tH
Sidney Diamond* and David Bonen*
School of Civil Engineering, Purdue University, West Lafayette, Indiana
Morphological features of hydrated portland cement paste
exhibited on carefully polished surfaces have been critically
examined using backscatter mode scanning electron
microscopy. A new interpretation and classification of such
features is proposed. The microstructure is seen to consist
of distinct grains of the order of 10 pm and larger (“pheno-
grains”) set in a cellular groundmass of smaller particles
and pores. Most of the phenograins are dense pseudo-
morphs of the larger cement grains, but some are large cal-
cium hydroxide crystals, and in some cements a few may
represent inert filler grains added to the cement. The phe-
nograins that are pseudomorphsof cement particles may be
solid, gapped, or hollow; and, at a given age, various stages
of hydration are represented in different grains. While
many pseudomorph phenograins consist of a simple core of
unhydrated material surrounded by a uniform shell of
hydration product, more complex and irregular structures
are also found. Relationships between these features and
earlier classifications of cement hydration product particles
are discussed, and implications with respect to difficulties in
image analysis of hardened cement paste are examined.
I. Introduction
H ARDENED portland cement paste (hcp), the binder compo-
nent of portland cement concrete, occurs in relatively thin
zones (several hundred micrometers thick) between sand and
coarse aggregate (rock) particles. For simplicity, laboratory
studies are often carried out on separately prepared hcp mixed
and cured without sand or coarse aggregate. Such preparations
are known to display microstructural features similar to those of
hcp in concrete.
Scanning electron microscope (SEM) studies of the micro-
structure of hcp in various cement pastes have been carried out
for a number of years by various workers,’“ primarily using the
secondary electron mode. Specimen preparation has mostly
been as fracture surface mounts, although doubts have been
raised as to the representatives of the surfaces so produced.
More recently, plane polished surface mounts examined in the
backscattered electron mode have been shown by several work-
ers (for example, Refs. 7-9) to provide useful quantitative and
qualitative information. Backscattered SEM provides represen-
tative surfaces and permits a much more revealing picture of the
individual textural features in hcp to be obtained. It therefore
permits a much greater appreciation of their spatial relation-
ships and juxtapositions. Furthermore, with such specimens the
ability to carry out accurate and fully corrected chemical analy-
ses of individual features by energy-dispersive X-ray analysis
(EDXA) permits a much closer appreciation of differences in
T. 0. Mason4ontributing editor
Manuscript No. 19531 I , Received September 16, 1992; approved February 22,
1993.
This work was carried out as part of the Purdue University component of the pro-
gram of the National Science Foundation Center for the Science and Technology of
Advanced Cement Based Materials.
‘Member, American Ceramic Society.
2993
47907
chemical compositions of the various morphological features
that are found.
Despite the large number of microstructural studies of hcp,
its various features cannot be described unequivocally, as there
are no adequate descriptive terms. The terms inner and outer
products are genetic terms and are poorly suited as descriptive
terms, as are the terms lute and undesignutedproducts (see dis-
cussion item 6). In our opinion the lack of descriptive nomen-
clature constrains and prevents detailed description and
understanding of the hcp microstructure. In this paper we have
attempted to provide a new description of what we consider to
be important features of the structure of hcp. None of the indi-
vidual features discussed is new, except perhaps for certain
details of the groundmass. However, we propose a radically
new but hopefully appropriate nomenclature and classification
for the entities described, and illustrate this by specific micro-
graphs. The objective is to provide a framework for a more real-
istic understanding of the structure of hcp and, subsequently,
for helping to interpret the properties of this material in terms
of structure.
In this work, in addition to a large number of micrographs,
several hundred fully ZAF-corrected EDX analyses have been
carried out on representative individual features of the classes
defined here. These analyses and the insights derived from
them will be addressed in a subsequent publication.
11. Materials and Methods
All of the examinations reported here were carried out on hcp
prepared from a normal ASTM Type I portland cement. The
mill analysis supplied by the manufacturer indicated the com-
position to be as follows: CaO, 64.87%; SiO,, 20.82%; AI,O,,
5.29%; Fe,O,, 2.12%; MgO, 1.35%; Na,O, 0.12%; K,O,
0.58%; SO,, 3.04%; loss on ignition, 1.74%. The cement was
mixed with deionized water for 8 min in an evacuated chamber
mounted on a paint shaker to prepare cement pastes at nominal
water:cement (w:c) ratios of 0.4, 0.5, and 0.6. After 1 d, the
specimens were demolded and cured in Ca(OH),-saturated
water for periods ranging from 1 d to 1 year.
After curing, the hydration was stopped by immersing indi-
vidual slices of the specimens in acetone. The specimens were
then impregnated in ultralow-viscosity epoxy mixture, evacu-
ated, and oven cured at about 95°C for about 3 h. The impreg-
nated, cured specimens were again sliced, using a diamond
saw, and the surface destined for examination was polished
using successively finer grades of diamond-bound grit down to
15 Fm. Final polishing was carried out with great care, using
3-pm and the 1-pm diamond cloth. The equipment used was
semiautomatic; the degree of pressure and the times of pol-
ishing were gauged by the operator as being appropriate for
each specimen. It appears to be necessary to avoid overpolish-
ing at each stage if the details of the delicate groundmass struc-
ture are to be properly revealed. After polishing, the specimens
were sputter coated with a 5-nm-thick layer of Pd.
Examination was carried out using an Akashi Beam Technol-
ogy (Tokyo, Japan) 55A SEM equipped with a GW Electronics
30A backscatter detector and a Tracor Northern (Middleton,
WI) 5505 EDXA system.
2994 Journal of the American Ceramic Society-Diamond and Bonen
111. Microstructural Features of hcp
hcp is well understood to be composed of CSH’ and calcium
hydroxide (CH) derived from the hydration of the portland
cement components, of residual unhydrated cement constit-
uents, and of minor hydrated components including ettringite,
calcium monosulfoaluminate, and occasionally others. For
pastes of a reasonable degree of hydration, the dominant com-
ponent is CSH.
As a result of sustained study of the morphological features
of hcp as revealed in backscattered SEM images, it has become
inescapable to us that “ordinary” hcp found in all the portland
cement pastes examined is best thought of in terms of two dif-
ferent primary morphological entities-“phenograins” and
“groundmass”-as described and illustrated below. After estab-
lishing these primary distinctions, an appropriate series of sub-
divisions of each category of morphological unit is then
attempted and illustrated in turn.
( I ) Phenograins and Groundmass
Figure 1 serves to illustrate what we consider to be the pri-
mary morphological distinction in hcp, as discussed above. The
figure is a field on a specimen of a 3-d-old w:c 0.4 paste. Exam-
ination reveals that the field consists of large solid-appearing
grains embedded in an obviously porous matrix of much finer
material. The same distinction could be made in essentially all
of the hcp fields we examined, of whatever age or w:c ratio.
Thus, we consider that a primary breakdown of microstructural
units in hcp should distinguish between these larger, distinct
grains and the groundmass component. The term “phenograin”
(pheno, from the Greek for “distinct”) is suggested for any
large distinct grain embedded in the groundmass. The term
phenograin is reserved for these conspicuous grains in analogy
to the term phenocryst, which is used in petrography for the
larger crystals embedded in a finer matrix of igneous or meta-
morphic rock having porphyritic texture.
In petrography, no specific sizes are associated with either
phenocrysts or groundmass particles. Rather, “it is the differ-
ence in size between the phenocrysts and the particles of the
groundmass that is the distinguishing feature. ’’I0 In distinguish-
ing phenograins, as defined here, from groundmass, the situa-
tion is somewhat similar. Our working definition is that the
phenograins are sufficiently larger than the component grains of
the groundmass that they are distinct from it. In practical terms,
‘The customary cement chemical notation is used here: C IS CaO, S IS S O l , A is
AI,O,, F is Fe,O,, s
is SO,, H is H,O; thus C,S is 3CaO,SiO, is Ca,SiO,, etc.
Fig. 1. Backscattered electron micrograph of 3-d-old paste illustrat-
.
ing the appearance of several types of phenograins embedded in a
, _ I n1,
Vol. 76, No. 12
this appears to mean that the lower bound of phenograin size is
of the order of 10 pm or so, although as pointed out by one of
the reviewers of this paper, this is a “soft” rather than a hard
boundary.
An important reason for stressing the distinction between
phenograins and groundmass, perhaps more important than the
size differential, is the obvious gross porosity of the latter. With
certain exceptions, discussed below, phenograins are free of
obvious porosity on the size scale viewable in backscattered
SEM (although certainly not on a mesopore or micropore
scale). In contrast, the groundmass, even of older and well-
hydrated pastes, is heavily and visibly porous, to the degree
that the local bulk density must be very much lower than that of
the phenograins. This state of affairs has been recognized pre-
viously, for example by Scrivener,” but its importance some-
how has not been fully appreciated in the field.
The phenograins are composed of several different classes of
material. Most of them are derived from larger preexisting
cement particles which have remained unhydrated or have
partly or completely hydrated in situ. Others are larger grains or
agglomerates of CH, a secondary product of cement hydration,
and still others are particles of insoluble nonclinker origin
materials deliberately added to cement by the manufacturer.
(2) Varieties of Phenograins Observed: Solid, Gapped, and
Hollow Grains
As mentioned previously, most, but not all of the pheno-
grains are visibly solid grains. However, observations indicate
that some are appropriately described as “gapped” and others as
“hollow” grains. Examples of all of these kinds of grains have
been described in the literature.
The phenograins shown in Fig. 2 (for the same paste as Fig.
1) range in size from about 10 to about 40 pm in longest dimen-
sion and are obviously of several different categories with
respect to their chemical composition, as is indicated by their
varying gray levels. Nevertheless, all of the grains, even those
that are obviously composed of more than one phase, are repre-
sentative of solid phenograins, in that no obvious gap or hollow
structures are visible. In contrast, in Fig. 3 (from a 1-d-old w:c
ratio 0.5 paste) a phenograin is pictured that is surrounded by a
thin shell from which it is separated by a gap of the order of 2
pm. The phenograin itself is largely unhydrated C,S; the gap
separates it from a thin layer of hydration product that is largely
CSH. The pattern of progressive development in the in situ
hydration of large cement grains leading to the existence of
such gaps has been documented by, for example, Pratt and
‘‘
Ghose. Such phenograins are obviously described as gapped
(as distinguished from solid) phenograins.
Fig. 2. Backscattered electron micrograph of 3-d-old paste illustrat-
ing variations in solid phenograins with respect to bright and dark com-
nnnentP (wntprlrpment = 0 4)
December I993 Microstructure of Hurdened Cement Pusre-A New Interpretation
Fig. 3. Backscattered electron micrograph of 1 -d-old paste illustrat-
ing a gap between unhydrated residual C,S and outer hydration rim
(water/cement = 0.5).
In some phenograins, wider gaps are observed, indicating
further hydration and removal of material from the central core.
Where the gap is so wide and any remaining core so small, it is
no longer reasonable to speak of the grain as a gapped pheno-
grain; rather, it becomes sensibly designated as a hollow pheno-
grain. This stage has been reached in two side-by-side grains
depicted in Fig. 4, from a 28-d-old w:c ratio 0.5 paste. The
larger bright residual solid remnants within both grains are C,S;
the two small angular remnant pieces in the center of the grain
at the left are ferrite.
A virtual end-member in this progression is illustrated in Fig.
5 from a 3-d-old w:c ratio 0.4 paste. Here an approximately
18-pm phenograin has been completely hollowed out, except
for a residual plug of material which on analysis proved to be
calcium monosulfate hydrate.
The existence of hollow-shell hydration grains in hcp was
first pointed out by Hadley in this laboratory in 1972,’’ and
such features have been detected by most observers since then.
Hollow-shell grains derived from smaller cement grains also
occur in the groundmass, where indeed they are much more
plentiful.
Fig. 4. Backscattered electron micrograph of 28-d-old paste show-
ing two adjacent phenograins classed as hollow phenograins. In the
upper grain the residual core is C,S; in the lower core the residual
grains are ferrite and C,S (watedcement = 0.5).
2Y95
Fig. 5. Backscattered electron micrograph of 3-d-old cement paste
showing hollow phenograin. The material in the center is calcium
nionosulfoaluminatehydrate (waterkement = 0.5).
(3) Classijication of Solid Phenograins
Based on our overall examinations, it appears that solid phe-
nograins may usefully be divided into several subclasses. We
distinguish between incompletely hydrated and completely
hydrated solid phenograins (both obviously derived from
cement particles) and o t h e r s d i s t i n c t grains either of CH laid
down during hydration or of insoluble substances in the cement
other than portland cement per se.
In Fig. 6 (from a 1-year-old w:c 0.4 paste), attention is called
to the approximately 40-pm grain designated “a” on the right
side of the figure. It is evident that this grain is composite in
character, with a very bright central core and a darker, uniform
gray rim about 5 p m or so in thickness. It is evident that the
bright core i s an unhydrated cement component, in this case
shown to be C,S, using EDXA. The surrounding rim of CSH
hydration product is obviously developed around the core as a
result of in situ hydration of the C,S grain within it. This CSH
rim is compact and dense in character but has a much darker
gray level than the unhydrated core. The effective backscatter
coefficient of the rim is reduced presumably both by the non-
evaporabie water in its structure and by vacant spaces or “gel
pores” within it that formerly contained evaporable water. It is
evident that this phenograin is an incompletely hydrated
phenograin.
Fig. 6. Backscattered electron micrograph of 1 -year-old paste exhib-
iting several types of incompletely hydrated solid phenograins
(water/cement = 0.4).
2996 Journal of the American Ceramic Society-Diamond and Bonen
The shell of incompletely hydrated phenograins is not always
as uniform as it is in this particle. In the same figure, attention is hcp. These are particles in the size range of about 1 to 5 pm.
drawn to the similar-sized grain designated “b”. Here both the
unhydrated core and the surrounding hydrated CSH layer are
irregular; the core is partly composed of residual ferrite, and the
surrounding hydrated layer is incomplete or missing in some
sectors. Another variant can be seen in the two slightly smaller
solid phenograins designated “c” and “d’ in the figure. Both are
composed of central cores of unhydrated C2S. Despite the I -
year age of the paste, only thin layers of hydration products
have been developed around them.
Further illustrations of variant incompletely hydrated solid
phenograins are shown in Fig. 7, for a 28-d-old w:c 0.4 paste.
The approximately 4 0 - p n grain designated “a” is similar to the
grain designated “a” in the previous figure, except that the
hydration rim here is much thicker and occupies about 213 of
the exposed surface. Incidentally, the brighter strip near the
lower right boundary of this grain is a thin zone of residual fer-
rite. Below grain “a” the smaller dark grain designated “b” is
completely hydrated and now consists entirely of compact CSH
occupying the former position of a specific clinker grain.
Clearly this is an end-member of the incompletely hydrated
solid phenograin category which has passed over into the cate-
gory of completely hydrated solid phenograins.
It is of interest to note that as early as 1969 William~on‘~ space of roughly the same size as the groundmass particles, the
observed by secondary electron SEM of fracture surfaces that
“a hydration product forms inside the anhydrous cement grains
and forms a pseudomorph of the original cement grain.” It is
quite evident from the micrographs he published that the “pseu-
domorphs” are identical to the fully hydrated phenograins
described here.
Figure 7 also contains other phenograins. One of them is the
large striated grain designated “c”. This grain is composed
entirely of CIS, but in a sense it can be considered a partly
hydrated phenograin. The visible striae represent two sets of
polysynthetic twin crystals, preexisting in the original p-CIS.
Ordinarily these twins are not seen in the original C,S except
after deliberate etching treatment. In the present case, the more
reactive material of the grain appears to have been removed by
hydration. What is left is considered to be an incompletely
hydrated solid phenograin consisting of CIS and showing no
noticeable hydration rim.
Figure 7 also contains examples of CH-containing “other”
solid phenograins. The intermediate gray areas designated “d”
in Fig. 7 represent irregularly shaped deposits of CH dispersed
widely over the field. Another CH phenograin is the geometri-
cally regular grain designated “e” in Fig. 6.
The existence of CH in phenograins does not, of course, pre-
clude the existence of small CH particles in the groundmass,
Fig. 7. Backscattered electron micrograph of a 28-d-old paste show-
ing additional varieties of solid phenograins (waterkement = 0.4).
Vol. 76, No. 12
which often contains a substantial part of the total CH in the
Unfortunately, there is no absolutely sharp distinction between
the two classes; intermediate-sized, irregular masses of CH
occur occasionally that might be tallied either way. However, it
should be noted that those CH grains that were classified by us
as phenograins display a somewhat different chemical compo-
sition, using EDXA, than the groundmass CH in the same
pastes, as will be described in a subsequent publication.
Besides CH, “other” solid phenograins found in some
cement pastes include filler particles (limestone, dolomite,
quartz, etc.) incorporated with the cement by the manufacturer
as permitted by many current specifications, and solid fly ash,
pozzolan, slag, and large silica fume grains.
(4) Components of the Groundmass
As indicated earlier, the first distinction in our morphological
classification of microstructural elements in hcp is the separa-
tion between distinct phenograins and groundmass. The
groundmass comprises a significant portion of the area exposed
on any plane surface in hcp. We distinguish it from the pheno-
grains embedded in it by virtue of the smaller sizes of the indi-
vidual particles that comprise it, and by virtue of the fact that
these particles are themselves embedded in interconnected pore
whole exhibiting a distinctly cellular texture. The latter is
extremely important. One of the main reasons for making the
primary distinction between phenograins and groundmass is the
obviously different texture of the groundmass and its very
much greater local porosity.
We have found the solid portion of the groundmass to be
composed of CSH, CH, and smaller amounts of calcium mono-
sulfoaluminate hydrates, ettringite, and other phases.
We recognize within the groundmass areas several different
geometrical components. These include a skeletal solid com-
ponent, an amorphic solid component, and the pore space
itself.
Figures 8 and 9 portray these structural elements, along with
a few phenograins of types previously discussed.
In Fig. 8, from a 3-d-old w:c 0.4 paste, the distinction
between skeletal and amorphic components of the groundmass
is illustrated. The feature marked “a” is what we have termed a
skeletal component. It is very thin, high-aspect-ratio rib clearly
forming part of the cellular structure of the groundmass. The
feature marked “b” is what we have termed an amorphic com-
ponent. It is a broad, irregular mass that is clearly not a cellular
rib. It is distinguishable by a generally lower aspect ratio than a
skeletal particle and is of sensibly “amorphic” (i.e., nonregu-
lar) character. Many amorphic particles appear “fuzzy” and
Fig. 8. Backscattered electron micrograph of a 3-d-old paste illus-
trating the cellular texture of the groundmass and illustrating its fea-
tures (waterkement = 0.4).
December 1993 Microstructure of Hardened Cement Paste-A New Interpretution
Fig. 9. Backscattered electron micrograph of another field of a 3-d-
old paste specimen further illustrating the texture of the groundmass
(waterkernent = 0.4).
incompletely solid, in contrast to the hard edges characteristic
of skeletal particles.
Also prominently visible in the groundmass of Fig. 8 are
clearly distinguishable pores between the solid elements, rec-
ognizable by their fully black gray level. In this figure, these
range in size downward from about 5 pm and are irregular to
polygonal in shape.
Figure 8 also contains two distinct phenograins as well as the
groundmass. The upper one is fully hydrated. The lower one is
a gapped phenograin, with a uniform hydration rim of about 3
to 4 pm and a gap incompletely separating it from two very
bright C,S grains. The gap between the residual C2S and the
hydration rim at the upper left is close to 5 km. Note that this
space within the gapped phenograin constitutes a different kind
of pore than the voids within the groundmass.
Figure 9, also from the 3-d-old w:c 0.4 paste, is another
illustration of the nature of the groundmass components in
CSH. Features similar to those exhibited in Fig. 8 are seen.
Close observation of the details of the structure of the
groundmass, especially in Fig. 9, reveals that a number of
“cells” can be found which are apparently hollow-shell hydra-
tion grains (“Hadley grain^"'^) derived from small (less than 5
pm) cement particles. Two such cells are marked “a” and “b”
in Fig. 12. Similar features have been illustrated by others, for
example, by Scrivener (Fig. 41 in Ref. 8).
Figures 8 and 9 show fine details of the cement paste ground-
mass structure that are not readily visible on specimens pre-
pared with only casual attention to surface polishing.
Observations of the structure of the groundmass of hcp, and of
other details as well, require very careful attention to polishing
technique in order to avoid smearing and obscuring of this more
delicate portion of hcp.
(5) Addilional Details
The classification of microstructural elements so far pre-
sented has been kept mostly free of discussion concerning the
genetic development of the various elements. A full discussion
of the sequential development of the microstructure is beyond
our intended scope, but certain observations relating to the
developmental processes are illustrated in this section.
One of the striking and unexpected features of the cement
pastes we have examined is the great variation in pattern of
hydration of individual cement grains adjacent to each other in
the hcp. Figure 10(a), from a 28-d-old w:c 0.4 paste, provides
an illustration of this feature.
We identify a total of 11 distinct phenograins (exclusive of
CH phenograins) in the micrograph, as outlined in the accom-
panying tracing (Fig. 10(b)). All of these represent individual
cement grains hydrated in sifu. Of these, four (Nos. 1, 8, 10,
2997
11) are indicated by their uniform gray level as being fully
hydrated. At the other extreme, Nos. 3 and 9 have hardly
hydrated; most of their exposed surface comprises bright,
unhydrated cement (largely C,S), with only a thin zone of CSH
around their perimeters. The other phenograins, Nos. 2, 4, 5,
6, and 7, display intermediate degrees of hydration. We call
attention in the following section to some individual features of
the various grains.
Grain No. 2, at the very top of the figure, is only partly visi-
ble. Grain No. 4 is quite straightforward, comprising a small
residual core of C3S entirely surrounded by a thick hydrated
zone. Grain No. 5 is much more complex. It shows a vertically
elongated central zone of C3S, terminating above in a thin dif-
fuse tail. To the left of the C3Sand embedded in the CSH hydra-
tion rim are two small bright rounded crystals of unhydrated
C,S, separated from the C3S and from each other by CSH.
Additionally, below the central C,S core is a bright inclined nar-
row crystal of ferrite. Grain No. 6 is composed of several dif-
ferent separate bright C,S and ferrite crystals irregularly
surrounded by CSH. Grain No. 7 is again different, being com-
posed of two lateral zones: a zone of CSH on the left, and a
bright ferrite zone on the right. Above and to the right of the
ferrite are separate intermediate gray CH grains which presum-
ably were not within the boundary of the original cement grain.
In view of this individual variability of in situ hydration of
the larger cement grains, it does not seem meaningful to
attempt to discuss an average thickness of CSH rim developing
in a given time. Some cement grains, presumably composed
largely of C,S, hydrate fully; others, adjacent to them and in
many cases also composed largely of C,S, hydrate only to a
minimal extent.
Finally, an observation that cannot be illustrated must be
made. In all of the examinations of the various regions in the
different pastes examined, in no case did we find patches of
either identifiable ettringite or identifiable calcium monosulfate
hydrate phases in the hydrated portions of solid or gapped phe-
nograins. Ettringite and calcium monosulfoaluminate were
both found many times in the groundmass, and the monosulfate
was occasionally detected as small deposits within the hollow
spaces in hollow phenograins.
IV. Discussion
The microstructural features of hcp documented in this paper
and implications drawn from them deserve some further
comment.
( 1 ) The single most important point of this paper is the
explicit recognition and illustration that CSH in hcp is morpho-
logically either a constituent of a phenograin or else a
component of the locally porous, cellular groundmass. As dis-
cussed in point 7 below, morphological classifications of CSH
particles have been suggested in the past by various workers,
including the first-named author, based on high-magnification
examination of fracture surfaces. These continue to have valid-
ity, but, in our present view, the structural distinction between
phenograin CSH and groundmass CSH and their spatial rela-
tionship (i.e., the embedding of the phenograins in the ground-
mass) are paramount.
(2) It appears from the results of hundreds of EDXA analy-
ses carried out over the cement paste specimens depicted here
that there are small but consistent differences in the chemical
compositions of the two classes of CSH. A paper detailing
these differences will be submitted for publication separately.
(3) The finding that adjacent, primarily C,S-bearing,
cement grains of similar appearance vary so widely in degree of
hydration obviously requires explanation. Possible explana-
tions might include differences in C3Spolymorphs, differences
in impurity content, or differences in lattice strain reflecting
nucleation at various stages along the kiln axis and exposure to
different cooling rates in different-sized nodules of the clinker.
It should be recalled that cement grains that wind up in adjacent
2998 Journal ojthe American Ceramic Society-Diamond and Bonen
Fig. 10. (A) Backscatteredelectron micrograph of a 28-d-old paste specimen showing solid phenograins representing various patterns of hydration
(water/cement = 0.4). ( B ) Traces of the outlines of the individual grains discussed.
positions in a cement paste may have been nucleated in differ-
ent temperature zones within the kiln.
(4) The micrographs provide clear indications that a con-
siderable volume of large pores (up to -5 p m in diameter) exist
in hcp. Pores of this size range are not represented (or are very
much underrepresented) in published mercury intrusion pore
size distributions of hcp.”-” Mercury intrusion porosimetry is
well known (a) to provide only an incomplete tally of the pore
space within hcp, a considerable fraction of the total volume
being unaccounted for, and (b) to measure entry diameters
rather than actual diameters of isolated spaces. If it is assumed
that the cellular structure of the groundmass is only partially
interconnected in three dimensions and the interconnections are
relatively narrow, no necessary discrepancy exists. Quantitative
indications that this is so have been demonstrated by Scriv-
ener.” Unfortunately, appreciation of the limitations of mercury
intrusion porosimetry as a method of determining pore size dis-
tributions is not universal, and many workers are unaware of
the significant volume of the multimicrometer voids in the cel-
lular groundmass of ordinary hcp.
In this context, a useful and nearly comprehensive discussion
of the complexity of the pore structure of hcp was provided
some time ago by Parrott.’x
(5) The geometric details of the backscattered electron
images of hcp exhibited here are extremely complex, and this
complexity influences the nature of image analysis applications
that can be carried out on hcp. Using gray level differentiation,
it is possible to determine relative areas of unhydrated phases,
to recover most of the CH, to measure the bulk areas of CSH
and other hydrated phases, and to measure the area of the visi-
ble pores. However, it is not feasible to differentiate between
the CSH component of the phenograins and the CSH in the
groundmass, as their gray levels overlap each other. In this con-
text, the discussion by BoneniYis of interest. Feature analysis is
not feasible for the groundmass components, and while the
phenograins may be treated as features in the image analysis
sense, their complexity renders such analysis exceedingly
difficult.
(6) The question of the relationship between the interpreta-
tion of hcp structure provided here and the “inner product”-
“outer product” dichotomy propounded in the cement literature
over the years is a vexing one. Taylor2’ observed that “the insitu
hydration products have often been called ‘inner product’, but
this term may be criticized on the grounds that the apparent out-
lines may lie within the true ones, and ‘late product’ may be a
better description.” With respect to CSH here described as
groundmass components, Taylor further observed that “this
Vol. 76, No. I2
material is often called ‘outerproduct’, but the term is impre-
cise, as it must include not only products formed in what was
originally water-filled space, but also products that formed in
space initially occupied by the interstitial material or by the
smaller cement grains, the outlines of which can no longer be
distinguished. The term ‘undesignated product’ is preferable.”
In our opinion, the evident morphological distinction between
the groundmass and the phenograins provides the natural basis
for the appropriate classification, without invoking any genetic
or otherwise indeterminable characteristics.
(7) Similarly, the relationship between the present observa-
tions and the classification of CSH into particle types described
by one of us many years ago’ based on examination of fracture
surfaces at higher magnifications needs mention. It appears that
Type I and Type I1 CSH particles are constituents of the
groundmass as presently identified, and the very fine and
densely packed Type 111 particles represent a higher magnifica-
tion view of the CSH constituents of phenograins. The Type IV
category, thought at the time to represent a separate class of
inner product CSH, also appears to correspond to CSH constit-
uents of phenograins.
V. Conclusions
A reexamination of the morphology of hardened cement
paste based on observations of polished surfaces using back-
scattered SEM supplemented by EDXA of individual compo-
nents leads to the following picture:
(1) Microstructurally, hcp comprises two distinct kinds of
structural u n i t s d i s t i n c t grains (“phenograins”) set in an obvi-
ously highly porous groundmass. The phenograins may be
superficially, partially, or fully hydrated clinker grains, distin-
guishable crystals of calcium hydroxide, or filler particles in
some cements. The groundmass is seen to be cellular in charac-
ter and to consist of CSH in either skeletal or amorphic form
embedded in intersecting pores.
( 2 ) Phenograins representing partly hydrated cement grains
show great variation in extent of hydration from grain to grain
in the same area. The geometric pattern that is developed of the
hydrated material with respect to the residual unhydrated
cement also varies widely; only sometimes does it take the
expected form of a uniform shell of CSH surrounding an unhy-
drated core.
(3) The CSH in hydrated portions of phenograins displays
a uniform texture and a much lower effective backscatter coef-
ficient than any of the cement components from which it is
derived, making recognition easy. Further, on the scale at
December 1993 Microstructure of Hardened Cement Paste-A New Interpretation
which backscatter detectors permit observations to be made
(usually of the order of a few thousand magnifications or less),
this CSH appears to lack visible porosity.
(4) A considerable volume of pore space in the range of
sizes up to -5 pm occurs in the groundmass and constitutes a
cellular structure. These pores are significantly coarser than the
coarsest pores normally tallied in mercury intrusion pore size
distributions of hcp. Mercury may not intrude into all of the cel-
lular pores and records others only in terms of entry diameters.
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