured. During this induction time, so long as it is

continuously mixed, the cement can be held ready for pouring. Following induction, the reaction rate accelerates to ap- proximately dα/dt = 1 day 1 . At this point the hydration pro- cesses are limited by the nucleation and growth of the hydration products. This acceleration stage (III in Figure 7) is characterized by rapid hydration of C 3 S, followed slowly by the hydration of C 2 S(13):

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2(2CaO SiO 2 )(s) + 4H 2 O(aq)

for Everyone 2(2CaO SiO 2 )(s) + 4H 2 O(aq) 3CaO 2SiO 2 3H 2 O(s)

3CaO 2SiO 2 3H 2 O(s) + Ca(OH) 2 (aq)

(9)

During this process, calcium hydroxide reaches its maximum concentration in the solution and then begins to precipitate out as crystalline calcium hydroxide, referred to as Portlandite by cement chemists (7, 13, 15). As the solution becomes con- centrated with solid product the rate of hydration slows and becomes diffusion controlled. The reactions slow to nearly negligible rates but continue for weeks as the CSHgel con- tinues to form.

Calcium Silicate Hydrate (‘CSH’) Gel Formation:

NMR Studies In its final form, cement is a suspension of calcium hy- droxide, Ettringite, and unreacted clinker materials in a solid solution of mineral glue called CSHgel (13, 15). The for- mation of CSHgel is vital to the understanding of cement hydration processes. One of the most powerful tools for studying the reac- tions of cement hydration is solid-state nuclear magnetic reso- nance spectroscopy (2123). Cements are rich in several NMR active isotopes: 1 H, 29 Si, 27 Al, and 23 Na. 29 Si magic angle spinning (MAS) NMR can be used to examine the sili- conoxygen bonding in a cement sample as a function of hy- dration time. This facilitates the understanding of CSHformation (6, 22). Various forms of SiO bonding are shown in Figure 8 (24, 25). The basic tetrahedral unit, (SiO 4 ) 4 , is referred to in this field as a Q 0 unit, where the superscript on Q refers to the number of (SiO 4 ) 4 units attached to the central (SiO 4 ) 4 unit. Q 1 represents a dimer and Q 2 corresponds to silicon atoms within a polymeric chain of (SiO 4 ) 4 units. Q 3 and Q 4 correspond to silicon centers from which increasingly complex degrees of chain branching occur, as shown in Fig- ure 8 (25). 29 Si NMR is especially useful for examining SiO bond- ing because an increase in the number of (SiO 4 ) 4 units bonded to each Si center produces an increase in the average electron density around the central Si atom. This leads to a more negative chemical shift, relative to tetramethylsilane (TMS), for successively increasing n values in Q n (see Figure 8 for typical values). In the pre-induction period of cement hydration, 29 Si MAS NMR shows the presence of monomeric (SiO 4 ) 4 units, Q 0 . 1 H NMR shows that in the first few minutes protona- tion of the (SiO 4 ) 4 units also occurs, an indication that the surface hydroxylation mentioned previously (eqs 13) is prob- ably the first step of the reaction (13, 24). As the reaction continues, signals corresponding to Q 1 units become pre- dominant, indicating a dimerization of (SiO 4 ) 4 units. As time passes the intensities of the Q 1 signals decrease, and signals corresponding to polymerization of the dimers, Q 2 , increase. Crystallographic and NMR studies have shown that the pri- mary species formed are pentamer (Si 5 O 16 ) 12 and octamer (Si 8 O 25 ) 18 units (13). It is interesting to note that Q 3 and Q 4 signals are not observed for silicon in the hydration of Portland cement, in- dicating that polymerization takes place predominantly in a linear fashion without branching. 29 Si MAS NMR spectra

of pure C 2 Sand pure C 3 Sin comparison with a Portland cement (PC) sample that had been hydrated for 28 days are shown in Figure 9. Broad Q 1 and Q 2 signals in the 75 to 88 ppm region of the cement sample show the presence of dimer and linear polymer units. However, the signal corre- sponding to C 2 Sin the hydrated cement sample remains essentially unchanged after 28 days, which shows the slow hydration rates of C 2 Srelative to C 3 S. This is why the pro- duction of C 3 Sin the cement clinker is so vital for effective cement hydration (24). Data from NMR experiments such as these, combined with X-ray crystallography and microscopy, can be used to postulate a general structure for the cement paste. CSHgel has structural features similar to that of two naturally occurring minerals: Tobermorite and Jennite (13, 20). In fact, CSHgel is often referred to as Tobermorite gel in the cement litera- ture. These minerals, shown schematically in Figure 10, are characterized by linear Q 2 type O Si O bonding and are formed as multiple layers separated by layers of Ca 2 or Ca(OH) 2 .

O

O

Q 0 = -70 ppm Q 1 = -80 ppm O O O Si O
Q 0 = -70 ppm
Q 1 = -80 ppm
O
O
O
Si
O
O
Si
O
Si
O
O
O
O
Q 2 = -88 ppm
O
O
O
Si
O
Si
O
O
Si
O
O
O
O
O
O
Si
O
Q 3 = -98 ppm
O
O
O
O
O
Si
O
O
Si
O
Si
O
O
O
O
O
O
Si
O
Q 4 = -110 ppm
O
O
O
O
O
Si
O
O
Si
O
Si
O
O
O O
O
O
Si
O

O

Figure 8. Various arrangements of siliconoxygen bonding are ex- pressed using a superscripted Q, where the superscript refers to the number of (SiO 4 ) 4 units bound to the central (SiO 4 ) 4 unit in the cluster. The average 29 Si NMR signals (relative to TMS) are also shown for each unit. For simplicity, charges are omitted.

Cement Degradation

Crumbling cement, rust stains, and cracks in reinforced concrete are commonly observed. These are a few examples of a serious problem that costs North Americans nearly a bil- lion dollars a yearcement corrosion (26). Corrosion in ce- ment and concrete materials is a twofold problem because the cement material and the steel reinforcement are both sus- ceptible to corrosion, and the weakening of one generally ac- celerates the degradation of the other. Although cement corrosion is complicated, the action of water is a common factor (27). Cement is a porous material containing a dual network of pores. The capillary pore system, with a distribution of di- ameters that range from 50 to 1000 nm, extends throughout the system, acting as channels between various components of the system. The cement gel itself contains a network of gel pores, with diameters on the order of 1050 nm (19, 28).

with diameters on the order of 10 – 50 nm (19, 28). Figure 9. 2 9

Figure 9. 29 Si NMR examination of cement hydration: (A) pure dicalcium silicate, (B) pure tricalcium silicate, (C) Portland cement sample hydrated at 40% by mass of water for 28 days. (A) and (B) show Q 0 29 Si NMR signals (~ 70 ppm). The addition of Q 1 and Q 2 29 Si signals ( 80 to 90 ppm) is seen upon hydration. The slow hydration rate of dicalcium silicate is shown by a large peak of unreacted pure material at about 70 ppm (22).

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Physical properties of cement such as its elastic modu- lus, fire resistance, and durability are directly related to the amount of water present (29). Cement is generally 3040 mass % water, which is present in three forms:

1.

2.

3.

A

B

Chemically bound water: Water of hydration chemi- cally bound to the cement precursor materials in the form of hydrates. This comprises more than 90% of the water in the system.

Physically bound water: Water adsorbed on the sur- faces of the capillaries. This water is most predomi- nant in the small gel pores of the system.

Free water: Water within larger pores that is free to flow in and out of the system. The amount of free wa- ter depends on the pore structure and volume, the rela- tive humidity, and the presence of water in direct contact with the cement surface, such as in water-bear- ing cement pipes and marine structures (19, 27, 30).

− − O OH O OH Si Si O O O O O O Si
O
OH
O
OH
Si
Si
O
O
O
O
O
O
Si
Si
Si
Si
O
O
O
O
O
O
O
O
Ca
Ca
Ca
Ca
Ca
Ca
Ca
Ca
O
O
O
O
O
O
O
O
Si
Si
Si
Si
O
O
O
O
O
O
Si
Si
HO
O
O
HO
8H 2 O
Ca 2 +
8H 2 O
Ca 2 +

Tobermorite

[Ca 4 (Si 3 O 9 H) 2 ]Ca 2 . 8H 2 O

− − O OH O OH Si Si O O O O O O Si
O
OH
O
OH
Si
Si
O
O
O O
O O
Si
Si
Si
Si
O
O
O O
O O
O O
Ca
Ca
Ca
Ca
Ca Ca
Ca
Ca
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
OH
Ca
Ca
Ca
Ca
Ca
Ca
Ca
Ca
O
O
O
O
O
O
O
O
Si
Si
Si
Si
O
O
O
O
O
O
Si
Si
O
OH
O
6H 2 O
Ca 2 +
6H 2 O
OH
Ca 2 +

Jennite

[Ca 8 (Si 3 O 9 H) 2 (OH) 8 ]Ca 2 .6H 2 O

Figure 10. Cement paste is believed to closely resemble the miner- als Tobermorite and Jennite. These minerals are characterized by layers of polymerized silicon oxide cross-linked with calcium oxide or calcium hydroxide (13).

629

Chemistry for Everyone

Corrosion of cement due to water can be discussed in terms of physical and chemical corrosion.

Physical Corrosion of Cement

Physical corrosion of cements is attributable to the physi- cal properties of water, especially its volume change during freezing and its ability to dissolve cement components. The most significant problem concerning degradation of cements is the free water in the system. When cement is hydrated, most of the water used in the process is taken up as hydrates. If too much water is present, the remaining water is able to move through the cement causing various problems. Drying of a cement or concrete paste is an important factor in the physical corrosion of cement. As a cement paste hydrates over a period of several months, its porosity de- creases. Initially, the drying process takes place through cap- illary flow of water in the larger pore system. As porosity decreases, the drying process slows and becomes diffusive (13,

28).

Higher water:cement ratios in the hydration reactions result in larger pore sizes as the cement gel forms, and these pores contain a larger volume of water. Larger pore sizes also lead to faster drying rates, which is a serious problem in ar- eas with low humidity. When cement is exposed to low hu- midity, free water in the large pores (> 50-nm diameter) evaporates quickly. This water removal is not serious if the cement is in contact with water periodically because large pores also quickly fill with water. However, if cement is ex- posed to an extended period of low humidity and high tem- peratures, adsorbed water in the gel pores of the cement will evaporate. This process leads to drying shrinkage. Drying shrinkage is destructive because partially filled gel pores (550-nm diameter) contain water menisci that exert consider- able tensile stress on the walls of the pores. This stress leads to microcracking and eventually weakens the material. The use of aggregates minimizes the effect of drying shrinkage because aggregates increase the elastic modulus and compres- sive strength of the finished product (28). Cements in maritime climates at midlatitudes are par- ticularly susceptible to stress owing to a process known as freezethaw cycling (6, 28, 30). Freezethaw cycles occur in winter when ambient temperatures hover near 0 C. In these climates freezethaw cycles can occur on nearly a daily basis in a typical winter season. Freezethaw cycles are damaging to cements because of the 9% volume increase of water upon freezing (31). When water in the capillary pores freezes, it expands and exerts stress on the pore walls. This leads to microcracks, which can in turn fill with water during the sub- sequent thaw period. Stress exerted in the microcracks dur- ing further freezing will extend the cracks until macroscopic cracking is observed. While freezethaw degradation gener- ally is most serious at the surfaces of the cement structure, extensive cracking will allow the penetration of water deeper into the structure leading to the eventual failure of the sys- tem (6, 30). Crystalline calcium hydroxide makes up about 10% of the volume of most common cements (5, 13, 15), and seri- ous physical corrosion of cements results from the leaching of calcium hydroxide (15). With a room-temperature solu- bility of 1.7 g L (15), calcium hydroxide can be easily dis- solved in free water within cement pastes. This is especially

problematic with pure water, for example, rain water, melted snow, and condensation within pipes (32). Removal of cal- cium hydroxide leaves void volumes within the cement, caus- ing a loss of strength and allowing the deeper penetration of leaching waters (15, 27, 30). Calcium hydroxide leaching can be observed in a spec- tacular effect: opaque white material appears to ooze out of concrete walls or hang in a stalactite formation from con- crete ceilings. In this case, water containing dissolved calcium hydroxide has leached out of the concrete and evaporated, leaving behind a layer of calcium hydroxide that reacts with carbon dioxide to form calcium carbonate (15)

Ca(OH)

(10)

in a process known as efflorescence. 5 Efflorescence is often a sign of water seepage problems in the concrete or cement structure.

Chemical Corrosion of Cement

Water also carries chemical agents into cement pastes that react to destroy various components of the cement. A seri- ous problem is the action of acidic waters from acid precipi- tation, industrial effluent, or the decay of organic matter (6, 15, 32). Acids also lower the pH of the pore water within cement pastes, which otherwise has a pH of 1113 owing to the large amount of calcium hydroxide present (5, 15, 30). Lowering the pH will also increase the rate of the corrosion of the iron in iron-reinforced cement. The conversion of calcium hydroxide to calcium carbon- ate through the action of carbon dioxide in the atmosphere is a problem for all types of cement. This can take place di- rectly on the surface (efflorescence), or as the CO 2 diffuses into the cement (5, 15, 30):

(11)

(12)

2 (s) + CO 2 (g)

15, 30) : ( 1 1 ) ( 1 2 ) 2 (s) + CO 2

CaCO

3 (s)

+ H

2

O(l)

CO

2 (g) + H 2 O(l)

H 2 CO 3 (aq) CaCO 3 (s) + 2H 2 O(l) Ca(HCO ) 2
H
2 CO
3 (aq)
CaCO
3 (s)
+ 2H
2 O(l)
Ca(HCO
)
2 (aq)
3
CO 3 (aq) CaCO 3 (s) + 2H 2 O(l) Ca(HCO ) 2 (aq) 3 2CaCO

2CaCO

3 (s)

+ 2H

2 O(l)

H

2 CO 3 (aq) + Ca(OH) 3 (s)

H

2 CO 3 (aq) + CaCO 3 (s)

3 ) 2 (aq) + Ca(OH) 2 (s)

(13)

(14)

This process, called carbonation, depletes the cement of cal- cium hydroxide and leaves CaCO 3 deposits inside the cement. Another problem, particularly in marine environments, is the action of corrosive sulfates such as ammonium sulfate and magnesium sulfate on cement. These salts react with cal- cium hydroxide to form calcium sulfate (12, 15):

Ca(HCO

(NH 4 ) 2 (SO 4 )(aq) + Ca(OH) 2 (s)

(NH 4 ) 2 (SO 4 )(aq) + Ca(OH) 2 (s) CaSO 4 (s) + 2NH

CaSO 4 (s) + 2NH 3 (aq) + 2H 2 O(l)

(15)

Mg(SO 4 )(aq) + Ca(OH) 2 (s)

+ 2H 2 O(l) (15) Mg(SO 4 )(aq) + Ca(OH) 2 (s) CaSO 4 (s) +

CaSO 4 (s) + Mg(OH) 2 (aq)

(16)

Reactions that deplete cement pastes of calcium hydroxide are particularly destructive because the products are usually materials with significantly larger volumes. For example, the volume of calcium sulfate, 74.2 mL mol, formed in eqs 15

and 16 is more than twice the volume of the calcium hy- droxide removed, 33.2 mL mol (5). This volume change leads to stresses and cracks that further accelerate the pro- cesses discussed above.

Behavior of Water in Cement

Understanding the behavior of water in porous cement

is central to the understanding of cement corrosion. Various

theoretical and statistical-mechanical approaches have been used to try to describe the movement and distribution of water in the pores of cement (27, 3335). However, for many years examination of water in cement pastes was hindered by the absence of viable experimental techniques for observ- ing its presence. Recent developments in nuclear magnetic resonance imaging have provided valuable experimental data

(6).

Magnetic resonance imaging (MRI) is a common tech- nique used in imaging materials, especially biological mate- rials. MRI is typically used to measure the spatial distribution of water in a material (21, 36, 37). It is based on the prin- ciple that the nuclear magnetic resonance frequency of a nucleus, such as 1 H, in a magnetic field gradient is propor- tional to its spatial position in the magnetic field gradient

ν

=

γ

(1

α

)(

B

0

+

Gz (

z

))

2 z

=

ν

0

+

kz

(17)

where ν is the observed NMR frequency, γ is the magneto- gyric ratio of the nucleus, α is the chemical shielding of the nucleus, B 0 is the magnetic field associated with a static field measurement, G z (z) is the magnetic field gradient (dB/dz), ν 0 is the NMR frequency in the static field (B 0 ), k is a scal- ing constant for the signal, and z is the position of the nucleus in the field (21). Figure 11(A) shows two nuclei in a mag- netic field gradient G z = dB z dz. In Figure 11(B) an inter- ferogram is produced when a 90 radio frequency pulse is applied. Fourier transformation of the signal in (B) produces two peaks separated by ∆ν = γG z dz , shown in Figure 11(C). The width of the individual peaks is proportional to (πT 2 ) 1 , which gives a resolution, dz,

dz

G

z

1

π

T

2

(18)

where T 2 is the spinspin relaxation time of the nucleus (22, 23). The shift in the NMR frequency of a nucleus is propor- tional to the position of the nucleus in the sample, while the signal intensity corresponds to the amount of that nucleus present. Water in gel pores is tightly confined and is susceptible to the effects of various paramagnetic species in the sample including iron and aluminum (6). These factors combine to make the spinspin relaxation times short, dramatically de- creasing the effective resolution (6, 37). For example, using conventional MRI techniques, a field gradient of about 10

T m is necessary for a resolution of 10 mm in a cement paste

(6). This is much greater than the normal field gradients used in MRI, but is on the order of the stray fields associated with the superconducting magnets of high-resolution NMR in- struments. 6 In 1988, a MRI technique known as stray field imaging (STRAFI) was developed (38). In this experiment a

Chemistry for Everyone

sample is moved through a stationary field gradient of a su- perconducting magnet. STRAFI experiments have allowed the detailed examination of water in solid cement samples

(35).

Imaging techniques such as STRAFI are useful for ex- amining the effectiveness of waterproof coatings. One of the easiest ways to prevent cement corrosion is to prohibit the movement of water in and out of the material by establish- ing a waterproof barrier on the exposed surfaces (6, 30). A wide variety of surface coatings are used in the waterproof- ing of cements; for example, a common class of waterproof- ing agents is silanes (22). The rate and depth of surface water absorption into the cement surface can be compared for a series of coatings and treatments. The depth and durability of the surface treatment can also be examined for various ap- plications (6, 22). A STRAFI image of a Portland cement sample coated with methyltrialkoxysilane is shown in Figure 12. The images show penetration of the silane coating as it is repeatedly applied to the surface. After 24 hours the coat- ing penetrates to a depth of about 2.5 mm. A comparison of the water penetration in treated and untreated Portland ce- ment is shown in Figure 13. The treated sample shows water on the surface (intense surface signal) and the silane coating

A dB z G z = dz z dz B
A
dB z
G z =
dz
z
dz
B
t C 1 width ~ πT 2 0 ν ∆ν = γ G z dz
t
C
1
width ~ πT 2
0
ν
∆ν = γ G z dz
M
90 o pulse

Figure 11. Schematic of conventional MRI experiment. (A) Two nu- clei situated in a magnetic field gradient, G z , are separated by dz. (B) A 90 RF pulse is used to obtain an interferogram of the nuclei in the sample. (C) Fourier transformation of (B) gives two peaks separated by a frequency proportional to their separation in the sample (21).

631

Chemistry for Everyone

penetrating to about 23 mm. The untreated sample shows

ramped magnetic field gradient that is much easier to con-

(40):

little surface water but significant water penetration to 89

trol than the oscillating gradients used in conventional SPI

mm

after 24 hours (22). While STRAFI is a powerful technique for examining

(28, 29, 40). While conventional MRI, including STRAFI, measures all resonance frequencies simultaneously and

the water content of a cement paste, it is limited to relatively small sample sizes (2-cm diameter) because of magnetic

deconvolutes using a Fourier transform, SPRITE uses a pro- cess called position encoding where only one frequency, cor-

field

constraints. Studies of concrete are limited to those with

responding to a particular encoding time, t p , is measured. The

very

small aggregates such as fine gravels and sands (28).

spatial position, z, of the analyte nucleus is encoded in re-

Another way of alleviating the problem of short T 2 while avoiding enormous field gradients is through the use of single

ciprocal space such that the signal, S(k), is proportional to k

point imaging (SPI; ref 21, 39). SPI is an MRI technique

that uses an oscillating field gradient in which signals are mea-

sured at a constant encoding time, t p , following a radio fre-

quency (RF) pulse. A recent variation on SPI developed by Balcom et al. (40) has proven useful in the examination of water in cement samples. This technique, called SPRITE (single point ramped imaging with T 1 enhancement), uses a

point ramped imaging with T 1 enhancement), uses a Figure 12. One-dimensional STRAFI image of a

Figure 12. One-dimensional STRAFI image of a Portland cement sample coated with methyltrialkoxysilane. The coating is applied every 30 minutes during the analysis. The signals show the ingress of the polymer coating into the cement to a depth of about 2.5 mm after 24 hours (22).

the cement to a depth of about 2.5 mm after 24 hours (22). Figure 13. One-dimensional

Figure 13. One-dimensional STRAFI of Portland cement samples in contact with water for 24 hours. Sample A was treated with methyl- trialkoxysilane. Sample B was untreated and shows deep penetra- tion of water into the cement surface (22).

k

==

1

2πγG

z,max p

t

(19)

With a constant encoding time, k is inversely proportional to the maximum field gradient, G z,max . A schematic SPRITE imaging sequence and resulting image are shown in Figure 14. Following an RF pulse a single frequency is measured after a desired encoding time, t p . Next, the field gradient is ramped and the sequence is repeated. Each sequence gives the nuclear density at a particular point in the sample. Through repetition of the sequences at varying G z,max an im-

A RF RF RF RF RF t p t p t p t p t
A
RF
RF
RF
RF
RF
t p
t p
t p
t p
t p
z 1
z 2
z 3
z 4
z 5
Time
B
G
z
Time
C
z 1 z 2 z 3 z 4 z 5 Signal
z 1
z 2
z 3
z 4
z 5
Signal

z

Figure 14. Schematic of the SPRITE imaging sequence: (A) the sig- nal is measured after a time, t p , has elapsed from an RF pulse; (B) the ramping of the field gradient that accompanies the measure- ment of signal; (C) each successive sequence will show the density of the analyte nucleus at a particular position, dictated by the gra- dient used during that sequence (40).

Signal at z 1

age is produced. SPRITE and other SPI techniques take longer than conventional MRI techniques, but are less sus- ceptible to noise and magnetic inhomogeneities in the sample because only one frequency is analyzed at a time (21, 28, 29, 39, 40). SPRITE is also useful because signal resolution de- pends only on the size of G z,max and the ramping sequence used, not on the T 2 of the analyte nucleus (40). SPRITE can be used to examine the behavior of pro- tons in a concrete sample as a function of physical param- eters such as temperature. From eq 19 it can be shown that keeping G z,max and t p constant results in repeated measure- ments of protons in a defined position, z. The intensity of the signal can be observed as a function of temperature, shown in Figure 15. Through an adjustment of parameters such as G z,max , RF flip angles, and t p , the experiment can be tailored to be sensitive to a nucleus of defined T 2 . This al- lows the ability to differentiate between the protons of free liquid water (T 2 200 µs) and ice (T 2 10 µs) in a cement sample. By following the appearance and disappearance of free water at various regions of a cement sample in the freezethaw cycle, characteristics of the material can be examined (29, 40). In cement gels, MRI has shown that water freezes in two steps. The first step occurs between 0 and 2 C, where free bulk water and water in the capillary pores freeze (29). This freezing-point variation is due to a freezing-point depression phenomenon caused by vapor pressure lowering in the cap- illaries and related to the pore size of the capillaries by the Kelvin equation (29),

T

=

2

γ MT

0

r

ρ ∆

H

(20)

where T is the freezing-point depression, γ is the surface tension of the liquid, M is the molecular weight, T 0 is the normal freezing point, r is the pore radius, ρ is the density of the absorbate, and H is the molar enthalpy of fusion (41). Information on the freezing-point depression of water in a cement sample is valuable for the determination of pore dis- tributions in these materials. As ice forms in a cement sample the internal pressure of the closed system increases owing to the volume expansion of water. The resulting pressure increase once freezing begins in the gel pores forces the migration of water from the gel pores to larger pore regions where ice will form immediately. This results in a secondary freezing point at about 40 to 45 C (29). Figure 16 shows a measurement of these two freez- ing phenomena for a cement sample measured using an SPI technique (29), in which the evaporable water content of a concrete sample is measured as a function of temperature as the sample is slowly cooled (2 K hr). The first freezing event is seen between 0 and 1.6 C. As the sample temperature is lowered the amount of evaporable water decreases slowly at freezing temperatures corresponding to the respective pore sizes present. The large change at 0 to 1.6 C shows that the majority of evaporable water present is contained in large pores. The second major freezing event, associated with the desorption and freezing of water from the gel pores, is shown at 45 C. Other studies have shown that evaporable water can still exist in cement samples at temperatures as low as 90 C (29).

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Corrosion of Steel Reinforcement

Reinforced concrete is often used in bridge decks, roads, and sidewalks. One of the most serious threats to concrete in cold climates is the use of deicing salts in the winter to ensure safe conditions for motor vehicles and pedestrians

A

B

G z

C

RF

RF

RF

RF

RF

t p

vehicles and pedestrians A B G z C RF RF RF RF RF t p T

T 1

t p

and pedestrians A B G z C RF RF RF RF RF t p T 1

T 2

t p

A B G z C RF RF RF RF RF t p T 1 t p

T 3

t p

B G z C RF RF RF RF RF t p T 1 t p T

T 4

t p

RF RF RF RF RF t p T 1 t p T 2 t p T

T 5

Time

Time

t p T 1 t p T 2 t p T 3 t p T 4
T 1 T 2 T 3 T 4 T 5 Temperature Figure 15. Schematic of
T 1
T 2
T 3
T 4
T 5
Temperature
Figure 15. Schematic of SPRITE used for temperature dependent
measurements. (A) The normal SPRITE sequence from Figure 14 is
used again, but (B) the field gradient is kept constant. (C) This al-
lows for a repeated measurement of the signal density for analyte
nuclei at a particular position in the sample as a function of tem-
perature (40).
1.0
0.8
0.6
0.4
center
- drying face
-
0.2
0.0
-50
-40
-30
-20
-10
0 10
u)(arb.Magnetization

T / °C

Figure 16. Magnetization signal for evaporable water in a sample of Portland cement mixed with 14-mm diameter graded quartz ag- gregate measured using SPRITE as a function of temperature. Freez- ing of water is associated with a decrease in signal intensity (29).

633

Chemistry for Everyone

(6, 15, 26, 42, 43). Chloride ions, when transported by wa- ter, attack steel reinforcement (rebar) of these structures caus- ing them to weaken from within. High pH is important for minimizing the rate of steel rebar corrosion because it allows the formation of a passive oxide layer on the surface of the metal (6, 30). Low pH aqueous states caused by the leaching of calcium hydroxide from the cement, combined with chlo- ride ion ingress, causes extensive rebar corrosion in short pe- riods of time. Chloride ions set up redox reactions along the rebar, as shown by the following equations (26):

O

2 (g)

+

2Fe(s)

2H 2 O(l) +

4e

2Fe

2 (aq) + 4Cl (aq)

2FeCl

2 (aq) + 4OH (aq)

(aq) + 4Cl (aq) 2FeCl 2 (aq) + 4OH (aq) 2Fe 2 (aq) + 4e 4OH

(aq) + 4Cl (aq) 2FeCl 2 (aq) + 4OH (aq) 2Fe 2 (aq) + 4e 4OH

(aq) + 4Cl (aq) 2FeCl 2 (aq) + 4OH (aq) 2Fe 2 (aq) + 4e 4OH

(aq) + 4Cl (aq) 2FeCl 2 (aq) + 4OH (aq) 2Fe 2 (aq) + 4e 4OH

2Fe 2 (aq) + 4e

4OH

(aq)

2FeCl 2 (aq)

2Fe(OH) 2 + 4Cl (aq)

2Fe(OH)

2

+ 1 / 2 O 2 (g)

2H2 3 + Fe O (s)

2

3

+

Fe

O

(s)

2

O(l)

2Fe(s) +

3 / 2 O 2 (g)

Fe2Fe(s) + 3 / 2 O 2 (g) 2 O 3 (s)

2

O

3

(s)

(21)

(22)

(23)

(24)

(25)

(26)

Chemical attack of chloride ions is destructive because it not only reduces the amount of hydroxide ion and iron, but it also acts in a catalytic manner. Transport of chloride ions throughout the system is also increased as cracks form as a result of the other decay processes. Furthermore, patching can create localized corrosion cells between the rebar in the

steel rebar DC power supply Cl + H O H + OH 2 O H
steel
rebar
DC power supply
Cl
+
H
O H
+ OH
2
O
H
+ OH
Cl
H 2
electrolyte gel

concrete sample

Figure 17. Schematic of electrochemical chloride extraction (ECE). A dc voltage of 1030 000 V is applied between the steel rebar (anode) and an electrolyte gel (cathode) on the surface of the con- crete. Hydrolysis of water takes place at the rebar and chloride ions are repelled from the concrete into the electrolyte gel (43).

existing chloride-contaminated concrete and in the new chloride-free patch, accelerating the concrete corrosion (43). Waterproof coatings will stop the introduction of new chloride ions, but will not remove the chloride ions already

present in the system. Coatings also become ineffective if the concrete surface is cracked or damaged (26, 43). A particularly interesting approach to treating chloride ion ingress is electrochemical chloride extraction (ECE), in which chloride ions are effectively pulled from the concrete.

A dc circuit, shown in Figure 17, is set up using rebar as the

anode and an electrolyte gel packed on the concrete surface

as the cathode. When a dc potential of 10,00030,000 V is

applied, water hydrolyzes at the anode, replenishing the hy- droxide content of the system. The negatively charged steel rebar repels chloride ions to the surface of the concrete and into the electrolyte gel. After 48 weeks the process is com- plete, at a fraction of the cost of replacement (43). After seal- ing with a waterproof coating, the concrete is effectively protected against further rebar corrosion. Structures with extremely problematic chloride ion prob- lems, such as ocean piers, can be cathodically protected by constant maintenance of the rebar at a negative potential of about 10,00030,000 V (43).

Concluding Remarks

The study of cement offers an opportunity to explore the chemistry of earth materials, their preparation, and re- sulting properties. Furthermore, examination of cement deg- radation comprises an extensive part of modern cement chemistry. Recent innovations in research techniques have made the study of cement preparation and degradation be- havior more accessible. Improvement of corrosion resistance in cement and concrete structures would significantly lengthen the lifetime of applications using these materials, potentially saving billions of dollars worldwide.

Acknowledgments

This work was supported by the Natural Sciences and Engineering Research Council of Canada and the Izaak Walton Killam Trusts.

Notes

1. Portland stone, a gray stone quarried from the Dorset

region of England, was a commonly used building material in

Europe in the 16th19th centuries (2, 7).

2. Founded in 1898, ASTM International is a nonprofit orga-

nization that provides a global forum for the development and pub- lication of voluntary consensus standards for materials, products,

systems, and services. See http://www.astm.org (accessed Mar 2003).

3. Fluxing is a process that promotes fusing of materials, in

this case by lowering of the melting point of a mixture by adding another component (7).

4. Ettringite is a collective term referring to the various alu-

minate and sulfoaluminate phases present in the clinker material.

5. Efflorescence is the blossomingto a powdery substance

on exposure to air.

6. The stray field near a 9.4 T (400 MHz) NMR magnet is

on the order of 60 T m.

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