Professional Documents
Culture Documents
by Waldemar A. Klemm
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
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.
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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.
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.
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.
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.
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.
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.
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.
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.
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.
REFERENCES
Adams, Lawrence D. and Larkin, E. E., “A Method for the Measurement of Periclase Grain Size
in Portland Cement and Clinker,” oral presentation, American Ceramic Society Regional
Meeting, San Diego, California, USA, October 1983.
Adams, Lawrence D., “30-Year Study on High-MgO Cement,” oral presentation, Symposium on
Soundness of Hydraulic Cements, ASTM Spring meeting, St. Louis, Missouri, USA,
June 18, 1997.
Ali, M. M. and Mullick, A. K., “Volume Stabilization of High MgO Cement: Effect of Curing
Conditions and Fly Ash Addition,” Cement and Concrete Research, Vol. 28, No. 11, 1998,
pages 1585 to 1594.
Allen, J. H., Klemm, W. A., and Luker, J. P., “Expansive Cement,” United States Patent
3,884,710, May 20, 1975.
Allen, W. C. and Snow, R. B., “The Orthosilicate-Iron Oxide Portion of the System CaO–FeO–
SiO2,” Journal of the American Ceramic Society, Vol. 88, No. 8, 1955, pages 264 to 280.
Ananenko, N. F., “Magnesium Oxide in Portland Cement,” Proceedings of the 8th International
Congress on the Chemistry of Cement, Vol. VI, Rio de Janeiro, Brazil, 1986, pages 143 to 148.
Arjunan, P. and Kumar, A., “Rapid Techniques for Determination of Free Lime and Free
Magnesia in Cement Clinker and Portlandite in Hydrates,” Cement and Concrete Research,
Vol. 24, No. 2, 1994, pages 343 to 352.
Bleininger, Albert Victor, The Manufacture of Hydraulic Cements, Fourth Series, Bulletin No. 3,
Geological Survey of Ohio, Columbus, Ohio, USA, 1904.
Boikova, A. I., Fomicheva, O. I., and Luginina, I. G., “Phases in High-Magnesium Clinkers,”
Proceedings of the 10th International Congress on the Chemistry of Cement, Vol. 1, Gothenburg,
Sweden, 1997, pages 1i057 to 1i062.
15
Brown, L. S. and Swayze, M. A., “Autoclave Tests and the Microscope,” Rock Products,
June 1938, pages 65 to 69.
Cement and Lime Manufacture, “Prevention of Expansion of Cement Made with Clinker Rich in
Magnesia,” Vol. XXIX, No. 1, January 1956, pages 1 to 6.
Cherney, E. A. and Hooton, R. D., “Cement Growth Failure Mechanism in Porcelain Suspension
Insulators,” IEEE Transactions on Power Delivery, Vol. PWRD-2, No. 1, January 1987,
pages 249 to 255.
Daugherty, K. E., Luker, J. P., Allen, J. H., and Klemm, W. A., “Expansive Cement,” United
States Patent 4,002,483, January 11, 1977.
Force, H. J., “Autoclave Boiling Test for Cement,” Engineering News, Vol. 67, No. 24, June 13,
1912a, pages 1111 to 1116.
Force, H. J., “Autoclave Test for Cement,” Board of Trade and Engineering Journal, November
1912b, pages 13 to 17.
Fox, J. J., “The Influence of Iron Oxide in Clinker on Autoclave Expansion Resulting from
Magnesia,” The Autoclave Test in Plant Control, presented at the General Session of the Spring
Meeting (New York), Portland Cement Association, Chicago, May 1937, pages 63 to 64.
Gaze, M. E. and Smith, M. A., “High Magnesia Cements I: Curing at 50ºC as a Measure of
Volume Stability,” Cement Technology, Vol. 4, No. 6, November/December 1973,
pages 224 to 236.
Gebauer, J., “Effect of High MgO Content in Cement Upon Long-Term Properties of Concrete,”
Proceedings of the 8th International Congress on the Chemistry of Cement, Vol. VI, Rio de
Janeiro, Brazil, 1986, pages 154 to 157.
Glasson, D. R., “Reactivity of Lime and Related Oxides IX: Hydration of Magnesium Oxide,”
Journal of Applied Chemistry, Vol. 13, March 1963, pages 119 to 123.
Glasson, D. R., “Reactivity of Lime and Related Oxides XI: Production of Dolomitic Lime,”
Journal of Applied Chemistry, Vol. 14, March 1964, pages 121 to 128.
16
Gonnerman, H. F., “Report of Working Committee on Volume Change and Soundness of
Portland Cement,” Proceedings of the Annual Meeting of American Society for Testing
Materials, Vol. 34, Part I, Philadelphia, Pennsylvania, USA, 1934, pages 356 to 360.
Gonnerman, H. F., Lerch, William, and Whiteside, Thomas M., Investigations of the Hydration
Expansion Characteristics of Portland Cements, Research Department Bulletin 45, Portland
Cement Association, Chicago, Illinois, USA, June 1953, 168 pages.
Gouda, George R. and Bayles, James, “How the Cooling Process Affects the Distribution and
Particle Size of Periclase (MgO) Crystals,” Proceedings of the Third International Conference
on Cement Microscopy, International Cement Microscopy Association, Houston, Texas, USA,
1981, pages 89 to 98.
Gutteridge, W. A., “On the Dissolution of Interstitial Phases in Portland Cement,” Cement and
Concrete Research, Vol. 9, No. 3, 1979, pages 319 to 324.
Hauser, Karl, “Expansion of Cements: Cause and Control,” Journal of Cement, Concrete &
Aggregates, Vol. 20, No. 1, 1998, pages 192 to 193.
Hawkins, P. and Hayden, K. L., “The Effect of Free MgO in Clinker on Volume Stability,”
Paper 18, Cement Chemists Seminar, Portland Cement Association, Skokie, Illinois, USA, 1976,
21 pages.
Hawkins, Peter, “Factors Effecting the Amount of Periclase in Cement and its Effect on Volume
Stability,” oral presentation, Symposium on Soundness of Hydraulic Cements, ASTM Spring
meeting, St. Louis, Missouri, USA, June 18, 1997.
Helmuth, Richard and West, Presbury B., “Reappraisal of the Autoclave Expansion Test,”
Journal of Cement, Concrete & Aggregates, Vol. 20, No. 1, 1998, pages 194-219. (PCA R&D
Serial No. 1955a, Portland Cement Association, Skokie, Illinois, USA, 1997, 44 pages.)
Hu, Guojun, “The Application of High Magnesium Oxide Content Limestone in Cement
Industry,” Proceedings of the 10th International Congress on the Chemistry of Cement, Vol. 1,
Gothenburg, Sweden, 1997, pages 1i023 to 1i030.
Humphrey, Richard L. and Jordan, William, Jr., Portland Cement Mortars and Their Constituent
Materials, Bulletin No. 331, Department of the Interior, United States Geological Survey,
Washington, D.C., USA, 1908, 130 pages.
Insley, Herbert and McMurdie, Howard F., “Minor Constituents in Portland Cement Clinker,”
RP1074, Journal of Research of the National Bureau of Standards, Vol. 20, February 1938,
pages 173 to 184.
Katyal, N. K., Ahluwalia, S. C., Parkash, R., and Sharma, R. N., “Rapid Estimation of Free
Magnesia in OPC Clinker and 3CaO:1SiO2 System by Complexometry,” Cement and Concrete
Research, Vol. 28, No. 4, 1998, pages 481 to 485.
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Kogan, L. S. and Nikiforov, Yu V., “Manufacturing Portland Cement with High MgO Content,”
Tsement, Vol. 31, No. 1, 1965, pages 9 to 11.
Lerch, Wm., “The Cause of Unsoundness in Portland Cement,” Paper No. 20, Portland Cement
Association Fellowship at the National Bureau of Standards, Washington, D.C., July 1929,
19 pages.
Liu, Zheng, Cui, Xuehua, and Tang, Mingshu, “Hydration and Setting Time of MgO-
Type Expansive Cement,” Cement and Concrete Research, Vol. 22, No. 1, 1992, pages 1 to 5.
Liu, Zheng, Tang, Mingshu, and Cui, Xuehua, “Expansion of Cement Containing Crystalline
Magnesia With and Without Fly Ash and Slag,” Journal of Cement, Concrete & Aggregates,
Vol. 20, No. 1, 1998, pages 180 to 185.
Malolepszy, Jan, “Stabilization of Magnesia Portland Cement by Fly Ash,” Cement Wapno Gips,
Vol. 28, No. 6, 1973, pages 207 to 209.
Mehta, P. K., “History and Status of Performance Tests for Evaluation of Soundness of
Cements,” Cement Standards – Evolution and Trends, ASTM STP 663, American Society for
Testing and Materials, Philadelphia, Pennsylvania, USA, 1978, pages 35 to 60.
Mehta, P.K., Pirtz, D., and Komandant, G. J., “Magnesium Oxide Additive for Producing
Selfstress in Mass Concrete,” Proceedings of the 7th International Congress on the Chemistry of
Cement, Vol. III, Paris, France, 1980, pages V-6 to V-9.
Narang, K. C., Ghosh, S. P., and Sharma, K. M., “Microstructural Characteristics of Sound and
Unsound Clinkers with Varying MgO Content,” Proceedings of the Third International
Conference on Cement Microscopy, International Cement Microscopy Association, Houston,
Texas, USA, 1981, pages 140 to 153.
PCA, “Portland Cement: Past and Present Characteristics,” Concrete Technology Today, Vol.
17, No. 2, Portland Cement Association, Skokie, Illinois, USA, July 1996, pages 1 to 4.
Phillips, Bert, Sōmiya, Shigeyuki, and Muan, Arnulf, “Melting Relations of Magnesium Oxide-
Iron Oxide Mixtures in Air,” Journal of the American Ceramic Society, Vol. 44, No. 4, 1961,
pages 167 to 169.
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Ramachandran, V. S., “A Test for “Unsoundness” of Cements Containing Magnesium Oxide,”
Proceedings of the 3rd International Conference on the Durability of Building Materials and
Components, Helsinki/Espoo, Finland, 1984, pages 46 to 54.
Rehsi, S. S. and Garg, S. K., “20-Year Study on Hydration of High Magnesia Cement with Fly
Ash at Ambient Temperature,” Proceedings of the 9th International Congress on the Chemistry
of Cement, Vol. IV, New Delhi, India, 1992, pages 684 to 690.
Royak, S. M., Myshlyaeva, V. V., and Chernyakhovskii, V. A., “Properties of Cements with
Increased Content of MgO After Long-Lasting Setting,” Tr Gos Vses Nauchn-Issled and Inst
Tsement Prom, No. 19, 1963, pages 30 to 51. (Chemical Abstracts, June 21, 1965).
Schmitt-Henco, Carl Heinrich, “Process for the Manufacture of Sound High-Magnesia Portland
Cements, German Patent Auslegeschrift 1,696,663, 30 December 1971.
Schmitt-Henco, C., “Magnesium Oxide Content of Clinker, Autoclave Test and Soundness,”
Proceedings of the VI International Congress on the Chemistry of Cement, Supplementary paper,
Section I, I-3, Moscow, USSR., 1974, 11 pages.
Stevenson, Richard W., Blue Circle Cement Company, personal communication, regarding
control of autoclave expansion by use of MgO to Fe2O3 ratios, to W. A. Klemm, Construction
Technology Laboratories, Inc., April 3, 2000.
Taylor, Frederick W. and Thompson, Sanford E., A Treatise on Concrete, Plain and Reinforced,
John Wiley & Sons, New York, 1906.
Timucin, M. and Morris, A. E., “Phase Equilibria and Thermodynamic Properties of Lime-Iron
Oxide Melts Containing up to 30 Percent SiO2: 1450º and 1550ºC Sections,” The Reaction
Parameters of Lime, STP 472, American Society for Testing and Materials, Philadelphia, 1970,
pages 25 to 31.
Vaughan, H. H., “Hard-Burned Lime Rather than Hard-Burned Magnesia Causes Expansion in
Autoclave?” Rock Products, June 1938, pages 70 to 71.
Welch, J. H., “Phase Equilibria and High-Temperature Chemistry in the CaO–Al2O3–SiO2 and
Related Systems,” The Chemistry of Cements, Second Printing, H. F. W. Taylor, ed., Academic
Press, London, 1972, pages 49 to 88.
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Wells, Lansing S. and Taylor, Kenneth, “Hydration of Magnesia in Dolomitic Hydrated Limes
and Putties,” RP1022, Journal of Research of the National Bureau of Standards, Vol. 19, No. 3,
September 1937, pages 215 to 236.
White, Alfred H., “Volume Changes of Portland Cement as Affected by Chemical Composition
and Aging,” Proceedings of the Annual Meeting, Vol. 28, Part II, American Society for Testing
Materials, Philadelphia, Pennsylvania, USA, 1928, pages 398 to 431.
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