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Some Factors Affecting the Decomposition of Three

Commercial Zinc Organodithiophosphates
a
Fred G. Rounds
a
Research Laboratories , General Motors Corporation , Warren, Michigan, 48090
Published online: 25 Mar 2008.

To cite this article: Fred G. Rounds (1975) Some Factors Affecting the Decomposition of Three Commercial Zinc
Organodithiophosphates, A S L E Transactions, 18:2, 79-89, DOI: 10.1080/05698197508982749

To link to this article: http://dx.doi.org/10.1080/05698197508982749

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 Some Factors Affecting the Decomposition of Three
Commercial Zinc Organodithiophosphates
FRED G. ROUNDS, ASLE
Research Laboratories
General Motors Corporation
Warren, Michigan, 48090
Downloaded by [UQ Library] at 01:02 22 November 2014
Despite the widespread use of ziizc organodithiophosphates
(ZDP's) as antiwear additives, lzow the ZDP's perform their
antiwear function i s still vague. Thermal decompositiovc of
Z D P ' s alzd the formation of a protective antiwear coating by
the decomposition products i s one popular theory; but the
correlation between thermal decomposition temperature and
aizliwear performance leaves something to be desired. T o
determine ij other factors injuence ZDP behavior, benclt
deccmPosition studies were conducted o n three commercial
ZDP7s i n which the ejects o j o:xygea, water, other additives
in the blend, and the base oil were investigated. For these
studies, the bulk oil changes were followed by infrared
spectroscopy, volatiles formation by pressure measurements,
solids formation by ceiztri&gation afld subsequent elemental
analysis and surface coating formation on steel balls by x-ray
juoresce?zce spectroscopy. I t was found that the decomposition
of ZDP's i s ajected by oxygen availability, water, other
additives in the blend, and the base oil. Thus, simple thermal
decomposition i s not a n adequate explanation; and a better
theory i s needed to explain the antiwear behavior of ZDP's.
INTRODUCTION
Although zinc organodithiophosphates (ZDP's) were
initially added to automotive lubricants to control oxida-
tion, the ZDP's were found to effectively control the wear
of engine valve train components and are now the most
widely used antiwear additives in engine oils. Examination
of used engine components has shown that the atomic
ratios for ZDP-derived elements on rubbing surfaces are
typically 1 Zn: 1.8 P : 0.7 S compared to 1 Zn: 2 P: 4S for
Presented at "Symposium on Colloid and Surface Chemical
Aspects of Lubrication and Lubricants," (Society
of Chemical Industry) University of Brirtol,
England, September, 1973.
the original additive. The large difference in sulfur for the
two cases indicates that additive decomposition is an
essential step leading to antiwear performance. However,
the nature of the ZDP decomposition and subsequent
surface coating formation has not been adequately
resolved.
Since ZDP's thermally decompose a t temperatures which
can occur a t rubbing surfaces, one popular theory is that
ZDP thermal decomposition products form a protective
antiwear coating either by directly reacting with the
rubbing surfaces (I) or by in situ polymerization a t the
rubbing surfaces (2). Detailed studies on pure ZDP's
have shown the thermal decomposition products of
dialkyl ZDP's to be gases (initially an olefin followed by a
mercaptan and other sulfur compounds) (3-8) and a solid
residue (variously described as a metathiophosphate (7)
or an organic polymer [Z, 3'81). No oil-soluble intermediate
decomposition products have been reported for dialkyl
ZDP's but the formation of a phenol has been reported for
an aryl ZDP (9). Further, ZDP thermal decomposition
can be acid catalyzed (5, 8). Whether the solid residues
from the thermal decomposition studies are the same as
the surface coatings found on valve train components has
not been determined.
Automotive experience has shown that those ZDP's that
decompose a t lower temperatures are generally more
effective antiwear agents than those that decompose a t
higher temperatures (1, 10). However, enough exceptions
to the thermal decomposition temperature-antiwear effec-
tiveness correlation have been observed (11, 12) to suggest
that other decomposition mechanisms are also involved.
Since the ZDP's are salts, oxidation, hydrolysis, and
catalysis by other components in the lubricant blend are
possible decomposition mechanisms. The objective of the
present investigation was to determine whether the
decomposition of three representative commercial ZDP's
blended in oil was significantly affected by oxygen, water,
 other additives in the blend, or base oil composition; all
factors present in automotive service.
TEST EQUIPMENT AND PROCEDURE
I nfoniiation on the three coniniercial zinc organodithio-
phosphates investigated is summarized in Table 1. ZDP-A
:inti the more stable ZDP-B have been used extensively in
spark ignition engine oils, whereas ZDP-C has been used
in Diesel engine oils. The organic group listed for each
ZDP is the best guess based on infrared and Nh4R spec-
troscopy. Also given are the deconiposition temperatures
as deteniiined by isoteniscope, (11) differential scanning
calorimetry (DSC), and themial gravimetric measurenient.
'I'he decomposition temperature for ZDP-C was lowered
substantially when the test atniosphere was changed from
nitrogen to air, whereas the corresponding values for
%Dl?'s A and l3 were unaffected by the atniosphere change.
The shapes of the DSC traces differed significantly among
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tlic three ZDl?'s.
The ZDP concentration selected for study, 2 wt percent,
was arbitrary but within the range of coniniercial practice.
'I'he base oil for most of the work was a highly refined
n:lphthcnic base mineral oil containing 0.4 percent of
2,G ditertiary butyl-$-methyl phenol (D131'C) as an oxida-
tion inhibitor. A few tests were run using nionoisopropyl
biphenyl containing 0.5 percent DBPC as the base oil.
Prior to using the aromatic hydrocarbon, it was percolated
through silica, gel.
The procedure fur evaluating the ZDP's consisted of
several steps. An indication of when the ZDP's decomposed
a t L: given teiiiperature was obtained by following pressure
(gaseoi~sproduct formation) as a function of time in a
TA~L E
1-PROPERTIES 01: COMMERCIAL ZINC ORGANODITHIOPHOSPHATES
ZDP-A
SECONDAKY
Organic Radical*
Elemental Analysis,
wt. %
Zn . . . . . . . . . . . . . . . . . . .
P ....................
S. . . . . . . . . . . . . . . . . . . .
Percent Active Material
I n Package. . . . . . . . . . .
Thermal Decomposition
Temperature, "C
(a) By Isoteniscope
I n Nitrogen.. . . .
(b) By Differential
Scanning
Calorimetry
I n Nitrogen.. . . .
I n Air. . . . . . . . . .
(c) By Thermal
Gravimetric
Measurement
I n Air.. . . . . . .
* Best guess based on NMR and infrared spectrographic analyses.
stainless steel, bomb heated in an oil bath. For these
experiments, 100 nil of test oil plus fifteen 7.9 mm CVD
(carbon vacuum deoxidized) 52100 steel balls were placed
in a glass test tube (38 X 305 mm) within the bomb
(702 ml) and 130 nil of the base oil was used as a heat
transfer medium between the test tube and the bomb wall.
Most of the tests were run a t 177 C using an air atmosphere
but temperatures from 157 to 204 C were investigated.
Starting from atmospheric pressure, pressure was fol-
lowed as a function of time until the pressure reached a
stable equilibrium or a time limit of 520 minutes was
reached. The reported pressure rises for the ZDP's have
been corrected for the base oil or base oil plus second
additive contributions. The observed pressure rises were
the net result of additive deconiposition reactions forming
gaseous products tending to raise pressure and reactions
reducing the amount of gaseous materials present in the
bomb tending to reduce pressure.
Once the pressure-time history was established, experi-
nients were run a t intermediate test times in an effort to
determine what changes in the lubricants caused the
observed pressure changes. Beaker experiments were
chosen for these intermediate test times to permit more
rapid quenching of any reactions that might be occurring.
For the beaker experiments, 100 ml of the test oil plus
fifteen 7.9 mni CVD 52100 steel balls were heated in
500 ml tall form beakers covered with ribbed watch glasses
and the oil bath was again used as the heat source.
At the conclusion of either the bomb or beaker experi-
ments, analyses were made to determine the lubricant
changes that occurred. A n precipitate formed in the used
oil was removed by centrifugation, weighed and analyzed
for elemental composition. T o follow bulk oil composition
ZDP-B ZDP-C
PRIMARY ALKYL
ALKYL ALKYL ARYL
4-Methyl-2-Pentyl 3-Methyl-1-Butyl Heptylphenyl
8.7 8.8 3.2
8.0 8.0 2.8
16.5 16.5 5.9
85 81 46
185 214 310
169
168
183 Not Run 183
 Some Factors Affecting the Decomposition of Three Commercial Zinc Organodithiophosphates 81

changes, a conventional differential infrared spectrographic

technique was used. The spectra were obtained with a Z D P DECOMPOSITION
double beam, grating infrared spectrometer employing 2x
slit width and matched 0.47 mm KBr cells. The peaks - 20
used to follow ZDP decomposition and new product
formation are listed in Appendix 1. The elemental com-
position of surface coatings formed on the steel balls
(i.e., P, S, and Zn) was determined by X-ray fluorescence.
Mg was determined by a wet chemical technique. No
attempt was made to analyze the gaseous products
formed since it was believed that the gaseous products
played, a t most, only a minor role in the formation of the - -10
protective antiwear coating.
To obtain a measure of the effect of oxygen, a few bomb
experiments were conducted in a low oxygen atmosphere.
An estimated 99 percent reduction in oxygen was obtained
by evacuating the bomb containing the test oil to 110
Pa(1 kPa = 0.145 psi), pressurizing with prepurified
grade nitrogen ( < 5 ppm Oz nominal) and repeating the
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cycle three times. (13, 14) (In related experiments, this

procedure reduced the dissolved oxygen content of the
same oils from 55 to 0.2-0.5 ppm)
To study the effect of water, added water concentrations
of 0.15 and 0.5 wt percent were dispersed in the ZDP
blends ultrasonically. These water concentrations cor-
TIME - MIN.
respond to the maxima observed in used engine oils after Fig. I-Effect of time ot 177 C on decomposition of ZDP-A
mixed city-suburban-expressway and short trip services,
respectively. I t was necessary to redisperse the water in the low considering that the atomic ratios in the original
blends prior to each test to ensure a uniform test sample. molecule are 1 Zn: 2 P: 4 S. The relationship between
antiwear effectiveness and surface coating composition or
TEST RESULTS amount has not been established.
Shown in Fig. 2 are the decomposition characteristics of
The decomposition characteristics of ZDP-A (secondary
ZDP-B and ZDP-C tested under the same conditions. The
alkyl ZDP) a t 177 C in air are illustrated in Fig. 1. The
induction period for ZDP-B (primary alkyl ZDP) was
pressure rise data show that there was an induction period
much longer than that for ZDP-A, 300 minutes vs. 75
of about 75 minutes before the pressure rose to a peak a t
minutes. During this induction period, there was a measur-
about 200 minutes followed by a gradual decrease in pres-
able loss of pressure and an oil-soluble decomposition
sure a t longer test times. Infrared spectrographic analysis
product (or mixture of products) labeled compound Z
of the used oil samples demonstrated that bulk oil de-
(see Appendix 1) was formed but only limited decomposi-
composition of ZDP-A commenced near the end of the
tion of ZDP-B was detected. The amount of compound Z
induction period and was essentially complete after 300
detected peaked a t the time for the start of rapid ZDP
minutes. All the infrared peaks of the ZDP disappeared a t
decomposition, 350 minutes, and decreased sharply a t
the same rate with one exception, the 660 cm-' peak, - .
which is one of three peaks a;tribu.ted to P = S. The 660
ZDP-E ZDP-C
cm-' peak, which disappeared much more rapidly than IW
the other peaks, has been attributed to the basic double
salt (15) suggesting that some of the double salt was
-
-
u

O
75

present in the original additive package and that the d

2 M
basic salt decomposed before the normal salt. Precipitate g
formation started near the end of the induction period and 25
C
peaked a t 300 minutes. Why the weight of precipitate
0
decreased at the longest test time, even though no change m
in the composition was detected, is unknown.
Surface coating formation data a t the bottom of Fig. 1 m
E
show that little surface coating formation occurred until B
1m
the end of the induction period. Then the amounts of S,
P and Zn increased rapidly for a limited time but changed o
o 1m zm 3m am m o IW m m am
little after about 125 minutes. The predominant elements TIMI - MIN.
on the surface were P and Zn, whereas S was conspicuously Fig. 2-~ffect of time a t 177 C on ZDP decomposition
 longer test times. Following the induction period, additive
decomposition proceeded rapidly but there was little
accompanying pressure rise. Precipitate formation com-
menced a t the end of the induction period which also
corresponded to the start of compound Z disappearance,
suggesting that compound Z was a precursor for precipitate
formation. Surface coating formation stayed a t a low
level until the end of the induction period and then
increased in an ill-defined manner.
The behavior of ZDP-C was quite different. With this
alkylaryl ZDP, additive decomposition, as measured by
infrared spectroscopy, commenced immediately despite
the 310 C thermal decomposition temperature, and pro-
gressed linearly with time. Accompanying the ZDP
decomposition was the formation of a mixture of oil-
soluble products. The relative intensities and locations of
some of the new peaks matched those for a para-substituted
alkyl phenol; the other new peaks have not been identified
(see Appendix 1). Others have also reported phenol
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formation. (9) With this additive, there was an even
greater pressure loss than that for ZDP-B and there was
no subsequent rapid pressure rise. Precipitate formation
was delayed until over 70 percent of the ZDP had decom-
posed. Surface coating formation remained a t a low level
until precipitate fom~ationstarted; then the amounts of
Zn and P on the surface rose sharply to values well above
those observed for the other two ZDP's.
The composition of the precipitate formed also varied
with the ZDP tested. Elemental analyses listed in Table 2
show that the precipitate compositions for the three ZDP's
differed primarily in the sulfur content. For ZDP-A, the
sulfur content was about 12 percent; for ZDP-B, about
5 percent; and for ZDP-C, about 1 percent. Also, the
observed C/H ratio for ZDP-C was much lower than that
for the other two ZDP's or the C/H ratio for the alkylaryl
group in ZDP-C. In one instance, iron was measured but
the level, 0.2 percent Fe, was low enough to suggest that
steel balls made little if any direct contribution to precipi-
tate fom~ation.
Effect of Temperature
To determine whether the appearance of compound Z
during the induction period for ZDP-B and the lack of a
similar oil-soluble decomposition product appearing during
TABLE2-EFFECT OF ZDP ON PRECIPITATE COMPOSITION
ELEMENTAL WT. yo
ANALYSIS,
C/H*
Zn P S C H RATIO
ZDP-A . . . . . . . . 24.4 17.1 12.3 15.3 2.5 6.1
ZDP-B.. . . . . . . 24.4 15.1 5.0 19.7 3.6 5.5
ZDP-C ........ 29.8 19.6 1.0 6.9 2.5 2.8
* C/H Ratio for Alkyl Group in ZDP Molecule (based on data in
Table 1):
ZDP-A = 5.5
ZDP-B = 5.4
ZDP-C = 8.2
the induction period for ZDP-A was associated with the
lengths of the induction periods, tests were run a t tem-
peratures selected to vary the induction period from about
25 to 300 minutes with both ZDP's. With ZDP-A, no
evidence of an oil-soluble decomposition product was
detected independent of the induction period length,
whereas with ZDP-B the oil-soluble product was detected
in each case; the amount decreased as the induction period
was shortened by increasing the temperature. Both the
maximum amounts and the compositions of the precipitates
were independent of temperature for either ZDP-A or B.
Phosphorus surface coating formation data from the
temperature studies are shown in Fig. 3. For ZDP-A, the
level of phosphorus detected a t each temperature generally
passed through a maximum but the magnitude of the
maximum was not greatly affected by temperature. For
ZDP-B, on the other hand, the maximum phosphorus
level increased with increasing temperature to values well
above those for ZDP-A. With ZDP-C, the time to the first
increase in phosphorus shortened as the temperature
increased. For all three ZDP's, much the same pattern
was observed for the other elements, Zn and S.
Effect of Oxygen
To determine whether the decomposition of ZDP's was
affected by oxidation, some experiments were run with
reduced oxygen present. Pressure developments using
normal and low oxygen are compared in Fig. 4. With
ZDP-A, there was little difference between results of the
normal and low oxygen experiments up to about 200
minutes. At longer test times, the data suggest that the
decrease in pressure observed for the normal air experi-
ments was due to oxygen consumption. (Only a slight
pressure decrease was observed for the base oil alone.) At
either oxygen level, no evidence of base oil oxidation for
the ZDP blends was detected by infrared spectroscopy (no
carbonyl formation detected a t 1710 cm-I). When testing
ZDP-B and ZDP-C with reduced oxygen available, no
pressure decrease was observed with either ZDP, indicating
that oxygen consumption was probably responsible for the
pressure decrease observed in the normal oxygen case.
A summary of the effects of reduced oxygen is given in
Table 3. For ZDP-A, the reduction in oxygen availability
ZOP -A ZOP -B ZOP -C
0 200 400 0 200 400 0 200 400
-
TIME MIN.
Fig. 3-Effect of temperature on surface coating formation phosphorus
monitored.
 --
-

;J>
Some Factors Affecting the Deconlposition of Three Commercial Zinc Organodithiophosphates

o-o,o-o-
I
ZDP-A

ZoP-B

ZDP-C
I
,OW O2

NORMAL O2

LOW o2
,

I
For ZDP-B, on the other hand, the reduction in oxygen
availability caused some significant changes in the used
oil and precipitate analyses. In the low oxygen case, no
oil-soluble decomposition products (compound Z) were
detected, compared to 32 percent with normal oxygen, but
no intermediate test times were checked. T h e ZDP loss
and precipitate formed values were significantly reduced
which was reflected in the gaseous product formed data.
Further, the composition of the precipitate was changed
with sulfur increased from 5 to 13 percent by the oxygen
reduction without a corresponding change in the other
measured elements; i.e., Zn, P, C, and H. Reducing the
oxygen reduced both zinc and phosphorus on the surface
but may have increased sulfur.
83

T h e largest effects of reduced oxygen were observed with

ZDP-C. With this additive, the reduction in oxygen
greatly reduced both additive decomposition and the
amount of phenol fomied, and eliminated precipitate
formation. Similarly, the surface coating composition was
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-0p- greatly altered by the change in oxygen level, with zinc

and phosphorus being practically eliminated by the
reduced oxygen.

I 1 I I No.MA. I o2
Effect of Water

T o check the importance of hydrolysis as a decomposi-

TIME - MIN.
Fig. 4-Effect of oxygen concentration on ZDP decomposition
had little effect on either the used oil or precipitate
analyses. The insensitivity of ZDP-A to the presence of
oxygen is in accord with the observations of Ashford,
et al ( 6 ) .However, the composition of the surface coating
was altered with the level of zinc being drastically reduced
by the absence of oxygen.
tion mechanism, experiments were run with water added
to the ZDP blends. Ultrasonically dispersing the water in
the Z D P blends caused the formation of a white precipitate
(about 1 percent of the Z D P present) which infrared
spectra suggest was a mixture of sulfates with some
phosphate.
The effects of added water on ZDP decomposition are
illustrated in Fig. 5 . The induction period and 50 percent
ZDP loss times were generally reduced by the added water,

TABLE
3-EI;I:ECT OF OXYGEN ON ZDP DECOMPOSITION

ZDP-A ZDP-B ZDP-C

NORMAL LOW NORMAL LOW NORMAL LOW
0 2 0 2 0 2 0 2 0 2 0 2

Test Time, Blin at 177 C . . . . . . . . . 300 360 450 400 420 400
Oil Analysis
ZDP Loss, Percent. . . . . . . . . . . . 98 94 52 36 85 34
Phenol Formed, Percent.. . . . . . . . . . ... ... ... 69 13
Precipitate Formed, Percent. . . . 41 35 20 11 13 0
Gaseous Prod. Formed, Moles/
Mole Add*. . . . . . . . . . . . . . . . . 1.0 1.2 -0.3 0.1 -2.3 0.4
Precipitate Analysis
Zn, Weight Percent.. . . . . . . . . . . 24.4 25.0 24.4 29.6 28.8t ...
P, Weight Percent.. . . . . . . . . . . . 17.1 17.9 15.1 13.7 17.2t ...
S, Weight Percent. . . . . . . . . . . . . 12.3 15.6 5.0 13.1 0.4t ...
C, Weight Percent.. . . . . . . . . . . . 15.3 12.6 19.7 18.5 9.0t ...
H, Weight Percent. . . . . . . . . . . . 2.5 2.5 3.6 3.4 2.91 ...
Strrjace Coating Analysis
Zn, mg/m<. . . . . . . . . . . . . . . . . . 100 7 50 29 65 4
P, mg/ma.. . . . . . . . . . . . . . . . . . . . 99 76 61 33 128 8
S, mg/mZ.. . . . . . . . . . . . . . . . . . . . 50 44 12 23 90 87

* See Appendix B for method of calculation.

t At 191 C, sample at 177 C, too small for complete analysis.
 ZDP-A showing the least effect and ZDP-C the greatest. TABLE4--EFFECT OF WATER AND OLEIC ACID
Accelerated ZDP decomposition would be expected'from ADDITIONS ON PRECIPITATE COMPOSITION
the formation of acidic hydrolysis products. Precipitate
analyses in Table 4 show that the effects of adding water Weight Percent
ADDED -
or oleic acid were the same; i.e., the sulfur content of the COMPOUND Zn P S C H
precipitates from ZDP's A and B was reduced, whereas
ZDP-A. . . None
that for ZDP-C was unaffected. Water
The surface coating fonnation data a t the bottom of Fig. Oleic Acid
5, which were obtained a t fixed test times, also indicate ZDP-B . . . None
that the effect of water additions depended on the ZDP. Water
Although the amounts of Zn and P decreased for ZDP's Oleic Acid
ZDP-C. . . None
A and 13, the opposite was true for ZDP-C. Sulfur was Water
unaMected or reduced by water additions, except for the Oleic Acid
0.5 percent water added point for ZDP-B. I t is interesting
to note that the surface coating with ZDP-C was the most
aflected by water additions whereas the precipitate for
ZDP-A ZDP-A r ACID ZDP-A DETtRCiNT
ZDI?-C (see Table 4) was the least affected. 11% OLiIC ACID1 I33 OVfRBASiD MACKtSlUM SIJLFONAIL.

1W

Effect of Other Additives -

,-., m m
4
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z0 75
-
In most practical applications, lubricants contain a I0

number of additives besides the ZDP. Simple mixing with =-2 M

0:

I
E
0:
lubricating oil dispersants has been shown to alter the 0
$ 25 0:
e
infrared spectra of a ZDP (16). To check the effect of -10

other additives on the decomposition of ZDP's, a limited 0

study was made using oleic acid (a friction modifier) and

an overbased magnesium sulfonate (a detergent) as
second additives.
As illustrated in Fig. 6, the second additives can have a
marked efiect on ZDP decomposition. Adding 1 percent
TIM - MIN.
oleic acid (technical grade) to the ZDP-A blend sharply Fig. 6-Effect of second additives on the decomposition characteristics
reduced the induction time and the time to peak pressure of ZDP-A.
in agreement with others (5, 8). However, the general
shi~peof the pressure-time curves as well as the maximum along with the ZDP (carbonyl peak a t 1710 cm-I de-
level of precipitate forn~ationremained about the same. creased) and that there was some ester formation (carbonyl
The infrared spectra indicated that oleic acid disappeared peak a t 1725 cm-' formed). These observations suggest
that oleic acid was an active participant in the decomposi-
tion reactions rather than merely a catalytic agent. Oleic
acid had little effect on surface coating formation but did
alter the precipitate composition as noted earlier (Table
4).
The effect of adding a commercial overbased magnesium
sulfonate detergent (TBN = 300) was quite different. With
the detergent present, the decomposition of ZDP-A was
greatly retarded. When decomposition did occur, the
decomposition products were retained in the oil phase as
compound X (Infrared peaks listed in Appendix 1) and
no precipitate formed. These observations are in agreement
with those reported by Gallopoulos (11). In addition, the
pressure loss during the induction period suggests that
oxygen was consumed in the formation of compound X.
After the induction period, however, pressure rose sharply
to levels well above those observed for the ZDP alone.
Further, the detergent greatly reduced surface coating
formation even after the end of the induction period.
0 0.2 0.4 0 0.2 0.4 0 0.2 0.4
The effects of these two second additives on the decom-
ADDED WATER -WT.%
position of the three ZDP's are compared in Fig. 7. As
Fig. 5-Effect of added water on ZDP decomposition and surface was the case with ZDP-A, adding oleic acid to ZDP-C
coating formation. accelerated ZDP decomposition, whereas adding the
 Some Factors Affecting the Decomposition of Three Commercial Zinc Organodithiophosphates 85

18). To see if ZDP decomposition was base oil dependent,

ZDP-A ZDP-B ZDP-C
I I I I the three ZDP's were evaluated in base oils that repre-
sented extremes in additive response: a white oil containing
49 percent Cp, 49 percent CN and 2 percent C A by ndm
analysis and an aromatic hydrocarbon, rnonoisopropyl
biphenyl (MIPB).
The decomposition of ZDP-A in the two base stocks is
ZDP . AClD
illustrated in Fig. 8. By changing from the white oil to the
aromatic, both the induction period and the time to peak
TIM - hllN. pressure were reduced. In the aromatic hydrocarbon,
Fig. 7-Effect of second additives on the decomposition of three ZDP's. limited formation of an oil soluble material (compound X)
Second additive: Acid = 1 percent oleic acid Detergent = 3 percent
was detected during the induction period and somewhat
over based magnesium sulfonote.
greater precipitate formation occurred. Surface coating
detergent (the overbased magnesium sulfonate) to ZDP-C
retarded decomposition. ZDP-B was different in that both BASE OIL: WHITE OIL BASE OIL: MONOISOPROPYL BIPHENYL

second additives accelerated ZDP decomposition but oleic 1M

ZDP DECOMPOSITION

acid was much more effective. If the data for the three
ZDP's are compared, it will be noted that the rate of ZDP
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decomposition in the presence of either oleic acid or the

detergent was controlled primarily by the second additive,
tending to minimize the effect of the ZDP alkyl group. In
all cases, the second additives disappeared along with the
original ZDP molecule, additional evidence that the second I SURFACE COAllNG FORMATION I
additives are active participants rather than merely acid
or base catalytic agents.

Effect of Base Oil

Studies have shown that the effectiveness of some T l h E - MIN.
additives depends on the composition of the base oil (17, Fig. 8-Effect of base oil on ZDP-A decomposition

A pparenl
Oxygen
Constin~plion
Moles/
Mole of ZDP
Low 0 2 Gas (1.2 moles)+ Precipitate (1 Zn:l.SP:1.3SI . . . . . . 0
Gas (1.0 mole) + Precipitate (1 Zn:l.SP:lS). . . . . . . 0
Gas (1.0 mole) + Precipitate (1 Zn:1.6P:0.6S) . . . . . . 0
-+- Precipitate (1 Zn:1.7P:0.3S) . . . . , , 0
+ Liquid (Compound X) . . ,. , , , 0.5
Low 01 Gas (0.1 moles) +
Precipitate (1 Zn:l.OP:0.9S) . 0

Liquid +Gas (0.2 moles) + Precipitate (1 Zn:1.3P:0.4S) . 0.3

(Compd. Z)
Normal 0 2 + HzO Liquid
'- (Compd. Z)
-Gas (0.8 moles) + Precipitate (1 Zn:1.4P:O.2S) . 0

Normal 0 2 + Oleic Acid Liquid +Gas (1.1 moles) + Precipitate (1 Zn:1.5P:0.2S) . 0

+Gas(O.lmole) . . . . . . . . 0.5

Low 0 2
.Liquid + Phenol + Gas (0.4 moles) . . . . . . . . . 0
Liquid + Phenol-Gas (0.1 moles) + Precipitate
c

.
c (1 Zn:1.3P:O.O3S) . . . . . . . . 2.3
ZDP-C
(Alkyl Aryl)
Normal 0, +H z 0 . +
Liquid Phenol +
Gas (2.0 moles)+Precipitate
c
(1 Zn:1.8P:O.O6S) . . 0
Normal 0 2 + Oleic Acid .Liquid +
c
Phenol+Gas (1.4 moles) Precipitate +
(1 Zn:l.lP:0.2S) . . 0
Normal 0 2 + Detergent Liquid + Phenol-+Gas (0.6 moles). . . . . 1.7
r
Fig. 9-Decomposition characteristics of ZDP's at 177 C
 formation, however, was reduced in the aromatic hydro-
carbon. Similar studies with the other two ZDP's indicated
that both behaved like ZDP-A in that changing to the
aromatic hydrocarbon tended to accelerate ZDP decom-
position and reduce surface coating formation.
DISCUSSION
Row do these results compare with the literature? In
agrccment with others, gaseous products and a solid
residue (precipitate) were obtained. In addition, however,
oil-soluble intemlediate products were detected in many
instances by infrared spectroscopy but their composition
has not been determined.
Some estimates of the net amount of gaseous products
formed (see Appendix 2) are listed in Table 3. Negative
moles/mole of ZDP values are believed to be caused by
oxygen consumption. None of the values calculated, which
ranged from 1.0 to -2.3 moles/mole of ZDP, approached
thc 2 moles of gases/mole of ZDP reported by Luther and
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Sinha (4) or Dickert and Rowe (8).Both the presence of
oxygcn and the base oil in the present experiments may
have contributed to the reduced net pressure rise. Further,
thc olefins and mercaptans formed during decomposition
may have reacted under the test conditions of the present
work to foml sulfides, (19) thus lowering the net moles of
gaseous products present.
The prccipitate elemental analyses generally correspond-
ed to those reported by Brazier and Elliott (7). Infrared
spectra obtained on the precipitates suggested a mixture
of sulfate and phosphate with some residual hydrocarbon
groups present. The carbon-hydrogen ratio of the precipi-
tate from the aromatic and highly refined mineral oil
studies with ZDP-A suggest that some of the residual
hydrocarbon groups may have come from the base oil.
'The course of ZDP decomposition under various condi-
tions has been summarized in Fig. 9. In this figure, the
net gaseous product fornlation is given in moles/mole of
ZDP and the precipitate analyses are given in terms of
atomic ratios. The deconlposition of ZDP-A (secondary
alkyl ZDP) is perhaps the most straightforward. With
either normal or reduced oxygen available, the amount of
gaseous products formed and the composition of the
precipitate were essentially the same and there was no
apparent oxygen consumption. Adding oleic acid slightly
reduced the gaseous product formation and both water and
oleic acid lowered the sulfur content of the precipitate but
still there was no apparent oxygen consumption. In
contrast, the presence of the detergent increased gaseous
product formation, prevented the formation of a precipi-
tate (or prevented its agglomeration) and caused the
consumption of 0.5 mole of oxygen/mole of ZDP. Thus
thermal decomposition appears to be the primary de-
con~positionn~echanism for ZDP-A. However, when a
second additive or water was present, other competing
mechanisms probably become involved.
ZDP-B (the primary alkyl ZDP) exhibits a somewhat
different behavior. With low oxygen, only limited ZDP
decomposition occurred and little change in pressure was
detected. With normal oxygen, in contrast to ZDP-A, a
loss in pressure was observed for ZDP-B well after ZDP
decomposition had begun, even though the probable
alkyl group in ZDP-B would be expected to yield products
a t least as volatile as those from ZDP-A and, consequently,
a t least as great a pressure rise. The characteristic odor
was the same for both decomposed ZDP's. Both the
pressure loss and the formation of compound Z were
eliminated when the oxygen was reduced, whereas the
sulfur content of the precipitate increased. These observa-
tions point to the active role of oxygen in the decomposi-
tion of ZDP-B. The addition of either water or oleic acid
increased gaseous product formation but reduced the
sulfur content of the precipitate. With the detergent
present, virtually no gaseous products or precipitate were
detected. However, the detergent again caused the con-
sumption of 0.5 mole of oxygen/mole of ZDP. Thus the
decomposition of ZDP-B appears to be a mixture of
thermal and oxidative decomposition processes which are
promoted by the presence of acidic materials.
The decomposition of ZDP-C (alkylaryl ZDP) requires
a still different explanation. With this aromatic ZDP, a
pressure loss corresponding to 2.3 moles of oxygen was
observed with normal oxygen present, whereas with
reduced oxygen this pressure loss was virtually eliminated,
as was precipitate formation. Still the phenol and other
soluble decomposition products were formed under the
low oxygen test conditions. Since alkyl phenols exhibit
low volatility, little contribution of the phenol to the
observed pressure would be expected. However, the addi-
tion of water or oleic acid led to gaseous product formation
and prevented apparent oxygen consumption. Although
the detergent also promoted gaseous product formation,
it was not as effective as oleic acid. These results suggest
that the decomposition of ZDP-C is primarily an oxidative
process in contrast to the mainly thermal decomposition
processes for the two alkyl ZDP's.
If the results for the three ZDP's are compared, there
are a number of similarities. In each case, the presence of
oleic acid promoted the thermal decomposition of the
ZDP, tending to override the effect of the organic group,
and inhibited the oxidative decomposition, perhaps by
reducing the time available for the oxidation reactions.
The detergent on the other hand, apparently promoted
oxidative reactions which resulted in more soluble (or less
easily precipitated) reaction products. Limited light scat-
tering experiments failed to show any evidence of sus-
pended material when the detergent was present.
The apparent role of oxygen in the decomposition of
ZDP's is interesting in view of the fact that the ZDP's
are antioxidants (peroxide decomposer type) and the base
oil contained DBPC (a free radical inhibitor type anti-
oxidant). The combination would be expected to be very
effective in preventing base oil oxidation as was observed.
During more extensive second additive studies to be
reported in a future paper, it was observed that the addi-
tion of other free radical type antioxidants had no effect,
whereas some peroxide decomposer type antioxidants
significantly delayed ZDP decomposition. Dickert and
 Some Factors Affecting the Decomposition of Three Commercial Zinc Organodithiophosphates 87

TABLE5-COMPARISON OF PRECIPITATE AND SURFACE COATING COMPOSITIONS

ZDP-A,. . . . . . . . Normal Air 157 1 Zn: 1.4 P : 0 . 9 S 1 Zn: 2.8 P: 1.4 S

166 1 Zn: 1.6 P : 1.2 S 1 Zn: 0.3 P : 1.1 S
177 1 Zn: 1 . 5 P : 1.0 S 1 Zn: 2.0 P : 1.0 S
191 1 Zn: 1.6 P : 0.9 S 1 Zn: 0.07P: 0.4 S
Low 0 2 177 1 Zn: 1 . 5 P : 1.3 S 1 Zn: 23 P : 13 S
ZDP-B.. . . . . . . . Normal Air 177 1 Zn: 1.3 P : 0.4 S 1 Zn: 2.6 P : 0.5 S
191 1 Zn: 1.5 P : 0.4 S 1 Zn: 4.9 P : 3.9 S
204 1 Zn: 1.5 P : 0.4 S 1 Zn: 2.1 P : 3.4 S
Low 0 2 177 1 Zn: 1.0 P : 0.9 S 1 Zn: 2.3 P : 1.6 S
ZDP-C.. . . . . . . . Normal Air 177 1 Zn: 1 . 3 P : 0.03s 1 Zn: 1.5 P : 0.2 S
191 1 Zn: 1 . 3 P : 0.03s 1 Zn: 7.1 P : 2.1 S
Low 0 2 177 No Precipitate 1 Zn: 4.2 P : 44 S

Rowe (8) also observed that free radical inhibitor anti- used oils, precipitate weight and compositions and surface
oxidants had no effect but they reported that the addition coating compositions depended on the org,znic group in the
of benzoyl peroxide delayed ZDP decomposition until the molecule and the available oxygen. Changing the test
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peroxide addition was discontinued. Further work to
clarify the role of peroxides in ZDP deconiposition is
needed.
Bulk oil decomposition of the ZDP appears to be essen-
tial for the forniation of a surface coating. For all three
ZDP's, surface coating formation did not begin until after
the induction period ended and precipitate formation
began. Further, the addition of the detergent, which
prevented precipitate formation, also restricted surface
coating formation. Thus, the question becomes; Is there a
direct relationship between precipitate and surface coating
formation?
If ZDP decomposition products polymerize a t the
surface, as has been proposed, (2) the elemental composi-
tions of the precipitate and the surface coating should be
the same. To check this theory, the precipitate and surface
coating compositions for several test conditions are com-
pared in Table 5. For a given ZDP, the precipitate analyses
changed little with test conditions whereas the surface
coating compositions varied considerably, especially for
the low oxygen condition. ~ l t h o u g hsome of the variation
in the surface was the
differences are large enough to indicate that in many cases
the compositions of the precipitate and the surface coating
were different.Thus, direct reaction of ZDP decomposition
products with the surface seems a more likely explanation
for surface coating formation than polymerization and
subsequent adsorption of the polymer.
A more detailed discussion of the decomposition of these
temperature or the base oil composition altered the ZDP
decomposition rate but not the products formed. The
presence of other additives or water in the blend not only
accelerated or retarded ZDP decomposition but also
altered the composition of the decomposition products.
Based on these observations, it is believed that thermal
decomposition was the primary mechanism for ZDP-A
(secondary alkyl ZDP), thermal and oxidative decomposi-
tion processes were both involved with ZDP-B (primary
alkyl ZDP), and primarily oxidative decomposition pro-
cesses were responsible for ZDP-C (alkylaryl ZDP) de-
composition a t the test temperatures studied. Water and
oleic acid additions appeared to accelerate thermal de-
composition reactions, whereas the overbased magnesium
sulfonate addition appeared to promote oxidation reactions.
ACKNOWLEDGMENT
The author would like to thank the members of the
Analytical chemistry D~~~~~~~~~who analyzed the
precipitates, determined the surface coating compositions,
measured the ZDP decomposition characteristics by DSC,
and tolerated the odors while the infrared spectra were
being run.
REFERENCES
(1) Rowe, C. N. and Dickert, Jr., J. J., "The Relation of Antiwear
Function to Thermal Stability and Structure for Metal 0, 0-
Dialk~l~hos~horodithioates," ASLE Transaclions, 10, 85-90
(1967j.' '

ZDP's will have to wait for better analyses of the various
deconiposition products. However, the data presented
offer ample proof that thermal decomposition is only one
of several important reaction mechanisms for ZDP's.
SUMMARY AND CONCLUSIONS
In bomb and beaker studies on three commercial
ZDP's, it was found that the nature and amounts of
deconiposition products formed as indicated by pressure-
time histories, infrared spectrographic analyses of the
(2) Feng, I-Ming, Perilstein, W. L., and Adams, M. R., "Solid
Film Deposition and Non-Sacrificial Boundary Lubrication,"
ASLE Transactions, 6 . 60-66 (1963).
(3) Feng, I-Ming, "Pyrolysis of Zinc Dialkyl Phosphorodithioate
and Boundary Lubrication," Wear, 3,309-311 (1960).
(?) Luther, H. and Sinha, S. K., "Zur Reaktionskinetik der ther-
mischen Zersetzung vo" ~inkdialk~ldithiophos~haten," ERDOL
U N D KOHLE, 17, 91-97 (1964).
(5) Hannenman, W. H. and Porter, R. S., "The Thermal De-
composition of Dialkyl Phosphates and 0, 0-Dialkyl Dithio-
phosphate3," J. 0rza,z1c ~lretrt:,29, 2996-2998 (1964);
(6) Ashford, J. s., Bretherick, L., and Gould, P. "The Thermal
Decomposition of Zinc Di-(4-Methyl Pentyl-2) Dithiophos-
hate," J . .4ppl. Chetn., 15, 170-178 (1965).
 (7) Brazier, A. D. and Elliott, J. S., "The Thermal Stability of
Zinc Dithiophosphates" J. Inst. Petrol., 53, 63-76 (1967).
(8) Dickert, Jr. J. J., and Rowe, C. N., "The Thermal Decomposi-
tion of Metal 0, 0-Dialkylphosl~horodithioates," J. Orgarzic
Clroir., 32, p. 647-653 (1 967).
(9) Stanton, G. &I.and Uarrall, E. M., TI, "Decomposition Charac-
teristics of Some Diaryl Zinc, Cadmium, Ammonium and
Nickel Dithiophosl)hates," ACS Petroleum Division Preprints,
14, NO. 4, A 59-A67 (1969).
(10) Japne, G. J. J. and Elliott, J. S., "The Load-Carrying Properties
of Some Metal Phosphorodithioates," J. Ilzsl. Pelrol., 56,
42-49 (1970).
(11) Gallopoulos, N. E., "Thermal Decomposition of Metal Diakyl-
dithio~~hosphate Oil Blends," ASLE Transactions, 7, 55-63
(1964).
(12) Allum, K. G. and Forbes, E. S., "The Load Carrying Properties
of hfetal Dialkyl Dithiol~hosphates:The Effect of Chemical
Structure," Iltst. Afeclt. Ewg. Proc., 1968-69, 183 p t 3P, 9-16
(1969).
(13) Schweitzer, P. H. and Szebehely, V. G., "Gas Evolution in
Liquids and Cavitation," J. Applied Plays. 21, 1218-23 (1950).
(14) Baldwin, R. R. and Daniel, S. G . "The Solubility of Gases in
Lubricating Oils and Fuels," J. Insl. Pelrol., 39, 105-241 (1953).
(15) Wystrach, V. P., Hook, E. O., and Christopher, G. L. M.,
"Basic Zinc Double Salts of 0, 0-Dialkyl Phosphorodithioic
Acids," J. Organic Chent., 21, 705-707 (1956).
(16) Gallopoulos, N. E. and, Murphy, C. K., "Interactions Between
a Zinc Diakylphosphorodithioate and Lubricating Oil Dis-
persants," ASLE Tmrrsacrions, 14, 1-7 (1971).
(17) Rounds, F. G., "Some Effects of Nonbydrocarbon Rase Oil
Constituents on the Friction and Surface Coating Formation
Obtained with Three Additives," ASLE Tra~zsaclions,11, 19-30
(1968).
(18) Rounds, F. G., "Effect of Aromatic Hydrocarbons on Friction
and Surface Coating Formation with Three Additives," ASLE
Transaclions, 16, 141-49 (1973).
(19) Hoffert, W. H. and Wendtner, K., "Reaction of Sulfur, Hydro-
gen Sulfide, and Mercaptans with Unsaturated Hydrocarbons,"
J. Inst. Pelrol. 35, 171-191 (1949).

APPENDIX 1
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Infrared Peaks Used to Follow Additive Loss and New Product Formation
Frequency, cm-I
%I) P Decoln positio~t
ZD.1'-A 540,
v-
P=S
--
635, 650, 660, 750, 775, 850, 970, 1055, 1100, 1115, 1135, 1155, 1175
P-0-C
"
H-C
Z:D 1'43
-- ---
550, 640, 660, 670, 840, 850, 960, 1000, 1020, 1140, 1165, 1390

%UP-C
- P=S H-C P-0-C
560, 640, 660, 830, 920, 940, 1165, 1200, 1500
P=S
-+
P-0-C C-H (Aromatic)
H-C

Loss of Otl~erAdditives
:I1 13'1)C
--
855, 1150, 1225, 3640

Oleic Acid

Mg Sulfonnte
- C=O
H-C
1710, 1755
OH

430, 850, 1420, 1500, 3400 (Broad)

New I+oducts Formed

From ZDP-A 510, 560, 600, 910, 925, 1040, 1060, 1080, 1105, 1125, 1145, 1160, 1190, 1230, 1 2 5 0
(Con~poundX)
I+om ZDP-B 1060, 1110, 1145, 1165, 1210, 1 2 3 0
(Co~npoundZ)
I7roni ZDI?-C
(Phenol)
--
535, 800, 825, 1170, 1225, 1510, 1585, 1605, 3570, 3610
OH
(Other) 970, 1020, 1100, 1235, 1315
I+om Oleic Acid 1760

-
1725,
(Ester)
For References, 550, 740, 775, 805, 825, 1170, 1230, 1260, 1510, 1595, 1615, 3550, 3610
p-.lsoanlyl OH
Phenol

NO'I'E: C-H peaks for the additives in the 1300-1450 and 2600-3100 cm-I regions generally were marked by the base oil
C-H peaks.
 Some Factors Affecting the Decomposition of Three Commercial Zinc Organodithiophosphates 89

APPENDIX 2
Pressure Changes-Possible Sources
The observed change in bomb pressure with time is the net result of the following:
APobs = APsystem + A P b a s e oil + APadciitive

where APsyatem = A p t h e r m e 1 expansion - APleaks

A P b a s e oil = A P o i l vaporization - A P g a s removal b y reaction
APadditive = A p g s s e o u s product formation - APgns removal b y reaction

'I'he AYndditive was measured by subtracting the pressures observed with the base oil alone from the pressures observed
with the base oil plus additive. The bomb volume was 700 cc and the volume of the oil (100 cc) plus heat transfer oil
(130 cc) plus steel balls (20 cc) was 250 cc leaving a net volume of 450 cc for gases. If PI = observed pressure for base oil
and Pz = observed pressure for base oil plus additive:
P1 VI = nlRTl
Apadditivo = P z - PI P2vz = nZRTz but R is constant and V1 = V z and T I = Tz
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-
since n2 = P 2 V 2 , then number of moles of gaseous products formed or removed =
RT2

kPa-cc
V 2 = 450 cc, T2 = 273 + 177 = 450 K, R = 8300 OK-g moles

moles of gas formed = nz - nl = -(450)(18'6) = 2.24 X 1W3g moles

(8300) (450)
For ZDP-A, number of moles additive present is:
Fraction of active material in additive package = 0.85
h4olecular Weight of additive = 659
1
2 cc (0.87 g/cc) (0.85) - = 2.24 X l W 3 g moles additive present
659
2'24
lo-' = 1.00 g moles gas formed/g mole additive present
' ' 2.24 X l W 3