Tribology International 34 (2001) 389–395

www.elsevier.com/locate/triboint

A review of zinc dialkyldithiophosphates (ZDDPS):

characterisation and role in the lubricating oil
Allyson M. Barnes *, Keith D. Bartle, Vincent R.A. Thibon
School of Chemistry, University of Leeds, Leeds LS2 9JT, UK

Received 4 August 2000; received in revised form 26 February 2001; accepted 5 March 2001

Abstract

This is a review of the additive, zinc dialkyldithiophosphate (ZDDP), which is found commonly in lubricating oil where it plays
a role as both an antioxidant and an antiwear additive. This zinc complex is highly effective but its mechanisms of action have
not been definitively reported. This review covers work pertaining to the characterisation and mechanisms of action of ZDDP and
includes studies carried out by sophisticated instrumentation as well as laboratory studies. There are some references to the nature
of the antiwear films generated by ZDDP and the usefulness of its derivatives.  2001 Elsevier Science Ltd. All rights reserved.

Keywords: Additive; Antioxidant; Antiwear; Zinc dialkyldithiophosphate

1. Introduction work has been published concerning the role of ZDDP

in preventing antiwear and some of the references high-
Zinc dialkyldithiophosphates are lubricating oil addi- light the sophisticated techniques currently being used
tives. Much use is made in modern industry of lubricat- in the characterisation of both ZDDP products and the
ing oils. The main functions of such oils are fourfold: nature of the antiwear films generated by them.

1. to prevent wear between surfaces of an engine;

2. to serve as coolants or heat transfer mediums;
3. to help seal at compression rings; and
4. to suspend matter, thus helping to keep engines clean.
Additives are necessary to enhance aspects of an oils
performance and replace compounds which may have
been lost in the refining of an oil. Additive packages are
typically present at around 10% w/w of the final blend,
although this can vary depending on the final appli-
cation. ZDDPs are used mainly for their antioxidant
properties and their ability to prevent wear. The ZDDP
complexes are manufactured by reaction of alcohols,
phosphorus pentasulphide and zinc salts. The resulting
complexes are not completely pure and it has been com-
mented that the lack of purity in a sample can lead to
difficulty in its analysis [12]. The following review
covers different aspects of ZDDP behaviour and includes
references of analysis as well as applications. Much
* Corresponding author.
2. ZDDP as an antioxidant
Antioxidants act to retard oxidation of the lubricating
oil, thus preventing the formation of corrosive products.
Gilks [1] and Mahoney [2] have described the different
types of antioxidants available. Antioxidants act in two
different ways, by inhibition of peroxides or by radical
scavenging. ZDDPs exhibit both types of antioxidant
behaviour. Radical scavengers react with peroxy radicals
thus preventing further propagation of the free radical
chain. Peroxide inhibitors react with hydroperoxide mol-
ecules preventing formation of the peroxy radicals. Bai-
ley [3] has discussed different modes of antioxidant
action and different classes of antioxidant. The degra-
dation of ZDDP is very complex and much work has
been dedicated to understanding the mechanisms of its
degradation and its interactions with other additives. One
approach has been to chemically model an oxidation by
oxidising ZDDP in the laboratory and monitoring the
reaction by analytical methods. Advantages of this
method are that known parameters can be set and

0301-679X/01/$ - see front matter  2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 3 0 1 - 6 7 9 X ( 0 1 ) 0 0 0 2 8 - 7
390 A.M. Barnes et al. / Tribology International 34 (2001) 389–395
unwanted complications by other additives or base oil
can be avoided. However, the disadvantage is that this
is an artificial situation and does not necessarily correlate
with the engine or emulate processes occurring within
it. Burn et al. [4] used this approach to study the
decomposition of cumene hydroperoxide (CHP) in the
presence of ZDDP. Although a definitive mechanism of
degradation of ZDDP could not be produced, the three
stages of breakdown were postulated. The authors
observed an initial fast stage, in which the disulphide
was identified as an initial degradation product, followed
by a slow induction stage and lastly, a final fast stage.
It appeared that the reaction was catalytic in nature but
ZDDP was not thought to be the catalyst. A zinc sulphate
was identified as a final product. Paddy et al. [5,6] used
a similar reaction to study the oxidation of ZDDP by
CHP. The group used HLPC and 31P-NMR to follow the
reactions. Products were identified and first-order kin-
etics proposed. The usefulness of 31P-NMR in elucidat-
ing detail in degradation of ZDDP was demonstrated.
Burn et al. [7,8] have also used 31P-NMR to follow the
hydrolysis of ZDDP. Major intermediates and products
were identified and individual reaction rates were
determined. A comprehensive mechanistic pathway was
proposed. Burn also found that in organic solvents, the
basic form of ZDDP dissociates to form zinc oxide
which inhibits hydrolysis of normal ZDDP and has to
be consumed before hydrolysis can take place. Harrison
and Kikabhai [9] have also studied the behaviour of
ZDDPs in solution and noted the dissociation of ZDDP
to ZnO.
The activity of ZDDP when mixed with used oil was
investigated by Johnson et al. [10,11]. Interactions
between ZDDP and oxidation products were thought to
have led to the observed decrease in activity.
Brazier and Elliot [12] investigated the thermal
decomposition of ZDDPs and reported that most ZDDPs
decompose in two stages. The thermal stabilities of
ZDDPs derived from straight chain primary alcohols
were seen to increase with increasing carbon number.
The authors reiterated the lack of definitive mechanistic
information and suggested that this could be due in part
to a lack of availability of pure compound.
3. ZDDP in the engine
Some workers have tried to follow the reactions of
ZDDP in an engine environment. Korcek et al. [13] car-
ried out a study of ZDDP decay. ZDDPs were added to
used oil and subjected to engine testing. The authors
noted the formation of an antioxidant species capable of
much higher activity than that of the original antioxidant.
The authors did not elucidate a detailed mechanism of
ZDDP reactions due to the difficulty of the task and the
complex nature of the engine environment. Peng et al.
[14] followed the degradation of ZDDP in a fully formu-
lated engine oil by 31P-NMR. It was concluded that the
degradation process was complicated but several gener-
alisations were made. The degradation process was seen
to be temperature dependent, which affected the degra-
dation products, ZDDP was seen to complex with suc-
cinimide dispersants in the fresh oil, but interestingly the
ZDDP was released during operation of the engine.
4. Analysis of ZDDPs
ZDDPs have been analysed in the laboratory by use
of thin layer chromatography (TLC). Coates [15]
developed a method whereby TLC plates were
developed in ninhydrin and good separation was seen.
Lewkowitsch [16] titrated the copper salt of a ZDDP
which had been formed in a pre-reaction. Capillary
supercritical fluid chromatography (cSFC) was used by
Ashraf [17] to analyse lubricating oil additives, including
ZDDP. Thermal analysis was performed by El Naga and
Salem [18] to look at the stability of oils. The authors
deduced some breakdown mechanisms for ZDDP which
concurred with other work published in the literature.
Harrison and Kikabhai [19] have investigated the effect
of nitrogen donor molecules on the thermal stability of
ZDDPs. The nitrogen donor molecules were seen to bind
to the zinc atom and the resulting complexes showed
synergistic and antagonistic effects on the thermal stab-
ility of ZDDP. In the review by Schumacher [20] on
applications of thermal methods in tribology, the syner-
gistic effect between copper oleate and ZDDP was dem-
onstrated. Various parameters including atmosphere,
temperature, pressure, sample mass, pan type and anti-
oxidant were discussed. Harrison and Brown [21]
reported the thermal decomposition of ZDDPs on a
stainless steel metal surface by the use of external
reflection Fourier Transform infrared (FTIR) spec-
troscopy, 31P-MAS NMR and scanning electron
microscopy (SEM). No films were seen on the metal sur-
face at temperatures less than or equal to 150°C but
brown or black deposits were seen at 200 and 260°C.
The films seen at 200°C seemed to be weakly adsorbed
but uniform in composition whilst those at the higher
temperature were inhomogeneous and seemed to contain
mixtures of zinc alkylmonothiopyrophosphates and zinc
polyphosphates. Cardwell et al. [22] developed a
method, using electrospray mass spectrometry (ESMS),
for the qualitative analysis of engine oil inhibitor and
antiwear additives. Although neutral Zn(DTP)2 com-
pounds cannot be studied by ESMS, ionic products for-
med by reaction with dimethyl sulphoxide or excess
dithiophosphate ions can be analysed. The authors went
on to analyse commercial engine oil additives and were
able to detect differences between ZDDPs which had
been manufactured with different alcohols. Willermet et
 A.M. Barnes et al. / Tribology International 34 (2001) 389–395
al. [23] used reflection–absorption infrared (IR), X-ray
photon spectroscopy (XPS) and auger spectroscopy to
study tribochemical films formed from fully- formulated
engine oils which contained ZDDPs. The authors dem-
onstrated by the spectra of the films that the decompo-
sition route of the ZDDP was probably thermo-oxidative
and that the products formed were amorphous orthopho-
sphates and pyrophosphates. Rhodes and Stair [24] stud-
ied the effects of ZDDPs on hydrocarbon films adsorbed
on iron substrates. XPS was used to study various bases-
tocks and three different ZDDPs. The authors com-
mented on the effect of the base oil on oxide film
reduction and the role of the ZDDP.
An investigation of the hydrolysis of commercially
available ZDDPs has been carried out by Burn et al.
[25]. An excess of water was added to ZDDPs which
were heated to 85°C. Aliquots were removed period-
ically and analysed by 31P-NMR. Hydrolysis products
were identified and seemed fairly consistent with pre-
vious work done by the authors. The kinetics of hydroly-
sis were discussed, taking into account the nature of the
substituent alkyl groups.
The work carried out by Yamaguchi and Ryason [26]
looked at the initial adsorption of ZDDPs onto an alu-
minium oxide surface. The molecular composition of the
initial film was studied by inelastic action tunnelling
spectroscopy (IETS). Distinct differences were seen
between primary, secondary and aryl ZDDPs. The spec-
tra recorded for commercial primary and secondary
ZDDPs suggested that the P–O–C group was retained
during adsorption. The authors also commented on the
differences noted between the spectra of commercial
ZDDPs (mixture of neutral and basic ZDDPs) and pure
neutral ZDDPs. The authors suggested that the degree
of P=S bonding to the surface is a key factor in the effec-
tiveness of antiwear performance and that IETS is a suit-
able means of screening wear inhibitors.
Armstrong et al. [27] gave a short summary of the
classified molecular structures of ZDDPs. Computational
methods were used to study the geometries, charge dis-
tributions and relative energies of the various forms of
ZDDP. The authors go on to discuss in detail the bond
lengths and angles for monomeric, neutral and basic
forms of ZDDP. From their studies the authors con-
cluded that the basic ZDDP formed the most stable struc-
ture.
Thibon et al. [28] have shown an application of capil-
lary electrochromatography (CEC) in the analysis of
ZDDP. The separation electrolytes were optimised
specifically to ZDDP. A brief description of CE theory
was given and the authors explained that due to long
migration times the use of reversed polarity was neces-
sary. Four commercial ZDDPs were analysed and it was
noted that the peak related to the structures of the ligands
[(RO)(RO)PS2]⫺ and not the ZDDP itself.
Lambropoulos et al. [29] established the problems
391
encountered when using reversed-phase HPLC before
going on to describe the conditions for successful nor-
mal-phase HPLC. Conditions were optimised for a
ZDDP synthesised using isopropyl alcohol, where the
mobile phase consisted of isopropylamine:acetic acid:-
methanol in chloroform. Eleven ZDDPs synthesised
from 11 different alcohols were separated using a hep-
tane-based eluant and showed consistent data with thin-
layer chromatography results. The authors showed that
the ZDDPs eluted intact and concluded that normal
phase HPLC could be used, without gradient elution, for
the analysis of ZDDPs. Windahl and Cardwell [30]
showed by electroscopic mass spectrometry (ES) and
cyclic voltammetry (CV) that ZDDPs were not eluted as
intact chelates under reversed-phase HPLC conditions.
Reversed-phase chromatography of ZDDPs was difficult
due to the low solubility of ZDDPs in an aqueous solvent
and the high back pressures of the column.
5. ZDDP as an antiwear/extreme pressure (EP)
additive
Whenever two metal surfaces are forced together with
insufficient lubrication, the potential for wear occurs to
the detriment of the metal surfaces. ZDDP is widely used
for its antiwear properties. Coy and Jones [31] heated
samples of ZDDP in mineral oil to thermally degrade
the ZDDP. NMR was used to identify the decomposition
products, which were then synthesised and tested for
extreme pressure performance in the four-ball wear test
apparatus (the four-ball apparatus is an industry-recog-
nised wear test, whereby a moving ball is rotated against
three fixed balls under specified conditions). ZDDPs
were heated to 180°C and aliquots analysed after 1, 4,
8 and 16 h. 31P-NMR and 1H-NMR were used to provide
details of the structures of the decomposition products.
The nature of the products indicated that intermolecular
transfers of alkyl groups had occurred as well as
migration of alkyl groups and intermolecular transfer of
sulphur. X-ray fluorescence spectroscopy was used to
analyse precipitates generated in the heat experiments.
The four-ball tests indicated that, even when most of the
ZDDP additive had decomposed, little effect was seen
on the EP performance, suggesting that the products
themselves had high EP activity.
Willermet and co-workers [32–35] have published
extensively concerning the role of ZDDPs as antiwear
agents. The work included studying the degradation pro-
ducts of ZDDP to assess the antiwear properties of these
products; the products were found to be less effective as
antiwear agents than ZDDP. One of the principal degra-
dation products was found to be the disulphide, which
on subsequent synthesis and wear testing was shown to
be inferior to the ZDDP.
Work by Spedding and Watkins [36,37] suggested that
392 A.M. Barnes et al. / Tribology International 34 (2001) 389–395
products formed by hydrolytic decomposition of ZDDP
in oil solution, namely alkyl sulphides and zinc polypho-
sphates, have a role to play in the protection of the
engine. Kawamura [38] related the chemical reactivity
of ZDDPs to wear by use of thermal analysis. The height
of a differential thermal analysis (DTA) peak was related
to the wear scar diameter; differences were observed in
the DTA between primary and secondary ZDDPs.
Film thickness and properties of both neutral and basic
diisobutyl zinc dithiophosphates were studied by
Georges et al. [39]. A sliding force apparatus (SFA) was
used to carry out the investigations. Neither the neutral
or basic ZDDP formed films which could be displaced
by sliding, unlike those films generated by dodecane.
The films were characterised by measurement of the
elastic and shear moduli. Dynamic light scattering had
been used to detail the molecular dimensions of ZDDPs
and this information was then related to the film thick-
nesses measured. In the work by Taylor et al. [40] both
the kinetics of film formation and the morphology of the
film have been studied. The work details the nature of
the film generated by ZDDP additive in specific areas
and the consequences on wear protection and friction.
The authors give a brief discussion to previous means
of analysing ZDDP films and studies which have aided
the understanding of how ZDDPs function. The work
carried out was performed using a rolling/sliding contact
to simulate field conditions. Film thicknesses were meas-
ured by a spacer layer imaging method (SLIM). ZDDP
was shown to form a thick film in the region of the rub-
bing surfaces which reached a limiting thickness which
could be seen to increase with increases of temperature.
The authors also discuss the observation that ZDDP can
cause an increase in friction during the mixed lubrication
regime. The roughening of surfaces by ZDDP is shown
and the subsequent effect on friction between surfaces.
The wear capacities of different oil blends were tested
on the four-ball wear tester by Sheasby et al. [41].
Materials tested were steel, silicon nitride and zirconia.
A solution which contained ZDDP was tested on all
three materials. Glassy films were generated for the steel
ball which provided wear protection. The silicon nitride
ball was also protected by the formation of discrete
‘pods’ of antiwear material. Wear protection was not
evident for the zirconian ball until the viscosity of the
base oil was increased.
So and Lin [42] established a model to study the
decomposition of ZDDP and the growth of the chemical
film generated on a surface. Rather than focusing on the
chemical reactions which occur prior to the generation
of the film, the predictive models focus on the nature of
the contact surfaces and the diffusion which controls the
rate of film formation. The conditions employed main-
tain boundary lubrication throughout. Work was carried
out on a gel-like material which was generated when
temperatures exceeded 120°C and the authors then went
on to discuss the effect of type of ZDDP, surface charac-
teristics and temperature.
Work has been done by Yin et al. [43] using XANES
to study the antiwear films generated by primary and
secondary ZDDPs. P and S L-edge XANES spec-
troscopy was used. By comparison with model com-
pounds the appearance of metaphosphate (isopropyl-
ZDDP film) and pyrophosphate (butyl-ZDDP) was
shown.
Fuller et al. [44] have carried out a spectroscopic
study using XANES to identify S and P containing spec-
ies, originating from ZDDPs, generated in thermal and
tribochemical films. Tribochemical films were generated
using a Cameron–Plint wear tester and thermo-oxidative
films were generated by suspending coupons into heated
oil solutions. The additives themselves were decom-
posed by heating in an oven. Spectra of the thermally
decomposed additive samples showed the formation of
phosphates and aryl ZDDP was shown to be more ther-
mally stable than both primary and secondary ZDDPs.
The thermally-generated and tribological films were also
analysed. A comparison was made between the basic and
neutral forms of the ZDDPs. It was commented that in
aryl tribo-films, long chain polyphosphates were present
throughout whereas in alkyl tribo-films the long chain
polyphosphates were present in the topmost surface with
short chain polyphosphates found in the bulk.
The same group [45] have used XANES spectroscopy
to investigate the effect of decomposition of ZDDP on
antiwear and thermal film formation. 31P-NMR was used
to characterise solutions of the ZDDP after various heat-
ing protocols. Increased heating times caused increased
film thickness and increased levels of wear.
A correlation between film thickness and levels of
wear was not seen. Films which had been heated to tem-
peratures of 200°C gave way to catastrophic wear. Com-
position of the films was related to temperature and
mechanisms of formation were proposed. Belin et al.
[46] have studied the nature of antiwear films using
extended X-ray absorption fine structure (EXAFS).
Experiments investigated the cam follower wear of two
engines. The results detect short-range order in the anti-
wear film, but long-range order was not seen indicating
that the films are highly amorphous. The presence of
Zn–O bonds was seen and the results from the laboratory
were shown to compare well with results recorded on
actual wear debris.
The study by Wan et al. [47] investigated antiwear
action of ZDDP on an aluminium alloy. Experiments
were performed using an SRV (industry) test rig, steel
balls and aluminium alloy blocks. Several ZDDPs were
used together with other metal alkyldithiophosphate salts
of general formula [(RO)2PS2]nMxOy. A liquid paraffin
base stock was used. In comparison to the base stock
alone it was seen that a commercial ZDDP actually pro-
duced a larger wear volume, had a rougher wear surface
 A.M. Barnes et al. / Tribology International 34 (2001) 389–395
and was ineffective at reducing the friction coefficient.
In conclusion, the authors did not recommend ZDDP for
lubricating aluminium alloy.
Sheasby et al. [48] devised a means to simulate a reci-
procating wear regime to test the efficacy of ZDDP as
an antiwear agent. A ball was spun upon the point of
contact on a rotating countersurface. Both sapphire and
steel were used as counter contact surfaces and blends
were tested with and without the presence of a second
additive. A matrix of blends was tested, with and without
spin of the ball. In general, if a blend gave good wear
protection, this was enhanced by spin when a sapphire
surface was used but worsened when the surface was
steel. The presence of a second additive was seen to be
deleterious to the performance of the anti-wear films.
SEM was used to study the nature of the films generated.
Ferrari et al. [49,50] have used multi-edge X-ray
absorption spectroscopy to investigate the nature of tri-
bological interfaces. The technique was developed by
use of model compounds and was then applied to in situ
studies of steel/oil interfaces. The ZDDP was presumed
to have influenced the surface structure of the metal and
at high temperatures the presence of a Zn–O bond was
seen. The authors present a model of structural changes
occurring at the steel interface and postulate the theory
of the mechanisms occurring.
6. ZDDP and interactions with other engine oil
components
Several groups have carried out research into the way
that ZDDP interacts with other components in the
engine oil.
Inoue and Watanabe [51] addressed the possibility of
interactions between other additives and ZDDPs. Inter-
actions can be synergistic or antagonistic. Reactions
were seen to occur between succinimides and ZDDPs.
Hsu and Lin [52] studied effects between ZDDPs with
succinimides and calcium sulphonates. Individually,
synergistic effects were seen with both succinimides and
calcium sulphonates but this was not seen to be the case
in a three component system. Barcroft and Park [53]
used a ‘hot-wire’ technique, whereby a stainless steel
wire was heated by electrical current, to evaluate ZDDPs
alone and in conjunction with other additives; a polyme-
thacrylate viscosity improver, a succinimide dispersant,
an overbased calcium sulphonate and an overbased cal-
cium alkylsalicylate. SEM was used to study film forma-
tion on the wire. Whilst the methacrylate did not appear
to affect the film which was formed by the ZDDP alone,
the metal-containing additives and the succinimide did
affect the films, either the rate of reaction, film thickness,
morphology or film composition. The authors went on
to test fully formulated oils and showed agreement
between the hot-wire method and an industry scuffing
393
test. The interactions between diesel soot and decompo-
sition products of ZDDP were investigated by Hosonuma
et al. [54]. Used oils from a Japanese valve train wear
engine test were mixed with soot particles and tech-
niques such as thin layer chromatography and IR spec-
troscopy carried out. The four-ball antiwear test was also
carried out, the oils seemed to retain some antiwear per-
formance and the authors attributed this to the phos-
phorus-containing decomposition compounds. The soot
appeared to adsorb the zinc-containing decomposition
products but not those which contained phosphorus. Bar-
tha et al. [55] carried out a study of the interaction
between PIB-succinimides and engine oil additives. Dif-
ferent types of succinimides were studied with a range
of concentrations of ZDDP. The strength of interaction
was measured as was the effect of the interaction on the
efficiency of the dispersant.
Wu and Dacre [56] have carried out an investigation
of the action of ZDDP onto SKF-3 steel. Fundamental
work was carried out using just ZDDP in a hydrocarbon
base stock. A radioactive ZDDP solution was used to
determine the amount of adsorption occurring. It was
proposed that two different types of adsorption occur and
the method of adsorption is temperature dependant, phy-
sisorption at low temperatures and chemical adsorption
at high temperatures. The effect of co-additives were
also determined: both mono- and bis-succinimides were
observed to suppress adsorption maxima of ZDDP which
had been recorded in the absence of any co-additive.
This was also true when phenate was added. The authors
offered explanations of adsorption behaviour of ZDDP
in the presence of co-additives.
Work done by Yin et al. [57,58] has included the
study of effects of physical parameters and effects of
detergents and dispersants on the antiwear films gener-
ated by ZDDP.
The complexity of behaviour of ZDDP is apparent
from the range of papers contained in this review as is
the importance of its role as an engine protector.
Acknowledgements
A.M. Barnes would like to thank DERA for financial
support of this project and V.R.A. Thibon thanks Esso
International for a grant.
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