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Chemistry and Technology of

Polysulfide Sealants
a b
A. M. Usmani
a
University of Dayton Research Institute, Dayton,
Ohio, 45469
b
Research Institute, University of Petroleum and
Minerals, Dhahran, Saudi Arabia
Published online: 06 Dec 2006.

To cite this article: A. M. Usmani (1982) Chemistry and Technology of Polysulfide

Sealants, Polymer-Plastics Technology and Engineering, 19:2, 165-199

To link to this article: http://dx.doi.org/10.1080/03602558208067730

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 P0LYM.-PLAST. TECHNOL . ENG., 19(2). 165-199 (1982)

CHEMISTRY AND TECHNOLOGY OF POLYSULFIDE

SEALANTS
A . M . USMANI*
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University of Dayton Research Institute

Dayton. Ohio 45469

I. INTRODUCTION ........................ 166

I1. CHEMISTRY . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
A. Monomers . . . . . . . . . . . . . . . . . . . . . . . . . . 167
B. Polymerization Reactions and Processes . . . . . . . . . . . 167
C . Copolymerization . . . . . . . . . . . . . . . . . . . . . . 169
D. Modifications . . . . . . . . . . . . . . . . . . . . . . . . 169
I11. PROPERTIES OF POLYSULFIDE POLYMERS . . . . . . . . . 171
A. Properties of Liquid Polymers . . . . . . . . . . . . . . . . 171
B . Effect of Molecular Weight and Cross-Linking on
Physical Properties . . . . . . . . . . . . . . . . . . . . . . 171
C. Solvent Resistance . . . . . . . . . . . . . . . . . . . . . . 173
D. Low-Temperature Properties . . . . . . . . . . . . . . . . . 174
E. High-Temperature Properties . . . . . . . . . . . . . . . . . 177
F. Viscoelastic Properties . . . . . . . . . . . . . . . . . . . . 178
IV. COMPOUNDING OF POLYSULFIDE SEALANTS. . . . . . . . 178
A. CuringAgents. . . . . . . . . . . . . . . . . . . . . . . . . 179
B. Cure Modifiers . . . . . . . . . . . . . . . . . . . . . . . . 179
C. Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
D. Plasticizers . . . . . . . . . . . . . . . . . . . . . . . . . . 181
E. Adhesion Additives . . . . . . . . . . . . . . . . . . . . . . 181
.
F Typical Commercial Products . . . . . . . . . . . . . . .. 181
G. Typical Composition . . . . . . . . . . . . . . . . . . . . . 181

*Present address: Research Institute. University of Petroleum and Minerals.

Dhahran. Saudi Arabia.
165

.Copyright 0 1983 by Marcel Dekker. Inc .

 166 USMANI

V. PROCESSING AND MANUFACTURE OF POLYSULFIDE

SEALANTS............................ 185
VI. CHARACTERIZATION AND TESTING . . . . . . . . . . . . . 185
A. Physical, Rheological, and Mechanical Characterization
Methods.. . . . . . . . . . . . . . . . . . . . . . . . . . 185
B. Chemical Characterization Methods . . . . . . . . . . .
.. 187
VII. ADHESION CONSIDERATIONS ................ 189
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A. General Background Information . . . . . . . . . . . . . . 189

B. Adhesion Improvement via Polysulfide Modification. . . . . 192
C. Polysulfide Adhesion Improvement via Primers . . . . . . . 192
D. Adhesion of Polysulfide Sealant onto Polyurethane:
Mechanism Proposed by Usmani . . . . . . . . . . . . . . . 192
VIII. APPLICATIONS ......................... 193
IX. FUTURE PROSPECTS . . . . . . . . . . . . . . . . . . . . . . 196
X. CONCLUSIONS . . . . . . . . . . . . . . . . . . . . . . . . . 197
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198

1. INTRODUCTION

The highly reactive terminal mercaptans of liquid polysulfide polymers can be

converted into high molecular weight products very easily at ambient tempera-
tures by oxidation or by reaction with other active polymers. Polysulfides
have excellent solvent resistance, predictable cure, good low-temperature per-
formance, good weathering, and excellent adhesion to many substrates. This
combination of properties has given polysulfide polymers a modest but signi-
ficant position as specialty polymers since their commercialization in 1929.
Polysulfide sealants have found wide acceptance in industries, e.g., con-
struction, aircraft, automotive, marine, and insulating glass. In fact, poly-
sulfide sealants were the first elastomeric sealants used in the construction
industry and continue today, to a large extent, the standard against which
other sealants are compared. Polysulfide sealants, although facing strong chal-
lenges by silicones and polyurethanes, continue to be the dominant segment
of the elastomeric sealant market [ 1-61 .
In this paper we review chemistry, properties, compounding, processing
and manufacturing, characterization and testing, applications, and future
 POLYSULFIDE SEALANTS 167

prospects of polysulfide sealants. For completeness, we will also include

a brief overview of adhesion and rheological considerations.

II. CHEMISTRY

A. Monomers
The polysulfide polymers are prepared by condensation of organic polyhalides
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with inorganic polysulfides in aqueous suspension. The principal monomer is

bis-Zchloroethyl formal. Ethylene dichloride is used in special polymers. Gen-
erally, most products contain some cross-link precursor, e.g., 1,2,3-trichloro-
propane. Bis-4chlorobutyl formal and bis-4-chlorobutyl ether are used in
small amounts where improvement in low-temperature performance is required.
Properties of important dihalides used in the preparation of polysulfide
polymers are shown in Table 1.
Sodium disulfide is primarily the alkali polysulfide used although some
special polymers may contain structures, e.g., monosulfide or tetrasulfide.

6. Polymerization Reactions and Processes

The polysulfide polymers are prepared as suspensions by condensation of the
dihalide monomer with polysulfide in aqueous solution [7] . Bis-Zchloroethyl
formal is the usually used monomer and 0.1-4.0% 1,2,34richloropropane is
added as a cross-linking agent. In conducting polymerization, the standard
practice is to feed the dihalide monomer into the aqueous polysulfide solution
containing specific suspending and nucleating agents. A combination of an
alkyl naphthalene sulfonate with magnesium hydroxide sol prepared in situ is
commonly used. The polymerization reaction that produces high molecular
weight polymer is

nC1C2H40CH20C2H4C1t nNa2S2.25 -~CzH40CH20CzH&.2s)n+

2nNaC1

The sulfur is present as a mixture of disulfide and trisulfide.

Liquid polysulfide polymers which are commercially more important than
the solid elastomers range from a molecular weight of 1000 to 8000. They are
prepared from the high molecular weight polymer described earlier. High
molecular weight polymer is split into segments which are simultaneously
terminated by mercaptan groups:

RSSR t NaSH t NaHS03 - 2RSH + Na2SzO3

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TABLE 1
Properties of Dihalides
Monomer Formula BP ("C) do
Bis-2-chloroethyl formal CH2(0CH2CH2Cl)2 105-1 06/14 1.4557
1,2,3Trichloropropane CH2Cl CHCl CHzCl 156 1.4835
Ethylene dichloride CHZCl CHzCl 83.6 1.4443
Bis-4-chlorobutyl ether O(CH2CH2CHzCH2Cl), 1 25-1 28/ 12 1.4589
Bis-4chlorobutyl formal CH2(OCH2CH2CH2 CH2Cl)z 154-1 56/3 1.4066
 POLYSULFIDE SEALANTS 169

The concentration of the splitting salts regulates the average molecular

weight of the liquid polysulfides. For example, Thiokol LP-2 has the following
average formula:

C. Cop01y mer ization

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Use of a mixed dihalide monomer feed in a conventional polymerization will

produce random copolymers. A block copolymer cannot be prepared by step-
wise addition of the monomers. During copolymerization, interchange takes
place, resulting in randomization. To prepare block copolymers it is best to
prepare individual mercaptan-terminated polymers, blend them in the desired
proportion, and then cocure the blended system by conventional techniques.

D. Modifications
-
Liquid polysulfide polymers readily react with epoxy resins under basic condi-
tions to form a block copolymer. The polysulfide-epoxy block copolymer
has significantly higher impact resistance and more flexibility than epoxy [8,
91.

R-SH + C-C-R'-C-C
\/ \I
- R-S-C-C-R'-C-C
I \I
0 0 OH 0

Generally, the lower molecular weight liquid polymers (e.g., Thiokol LP-3
and LP-33) are useful for epoxy modification. For most applications, the
diglycidyl ether of bisphenol A'derived liquid epoxies are most suitable. The
most widely used epoxies are in the viscosity range of 80 to 200 P and have
an epoxy equivalent of 175 to 210.
The reaction between liquid polysulfide polymer and epoxies is catalyzed
by organic amines, e.g., dimethylaminomethyl phenol, tridimethylamino-
methyl phenol, diethylenetriamine, and benzyldimethylamine. The reaction
of liquid polysulfide polymer with an epoxy resin and a primacy amine is

RSH t C-C-R'-C-C t R'"H2 --RS-C-C-R'-C-CNHR"-

\I \I I I
c) 0 OH OH
 170 USMANI

Villa [ 10-121 has modified liquid polysulfide polymers by reaction with

either vinyl cyclohexane diepoxide or abietic acid. The modified products
were used as effective additives. While the reaction between liquid polysulfide
polymer and abietic acid is not fully known, Villa has theorized that the reac-
tion proceeds with inversion of a mercaptan terminal to a hydroxyl terminal
followed by esterification [ 101. The reaction is depicted as

HSf C~&0CH~0CZH4SSfnC2H4OC2&SH'
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Liquid polysulfide
I Heat
HSf CzH40CHzOCzH4SSfnCzH4SCHZCH20H
Terminal inverted polysulfide
I

Abietic,acid

HSf C2&0*CH20C2&SS+nC2H4SCH~CH.~OOC

CH (CH 3) 2
Abietate modified polysulfide polymer

The epoxy modified polysulfide polymer useful as an additive was prepared

by Villa by reacting low molecular weight polysulfide with a diepoxide, e.g.,
vinyl cyclohexane diepoxide in a solvent medium in the presence of an acid
catalyst [ 111. The chemical reaction is

HSfRSS),-RSH
Polysulfide
+0 ocfi3Hz
polymer Vinyl cyclohexane epoxide

I
 POLYSULFIDE SEALANTS 171

HSfRSS), -R-S- C-6J-( %H

HO'

Epoxy modified polysulfide

Gudev and Stoyanova have reacted low molecular weight polysulfide poly-
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mers with hydroxyl-containing coal tar wastes to prepare long-lived elastic

sealants [ 131 .

111. PROPERTIES OF POLYSULFIDE POLYMERS

A. Properties of Liquid Polymers

Liquid polysulfide polymers are manufactured by Thiokol Specialty Chemicals
Division under the tradename LP and are available in a series of viscosities and
cross-link densities to meet the needs of various application areas, see Table
2 [14, 151.
Generally, polymers in the 400-500 P viscosity range are used in sealants
and adhesives, whereas the lower viscosity polymers are generally used for
flexibilizing epoxy casting compounds.
Viscosities of liquid polymers range from about 12 P for LP-3 to 1200 P
for LP-31. The relationship between viscosity and molecular weight is gov-
erned by the following equation:

where 77 = viscosity in poises

K = 5.0 k 1.0 X lo-'
Q = 2.75 ? 0.03
M = molecular weight

B. Effect of Molecular Weight and Cross-Linking on Physical Properties

The tensile properties of unfilled polysulfide polymers are rather poor. However,
suitable reinforcement by pigments can lead to products of adequate tensile and
elongation properties. The molecular weight of a liquid polymer before cure
also influences the physical properties of the cured polymer. It is difficult, how-
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TABLE 2
Properties of Liquid Polysulfide Polymers'
Property LP-31 LP-2 LP-32 LP-12 LP-3 LP-33 LP-370
Color, MPQC-29A 150 max 150 max 100 max 80 max 50 max 30 max Clear, amber
Viscosity, poises 77°F (25OC) 950-1 550 4 10-5 25 410-525 410-525 9.4-14.4 15-20 11.5-14.5
pH range 6.5-7.5 6.5-7.5 6.5-7.5 6.5-7.5 6.0-8.0 6.0-8 .O 6.0-8.0
Moisture content, % 0.1 2-0.22 0.12-0.22 0.1 2-0.22 0.12-0.22 0.1 max 0.1 max 0.15
Mercaptan content, % 1.0-1.5 1.50-2 .OO 1.50-2.00 1.SO-2.00 5.9-7.7 5.0-6.5
Specific gravity at 25"/25"C 1.31 1.29 1.29 1.29 1.27 1.27 1.108
Average molecular weight 8000 4000 4000 4000 1000 1000 1200
Refractive index 1.5728 1.5689 1.5649
Pour point, OF ("c) 50 (10) 45 (7) 45 (7) 45 (7) -15 (-26) -1 0 (-23)
Flash point (Pensky-Marten
CC), OF ("C) 437 (225) 406 (208) 414 (212) 406 (208) 345 (174) 367 (1 86)
% Cross-linking agent 0.5 2.0 0.5 0.2 2.0 0.5
Low temperature flexibility
( G 10,000 psi), " F ("C)
(703 kg/cm2) -65 (-54) -65 (-54) -65 (-54) -65 (-54) -65 (-54) -65 (-54)

aAll liquid polysulfide polymers are based on bis-2-chloroethyl formal except LP-370 which is based on bis-4-chlorobutyl ether
monomer.
 POLYSULFIDE SEALANTS 173

TABLE 3
Effect of Molecular Weight on Physical Properties
Formulations
Polymer LP-2 LP-3
Polymer 100 100
Lead dioxide 7.5
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Manganese dioxide 3
m-Dinitrobenzene 1
SRF black 60 60
Cure time 24 h at room 24 h at room
temperature temperature

Physical Properties of Cured Polymer

Tensile strength, psi 900 600
Elongation, 76 450 450
Hardness, Shore A 65 45

ever, to make generalizations about the effect of molecular weight on physical

properties since oxidative curing may also influence this aspect. The liquid
polymer can be cured with a wide variety of oxidizing agents.
Higher tensile strength is obtained with the higher molecular weight mate-
rials (Table 3). The effect of branching on the physical properties of polysul-
fide liquid polymers is shown in Table 4 [16].

C. Solvent Resistance
Cured liquid polysulfide compositions have excellent resistance to a wide vari-
ety of oils and solvents, e.g., aliphatic and aromatic hydrocarbons, esters, ke-
tones, dilute acids, and alkalides. Table 5 shows the properties of two poly-
sulfide polymers cured with conventional filled formulations. The data pre-
sented are only trends and not absolute since the results are dependent on the
efficiency of cure. Systems that are not properly compounded have somewhat
poorer solvent resistance.
Swelling tests on cured, filled polysulfides were conducted by Usmani et al.
[ 171. Weight gain versus immersion time is shown in Fig. 1. With jet reference
fuel (JRF) an equilibrium is quickly established. During early immersion in
water, the weight gain is linear with time. Later, a square-root weight gain
 174 USMANI

TABLE 4
Effect of Cross-Linking on Physical Properties
of Polysulfide Polymers
~ ~ ~~ ~

Formulation
Polymer 100 100 100 100 100 100
Cross-linking, %a 4.0 2.0 1.5 1.0 0.5 0.1
SRF black 30 30 30 30 30 30
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Stearic acid 1 1 1 1 1 1
C-5 Acceleratorb 15 15 15 15 15 15
Set time (h) 2 4 5 5 6 6

Physical Properties of Molded Sheets

after Curing 10 min at 16OoC
Tensile (psi) 550 500 550 675 575 500
Modulus300%(psi) 500 375 350 275 250 200
Elongation (%) 310 420 700 850 930 1000
Hardness, Shore A 55 53 53 53 45 40

Physical Properties of Sheets after

Heat Aging 70 h at 1OO°C
Tensile (psi) 550 525 675 650 650 650
Modulus 300% (psi) 425 450 375 375 300
Elongation (%) 250 370 500 600 600 650
Hardness, Shore A 62 58 54 53 53 50

aMole percent of trifunctional monomer in polymer feedstock.

bA 50% suspension of lead oxide in a plasticizer, e.g., dibutyl
phthalate.

versus immersion time relationship holds. No testing beyond 1400 h was

done.

D. LowTernperature Properties
The glass transition temperature (Tg)of polysulfides depends on the hydrocar-
bon moiety and the length of the polysulfide chain. The amount of cross-
 POLYSULFIDE SEALANTS 175

TABLE 5
Solvent Resistance of Cured Polysulfide Polymers
Volume Increase (%) after
30-d Immersion at 80°F
Solvent LP-2 1p-32

Benzene 195 315

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Toluene 95 140
Xylene 40 60
Motor oil 5 5
Diesel oil 5 5
Aromatic aviation, SR-10 5 5

Ethyl acetate 40 65
Dibutyl phthalate 30 55
Tricresyl phosphate 10 15
Linseed oil 5 5

Ethyl alcohol 5 5
Butyl alcohol 5 5
Ethylene glycol 5 5
Ethyl cellosolve 15 25
Acetone 40 50
Methyl ethyl ketone 55 90

Ethylene dichloride 440 600

Carbon tetrachloride 55 80
Trichloroethylene 275 400
Perchloroethylene 30 45
Chlorobenzene 270 475

linking monomer used is small and therefore it does not influence Tg. Gener-
ally, the greater the hydrocarbon content, the lower is the Tg;the higher the
rank of the polysulfide, the higher is Tg.In Table 6 the glass transition tem-
peratures of the elastomeric polysulfides are given. Polysulfides based on
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176

m
0
::
% 'NIVE) I H D I 3 M
0
USMANI
 POLYSULFIDE SEALANTS 177

TABLE 6
Glass Transition Temperatures of Elastomeric Polysulfides
~~~~

Polymer Tg ("C)
Poly(ethy1ene disulfide) -27
Poly(ethy1ene tetrasulfide) -24
Poly(ethy1 ether disulfide) -53
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Poly(ethy1 ether tetrasulfide) -40

Poly(ethy1 formal disulfide) -59
Poly(pentamethy1ene disulfide) -72
Poly(hexamethy1ene disulfide) -74
Poly(buty1 formal disulfide) -7 6
Poly(buty1 ether disulfide) -76

bischloroethyl formal show no evidence of crystallization at low tempera-

tures.

E. High-Temperature Properties

The thermal stability of polysulfide polymers depends on the composition of

the polymer backbone as well as the curing agent used to vulcanize the poly-
mer. Commercially available polysulfide polymers are based on the ethyl for-
mal disulfide backbone; therefore, the characteristics of the ethyl formal struc-
ture will regulate the upper temperature limits. The initial attack on the ethyl
formal structure is an acid-catalyzed hydrolytic attack on the formal group by
trace amounts of water-releasing free formaldehyde. Formaldehyde reduces
the disulfide bonds to mercaptan. The formic acid so generated catalyzes the
hydrolysis of the formal group. The terminal mercaptan group can react with
a hydroxyl group to give a monosulfide bond and released water. The sequence
of reactions is
 178 USMANI

The degradation results in weight loss and loss of flexibility due to forma-
tion of a monosulfide structure since disulfide and formal groups offer a flexi-
bilizing effect through free rotation. Calcium oxide is an effective stabilizer
since it is both capable of neutralizing formic acid and absorbing water. How-
ever, practical cure rates cannot be achieved in anhydrous systems by the
metal dioxide curing agents normally used with liquid polysulfides.
Another source of thermal instability arises due to metal incorporation in
the polymer from the reaction of mercaptan with metal oxides. Formation
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of mercaptide groups can be minimized by incorporation of small amounts of

sulfur.
Many studies in compounding have been conducted to determine oxidizing
agents that will mitigate mercaptide formation. Particularly useful are man-
ganese dioxide and various chromate salts. Sealants formulated with these
curing agents provide continuous service at 250°F.

F. Viswelastic Properties
The viscoelastic properties of polysulfide polymers have been extensively
studied by Tobolsky [ 181. Polysulfide polymers are unique in their ability to
internally relieve stress in the cured state by interchange reactions between mer-
captan and disulfide linkages. The stress decay of cross-linked elastomer fol-
lows the equation

F(t) = F(O) t exp -‘IT

where F(t) = final stress

F(0)= initial stress
t = time
7 = relaxation constant

The relaxation constant for polysulfides at 80°C for various curing agents
is shown in Table 7. This ability of polysulfides to relieve stress is extremely
valuable in maintaining adhesion in joints subjected to movement.

IV. COMPOUNDING OF POLYSULFIDE SEALANTS

To obtain the optimum properties, a polysulfide sealant must be specifically

formulated to meet the desired requirements. Working life should be adjusted
in the desired range, and the catalyst and compound adjusted for storage suit-
 POLYSULFIDE SEALANTS 179

TABLE 7
Chemical Relaxation Time (7)at 8OoC for Cured Polysulfide Polymers
Curing agent Phr T (h)
Lead oxide 7.3 0.68
Lead oxide plus 5 d of heating at 80°C 7.3 15
Manganese dioxide plus morpholine *
18.9 2.0 32
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2,4-Toluene diisocyanate plus

N-methyl-2-pyrolidone 7.0 k 0.5 200

ability. Suitable fillers should be dispersed and selected adhesion additives

should be incorporated. The various aspects of compounding such as curing
agent, curing modifier (retarder, accelerator), filler, plasticizer, and adhesion
additive are discussed in the following paragraphs. Typical commercial prod-
ucts and typical compositions are also included for completeness.

A. Curing Agents

The mercaptan-terminated liquid polymers are polymerized to rubbery solids

by use of oxidizing agents. The curing agents most commonly used are oxygen-
donating materials, e.g., lead dioxide, activated manganese dioxide, calcium per-
oxide, cumene hydroperoxide, the various alkaline dichromates, and p-quinone-
dioxime. The generally accepted mechanism of cure is

2-RSH + (0) ---RSSR + HzO

The curing rate may be modified by using specific additives. In general, the
pH of the system governs the curing rate; acidic materials retard whereas alka-
line materials accelerate the cure.
The curing agent selection is based on many factors, e.g., cure rate, heat
stability of cured composition, and elastomeric properties. For aircraft seal-
ants, manganese dioxide (Mn02, active grade), alkaline dichromate, and lead
dioxide (F'b02, medium grade) are the most common curing agents. A more
complete list of curing agents for liquid polysulfides is given in Table 8.

B. Cure Modifiers
The oxidation and reaction of mercaptan groups is accelerated in an alkaline
environment and retarded in an acidic condition. Therefore, pH plays an im-
 180 USMANI

TABLE 8
Curing Agents for Liquid Polysulfides
Inorganic oxides Inorganic peroxides Inorganic oxidizing agents
ZnO FeO ZnOz FeOz NaCr04 NaC104
PbO FezOz PbOz As203 KCr04 KC104
MgO COO MgOz SbZ03 NazCrzO7 Ba(C104)2
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CaO CuO CaOz Sb20s KzCrz07 NaZB407

BaO MnOz SnOz (NH4)ZCrZ 0 7

TeOz Pb304
SeOz
Organic peroxides Oxidizing agents Miscellaneous
Benzoyl peroxide Nitrobenzene Polyisocyanates
Dicumyl peroxide Dinitrobenzene Reactive phenols
Cumene hydroperoxide Other nitro compounds Diepoxy resins
Butyl hydroperoxide Oximes Organic titanates
Butyl perbenzoate Organic borates
Organic silicates

portant role in cure rates. Examples of retarders are stearic acid and metallic
stearates. Typical accelerators are amines, inorganic bases, water, dinitroben-
zene, and sulfur.

C. Fillers
Fillers increase the strength, impart needed rheological properties, and reduce
the cost of the sealant. Filler reinforcement of polysulfide sealants significant-
ly increases the tensile properties. The increase is related to type of filers, its
particle size, and the type of cure. Indiscriminate selection of the filler can
ruin the performance of a polysulfide sealant. Therefore, filler selection and
filler loading should be carefully established. Factors such as pH, particle size,
surface area, and surface treatment should be taken into consideration.
The classes of fillers used in formulating polysulfide sealants are calcium
carbonates (wet or dry ground limestone, chalks, or precipitated carbonates),
carbon blacks (furnace and thermal), clays (calcined), silica and silicate filers,
 POLYSULFIDE SEALANTS 181

and titanium dioxide (rutile is chalk resistant and preferred over anatase). In
general, sealants are prepared using a combination of fillers to obtain the de-
sired effect. In Table 9, examples of the various fillers are shown together
with the physical properties at various loadings.

D. Plasticizers
Plasticizers improve the working properties of the sealant while lowering its
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modulus. The plasticizer must be compatible with the cured sealant and
should have low volatility. Polymeric and ester-type plasticizers are common-
ly employed.

E. Adhesion Additives
The incorporation of adhesion additives is known to improve adhesion. Typical
examples are phenolic resin additives, e.g., Methylon AP-108, Durez 10674,
Bakelite Resin BRL 2741, and Resinox 468. Epoxies also perform well as ad-
hesion promoters. In some instances silanes (e.g., A-187 and A-189) are known
to improve polysulfide adhesion.

F. Typical Commercial Products

Some commercially available two-part aircraft polysulfide sealants are shown
in Table 10.

G. Typical Composition
A typical polysulfide sealant consists of two parts:

A sealant base component

An accelerator (catalyst) component

Normally nine parts by weight of the sealant base component are mixed with
one part by weight of accelerator component to give the polysulfide sealant.
The typical composition of a typical polysulfide integral fuel tank sealant is
shown in Table 11 [ 191.
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TABLE 9
Effects of Fillers on Sealant (LP-32 based) Properties
Cured sealant Heat aged 1 week at 212OF
Tensile Tensile
PPh of strength Elongation Hardness strength Elongation Hardness
Filler LP-32 Composition (psi) (%) (Shore A) (psi) (%I (Shore A)
None (control) 100 350 30 150 300 37
Pelletex SRF 30 Furnace black 600 800 52 870 810 60

Sterling MT 20 Thermal black 280 7 30 39 420 730 44

40 530 800 49 650 820 55
Calcene TM 30 Calcium carbonate 320 720 47 550 720 54
50 (ppt coated) 510 650 51 6 20 790 58
Multifex MM 30 Calcium carbonate 320 610 43 410 650 51
50 (PPt) 520 770 45 530 780 54
Witcarb RC 30 Calcium carbonate 380 730 43 410 620 49
50 (ppt coated) 580 820 45 560 680 52
York whiting 30 Calcium carbonate 120 590 36 160 440 45
50 (ground) 150 540 41 180 430 50
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Calwhite 30 Calcium carbonate 180 500 43 240 600 47

50 (ground ) 21 0 600 45 210 730 48
OMYA BSH 30 Calcium carbonate 190 460 43 200 600 47
50 (ground) 220 590 47 230 700 49
Icecap K 30 Calcined clay 290 5 70 43 370 630 50
50 320 550 49 380 730 55
Cabosil 15 Silica 480 850 46 650 1030 50
HiSil233 15 Silicate 360 850 45 480 900 47
Lithopone 40 ZnS-Bas04 280 760 40 400 880 45

Blanc fixe 40 Bas04 220 620 40 260 840 42

Titanox RA50 40 Ti02 360 860 44 500 990 50
Zinc sulfide 40 ZnS 425 830 38 480 940 45
Aluminum flakes 30 Aluminum powder 220 170 45 320 130 55
 184 USMANI

TABLE 10
Partial List of Commercially Available Aircraft Polysulfide Sealants
Specification Sealant designation Type cure Supplier
MIL-$8802 Chem Seal 3204 MnO2 Chem Seal Corp. of
America
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MIL-$8802 PRC 1440 MnO2 Products Research

& Chemical Corp.
MIL-$8802 PRC 1442 Dichromate Products Research
& Chemical Corp.
MIL-$8802 Proseal 890 Mn02 Essex Chemical
Corp.
MIL-$8802 GC 408 MnOz Goal Chemical
Sealants Corp.
MIL-$83430 PRC 1750 Mn02 Products Research
& Chemical Corp.
MIL-$83430 Proseal 899 MnOz Essex Chemical
Corp.

TABLE 11
Chemical Composition of a Typical Polysulfide Sealant
Ingredient Source Fundion(s) Percent
~~ ~~~ ~ ~~ ~

Calcium carbonate Base Filler, reinforcer 26.15

Titanium dioxide Base Filler, opacifier 3.10
Liquid polysulfide
polymer Base Vehicle 58.50
Volatile diluent Base Viscosity adjuster 2.25
Manganese dioxide Accelerator Curing agent 5.53
Oily fraction (processing
Oil) Accelerator Modulus adjuster 3.95
Volatile diluent Accelerator Viscosity adjuster 0.5 1
 POLYSULFIDE SEALANTS 185

V. PROCESSING AND MANUFACTURE OF

POLYSULFIDE SEALANTS

The polysulfide sealant production basically involves mixing and dispersion

operations. Thus equipment used in such industries as coatings and ink are
applicable to sealant manufacture. However, heavy duty equipment is gener-
ally required since the viscosities of the finished sealants are high, up to 60,000
P. Typical equipment used are sigma blade mixers, kneader-extruders, and
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high-speed dispersators. A three-roll paint mill gives excellent processing, i.e.,

maximum uniformity, fineness of grind, and reduction of occluded air. Trans-
ferring finished sealants requires the use of heavy duty displacement pumps.

VI. CHARACTERIZATION AND TESTING

A. Physical, Rheological, and Mechanical Characterization Methods

Physical, rheological, and mechanical characterization methods and specifica-
tions for integral fuel tank sealants are provided in MIL-S-8802E and MILS-
83430. These are specific gravity, nonvolatile content, viscosity of base com-
pound, flow, application time, working life, tack-free time, standard curing
rate, fluid immersed curing rate, resistance to thermal rupture, low-temperature
flexibility, peel strength, resistance to hydrocarbons, tensile strength and elon-
gation, chalking, accelerated storage stability, viscosity of curing compound,
and hydrolytic stability.
Parallel plate rheometry (PPR) and dynamic mechanical analysis (DMA) are
two characterization methods that can be useful for polysulfide sealants. Al-
though these methods have not been used in the past for characterizing poly-
sulfide sealants, we feel that PPR and DMA will provide valuable information
and should therefore be developed. We briefly describe PPR and DMA below.
Polysulfide sealant flow viscosity in the uncured state and as the curing
proceeds can be a very valuable measurement. PPR can be used to measure
rheology as a function of cure.
The determination of sealant/curative flow viscosity and the change in vis-
cosity with time and temperature are important for application. In the micro-
parallel plate rheometer, the flow system is a fluid being squeezed out from
two horizontal plates under application of a constant force. The measured
variable is the separation of the plates with time (using a Perkin-Elmer TMS-2
thermomechanical analyzer).
 186 USMAN I

Using the equation of motion for incompressible fluids, Dienes and Klemm
[20] have developed the equations that describe the behavior of a parallel
plate rheometer. The equation that describes the behavior where the fluid
completely fills the gap between the two plates is

Q = (h3~/3d?4)/(-&hie)

where Q = viscosity of the fluid

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h = separation of the plates at time 0

I;= the applied force
R = radius of the plate
-dh/d8 = the approach velocity of the plates at time 8

The above equation can be integrated with respect to 0 to get

where ho = plate separation at time i3 = 0. Thus, when l/h2 is plotted against

0, Q can be calculated from the slope.
Let us turn out attention to DMA. In the last 5 years the DMA methods,
which have been for more than 30 years either tools of fundamental research
or academic curiosity, have become widely popular. Introduction of automatic
experimental control, data analysis, and display have made DMA a valuable
tool. In polymers, DMA can be utilized to study the effect of water vapor,
comparing similar polymers, cross-linking optimization in thermoset resins,
correlation with fabrication, following cross-linking kinetics, effects of various
cross-linkers, and effect of plasticizers on polymer properties.
DMA offers a unique method to study cross-linking of polysulfide sealants.
The ability to study the systems before, during, and after cross-linking on one
specimen provides an efficient means to determine the unambiguous history
of the transformation from tractable prepolymer to intractable products.
A DuPont 981 DMA can be used to check cured polysulfide sealant. In
DMA, a viscoelastic material is physically stressed and then released, resulting
in deformation or strain of the material. A portion of this stored deformation
(strain) energy is returned as oscillation of the sample at a rate that is a funda-
mental property of the material. If the material were perfectly elastic, the re-
sulting frequency of the resultant oscillation of the material would be equal
to the frequency of the applied stress, with the resulting frequency of the re-
sultant oscillation being a function of the modulus (stiffness) of the material.
For viscoelastic materials, however, a portion of the deformation energy is
 POLYSULFIDE SEALANTS 187

dissipated due to molecular motion, resulting in a damping of the deformation-

induced oscillation.
In the DuPont 981 DMA, a sample is sinusoidally oscillated at its resonant
frequency at a preselected amplitude. In order to maintain the applied stress
at a constant amplitude, the energy dissipated by the material is added on to
the next cycle. This makeup energy is a direct measure of sample damping
(energy dissipation) and is related to tan 6.
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B. Chemical CharacterizationMethods
Mechanical and physical quality control tests on polysulfide sealants can pro-
duce erroneous and misleading results, especially in predicting long-term per-
formance. Problems such as poor adhesion to substrates, inadequate cure,
chalking, and short working life can frequently occur, resulting in tedious and
costly repair and the loss of time. We therefore feel that there is a need to de-
velop consistent and reliable analytical techniques for the chemical character-
ization of polysulfide sealants that can detect compositional variations and
relate these variations to physical and rheological property changes of cured
and uncured sealants.
The composition determination of polysulfide sealants has been extensively
studied by Usmani [21]. Both sealant base and accelerator components can
be resolved into various components. The sealant component can be reduced
in viscosity by methylene chloride and then separated quantitatively into
filler and vehicle by using a centrifuge operating at 5000 rpm for a period of
about 15 min. For quantitative analysis, the binder in methylene chloride
should be removed after the first centrifugation. The filler should be reworked
with methylene chloride and recentrifuged. This process should be repeated
one more time. The binder fractions should be combined and dried in a vac-
uum oven at 60°C for 16 h. Similarly, the filler portion should be dried in a
vacuum oven at 60°C for 16 h. The percent solid of the sealant base compo-
nent can be determined (at 6OoCin a vacuum oven for 24 h). Based on these
determinations, the sealant components’ composition in terms of percent
filler, vehicle, and volatile diluents can be calculated.
The filer fraction can be analyzed by energy dispersive x-ray analysis
(EDXA) and scanning electron microscopy (SEM). The vehicle fraction can
be analyzed by nuclear magnetic resonance (NMR)spectroscopy and gel per-
meation chromatography (GPC).
In a similar vein, it is possible to quantitatively separate and analyze com-
ponents of the accelerator component. The accelerator component can be
thinned down by acetone and then separated by centrifugation.
 188 USMANI

The polysulfide sealant composition alteration methodology has been de-

veloped by Usmani [22]. In a two-part polysulfide sealant, composition al-
teration involving a fured increase or decrease across the board for either the
sealant base component or the accelerator component is relatively easy to ac-
complish. For instance, a 10% increase in all sealant base components may
be desired in the final polysulfide sealant. In this case, we should use 10 parts
sealant component (instead of 9 parts as with the normal formulation) with 1
part accelerator component. Similarly, any percent decrease of all sealant
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base components can be accomplished by proper adjustment of sealant and

accelerator components. On the other hand, alteration not involving all ingre-
dients of a component but only one or two cannot be done by ratio adjust-
ment of the sealant base and accelerator components.
When formulative changes involving one or two ingredients are desired,
separating the polysulfide sealant components into individual and well-resolved
ingredients is essential. Separated ingredients can be recombined to achieve
the desired formulative change. Exact knowledge of the chemical identity of
the ingredients is not essential to the success of the method. In addition, quan-
tification of all ingredients of the components is not required except for the
ingredient in which a formulative change is desired. However, if formulative
changes involving most ingredients are required, we feel it would be desirable
to know the composition of the total polysulfide sealant.
Our formulative alteration methodology as applicable to polysulfide seal-
ants is shown in Fig. 2. We have cited several typical examples. The method
involves either “taking out” (“subtraction”) or “adding in” (“addition”) in-
gredients to the normal polysulfide formulation. The advantage of this method
is that even in the “addition” mode we are not confronted with the problem
of adding some ingredient which may be a close match to the actual ingredient.
In fact, the added ingredient is extrkted from the same sealant compound.
Usmani has proposed a number of analytical methods to implement quality
assurance in a polysulfide sealant [23]. These include infrared spectroscopy,
x-ray fluorescence spectroscopy, wavelength dispersive x-ray analysis, energy
dispersive x-ray analysis, gel permeation chromatography, reversed-phase
liquid chromatography, paper high-voltage electrophoresis, thin layer chro-
matography, and differential scanning calorimetry.
Analytically, the cure of a polysulfide sealant was measured by infrared
spectroscopy by Fountain and Haas [24]. These authors used a commercial
two-part polysulfide sealant (Products Research’s PR-1422-A4). One compo-
nent was a fded liquid polysulfide polymer, whereas the other component
was lead oxide paste in an organic base acting as curative. During cure, disap-
pearance of the absorption peaks at 1670 and 770 cm-’ was observed. Both
 POLYSULFI DE SEALANTS 189

bands are due to the curative component. The 1670 cm-’ peak shifts to
1600 cm-’ during cure, and this suggests ligand exchange may be taking place
with the liquid polysulfide polymer. For a given base-curative ratio at con-
stant temperature, it was found that the 2250, 1670, and 770 cm-’ peaks dis-
appear proportionally to each other during cdre, indicating that the degree of
cure can be measured by infrared spectroscopy.
Soon after mixing, infrared spectroscopy can quickly tell the amount of
curing agent added to the sealant. This is done by using the band ratioing
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technique. The curing agent peak disappears at 1670 cm-’ as the curing pro-
gresses, whereas a peak resulting from the base filler does not vary during
cure (870 cm-’). The band ratio of peaks at 870 and 1670 cm-’ can be
plotted against parts of curing agent per 100 parts of the polysulfide base.
Fountain and Haas [24] have furthermore demonstrated that infrared spec-
troscopy data can be correlated with a mechanical property (peel strength).

VII. ADHESION CONSIDERATIONS

A. General Background Information

A polyurethane coating is used on a fuel tank’s interior surfaces prior to appli-
cation of a polysulfide sealant. The sealant/coating combination works well
initially and there is apparently adequate adhesion of the polysulfide rubber
to the polyurethane coating. Upon extended aircraft usage, however, leaks do
develop. Repair of these leaks, by removing the old polysulfide rubber and
then applying a fresh sealant, has been unsatisfactory due to poor adhesion of
the new sealant to the “aged” polyurethane surfaces.
The factors responsible for the poor adhesion of the polysulfide sealant to
“aged” polyurethane coating were determined by Usmani et al. [ 2 5 ] . These
authors studied coating aging, use of primers, and determined factors govern-
ing coating-sealant interfacial integrity. They also analyzed results obtained
in terms of the chemical reactions involved, attractive forces, and other bond-
ing considerations.
Using transmission and surface reflectance infrared spectroscopy, Usmani
et al. monitored concentration changes in NCO groups of artificially aged poly-
urethane coatings [25]. The NCO concentration was found to deplete both
by heat and moisture. Heat treatment of polyurethane coating at 121°C
for 48 h produce a surface to which the polysulfide sealant would not
stick.
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Formulation
Alteration Mode

Base Volatile1
Normal Formula Pol ysu lfide Diluent 22.5 55.3 Oil 39.5
IProcessing) Volatile
7
1
585.0

4 -5.5g
I
Decrease 10%Mn02

Method: For 1000 g total batch, the normal amount of accelerator component is 100 g. From calculation we find
that 9.95 accelerator component contains 5.5 g Mn02. Centrifuge 9.95 g accelerator component; discard
MnOz but quantitatively save the recovered centrifuged fluid and mix it with 90.05 g accelerator compo-
nent to give the “constituted” accelerator component. Mix “constituted” accelerator component with
900 g sealant base component to give desired formulative change.
1 -58.59

Decrease 10%Liquid
Polysulfide

Method: Calculation shows 90.0 g sealant base contains 58.5 g liquid polysulfide. Centrifuge 90.0 g sealant base;
discard liquid portions but quantitatively save centrifuged fillers. Washed and dried filler is now ready t o
be mixed with the sealant base. Centrifugation also removes 2.25 g of volatile diluent. This being the
case, to the remaining 910 g sealant base not only the recovered filler should be dispersed but also 2.25 g
volatile diluent should be added. Volatile diluent can be easily trapped into a Dry Ice trap from sealant
base at 60°C under vacuum. While making “constituted” base, care must be taken that the recovered
filler is well dispersed into the balance of the base. Mix “constituted” base with 100 g accelerator com-
ponent to give desired formulative change.
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1 +26.1 g 1 +3.1 g

r--1
Increase 10% ; caco3; Fa;?
I287.6 1 ‘34.1
Filler L---A L--_I I

Method: This formulative change involves “addition” rather than “ ~ ~ b t r a c t i o nfrom

” the formula. However, addi-
tion does not involve using dissimilar material from an outside source but from “within“ the sealant.
Using an adequate amount of sealant base, centrifuge, recover, and dry about 50 g of the filler. Take
900 g of sealant base component and into it disperse 29.2 g of mixed filler. To the “constituted” base,
add and mix 100 g accelerator component and this new formula will reflect a 10% filler increase.

I------
Increase 10% 1Process:ng ;
Processing Oil ‘Oil 49.4 I
L-----I

Method: “Addition” is involved in this formula adjustment. Using an adequate amount of accelerator component,
recover about 15 g of the processing oil. Take 100 g of accelerator component and stir in 9.9 g of pro-
cessing oil to prepare “constituted” accelerator component. Mix it with 900 g of sealant base to obtain
the desired formulative change.

FIG. 2. Polysulfide formulation alteration methodology.

 192 USMANI

B. Adhesion Improvement via Polysulfide Modification

One way to improve the adhesion of a sealant to aged polyurethane panels is
to add an epoxy resin to the sealant formulation. Epoxy modification of poly-
sulfide improves the adhesion to polyurethane panels artificially aged for 48
h a t 121OC [25].

C. Polysulfide Adhesion Improvement via Primers

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An alkyl phosphato titanate, a mercaptofunctional silane, an oxiranefunctional

silane, and polyfunctional isocyanate-type primers were evaluated by Usmani
et al. [25].
All primers were applied to artificially aged polyurethane panels (48 h at
121°C). The peel data indicated that the titanate and mercaptofunctional
silane are effective adhesion promoters, whereas oxiranefunctional silane and
polyisocyanate are ineffective primers.

D. Adhesion of Polysulfide Sealant onto Polyurethane:

Mechanism Proposed by Uomani
Any proposed mechanism must be consistent with the experimental findings.
Before we describe a proposed mechanism, let us first review briefly the ex-
perimental data that we have generated and our conclusions therefrom [25].

1. Newly or slightly aged polyurethane coatings contain residual NCO

groups that function as an internal coupling agent for the polysulfide sealant.
The coupling reaction can be described as follows:
tr - o- - - -/-r
R-N=C=O + R‘-SH - //
R;cNH-C-S?R’
L-- ---,J
II //

Contained in
the cured Polysulfide
polyurethane sealant Thiourethane

Because of good wetting of the polyurethane surface and a high concentration

of the polysulfide, the above-described internal coupling reaction takes place
readily. This coupling produces excellent adhesion.
2. The solvent of the primer softens the aged polyurethane surface as evi-
denced by lowering of T,. The titanate softens more due to its chelate nature.
 POLYSULFIDE SEALANTS 193

3. The titanate slightly slows the curing of the polysulfide sealant. Slower
curing is known to produce improved adhesion.
4. The titanate interacts with the incoming polysulfide sealant and an in-
tact layer of Ti-S is formed; the Ti/S ratio was found to be 1/2. The reaction
between Ti and S can take place. On the other hand, we found no evidence
of titanate binding with the coated polyurethane surfaces.
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A schematic of the Usmani proposed mechanism with the newly coated

polyurethane is shown in Fig. 3.
Let us now turn our attention to the “aged” polyurethane coated surface.
Most of the surface isocyanate (NCO) groups have been consumed either by
the original polysulfide sealant application or by heatlhumidity as in “artifi-
cially aged” samples. Complete curing of the polyurethane coating has also
hardened the coating, both in bulk and at the surface. The adhesion of poly-
sulfide sealant, if applied to such a surface, will be due to slight interdiffusion,
dipole-dipole attraction, and Van der Waals attractive forces. These electronic
forces will be insufficient; therefore, the peel strength will be very low and the
interface will be prone to desorption by moisture and JRF or even heat (be-
cause of increased Brownian motion). Prior to applying the polysulfide seal-
ant, an application of a titanate primer improves the adhesion situation. The
titanate primer reacts with the polysulfide sealant as we have indicated above
and also slows its curing. Another reason the primer functions is by removing
or lifting a monomolecular (or thicker) water layer from the polyurethane sur-
face and allowing the sealant to “wet” or get “closer” to the polyurethane.
The water monolayer removal from the polyurethane improves adhesion.
The formation of a “soft Ti-S layer” also helps in adhesion. The titanate does
not chemically interlock with the “aged” or newly coated polyurethane sur-
face but softens, diffuses into the coating, and anchors due to a combination
of mechanical interlocking and increased dipole-dipole attraction and Van der
Waals forces (shown in Fig. 4).
The epoxy-modified polysulfide has improved adhesion because epoxy
groups can react with urethane groups and the hydroxyl and nitrogen groups
increase the electronic attractive forces.

VI 11. APPLICATIONS

The polysulfide sealants have unique properties that can be put to very de-
manding uses. These have excellent resistance to hydraulic and aircraft fuels,
 194 USMANI
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NEWLY COATED POLYURETHANE; POLY SULFIDE

REPRESENTS CROSSLINKED SEALANT
POLYURETHANE POLYMER CONTAINING
RESIDUAL UNREACTED NCO
(SHOWN BY -1.

POLYSULFIDE
INTERFACE
POLYURETHANE

NEWLY APPLIED POLYSULFIDE SEALANT: AND

CURING HAS COMMENCED

1 SLOW REACTION WITH

FORMATION OF THIOURETHANE
THAT RESISTS DESORPTION

CURED INTEGRAL FUEL TANK SEALANT

FIG. 3. Polysulfide sealant on newly coated polyurethane surface. Courtesy

of Rubber Chemistry and Technology, American Chemical Society.
 POLYSULFIDE SEALANTS 195

+ TITANATE
PRIMER

"AGED" POLYURETHANE SURFACE;

NO FREE NCO
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+
POLY SUFIDE
SEALANT
TITANTED SURFACE
REPRESENTS TITANATE PRIMER

POLYSULFIDE APPLIED ON TITANATED SURFACE

SLOW TITANATE - POLYSULFIDE REACTION

CURED INTEGRAL FUEL TANK SEALANT

FIG. 4. Adhesion onto aged polyurethane surface. Courtesy of Rubber

Chemistry and Technology, American Chemical Society.
 196 USMAN I
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FIG.5. Depiction of major fields of polysulfide sealant applications.

weather, water, water treatment chemicals, UV light, and salt spray; excellent
flexibility over a wide temperature range; adhesion; and long-term perform-
ance.
The fields of polysulfide polymer applications are shown in Fig. 5. The
end-uses are illustrated in Fig. 6.

IX. FUTURE PROSPECTS

The total United States production of fabricated rubber products is about 5

million metric tons [26]. The polysulfide sealant amounts to roughly 15 mil-
lion pounds. Because of depressed automotive and construction markets, poly-
sulfide sealants have not fared well ciuring the past several years. The market
for aircraft sealant was relatively stable.
Despite challenge by newer types of materials, polysulfide sealants will con-
tinue to dominate the elastomeric sealant market. No drastic increase or de-
crease in the volume is forecast for the next 5 years or so.
 POLYSU LFI DE SEALANTS 197

0 SEALING INTEGRAL
FUEL TANKS
0 SEALING PRESSURIZED
CABINS
0 POTTING ELECTRICAL
CONNECTORS
0 SEALING BOLTED
STEEL TANKS
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D GLAZING OF
W I NDS H IELD
FUEL BINDER I GLAZING OF
0 RELIEF Pk~s REAR LIGHTS
0 PRINTING ROLL I RECREATIONAL
0 DENTAL VEHICLES
IMPRESS ION 0 VIBRATION
0 HOSE,GASKET DAMPING (TRAILERS
D GAS TANK LINER

\
0 CURTAIN NALL
0 WOODEN AND 0 OTHER BUILDING
FIBER GLASS EXTERIOR JOI NT
DECKS OF 0 IiIGHWAY JOINT
PLEASURE CRAFT 0 AIRFIELD
0 INSULATED
GLASE
0 CANAL
0 SWIMMING POOL

FIG. 6. Diversity of end uses.

X. CONCLUSIONS

In this paper the published literature and patents on polysulfide sealants have
been reviewed in detail. We have described chemistry, properties, compound-
ing, processing and manufacturing, characterization and testing, major appli-
cations, and future prospects of polysulfide sealants. Factors governing ad-
hesion and the mechanism of adhesion as proposed by Usrnani have also been
discussed.
 198 USMANI

Since the chemical characterization methods for polysulfide sealants have

not been studied, investigators are encouraged to study them to further extend
the usefulness of polysulfide sealants.

Acknowledgments

Special thanks goes to Mrs Jeanne Drake (University of Dayton Research In-
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stitute) for producing this paper. Helpful assistance given by Drs R. P. Chartoff,
J. M.Butler, I. 0. Salyer, and B. Wilt (all of the University of Dayton) is also
gratefully acknowledged by the author.

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 POLYSULFIDE SEALANTS 199

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