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Fundamental Investigation of the Chemical and Mechanical Properties of


High-Temperature-Cured Oilwell Cements
Jeffrey J. Thomas, Simon James, J. Alberto Ortega, Simone Musso, Francois Auzerais, Schlumberger
Konrad J. Krakowiak, Ange-Therese Akono, Franz-Josef Ulm, Roland J.M. Pellenq, Department of Civil and
Environmental Engineering, Massachusetts Institute of Technology
Copyright 2012, Offshore Technology Conference
This paper was prepared for presentation at the Offshore Technology Conference held in Houston, Texas, USA, 30 April3 May 2012.
This paper was selected for presentation by an OTC program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Offshore Technology Conference and are subject to correction by the author(s). The material does not necessarily reflect any position of the Offshore Technology Conference, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Offshore Technology Conference is prohibited. Permission to
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Abstract
With the search for hydrocarbons moving to more extreme environments, including deepwater, one of the challenges
associated with cementing is ensuring the long-term integrity and mechanical properties of the cement at high temperatures
(HT). To avoid strength retrogression at temperatures above about 110C, silica is added to the cement. This makes the
hydration process (setting and curing of the cement) more complex, as initially formed hydration products are replaced by
more stable phases over time. To study the nanostructure and mechanical properties of HT-cured cement, we applied a
variety of techniques including small-angle neutron scattering (SANS), transmission electron microscopy (TEM),
nanoindentation, and micro-scratch testing on small cement samples and investigated their structure and properties under a
variety of conditions. We observed that, at HT, there is a general coarsening of the nanometer-scale structure of the set
cement paste over time, with associated degradation of the properties. We show that the rate of coarsening depends strongly
on the initial curing conditions, providing possible strategies for improving the properties and performance of HT-cured
cement. The findings may have particular application to geothermal wells and steam injection wells.
1. Introduction
Oilwell cementing, in which the annular space between the drilled formation rock and the steel casing pipe is filled with a
cement slurry, presents significant challenges due to the wide range of environmental conditions encountered. In particular,
the high temperatures and pressures experienced in deep wells generate significant changes in the chemical nature and
morphology of the hydration products (Taylor, 1997). At near-ambient conditions, the main hydration product of Portland
cement is calcium-silicate-hydrate (C-S-H) gel with a Ca/Si molar ratio (C/S) of about 1.7 (Richardson and Groves, 1992,
Taylor, 1997). The C-S-H phase has an amorphous or poorly crystalline nature and a high specific surface area, and is
responsible for the generally excellent engineering properties of cement and concrete cured under normal conditions. As the
curing temperature increases to about 110!C, the C-S-H phase becomes increasingly crystalline but retains its general
structure and properties. Above 110!C, a different phase, alpha-dicalcium silicate hydrate (Ca2SiO2(OH)2) becomes stable
and replaces C-S-H. As the C-S-H phase converts to Ca2SiO2(OH)2, the permeability increases and the strength decreases.
To avoid this, oilwell cements for use above 110!C contain a significant amount of silica (approximately 35% by weight of
cement) to lower the C/S of the hydration products to about 1. Under these conditions, a range of crystalline calcium silicate
hydrate minerals with generally acceptable engineering properties can form (Taylor, 1964, Kalousek, 1968, Eilers and Root,
1976).
While the equilibrium phases over a wide range of conditions are well established (e.g. Shaw et al., 2000, Meller et al.,
2009), metastable phases often form and linger for extended periods of time. In addition, the morphology of the products are
also highly variable. Thus, it is quite difficult to predict the nature of the hydration products that will develop under
particular conditions of time, temperature and pressure. Here we apply novel techniques to investigate the properties of
cement/silica blends cured at high temperature and pressure. Small-angle neutron scattering (SANS) and transmission
electron microscopy (TEM) are used to obtain information about the nanometer-scale structure, and nanoindentation and
microscratch testing are used to determine the mechanical properties.
The effect of curing time is investigated, as well as the effect of two-stage curing where initial curing is at a lower
temperature. As the curing time and temperature increase, the nanostructure coarsens. Specifically, the size of the smallest

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solid features increases and the specific surface area decreases. The rate of coarsening depends strongly on the initial curing
step. After extended curing at an intermediate temperature of 175!C, further curing for 1 week at 200!C does not cause much
coarsening. However, if initial curing at 175!C is for a short time, or if the initial curing temperature is too low to cause the
quartz to react, then subsequent curing for 1 week at 200!C generates significant coarsening. This coarsening process can
negatively affect the mechanical properties and permeability of the cement sheath, and should be taken into account when
designing high-temperature, high-pressure (HTHP) cementing jobs.
2. Experimental
2.1. Materials and curing procedure
Cement specimens discussed in this paper were all made with the same basic mix design consisting of a commercial Class G
cement, silica flour, and water. The silica flour was added at 35 wt% by weight of cement, the water/cement mass ratio was
0.45, and the water/solids mass ratio was 0.33. The slurry resulting from this mix design contains 35 vol% cement, 15 vol%
silica, and 50 vol% water, and has a density of 2.03 g/cm3. Silica flour is crystalline silica (quartz) made by grinding silica
sand. The mean particle size is about 20 m, making it somewhat coarser than the cement. All of the slurries were cured at a
pressure of 20.7 MPa. The curing times and temperatures were varied, as described in Table 1. After the curing regime
described in Table 1, specimens were stored under water in sealed containers at room temperature until they were prepared
for analysis.
Table 1: Curing conditions for samples discussed in this paper.
Sample ID

Curing conditions

MA1

1 week at 200!C

MA2

1 year at 200!C

NA1

6 days at 30!C

NA2

17 h at 175!C

NA3

8 days at 175!C

NA1-200

6 days at 30!C, then 1 week at 200!C

NA2-200

17 h at 175!C, then 1 week at 200!C

NA3-200

8 days at 175!C, then 1 week at 200!C

2.2. Sample Preparation


The sample preparation method varied depending on the analysis technique. For nanoindentation and microscratch testing,
samples were sliced with a diamond saw to expose a fresh surface. The sample was then polished using alumina grinding
papers of increasing fineness to obtain a flat, reflective polish. For small-angle scattering, a water-cooled diamond saw was
used to cut thin slices, which were then ground by hand using water as the lubricant until the desired thickness of about 0.4
mm was obtained, and analysis was performed in the water-saturated state. The SANS analysis was performed at the
National Center for Neutron Research in Gaithersburg, MD. For TEM imaging, samples were ground with a mortar and
pestle to a fine powder and dried under vacuum. The nanoindentation, microscratch, and TEM imaging were performed at
the Massachusetts Institute of Technology (MIT).
3. Novel characterization methods
3.1. Nanoindentation
The indentation technique consists of establishing contact between the indenter material (typically diamond) and the flat
surface of a sample, and measuring the penetration depth as a function of the applied load. The length scale in the material
that is probed depends on the depth of the indented volume, which is roughly three times the indentation depth (Ulm et al.,
2010). Modern instrumented nanoindentation instruments provide the ability to investigate mechanical properties at the submicron scale. Previous investigations of cement pastes have found that an indentation depth of approximately 150 nm is
small enough to ensure minimal interaction between separate mechanical phases (Constantinides and Ulm, 2007).
In general, the analysis of the indentation load-depth response yields two properties of interest: the indentation modulus
and hardness. The measured indentation modulus, M, can be related to the elastic properties of the indented material using
elastic contact mechanics (Oliver and Pharr, 1992), whereas the indentation hardness H is representative of the strength
content. For heterogeneous materials such as hydrated cement, nanomechanics characterization requires that multiple

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indentation tests be performed at different locations on the sample surface, so that the results can be analyzed statistically
(Constantinides et al., 2006). In this investigation a grid approach is used, with indents performed automatically at each
vertex of a N!N square grid pattern superimposed on the sample surface (see Fig. 1a). This generates N2 separate values of
the indentation modulus and indentation hardness, associated with different locations on the surface (see Figure 1b). A
typical grid value is N=20, giving 400 separate indents.
From the results of the grid test, a statistical cluster analysis is used to separate the values into mechanically distinct
phases, each with its own mean characteristic value of M and H. This statistical separation using normal mixture models is
indicated by the ellipses in Figure 1b. This approach has previously allowed the fundamental mechanical response of small
material volumes of C-S-H gel within hardened cement paste cured at near-ambient conditions to be directly investigated and
quantified (Constantinides and Ulm, 2004), and these results have also been analyzed in conjunction with SANS data for
cement paste (Jennings et al., 2007).
It should be noted that the values obtained from the cluster analysis are the homogenized properties of the phases at the
length scale of hundreds of nanometers, whereas it is well established that cement hydration products generally have internal
porosity at length scales down to about 1 nm. Based on the assumption that the homogenized phases consist of fundamental
solid particles packed together at a well-defined packing density, both the mechanical properties of the solid particles and the
packing density can be obtained from the reverse application of a self-consistent micromechanical model (Ulm et al., 2007).

ly

lx

a)

b)

Figure 1: a) Schematic of the statistical grid indentation technique for heterogeneous materials, b) Scatter diagram of the grid
indentation results for sample MA1, together with the statistical grouping into mechanically distinct phases. The ellipses indicate
the limits of three standard deviations. The results of the cluster analysis are given in Table 2.

3.2. Small-angle neutron scattering


Small-angle neutron scattering provides a great deal of information about the micro- and nanostructures of disordered
heterogeneous materials. The most versatile and sensitive SANS instruments can produce a statistically averaged
characterization across length scales ranging from approximately 1 nm to 10 m. SANS has some important advantages for
characterizing the nanometer-level structure of cement-based materials when compared to other techniques such as gas
sorption and TEM. The SANS analysis is non-invasive and does not require drying. It can even be conducted in situ without
disturbing the hydration process.
A SANS experiment is performed by passing a beam of neutrons through a relatively thin specimen. Some of the
neutrons will be scattered out of the incident beam direction by a small angle due to heterogeneities within the
microstructure, and these scattered neutrons are registered on a position-sensitive neutron detector. The angular profile of the
small-angle scattered (SAS) intensity can be analyzed to determine the statistically representative size distribution, volume
fraction and form of the scattering features, and microstructure models that assist in the interpretation of the scattering data
have been developed for many materials, including hydrated cement (Allen, 1991, Allen and Thomas, 2007). The geometric
angle of scatter between the incident and scattered beam, 2", is converted into a scattering vector of magnitude Q =
(4#/$)sin", where $ is the neutron wavelength. In general, fine microstructure features generate scattering at relatively large
scattering angles or Q values, while coarse features generate scattering at small Q. The absolute-calibrated scattered
intensity, I(Q), tends to decrease with increasing Q.

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Figure 2: SANS data for Class G cement + 35% silica systems hydrated at 30C (sample NA1) and at 175C (NA3). The silica (quartz)
does not react at 30C. The angled lines illustrate the fractal scaling regimes in the 30C paste, with the volume fractal at higher Qvaues and surface fractal at lower Q.

Figure 2 shows SANS data for Class G cement with 35% SiO2 hydrated at 30C and at 175C. The data are plotted on a
log-log scale as I(Q)Q4 vs. Q, a form that highlights differences in related datasets. Since quartz is essentially unreactive in
cement paste at 30!C, the 30!C specimen can be considered a normally cured cement paste containing inert inclusions that are
too coarse to generate small-angle scattering at this Q-range.
SANS data for cement hydrated under near-ambient conditions has been analyzed extensively, for example to elucidate
the effects of drying (Thomas et al., 2008) and calcium chloride acceleration (Thomas et al., 2009). Three regimes of interest
are generally observed, as with the 30C specimen shown in Figure 2. At lower Q-values, two power-law regimes are
observed with different slopes, corresponding to volume fractal and surface fractal scaling behavior within the nanoscale
hydration products, which consist primarily of C-S-H gel. At highest Q (representing the smallest microstructural features) a
brief, nearly horizontal, Porod scattering regime is observed. The Porod scattering permits the specific surface area of the
specimen, ST, to be calculated according to:
!! !

!!
!!"#!

where CP is the Porod constant, equal to the constant value in the Porod regime from a plot of the form of Figure 2, and %&2 is
the neutron scattering contrast between the solid phase and the pore fluid, which can be calculated from the phase
compositions. The volume fractal scattering is associated with the arrangement (packing) of primary C-S-H gel particles (of
size 45 nm) and is limited to relatively high Q values. The surface fractal scaling can be associated with the deposition of
hydration product onto the originally smooth surface of the cement grains. This fractal roughness extends upward in size to
include relatively large (micron-scale) features such as calcium hydroxide crystals.
The SANS response of the specimen cured at 175!C shown in Figure 1 has some similarity to the 30!C specimen, yet is
clearly different. The scattered intensity is higher across the Q-range; this can be attributed to the reaction of the silica which
results in a greater amount of calcium silicate hydrate product with a nanoscale morphology. The Porod scattering extends
somewhat lower in Q, indicating the fundamental building blocks of the nanostructure are larger. Finally, there is no
indication of a change in fractal scaling. Analysis of high-temperature-cured specimens is discussed further in the Results
section.
3.3. Microscratch testing
Scratch tests are widely used to characterize the fracture resistance of brittle materials because they are relatively simple and
inexpensive to perform. With the test, a stiff blade is used to apply a scratch along the surface of interest using a known
load. From the applied load and the depth and width of the scratch, the mechanical properties can be inferred. To determine
the fracture properties, we use a recently developed analytical framework (Akono and Ulm, 2011) that allows the

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determination of the fracture toughness of the specimen from scratch test data. This is a significant advance in the utility of
the scratch test, as fracture toughness is perhaps the most critical material parameter controlling the risk of fracture.
The relationship between the scratch test and fracture toughness is:
!!

!!"

! !!

where Kc is the fracture toughness, p is the perimeter of the scratch probe, A is the projected contact area, and FT is the
scratch force.
In the present paper, the data used to calculate the fracture toughness are generated from an automated microscratch tester
with a spherical tip of radius 200 m. A vertical force was increased continuously along a scratch path of 3 mm, resulting in
scratch depths ranging from about 0 to 150 m. Results of a microscratch test are shown in Figure 3. Once the ratio of the
scratch depth d to the tip radius R is greater than 0.13, the value of the fracture toughness parameter obtained from Eq. 2
stabilizes to a constant value of 4.0 0.24 MPa m1/2.
Previously, data from a commercial scratch test machine was used to determine the fracture toughness of oilwell cement
samples cured at high temperatures (Ulm and James, 2011). In that case, the scratch widths ranged from 2.5 to 10 mm and
the scratch depths ranged from 0.1 to 0.35 mm, significantly larger than the microscratch test. The fracture toughness values
obtained from this rather macroscopic test fell within a rather narrow range of 0.65 to 0.83 MPa m1/2, much lower than the
results of the microscratch test reported here. This indicates that heterogeneities in the material between the micrometer scale
and the millimeter scale, likely related to porosity, entail a loss of fracture resistance; a phenomenon not observed for
homogeneous materials.

Figure 3: Microscratch results for sample NA1-200. The upper image shows the 3-mm scratch after the test. The y-axis value
corresponds to the fracture toughness according to Eq. 2 once the value has stabilized. R is the radius of the indentor tip and d is
1/2
the scratch depth. The solid black line represents the calculated value of Kc=4.0 0.24 MPa m .

4. Results and Discussion


4.1. Effect of curing time at 200C
The first specimens to be considered are MA1 and MA2, which were cured at 200!C for 1 week and 1 year, respectively. Xray diffraction (XRD) analysis of these specimens shows peaks associated with xonotlite. These peaks are larger and more
distinct in sample MA2. This could indicate the presence of a semi-amorphous C-S-H type phase at 1 week that does not
contribute XRD peaks, or could indicate the growth of the xonotlite crystals between 1 week and 1 year, resulting in better
diffraction statistics. No peaks associated with quartz were observed even at 1 week, indicating full conversion of the silica
into the hydration products.
Figure 4 shows the SANS response of samples MA1 and MA2. Comparison of these datasets clearly indicates a
coarsening of the microstructure between 1 week and 1 year, as evidenced by a decrease in the scattered intensity at higest Q-

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values (arising from the smallest features at the scale of a few nanometers) and by a shift to the left at lower Q-values. In
accordance with this apparent coarsening process, the total internal surface area, ST, calculated from Eq. 1 decreases from 92
m2/cm3 at 1 week to 44 m2/cm3 at 1 year (see Table 2).
TEM images of these specimens were also obtained at multiple locations, and representative images are given in Figure 5.
These images show a nanostructure comprised of rodlike solid particles in both specimens, with significantly larger features
present in the 1-year specimens (MA2). Image analysis indicates that the average particle width for the 1-week sample
(MA1) is 14 nm, while the average width at for the 1-year sample (MA2) is 52 nm. This increase in the particle size with
curing time is consistent with the decrease in specific surface area noted above.
Grid nanoindentation was performed on both specimens. The statistical separation of the individual indent results into
mechanically distinct phases is given in Table 3. For sample MA1, phase 4 with the highest hardness and stiffness can be
associated with residual unhydrated clinker or quartz, present at a low volume fraction of 0.05. This phase is not present in
sample MA2, indicating that some additional reaction occurs between 1 week and 1 year. Phases 1, 2, and 3 in both samples
can be associated with hydration products.
While the cluster analysis provides the mechanical properties at the scale of the indentation process (hundreds of
nanometers), both the SANS and TEM results indicate fine structure at length scales below this. Previously, to analyze
nanoindentation results from ambient-cured cement paste, a continuum micromechanics model was used to determine the
properties of the solid building blocks of the nanostructure. Using a self-consistent scheme for granular porous media, this
analysis determined that mechanically distinct phases identified from the cluster analysis were in fact comprised of the same
solid nanoscale C-S-H particles arranged into different packing densities (Constantinides and Ulm, 2004).
The type of analysis was also applied to the nanoindentation data for the high-temperature cured oil well cements MA1
and MA2 given in Table 2. This analysis assumes that the micro-level phases indentified from nanoindentation are
comprised of the same solid particles with different packing densities (Constantinides et al., 2006). If this is not the case,
then the self-consistent analysis will fail to converge, so the analysis is in fact a test of this assumption. With the
micromechanics model, the solid (particle) properties controlling the indentation modulus M are the solid modulus, ms, and
the cohesion between particles, cs, whereas the indentation hardness H is controlled by the solid hardness, hs, and the friction
between particles, '.

Figure 4: SANS data for specimens MA1 and MA2 cured at 200C for 1 week and 1 year, respectively.

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"##$%&

"##$%&

Figure 5: TEM images of samples MA1 (left) and MA2 (right), clearly indicating the coarsening of the fundamental rod-shaped
particles after extended curing at 200!C.

Table 2: Specific surface area, ST, and fracture toughness, Kc.


2

1/2

Sample ID

ST (m /cm )

Kc (MPa m )

MA1

92 8

3.71 0.39

MA2

44 5

2.55 0.61

NA1

82 7

3.61 0.43

NA2

142 11

4.10 0.21

NA3

123 10

3.80 0.36

NA1-200

72 9

---

NA2-200

68 8

4.00 0.24

NA3-200

115 10

3.99 0.27

Table 3: Results of the cluster analysis of indentation data for samples MA1 and MA2.
Sample MA1
Phase

M (GPa)

22.8

33.6

46..8

116

H (GPa)

0.6

1.1

2.3

9.0

Volume fraction

0.31

0.54

0.10

0.05

M (GPa)

21.1

31.6

49.3

H (GPa)

0.6

1.1

2.3

Volume fraction

0.37

0.51

0.12

Sample MA2
Phase

Fitting results from application of the micromechanics model to data from specimens MA1 and MA2 are shown in Figure
6, and the fit results are listed in Table 4. For both samples, the predicted values of M and H based on fixed values of the
solid particle properties are in good agreement with the nanoindentation data for the three hydration product phases (see
Table 3). Thus we conclude that the HTHP-cured oilwell cements fit within the same nanomechanical framework as

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hardened cement paste, being composed of fundamental solid building-block particles. The particle properties themselves
are
different, however. For ambient-cured cement paste, the C-S-H particle properties are ms = 65 GPa and hs = 3 GPa
(Constantinides and Ulm, 2004), while the values for samples MA1 and MA2 are considerably higher (ms = 80-90 GPa, hs =
5-7 GPa). This is not surprising, given the more crystalline nature and lower solid water contents of HTHP hydration
products such as tobermorite and xonotlite.
To determine the mechanical properties of the specimens, microscratch tests were performed as described in section 3.3.
The results for the fracture toughness are listed in Table 2. The fracture toughness decreases by about 30% between 1 week
(MA1) and 1 year (MA2) at 200!C. This decrease could be related to changes in mineralogy (i.e., increased amount of
xonotlite) or to the coarsening process noted above.

Figure 6: Results of micromechanical model fits to nanoindentation data for samples MA1 (top) and MA2 (bottom), showing the
indentation modulus and hardness (M and H) plotted against the packing density (eta) of solid particles. For each sample, data from
the three phases identified by the cluster analysis (open circles) falls on the same fit line (solid line), indicating that the solid particle
properties are the same for each phase.

Table 4: Solid particle properties for specimens MA1 and MA2.


MA1

MA2

ms (GPa)

86.7 7.8

79.4 2.7

hs (GPa)

6.8 1.3

5.5 0.4

cs (GPa)

0.40 0.06

0.38 0.02

0.48 0.02

0.43 0.02

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4.2. Effect of initial curing temperature


To test the effect of the initial curing temperature on the coarsening phenomenon, specimens were cured at 30!C for 6 days,
and at 175!C for either 17 h or for 8 d. For each of these specimens, a companion was given a further curing treatment of 1
week at 200!C (see Table 1). The SANS response of these specimens is shown in Figure 7. The SANS results indicate that
the precuring treatment does indeed have a stong influence on the later coarsening at 200!C. For intial curing at 30!C and for
17 h at 175!C, the treatment at 200!C caused rather dramatic coarsening. In contrast, for the specimen precured at 175!C for
8 days, only minimal coarsening occurs at 200C. Similarly, the sample cured at 200C for 1 week with no precuring (MA1)
remained relatively uncoarsened.
We hypothesize that the morphology of the hydrated microstructure, and the rate of coarsening, depend on the relative
timing of the reaction of the cement and the silica flour. While Class G cement reacts readily at all temperatures, the silica
flour only becomes reactive above about 100C. For the sample precured at 30C, the cement will have first converted to
normal hydration products (C-S-H gel and calcium hydroxide) with no reaction of the silica. Only when the temperature is
raised to 200C will the silica flour begin to react. Based on the present results, it appears that the reaction between these
hydration products and quartz at high temperature produces a relatively coarsened microstructure, as shown in Figure 7, at
left. On the other hand, when the sample is cured at a high temperature from the start, then the cement and silica react
together, forming a microstructure that resists coarsening (e.g. sample MA1 in Figure 4). For precuring at 175C, the length
of the precuring is important. Precuring for only 17 h at 175C does not react much of the silica flour, so the subsequent
hydration at 200C generates a coarsened microstructure as with 30C precuring (Figure 7, center). However, after 188 h at
175C the silica flour has largely reacted, so subsequent hydration at 200C causes relatively little coarsening (Figure 7, at
right).
Recently, Makar and Luke (Makar and Luke, 2012) also reported on the effects of precuring on the properties of HTHP
cement-silica blends. They found that precuring at 35!C favored the formation of xonotlite over tobermorite, and they
speculated that the reaction of C-S-H and calcium hydroxide with silica flour at high temperatures favors xonotlite formation,
while rapid hydration of the cement and silica together favored tobermorite, which is consistent with the present findings.
Analysis of specimens MA1 and MA2 indicate that even when tobermorite forms initially at 200!C, xonotlite will then
eventually form at longer times.
While it seems clear that both the mineralogy and the morphology of the hydration products can affect the mechanical
properties (Kyritsis et al., 2009), it is difficult in either case to make specific predictions or recommendations. Makar and
Luke (Makar and Luke, 2012) found that for specimens precured at 35!C and then cured for 1 d at 230!C, the compressive
and flexural strengths of the specimens decreased as the length of the precuring time increased from 1 d to 28 d. They
speculated that this decrease was a result of morphological changes, because all these specimens contained primarily
xonotlite. For the present samples, the precuring treatment did not have a statistically significant effect on the fracture
toughness of specimens cured at 200!C (see Table 2), despite differences in the surface area and nanostructure as measured
by SANS.

Figure 7: SANS results showing the nanostructural effects of curing for 1 week at 200!C after various precuring treatments.
Left: Precuring for 6 days at 30!C. Middle: Precuring for 17 h at 175!C. Right: Precuring for 188 h at 175!C.

10

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5. Conclusions
The nanostructure and mechanical properties of Class G oilwell cement blended with 35% silica and cured at temperatures
ranging from 30!C to 200!C were analyzed using a variety of techniques. SANS and TEM were used to characterize the
nanostructure of the hydration products, grid nanoindentation was used to determine the nanoscale mechanical properties and
volume fractions of the hydration products, and micro-scratch testing was used to determine the fracture toughness. Curing
at 200!C causes a general coarsening of the nanometer-scale structure of the hardened cement paste over time, with
associated degradation of the properties. The specific surface area and fracture toughness decrease, while the average size of
the nanoscale solid features increases. The SANS response of HT-cured specimens loses the fractal scaling seen at lower
temperatures.
Statistical analysis of the grid nanoindentation results of HT-cured specimens indicates that at least three mechanically
distinct hydration products are present. Application of a self-consistent micromechanical model to this data indicates that
these phases can all be associated with different packing densities of the same fundamental solid nanoparticles, as has
previously been demonstrated for ambient-cured cement paste. This is an important and unanticipated finding, given the
significant nanostructural and compositional differences associated with HTHP oilwell cements. The solid nanoparticle
properties resulting from HT curing differ from those found after ambient curing, having higher elastic modulus and hardness
values. This difference can be attributed to the greater crystallinity and lower water content of the hydration products at high
temperatures.
The effect of precuring at a lower temperature on the coarsening process was also tested. Specimens were precured at
30!C for 6 days, and at 175!C for either 17 h or for 8 d. For each of these specimens, a companion was given a further curing
treatment of 1 week at 200!C to test the resistance to coarsening. For initial curing at 30!C and for 17 h at 175!C, the
treatment at 200!C caused rather dramatic coarsening. In contrast, the specimen precured at 175!C for 8 days exhibited
minimal coarsening, similar to the sample cured at 200C for one week with no precuring. We hypothesize that the
morphology of the hydrated microstructure, and the rate of coarsening, depend on the relative timing of the reaction of the
cement and the silica flour. Reaction between prehydrated cement and quartz at high temperature produces a relatively
coarsened microstructure, while the simultaneous hydration of cement and silica forms a microstructure that resists
coarsening. Despite the observed effect on the final microstructure, the precuring treatment did not affect the fracture
toughness. Thus we conclude that the relationship between the morphology, phase composition, and properties of HTHPcured cements is complex, in agreement with previous investigations.

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