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434 Lubricant Additives: Chemistry and Applications
The use of phosphates in soluble oils is less extensive, but there are a few examples of trialkyl
phosphates being used in drawing and ironing operations [93,94]. Although the phosphates possess
low toxicity and excellent EP/AW and RP properties, their use in soluble oils for metalworking
additives has been limited due to their stimulation of microbial growth that can lead to contact
dermatitis or worse after prolonged worker exposure [10,69,95,96].
Phosphates have also been used in combination with amines, and this provides not only
additional EP/AW protection but also both anionic (phosphate) and cationic (ammonium) RPs in a
single salt [85].
Another area where phosphates have been extensively used is in aviation turbines in which low
ash properties of TCP are desirable [97]. Although the TCP produced in the 1940s and 1950s did
possess a considerable amount of triorthocresyl phosphate (TOCP), which increased concerns of
neurotoxicity, the TCP now commercially available can have TOCP levels as low as parts per billion
(ppb) and are not a signi cant concern [98].
17.4.13 NITROGEN RING STRUCTURES
Although tertiary amines have gained wide acceptance in various RP formulations for their
ability to neutralize acids, the nitrogen heterocycles have also found use in many common RP
applications. The most common type of nitrogen ring structures are imidazolines, benzotriazoles,
thiazoles, triazoles, imidazoles, and the mercaptobenzothiazoles (Figure 17.7), as well as any of
their common derivatives that include a basic nitrogen in their structure. Owing to the volatile
nature, these materials can be used as VCIs and are particularly effective in metal equipment such
as engine blocks made from cast iron or aluminum [99]. Additionally, the absence of an inorganic
salt minimizes the possibility of dry residue formation.
It has also been found that some imidazoline derivatives have low toxicity in the marine
environment and are useful in offshore oil and gas production [64,100]. Although the mechanism
is still unclear, it appears as if the highly basic nitrogen in the ring structure is converted to a less
basic salt (by reaction with organic acids), which renders the molecule less toxic in the marine
environment [64].
Although many amine heterocycles have been proposed, due to their relative low cost and high
RP effectiveness, primarily imidazoline and its derivatives have found use in grease, soluble oils,
rolling, cutting, drilling, turning, grinding, wire drawing, stamping, and sheathing with varying
levels of success. Additionally, the imidazolines can be used alone or combined with a number of
organic acids to make the ashless amine salt, which have been demonstrated to be very effective in
RP (Figure 17.11).
17.5 CORROSION TESTING
RPs can be used in various end-use lubricant applications, and as a result, there are a wide variety
of industry standard rust and corrosion tests available to the formulator. Although industrial
organizations such as the American Society for Testing and Materials (ASTM) list many commonly
performed test methods, there are a host of international (Deutsche Norm Test Methods [DIN],
International Standards Organization [ISO], Association Française de Normalisation [AFNOR], or
Institute of Petroleum [IP]) and Original Equipment Manufacturer [OEM] methods that are com-
monly used to screen corrosion and RPs. The most common ASTM corrosion testing used for RPs
and corrosion inhibitors are listed in Table 17.3 along with cross-references to various industry and
international methods.
ASTM D1401—Water separability characteristics of petroleum and synthetic uids. This
test determines the ability of lubricating uids, such as rust and oxidation-inhibited indus-
trial gear lubricant, hydraulic oils, and turbine oils that have viscosities in the range of
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Corrosion Inhibitors and Rust Preventatives 435
FIGURE 17.11 Common nitrogen ring structures.
N
N
R
R
N
N
R
R
Imidazoline
Imidazole
N
S
Thiazole
Benzotriazole
Triazole
N
O
H
Morpholine
N
N
N
R
N
N
N
R
N
H
R
Pyradine
N
H
R
Quinoline
Tolyltriazole
N
N
N
R
CH
3
28.8–90 cSt at 40ºC to separate from water. Although not a standard corrosion test, it is
widely used in the lubricant industry to screen potential RP lubricant formulations where
in some applications water shedding is desired (slushing and rolling oils), whereas in other
applications, emulsi cation is required (soluble oils for metalworking). The demulsibil-
ity characteristics of lubricating oils (ASTM D2711) measures an industrial gear lubri-
cant’s ability to separate from water, similar to the ASTM D1401 method, whereas the
demulsibility characteristics of lubricating oils (ASTM D2711) test is primarily used to
test medium and heavy-viscosity (ISO 220–ISO 1500) industrial gear lubricants’ ability to
separate from water.
ASTM D130—Copper strip corrosion test. This test is used to evaluate the corrosive tendencies
of oils to copper-containing materials, while ASTM D4048 is used for grease. A result of
1b slight tarnish or 2a moderate tarnish is considered a passing result in most applications.
This test is particularly sensitive to active sulfur (ASTM D1662) and can be easily passed
if an inactive sulfur additive is used in the RP formulation.
ASTM D665—Turbine oil rust test. This test is designed to measure the ability of industrial
oils to prevent rusting under conditions of water contamination. To pass the test, the
specimen must be completely free from visible rust when examined without magni cation
under normal light. This test was developed for steam-turbine oils and is one of the oldest
standard corrosion tests and has found utility in various applications (aviation oils, RP oils,
gear oils, and hydraulic uids).
ASTM D1748—Standard test method for rust protection by metal preservatives in the
humidity cabinet. This test method is used for evaluating the rust-preventive properties of
metal preservatives under conditions of high humidity at 49°C. The polished steel panels
coated with RP oil are hanged vertically in a humidity cabinet where the water vapors
from the bottom of the cabinet contact the panel. At different time intervals, the panels are
removed from the cabinet and observed visually for any rust or stains. The time is recorded
when the rust or stains are observed or alternatively the area percent rust can be noted at a
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436 Lubricant Additives: Chemistry and Applications
TABLE 17.3
Corrosion Test Cross-Reference
Description
Test Method
ASTM DIN ISO IP FTM
Oil
Detection of copper corrosion from petroleum
products by copper strip tarnish test
D130 51 759,
51 811
2160 154 791 5225
Standard method for rust-preventing characteristics
of inhibited mineral oil in the presence of water
D665,
D3603
51 355,
51 585
7120 135 791 4011,
791 5315
Standard test method for water seperability of
petroleum oils and synthetic uids
D1401 — — — —
Standard test method for rust protection by metal
preservatives in the humidity cabinet
D1748 50 017* — 366 791 5310
Standard test method for iron chip corrosion for
water-dilutable metalworking uids
D4627 51 360P2*,
51 360P1*
— 287*, 125* —
Standard test method for corrosiveness of
lubricating uid to bimetallic couple
D6547 — — — 791 5322.2
Standard practice for operating salt spray (Fog)
apparatus
B117 50 021-SS* 9227-SS* 791 4001.2
Method of acetic acid-salt spray (Fog) testing B287 51 021-
ESS*
9227-AASS* — —
Standard method for copper-accelerated acetic
acid-salt spray (Fog) testing (CASS Test)
B368 50 021-
CASS*
9227-CASS* — —
Standard practice for conducting moist SO
2
tests G87 50 018-
SWF*
3231 — —
Grease
Standard test method for determing the corrosion
preventative properties of lubricating grease
D1743 — — — 791 4012
Standard test method for detection of copper
corrosion from lubricating grease
D4048 — — — 791 5309
Standard test method for corrosion-preventive
properties of lubricating greases in presence of
dilute synthetic sea water
D5969 — — — —
Standard test method to determine the corrosion
preventative properties of lubricating greases
under dynamic wet conditons (Emcor test)
D6138 51 802 — 220 —
Transport
Standard test method for the evaluation of
corrosiveness of deisel engine oil at 121°C
D5968 791 5308.7
Standard test method for evaluation of rust
preventative characteristics of automotive
engine oil
D6557
*
Similar test conditions to ASTM method
speci ed time interval. Depending on the application 1000, 2000, or 4000 h are considered
passing results.
ASTM B117—Standard practice for operating salt spray (fog) apparatus. Although not a
speci c method, this practice covers the apparatus, procedure, and conditions required to
create and maintain the salt spray (fog) test environment at 35°C. This practice prescribes
neither the type of test specimen or exposure periods to be used for a speci c product nor
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Corrosion Inhibitors and Rust Preventatives 437
the interpretation to be given to the results. As a result, there are many OEM, military,
and international variations to this method, and speci cations must be agreed by the buyer
and the seller. The most common form of this test is the FTM-791C 4001.2; it describes
the most common time, temperature, and salt concentrations used for this testing. It is
considered as an industry standard test procedure and is used to compare different RP
formulations on a relative basis. A typical passing rating can range from 100 to 2000 h,
but an absolute number is generally not speci ed as the test formulation is most commonly
related to a standard reference uid for performance evaluation.
A list of the standard test conditions for the most common RP tests is provided in
Table 17.4, where the order of severity increases as follows:
ASTM D665A < ASTM 665B < ASTM D1748 < FTM 4001.2 < CASS
ASTM D4627—Test method for iron chip corrosion for water-dilutable metalworking
u i d s . This method was designed to determine the relative corrosion rate of a water-
dilutable metalworking uid by using typical cast iron chips found during machining as
the test specimen. The procedure uses ∼2 g of clean cast iron chips that are spread onto
a lter paper in a petri dish, the uid mixture is then pipetted on to the chips, and the
dish is covered. After a certain period of time (typically 24 h), the chips are removed,
and the paper is examined for staining. The test is typically evaluated as a pass or fail
criterion using successive dilutions of a water-dilutable metalworking uid. There are
many slight variations of this basic procedure (IP-287 or DIN 51 360P1 and IP-125 or DIN
51 360P2), and typically, the method is modi ed to accommodate prevailing conditions
of the end user. Results are evaluated by determining the lowest concentration of soluble
oil necessary to prevent rust appearing on the lter paper or on the iron chips where
typically a concentration of 2–5% is considered acceptable. This procedure remains an
excellent low-cost screening tool to evaluate relative effectiveness of an RP in water-dilu-
table metalworking uids.
ASTM D6547—Standard test method for corrosiveness of lubricating uid to bimetallic
couple. This test method covers the corrosiveness of hydraulic and lubricating uids to
a bimetallic galvanic couple and replicates Fed-Std No. 791, Method 5322.2. It uses the
same apparatus, test conditions, and evaluation criteria, but it describes test procedures
more explicitly.
TABLE 17.4
Typical Corrosion Test Conditions
Method ASTM D665A&B ASTM D1748 FTM 4001.2 CASS
Type Rust test Humidity cabinet Salt spray Acetic acid — salt
spray
Time (h) 4 100 24 5
Temperature (ºC) 60 49 35 35
Conditions Distilled water or
synthetic sea water
Distilled water 5% NaCl 5% NaCl + 0.2%
acetic acid
Test panel Steel rod Sandblasted cold
rolled steel
Cold nished
steel
Cold rolled steel
Grade AISI/SAE 1010
(BS 970)
AISI/SAE 1009C AISI/SAE 1010 AISI/SAE 4130
Dimensions 5" × 2 × 11/16" 4" × 2" × 1/3" 3" × 2" × 1/8" 6" × 4" × 1/8"
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438 Lubricant Additives: Chemistry and Applications
ASTM D1743—Standard test method for determining corrosion preventive properties of
lubricating greases. This test method covers the determination of the corrosion- preventive
properties of greases using grease-lubricated tapered roller bearings stored under wet
conditions. This method distributes a lubricating grease sample in a roller bearing by
running a bearing under a light thrust load. This test method is based on CRC Technique
L 41
2
that shows correlations between laboratory results and service for grease-lubricated
aircraft wheel bearings.
ASTM D5969—Standard test method for corrosion-preventive properties of lubricating
greases in presence of dilute synthetic sea water environments. This test method covers
the determination of the corrosion-preventive properties of greases using grease- lubricated
tapered roller bearings exposed to various concentrations of dilute synthetic sea water
stored under wet conditions. It is based on test method D 1743, which is practiced using
a similar procedure and distilled water. The reported result is a pass or fail rating as
determined by at least two of the three bearings.
ASTM D6138—Standard test method for determination of corrosion-preventive properties
of lubricating greases under dynamic wet conditions (Emcor test). This test measures the
ability of a grease to protect a bearing against corrosion in the presence of water. This
test method covers the determination of corrosion-preventive properties of greases using
grease-lubricated ball bearings under dynamic wet conditions. It is a dynamic test where
two sets of grease-coated bearings are immersed in water and a series of running and rest-
ing periods are in rotation. At the end of the test, the raceways of the bearing outer rings
are inspected for rust and evaluated. This method is equivalent to IP-220, DIN 51 802, and
the Emcor/SKF water wash test.
ASTM B368—Standard test method for copper-accelerated acetic acid salt spray (fog)
testing (CASS test). Although the ASTM B368 method is typically used for hard coatings
(galvanized or painted surfaces), extended outdoor exposure oil and soft coatings can be
tested as an alternative to the milder conditions of the salt spray (fog) method. In ASTM
B368, the corrosiveness of the standard salt spray test is increased by lowering the pH or
increasing the operating temperature. Several domestic automotive OEMs have their own
versions of this test (Ford BG105-01 and GM 4476P), which address their own speci c
materials requirements.
ISO 6988—Metallic and other nonorganic coatings, sulfur dioxide test with general
condensation of moisture. The Kesternich Cabinet (with SO
2
added) is used for metallic
and organic hard coatings for long-term outdoor exposure. The Kesternich test simulates
the detrimental effects of acid rain and the test calls for dissolving sulfur dioxide in distilled
water. The chamber is heated for 8 h at 100% relative humidity. After 8 h, the chamber
vents the excess sulfuric dioxide and returns to room temperature. The cycle is repeated
every day, and the results are reported as pass/fail after speci ed duration after a visual
inspection for rust (Table 17.5).
17.6 FUTURE REQUIREMENTS
The demand for RPs in lubricants will continue for many years, in part due to higher demand in
the developing countries such as Brazil, Russia, China, and India (BRIC) and the aging of existing
OEM equipment that is currently used in the developed world. The current market drivers for new
RPs will continue to be environmental and health concerns.
New environmental requirements for RPs address various shortcomings of the current
commercial chemistries. For amine-based products, there is a desire for lower marine toxicity
(ecotoxicity), which is driving the industry toward alternative eco-friendly products, whereas for
the classic barium-based products, there is a drive to reduce the heavy metal content and replace
them with less-hazardous metals (i.e., Na, Ca, or Mg). Additionally, the waste disposal of the nal
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Corrosion Inhibitors and Rust Preventatives 439
TABLE 17.5
Commercial Rust Preventatives/Corrosion Inhibitors
Manufacturer Chemistry Trade Name
Air Products Alkylamine
Akzo Nobel Fatty imidazoline Armohib
Akzo Nobel Amine sulfonate Armohib, Armeen, Duomeen,
Akzo Nobel Alkylamine Triameen
Akzo Nobel Ammonium thiocyanate
Akzo Nobel Quaternary ammonium compounds Arquad
Akzo Nobel Ethoxylated alkyl amine Ethomeen, Ethoduomeen
Arch Chemical Hydrazine Scav-Ox
Arizona Chemical Dimerized fatty acid Century, Unidyme
BASF (formerly PPG/Mazer) Alkylamine Mazon
Chemtura Calcium sulfonate Calcinate
Chemtura Barium sulfonate Surchem, Petronate
Chemtura Oxidized petrolatum Oxpet
Chemtura Sodium sulfonate Petronate
Ciba Succinic acid ester Irgacor
Ciba Polycarboxylic acid Irgacor
Ciba Sodium sebecate Irgacor
Ciba Nonyl phenoxy acetic acid Irgacor
Ciba Amine phosphate Irgalube
Ciba N-acyl sarcosine Sarkosyl
Ciba Imidazoline derivatives Amine
Cognis Dimer acids
Cognis Fatty acid ethoxylate Eumulgin
Cognis Alkylamine Texamin
Dover (formerly Keil) Carboxylic acid salt Synkad
Dover (formerly Keil) Boramide Synkad
Dover (formerly Mayco) Carboxylic acid salt Mayco
Dover (formerly Mayco) Barium sulfonate Mayco
Dow (Angus Chemical) Amino alcohol AMP AEPD, Corrguard
Dow (Angus Chemical) Oxazoline Alkaterge
Dupont Dilauryl acid phosphate Ortholeum
Dupont Dibasic acids Corfree
Grace Construction Calcium nitrite DCI Corrosion Inhibitor
Georgia Paci c Ethanolamine borate Actracor
Georgia Paci c Ethanolamine carboxylate Actracor
Georgia Paci c Alkanolamide Actramide
Halox Alkyl ammonium salt Halox
Halox Alkanol amine/boric acid/phosphoric acid Flash-X
Huntsman Amine borates Diglycol amine
Huntsman Ethanol amines MEA, DEA, TEA
Huntsman Polyether amines Jeffamines
Huntsman Castor oil ethoxylates
Huntsman Aminomethyl propanol AMP
King Industries Dinonylnaphthalene sulfonate Na-Sul
King Industries Alkyl amines K-Corr
King Industries Acid amine salts K-Corr
Lonza Quaternary ammonium carbonate Carboshield
Lonza Quarternary ammonium chloride Uniquat
Lonza Imidazoline derivatives Unamine
(continued)
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440 Lubricant Additives: Chemistry and Applications
TABLE 17.5
(Continued)
Manufacturer Chemistry Trade Name
Lubrizol Calium sulfonate Alox, Lubrizol
Lubrizol Barium sulfonate Alox, Lubrizol
Lubrizol (Alox) Oxidized petrolatum Alox
Oxy-Wax Oxidized wax Hypax
Pilot Chemical Sodium sulfonate Aristonate
Pilot Chemical Ethanolamine sulfonate Aristonate
Pilot Chemical Calcium sulfonate Aristonate
PMC Specialties Benzotriazole Cobratec
PMC Specialties Tolyltriazole Cobratec
PMC Specialties Carboxybenzotriazole Cobratec
PMC Specialties Sodium tolyltriazole Cobratec
PQ Corporation Sodium silicate PQ
R.T. Vanderbilt Succinic acid ester Vanlube
R.T. Vanderbilt Barium sulfonate Vanlube
R.T. Vanderbilt Imidazole Vanlube
R.T. Vanderbilt Amine phosphate Vanlube
Rohm & Haas Alkylamines Primene
Uniqema Proprietary Perfad
Uniqema Fatty acid derivatives Prifac, Priolene, Pripol
Uniqema (formerly Mona) Borate esters Monacor
Uniqema (formerly Mona) Amine carboxylate Monacor
Uniqema (formerly Mona) Amine phosphate Monacor
Uniqema (formerly Mona) Phosphate ester Monalube
Uniqema (formerly Mona) Imidazone Monazoline
end product has been a great concern in both lubricant and metalworking applications and has
driven the market to pursue more biodegradable products that could be based on new chemistries
or natural fats and esters.
Although the majority of the severe health effects such as the carcinogenicity of the hexavalent
chromium products have, for the most part, been addressed, there are still concerns for sporadic
outbreaks of acute and chronic symptoms. In particular, the public health concerns for the reduction
of contact dermatitis for machine shop workers has lead to increase demand for amine-free lubricant
and metalworking uids, using alternative technologies such as sulfonate or low-toxicity amines.
Additionally, although contact dermatitis is generally viewed as an acute symptom, the occurrence
of hypersensitivity pneumonitis (HP or machine operators lung) can lead to a chronic condition that
may require hospitalization in its most extreme cases. As a result, regular worker health checkups
and air quality monitoring are standard practices now in many metalworking shops.
Generally, workers employed in industrial manufacturing are safer now due to tougher regulations
from industrial and governmental bodies, which has led to the search for alternative chemistries.
As a result of both environmental and health concerns, the RP suppliers will continue to develop
alternative technologies that incorporate a cradle-to-grave approach to product stewardship.
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