FEATURE ARTICLE

Dr. Neil Canter / Contributing Editor

Status of medium- and long-chain

Chlorinated Paraffins
Will their use be restricted? And what are the alternatives?

CHLORINATED PARAFFINS ARE THE MOST

WIDELY USED EXTREME PRESSURE (EP)
additive in the marketplace. They were
Preparation of Medium-Chain Chlorinated
introduced in the 1930s and are avail- Paraffin - (MCCP)
able in varying degrees of carbon chain
length and chlorine content.1
Chlorinated paraffins are prepared
from the reaction of chlorine with a
paraffin or olefin of a specific chain
length (see Figure 1). The current
types of chlorinated paraffins are dis-
tinguished by chain length ranges and Figure 1 | Chlorinated paraffins are produced through the reaction of chlorine with a paraffin
are shown in Table 1. or olefin as shown for an MCCP. (Figure courtesy of Qualice LLC.)
Regulation of chlorinated paraffins
started in the 1980s with the reporting
of a U.S. National Toxicology Program ously started to move away from this
study on a specific short-chain chlori- specific chlorinated paraffin chain in
nated paraffin (SCCP) and long-chain the mid-1990s when EPA ordered SC-
KEY CONCEPTS chlorinated paraffin (LCCP). A his- CPs to be subjected to Toxic Release In-
torical perspective on the regulation of ventory reporting and mainly switched
• Uncertainty remains about how chlorinated paraffins can be found in to medium-chain chlorinated paraffins
EPA will regulate
reg l te chlorinated
chlorinateed a recent STLE Webinar2 that was sum- (MCCPs).4
paraffi .
paraffins. marized in the February 2016 TLT. The PMN process in the U.S. en-
In 2012 the U.S. Environmental ables EPA to review “new substances”
• The MWF industry must accept
accept
p Protection Agency (EPA) required, via that companies want to introduce com-
that use of current
rrent chlorinated
chlori t d a consent decree, that the chlorinated mercially and be listed on the TSCA In-
paraffins will probably
ly endd at paraffin producers submit premanu- ventory. EPA indicated that in 2012 the
some point in the future.
future. facturing notifications (PMNs) for chlorinated paraffin suppliers agreed to
medium- and long-chain chlorinated have medium- and long-chain chlori-
• Combinations
Combinat s of alternatives
altern t es paraffins.3 As part of this arrangement, nated paraffins treated as new sub-
are needed because no single manufacturing and importation of SC- stances under TSCA section 5.
alternative works in
in every case. CPs in the U.S. ceased. The metalwork- The big concern for EPA is that the
ing fluid (MWF) industry had previ- currently used CAS numbers on the

34 • MARCH 2016 T R I B O LO GY & LU B R I CAT I O N T EC H N O LO GY W W W. ST L E .O RG

Current Types of Chlorinated Paraffins TSCA database for chlorinated paraf- in evaluation of the risk assessments for
fins are too general (see Table 2). EPA MCCPs and LCCPs.7 Interested parties
believes that any chlorinated paraf- were asked to respond back with data
fins approved for use now and in the and/or comments by Feb. 22, 2016.
future must have CAS numbers with A coalition of industry organiza-
more specific chemical structure de- tions has now been organized to re-
scriptions. spond to EPA’s action in (1.) with-
In 2012 and based on PMN sub- drawing the general CAS numbers and
missions, EPA initiated a further risk descriptions for the chlorinated paraf-
assessment of MCCPs and LCCPs that fins now on the TSCA Inventory and
Table 1 | The current types of chlorinated was completed in November 2014. A (2.) requiring producers and import-
paraffins are defined by specific chain redacted version of EPA’s risk assess- ers to submit PMNs so that they can
length ranges. (Table courtesy of Chemical ment is now available through a link be placed back on the TSCA Inventory
Solutions.) on the Independent Lubricant Manu- under more specific CAS numbers and
facturer’s Association’s (ILMA) Web- descriptions.
site.5 EPA’s preliminary conclusions are There is general chemical indus-
that MCCPs and LCCPs “present acute try concern that EPA may use this ap-
and chronic risks to aquatic organisms” proach on other chemical substances
and “may be very persistent and bioac- currently used commercially. The
cumulative.” lead industry organizations working
For these reasons, EPA in January with EPA are the American Chemistry
Current Chlorinated Paraffins CAS
Numbers on the TSCA Database 2015 gave chlorinated paraffin produc- Council and ILMA. They are proposing
ers two options: three alternatives for EPA to consider in
dealing with MCCPs and LCCPs.
1. Stop selling MCCPs and LCCPs
immediately. 1. Complete the ongoing review of
2. Not produce or import MCCPs MCCPs and LCCPs under the
and LCCPs after May 31, 2016. TSCA work plan and if scientifical-
ly justified proceed with a TSCA
In effect, EPA will be impacting 99% section 6 rulemaking to impose
of the chlorinated paraffins sold in the disposal restrictions.
Table 2 | The currently listed CAS numbers marketplace to the metalworking fluid 2. After an opportunity for industry
for chlorinated paraffins on the TSCA data- industry. As part of a presentation from input, promote an SNUR imposing
base are very general in description. (Table Dr. Maria Doa of EPA in September appropriate disposal restrictions.
courtesy of Chemical Solutions.) 2015, the agency has now decided to
delay the stoppage of production and 3. Obtain peer review of the draft
importation of MCCPs and LCCPs to risk assessment and issue a request
mid-2017.6 for information on appropriate
An important consideration is that risk management controls for MC-
no deadline has been established for CPs and LCCPs.
when usage of MCCPs and LCCPs in
the U.S. must cease. The metalwork- As of the end of January 2016, the
vLCCPs Cleared by EPA ing fluid industry is waiting for EPA goal of the industry coalition remains
to develop a Significant New Use Rule to have EPA review MCCPs and LCCPs
(SNUR) to deal with the issue of critical under TSCA section 6, which covers
applications for which acceptable sub- existing chemicals and enables the in-
stitutes are not available by the even- dustry to provide EPA with input.
tual ban date. As of the end of January 2016, it is
EPA is willing to obtain industry in- unclear exactly what will occur except
put on “critical uses” for MCCPs and that the MWF industry should realize
LCCPs that might impact the agency’s that use of MCCPs and LCCPs will prob-
Table 3 | The CAS numbers for vLCCPs listed final approach for dealing with these ably end at some point in the future.
on the TSCA database are defined by much two additives. In December 2015, EPA This means that MWF formulators
more specific descriptions. (Table courtesy published a notice in the Federal Regis- must reformulate their products to re-
of Chemical Solutions.) ter requesting new data for them to use place MCCPs and LCCPs with viable

W W W. ST L E .O RG T R I B O LO GY & LU B R I CAT I O N T EC H N O LO GY MARCH 2016 • 35

 of a carbon chain length below C21.”
The vLCCPs currently cleared by
Preparation of Very Long-Chain Chlorinated EPA and commercialized are shown by
Paraffin - (vLCCP) CAS number and description in Table
3 on page 35. These compounds are
characterized by specific carbon chain
lengths in contrast to the CAS num-
bers for the other chlorinated paraffins
shown in Table 2.
MacNeil says, “vLCCPs are fully
registered under TSCA and are not un-
der EPA risk assessment at this time.”
Figure 2 | vLCCPs, currently cleared by EPA, are produced in the same manner as the other While comparable to MCCPs and
chlorinated paraffin types. (Figure courtesy of Qualice LLC.) LCCPs in chemical composition,
vLCCPs exhibit higher molecular
weights and as a consequence higher
alternatives. As a follow-up to a past vLCCP viscosities. MacNeil says, “vLCCPs
article on chlorinated paraffins,8 the An example of EPA’s new approach on have higher viscosities than mid-chain
following companies were contacted chlorinated paraffins is the recently and long-chain chlorinated paraffins
again to provide updates on alterna- commercialized very long-chain chlo- at equal chlorine content due to the
tives to chlorinated paraffins: rinated paraffins (vLCCPs, see Fig- length of the carbon chain. The phe-
ure 2). As shown in Table 1, vLCCPs nomenon is familiar to compounders of
• Afton Chemical Corp. cover chlorinated paraffins with chain metalworking fluids as a similar effect
• Croda Inc. lengths between C21 and C30. STLE- occurs in base oils.”
• DIC Corp. member James MacNeil, product man- Formulating with vLCCPs can pres-
• The Elco Corp. ager for Qualice LLC in Hamlet, N.C., ent some new challenges to the metal-
• The Lubrizol Corp. says, “The paraffins used to prepare working fluid formulator due to their
• Qualice LLC. vLCCPs cannot contain more than 1% higher chain length. MacNeil says,

Figure 3 | An emulsifiable oil concentrate prepared with vLCCP is shown on the left. The formulation is in the middle and 5% dilutions in 200
ppm and 400 ppm water are shown on the right. (Figure courtesy of Qualice LLC.)

36 • MARCH 2016 T R I B O LO GY & LU B R I CAT I O N T EC H N O LO GY W W W. ST L E .O RG

“vLCCPs have comparable solubility
in oil for neat oil formulations as com-
pared to MCCPs and LCCPs and also
Typical EP Activation Ranges
can be emulsified to create water-based
metalworking fluids.”
An example of a sample emulsifiable
oil formulation containing vLCCPs
used at a treat rate of 10% is shown in
Figure 3. MacNeil says, “We developed
the formulation known as 94A with the
additives shown using naphthenic oil
as the base stock. The formulation is
stable at a 5% dilution in 200 ppm and
400 ppm hard water as shown.”
MacNeil considers vLCCPs to be a
useful tool for the MWF formulator to
consider as an alternative to LCCPs and
MCCPs. He adds, “Some care in formu-
Figure 4 | The different temperature ranges where boundary lubricity additives and extreme
lating will be needed with the higher pressure additives operate are shown. (Figure courtesy of Afton Chemical.)
viscosity of vLCCPs. Though the higher
viscosity of vLCCPs dictates that their
maximum chlorine content be around sure that under a given set of operat- stability and be more expensive.”
50% by weight as opposed to 60% for ing conditions the chlorinated paraffin STLE-member Ben Faber, metal-
an MCCP, the difference is quite small alternatives will exhibit comparable working product manager for The Lu-
in a formulated product. At a treat rate performance. In assessing boundary lu- brizol Corp. in Wickliffe, Ohio, says,
of 20% in a formulated metalworking bricity additives and extreme pressure “Chlorinated paraffins undoubtedly
fluid, the 10% difference in chlorine additives, formulators must realize that provide great extreme pressure lubri-
content translates into a 2% difference they operate within different tempera- cation, but there are other alternatives
if both chlorinated paraffins are used at ture ranges as shown in Figure 4. that do not have the associated envi-
a treat rate of 20% in the formulation.” ronmental and regulatory concerns.”
BENEFITS Faber believes that by switching to
ALTERNATIVE CHLORINE-FREE Anthony Jarvis, R&D manager, global chlorine-free alternatives, formulators
EP ADDITIVES MWF product development for Afton can achieve greater flexibility with their
There are a number of alternative chlo- Chemical Corp. in Manchester, UK, fluids. Extreme pressure additives can
rine-free EP additives that can be sub- indicates that alternatives to chlori- be combined to activate at broader tem-
stituted for MCCPs and LCCPs in the nated paraffins offer advantages such peratures that allows fluids to be used in
main metalworking fluid types (neat as having regulatory approval for use, more applications. In general, phospho-
oils, emulsifiable oils and semisyn- being able to be biodegradable, having rus additives activate at a lower temper-
thetic fluids) where chlorinated paraf- greater ease of disposal, having a more ature and sulfur additives activate at a
fins are used. Most of the respondents favorable image from an environmen- higher temperature relative to chlorine.
list the following types as possibilities: tal standpoint and having no chloride- “As part of this flexibility, formula-
based corrosion issues that chlorinated tors also may be able to use lower treat
• boundary lubricity additives (com- paraffins can face during application. rates of additives such as sulfurized ole-
plex esters, polymeric esters and In the latter case, Jarvis says, “Chlo- fins and polymeric esters,” says STLE-
polyalkylene glycols) rinated paraffin alternatives do not lib- member Gabe Kirsch, metalworking
• phosphorous containing additives erate hydrogen chloride during use, product manager for The Lubrizol Corp.
(phosphate esters, phosphites and which reduces fumes and staining.” He continues, “Some chlorine replace-
phosphonates) But these alternatives also have some ment chemistries are more compatible
disadvantages. Jarvis says, “Alternatives with use in water-based fluids, especially
• sulfur-based additives (sulfurized ole- for chlorinated paraffins can be less polymeric esters and phosphorus addi-
fins, sulfurized fats, oils and esters) flexible in terms of applications and tives. Some additives require no emulsi-
• overbased calcium sulfonates. the choice of carrier base stocks (min- fier whatsoever and can allow for syn-
eral oils and water) used in formulating thetics with improved lubricity.”
One of the challenges faced by met- them, have more difficulty in developing One other advantage for chlorinated
alworking fluid formulators is making stable formulations, have less hard water paraffin alternatives cited by Kirsch is

Launched in 1977, Voyager 1 is so far from the Earth it takes radio signals traveling at the speed of light 14 hours to reach it. 37
fewer staining and residue problems.
He explains, “Through the machining Soluble Oil Emulsion Temperature Curve
process, chlorinated paraffin residues
can cause undesirable ferrous corro- WŽůLJŵĞƌŝĐƉŚŽƐƉŚŝƚĞĞƐƚĞƌ
sion, which is often overcome with non-
chlorinated additives. In addition, chlo-
rinated paraffin residues are notoriously
difficult to remove in some applications,
whereas chlorine-free alternatives are
typically easier to clean off of a surface.”
STLE-member Larisa Marmer-
stein, R&D chemist for Elco Corp. in
Cleveland, says, “Besides an improved

environmental profile, chlorinated
paraffin-free alternatives when used in
metalworking fluids can contribute bet-
ter tool life and finish on metal parts, Figure 5 | Results from a 4-ball EP ramp test (ASTM D2783) are shown comparing a chlori-
easier cleaning and the ability to keep nated paraffin-based emulsifiable oil with a polymer phosphite ester-based emulsifiable oil.
the cutting tool cooler especially in an (Figure courtesy of Elco Corp.)
emulsifiable oil.”
The last benefit is seen in a 4-ball
EP ramp test (ASTM D2783) where the REPLACEMENT STEPS methods such as the Microtap and the
load is increased from 10 to 160 kgf STLE-member Mandi McElwain, lead Twist Compression Test.
over a period of 20 minutes. No heat is application scientist-lubricants for Cro- Depending on the application, it
applied during the test. da Inc. in New Castle, Del., provides may be useful to evaluate the perfor-
Marmerstein says, “We evaluated an guidance on how MWF formulators mance with more than one metal. In
emulsifiable oil based on a polymeric can move forward with replacing MC- our experience, when certain complex
phosphite ester versus an emulsifiable CPs and LCCPs. She says, “Formula- esters are combined with phosphate es-
oil based on a chlorinated paraffin. The tors can start by directly replacing the ters or sulfurized olefins, synergies are
temperature changes over the 20-minute chlorinated paraffins they are using present. So the formulator could simi-
time frame. Figure 5 shows that the tem- with one of the alternatives. The next larly evaluate formulations containing
perature of the chlorinated paraffin-free step is to evaluate the performance of more than one EP alternative.”
alternative fluid is more than 10 F lower their chlorinated paraffin-free formula- For example, Figure 6 shows Micro-
than for the chlorinated paraffin-based tion with modern and meaningful test tap data from the evaluation of cutting ÎÎÎÎÎ
fluid by the end of the test. The gap be-
tween the two fluids is as much as 40
F more than halfway through the test.” Microtap Cutting Efficiency – Formed Tap
Hiroshi Sakata, manager polymer
technical group for DIC Corp. in Chiba,
Japan, believes that active and inactive
sulfurized additives can provide benefits
for formulators as chlorinated paraffin
alternatives. He says, “For metal cutting
applications, an inactive 30% sulfurized
olefin can be effective in drilling, milling
and turning operations in both neat oils
and water dilutable fluids. In such metal
forming applications as cold forming,
stamping and fine blanking, the inactive
30% sulfurized olefin also can be effec-
tive. If the metal forming applications are
compatible, a low-temperature, active
30% sulfurized olefin also can be useful
because it performs well at keeping fric- Figure 6 | Microtap test data comparing straight oils formulated with different additives is
tion low over a wide range of loading.” shown. (Figure courtesy of Croda Inc.)

38 • MARCH 2016 T R I B O LO GY & LU B R I CAT I O N T EC H N O LO GY W W W. ST L E .O RG

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 Tapping Torque Testing Result lator should take to replace chlorinated
paraffins in a specific application. He
says, “The first step is for the formu-
lator to find a lubrication test or tests
that replicate the intended application.
Then the next step is to identify the
most effective chlorine replacement al-
ternatives, and do not forget synergistic
combinations of additives. In the case
of water-based fluids, make sure that
the emulsifier performance is balanced
and the formulation makes a stable
emulsion (adjust if necessary). The
fourth step is to use laboratory bench
tests to discriminate performance, and
lastly lab tests should be confirmed
with either in-house computerized nu-
merical control machine testing or field
trial testing that matches the intended
application.”
Jarvis provides some guidelines for
assisting formulators with replacing
chlorinated paraffins. He says, “Gener-
ally if a system containing )10% chlo-
rinated paraffins is being replaced, then
Figure 7 | Three cutting oils prepared with different EP additives in Group II base oil are evalu-
ated on carbon steel and an aluminum alloy in a tapping torque test. (Figure courtesy of DIC.) for metal removal and forming process-
es this can be achieved with a reason-
able degree of confidence. However,
ÎÎÎÎÎ oils containing various additives on gistically with sulfurized additives. He higher chlorinated paraffin-containing
1018 steel using forming taps. The treat says, “For neat oils, overbased calcium formulations become more difficult to
rate for the various additives is shown sulfonate is an additive typically used predict.”
on the left. McElwain says, “We found with sulfurized additives. In form- Jarvis continues, “Replacing chlo-
in this specific study that the combina- ing fluids, several kinds of additives rinated paraffins will probably require
tion of a complex ester with a phos- such as sulfurized fatty additives, non- the formulator to completely re-ex-
phate ester displayed 14% lower torque sulfurized fatty additives, overbased amine all aspects of the formulation.
at a lower treat rate than a cutting oil calcium sulfonates, phosphate esters, It will require a complete matrix in-
formulated with chlorinated paraffin.” etc., are added. It is very important for cluding various levels of EP and film
Sakata focuses on replacing chlo- metalworking formulators to know strength additives.”
rinated paraffins with sulfurized ad- what kind of synergistic effect can be
ditives. He says, “The most important obtained by mixing several additives to DIFFERENTIATE THE PERFORMANCE
difference between sulfurized EP ad- replace chlorinated paraffin.” OF CHLORINE-FREE EP ADDITIVES
ditives and chlorinated paraffins is Figure 7 contains a tapping torque Marmerstein recommends that the for-
the operating temperature of these study done comparing the performance mulator evaluate chlorinated paraffin-
additives. Since chlorinated paraffins of 30% and 40% active sulfurized ad- free formulations using a wide vari-
react with metal surfaces at lower tem- ditives at a treat rate of 2.5% with 50% ety of tests. She says, “In addition to
peratures than sulfurized additives (see chlorinated paraffin at a comparable standard tests, we often use a modified
Figure 4), chlorinated paraffins start to treat rate. Sakata says, “We evaluated 4-ball test, where the load on the ball is
work at lower temperatures and load- the cutting oils on carbon steel and an slowly increasing over a 20-minute pe-
ings. Therefore when formulators work aluminum alloy used in die casting. riod. This test is more severe than the
with sulfurized EP additives, they need With both metal alloys, the 30%, low- regular 4-ball wear test and allows for
to add additional additives to develop temperature active sulfurized additive better differentiation of additive effects
chlorinated paraffin-free fluids that ex- displays superior performance com- in the fluids (see Figure 5).”
hibit comparable performance.” pared to the 50% chlorinated paraffin Jarvis believes that lab-based tests
Sakata continues by recommending and the 40% sulfurized additive.” should be performed on rudimentary
specific additives that can work syner- Faber offers five steps that a formu- oil/water emulsions to assess the inher-

40 Light takes 4.5 years to travel to the nearest star other than the sun, 100,000 years to travel
 ent performance of the alternative additive compared to the
chlorinated paraffin it is replacing. He adds, “A wide range of Hille Press Data Acquisition
laboratory tests are available to evaluate the lubricity and EP
characteristics of a fluid. Some examples include the Draw-
Bead, Reichert, High Frequency Reciprocating Rig and the
Hille Press.”
Figures 8 and 9 demonstrate the capabilities of the Hille
Press test. Jarvis says, “This test involves the use of a labora-
tory scale deep drawing machine in which test blanks are
coated with a lubricant, clamped at a fixed pressure and ex-
truded through the use of a traveling punch. As shown in
Figure 8, punch pressure (or resistance to deformation) is
measured versus punch displacement until failure is reached.
The objective is to find the lowest additive treat rate that
displays the best combination of lowest punch pressure and
highest punch displacement.”
Typically an additive candidate is evaluated at treat rates
of 0.5%, 2.5%, 7.5% and 20% in base oil and applied to the Figure 8 | In the Hille Press test, punch pressure (or resistance to
stainless steel blank (see Figure 9). Jarvis says, “We use MCCP deformation) is measured versus punch displacement until failure is
(additive 1) and two polymeric lubricant additives (additives reached. (Figure courtesy of Afton Chemical.)
2 and 3) as industry standards. The remaining 16 additives
are taken from a range of MWFs and other lubricants. High-
performing additives display superior boundary lubrication
and interact very effectively with metal surfaces.” Hille Press Results for Stainless Steel
Kirsch says, “In addition to the tests previously described,
we are investigating the use of traditional tribological tests
including the mini traction machine and Cameron Plint to
determine how best to evaluate alternatives to chlorinated
paraffins.”
McElwain indicates that formulators need to evaluate
other properties besides boundary lubricity and extreme pres-
sure characteristics to determine if chlorinated paraffin-free
alternatives will provide comparable performance. She says,
“Formulators should evaluate such properties as concentrate
stability, foam, tramp oil rejection and emulsion stability. If
results from these bench tests and from lubricity tests are
promising, then field performance will test the real-life vi-
ability of these chlorinated paraffin-free alternatives.”

EVALUATING SYNERGISTIC COMBINATIONS

Kirsch maintains that the MWF fluid industry has speculated Figure 9 | Hille Press test results on stainless steel for 19 additives
for many years on the exact mechanism behind the synergies evaluated at four treat rates is shown. (Figure courtesy of Afton Chemical.)
seen with various additive combinations. He says, “Extreme
pressure additive performance can often be enhanced through
synergy with other similar additives. By using materials that
broadly function between 200-1,000 C, many to most met-
alworking and metal forming operations will gain improved relative affinity may be impacted by temperature, explaining
tool life and processing speeds.” why EP additives ‘activate’ at different temperatures. When
Various synergisms are evaluated in a tapping torque test additives are used in combination, each additive may perform
conducted on 1018 carbon steel. Five additive combinations independent of the other or synergistically.”
are tested with LCCP being the reference. As shown in Figure Marmerstein says, “Phosphite esters work synergistically
10, a combination of sulfurized olefin, overbased sulfonate with sulfurized olefins and triglycerides, showing significant
and sulfurized fat displays the best performance. improvement in extreme pressure and tapping torque results.”
McElwain says, “We believe that certain additives have a Jarvis cautions that further research must be done to
higher propensity to bond ionically to the metal surface. This clearly identify additive synergisms. He says, “More work is

the width of the galaxy and 100 billion years to travel across the observable universe. 41
 44 by metalworking fluid type. While
Tapping Torque Test, 1018 Steel Form, there appears to be a wide choice of op-
20% Additive in Group I Base Oil tions, each alternative additive exhibits
some weaknesses.
Byers says, “Sulfurized EP additives
can generate odors that are objection-
able and even dangerous since they can
originate from the presence of hydro-
gen sulfide. This additive type also can
stimulate microbial growth, cause fer-
rous corrosion, foam and stain copper
alloys. Use of sulfurized additives with
nickel-based alloys should be avoided
because of the danger of forming a low
melting point eutectic that weakens the
metal surface.”
The main phosphorus-based EP
Figure 10 | Five additive combinations blended in Group I base oil are evaluated with LCCP as
the reference on 1018 carbon steel in a tapping torque test. (Figure courtesy of The Lubrizol Corp.) additive is phosphate esters, which are
known to stimulate microbial growth
and generate foam in water-based met-
required on the mechanisms by which where chlorinated paraffins are needed alworking fluids. Byers says, “Phos-
certain chlorinated paraffin replace- include military applications (such as phate esters also can be too reactive
ment technologies work synergistically aviation fasteners), heavy-duty stamp- with other components in the formula-
when in combination with each other.” ing and drawing, fine blanking, form- tion and create problems when used in
ing high strength, heavy gauge steels, straight oils, including causing hydro-
FORMULATOR PERSPECTIVE older dyes, heavy-duty broaching and lysis if water contamination is present,
With many options to choose to re- machining stainless steel. In the latter act to emulsify water and require high
place chlorinated paraffins, metalwork- case, chlorinated paraffins are the only maintenance.”
ing fluid formulators are faced with a effective EP additive for this particular Other alternative additives also have
major challenge in replacing MCCPs class of metal alloys.” weaknesses including fatty esters that
and LCCPs in their products. Former Alternative additives available to the can readily hydrolyze in the alkaline
STLE President Jerry Byers, now an in- formulator are listed in Table 4 on page environment of metalworking fluids,
dependent consultant in The Villages, forming metal soaps that can lead to
Fla., says, “Formulators that typically foaming and concentrate instability
have at least 200 products are faced over time.
with having to deal with formulations The Formulator’s Byers sums up the challenges facing
that can contain between 15-20 ingre- Challenge formulators: “Combinations of alterna-
dients.” tive additives will be needed because
Regulations are restricting the no single alternative will work in every
number of ingredients available to the case and each of the alternatives has
formulator, which is making the chal- problems. Product costs will increase
lenge harder. “In effect, it is like trying by as much as 50%. But formulators
to write a novel with fewer and fewer should expect shorter sump life, high-
letters in the alphabet,” says Byers, er disposal volumes and higher biocide
editor of Metalworking Fluids, Second usage.”
Edition (available at www.stle.org). See Additional details on the formula-
Figure 11. tor’s perspective can be found in a re-
MCCPs and LCCPs exhibit a great cent presentation.9
degree of flexibility that enables them
to be used in a wide range of fluids and FUTURE FOR ALTERNATIVE
applications. While replacing them EP ADDITIVES
Figure 11 | The analogy can be drawn that
with alternative EP additives is do-able the fewer ingredients available to formula- As the metalworking fluid industry
in most cases, Byers points out that tors due to regulations is comparable to turns to finding alternatives for MC-
there are applications that need chlo- writing a novel without a complete alpha- CPs and LCCPs, the respondents were
rinated paraffins. He says, “Operations bet. (Figure courtesy of Jerry Byers.) asked to predict what extreme pressure Î Î Î Î Î

42 • MARCH 2016 T R I B O LO GY & LU B R I CAT I O N T EC H N O LO GY W W W. ST L E .O RG

Efficiency from
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Open up new potential — Let it flow.

 tween these additives can often provide
Alternative Additives by Metalworking Fluid Type effective solutions for the formulator.”
Jarvis sees the future from the short/
medium- and long-term perspectives.
He says, “Over the short/medium-term,
the current chlorinated paraffin-free EP
additives will need to be used. Additive
suppliers will be utilizing their R&D
programs to develop newer approaches
over the long term.”
Marmerstein predicts that formula-
tors will be working with combinations
of various types of chlorinated paraffin-
free EP additives. She says, “Various sul-
fur, phosphorus and nitrogen compo-
nents will be used in combination. For
severe applications, formulators will
work with active sulfurized olefins and
fats in combination with phosphorus and
amine chemistries to achieve improved
lubricity, antiwear and lower friction.”
Table 4 | Alternative additives available to the formulator are listed by metalworking fluid The current uncertainty about when
type. (Table courtesy of Jerry Byers.) MCCPs and LCCPs will be phased out
is not stopping formulators from seek-
ing and evaluating alternatives. This
ÎÎÎÎÎ additives will be available for formula- Kirsch feels that finding additive process will continue now and in the
tors in the future. synergies will be the key to replac- near future at a steady pace that may
McElwain says, “Formulators will ing MCCPs and LCCPs. He says, “As need to be accelerated depending upon
need to rely on existing chlorinated machining and stamping operations when the use of main chlorinated par-
paraffin-free extreme pressure additives increase in operational severity (e.g., affin types must cease in the U.S.
in the near future. New product intro- higher pressures, faster speeds and
ductions will take place in more of an feeds, etc.), fluids need to respond to
evolutionary as opposed to revolution- this demand without compromising Neil Canter heads his own
ary manner as the metalworking fluid part and tooling integrity. Many ex- consulting company, Chemical
industry gains a better handle on what treme pressure additive alternatives to Solutions, in Willow Grove, Pa.
applications will need better upgrades chlorinated paraffins are already avail- You can reach him at
from MCCPs and LCCPs.” able to the formulator. Synergies be- [email protected].

REFERENCES
1. Kelley, T., Fensterheim, R. and Jaques, A. (2009), “Chlorinated paraffins,” Compoundings, 59 (4), pp. 21-23.
2. Canter, N. (2015), “Chlorinated paraffins: Where do we go from here?” STLE Webinar, June 10, 2015.
3. Please see www.epa.gov/assessing-and-managing-chemicals-under-tsca/assessments-tsca-work-plan-chemicals.
4. In December 2014, EPA issued a notice requiring any future use of SCCPs required an SNUR.
5. Please see www.ilma.org/resources/docs/MCCP-LCCP_Redacted_EPA_Review_RA_Nov2014.pdf.
6. Doa, M. (Sept. 2015), “Chlorinated paraffins,” Presented at the 5th International Conference on Metal Removal Fluids in Chicago, Ill.
7. EPA. (December 23, 2015), “Chlorinated paraffins: Request for available information on PMN risk assessments,” Federal Register
80 (246), pp. 79886-79888.
8. Canter, N. (2014), “EP additives: Regulatory updates of chlorinated paraffins and options on alternatives,” TLT, 70 (9), pp. 10-19.
9. Byers, J. (Sept. 2015), “Formulator’s perspective: How to move on from chlorinated paraffins,” Presented at the 5th International
Conference on Metal Removal Fluids in Chicago, Ill.

44 A beam of light can surround the Earth 7.5 times in one second.