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ABSTRACT
Sorption isotherms of a number of gypsum building materials have been measured using different drying protocols. The results
show that the isotherms are sensitive to the initial drying conditions. The current ASTM test method recommends that gypsum
materials be dried at 40°C (104°F), but the drying relative humidity is not specified. The intent of the relatively low drying temper-
ature is to remove the hygroscopically bound water and to prevent the loss of chemically bound water. It was found that drying
at 40°C (104°F) and about 0.2% relative humidity in an oven flushed with dry air results in loss of the chemically bound water,
while drying at 40°C (104°F) and 11-12% relative humidity in a vented oven does not sufficiently dry the material. Drying at
23°C (73°F) and ~0.5% relative humidity as obtained in an oven or enclosure flushed with dry air or in a desiccator is recom-
mended for these types of materials.
K.E. Wilkes is a distinguished R&D staff member, J.A. Atchley is a research technician, and P.W. Childs is a staff engineer, Building Enve-
lopes Group, Engineering Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tenn.
©2004 ASHRAE.
drite upon heating is a well-known phenomenon. It contributes between 11.3% and 97.4% at a temperature of 23°C (73°F)
directly to the effectiveness of gypsum board as a fire barrier. (ASTM 2003a, 2003c). The desiccators were placed inside
When one surface of gypsum board is exposed to a fire, the controlled temperature/humidity cabinets where the tempera-
water of hydration is slowly released as steam. Since the ture was controlled at 23.0±0.1°C (73.4±0.2°F). Measure-
chemical reaction is endothermic, heat transmission through ments were started at the lowest RH and, after equilibrium was
the board is retarded. A dehydrated zone propagates through reached, the specimens were transferred to the next higher RH
the thickness of the board, with the temperature on the other until measurements had been made over the range of RHs.
side of the zone never greatly exceeding 100°C (212°F). This The specimens consisted of about 10 to 15 grams (0.02 to
is below the temperature at which lumber begins to ignite or 0.03 lb) of material cut roughly into 13 mm (0.5 in.) cubes. The
at which steel begins to lose its strength (Gypsum Association specimens were contained in 60 mL (2 fluid oz) flint glass jars
1982). with tightly fitting polypropylene lids from which the card-
The loss of water of hydration is also utilized in ASTM board liners had been removed. The lids were placed on the
Test Method C 471M-01 for quantitative chemical analysis of jars for weighings on a balance that had a capacity of 5 kg (11
gypsum and gypsum products. The amount of free water lb) and a resolution of 1 mg (2 ×10–6 lb). Each data point is the
contained in a sample is determined by heating to 45±3°C average of three replicates, as specified by C 1498.
(113±6°C) for two hours and measuring the mass loss. The
amount of chemically combined water is determined by heat- MATERIALS TESTED
ing to 215-230°C (419-446°F) for two hours and measuring
the mass loss. The mass loss at the higher temperature is used Sorption isotherm tests were performed on the following
to calculate the purity of gypsum or the amount of gypsum or commercially available materials:
gypsum plaster in gypsum products (ASTM 2003b).
Gypsum usually dehydrates in a two-step process, • Nominal 12.7 mm (0.5 in.) thick regular gypsum wall-
converting first to hemihydrate and then to anhydrite. board (SHEETROCK Brand Gypsum Panels manufac-
However, under low water vapor partial pressure (or low RH), tured by the United States Gypsum Company, a division
gypsum can convert directly to anhydrite. Gypsum is usually of USG Corporation). Gypsum wallboard consists of a
considered to be stable at temperatures lower than 40°C noncombustible core that is essentially gypsum, sur-
(104°F), and the dehydration reactions are kinetically inhib- faced with paper bonded to the core (ASTM 2004a,
ited (Wirsching 1985). 2004b, 2004c). Tests were also performed on the gyp-
The specification in ASTM C 1498-01 of drying at 40°C sum core of the wallboard.
(104°F) is intended to prevent the transformation of gypsum to • Nominal 12.7 mm (0.5 in.) thick regular treated core
hemihydrate or anhydrite so that the measured sorption gypsum sheathing board (SHEETROCK Brand Gypsum
isotherm will correspond to gypsum. This paper presents Sheathing manufactured by the United States Gypsum
results of sorption isotherm measurements on several Company). Treated core gypsum sheathing board con-
commercial gypsum building materials, performed with sists of a noncombustible core that is essentially gypsum
several drying procedures. Also presented are results of drying with a water-resistant material incorporated into it, sur-
experiments on gypsum with the paper facing removed and on faced on both sides with water-repellent paper bonded to
the thermodynamics of the chemical reactions involved in the the core (ASTM 2004a, 2004c, 2004d).
loss of water of hydration. • Nominal 12.7 mm (0.5 in.) thick glass mat gypsum sub-
strate (DensGlass Gold Exterior Guard manufactured by
EXPERIMENTAL PROCEDURES the G-P Gypsum Corporation, a subsidiary of Georgia-
Two ovens were used to dry the specimens. One oven Pacific Corporation). Glass mat gypsum substrate con-
was ventilated with openings to the ambient air. It is expected sists of a noncombustible water-resistant core that is
that the dew point within this oven would be nearly the same essentially gypsum, surfaced with glass mat that is par-
as in the ambient air and, thus, the RH within the oven would tially or completely embedded in the core (ASTM
be a function of the oven temperature and the temperature 2004e). The glass mat gypsum substrate tested also had
and RH of the air surrounding the oven. The other oven was a primer coating.
tightly sealed and was continuously flushed with
compressed air piped in from the laboratory’s power plant. (Proprietary trade names are listed only as an aid to identify
The air was dried at the power plant to a dew point that varied the material tested and do not constitute an endorsement of
between –40°C (–40°F) and –51°C (–60°F), depending upon that product either by the authors or by the U.S. Government
the condition of the drying columns. or by ASHRAE. The reader is cautioned that manufacturers
After drying, the specimens were placed in airtight desic- may change products over time while retaining the same
cators containing saturated salt solutions that maintained RHs brand name.)
2 Buildings IX
Table 1. Mass Loss During Drying of Gypsum Sorption Isotherm Specimens
Mass Loss, %
Drying Conditions Wallboard Core Wallboard Sheathing Board Glass Mat Substrate
40°C (104°F), ~0.2% RH 16.8* — 15.2* 17.9*
23°C (73°F), ~0.5% RH 0.25† 0.57‡-0.64† 0.68† 0.23†
40°C (104°F), 0.09‡-0.13† 0.21‡ — —
11-12% RH
*
Preconditioned at 23°C (73°F), 50% RH
†
Preconditioned at laboratory conditions, ~22-25°C (~72-77°F), ~25-35% RH
‡
Preconditioned at 23°C (73°F), 32.9% RH
RESULTS AND DISCUSSION while the other specimens were conditioned at lower RHs of
25-35%. From the sorption isotherm data in Table 3 (to be
Sorption Isotherms discussed later), it can be seen that the main effect of these
The first set of specimens was dried at 40°C (104°F) in the differences in preconditioning would be that the mass losses
oven flushed with dry air. Based on the power plant’s dew for specimens dried at 40°C (104°F) and ~0.2% RH would
point, the RH should be less than ~0.2%. Mass losses observed have been about 0.1-0.2% lower than the values in Table 1 if
during drying at this condition ranged from 15% to 18% (see these specimens had been preconditioned at 32.9% RH instead
Table 1). The second set of specimens was dried at a lower of 50% RH. The large difference in mass loss between these
temperature of about 23°C (73°F), at which the RH should be specimens and the others remains. The differences in precon-
less than ~0.5%. As shown in Table 1, the mass losses were ditioning have no effect on the sorption isotherms to be
much smaller, ranging from 0.2% to 0.7%. It is considered that discussed next.
Sorption isotherms for the specimens dried at 40°C
the mass losses at the lower drying temperature are due to loss
(104°F) and ~0.2% RH are given in Table 2 and Figure 1.
of hygroscopic moisture, with the higher losses for the wall-
Isotherms for the four specimens were very similar. The mois-
board and sheathing board being due to moisture in the paper
ture content (MC) increased to about 4-5% at 11.3% RH, then
facings. The much higher mass losses during drying at 40°C
increased slowly as the RH was increased to 75.4% or 84.6%,
(104°F) are attributed to loss of water of hydration as the
after which it increased sharply to about 17-20%, and finally
gypsum (CaSO4•2H2O) was transformed to anhydrite
ended at around 20-23% at the final RH of 97.4%. The first
(CaSO4). Conversion of pure gypsum to pure anhydrite would
increase is attributed to transformation of anhydrite (CaSO4)
be accompanied by a mass loss of 20.9%. The smaller mass
to hemihydrate (CaSO4•½H2O). An increase of 6.6% would
losses in Table 1 are due to other materials in the products,
be expected for pure materials, and the lower measured values
such as the paper and glass facing materials, as well as silica are due to other constituents, such as paper, glass, and silica as
and other constituents within the gypsum core. mentioned earlier. The large increase at 84.6% or 94.0% is
An additional specimen of wallboard core was dried first attributed to transformation of hemihydrate (CaSO4•½H2O)
at 40°C (104°F) and ~0.2% RH and then at 204°C (399°F) in back to gypsum (CaSO4•2H2O). Conversion from pure anhy-
the vented oven (204°C [399°F] is the recommended temper- drite to pure gypsum would be accompanied by a 26.5%
ature for recharging of calcium sulfate desiccants, at which increase in MC and, again, the smaller measured MCs are due
temperature essentially all water should be removed). The to the other constituents.
mass loss during the first drying step was 16.8% (the same as Sorption isotherms for specimens dried at 23°C (73°F)
the similar specimen in Table 1), and it was 17.8% after the and ~0.5% RH are given in Table 3 and Figure 2. The MCs
high temperature drying. The extra mass loss at the high with these drying conditions are much smaller than those for
temperature is at least partly due to volatilization of other drying at 40°C (104°F) and ~0.2% RH and are considered to
constituents of the gypsum core. Evidence for this was the be entirely due to hygroscopic moisture. The sorption
appearance of a white coating on the insides of the jars. isotherms for the wallboard and sheathing board were nearly
Specimens of wallboard and wallboard core were dried in identical, and were about a factor of two higher than the
the vented oven at 40°C (104°F) and ~11-12% RH. These two isotherms for the wallboard core and the glass mat substrate.
specimens experienced mass losses of only 0.2% and 0.1%, The difference between these two groups of isotherms is due
respectively; this is considered to be due to loss of part of the to absorption of moisture in the paper facings of the wallboard
hygroscopic water. and sheathing board.
As noted in Table 1, the specimens were preconditioned Sorption isotherms for wallboard and wallboard core
prior to drying at somewhat different conditions. The largest dried at 40°C (104°F) and ~11-12% RH are listed in Table 4
difference is that the specimens dried at 40°C (104°F) and and are compared in Figure 3 with isotherms for drying at
~0.2% RH were preconditioned at 23°C (73°F) and 50% RH, 23°C (73°F) and ~0.5% RH. The isotherms for drying at 40°C
Buildings IX 3
Table 2. Sorption Isotherms for Gypsum Materials Dried at 40°C (104°F) and ~0.2% RH
Moisture Content, %
Table 3. Sorption Isotherms for Gypsum Materials Dried at 23°C (73°F) and ~0.5% RH
Moisture Content, %
Figure 1 Sorption isotherms of gypsum materials dried at Figure 2 Sorption isotherms of gypsum materials dried at
40°C (104°F) and ~0.2% RH. 23°C (73°F) and ~0.5% RH.
4 Buildings IX
Table 4. Sorption Isotherms for Gypsum Materials Dried at 40°C (104°F) and 11-12% RH
Moisture Content, %
Figure 3 Sorption isotherms of gypsum wallboard and Figure 4 Comparison of sorption isotherms for gypsum
wallboard core. wallboard with data from literature.
(104°F) and ~11-12% RH are lower than those for drying at curves for drying at 23°C (73°F)/~0.5% RH and 40°C
23°C (73°F) and ~0.5% RH and are offset by roughly constant (104°F)/~11-12% RH. Cunningham and Sprott (1984) dried
values. While the MC difference for the wallboard core is only their specimens in an oven at an unspecified temperature.
about 0.1-0.2%, it is much larger for the wallboard. The Since their data are close to our curve for drying at 40°C
isotherms for drying at 40°C (104°F) and ~11-12% RH inter- (104°F)/~0.2% RH, it appears that their specimens were trans-
sect the x-axis near 10%, implying that no moisture is gained formed nearly to anhydrite, and that their curve includes the
from 0 to ~10% RH. On the other hand, the isotherms for effect of transformation back to hemihydrate with subsequent
drying at 23°C (73°F) and ~0.5% RH have the shape that is sorption of hygroscopic moisture and then transformation to
typical of porous building materials (Kumaran 2001). These dihydrate near 100% RH. Luck’s (1964) data do not show any
data show that drying in a vented oven at 40°C (104°F) is not sorption of moisture until RHs above 80% and may be low due
adequate to remove all of the hygroscopic moisture from to inadequate drying. The curve from Kumaran’s (2001)
gypsum building materials, especially those containing paper compilation of data is intermediate between our curves for
facings. drying at 23°C (73°F)/~0.5% RH and 40°C (104°F)/~0.2%
RH, and it appears to be influenced by partial transformation
Comparison with Literature Data to dehydrated phases.
Figure 4 compares sorption isotherms for wallboard
obtained with the three drying procedures with data from the Drying Experiments
literature. Richards et al. (1992) noted the importance of It is apparent that drying conditions can introduce large
drying temperature and dried their specimens at room temper- differences in the sorption isotherms for gypsum materials. In
ature in a desiccator containing dry CaCl2, for which the RH order to determine preferred drying conditions, a series of
was taken to be 1.4%. Their data are intermediate between our drying experiments was conducted on specimens of wallboard
Buildings IX 5
Figure 5 Drying the gypsum wallboard core in dry air. See Figure 6a Arrhenius plot for drying of gypsum wallboard
text for explanation of events marked with arrows. core in dry air.
6 Buildings IX
Figure 7 Drying of gypsum wallboard core in vented oven.
Buildings IX 7
These results show the difficulty in choosing conditions
for drying of gypsum materials in preparation for sorption
isotherm measurements. Drying in a vented oven at too low a
temperature does not remove all of the hygroscopic moisture
(this will also be the case for paper facings), but drying at too
high a temperature causes loss of chemically bound water.
Likewise, drying in a very low RH environment at too high a
temperature will also cause loss of chemically bound water.
Drying in a very low RH environment at the same temperature
as the isotherm measurements are performed appears to be the
logical choice.
8 Buildings IX
be accompanied by additional surface energy and lattice strain NOMENCLATURE
energies (not included in Equations 4 and 5) that would require ∆CP= specific heat at constant pressure difference between
higher temperatures or lower relative humidities to nucleate products and reactants, kJ/mol
hemihydrate or anhydrite within the dihydrate crystal lattice.
On the other hand, Kelly et al. note that dehydration of hemi- ∆G = Gibbs energy difference between products and
hydrate does not require a significant change in the lattice reactants, kJ/mol
(rhombohedral to hexagonal), and the thermodynamics curve ∆H = enthalpy difference between products and reactants,
correctly predicts this transformation. Studies by Hudson- kJ/mol
Lamb et al. (1996) and by Paulik et al. (1992) also confirm that ∆S = entropy difference between products and reactants,
these transformations occur by the nucleation and growth kJ/mol
mechanism. Impurities and admixes within the dihydrate Pv = vapor pressure, bar
would tend to provide sites for heterogeneous nucleation. This
R = gas constant
would be accompanied by a defect contribution to the Gibbs
energy that would tend to offset some of the surface and lattice T = temperature, K
strain energies. The net effect, however, is that the present data 0 = quantity evaluated at the standard state (298.15 K, 1 bar)
confirm that the reactions are kinetically inhibited. (For
general discussions of nucleation and growth within solid REFERENCES
phases and contributions to the Gibbs energy due to surface ASTM. 2003a. ASTM C 1498-01, Standard test method for
energy, lattice strain energy, and defect energies, see Kingery hygroscopic sorption isotherms of building materials. In
[1960] and Porter and Easterling [1992]). 2003 Annual Book of ASTM Standards, Vol. 04.06. West
For drying in the oven flushed with dry air, the thermo- Conshohocken, Pa.: American Society for Testing and
dynamics curves predict transformation from dihydrate to Materials.
anhydrite below 6-8% RH for temperatures of 23-40°C (73- ASTM. 2003b. ASTM C 471M-01, Standard test methods
104°F). This transformation was observed for temperatures as for chemical analysis of gypsum and gypsum products.
low as 30°C (86°F). However, the transformation did not occur In 2003 Annual Book of ASTM Standards, Vol. 04.01.
within 30 days at 23°C (73°F), probably because of the diffi- West Conshohocken, Pa.: American Society for Testing
culty of nucleation of anhydrite at this temperature. and Materials.
ASTM. 2003c. ASTM E 104-02, Standard practice for main-
CONCLUSIONS AND RECOMMENDATIONS taining constant relative humidity by means of aqueous
Drying conditions can have a very significant effect on solutions. In 2003 Annual Book of ASTM Standards,
sorption isotherms measured on gypsum building materials. Vol. 11.03. West Conshohocken, Pa.: American Society
Drying conditions must be sufficient to remove hygroscopi- for Testing and Materials.
cally bound water, but not so severe as to remove chemically ASTM. 2004a. ASTM C 11-03d, Standard terminology
bound water. Drying at 40°C (104°F) in a vented oven does not relating to gypsum and related building materials and
remove all of the hygroscopically bound water, especially for systems, in 2004 Annual Book of ASTM Standards, Vol.
gypsum materials that include paper facings. Drying at higher 04.01. West Conshohocken, PA: American Society for
temperatures in a vented oven runs the risk of removal of Testing and Materials.
chemically bound water. Drying under desiccated conditions ASTM. 2004b. ASTM C 36/C 36M-03, Standard specifica-
(such as a desiccator or an oven flushed with dry air) at slightly tion for gypsum wallboard. In 2004 Annual Book of
elevated temperatures will remove chemically bound water. ASTM Standards, Vol. 04.01. West Conshohocken, Pa.:
Drying under desiccated conditions at room temperature American Society for Testing and Materials.
(~23°C [73°F]) over a 30-day period did not remove chemi- ASTM. 2004c. ASTM C 1396/C 1396M-03a, Standard spec-
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large variations in literature data on sorption isotherms of ASTM Standards, Vol. 04.01. West Conshohocken, Pa.:
gypsum building materials appear to be related to the (often American Society for Testing and Materials.
unreported) drying conditions. Data reported here on speci- ASTM. 2004d. ASTM C 79/C 79M-04, Standard specifica-
mens dried at room temperature and ~0.5% RH are recom- tion for treated core and nontreated core gypsum sheath-
mended for use in modeling efforts. ing board. In 2004 Annual Book of ASTM Standards,
Vol. 04.01. West Conshohocken, Pa.: American Society
ACKNOWLEDGMENTS for Testing and Materials.
Funding for this project was provided by the U.S. Depart- ASTM. 2004e. ASTM C 1177/C 1177M-04, Standard speci-
ment of Energy, Office of Building Technology, State, and fication for glass mat gypsum substrate for use as
Community Programs under contract number DE-AC05- sheathing. In 2004 Annual Book of ASTM Standards,
00OR22725 with the Oak Ridge National Laboratory, Vol. 04.01. West Conshohocken, Pa.: American Society
managed by UT-Battelle, LLC. for Testing and Materials.
Buildings IX 9
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10 Buildings IX