The Role of Magnesium Oxychloride

as a Fire-resistive Material
J. F. M O N T L E * and K. G. M A Y H A N t

The authors discuss the use of magnesium oxychloride cements

as fire-resistive coatings and show how to calculate the duration of
protection offered by such materials.

INTRODUCTION
H E basic mechanism of fire-resistive materials, such as mastic, ce-
T mentitious, or fibrous materials, is by insulation. Although the defini-
tion of insulation with regard to the mechanism of the transfer of heat is
generally straightforward, insulation can be achieved by different and
varied mechanisms. The most important are low thermal conductivity,
chemical or physical reactions that absorb heat, transpiration, and re-
flection.
Low THERMAL CONDUCTIVITY
Protection from heat by means of low thermal conductivity is the ac-
cepted definition t h a t is normally intended to describe insulation. The
low thermal conductivity of simple insulation materials is the principle
means of protection for m a n y fire-resistive materials, such as sprayed
fibers. Insulation due to low thermal conductivity is a part of the fire-
resistive capabilities of most fire-resistive materials, as all materials are,
to some extent, insulators. A measure of the relative resistance of a coating
to heat transfer is used routinely in insulation calculations and is known
simply as the coefficient of thermal conductivity or k factor. Since air is
an extremely poor conductor of heat ff movement is restricted, the better
nonconducting or good insulating materials have m a n y air voids, which
tend to hinder heat transfer and thus increase the degree of insulation.
CHEMICAL OR PHYSICAL REACTIONS
There are m a n y fire-resistive materials in which a heat absorbing chem~
ical or physical reaction is a major contribution to their fire-resistive
capabilities. A few typical but not limiting examples of these types of
reactions are as follows.

*Director of Research, Carboline Company, St. Louis, MO.

~Professor of Chemical Engineering and Senior Investigator, Graduate Center for
Materials Research, University of Missouri, Rolla Rolla, MO.
201
 202 Fire T e c h n o l o g y
Intumescence: While the primary means of insulation from intumescing
coatings or mastics is from the insulative effect of the foam-char s t r u c t u r e
t h a t is created, a considerable a m o u n t of heat is absorbed in generating
coatings or mastics is from the insulative effect of the foam-char s t r u c t u r e
. . . . . . . . . . . . . . t~ . . . . . . . . . . . . . . . . . . . . . . . . .

Sublimation: Sublimation is the direct change of state of a solid material

to a gas and requires the input of a quantity of energy to achieve this
reaction.
Calcination: Calcination is defined as the production of a powder by
the action of heat. The term calcination is derived from the common
calcination example as CaCO3 ~ > CaO + CO2. This chemical reaction
requires heat input.
Thermal Hydroregeneration: The fire resisting mechanism b y thermal
hydroregeneration (water of crystallization) can be considered a form of
calcination as it is indeed a reaction where heat input is required to form
a powder and drive off a gas. In this mechanism for providing fire resis-
tance, heat is absorbed in removing waters of hydration and absorbed
water, the insulative materials acting as a heag sink. An example is as
follows:
CaSO4 • 2H20 ) CaSO4 • 1/2H~O ÷ 3/2H0.O.
Ablation: Ablation has become a common term in the space age, as
this is the mechanism of insulation of the nose cone of most o f the re-
entry spacecraft. Ablation is really not a separate category, as it could
be considered under one or more of the previously mentioned categories
since it implies t h a t heat is dissipated by melting, vaporization, or erosion.
Transpiration: When gases or vapors are formed by any of the various
mechanisms mentioned earlier due to the action of heat on a material,
frequently a porous structure will be formed. Energy will be required to
drive these gases or vapors through this porous matrix to escape from the
fire-resistive materials. This constitutes a considerable heat sink in some
materials and can be a major contribution to the overall fire-resistive
effect of a particular compound.
Reflection: Dark dull surfaces tend to absorb heat, and s m o o t h y shiny
surfaces tend to reflect heat. Reflection has been shown to be of significant
importance to the insulative capabilities of certain fire-resistive materials
by reudcing the surface temperature. The m a x i m u m surface temperature
t h a t would result in a fire would be the flame or gas temperature. Highly
reflective or non-heat-absorptive surfaces wilt be considerably cooler.

MAGNESIUM OXYCHLORIDE CEMENTS

Magnesium oxychloride is not a new material. The discovery of mag-
nesium oxychloride cement was announced to the French A c a d e m y of
Sciences by Sorel in 1867.1 A portion of this announcement is quoted as
 51[agnesium Oxychloride 203
follows: " I have the honor to submit to the judgement of the Academy
a new cement, a basic and hydrated oxychloride of magnesium. This
cement is formed by gauging magnesia with a more or less concentrated
solution of magnesium chloride; the cement is harder, the denser the solu-
tion. In most cases, I use a chloride of 20 ° to 30 ° B a u m e . "
The magnesium oxide-magnesium chloride-water reaction has been
studied by m a n y investigators, and a wide variety of uses for these ce-
ments has been derived. Since this material is, or can be made to be,
extremely hard, tough, and durable, m a n y uses have been developed to
take advantage of these characteristics. Possibly the greatest use is in
the field of flooring compounds. The incorporation of a variety of mineral-
or vegetable-based fillers can be utilized to achieve a range of physical
characteristics in the final compositions.
Magnesium oxide reacts with magnesium chloride solutions by different
stoichiometries, depending upon the degree of calcination of the original
magnesium oxide. Reactions that have been reported include: ~

2MgO + MgC12 + llH~O > 2MgO • MgC12 • llH.~O

3MgO + MgClo + 11H~_O 3MgO • MgC12 • 11H20

5MgO -k MgCI~ + 13H~O > 5MgO • MgC12 • 13H20

I t should be noted that there are disagreements as to which of these

reactions is the more dominant.
The first reaction has a weight ratio of magnesium oxide to magnesium
chloride of 1//1.18. The second has a weight ratio of 1/0.79, and the
third, 1/0.44.
While the ratio of magnesium oxide and magnesium chloride can be
varied depending upon the use and the desired properties, typical fire-
resistive materials will be between reactions 2 and 3. The h y d r a t e d water
contents (not free water) for the resulting magnesium oxychloride cement
for each of these three reactions are 54 percent, 49 percent, and 44 percent,
respectively.
Since other ingredients are used in magnesium oxychloride fire-resistive
formulations for structural reinforcement or color, a typical hydrated
water content of fire-resistive formulations would be approximately 35
percent of the dried film.

MAGNESIUM OXYCHLORIDE AS A
FIRE-RESISTIVE MATERIAL
The various mechanisms by which insulation can be achieved have
been stated. I t is of interest at this point to discuss how magnesium oxy-
chloride fire-resistive compounds function in each of these various mech-
anisms.
204 Fire Technology
INSULATION
The k for typical magnesium oxychloride cements is approximately
(0.5 B t u / h r - f t ~-° F/ft). This value is for the cement containing t h e water
of hydration and, thus, has only a partial bearing on the insulative ability
of magnesium oxychloride fire-resistive materials, as one m u s t consider k
after the water has been driven off. The actual k can be measured, and
also, based on structure and density, it can be calculated to be in the range
0.03 to 0.05 B t u / h r - f t 2-° F / f t .
HEAT ABSORPTION
Magnesium oxychloride fire-resistive materials typically contain ap-
proximate]y 35 percent water as water of hydration plus any absorbed
free water. When heated to approximately 570 ° F, the chemically bound
water will be released; the required energy input is approximately 1000
B t u per pound of water released. The magnesium oxyckloride cement
beneath the surface, and thus also the substrate, cannot be h e a t e d above
570 ° F until all of the water has been released and driven from t h e coating.
Because of the high water content and the high energy input required to
release the water, the insulative effect of the water of hydration is con-
siderable and constitutes the principal means of insulation.
TRANSPIRATION
Merely releasing the water requires a known a m o u n t of energy; how-
ever, before additional energy from the fire source can penetrate the
magnesium oxychloride cement to release further water, the w a t e r vapor
generated must be driven from t~e hydrated cement. Since, a t typical
fire temperatures, the water vapor occupies a volume approximately
2700 times the volume of hydrated water, large volumes of gas must be
removed. The cement structure remaining after the hydrated water has
been removed is still an integrally sound structure (although mechanically
weaker than the original cement). I t is a coherent sponge-like microporous
structure, and energy is required to force the generated vapors through the
porous matrix.
This insulating effect - - the absorbing of energy to drive the vapor
through the cement to prevent energy from being absorbed to create more
vapor - - contributes some to the overall insulative effect of magnesium
oxychloride cements b u t is difficult to measure and is estimated to be small
compared to the heat of hydration.
REFLECTION
The major means of energy transfer during a fire from the heat source
to the insulated surface is by radiation. Also, the ability of a fire-resistive
material to reflect rather than absorb radiation will affect its overall per-
formance as an insulator. Since magnesium oxide rates as an excellent
reflector (the standard used as a basis for efficiency of emission) and the
structure remaining after the removal of the water of hydration is basically
magnesium oxide, one should expect reflection to be a significant factor
Magnesium Oxychloride 205
in the overall insulative capability of magnesium oxychloride fire-resistive
coatings.
I f reflection from magnesium oxide is a major factor and since reflection
should be more significant in high intensity fires, it would seem logical that
magnesium oxychloride fire-resistive coatings should perform well in high
intensity fires, such as burning organic solvents. Test results confirm this
hypothesis.
However, in an artificial, oven fire, radiated heat is reflected back by
the oven walls. Thus, while reflection would be of considerable importance
in a typical exterior fire, it would not be a significant factor in an A S T M
E-119 test. Actual surface temperature readings with an optical pyrometer
showed differences between the oven wall and the magnesium oxychloride
surface of less than 100 ° F.

CALCULATIONS
Using available properties and experimental data regarding the per-
formance of magnesium oxychloride fire-resistive materials, we a t t e m p t e d
to set up a model to calculate the relative contribution of the different
modes of insulation to the overall insulative properties of a magnesium
oxychloride fire-resistive material.
For simplicity, assume an idealized system of one square foot in area
on a large flat surface, with a cross section as shown in Figure 1. At time
zero, before exposure to a fire, the interface is the same as the surface;
lc = lo, and lj~ = 0.
Two separate calculations must be made in order to determine the total
time required for the substrate temperature to rise from ambient to
1000 ° F. Since the temperature at the interface remains constant (570 ° F)
during the dehydration of the cement, it is necessary to determine the time
required for complete dehydration. It is then necessary to determine the
time required for the substrate to rise from 570 ° F to 1000 ° F due to heat
transfer through the dehydrated coating.
S

7
o /
s Qc
Figure 1. Schematic o/model. /

] %t
p L
_ . Ih T6
/ c

T8 Tt TS
Consider first the dehydration of the cement. A generalized equation.
expresses the overall energy balance as
Q~ = Q~ = Q,~ - (sHh - AE~) (1)
Since the temperature of the substrate is of primary interest, a spe-
cific energy balance can be written based upon the steel substrate B:
206 Fire T e c h n o l o g y

(lBp,) (C,,) (•-dTB

-~ ) = Q, = ko(Tr-T,) (2)
lc
The right-hand side of Equation 2 is dependent upon what has occurred
in lh(O). Therefore, this equation requires a knowledge of l~ or lh for
solution since l~ = lo -- lb.
Consider an energy balance at the interface I as shown in Figure 2.
Enthalpy, heat capacity, latent heats, sensible heat effects, diffusion
effects, etc. will be included in a general term A' where most probably
A' = AH~. The energy can then be expressed as:
dlc kh (T,(O) - Tz) (3)
(a') (P°) (-JO -) = l~

AI c
I
I
I -" QAO
I Figure 2. Energy balance at interface I.
I m=f
I
I

As a first approximation, it is assumed t h a t T~ = Ta. According to the

test procedure being employed, T~ must be f(O). We are assuming that the
lag time between Tc and Ts is small. Unless this simplification is made,
Equation 3 cannot be solved without a knowledge of the time dependency
of T~. Equation 3 can then be simplified as:
. dlc ) kh (T~-T~) (4)
(aHh) (p,) (-d-0- - lh
It can also be stated that:

dlCdo - dodl~ - ( ) (!) (5)

ph
This equation expresses the time for a given thickness of magnesium
oxychloride cement to lose all of its water of hydration at which time the
substrate temperature is assumed to be 570 ° F. The rate of dehydration
is proportional to the rate at which the heat is transferred to the inter-
face where dehydration is occurring and inversely proportional to the mag-
nitude of the beat sink (heat of dehydration).
Equations 4 and 5 can be combined to yield:

dlh = k ~ ( T , - T~) , and integrating, (6)

dO l~ AHhph
 Magnesium Oxychloride 207
0
f lh d~ = f dO (7)
o

Integrating and recognizing t h a t at 0 = 0, lh = 0. E q u a t i o n 8 can be

utilized to compute values of lh for given values of 0 for those time periods
where T~ increases to 570 ° F or for calculating values of 0 for known
lh(o) data.
l~ _ k~ (T~ - T ~ ) (o (8)
2 AHhp~
A graphical representation of Equation 8 is shown in Figure 3.
For calculating the time required for the substrate to reach 1000 ° F
from 570 ° F, account must be taken of the properties of the dehydrated
coating. The heat transferred can be represented as:
2 !
Q:_ qh _ k,, AT (9)
0 lh
Since q~ can be calculated di~'ectly, E q u a t i o n 9 can be utilized in the form

0 -
AT = temperature difference between
O' = 0 when T , = 570 ° F.
The summation of the values of 0
give the total time for the substrate
to 1000 ° F. Therefore, Qo = Q~, + Qg.
q~ lh (10)
k~ AT
the surface and substrate, and also
from Equations 8 and 10 will then
temperature to rise from ambient
In order to utilize these equations,

2.5

¢:: 2.0
o

Z
_o 1.5
_J
Figure 3. Depth of ablation of magnesium m
oxychloride vs time, A S T M E-119 fire test.
1.0
LL
0

:E
F-
a. 0.5
I,I

2 4
TIME (Hours)
208 Fire T e c h n o l o g y
some input data were necessary and some assumptions were made. The
input d a t a were based on an A S T M E-119 fire-resistance test a t Under-
writers' Laboratories, Inc.$ where 2 ~ inches of magnesium oxychloride
cement were applied to a 10WF49 column. The average column tempera-
tare versus time is as shown in Figure 3.
ASSUMPTIONS
(1) T~ = TG. The surface temperature of the magnesium oxychloride
was assumed to be the same as the gas or oven temperature.
(2) Specific heat of the steel column was taken as 0.12 Btu per pound
of mass over the entire temperature range.
(3) Since a 10WF49 column weighs 49 pounds per linear foot and has
approximately 5 square feet of area per linear foot, for simplicity the mass
is taken as 10 pounds per square foot of area.
(4) AH~ for magnesium oxychloride is approximately 1000 Btu per
pound of water.
(5) Typical magnesium oxychloride cements have a density of 60
pounds mass per cubic foot and contain 35 percent bound water (water
of hydration) by weight. Therefore, the heat of decomposition (AHh)
of magnesium oxychloridecements would be AH~ per pound of water times
the density of the cement times the percentage of bound water; or in this
case, aHh = I000 Btu X 60 Ibs X 0.35 = 2.1 X 104 Btu/ft~.
(6) k~ -- 0.04. This is a typical value for the density and structure of
the cement and can be computed from experimental data to be between
0.03 and 0.05 Btu/hr-ft2-° F/ft.
(7) Heat transfer to substrate (q~) would be the specific heat of the
substrate times the density of the substrate times the difference between
1000° F and the interface temperature during dehydration (570° F); or in
the case of the steel column, q~ = 0.12 Btu/Ib° F X 10 Ibs/ft2 X 430° F =
516 Btu/ft2.
EXAMPLE i
Let lh = i inch = 0.0833 ft. F r o m Equation 8 or Figure 4, the time
for Tb to reach 570 ° F is approximately 80 m i n (1.33 hr). F r o m Equation i0,
the time 0 required for Tb to rise from 570 ° to 1000 ° F is 0 = (516 X
0.083)/ 0.04(2000 - 570) = 42.828/57.20 = 0.75 hr. Total 0 = 1.33
+ 0.75 = 2.08 hrs.
EXAMPLE 2
Let lh = 2 inches = 0.167 ft. From Equation 8, 0 = 280 rain (4.66
hrs). From Equation 10, 0 = 1.50 hrs. Total 0 = 4.66 + 1.5 = 6.16 hrs.
Figure 5 i]/ustrates the composite use of Equations 8 and I0.

SUMMARY
In summary, we have shown t h a t the fire-resistive capability of mag-
nesium oxychloride cements can be readily calculated, and the theoretical
values agree closely with measured values.
 Magnesium Oxychloride 209
I000
2.5

~ 800
2.0
uJ
o
t-
,~ 6 0 0 o
n~ c
uJ 1.5
w
~- 4 0 0 O3
W
7 Z 1.0
_J
o 200 .-r-

0.5

TIME (Hours)
Figure 4. A S T M E-119 fire test time-tem-
perature curve, 2 ~ inches o[ magnesium TIME (Hours)
oxychloride cement.
Figure 5. Calculated time of protection for
magnesium oxychioride cement in an A S T M
E-119 fire test vs thickness.

The assumptions that were made can only improve the protective
capability. All possible errors introduced are going to make the calculated
values in error on the conservative side.
Also, under actual fire exposures, magnesium oxychloride cements
should perform better than anticipated from A S T M E-119 fire tests
because of radiation effects due to the low emissivity value for magnesium
oxide.
This information and the characteristics of low density, high adherence,
toughness, and impact strength justify the consideration of magnesium
oxychloride cements as fire-resistive materials for m a n y applications.

BIBLIOGRAPHY
~FMC C o r p o r a t i o n , I n o r g a n i c C h e m i c a l s Division, T e c h n i c a l D a t a S h e e t " T h e
P r e p a r a t i o n of M a g n e s i u m Oxychloride w i t h F M C Oxychloride M a g n e s i a . "
~Underwriters' L a b o r a t o r i e s , Inc., File R5357-2-3, A s s i g n m e n t 65C4363, J a n u a r y
18, 1966.
ACKNOWLEDGMENTS: T h e a u t h o r s wish to a c k n o w l e d g e D r . O. K. Crosser, Pro-
fessor of C h e m i c a l E n g i n e e r i n g , U n i v e r s i t y of M i s s o u r i - R o l l a , for his a s s i s t a n c e in
f o r m u l a t i n g t h e m a t h e m a t i c a l model. T h a n k s are also e x t e n d e d to M r . H. J. D a v i s ,
M D C o r p o r a t i o n , for his a d v i c e a n d s u g g e s t i o n s in p r e p a r i n g t h i s m a n u s c r i p t .
A c k n o w l e d g m e n t is also m a d e of t h e a s s i s t a n c e a n d c o n t r i b u t i o n s of S e y m o u r
K a w a l l e r a n d C h r i s M a g d a l i n of t h e C a r b o l i n e C o m p a n y .

NOMENCLATURE
B = Base substrate (usually steel}.
I = Interface (depth of removal of water of hydration at a given time.)
210 Fire Technology
S = O r i g i n a l s u r f a c e e x p o s e d t o a fire.
Tb = T e m p e r a t u r e b a s e (° F).
Tr = T e m p e r a t u r e i n t e r f a c e (570 ° F ) .
T , = T e m p e r a t u r e s u r f a c e (° F).
Ta = G a s t e m p e r a t u r e (° F).
= T h i c k n e s s o f steel
= T h i c k n e s s o f u n b u r n e d c e m e n t (ft).
= T h i c k n e s s o f d e h y d r a t e d c e m e n t (ft).
lo = O r i g i n a l = 1 ~ + l h (ft).
A' = H e a t effects a s s o c i a t e d w i t h d e c o m p o s i t i o n o f c e m e n t ( B t u / l b ) .
Q'~ = H e a t t r a n s f e r r e d to s u b s t r a t e f o r TB = 570 - - 1000 ° F ( B t u / h r -
ft~).
gh = Heat transferred to substrate, 570-1000 ° F (Btu/ft~).
q~ = H e a t t r a n s f e r r e d t h r o u g h d e h y d r a t e d c e m e n t u n t i l T~ = 570 ° F
(Btu/hr-ft~-).
= Heat transferred to substrate (Btu/hr-ft').
q~ -- H e a t t r a n s f e r r e d t h r o u g h h y d r a t e d c e m e n t , T < 570 ° F ( B t u / h r -
ft2).
Qo = Heat transferred overall (Btu/hr-ft~).
A = Cross sectional area normalized to 1 ft ~.
ktl~ = Thermal,conductivity of dehydrated cement (Btu/hr-ft ~--° F/ft).
AHh = Heat of decomposition of cement (Btu/Ib of mass).
AED = E n e r g y o f diffusion.
0 = T i m e (hr).
P = D e n s i t y (lbs m a s s / f t a ) .