Professional Documents
Culture Documents
edited by
Products of Chemistry
George B. Kauffman
California State University
Fresno, CA 93740
Figure 1. Roman aqueduct in Segovia, Spain, from the first century C.E. Courtesy Stephen L. Sass. Reproduced, with permission,
from ref 1.
623
More recent advances in materials-characterization techniques, such as X-ray crystallography, electron microscopy,
nuclear magnetic resonance spectroscopy, Mssbauer spectroscopy, infrared spectroscopy, and thermal analysis, have
allowed the systematic examination of cements chemistry and
the complex processes surrounding its production and hydration (2, 12). Scientific research has led to a better understanding 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 powder. The second step involves the hydration, mixing, and setting 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 including possibly impurities (7). Calcium silicates and calcium aluminates 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
C ompos it ion
Empirical Formula
C aO
C aO
SiO2
SiO2
A l 2O 3
A l 2O 3
Iron(III) ox ide
F e 2O 3
F e 2O 3
Dicalcium s ilicat e
2C aOSiO2
C a2SiO4
C 2 S
Tricalcium s ilicat e
3C aOSiO2
C a3SiO5
C 3 S
Tricalcium aluminat e
3 C a O A l 2 O 3
C a3A l 2O 6
C 3 A
C a4A l 2F e 2O 10
C 4 A F
(v ariable )
C S H
C aOSiO2
C aSiO3
C S
3C aO2SiO2
C a3Si2O7
C 3 S 2
2C aOA l2O3SiO2
C a2A l2SiO7
C 2 A S
3A l2O32SiO2
A l6Si2O13
A 3 S 2
C aOA l2O32SiO2
C aA l2Si2O8
C A S 2
A luminium s ilicat e
2A l2O32SiO2
A l4Si2O10
A 2 S 2
C alcium aluminat e
C aOA l2O3
C aA l 2O 4
C A
C alcium dialuminat e
C aO2A l2O3
C aA l 4O 7
C A 2
1 2 C a O 7 A l 2 O 3
C a12A l 14O 33
C 1 2 A 7
C alcium he x aluminat e
C aO6A l2O3
C aA l 12O 19
C A 6
624
1500
Cristabolite + L
x
A2S2
bo
1385
1405
1380
Corundum
1475
x 1850
1840
(-Al2O3)
(CaO)
C A
x15423
C3A
CA
1415 1605
C12A7
CA
x
CA6
1789
1860
CA2
CA6 Al2O3
Tridymite + L
C 3S2+
-CS
CaO + -C 2S
C 3S2+
C 3S +
-C 2S
C 3S2+
-CS -CS + Tridymite
-CS + Tridymite
1000
C 3S C 2S C 3S2
0
1553 1547
1590
1552
1380
1512 1500
1455
1350
CA2
1335
1470 1335
Lime
1512
CAS2
1265
C2AS
C3S
Two
Liquids
-CS+L
C 3S 2+
-C 2S
-C 2S
Temperature / C
C 3S +
-C 2S
C 3S2 + L
CaO + C 3S
CaO
Cristabolite + L
(CAS2)
1545
)
S2
2000
-C2 S + L
-C2S
C3S
1170
1318
1315
1345
(A 3
2570
C 3S + L
2130
2050
2150
ite
llite
Mu
C3S2
C2S
1368
Anorthite
1544
1460
C3S2 1307
1464
1310
2500
CaO + L
-CS
CS
x
1470
ym
d
Tri
1470
1436
Cr
ista
x
1698
1598
lite
Two x
liquids
e
nit
hle S)
Ge(C 2A
20
CS
60
40
100
80
(CaO)
(SiO2 )
mass % SiO2
Figure 2. The binary phase diagram of calcium oxide and silicon
dioxide. The region of interest is 030 mass % SiO2 where
tricalcium silicate (C3S) is formed (14).
CA 6+ L
CA 2+ L
CaO + L
1800
Al 2O3
+L
CA + L
C 3A + L
C 12A 7 + L
1400
CaO + C 3A
C 3A
C12 A 7
+ C 12A 7 + CA
CA +
CA 2
CA 2
+
CA 6
CA 6 + Al 2O3
Temperature / C
2200
1000
0
20
C3 A
40
C12 A 7
CA
60
(CaO)
CA 2
80
CA 6
100
(Al 2O3)
mass % Al2O3
625
Cement Hydration
Cement hydration is a familiar process. The cement powder is mixed with water and then is poured for the desired
application. The final cement product generally contains
about 3040 mass % water after hydration, and this value
varies little with the composition of the cement clinker. Although 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 composition of the clinker, the presence of foreign ions, the specific surface of the mixture, the initial water:cement ratio,
the curing temperature, and the presence of additives (13,
18).
The rate of hydration of C3S in a Portland cement clinker is shown in Figure 7. Immediately upon contact with
water C3S undergoes an intense, short-lived reaction, the
pre-induction period (I). The rate (d/dt, where is the degree of hydration or the fraction of cement precursor material that has been hydrated) is as high as 5 day1. This process
begins with the dissolution of C3S. Oxygen ions on the sur626
face of the C3S lattice react with protons in the water and
form hydroxide ions, which in turn combine with Ca2 to
form Ca(OH)2 (13):
O2(lattice) + H(aq)
2OH (aq) + Ca2(aq)
OH(aq)
(1)
Ca(OH)2(aq)
(2)
Temperature of
Liquid Formation /C
CaOSiO2
2065
CaOSiO2Al2O3
1455
CaOSiO2Al2O3Na2O
1430
CaOSiO2Al2O3MgO
1375
CaOSiO2Al2O3Fe2O3
1340
CaOSiO2Al2O3Na2OMgO
1365
CaOSiO2Al2O3Na2OFe2O3
1315
CaOSiO2Al2O3MgOFe2O3
1300
CaOSiO2Al2O3Na2OMgOFe2O3
1280
At the same time, silicate material from the C3S lattice surface enters the liquid phase (13):
SiO44(lattice) + n H(aq)
HnSiO4(4-n)(aq) (3)
(4)
(5)
Fraction of 'C3S'
Hydrated
0.25
IV
0.20
III
0.15
0.10
II
I
0.05
0.00
0
10
15
Hydration Time / h
B
Fraction of 'C3S'
Hydrated
1.0
0.8
IV
0.6
0.4
0.2
0.0
0
50
100
150
(6)
(8)
627
2(2CaOSiO2)(s) + 4H2O(aq)
3CaO2SiO23H2O(s) + Ca(OH)2(aq)
(9)
O
O
Si
Si
Si
O
O
Si
O
O
Si
Q2 = -88 ppm
Si
Q1 = -80 ppm
O
O
Si
O
O
Si
O
O
Si
Q3 = -98 ppm
O
Si
O
O
O
Si
O
O
Si
O
O
Si
O
O
Si
Si
O
O
Q4 = -110 ppm
O
Figure 8. Various arrangements of siliconoxygen bonding are expressed using a superscripted Q, where the superscript refers to
the number of (SiO4)4 units bound to the central (SiO4)4 unit in
the cluster. The average 29Si 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 billion dollars a yearcement corrosion (26). Corrosion in cement and concrete materials is a twofold problem because
the cement material and the steel reinforcement are both susceptible to corrosion, and the weakening of one generally accelerates 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 diameters 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).
Physical properties of cement such as its elastic modulus, 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. Chemically bound water: Water of hydration chemically bound to the cement precursor materials in the
form of hydrates. This comprises more than 90% of
the water in the system.
2. Physically bound water: Water adsorbed on the surfaces of the capillaries. This water is most predominant in the small gel pores of the system.
3. Free water: Water within larger pores that is free to
flow in and out of the system. The amount of free water depends on the pore structure and volume, the relative humidity, and the presence of water in direct
contact with the cement surface, such as in water-bearing cement pipes and marine structures (19, 27, 30).
A
OH
Si
O
Si
O
Si
Si
Si
Ca
Ca
Ca
Ca
Ca
Ca
Ca
Ca
O
Si
Si
Si
O
O
Si
Si
Si
HO
Ca2+
HO
8 H2O
OH
Si
Ca2+
8 H2O
Tobermorite
[Ca4(Si3O9H)2]Ca2 . 8H2O
B
OH
O
O
Si
O
O
Si
O
Si
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
Ca
O
Si
Si
O
Si
O
Si
O
Si
O
O
Si
Si
6 H2O
OH
Si
Si
OH
Ca2+
O
6 H2O
OH
Ca2+
Jennite
[Ca8(Si3O9H)2(OH)8]Ca2 .6H2O
Figure 10. Cement paste is believed to closely resemble the minerals Tobermorite and Jennite. These minerals are characterized by
layers of polymerized silicon oxide cross-linked with calcium oxide
or calcium hydroxide (13).
629
CaCO3(s) + H2O(l)
(10)
H2CO3(aq) + CaCO3(s)
Ca(HCO3)2(aq) + Ca(OH)2(s)
Ca(HCO3)2(aq)
(13)
This process, called carbonation, depletes the cement of calcium hydroxide and leaves CaCO3 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 calcium hydroxide to form calcium sulfate (12, 15):
(NH4)2(SO4)(aq) + Ca(OH)2(s)
CaSO4(s) + 2NH3(aq) + 2H2O(l)
(15)
Mg(SO4)(aq) + Ca(OH)2(s)
CaSO4(s) + Mg(OH)2(aq)
(16)
and 16 is more than twice the volume of the calcium hydroxide removed, 33.2 mLmol (5). This volume change
leads to stresses and cracks that further accelerate the processes discussed above.
where is the observed NMR frequency, is the magnetogyric ratio of the nucleus, is the chemical shielding of the
nucleus, B0 is the magnetic field associated with a static field
measurement, Gz(z) is the magnetic field gradient (dB/dz),
0 is the NMR frequency in the static field (B0), k is a scaling constant for the signal, and z is the position of the nucleus
in the field (21). Figure 11(A) shows two nuclei in a magnetic field gradient Gz = dBzdz. In Figure 11(B) an interferogram is produced when a 90 radio frequency pulse is
applied. Fourier transformation of the signal in (B) produces
two peaks separated by = Gzdz , shown in Figure 11(C).
The width of the individual peaks is proportional to (T2)1,
which gives a resolution, dz,
dz
1
Gz T2
Gz =
dBz
dz
z
dz
(1 )( B0 + Gz ( z ))
= 0 + kz
2z
90o pulse
sample is moved through a stationary field gradient of a superconducting magnet. STRAFI experiments have allowed
the detailed examination of water in solid cement samples
(35).
Imaging techniques such as STRAFI are useful for examining 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 establishing a waterproof barrier on the exposed surfaces (6, 30). A
wide variety of surface coatings are used in the waterproofing of cements; for example, a common class of waterproofing 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 applications (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 coating penetrates to a depth of about 2.5 mm. A comparison of
the water penetration in treated and untreated Portland cement is shown in Figure 13. The treated sample shows water
on the surface (intense surface signal) and the silane coating
(18)
width ~
1
T2
= Gz dz
Figure 11. Schematic of conventional MRI experiment. (A) Two nuclei situated in a magnetic field gradient, Gz, 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
ramped magnetic field gradient that is much easier to control than the oscillating gradients used in conventional SPI
(28, 29, 40). While conventional MRI, including STRAFI,
measures all resonance frequencies simultaneously and
deconvolutes using a Fourier transform, SPRITE uses a process called position encoding where only one frequency, corresponding to a particular encoding time, tp, is measured. The
spatial position, z, of the analyte nucleus is encoded in reciprocal space such that the signal, S(k), is proportional to k
(40):
1
2 Gz,max tp
k =
(19)
A
RF
RF
tp
z1
RF
tp
RF
tp
z2
RF
tp
z3
z4
tp
z5
Time
B
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).
Gz
Time
Signal
z1
z2
z3
z4
z5
632
Figure 14. Schematic of the SPRITE imaging sequence: (A) the signal is measured after a time, tp, has elapsed from an RF pulse; (B)
the ramping of the field gradient that accompanies the measurement of signal; (C) each successive sequence will show the density
of the analyte nucleus at a particular position, dictated by the gradient used during that sequence (40).
2 MT0
r H
A
RF
RF
tp
T1
RF
tp
RF
tp
T2
RF
tp
T3
tp
T4
T5
Time
Gz
Time
(20)
T1
T2
T3
T4
T5
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 allows for a repeated measurement of the signal density for analyte
nuclei at a particular position in the sample as a function of temperature (40).
1.0
Magnetization (arb. u)
T =
Signal
at z 1
0.8
0.6
0.4
- center
- drying face
0.2
0.0
-50
-40
-30
-20
-10
10
T / C
Figure 16. Magnetization signal for evaporable water in a sample
of Portland cement mixed with 14-mm diameter graded quartz aggregate measured using SPRITE as a function of temperature. Freezing of water is associated with a decrease in signal intensity (29).
633
(6, 15, 26, 42, 43). Chloride ions, when transported by water, attack steel reinforcement (rebar) of these structures causing 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 chloride ion ingress, causes extensive rebar corrosion in short periods of time. Chloride ions set up redox reactions along the
rebar, as shown by the following equations (26):
2 Fe(s)
O2(g) + 2 H2O(l) + 4e
2 Fe2(aq) + 4 Cl(aq)
2 FeCl2(aq) + 4 OH (aq)
2 Fe(OH)2 +
2 Fe(s) +
/2 O2(g)
/2O2(g)
2 Fe2(aq) + 4 e
(21)
4 OH(aq)
(22)
2 FeCl2 (aq)
(23)
2 Fe(OH)2 + 4 Cl (aq)
(24)
Fe2O3(s) + 2 H2O(l)
(25)
Fe2O3(s)
(26)
DC power supply
steel rebar
Cl
H2O
H + OH
H2O
H + OH
Cl
Notes
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 concrete. Hydrolysis of water takes place at the rebar and chloride
ions are repelled from the concrete into the electrolyte gel (43).
634
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