Update on

Magnesium Oxychloride Fireproofing

S E Y M O U R I. K A W A L L E R
Carboline Company
Tests of magnesium oxychloride fireproofing by potential users
has led to the development of improved formulations.

A Sparties
F I R E losses in industrial process plants continue to plague corn-
in this field, their materials engineers and loss prevention
experts have become acutely conscious of the inadequacy of the ASTM
E-119 test method for evaluating fire resistance in high intensity "pool fire"
exposures. Although ASTM has acknowledged the problem and has as-
signed a task force to develop a new fire test method for such facilities,
firms such as Exxon, Allied Chemical, and Mobil have devoted substantial
time, money, and effort in high intensity fire exposure testing programs
on their own initiative. Their aim has been not only to establish a more
meaningful fire test method for their needs, but also to investigate the
effectiveness of some of the newer materials that have been proposed for use
in fireproofing in hydrocarbon fires. One of the materials that has emerged
from these testing programs with significant cost-effective advantages has
been magnesium oxychloride.

CHARACTERISTICS
The fire protection mechanisms of magnesium oxychloride formulations
were described in detail in an earlier issue of Free TECHNOLOGY.1 This paper
reported on the development of stable formulations that do not exhibit the
characteristic sensitivity to high humidity, variations in applicator tech-
niques, water quality, temperature, and similar conditions, which have
been deterrents to more frequent use of magnesium oxychloride materials
in the past. Although the result of recent independent research 2 has con-
firmed the extraordinary fire protection capability of magnesium oxy-
chloride, new questions have been raised concerning some of its other
characteristics.
Exxon Company tests, for example, compared the fire protection offered
by magnesium oxychloride with that provided by the conventional
materials used by the company2 Gunite, lightweight concrete, and poured
in place concrete mixtures were tested in relation to a proprietary" mag-
nesium oxychloride. The magnesium oxychloride material provided
139
140 Fire Technology
TABLE 1. Weathering~Fire Endurance Test Exposure Data, Proprietary Magnesium
Oxyc~Joride (Pyrocrete 102)

Test Coating Protection rating (rain) *

date thickness Remarks 1st All A vg
12/11/73 ½ in. N o topcoat, no reinforcement, con- 72 76 74
ditioned for 1 m o n t h in lab, trowel
application
4/21/75 ½ in. N o topcoat, no reinforcement, aged 1 66 70 68
y e a r on m i d w e s t roof top, con-
ditioned 3 weeks in lab prior to
test, trowel application
4/22/75 ~ in. W i t h topcoat, no reinforcement, a g e d 63 72 68
1 y e a r on m i d w e s t roof top, con-
ditioned 3 weeks in lab prior to
test, trowel application

* P r o t e c t i o n r a t i n g is elapsed t i m e of flame exposure until s u b s t r a t e steel reached

1,000 ° F (538 ° C). 1st is t i m e until first significant t h e r m o c o u p l e reached 1,000 ° F. All
is t i m e until all significant t h e r m o c o u p l e s exceeded 1,000 ° F. A v g t i m e between 1st
t h e r m o c o u p l e r e a c h i n g 1,000 ° F a n d all significant t h e r m o c o u p l e s exceeding 1,000 ° F.

significantly superior protection for the steel. However, James Kayser,

who directed Exxon's fire test program, noted that, under chemical
analysis, aged samples of the material tested revealed a loss of 4 moles of
water per mole of magnesium oxychloride when compared with the freshly
cured samples. Since its water content has a direct relationship to a for-
mulation's fire resistive capability, Mr. Kayser speculated that fire pro-
tection could diminish as the material ages or is exposed to weathering.
He also noted that the material seemed too soft to endure the mechanical
abuse which might be anticipated in plant service. A laboratory program
was developed to investigate these questions.
A new formulation of magnesium oxychloride with a Shore D hardness
of 65-70 and compressive strength of 2,000 psi (13.8 MPa) - - hard enough
to provide durability comparable to c o n c r e t e - was used in this in-
vestigation. This compared to a Shore D hardness of 50-55 and compres-
sive strength of 650 psi (4.48 MPa), which characterized the earlier for-
mulations tested at Exxon.
In order to confirm that the new formulation would provide fire pro-
tection comparable to the product used in the Exxon tests, Factory Mutual
Research Corporation was asked to make a comparative fire test? The
newer material provided improved protection. It has the added advantage
of meeting current OSHA regulations that limit the use of asbestos in
sprayed fireproofings. Model building code authorities have approved the
substitution of the improved version in place of the discontinued Exxon-
tested formulation.
Since the catalyst for magnesium oxychloride is a magnesium chloride
salt, some corrosive effect on structural steel should be anticipated. The
laboratory test program was enlarged to include an investigation of cor-
rosion protection systems for exterior applications, which would not affect
the fire protection characteristics of the material.
Magnesium Oxychloride 141
TABLE 2. General Chemical Resistance Characteristics of Magnesium Oxychloride Fire-
proofing Materials

Exposure to
Exposure malerial Splash and spillage Fumes
Acetone N o effect No effect
Acetic acid (less t h a n 5 % ) Slight a t t a c k No effect
A m m o n i u m chloride N o effect No effect
Beer N o effect No effect
Benzene N o effect No effect
Chromic acid (less t h a n 5%) Attack No effect
Citric acid (less t h a n 5%) Slight a t t a c k No effect
Detergent N o effect No effect
Gasoline N o effect No effect
Hydrochloric acid (less t h a n 5 %) Severe a t t a c k No effect
Kerosine N o effect No effect
Milk No effect No effect
Oil, l u b r i c a t i n g N o effect No effect
Sodium chloride (less t h a n 25%) N o effect No effect
Sodium hydroxide (less t h a n 10 %) No effect No effect
Sulfuric acid (less t h a n 5 %) Attack No effect
Toluene N o effect No effect
Turpentine N o effect No effect
Wine N o effect No effect
Xylene N o effect No effect

NOTE: M a g n e s i u m oxychlorides are n o t r e c o m m e n d e d for immersion service.

Chemical resistance increases as density increases or by protective application of
selected topcoats.

The paper "Fire Protection for Chemical Plants ''5 recommends t h a t

concrete fireproofing, should be a miuimum of 2 in. (5.1 cm) thick for cor-
rosion protection on structural steel. At reduced thicknesses, sufficient
moisture penetration occurs to create a corrosive condition. However, at
a minimum thickness of 2 in. (5.1 cm), concrete provides a sufficient barrier
to moisture penetration to assure the integrity of the structural values
during the practical lifetime of the installation.
Magnesium oxychloride fireproofing formulations need not be applied
as thick as concrete (about a ½ in. thickness provides a 2-hr UL fire re-
sistive rating). Therefore, tests and evaluations were made with a for-
mulation application thickness of ½ in. Additional thicknesses, of course,
provide a greater barrier to moisture penetration and, therefore, reduced
corrosive activity. Observations of steel exposed to direct contact with
damp magnesium oxychloride reveals a distinctive dark black rust (gamma-
phase iron oxide), typical of corrosion which occurs in either a low oxygen
or a caustic environment. This contrasts with the lighter, reddish rusting
that develops when steel is exposed to ambient atmospheric conditions.
It was therefore concluded that entrapped, stagnant, moisture-laden air
in the interstices of the magnesium oxychloride limits the oxygen content
at the interface with the steel substrate to inhibit corrosion development.
Accelerated weathering tests and immersion testing have demonstrated
142 Fire Technology
TABLE 3. Rusting of Steel Substrate, Midwest United States Weathering Exposure

Magnesium
Primer Oxychloride Topcoat Results
None None None 1 month, overall surface
rusting
Vinyl-Alkyd None None 18 months, overall surface
rusting
Inorganic zinc None None 120 months, no effect
None Pyrocrete 102 None 3 months, complete surface
rusting
Vinyl-Alkyd Pyrocrete 102 None 18 months, no effect
Inorganic zinc Pyrocrete 102 None 18 months, no effect
None Pyrocrete 102 Chlorinated 3 months, complete surface
rubber rusting
Vinyl-Alkyd Pyrocrete 102 Chlorinated
rubber 18 months, no effect
Inorganic zinc Pyrocrete 102 Chlorinated
rubber 18 months, no effect
Vinyl-Alkyd None Alkyd 18 months, 40% surface
rusting
Epoxy-Polyamide None Epoxy-Poly- 18 months, 5% surface
amide rusting
Inorganic zinc None Chlorinated
rubber 18 months, no effect
Inorganic zinc None Epoxy-Poly
amide 162 months, no effect

Pyrocrete 102 is a proprietary magnesium oxychloride formulation manufactured by

the Carboline Company, St. Louis, Missouri.

t h a t galvanized steel, inorganic zinc primers, or even a thin-film alkyd-

t y p e primer could provide effective protection against con'osion of the steel
from contact with d a m p m a g n e s i u m oxychloride fireproofing.
T h e potential for loss of fire protection t h r o u g h chemical changes
due to aging or weather exposures was also studied. M a g n e s i u m oxychloride
formulations typically include a small q u a n t i t y of n o n s t r u c t u r a l m a g -
nesium chloride - - a surplus f r o m the catalytic reaction forming the m a g -
nesium oxychloride. This m a t e r i a l can be expected to leach out of the struc-
ture in cyclical w e t / d r y exposures.
An analysis of the chemical structure reveals that, w h e n m a g n e s i u m
oxychloride is exposed to 100 percent humidity, leaching of surplus m a g -
nesium chloride results in the f o r m a t i o n of m a g n e s i u m hydroxide. C a r b o n
dioxide extracted f r o m the a t m o s p h e r e combines with this c o m p o u n d to
form a surface layer of m a g n e s i u m chlorocarbonate (Mg OHm_ . MgC12 .
2MgCO~ . 6H20). T h i s surface barrier helps slow the leaching process.
As additional m a g n e s i u m chloride is leached, a surface crust of hydro-
magnesite ( 5 M g C O . 4 C 0 2 . 5 H sO) is formed. T h e s e insoluable carbonates
and hydromagnesites help to i m p r o v e the weathering stability of m a g -
nesium oxychloride materials. Applications dating b a c k m o r e t h a n fifty
years h a v e been recorded in exterior applications a n d are still sound.
Leaching, which occurs in organic coatings such as i n t u m e s c e n t mastics,
Magnesium Oxychloride 143
TABLE 4. Rusting of Steel Substrate, Water Fog (ASTM D-1735) Exposure

Magnesium
Primer Oxychloride Topcoat Results
None None None 1 week, overall surface rust
ing
Vinyl-Alkyd None None 1 month, 20 % surface rust-
ing
Inorganic zinc None None 78 months, no effect
None Pyrocrete 102 None i month, complete surface
rusting
Vinyl-Alkyd Pyrocretel02 None 16 months, 15% surface
rusting
Inorganic zinc Pyrocrete 102 None 16 months, no effect
None Pyrocrete 102 Chlorinated 1 month, complete surface
rubber rusting
Vinyl-Alkyd Pyrocrete 102 Chlorinated 16 months, slight edge rust-
rubber ing
Inorganic zinc Pyrocrete 102 Chlorinated
rubber 16 months, no effect
Vinyl-alkyd None Alkyd 12 months, 15% surface
rusting
Epoxy-Polyamide None Epoxy- 10 months, 10% surface
Polyamide rusting
Inorganic zinc None Chlorinated
rubber 16 months, no effect
Inorganic zinc None Epoxy-
Polyamide 16 months, no effect

Pyrocrete 102 is a proprietary magnesium oxychloride formulation manufactured

by the Carboline Company, St. Louis, Missouri.

produces a resultant loss of protection. Magnesium oxychloride, however,

is inorganic.
I n order to evaluate the effect of these chemical reactions on the
fire resistive characteristics of the formulation, it was decided to subject
the material to comparative fire testing after exposures to weathering
had resulted in chemical equilibrium= Comparisons were m a d e with samples
t h a t had n o t been in such exposures. T h e results are tabulated in the tables,
along with additional pertinent d a t a as reported a t the 1976 Corrosion '76
S y m p o s i u m of the National Association of Corrosion Engineers b y J a m e s
R. L o p a t a of the Carboline C o m p a n y , St. Louis, Missouri.

SUPPLEMENTAL EVALUATIONS
C o n c u r r e n t with l a b o r a t o r y testing, a field survey was initiated to
evaluate results in actual use. These job site inspections provided the
following information:
• Significant corrosion does not develop where applications are m a d e
on bare (unprimed) steel in interior installations.
• Exterior installations over steel, previously primed with a con-
ventional thin-film alkyd primer, showed minor signs of substrate cor-
rosion after 18-24 m o n t h s of exposure in the high h u m i d i t y environment of
144 Fire Technology
Baton Rouge, La. No such indications were observed in the environment
of Toronto, Canada. These installations were not protected by topcoat-
ing. Examination of installations of the system, further protected by a
chlorinated rubber topcoat, showed no signs of substrate corrosion after
2-3 years of weathering in areas having such extreme climatic variations as
are found in Houston, Texas and Montreal, Canada.
• Evaluations of similar installations where an inorganic zinc primer
was used in place of the thin-film alkyd showed complete absence of cor-
rosion evidence in both topcoated and nontopcoated installations. Exterior
installations of the magnesium oxychloride require a topcoat to comply
with the manufacturer's specifications. This topcoat provides protection
against atmospheric degradation of the formulation due to excessive
moisture penetration and subsequent freeze-thaw action.
° Actual fire experience is undoubtedly the most convincing test of
any fire protective material Such a rare opportunity for evaluating a
magnesium oxychloride coating occurred in a refinery fire in a liquefied
natural gas processing facility. An inspection report filed after the fires is
revealing. During the nine-hour fire exposure, a proprietary formulation of
magnesium oxychloride had effectively protected the steel. Experts who
examined the steel primer report that the coverage of only 9/16in. (14.28 ram)
of the magnesium oxychloride material provided sufficient protection to
limit the steel temperature to about 350 ° F (176° C) in an area where the
fire temperature was reported to have reached 2400 ° F - 2500 ° F (1315 ° C
- 1371 ° C). Concrete in this area spaUed to a depth of 6 - 8 in. (15.2-
20.3 cm) - - an indication that the sudden exposure to high heat creates ex-
pansion stresses in concrete which affect the fire resistive performance in
high intensity fire exposures. Such a reaction is not typical of magnesium
oxychloride formulations.

CONCLUSIONS
Exposure through aging or exposure to weather or ultraviolet-rich en-
vironments does not result in significant loss of fire resistance character-
istics in the magnesium oxychloride formulation tested.
Although unprimed magnesium oxychloride installations can be mildly
corrosive to structural steel (depending on the thickness of the installation),
applications as thin as ½ in. (12.7 ram) applied over a thin-film alkyd
primer and topcoated with a chlorinated rubber sealer can be expected to
provide excellent service in normal use. Substitution of an inorganic zinc
primer should be considered where extremely humid environmental con-
ditions are anticipated.

REFERENCES
1 Montle, J. F., and Mahan, K. G., "The Role of Magnesium Oxychloride as a Fire
Resistive Material," Fire Technology, Vol. 10, No. 3 (August 1974).
Rains, William A., "The New Era in Fire Protective Coatings for Steel," Civil
Engineering (September 1976).
Magnesium Oxychloride 145
'~ Kayser, J. N., "Testing Fireproofing for Structural Steel," Chemical Engineering
Progress, Vol. 70, No. 4 (April 1974).
Factory Mutual Research Corporation Test Reports Serial Nos. 224678 (April 5,
1974) aud 24656.1 (March 25, 1974).
5 Waldman, Sam, "Fireproofing of Structural Steel in Chemical Plants," Chemical
Engineering Progress, Vol. 64, No. 8 (August 1968).
s DiSflvester, Carl, "Fire Inspection o5 Refinery Fire," published by the Carboline
Company (St. Louis, Mo.).

ACKNOWLEDGMENTS; The author extends thanks and appreciation to Mr. Chris

F. Magdalin, Fireproofing Group Leader, and Mr. James R. Lopata, General Manager,
both of the Carboline Company, St. Louis, Missouxi. Without their technical expertise
and editorial input, this paper could not have been offered.