CEMENT and CONCRETE RESEARCH. Vol. 24, pp. 186-188, 1994. Printed in the USA.

0008-8846/94. $6.00+00. Copyright 1993 Pergamon Press Ltd.

A R E P L Y TO F U R T H E R COMMENTS BY D. BONEN
ON THE PAPER
" Q U A N T I T A T I V E B A C K S C A T T E R E D E L E C T R O N ANALYSIS
OF C E M E N T PASTE"1

Hong Zhao2 and David Darwin

Structural Engineering and Materials Laboratory
2006 Learned Hall, University of Kansas
Lawrence, Kansas 66045

The authors appreciate Bonen's continued interest in the subject of quantitative

backscattered electron imaging of cement paste.
Bonen has doubts about the applicability and reproducibility of the process. However,
since the original research (1, 2), thousands of images have been successfully acquired and
analyzed using the techniques described in the paper. The procedures described are specifically
designed for imaging large areas of cement paste to accurately obtain information on the morphology of the material. The statistical justification for imaging large areas was presented in the paper
(2) and re-emphasized in our reply (3) to Bonen's earlier discussion (4). The need for the calibration procedure is based on the fact that, in a multi-user facility, scanning electron microscope
settings change from day to day. In addition, within a single viewing session, the beam current
can be expected to change over time due to changes that occur in the SEM filament. The calibration
procedure (1, 2) allows the operator to correct the microscope settings and helps insure that the
grey levels obtained from backscattered electron (BSE) imaging consistently represent the same
backscattered electron coefficients by adjusting the output of the processed signal. While this
process may be done by eye, a random error will be superimposed on the resulting data, even
when the adjustment is made by an experienced operator. The procedures described in the paper
(2) involve the identification of specific phases within hydrated cement paste based on grey level
segmentation (referred by Bonen as binary segmentation). The grey levels selected to segment the
image are initially operator selected. Once set, however, the calibration procedure allows the grey
levels to be reproduced faithfully for multiple images of the same specimen and for similar specimens of the same material.
Bonen feels that it is "good practice to redefine the grey levels of the phases for every new
specimen mounted in the SEM" due to the dependance of interaction volume on specimen orientation and because "backscattered coefficients are defined only for an electron beam incident normal
to the surface." The authors disagree. The reason is that, while the interaction volume does
depend on the specimen orientation, the volume is relatively insensitive for small changes in angle,
1 CCR 22(4) 695-706 (1992)
2 Current address: RMS2 Engineers Design Group, Inc., 3785 NW 82nd Ave., Suite 209, Miami,
Florida 33166
186

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DISCUSSIONS

187

as are the backscattered electron coefficients (5). For the materials in hydrated cement paste, the
effect of an angle change of up to 8 degrees would have an imperceptible effect on the contrast
between the phases (6). Therefore, for reasonably well prepared and mounted flat specimens, the
backscatter coefficients and relative grey levels produced by the backscattered electron signal are
not sensitive to minor variations in specimen orientation, nor do they need to be redefined for every
new specimen mounted in the SEM.
Bonen does not agree with the authors belief that expanding the grey levels provides more
information and allows easier identification of phases. He states that "if there are minima in the
grey level histogram, discrimination between phases is straightforward" but that "where no minima
exists, expanding the grey level would do very little good, if any, to resolve this problem." He
then goes on to state that "lack of well-defined peaks does not prevent discrimination among
phases, as, for example, by a binary segmentation technique." The authors believe that Bonen is
missing an important point. When the contrast in the image is reduced, the ability of the operator to segment the image is decreased. The process of using a reduced image contrast throws away
useful information. This is information that is needed to initially segment the grey levels or to
"redefine the grey l e v e l s . . , for every new specimen," as advocated by Bonen. Since the ability
of the human eye to distinguish differences in grey level is quite limited, any reduction in the
available contrast between phases of interest reduces the reproducibility of any results based on that
grey level range. Therefore, the process of initially segmenting the grey levels should be done
with the highest possible contrast for the phases of interest. The authors agree that phase analysis
based on grey level segmentation may involve error. However, the desire is to keep that error to a
minimum.
The authors agree with Bonen that when backscattered electron coefficients overlap, x-ray
analysis is needed to identify individual phases.
Bonen disagrees with the authors' statement that chemical image analysis provides poor
spacial resolution, on the order of 5 to 10 micrometers. He states that "the resolution of chemical
image analysis is directly related to the resolution attained by the binary segmentation process, and
is about the same order as that of the backscattered imaging." Bonen is partially correct, and then
only if the images are acquired at low enough magnification and with low SEM accelerating voltage
that the lateral dimensions of the interaction volume are no larger than twice the pixel size. Under
these circumstances, the x-ray sampling volume (nearly equal to the interaction volume) will be
optimally sized with respect to the pixel (7). At an accelerating voltage of 10 kV, the depth of the
interaction volume (or electron range) for CSH is approximately 1.6 ~tm; the lateral dimensions of
the interaction volume are about one-half of the electron range. At 25 kV, the electron range is
about 7.6 Bm. For backscattered electrons, the sampling depth is about one-third of the electron
range (7). For a low density material like CSH, the lateral dimensions of the BSE sampling are
about one-tenth of the electron range. As a result of the differences in the dimensions of the
respective sampling volumes, x-ray spectra are generated from a region that is significantly larger
than that from which backscattered electrons are generated and can represent materials that are
significantly different from those in the phases at the specimen surface. The lower the magnification and the larger the pixel size, the less significant are differences in the lateral dimensions of the
sampling volumes since resolution is governed by the larger of the lateral dimension of the sampiing volume or the pixel size (7). Under any circumstances, x-ray spectra will be generated at a
greater depth than backscattered electrons. Another point to keep in mind is that quantitative
energy dispersive spectrometry is based on the assumption that the material being analyzed is
homogeneous - an assumption with questionable grounding for hydrated cement paste. Therefore,
chemical image analysis will produce an image in which individual phases can be identified only
approximately and from which the relative strength of the signal can be used to identify approximate phase boundaries. Backscattered electron imaging can be used in conjunction with chemical
image analysis to sharpen the phase boundaries.
As stated earlier (3), the authors believe that chemical image analysis is a powerful technique. However, the technique has its own drawbacks, since it takes much more time and provides poorer spatial resolution than backscattered electron imaging. For work carded out by the

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H. Zhao and D. Darwin

Vol. 24, No. 1

authors, the time required for imaging is important because of the large number of images needed
to obtain a statistically valid sample. Due to long acquisition time requirements, such a statistically
valid sample is virtually impossible to obtain with chemical image analysis, which is best used for
studying specific details in cement paste morphology. The authors agree that, by using a segmentation process, phases can be identified reasonably well; however, the uncertainty of the position of
the phase boundaries, based solely on chemical image analysis, is, as a general rule, greater than
that obtained from backscattered electron imaging. For that reason, the two processes are usually
used together (8).
The authors appreciate Bonen's persistence in trying to establish the terminology used to
describe the phases observed in polished specimens of hydrated cement paste. Diamond and
Bonen (9) have developed new terminology that was not available to the authors at the time of the
initial reply (3). At the highest level, Diamond and Bonen categorize the morphology of hydrated
cement paste as consisting of phenograins (meaning distinct grains) and groundmass (everything
else). Bonen states that "CH has been found to form intimate mixtures with the amorphic CSH
particles confined to the groundmass, and not with the outer hydration CSH shell of phenograin or
fully hydrated phenograins... " The "outer hydration shell of the phenograin" was referred to in
the paper (2) and in the authors' reply (3) as "inner product." The authors statement that "a
significant portion of the inner product has the same signal intensity as massive regions of calcium
hydroxide" is based on calibration settings selected to optimize the identification of the hydrated
phases. The statement means to convey a description of the signal within the region normally
referred to as inner product. With the settings used, the grey level range of some regions within
the "inner product"/"outer hydration shell of the phenograin" overlap those of clearly identifiable
regions of CH surrounded by "outer product"/"groundmass." Calcium hydroxide has been
observed within the boundaries of the inner product region by Rayment et al. (10, 11). The CH in
this region is likely in a microcrystaUine form, as observed by Groves (12), at a scale below 100
nm. At this scale, the differences in the sampling volumes of backscattered electrons and x-rays
will make differences in mean atomic number easier to identify than differences in chemistry.
References

1. Zhao, H. and Darwin, D., SM Report No. 24, Univ. of Kansas Center for Research, Lawrence, Kansas (1990).
2. Zhao, H. and Darwin, D., Cem. Concr. Res. 22, 695 (1992).
3. Zhao, H. and Darwin, D., Cem. Concr. Res. 23,754 (1993).
4. Bonen, D., Cem. Concr. Res. 23, 749 (1993).
5. Newbury, D. E., Yakowitz, H. and Myklebust, R. L., Appl. Phys. Lett., 23, 488 (1973).
6. Arnal, F., Verdier, P. and Vincinsini, P.-D., C. R. Acad. Sci. Paris, 268, 1526 (1969).
7. Goldstein, J. I., Newberry, D. E., Echlin, P., Joy, D. C., Romig, A. D., Lyman, C. E.,
Fiori, C. and Lifshin, E., Scanning Electron Microscopy and X-Ray Microanalysis, 2nd Ed.,
Plenum Press, New York and London.
8. Bonen, D. and Diamond, S., Mat. Res. Soc. Symp. Proc. 245,291 (1992).
9. Diamond, S. and Bonen, S., J. Am. Ceramic Soc. 76 (1993) (in press).
10. Rayment, D. L. and Majumdar, A. J., Cem. Concr. Res. 12, 753 (1982).
11. Rayment, D. L. and Lachowski, E. E., Cem. Concr. Res. 14, 43 (1984).
12. Groves, G. W., Cem. Concr. Res. 11,713 (1981).