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Elastomeric Sealing Material Selection

New water quality standards call for better chloramine resistance
By Valerie Combs September 26, 2010
The process of disinfecting potable water has been evolving over time due to the
implementation of more stringent health and safety requirements. Historically,
potable water has been disinfected using free chlorine at a residual level of ~0.5
PPM total residual chlorine; however, chloramine treatment of potable water by
municipalities is becoming more common at a residual level of ~4.0 PPM total
residual Cl2. This change has proven to be detrimental to elastomeric seals used for
both point-of-use and distribution-system applications. Choosing the correct sealing
material will ensure that the seal will last within the predicted life of the system.
Chloramination of potable water is the process of creating chloramines for
disinfection by combining chlorine and ammonia. Chloramination has become
widespread due to more stringent water quality standards. These standards have
been implemented to ensure that drinking water is safe for consumption. One of the
criteria for safe drinking water is to limit the amount of disinfection by-products
(DBPs) formed en route to the consumer. DBPs are carcinogenic and the levels have
been regulated by the EPA since 1979. DBPs are formed when chlorine reacts with
excess organic material in the water.
Water disinfection involves chlorine reacting with harmful substances in the water to
kill all matter harmful to humans. However, chlorine-containing byproducts with
detrimental health effects are formed during this process. These byproducts can
include chloroform and carbon tetrachloride. The primary disinfection process
involves disinfecting with free chlorine to kill all microorganisms. After this process
has been completed, ammonia is added to form chloramines to retain residual
disinfection while the water is being transported.
Chloramination has been used as a secondary disinfection method for over 100
years. It is typically not used as the primary method since the effectiveness is much
less than that of free chlorine for disinfection. Although chloramines do not have the
kill power of free chlorine (roughly 20 percent less1), chloramines have a much
longer residual life. Residual life is very important in potable water. Water may
travel through several miles of pipe to reach the final destination. During this
journey, organic matter has the potential to be introduced into the system. Since
free chlorine can dissipate quickly, water that has traveled a long distance may not
be as safe as intended. Chloramines ensure the water still has the ability to kill
microorganisms further downstream, thus creating safer water. Chloramines also do
not include the offensive taste and odor that accompanies potable water disinfected
with free chlorine.
Chloramine Chemistry
Chloramine is formed when chlorine and ammonia combine in an aqueous
environment. Primary disinfection of potable water can be accomplished using
either chlorine or ammonia. Upon the completion of primary disinfection, the second
component (chlorine or ammonia) is added to form chloramines. The most common
method is to chlorinate the water prior to adding the ammonia. This guarantees
adequate disinfection prior to adding the ammonia. Once the chlorine and ammonia

are added, the reaction begins. The reaction products are determined by the rate of
reaction. The three distinct molecules are monochloramine (NH 2Cl), dichloramine
(NHCl2), and nitrogen trichloride (NCl3). The desired primary molecule for
disinfection is monochloramine. The rate at which each molecule is formed is
dependent on two variables; pH of the water and ratio of reagents added (chlorine
to ammonia). The desired reaction product is monochloramine for several reasons.
Monochloramine is a better disinfectant than dichloramine and nitrogen trichloride.
In addition, the taste and odor is offensive when dichloramine and nitrogen
trichloride levels increase. The addition of chlorine and ammonia are critical to the
formation of a primarily monochloramine solution. The basic reaction of chlorine and
ammonia to form chloramines is shown in Figure 1.
As previously stated, the
formation of a
monochloramine solution is
NH2Cl + HOCl D NHCl2 + H2O (Dichloramine)
dependent on the pH of the
water and the ratio of
NHCl2 + HOCl D NCl3 + H2 (Nitrogen Trichloride)
chlorine to ammonia. At a pH
of 5.5 and greater, mostly
Figure 1. Mechanism for forming chloramines1
monochloramine is produced
with some dichloramine.
Above a pH of seven, there is monochloramine and only a trace amount of
dichloramine produced. Nitrogen trichloride is formed at a pH of less than three.
NH3(aq) + HOCl D NH2Cl + H2O (Monochloramine)

The second criterion for producing primarily monochloramine is the ratio of chlorine
to ammonia. The optimum ratio for the formation of monochloramine is four mg
chlorine/one mg ammonia as N (four-to-one). As the ratio of chlorine to ammonia is
increased, dichloramine begins to form along with the monochloramine. At a ratio of
chlorine to ammonia above eight-to-one, only dichloramine and nitrogen trichloride
are produced.
Elastomer Comparison
The rubber industry has a variety of polymer types to choose from when a new
sealing application arises Key questions needed to determine seal and material type
are: minimum and maximum temperatures, fluids to seal, and if the seal will be
static or dynamic. From this information a material recommendation is made. The
common polymer types currently used in the potable water industry are listed below
along with some of their characteristics.
Ethylene Propylene (EPM, EPDM): EPDM is currently the workhorse for the potable
water industry due to the excellent resistance to water and especially chlorinecontaining water. Seals utilizing EPDM rubber can be operated over a continuous
temperature range of -40 C to 150 C, with the seals being capable of intermittent
spikes up to 175 C. EPDM can be compounded to meet a wide variety of mechanical
properties including durometer, tensile, elongation, and compression set.
Compression-set resistance of EPDM seals is far superior to seals made from
thermoplastic and thermoplastic vulcanizate (TPV) materials.
EPDM materials serve a wide variety of industries and provide excellent sealing
ability for a range of fluids. However, this family of materials is not recommended
for hydrocarbon applications (petroleum grease, fuel, etc.). When exposed to
hydrocarbons, EPDM material exhibit severe swelling and rapid loss of mechanical
properties.
Nitrile Butadiene (NBR): This elastomer is typically used in the potable water
industry when there is a concern that the seal will come into contact with a
hydrocarbon-based material. Nitrile rubber performs well in water, but has poor
weatherability. The polymer backbone contains carbon-carbon double bonds

(unsaturation), which are weaker and more susceptible to weather and ozone attack
than a fully saturated polymer such as EPDM or silicone.
Silicone (VMQ): Silicone rubber is the best option when it comes to chloramine
resistance. The drawbacks to silicone rubber are cost and mechanical properties.
VMQ does not have the mechanical properties of other elastomer families. The
poorer mechanical properties are abrasion resistance, tear strength, and tensile
strength. However, silicone is exceptionally chloramine resistant and also
moderately resistant to petroleum oils.
Analysis
Chloramine attack on rubber materials has been described in several ways. The
typical methods of seal failure are loss of sealing force or gland overfills. When the
failure mode is loss of sealing force, the rubber has typically been eroded away from
the seal. This can lead to noticeable buildup in faucet screens or the water will
visibly contain small pieces of the seal. Once surface degradation begins, it will
progress quickly. The second type of failure, gland overfill, is a result of the seal
swelling excessively. Excessive swell can rupture the mating components and cause
a leak path. If the assembly does not rupture, there is a potential the water flow
path will be closed off due to the swelled seal.
Degradation Key
1. Complete degradation (entire surface), floaters
2. Complete degradation (entire surface), no
floaters
3. Internal degradation blisters
4. Severe swelling degradation
5. Edge degradation with floaters
6. Edge degradation (visible) or surface degradation
7. Severe swelling no degradation
8. Edge degradation with slight surface degradation
9. Slight edge/surface degradation (no visual signs)
10. No degradation
Table 1. Key for rating tested samples for
degradation and swell (developed by Parker
Hannifins Engineered Seals Division).
The standard method for testing the chloramine resistance of rubber is defined in
standard ASTM D6284. This standard gives the recipe for preparing the chloramine
solution, as well as the concentration used for testing and specimen size. All testing
and results performed by Parker Hannifin (www.parker.com) are per the below
conditions.

50 ppm total residual chlorine

Solution is changed daily

(except weekends and holidays)

Temperature is constant at 70 C

Volume of solution to surface area of the

rubber specimen is 20 mL/cm2 minimum

Sample size is 1 x 2 x 0.040 inch unless otherwise stated

Total residual chlorine is the combination of all chlorine-containing

compounds in the water. This includes free chlorine, monochloramine,
dichloramine, and nitrogen trichloride. Preparing the solution per ASTM
D6284 makes certain that monochloramine is the prevailing chlorine
compound.

A variety of materials were tested during the evaluation of chloramines-resistant

materials. The test matrix included the base polymers EPDM (Ethylene Propylene),
VMQ (Silicone), NBR (Nitrile), HNBR (Hydrogenated Nitrile), FKM (Fluorocarbon), and
ECO (Epichlorohydrin).
Degradation Methods
When exposed to chloramine containing water, the method of degradation varies
widely depending on the base polymer and the formulation. The main modes of
degradation are severe swelling, edges swelling with degradation, degradation
without swell, and crazing (surface attack). Each type of degradation poses unique
sealing problems. A key to determine the type and severity of degradation was
developed by Parker Hannifins Engineered Seals Division to aid in the analysis of
the samples. The key in Table 1 ranks the characteristics of the material on a scale
of one to 10 (10 = best).
Examples of each type are shown below:

Figure 2. Initial sample

vs. severe swelling no
degradation. The sample
after aging has swelled
>300 percent. Zero
degradation is present.
Rating = 7

Figure 3. Initial sample

vs. surface degradation.
Sample is showing signs
of surface attack and
crazing. When touched
or agitated, material is
dislodged from the
sample. Rating = 6

Figure 4. Initial sample

vs. edge degradation
with floaters (i.e.
elastomeric precipitate).
Sample has swelled and
is degrading on the
edges, when touched or
agitated, the degraded
pieces of material will
dislodge from the
sample. Rating = 5

Figure 5. Complete
degradation with
floaters. Material
exhibits severe
degradation after two
weeks, the sample has
not swelled, only
degraded. Rating = 1

Elastomers for Sealing

The degree of chloramine resistance is not the only criterion evaluated for sealing
applications. In order for a seal to perform, the seal must exert enough force on the
mating components to form the seal. As seals are aged in the compressed state, the
opportunity arises for the seals to permanently deform and take the new shape of
the compressed state. This is known as compression set.
Compression set is tested in the laboratory by compressing a sample a known
amount, aging the sample (usually elevated temperature), releasing the force from
the sample and allowing the sample to cool. If the sample does not return to the
original height, it has taken a set. Samples are measured for initial and final height
and the percentage of set is calculated. Low compression set is desired for seals.
100 percent set indicates that when compressed, the seal permanently deforms to
its compressed height. This result is undesired as it indicates that the seal will
rapidly lose sealing force over time.
Compression set measured in the chloramine solution is useful to determine the
effect of the fluid on the seal. The fixture (Figure 6) used for testing is a noncorrosive fixture that allows solution to contact both the OD and ID of a sample. Oring samples or a sample die-cut from an ASTM slab of uniform thickness can be
used for the test. Examination of the samples after exposure shows the samples are
only degraded where the solution is contacting the seal (ID and OD). The top and
bottom of the sample are unaffected. Figure 7 shows the degradation only where
the solution is in contact with the seal.

Figure 6. Compressionset fixture.

Figure 7. O-ring after

compression set testing
in 50 PPM total residual

chlorine @ 70 C, eight
weeks. Degradation is
seen on the OD and ID
of the o-ring, but not on
the top or bottom face
where the ring is in
contact with the fixture.

Looking at Figure 8, the volume changes for all three materials are very similar.
Figure 9 is a comparison of the compression-set properties and depicts a dramatic
difference between materials.

Figure 8. Chloramine
testing 20 ppm total
residual chlorine, 60C, 6
weeks.

Figure 9.
Compression set
comparison (lower %
is better). 25 percent
compression, 20 PPM
total residual chlorine,
60 C, 6 weeks.

After 1008 hours of aging in the chloramine solution, the Santoprene material has
taken a set of >85 percent in the chloramine fluid. As shown, similar formulations of
EPDM materials can provide very different compression-set properties. The 85A grey
material has a much higher compression set than the black, >60 percent and <10
percent, respectively.

Chloramine-Resistant Materials
The acceptance criterion for chloramines-resistant materials is zero degradation and
minimal swelling after aging at the specified conditions.
Parker Hannifin, for example, has developed several new chloramines-resistant
materials. Once a chloramines-resistant material was developed (zero degradation,
minimal swell), these materials were tested against a competitive material, also
marketed as chloramines-resistant.
A second type of test specimen was used for the chloramine testing in addition to
the standard specimen. The dimensions are 1.47 in ID, 1.75 in OD, and a height of
0.137 in. Figure 10 depicts the weight change against time (in weeks). The sample
type is listed below each chart in the description. Figure 10. Chloramine testing on
rings (1.47 x 1.75 x 0.137), competitive material, Rating = 1 vs. Parkers EJ273-

70: Rating = 9, and EJ274-70: Rating = 9.

The EPDM comparison in Figure 11 depicts a significant reduction in swell as well as
degradation. The competitive material is completely degraded and severely swelled
(>200%) after eight weeks.As shown in Figures 11, Parker Hannifins new
technology EPDM materials show improved property retention compared to the
competitive and standard materials.

Figure 10. Chloramine

testing on rings (1.47 x
1.75 x 0.137),
competitive material,
Rating = 1 vs. Parkers
EJ273-70: Rating = 9, and
EJ274-70: Rating = 9.

Figure 11. Parkers

EJ274-70 on the left
and the competitive
material on the right
after chloramine
testing. EJ274-70
Rating = 9,
competitive material =
1

Parker Hannifin has two material offerings for chloramine resistance; EJ273-70
Figure 11. Parkers EJ274-70 on the left and the competitive material on the right
after chloramine testing. EJ274-70 Rating = 9, competitive material = 1.
and EJ274-70 (internally lubricated). These materials are universal compounds and
will be used to make engineered shapes, complex over-molded seals, lathe-cut seals
or o-rings. Along with its molding capability, Parker Hannifin offers design
engineering assistance and material development opportunities for your specific
application. The design assistance includes seal and mating component design
recommendations, as well as FEA analysis. All compounds are available for
sampling.
Valerie Combs is a senior chemical engineer and laboratory manager at Parker
Hannifins Engineered Seals Division. For the past four years Ms. Combs has been
instrumental in the areas of compound development for the industrial, military,
aerospace, and transportation markets. Ms. Combss expertise has provided several
solutions to a variety of industry problems in these markets. Ms. Combs earned a
bachelors degree in Chemical Engineering from Tri-State University in Angola,
Indiana and is an active member of SAE, ACS-Rubber Division, and the Fort Wayne
Rubber Group.
www.parker.com

References
1. American Water Works Association, Research Foundation (AWAARF), 1993,
Chloramine Effects on Distribution System Materials, Denver, CO.: AWWARF.
2. Keller, Robert C. Ed. Krishna C. Baranwal and Howard L. Stephens, Basic
Elastomer Technology, 1st Ed., Baltimore, Md., The Rubber Division,
American Chemical Society.