Research & Development Information

PCA R&D Serial No. 2651

CEMENT SOUNDNESS AND THE

AUTOCLAVE EXPANSION TEST –
AN UPDATE OF THE LITERATURE

by Waldemar A. Klemm

© Portland Cement Association 2005

All rights reserved
KEYWORDS
ASTM C 151, autoclave expansion test, cement, clinker, free lime, free magnesia

ABSTRACT
The autoclave expansion test (ASTM C 151) is used to provide an index of potential delayed
expansion caused by the hydration of CaO and MgO in hydraulic cements. Questions have arisen
over the years regarding the effect of excess crystalline free MgO (periclase) on cement
soundness and concrete durability under actual service conditions. It has been suggested that the
autoclave expansion test is overly severe and will exclude cements that perform well in concrete
under field service conditions with no reduction in long-term durability. Other experimental
protocols and tests for soundness have also been developed and investigated over past years,
including an update of the Le Chatelier Soundness Test and a number of other modifications in
testing temperatures and time of testing. Chemical compositional influences on periclase
formation and the resistance of cement or concrete to expansion have also been identified. The
purpose of this literature review is to update and supplement previous reviews on this topic.

REFERENCE
Klemm, Waldemar A., Cement Soundness and the Autoclave Expansion Test: An Update of the
Literature, R&D Serial No. 2651, Portland Cement Association, Skokie, Illinois, USA, 2005,
20 pages.
 Cement Soundness and the
Autoclave Expansion Test –
An Update of the Literature
by Waldemar A. Klemm*

INTRODUCTION
Cement soundness generally can be considered to be a resistance to, or the lack of, any swelling,
cracking, or disintegration resulting from an expansive chemical reaction such as the hydration
of free lime (CaO) or crystalline free magnesia (MgO) in cement paste, mortar, or concrete.
Although the delayed formation of ettringite from the reaction of sulfates with calcium aluminate
also may result in deleterious expansion, this review is mainly concerned with the unsoundness
properties associated with free CaO and/or free MgO in cement.
In the United States, the autoclave expansion test (ASTM C 151) is used to provide an
index of potential delayed expansion caused by the hydration of CaO and MgO in hydraulic
cements. In other countries, cement soundness may be monitored by cement paste expansion in
boiling water with the Le Chatelier test apparatus. However, the Le Chatelier procedure
determines unsoundness from the hydration of free CaO only, whereas the autoclave procedure
measures cement paste expansion from either free CaO, free MgO, or both. However, it should
be noted that a high C3A and low C4AF content in cement, in addition to the known additive
effects of CaO and MgO, may also contribute to the total autoclave expansion.
Questions have arisen over the years regarding the effect of excess crystalline free MgO
(periclase) on cement soundness and concrete durability under actual service conditions. It has
been suggested that the autoclave expansion test is overly severe and will exclude cements that
would otherwise demonstrate acceptable field performance characteristics with no reduction in
long-term durability. In fact, there have been no reported cases of concrete failure within the last
60 to 100 years in the U.S. that can be attributed to a free MgO-induced unsoundness condition.
However, it has been argued also that this is the direct result of having such a rigorous autoclave
expansion test requirement in the ASTM C 150, Standard Specification for Portland Cement.
The purpose of this review of the technical literature is to update and supplement the
Helmuth and West (1998) reappraisal of the autoclave expansion test. Other significant reviews
include the history and status of performance tests for cement soundness evaluation (Mehta
1978) and the nature and characteristics of MgO in clinker and cement (Rehsi 1983). Dreizler
(1981) has investigated the causes of cement expansion due to periclase (crystalline MgO), and
identified the following factors as influencing cement soundness:
• MgO content of the raw materials
• Mineralogical composition of the raw materials
• Chemical composition of the raw materials

————————————
*Affiliated Consultant, Construction Technology Laboratories, Inc., PO Box 518, Apple Valley, California, 92307
USA.
 • Raw meal fineness
• Clinker burning
• Clinker cooling
• Periclase size and size distribution in the clinker
• Cement fineness
• Cement storage
• Cement additives

TECHNICAL LITERATURE SUMMARY

Historical Background
The association between the MgO content of portland cement and possible excessive expansion
had been made many years ago. Bleininger (1904) suggested that it was unjust to throw out a
cement containing 4% to 5% MgO, as many tests had shown that a magnesia content even up to
7% in an otherwise well proportioned cement had no deleterious influence. However, he did
acknowledge that Dyckerhoff (in the last half of the nineteenth century) had studied the effects
of MgO in cement and concluded that it is a dangerous ingredient, if present in large quantities,
due to its slower hydration. Bleininger showed data from Dyckerhoff's experiments which
demonstrated that hardened cements containing MgO in excess of 6% deteriorated with age and
exhibited both reduced tensile strength and excessive expansion after five years of storage.
Taylor and Thompson (1906) mentioned that many years earlier, a committee of the German
Portland Cement Manufacturers Association reported that magnesia up to 8% is harmless.
Dyckerhoff, also a member of this committee, presented a minority report stating that he had
found more than 4% MgO to be injurious.

Autoclave Expansion Test

The autoclave expansion test was first introduced by Force (1912a, 1912b) as a purchaser's
specification by the Delaware, Lackawanna & Western railroad in 1912. Force expressed the
opinion that the failure of cement to pass either the ordinary boiling test or the autoclave test was
not due to either free lime or free magnesia, but rather to the amount of coarse (greater than 200-
mesh sized) particles in the cement. He found that increasing the fineness of unsound portland
cement improved its quality and, if the material was fine enough, the cement in every case
became sound.
Bates (1927) reported the results of long-term tests on high MgO cements. It was found
that portland cement with a magnesia content of about 9.5% could be burned to produce a clinker
not materially different from one containing less than 4% MgO. Ten-year strengths of concrete
specimens made from cements containing as much as 14% MgO showed no marked
disintegration. Later work by Lerch (1929) on the boiling test for cement unsoundness
demonstrated that free lime alone was responsible any abnormal expansion, cracking, or
distortion of the cement pat. The testing of cements containing 5.0%, 8.0%, and 10.7% MgO
showed no unsoundness as measured by the 5-hour steam test (100ºC). The autoclave test,
however, was not evaluated.
In May 1937, at the Spring Meeting of the Portland Cement Association, a session
entitled “The Autoclave Test in Plant Control” was held in order to review and discuss recent

4
investigations on the autoclave expansion test. Following this, the recommendation of the PCA
laboratories for the adoption of the autoclave test and the maximum expansion limit of 1.0% was
unanimously accepted by the cement industry. However, in 1940, ASTM adopted the autoclave
test as a tentative standard (ASTM C 151-40T). The portland cement tentative standard (ASTM
C 150-40T) included a 0.5% maximum expansion limit rather than the 1.0% limit that had been
accepted by the cement industry. In 1942, the War Production Board raised the maximum
expansion to 1%, but in 1944 it was reduced again to 0.5%. Much later, in 1963, the autoclave
expansion limit was increased to 0.8% where it remains to the present time. Although it was
principally concern about the potential effects of MgO on soundness that initially led to this
adoption of the autoclave test, Vaughan (1938) concluded that it is mainly hard-burned lime
rather than hard-burned magnesia that causes expansion under autoclave conditions.

Correlation with Concrete

Brown and Swayze (1938) pointed out that the autoclave test had not yet been fully correlated
with service performance. No samples of cement were found to exist that represented bad
concrete. Microscopical studies were conducted on clinker and cements containing hard-burned
lime and hard-burned magnesia. It was found that MgO recrystallized as dense, compact
periclase crystals at rotary kiln temperatures. Its harmful expansion, however, seemed to be
inhibited by chilling the clinker so that the MgO was retained in solution in the glass. If clinker
was cooled slowly, more periclase crystallized out of the melt and larger crystals were formed. A
comparison of autoclave expansions was made on neat cement pastes, 1:2 mortars, and 1:1½:2½
concrete in which up to 5% hard-burned MgO had been added. In these tests, the neat paste with
2.5% added MgO expanded over 1% with further additions causing very high volume increases.
The mortar and concrete samples, upon autoclaving, expanded less than 0.2% with a 5% MgO
addition.
Although portland cement is accepted or rejected on the basis of the total quantity of
MgO in the cement or on the basis of the autoclave expansion test, little data exist to provide a
correlation between percentage of MgO (or periclase), autoclave expansion test results, and the
actual field performance of concrete. In a letter to Bryant Mather, J. B. Alexander (1973)
summarized some of the developments leading up to ASTM's adoption of the autoclave
expansion test method. Alexander related the details of a verbal report made at the 1937 PCA
Spring meeting by Professor C. H. Scholer (Kansas State College), who described tests that he
had conducted on concrete specimens stored under field conditions as well as other forms of
storage. Scholer stated that the only concrete specimens that showed excessive expansions were
the specimens made from cements exhibiting more than 15% expansion in the autoclave test.
Therefore, to be perfectly safe, he thought that the autoclave expansion limit for portland
cements might be as high as 10%.
Other work conducted by Gebauer (1986) showed that both portland cements and
blended portland cements produced with a clinker containing 7.5% MgO showed satisfactory
properties in a 4-year old concrete, with no evidence of deterioration. Concrete performance was
evaluated by optical microscopy, compressive strength determination of cores, and ultrasonic
pulse velocity measurements. Concrete test slabs were subjected to outdoor storage (Holderbank,
Switzerland), and companion slabs were stored in an indoor curing room at 20ºC and 95%
relative humidity. Surveillance of the two sets of concrete slabs was planned to continue for
twenty years.

5
Cement Fineness Effects
One of the factors that influence the amount of expansion that will occur when a cement is
autoclaved is the fineness or specific surface area of the cement being tested. Coarser ground
cements have always exhibited a greater amount autoclave expansion, all other things being
equal. Therefore, it is useful, when evaluating the historical literature on unsoundness
characteristics due to elevated amounts of MgO or free CaO, to consider also the progressive
increases in cement fineness over the past century. In the years 1905 to 1907, Humphrey and
Jordan (1908) conducted an extensive analytical and testing program on a number of cements,
aggregates, and mortars. A total of seven individual cement brands, as well as a blend of all
cements, was included in this test series. Sieve fineness values of the cements were determined.
The blended cement, representing an average fineness of all seven brands, had a 6.6% residue on
a No. 100 mesh sieve and a 24.3% residue on a No. 200 mesh sieve. This, by the present
standards, represents a relatively coarsely ground cement.
Almost thirty years later, Gonnerman (1934), representing an ASTM working committee
of ASTM C-1, submitted a report on the expansion of 11 portland cements during high-pressure
steam curing. Cement fineness values were given, and the average residue on a No. 200 mesh
sieve was 5.2%, and the average fineness (surface area) was found to be 160 m2/kg. In 1994,
ASTM Committee C-1 sponsored a survey of portland cements marketed in North America. The
National Bureau of Standards had conducted a survey of similar scope in 1953 and 1954. A
comparison between the 1990s cements and the 1950s cements showed a progressive change,
within all cement types, to higher fineness levels (PCA 1996). ASTM Type I portland cements,
for example, had an average fineness (Blaine) of 332 m2/kg in the 1950s, whereas the average
fineness had increased to 369 m2/kg in the 1990s.
In a study of sound and unsound cements, Narang et al. (1981) demonstrated the effects
of cement fineness on autoclave expansion. A high MgO-content cement ground to a fineness of
225 m2/kg showed an autoclave expansion of 7.06%. When the cement was ground to a higher
fineness of 350 m2/kg, the autoclave expansion dropped to 1.39%, and finally when the fineness
was increased to a value of 400 m2/kg, the resulting autoclave expansion was only 0.24%. It was
also found that cement ground from a rapidly cooled clinker gave a low autoclave expansion. By
microscopical examination, the periclase (crystalline MgO) in rapidly cooled clinker was found
as fairly uniform inclusions and varied in size between 10 to 16 µm in alite and 4 to 12 µm in
belite. In the case of cement ground from a slowly cooled clinker, the autoclave expansion was
found to be excessive. Periclase inclusions in slowly cooled clinker ranged in size from 20 to
25 µm and were confined mostly to the interstitial phases.

Periclase Size and Distribution

Gouda and Bayles (1981) also studied the clinker cooling process as it affected the crystallite
size and size distribution of periclase in clinker cooled by a planetary cooler (4.5% MgO) and
clinker cooled by a grate cooler (5.7% MgO). The more rapid cooling process resulted in smaller
periclase crystals that were predominantly located in the interstitial phases. No autoclave
expansion data were provided. Hu (1997) showed that, at a constant 5% MgO content, as the
lime saturation factor of a clinker composition increased, the free MgO (periclase) content and
the resulting cement autoclave expansion also increased. The distribution of MgO within the
different clinker phases, with varying lime saturation factor values, was also given. Boikova et

6
al. (1997) conducted detailed X-ray diffraction and electron probe microanalyses on the phase
composition and the chemical compositions of phases in commercial clinkers containing up to
7% MgO.
Studies by Kogan and coworkers (1965) showed that hard-burning mixes with only 1.5%
to 3% MgO often failed the autoclave test due to excessive amounts of free lime. The use of a
fluorspar (CaF2) mineralizer easily lowered the free lime content to less than 0.5%. Further tests
established that, by the use of 0.8% CaF2 in the raw mix, clinker containing 6% MgO could be
produced. Portland cement ground from such high-MgO clinker could pass the autoclave
expansion test because the fluorspar addition to a high-MgO raw mix had aided in the formation
of smaller periclase crystals and a more uniform distribution in the clinker. Additional work by
Nikiforov and Zosoulia (1980) showed that by the use of magnesium blast furnace slags and
other magnesium silicate-containing materials in a cement raw mix, the MgO content of the
clinker could be increased to 8.5%. The periclase that crystallized in the clinker was 1 to 7 µm in
size and uniformly distributed, thus producing a sound portland cement.

Long-Term Storage and Hydration

Soundness studies had been conducted for many years at Southwestern Portland Cement
Company (Southdown, Inc.) on the characterization of periclase in portland cement and the
autoclave expansion test. Adams (1997) reported much of this information in the Symposium on
Soundness of Hydraulic Cements at the ASTM Spring meeting. In 1937, cement from the
Fairborn, Ohio cement plant that contained 4.99% MgO and 0.22% free CaO was tested for
soundness. Paste bars were autoclaved at three different time periods, and other bars were stored
under water for twenty years. A paste bar that was autoclaved after 24 hours disintegrated from
excess expansion. However, the autoclave expansion of a bar after 3 days of water curing was
0.48% and that of a bar after 7 days of curing was 0.22%. Long-term water storage resulted in a
maximum expansion of 0.313% after 20 years, and a bar that was autoclaved after this 20 years
of water storage only expanded an additional 0.03%. Gonnerman, Lerch, and Whiteside (1953)
later obtained similar results in their exhaustive study of cement soundness.
In 1965, very high-MgO clinker was received at the Southwestern Portland Cement Co.
Victorville, California Research Laboratory from a cement plant in Uruguay (Adams 1997). The
clinker was ground in a laboratory mill (2% SO3) to a Blaine fineness of 333 m2/kg. The
calculated Bogue composition of the clinker was 60% C3S, 14% C2S, 5.4% C3A, and 9% C4AF.
The total MgO content was 6.5% (5.4% free periclase) and the free CaO content was 0.47%. The
determination of periclase size distribution showed that 80% of the periclase was less than 5 µm
in size and 20% was in the 5 to 15 µm size range. The autoclave expansion of the laboratory-
ground cement was 0.47%.
Paste bars were also stored under water for up to 30 years, and the expansion measured at
10 years was 0.33%, at 20 years was 0.38%, and after 30 years was 0.41%, a value of
approximately one half the present ASTM C 150 autoclave expansion limit for cement. About a
year after taking the 30-year length measurement, one of the paste bars was broken in half. Half
of the broken specimen was returned to the water bath and the other half was analyzed to
determine the amount of crystalline periclase remaining. Quantitative X-ray diffraction analysis
showed that slightly more than 40% of the original periclase content still remained unhydrated in
the paste specimen after a 31-year continuous exposure to water.

7
Gebauer (1986) also determined the amount of periclase hydration that occurred in concrete that
had been made with portland and blended cements ground from clinker containing 7.5% MgO.
The periclase content of the 1-day old concrete, determined by X-ray diffraction using the mortar
fraction of concrete cores, was found to be 0.73%. After four years, 70% of the periclase was
unhydrated (0.51% periclase remaining). After subsequent autoclave treatment of the 4-year old
sound concrete, 40% of the periclase still was unhydrated (0.29% periclase remaining in the
concrete). Gebauer concluded that his investigations confirmed the irrelevance of the ASTM
autoclave test for the performance of concrete in practice.

Hard-Burned Periclase Additions

This extremely slow rate of periclase hydration in high-MgO portland cements, clearly
demonstrated in the above two studies, also points out some unusual and conflicting analytical
results that also have been published over the years in the technical literature.
For example, White (1928) summarized the results of tests on volume changes of neat cement
bars in water that had been conducted over a period of 26 years. In this work, tests were
conducted in which additions of hard-burned MgO, ranging from 1% to 4%, were made to a
normal commercial portland cement in order to determine its effect on the expansion of paste
bars over the 26-year time period. Cements containing 3% and 4% additions of MgO did not
show a marked expansion until after 3 years in water, and then reached their maximum
expansion by 8 years. After attaining 1.0% expansion (3% MgO addition) and 2.3% expansion
(4% MgO addition), there was virtually no additional expansion of either up to 26 years.
Brown and Swayze (1938), in work that strongly supported the adoption of the autoclave
expansion test, also admixed light-burned and hard-burned MgO to portland cement in order to
determine their effect on the autoclave expansion. No expansion was found for cement mixtures
containing up to 5% of light-burned magnesia, as presumably this material hydrated before set
had taken place and, therefore, autoclaving the paste bars caused no damage. However, when
hard-burned MgO was added to the cement, all additions above 2.5% MgO failed the autoclave
expansion test.

Hydration at 50ºC
Gaze and Smith (1973) studied the expansion of cements under conditions of autoclaving and by
storage under water at a temperature of 50ºC. In these tests, a cement containing 1.05% MgO
was blended with 2% to 5% amounts of hard-burned periclase. The periclase was prepared by
calcination of MgCO3 at 1300ºC, followed by grinding to below 200 mesh, subsequent hard-
burning at 1500ºC, and then final screening to pass a 44 µm mesh sieve. X-ray diffraction
analysis showed the periclase to be fully hydrated both after autoclaving and after storage for one
year in 50ºC water.
In work by Hawkins and Hayden (1976) and Hawkins (1997), over 100 cement samples
were analyzed for their free periclase content, using quantitative X-ray diffraction analysis and
compared to the total chemical MgO content. Cements containing a range of natural (formed
during clinkering) crystalline periclase contents up to 4.6% (6% total MgO by chemical analysis
and varying periclase size distributions were hydrated at 50ºC for one year. This accelerated
curing gave expansion that increased with increasing periclase content, but appeared to be

8
independent of periclase size. None of the cements showed any distress or regression of strength,
including the 6% MgO cement, which exhibited a maximum expansion of 0.24%.
These data contrasted with the corresponding autoclave expansion results that showed
expansion to be dependent upon both size and amount of periclase. The cement with 6% MgO
exhibited an autoclave expansion of 8.75%. The work also suggested that satisfactory service life
could be obtained despite excessive autoclave expansion results. Hawkins also found that natural
clinker periclase cured at 50ºC in direct contact with immersion water did not hydrate completely
in one year, contrary to Gaze and Smith's results with admixed periclase, and also hydrated only
slightly more upon subsequent autoclaving.

Multiple Autoclave Cycles

Cherney and Hooton (1987), in a study of cement grout expansions causing porcelain insulator
failures, re-autoclaved cement paste bars for a total of ten standard 3-hour autoclave cycles.
Initially, this was considered an unusual test series as it is commonly assumed that the C 151
autoclave cycle is sufficient to hydrate all of the periclase to Mg(OH)2 (brucite), and that the
expansion should be complete. However, it was found that large expansions, relative to those
obtained after the first autoclave cycle, occurred for the first four or five cycles. Thereafter,
incremental expansions steadily diminished until the ninth or tenth cycle where very little or no
further expansion occurred. Royak et al. (1963), as part of an investigation on autoclave
expansion parameters of cements containing up to 15% MgO, also analyzed high MgO cement
pastes that had been stored for 11-years. The quantitative X-ray diffraction analysis of these
specimens showed that only 30% to 40% of the original periclase had hydrated during that time
period.
This clearly demonstrates that there are significant differences in the hydration
characteristics between natural occurring periclase in commercial kiln-burned clinker and the
periclase burned separately and then blended with cement. Welch (1972), in the chapter on phase
equilibria in cement clinker, points out that free MgO or periclase melts at above 2825ºC and is
one of the most refractory of oxides.

Periclase Crystallization
Therefore, unless MgO has first dissolved in the clinker liquid phase and then subsequently
crystallized as periclase upon clinker cooling, no other source of MgO would have reached a
sufficiently high temperature to actually melt. Periclase produced by burning separately at
1500ºC is a densely sintered material, but with somewhat different properties compared to those
of the periclase that crystallizes from the clinker melt phase. Even in the clinkering processes,
any free MgO in excess of what is capable of being dissolved in clinker melt (e.g., very high
MgO clinker), would have different particle size and hydration properties than either the normal
crystallized periclase in clinker or a separately burned and ground periclase material. Periclase
resulting from any undissolved excess of MgO in the raw mix may also contain significant
amounts of other trace or minor constituents such as ferrous iron that are also known to influence
the hydration rates of both free CaO and free MgO.

9
FeO Effects on Hydration
In phase equilibria studies, Allen and Snow (1955) determined from X-ray diffraction data that
lime may contain up to 10% FeO in solid solution. Timucin and Morris (1970) also investigated
lime-iron oxide melts and found that solid lime can dissolve up to a maximum of about 15% FeO
at about 1050ºC. In hydration experiments, pressed pellets of CaO and several CaO-FeO solid
solutions (2%, 3%, 4%, and 6% FeO) were sintered for 36 hours at 1100ºC, and then allowed to
hydrate at room temperature, in air of 55% relative humidity. Whereas the sample of pure free
CaO began to react immediately and was about 55% hydrated in ten hours, the CaO-FeO solid
solution containing 2% FeO was 10% hydrated in ten hours. As the amount of FeO increased, the
rate of hydration dramatically decreased. The CaO-FeO solid solution containing 6% FeO had
only undergone about 10% hydration after 100 hours.
Phillips et al. (1961) studied phase relations in the magnesium oxide-iron oxide system
that indicated an extensive solid solution of FeO in MgO may also occur at normal clinkering
temperatures. In view of the significant effect that FeO has on reducing the hydration rate of free
CaO, it might be expected that FeO could have a similar effect on the periclase hydration rate.
FeO (wüstite) also has the same cubic crystal structure as both free CaO and periclase.

Hydration Kinetics
Other investigations have been conducted on the hydration characteristics of lime and magnesia.
Wells and Taylor (1937) studied the hydration of MgO in hydrated dolomitic limes. Hydration
kinetics were determined at different temperatures (atmospheric pressure) as well as at various
autoclave steam temperatures. Generally, in hydrated dolomitic limes the calcium oxide is
completely hydrated, while the magnesia is only slightly hydrated. By the use of steam at 177ºC
(120 lb/in2 or 0.83 MPa), 95% of the MgO was hydrated in 40 minutes, while at 25ºC, about
75 days was required for the same amount of hydration. Glasson (1963) also investigated the
hydration kinetics of magnesium oxide, based upon a study of MgO that had been produced by
calcination of MgCO3 at 1000ºC. Hydration rates were determined on MgO samples that differed
widely in specific surface area. Therefore, the reaction rates differed considerably, with the
hydration reaction generally proceeding inwards from the outside of each oxide crystallite by an
advancing interface mechanism. Magnesia and limes prepared from their respective carbonates at
1000ºC showed similar hydration characteristics.

Hydrotalcite Formation
Long-term slow hydration of periclase in a hardened cement system, as is well known, results in
the correspondingly slow formation of magnesium hydroxide (brucite). Brucite, a rather
insoluble compound, has a solubility product (Ksp) of 5.61 × 10-12. However, either by slow
diffusion or by other mechanisms, some MgO may interact with alumina gel or other aluminate
phases and transform into a hydrotalcite (M4AH10) phase. Gollop and Taylor (1994), in a
microanalytical study of the one-year hydration of sulfate-resisting portland cements, suggested
that, in addition to brucite formation, magnesium appears to enter a hydrotalcite-type phase with
a 2.5 Mg/Al ratio. Although other magnesium-containing compounds are usually not expected,
Royak et al. (1963) reported, from X-ray diffraction analysis, the presence of the hydrous

10
magnesium silicate, serpentine, in a 12.3% MgO-containing cement paste that had been stored
under water for 11 years.

Raw Mix Composition Factors

It is been a generally useful “rule of thumb” that approximately 2% of the total MgO content in a
cement clinker will remain in solid solution in other clinker phases, and the remainder of the
MgO is expected to be present in the form of periclase crystals. Hu (1997) has presented data
showing the distribution of MgO as free MgO (periclase), MgO in alite and belite, MgO in the
ferrite phase, and MgO in other phases. The five cements that were characterized varied from
1.5% total MgO (0% free MgO) to 11.0% total MgO (6.9% free MgO). However, the amount of
periclase in clinker, the particle size, and the particle size distribution will vary considerably
based upon such factors as the chemical composition of the raw feed, the raw feed fineness, raw
feed mineralogy, clinkering temperature, and clinker cooling history. All of these may have a
direct influence on the amount of expansion that could result from the autoclave test procedure.
Compositional factors that have been investigated, in addition to the MgO present,
included the lime saturation factor, clinker SO3, and various other targets and ratios that include
amounts of Fe2O3 and Al2O3 available. Schmitt-Henco (1971) patented a process for
manufacturing sound high-MgO cements. It was found that an elevated-SO3 clinker (from CaSO4
additions to the raw mix or by the use of high-sulfur fuel) also prevented the excessive autoclave
expansion of high MgO cement. With 5% MgO-containing clinker with three levels of clinker
SO3, the cement autoclave expansion was 0.44% for a 2.17% SO3 clinker, approximately 4%
expansion for a 1.01% SO3 clinker, and a fully disintegrated specimen for a 0.37% SO3 clinker.
Further work (Schmitt-Henco 1974) showed that with a lower lime saturation factor (0.94 to
0.97) increasing MgO has no influence on the free CaO. With a higher lime saturation factor
(0.97 to 1.00), any increases in MgO content result in more free CaO and the risk of cement
unsoundness.

Iron Addition Effects

The amount of Fe2O3 in a raw mix design or ferrite in clinker has been associated with cements
being able to pass or fail the autoclave expansion test due to an elevated MgO content. In the
discussion portion of the White (1928) paper on volume changes of cement, R. H. Bogue
concluded that, “The free MgO will decrease as Fe2O3 increases in the mixture.” Fox (1937)
investigated the effects of Fe2O3 content of cements on their autoclave expansion due to MgO. A
series of nine cements were studied that ranged in MgO content from 1.2% to 5.0% and had
varying amounts of Fe2O3. The iron content was found to significantly reduce the autoclave
expansion of high-MgO cements. For example, a cement with 5.0% MgO and 2.3% Fe2O3 had
an autoclave expansion of 1.28%, whereas another cement containing 4.9% MgO and 3.6%
Fe2O3 expanded 0.15%.
Other extensive studies (Cement and Lime Manufacture 1956) were reported on a large
number of portland cements (5.25% to 6.97% MgO) that were characterized by chemical
composition and autoclave expansion. The results of these tests showed that C4AF is an excellent
stabilizer for MgO and is capable of a transformation of considerable amounts of MgO into a
non-expanding compound. It was suggested that lowering the alumina modulus and, thereby
lowering the C3A and increasing the C4AF contents, could readily counteract the autoclave

11
expansion influence of MgO, but it was conceded that the rapid cooling of clinker also has a very
beneficial effect on the stabilization of MgO.

Mix Design Guidelines

Other raw mix targets and guidelines have been demonstrated to be very useful in burning
clinker that contains a relatively large amount of MgO. Hauser (1998) developed a raw mix
formula that could be applied at any plant with high-MgO raw materials in order to eliminate
autoclave expansion failures. Although different kilns in a plant could have different mix control
criteria, each plant almost always had a different limit. In most cases, this limit, a critical ratio,
should not be exceeded in order to avoid expansion problems. The ratio was simply expressed as
the alumina plus magnesia, this total divided by the iron oxide, and a target limit of 2.7
maximum.
Another mix design ratio, which has been successfully used at one cement plant, is the
ratio of MgO to Fe2O3. This facility has operated with MgO contents as high as 5% without
expansion failures. Stevenson (2000) has analyzed plant data that show the relationships between
% MgO, the MgO:Fe2O3 ratio, and the resulting autoclave expansion values. The following
guidelines are used for raw mix control:
• MgO:Fe2O3 > 1.53 plant in trouble; autoclave expansion prevalent
• MgO:Fe2O3 > 1.40 danger zone; high probability of expansion;
any appreciable free CaO gives excess expansion
• MgO:Fe2O3 < 1.40 probability of expansion failure decreases rapidly
• MgO:Fe2O3 < 1.20 standard control target (maximum value) —
failure due to MgO very unlikely

Pozzolanic Additions
Many investigations have been conducted on the use of pozzolanic additives to cement and their
beneficial effect of such additives on reducing the autoclave expansion of cements, as well as the
reduction of any potential long-term expansion. Among others, Ali and Mullick (1998) and
Malolepszy (1973) have described the additions of fly ash for volume stabilization of unsound
high-MgO portland cements. Liu et al. (1998) studied the expansion of cement pastes containing
2% to 6% of an admixed commercial magnesia (calcined at 1100ºC in a rotary kiln), and
hydrated under water at 20º and 50ºC. The addition of 32% fly ash and slag reduced the
autoclave expansion of the cements containing admixed magnesia, but it was determined that fly
ash was more effective in this regard than slag added at the same concentration. The authors also
concluded that light-burned magnesia, calcined separately and then added to the cement, is quite
different from the normal periclase in clinker.
Ramachandran (1984) opined that one of the major objections to the use of the autoclave
method is that under high-pressure steam-curing conditions the cement paste forms a weaker
matrix than it would under normal curing conditions. It was found that the addition of 20% silica
sand (passing 100 mesh) to portland cement, when autoclaved, produced a matrix of equal
strength to that of a neat cement paste cured at ambient temperature for 28 days. Subsequent
autoclave testing of cement that contained silica sand and 4% to 5% additions of dead-burned
periclase (calcined at 1400ºC) showed a significantly lower level of expansion. The autoclave
method hydrated almost all added MgO, whereas curing at 50 or 100ºC resulted in only partial

12
hydration and lower expansion. It was concluded that the standard autoclave test is too severe,
and a solution is to use cement-SiO2 mixtures rather than cement alone for a more realistic
assessment of unsoundness.
Rehsi and Garg (1992) investigated the 20-year hydration at 27ºC of a high-magnesia
cement (10% MgO) and the same cement blended with 30% fly ash (equivalent to ASTM
Class F). It was determined that the high-MgO cement without fly ash showed an expansion of
1.83% after 14 years of storage, and the cement with fly ash, in contrast, expanded only 0.26%
after 20 years. No autoclave tests had been conducted on either of the cements. However, both
cements were found by X-ray diffraction analysis to still contain unhydrated periclase after the
entire 20 years of water storage.
Ananenko (1986) reported the results of 20-year expansion measurements made on three
cements with 5.2%, 6.0%, and 6.5% MgO, and also containing 15% additions of 3 different
pozzolanic materials (tripoli earth, fly ash, and tuff). Although the pozzolan-free cements failed
the autoclave test (5% to 12% expansion), the addition of the pozzolanic materials reduced the
autoclave expansion of each cement to less than 0.5%. The expansion values of all the cements
in the test series, over the 20-year storage period, were less than 0.4%. In order to enhance
soundness in high-MgO cements, it was recommended to produce as high a C3S content as
possible in the clinker and an elevated iron content. Clinkering mineralizers such as fluorspar
(CaF2) have also been found to be useful in this regard.

Expansive Cements
Although most of the work published in the technical literature has been focused on the nature
and causes of unsound performance of portland cements, it should also be noted that shrinkage-
compensating or expansive cements have been developed that utilize these same expansive
characteristics. These cements use, as the controlling expansive agent, free CaO (Allen 1975;
Daugherty 1977) and periclase (Mehta et al. 1980; Liu et al 1992).

Periclase Analysis
Well-formed crystalline and dendritic periclase may be readily identified and estimated by
examination of clinker with a petrographic microscope, as demonstrated, for example, in the
early work of Insley and McMurdie (1938). In addition, there are many other methods that have
been developed for the quantitative analytical determination of free MgO or periclase. In
practice, quantitative X-ray diffraction analysis is perhaps the most dependable and rapid
analytical method for the determination of periclase in clinker or portland cement. For the
quantitative analysis of periclase, Paluch (1996) utilized the hkl (200) interference peak, with a
d-spacing of 0.2106 nm (42.9º 2θ Cu Kα). Samples were ground to a maximum particle size of
40 µm, and then scanned over the range of 41.50º to 44.25º 2θ. Peak areas were used rather than
peak heights in order to avoid any of the problems associated with peak broadening from
samples ground too finely. The absolute analytical error for a periclase content of approximately
5% by mass is about 0.05% by mass. A detailed ASTM (2001) X-ray diffraction analytical
procedure is also provided for the quantitative determination of periclase, C4AF, and both cubic
and orthorhombic C3A phases in portland cement and clinker.

13
Arjunan and Kumar (1994) developed rapid wet chemical methods for the determination of free
CaO and free MgO in clinker or cement. Free CaO is determined by the ammonium acetate
method (AAM) and the free MgO is determined by the ammonium nitrate method (ANM). In
this latter procedure, both CaO and MgO are extracted with an alcoholic ammonium nitrate
solution, followed by two complexometric titrations with EDTA. With a buffered pH and mixed
indicator, the titration endpoint yields the total CaO and MgO. With a different pH and indicator,
only free CaO is determined. The difference between the two determinations provides the MgO
content in the test sample.
In another analytical procedure, Katyal et al. (1998) also determined free MgO in cement
and clinker by a preliminary extraction with an alcoholic ammonium nitrate solution, followed
by complexometric titrations with EDTA. Calcium was titrated with one indicator, and both
calcium and magnesium were co-titrated at pH 10, using a different indicator. Again, the free
MgO value was obtained by difference.

Selective Dissolution Methods

The chemical separation of periclase from clinker and cement can be accomplished by the
selective dissolution of all the other cement phases. The residual periclase obtained by this
process can subsequently be analyzed directly for particle size and particle size distribution
determinations, using either optical microscopy or a particle size analyzer. Adams and Larkin
(1983) developed an analytical method that was termed the “Triple Leach” method. Crushed
(passing No. 4 mesh) clinker or cement are first leached with a maleic acid and methanol
solution to dissolve silicates. Secondly, the maleic acid residue is leached with an acetic acid and
water solution (pH 3.2 to 3.3), and thirdly, this residue is leached with an acetic acid, potassium
fluoride, and water solution (pH 3.5 to 3.6). The three extraction treatments remove the silicate,
sulfate and aluminate phases, free lime, and about 80% of the ferrite phase. The remaining
residue is periclase.
Analytical procedures have also been developed at CTL, Inc. that utilized selective
dissolution methods for the isolation and characterization of periclase in cements and clinker. In
summary, cement or clinker is sequentially treated by two different selective dissolution
techniques to yield a periclase residue for chemical analysis, microscopical examination, and
particle size distribution studies. This procedure involves first selectively removing the silicate
phases, followed by removal of the interstitial phases.
The two selective dissolution techniques that form the basis for the isolation of periclase
include a salicylic acid and methanol solution procedure and also a very hot (95ºC) potassium
hydroxide (KOH) and sucrose (sugar) solution procedure. The salicylic acid-methanol procedure
(Takashima 1958) selectively dissolves alite and belite from the clinker or cement, leaving a
solid residue of aluminate, ferrite, periclase, and sulfates. Subsequently, the hot KOH-sugar
solution (Gutteridge 1979) selectively dissolves the remaining interstitial phases and sulfates,
leaving behind a solid residue of periclase.

ACKNOWLEDGEMENTS
The research reported in this paper (PCA R&D Serial No 2651) was conducted by Construction
Technology Laboratories, Inc., with the sponsorship of the Portland Cement Association (PCA
Project Index No. 98-05). The contents of this paper reflect the views of the author, who is

14
responsible for the facts and accuracy of the data presented. The contents do not necessarily
reflect the views of the Portland Cement Association.

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