Tribology Letters

, Volume 17, Issue 3, pp 469–489 | Cite as

The History and Mechanisms of ZDDP

  • H. Spikes


This paper reviews research into the mechanisms of action of the lubricating oil additive, zinc dialkyldithophosphate (ZDDP). The development of the use and research into ZDDP is first charted historically, starting with the additive's first introduction in engine oils in the late 1930s. Then our current state of knowledge of each of the main facets of ZDDP behaviour both in solution and at metal surfaces is identified and discussed. It is concluded that we now know a great deal about the properties and morphology of ZDDP antiwear films but still relatively little about the reaction pathways that lead to ZDDP film formation or about the kinetics of ZDDP film generation and removal.

Zinc dialkyldithiophosphate ZDDP ZnDTP antiwear history wear lubricant additives 


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  1. [1]
    A.M. Barnes, K.D. Bartle and V.R.A. Thibon, Trib. Intern.34 (2001)389.Google Scholar
  2. [2]
    A.J. Gellman and N.D. Spencer, Proc. I. Mech. E. Ser. J.216 (2002)443.Google Scholar
  3. [3]
    H.M. Wells and J.E. Southcombe, J. Soc. of Chem. Lond.39 (1920)51.Google Scholar
  4. [4]
    R.V. Kerley, SAE Tech.Paper 810849,(1981).Google Scholar
  5. [5]
    O. Beeck, J.W. Givens and E.C. Williams, Proc. Roy.Soc. Lond.A177 (1940)103.Google Scholar
  6. [6]
    A.B. Boehm, Proc. API Ann. Meeting 28(II)(1948)35.Google Scholar
  7. [7]
    G. Pritzker, Nat. Petr. News, Techn. Sect.37 (1945)R1001.Google Scholar
  8. [8]
    C.V. Smalheer and T.W. Mastin, Petr. Process.7 (1952)1780.Google Scholar
  9. [9]
    P.A. Asse.,US Patent 2261047,Oct 2th 1941.Google Scholar
  10. [10]
    E.W. Cook and W.D. Thomas Jr.,U.S.Patent 2344392,Mar. 14th 1944.Google Scholar
  11. [11]
    H.C. Freuler, U.S.Patents 2364283 and 2364284,Dec.5, 1944.Google Scholar
  12. [12]
    J.B. Bidwell and R.K. Williams, SAE Trans.63 (1955)349.Google Scholar
  13. [13]
    W.B. Chamberlin, J.C. Kelley and M.A. Wilk, SAE Tech. Paper 2003-01-1988 JSAE 20030347,presented Yokohama, May 2003.Google Scholar
  14. [14]
    R. Larson, Scient.Lubr.10(8)(1958)12.Google Scholar
  15. [15]
    T.W. Selby,in: Proc.13th Intern.Colloq.Tribology,Lubricants, Materials and Lubrication Engineering,supplement Esslingen Jan 2002,ed.W.J. Bartz,p.93.Google Scholar
  16. [16]
    E.H. Loeser, R.C. Wiquist and S.B. Twiss, ASLE Trans.1 (1958)329.Google Scholar
  17. [17]
    R.K. Brow, D.R. Tallant, S.T. Myers and C.C. Phifer, J.Non-Crystalline Solids 191 (1995)45.Google Scholar
  18. [18]
    M.J. Furey, ASLE Trans.2 (1959)91.Google Scholar
  19. [19]
    E.H. Loeser, R.C. Wiquist and S.B. Twiss, ASLE Trans.2 (1959)199.Google Scholar
  20. [20]
    P.A. Bennett, ASLE Trans.2 (1959)78.Google Scholar
  21. [21]
    P.A. Asse.Discussion to reference [20].Google Scholar
  22. [22]
    C.E. Legate and H.D. Burnham, Anal. Chem.32 (1960)1042.Google Scholar
  23. [23]
    I.M. Feng, Wear 3 (1960)309.Google Scholar
  24. [24]
    I-M. Feng, W.L. Perilstein and M.R. Adams, ASLE Trans.6 (1963)60.Google Scholar
  25. [25]
    H. von Luther and S.K. Sinha, Erdol u Kohle-Erdgas-Petroche-mie 17 (1964)91.(In German)Google Scholar
  26. [26]
    W.W. Hanneman and R.S. Porter, J. Org. Chem.29 (1964) 2996.Google Scholar
  27. [27]
    N.E. Gallopoulos, ASLE Trans.7 (1964)55.Google Scholar
  28. [28]
    J.S. Ashford, L. Bretherick and P. Gould, J. Appl. Chem.15 (1965)170.Google Scholar
  29. [29]
    J.J. Dickert and C.N. Rowe, J. Org. Chem.32 (1967)647.Google Scholar
  30. [30]
    A.D. Brazier and J.S. Elliot, J. Inst. Petrol.53 (1967)63.Google Scholar
  31. [31]
    H. von Luther and D. Staeck, Erdol u Kohle-Erdgas-Petroche-mie 22 (1969)530.(In German)Google Scholar
  32. [32]
    S.A. Francis and A.H. Ellison, J.Chem.Eng.Data.6 (1961) 83.Google Scholar
  33. [33]
    F.G. Rounds, ASLE Trans.7 (1964)11.Google Scholar
  34. [34]
    F.G. Rounds, ASLE Trans.9 (1966)88.Google Scholar
  35. [35]
    K.G. Allum and E.S. Forbes, Proc.I.Mech.E.183,(Pt.3P), (1968 -69)7.Google Scholar
  36. [36]
    G.J.J. Jayne, and J.S. Elliot, J.Inst.Pet.56 (1970)42.Google Scholar
  37. [37]
    M. Born, J.C. Hipeaux, P. Marchand and G. Parc, Lubr.Sci. 4 (1992)93Google Scholar
  38. [38]
    T. Colclough and J.I. Cunneen, J. Chem. Soc.62 (1964)4790.Google Scholar
  39. [39]
    A.J. Burn, Tetrahedron 22 (1966)2153.Google Scholar
  40. [40]
    J.A. Howard, Y. Ohkatsu, J.H.B. Chenier and K.U. Ingold, Can.J.Chem.51 (1973)1543.Google Scholar
  41. [41]
    R.J. Bird and G.D. Galvin, Wear 37 (1976)143.Google Scholar
  42. [42]
    R.J. Bird, R.C. Coy and J.F. Hutton, ASLE Trans.23 (1980) 121.Google Scholar
  43. [43]
    J.M. Georges, J.M. Martin, T. Mathia, Ph. Kapsa, G. Meille and H. Montes, Wear 53 (1979)9.Google Scholar
  44. [44]
    A. Tonck, J.M. Martin, Ph.Kapsa and J.M.Georges, Trib. Intern.12 (1979)209.Google Scholar
  45. [45]
    P. Cann, H.A. Spikes and A. Cameron, ASLE Trans.26 (1983)48.Google Scholar
  46. [46]
    P. Cann and A. Cameron, Trib.Intern.17 (1984)205.Google Scholar
  47. [47]
    E.S. Yamaguchi, P.R. Ryason, S.W. Yeh and T.P. Hansen, Trib.Trans.41 (1998)262.Google Scholar
  48. [48]
    R.C. Coy and R.B. Jones, ASLE Trans.24 (1981)77.Google Scholar
  49. [49]
    R.B. Jones and R.C. Coy, ASLE Trans.24 (1)(1981)91.Google Scholar
  50. [50]
    H. Spedding and R.C. Watkins, Trib. Intern.15 (1982)9.Google Scholar
  51. [51]
    T.P. Debies and W.G. Johnston, ASLE Trans.23 (1980)289.Google Scholar
  52. [52]
    R.C. Watkins, Trib.Intern.15 (1982)13.Google Scholar
  53. [53]
    I. Sieber, K. Meyer and H. Kloss, Wear 85 (1983)43.Google Scholar
  54. [54]
    J.M. Palacios, Trib.Intern.19 (1986)35.Google Scholar
  55. [55]
    J.M. Palacios, Wear 114 (1987)41.Google Scholar
  56. [56]
    S. Jahanmir, Trans.ASME J.Tribology 109 (1987)577.Google Scholar
  57. [57]
    H.J. Mathieu, R. Schumacher and D. Landolt, Wear 132 (1989)99.Google Scholar
  58. [58]
    B. Dacre and C.H. Bovington, ASLE Trans.25 (1982)546.Google Scholar
  59. [59]
    B. Dacre and C.H. Bovington, ASLE Trans.26 (1983)333.Google Scholar
  60. [60]
    S. Plaza, ASLE Trans.30 (1987)233.Google Scholar
  61. [61]
    J.M. Martin, J.L. Mansot, I. Berbezier and H. Dexpert, Wear 93 (1984)117.Google Scholar
  62. [62]
    J.M. Martin, M. Belin, J.L. Mansot, H. Dexpert and P. Lagarde, ASLE Trans.29 (1986)523.Google Scholar
  63. [63]
    J.M. Martin, J.L. Mansot, I. Berbezier, M. Belin and G. Balossier, Wear 107 (1986)355.Google Scholar
  64. [64]
    M. Belin, J.M. Martin and J.L. Mansot, Trib.Trans.32 (1989) 410.Google Scholar
  65. [65]
    P.A. Willermet, P.A. Mahoney and C.M. Haas, ASLE Trans. 22 (1979)301.Google Scholar
  66. [66]
    P.A. Willermet, L.R. Mahoney and C.M. Bishop, ASLE Trans.23 (1980)225.Google Scholar
  67. [67]
    M. Masuko, T. Ohkido, A. Suzuki and T. Ueno, 2003,in: Proc.30th Leeds-Lyon Symp.on Tribology:Transient Processes in Tribology,Lyon,Sept.2003,ed.Dowson,D et al.(Elsevier, 2004)359.Google Scholar
  68. [68]
    P.A. Willermet, S.K. Kandah, W.O. Siegl and R.E. Chase, ASLE Trans.26 (1983)523.Google Scholar
  69. [69]
    J.J. Habeeb and W.H. Stover ASLE Trans.30 (1987)419.Google Scholar
  70. [70]
    F. Rounds, Trib.Trans.36 (1993)297.Google Scholar
  71. [71]
    P.M. Cann, G.J. Johnston and H.A. Spikes, Proc.I.Mech.E. C208/87 (1987)543.Google Scholar
  72. [72]
    J. Bell, R. Coy and H.A. Spikes, Proc.Jap.Intern.Trib.Conf., Nagoya, 1990 505.Google Scholar
  73. [73]
    J.C. Bell, K.M. Delargy and A.M. Seeney,in:Proc.18th Leeds-Lyon Symp.on Tribology,Transient Processes in Tribology,Lyon,Sept.1991,ed.Dowson al,(Elsevier 1992)p. 387.Google Scholar
  74. [74]
    J.C. Bell and K.M Delargy,in:Proc.6th Int.Congress on Tri-bology,“Eurotrib '93”,Vol 2 (Budapest,Hungary,1993)p. 328.Google Scholar
  75. [75]
    J.S. Sheasby, T.A. Caughlin and J.J. Habeeb, Wear 150 (1991) 247.Google Scholar
  76. [76]
    P.M. Cann and H.A. Spikes, Trib.Trans.34 (1991)248.Google Scholar
  77. [77]
    F.M. Piras, A. Rossi and N.D. Spencer, Trib.Lett.15 (2003) 181.Google Scholar
  78. [78]
    P.A. Willermet, R.O. Carter III and E.N. Boulos, Trib.Intern. 25 (1992)371.Google Scholar
  79. [79]
    A.J. Pidduck and G.C. Smith, Wear 212 (1997)254.Google Scholar
  80. [80]
    O.L. Warren, J.F. Graham, P.R. Norton, J.E. Houston and T.A. Michalske, Trib.Lett.4,(1998)189.Google Scholar
  81. [81]
    J.F. Graham, C. McCague and P.R. Norton, Trib.Lett.6 (1999)149.Google Scholar
  82. [82]
    K. Topolovec-Miklozic and H.A. Spikes, ASME Trans.,J.Tribology,Sept., 2003 (Accepted for publication).Google Scholar
  83. [83]
    .M. Aktary, M.T. McDermott and G.A. McAlpine, Trib.Lett. 12 (2002)155.Google Scholar
  84. [84]
    M. Aktary, M.T. McDermott and J. Torkelson, Wear 247 (2001)172.Google Scholar
  85. [85]
    S. Bec, A. Tonck, J.M. Georges, R.C. Coy, J.C. Bell and G.W. Roper, Proc.R.Soc.Lond.A455,(1999)4181 488 H.Spikes/The history and mechanisms of ZDDP.Google Scholar
  86. [86]
    Z. Yin, M. Kasrai, G.M. Bancroft, K.F. Laycock and K.H. Tan, Trib.Intern.26 (1993)383.Google Scholar
  87. [87]
    M. Kasrai, M. Fuller, M. Scaini, Z. Yin, R.W. Brunner, G.M. Bancroft, M.K. Fleet, K. Fyfe and K.H. Tan, photoelectron Leeds-Lyon Symposium on Tribology,Lubricants and Lubrication,Leeds,Sept 1994,ed.D Dowson et al.(Elsevier,1995)p.659.Google Scholar
  88. [88]
    Z. Yin, M. Kasrai, M. Fuller, G.M. Bancroft, K. Fyfe,and K.H. Tan, Wear 202 (1997)172.Google Scholar
  89. [89]
    G.M. Bancroft, M. Kasrai, M. Fuller, Z. Yin, K. Fyfe,and K.H. Tan, Trib.Lett.3 (1997)47.Google Scholar
  90. [90]
    M. Fuller, Z. Yin, M. Kasrai, G.M. Bancroft, E.S. Yamaguchi, P.R. Ryason, P.A. Willermet and K.H. Tan, Trib.Intern. 30 (1997)305.Google Scholar
  91. [91]
    M.L. Suominen Fuller, M. Kasrai, G.M. Bancroft, K. Fyfe, and K.H. Tan Trib.Intern.31 (1998)627.Google Scholar
  92. [92]
    E.S. Ferrari, K.J. Roberts, M. Sansone and D. Adams, Wear 236 (1999)259.Google Scholar
  93. [93]
    K. Varlot, M. Kasrai, J.M. Martin, B. Vacher, G.M. Bancroft, E.S. Yamaguchi and P.R. Ryason, Trib.Lett.8 (2000)9.Google Scholar
  94. [94]
    M.L. Suominen Fuller, L. Rodriguez Fernandez, G.R. Massoumi, W.N. Lennard, M. Kasrai and G.M. Bancroft, Trib.Lett. 8 (2000)187.Google Scholar
  95. [95]
    J.M. Martin, C. Grossiord, T. Le Mogne, S. Bec and A. Tonck, Trib.Intern.34 (2001)523.Google Scholar
  96. [96]
    C. Minfray, J.M. Martin, T.R. Le Mogne and B. Hagendo., Thin Solid Films 447-448 (2003)272.Google Scholar
  97. [97]
    M. Eglin, A. Rossi,and N.D. Spencer, Trib.Lett.15 (2003) 199.Google Scholar
  98. [98]
    G.W. Canning, M.L. Suominen Fuller, G.M. Bancroft, M. Kasrai, J.N. Cutler, G. De Stasio and B. Gilbert, Trib.Lett.6 (1999)159.Google Scholar
  99. [99]
    M.A. Nicholls, G.M. Bancroft, P.R. Norton, M.G. Kasrai, G.-F. De Stasio, B.H. Bradley and L.M. Wiese, Trib.Lett.17 (2004)245.Google Scholar
  100. [100]
    S. Gunsel, H.A. Spikes and M. Aderin, Trib.Trans.36 (1993) 276.Google Scholar
  101. [101]
    L. Taylor, A. Dratva and H.A. Spikes, Trib.Trans.43 (2000) 469.Google Scholar
  102. [102]
    L.A. Taylor, R. Glovnea, M. Ribeaud and H.A. Spikes,in: Proc.ITC Conference,Nagasaki,Oct.2000,Vol II JST Tokyo 2001,p.1257.Google Scholar
  103. [103]
    H. Fujita and H.A. Spikes, Proc.30th Leeds-Lyon Symp.on Tribology:Transient Processes in Tribology,Lyon,Sept.2003, ed.Dowson, D et al.(Elsevier, 2004)37.Google Scholar
  104. [104]
    H. Fujita and H.A. Spikes, Proc.I.Mech.E Ser.J., 218 (2004) 265.Google Scholar
  105. [105]
    H. Fujita, R.P. Glovnea and H.A. Spikes, Presented at STLE Annual Meeting,Toronto,May 2004 and submitted for publication in Trib.Trans.Google Scholar
  106. [106]
    P.G. Harrison and T. Kikabhai, J.Chem.Soc.Dalton Trans. 4 (1987)807.Google Scholar
  107. [107]
    H.L. Fang and J.M. Millar, 4th Int.Symp.on the PerformanceEvaluation of Automotive Fuels and Lubes.,B' ham UK,May 1993,CEC/93/EL15Google Scholar
  108. [108]
    E.S. Yamaguchi, R.L. Primer, S.R. Aragon and E.Q. Labrador, Trib.Trans.40 (1997)330.Google Scholar
  109. [109]
    I. Haiduc, D.B. Sowerby and L. Shao-Fang, Polyhedron 14 (1995)3389.Google Scholar
  110. [110]
    V.P. Wystrach, E.O. Hook and C.L.M. Christopher, J.Org. Chem.21 (1956)705.Google Scholar
  111. [111]
    E.S. Yamaguchi, R.L. Primer, S.R. Aragon and E.Q. Labrador, Trib.Trans.41 (1998)233.Google Scholar
  112. [112]
    E.S. Yamaguchi, P.R. Ryason, E.Q. Labrador and T.P. Hansen, Trib.Trans.39 (1996)220.Google Scholar
  113. [113]
    E.S. Yamaguchi, A. Onopchenko, M.M. Francisco, C.Y. Chan, Trib.Trans.42 (1999)895.Google Scholar
  114. [114]
    .E.S. Yamaguchi, P.R. Ryason and E.Q. Labrador, Trib. Trans.36 (1993)367.Google Scholar
  115. [115]
    J.M. Georges, A. Tonck, S. Poletti, E.S. Yamaguchi and P.R. Ryason, Trib.Trans.41 (1998)543.Google Scholar
  116. [116]
    E.S. Yamaguchi, Trib.Trans.42,(1999)90.Google Scholar
  117. [117]
    D.R. Armstrong, E.S. Ferrari, K.J. Roberts and D. Adams, Wear 208 (1997)138.Google Scholar
  118. [118]
    L.J. Christmann, US Patent 1893018,Jan.3rd 1933.Google Scholar
  119. [119]
    T.H. Handley and J.A. Dean, Anal.Chem.34 (1962)1312.Google Scholar
  120. [120]
    R.K. Jensen, M.D. Johnson, S. Korcek, M.J. Rokosz, Lubr. Sci.10 (1998)99.Google Scholar
  121. [121]
    R.K. Jensen, S. Korcek, M.D. Johnson, Lubr.Sci.14 (2001) 25.Google Scholar
  122. [122]
    G.W. Kennerly and W.L. Patterson Jr., Ind.Eng.Chem.48(1956)1917.Google Scholar
  123. [123]
    S. Almalaika, M. Coker,and G. Scott, Polymer Degr.and Stability 22 (1988)147.Google Scholar
  124. [124]
    R.A. Willermet, R.O. Carter, P.J. Schmitz, M. Everson, D.J. Scholl and W.H. Weber, Lubr.Sci.9 (1997)325.Google Scholar
  125. [125]
    G. Hilgetag and H. Teichmann, Angew.Chem.(International Ed.)4 (1965)914.Google Scholar
  126. [126]
    H. Teichmann and G. Hilgetag, Angew.Chem.(International Ed.)6 (1967)1013.Google Scholar
  127. [127]
    K. Homann, P.I. Sanin, K. Meier and G.N. Kuzima, Trenie iIznos 3 (1982)780.(In English)Google Scholar
  128. [128]
    P.A.Willermet, D.P. Dailey, R.O. Carter III, P.J. Schmitz and W.Zhu, Trib.Intern.28 (1995)177.Google Scholar
  129. [129]
    J.J. Martin, Trib.Lett.6 (1999)1.Google Scholar
  130. [130]
    T. Sakamoto, H. Uetz, J. Fo ¨hl and M.A. Khoshwari, Wear }77 (1982)139.Google Scholar
  131. [131]
    G.W. Stachowiak and A.W. Batchelor, Engineering Tribology, 2nd ed.(Butterworth-Heinemann,Boston,2001).Google Scholar
  132. [132]
    M. Masuko, T. Hanada and H. Okabe, Lubr.Eng.50 (1994) 972.Google Scholar
  133. [133]
    I.M. Hutchins Tribology Friction & Wear of Engineering Materials.(E.Arnold,1992).Google Scholar
  134. [134]
    C. Benyajati, A.V. Olver and C.J. Harner in:Proc.30th Leeds Lyon Symp.on Tribology:Transient Processes in Tribology, Lyon,Sept.2003,ed.Dowson,D et al.(Elsevier,2004)601.Google Scholar
  135. [135]
    C. Bovington and H.A. Spikes,in:Proc.of the Intern.Tribology Conf.,Yokohama,October 1995,(JST,Tokyo 1996)p. 817.Google Scholar
  136. [136]
    G. Tripaldi, A. Vettor and H.A. Spikes, SAE Tech.Paper 962036 (1996).Google Scholar
  137. [137]
    L. Taylor, H. Spikes and H. Camenzind, SAE Tech.Paper 2000-01-2030 (2000)Google Scholar
  138. [138]
    L. Taylor and H.A. Spikes, Trib.Trans.46 (2003)303.Google Scholar
  139. [139]
    L. Taylor and H.A. Spikes, Trib.Trans.46 (2003)310.Google Scholar
  140. [140]
    Y. Zhu and S. Granick, Macromolecules 35 (2002)4656.Google Scholar
  141. [141]
    M. Kano, Y. Mabuchi, T. Ishikawa, A. Sano and T. Wakizono, Lubr.Sci.11 (1999)365.Google Scholar
  142. [142]
    J.M. Georges, J.M. Martin and J.F. Brison,in:Proc.6th Leeds-Lyon Symp.Thermal E.ects in Tribology,Sept.1979,ed. D.Dowson et al.(MEP Press,1980)p.307.Google Scholar
  143. [143]
    D.B. Barton, E.E. Klaus, E.J. Tewksbury and J.R. Strang, ASLE Trans.16 (1973)161.Google Scholar
  144. [144]
    M.A. Wilk, W.D Abraham and B.R. Dohner, 1996,in:Heavy Duty Diesel Engine Lubricants,SAE Techn.Paper Series,p.47.Google Scholar
  145. [145]
    H. So and Y.C. Lin, Wear 177 (1994)105.Google Scholar
  146. [146]
    C. Minfray, J.M. Martin, T. Lubrecht, M. Belin and T. Le Mogne,in:Proc.29th Leeds-Lyon Symp.on Tribology,Tribological Research and Design for Engineering Systems,Sept. 2002, ed.D Dowson et al. (Elsevier,2003)p.807.Google Scholar
  147. [147]
    N.H. Ray, Br.Polymr.J.11 (1979)163.Google Scholar
  148. [148]
    R.K. Brow, J.Non-Crystalline Solids 194 (1996)267. H.Spikes/The history and mechanisms of ZDDP 489Google Scholar

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