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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.
Temperature is constant at 70 C
Figure 5. Complete
degradation with
floaters. Material
exhibits severe
degradation after two
weeks, the sample has
not swelled, only
degraded. Rating = 1
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-
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.