The Viscosity-Temperature-Pressure

C. J. A. ROELANDS Relationship of Lubricating Oils and Its

Correlation With Chemical Constitution1
Chemical Engineer.

J. C. VLUGTER
Professor of Chemical Technology.
H. I. W A T E R M A N
Late Professor of Chemical Technology,
deceased on February 3 , 1 9 6 1 .
Laboratory for Chemical Technology,
The Technological University of Delft,
Holland
factorily applicable to all the aforementioned liquids in a wide range, that is, generally,
from about 20 to 150 deg C (68 to 302 deg F) and up to pressures of at least 3000 at-
Viscosities of twenty well-defined, representative mineral-oil fractions have been de-
termined at temperatures from 25 to 90 deg C (77 to 194 deg F) and at pressures up to
about 1000 atmospheres (15,000 psi) with the aid of a falling-needle viscometer.
An analysis has been made of both the present measurements and reliable data from
literature, which chiefly concern mineral oils and pure hydrocarbons, but also include
some silicones, fatty oils, and alcohols. Many literature data cover ranges of viscosity,
temperature, and pressure that are more extensive than those of the authors.
Newly developed empirical formulas are presented for the isobaric viscosity-tempera-
ture relationship, the isothermal viscosity-pressure relationship, and the complete
viscosity-temperature-pressure relationship. The formulas have been found to be satis-
mospheres (44,000 psi).
Diagrams derived from these formulas have proved particularly suitable for a sys-
tematic study of the correlation between, on the one hand, the temperature and pressure
variation of viscosity of the liquids concerned and, on the other hand, their chemical
constitution.
This is exemplified by the results for the mineral oils investigated. In fact, it proved
possible, presumably for the first time, to establish for mineral oils a really satisfactory
quantitative correlation between their viscosity-temperature-pressure dependence and
their chemical constitution; the latter has been characterized by the carbon distribution
according to the "Waterman analysis" in the form of the so-calkd n-d-M method.

I Introduction pressure is still hampered b y experimental difficulties. Neverthe-

THE viscosity of liquids is a property still poorly
understood. Advancing our relevant knowledge is not only of
scientific interest but also desirable for further engineering de-
velopments.
Being a property of state, viscosity is a function of temperature
and pressure. T h e great majority of investigations in the field of
the viscosity variation of liquids is confined to the temperature
dependence at atmospheric pressure. However, also at elevated
pressure is viscosity an important factor; but research at high
1 Condensed version of a paper presented at the 1962 ASME Spring
less, substantial information on the viscosity of liquids above
atmospheric pressure has gradually become available.
High-pressure viscometry offers several interesting possibilities
for gaining a deeper insight into the viscous behavior of liquids
and into the nature of the liquid state in general. Yet, it would
appear that most of the investigations have been induced b y the
engineering importance of the present subject rather than by its
scientific interest. Although the engineering aspects cover various
fields of application, they are particularly important in the field
of lubricants [1-7]. 2

Lubrication Symposium, June 4-6, 1962, Miami Beach, Fla.
Contributed by the Lubrication Division and presented at the
Winter Annual Meeting, New York, N. Y., November 25-30, 1962,
of T H E A M E R I C A N S O C I E T Y OP M E C H A N I C A L E N G I N E E B S . Manuscript
received at ASME Headquarters, September 13, 1962. Paper No.
62—WA-178.
II Experimental Part
Apart from a few minor technical details, the viscometer used
in the present investigations is identical with the falling-needle
2 Numbers in brackets designate References at end of paper.

Nomenclature
A, Ao = empirical constants M = molecular weight d = density
B, Bo = empirical constants Pp = viscosity-pressure pole n = refractive index
Ao PT = viscosity-temperature pole p — gauge pressure, atm (1 atm =
C = — , equation ( 8 )
PP" T = absolute temperature, deg K 1.0332 k g f / c m 2 = 14.696 psi)
C A = percentage of carbon atoms in — TP = pole temperature —p P = pole pressure
aromatic ring structure x,y = empirical constants
C N = percentage of carbon atoms in a = empirical constant
naphthenic ring structure
t) = dynamic viscosity, cP
CP = percentage of carbon atoms in
rjo = dynamic viscosity at atmos-
paraffinic chain structure
Y = p" pheric pressure
CR — CA + CV = total percentage of
carbon atoms in ring struc- YP = Pp" tjoo = dynamic viscosity at T = °°
ture Z log ?? tip = pole viscosity
Bp - log Tip ZP = - l o g jjp log = common or Briggsian logarithm,
D = , equation (9) logio
a = empirical constant

Journal of Basic Engineering DECEMBER 1963 / 6 0 1

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 type described by Boelhouwer and Toneman [8 J. The viscometer Table 2 Viscosity data of mineral-oil fractions tested
was immersed in a thermostat filled with distilled water, tem- Values of log 17, cP
perature being kept constant within ± 0 . 0 5 deg C. Pressures up
Gauge pressure in atm
to 1000 atm were supplied by a high-pressure bench, a pressure
Oil °C 0 300 500 750 950
balance being employed for measuring and controlling pressure,
to an accuracy of about ± 0 . 5 atm. 3 No. 1 25 1.188 1.444 1.604
40 0.944 1.180 1.324 L488 1! 623
The possible error in the experimentally determined viscosities 65 0.643 0.841 0.964 1.113 1.226
is estimated to be within ± 2 . 5 percent. 90 0.418 0.599 0.713 0.843 0.941
In Table 1 the twenty mineral-oil fractions examined are speci- No. 2 25 1.137 1.381 1.554
fied. Their average chemical compositions are expressed in terms 40 0.901 1.125 1.278 L453 1^592
of CA, CN, and CP, being the percentages of the total number of 65 0.603 0.809 0.936 1.084 1.200
90 0.392 0.576 0.691 0.824 0.923
carbon atoms that occur in aromatic ring, naphthenic ring, and 0.707
No. 3 25 0.289 0.461 0.570 0.806
paraffinic chain structure, respectively. These percentages have 40 0.174 0.336 0.437 0.552 0.649
been determined by the "Waterman analysis" in the form of the 65 0.009 0.158 0.252 0.364 0.443
so-called n-d-M method [9, 10]. 90 -0.126 0.026 0.109 0.211 0.289
No. 4 25 1.236 1.551 1.765 2.039 2.263
40 0.960 1.230 1.408 1.630 1.820
65 0.631 0.847 0.987 1.164 1.305
Table I Mineral-oil fractions tested 90 0.392 0.580 0.699 0.844 0.957
n-1d-M analysis No. 5 25 1.082 1.396 1.602 1.867 2.084
Oil 1.520
40 0.851 1.121 1.298 1.699
no. Designation CA CX C P
65 0.559 0.781 0.925 1.104 1.245
1 Venezuela: tin 1, fraction 7 13 21 66 90 0.339 0.538 0.665 0.814 0.932
2 No. 1, hydrogenated — 34 66 No. 6 25 1.404 1.700 1.882 2.122 2.292
3 Borneo: tin 2, fraction 2 9 55 36 40 1.129 1.390 1.555 1.755 1.912
4 Borneo: tin 2, fraction 10 35 34 31 65 0.772 0.997 1.138 1.306 1.436
5 No. 4, hydrogenated — 69 31 90 0.517 0.715 0.838 0.983 1.095
6 Mexico: tin 3, fraction 6 16 27 57 No. 7 25 0.531 0.717 0.835 0.980 1.094
7 Borneo: tin 4, fraction 7 33 22 45 40 0.380 0.549 0.657 0.787 0.887
8 Rumania: tin 5, fraction 5 15 22 63 65 0.187 0.338 0.432 0.542 0.630
9 Sumatra: tin 6, fraction 12 21 27 52 90 0.032 0.176 0.259 0.363 0.438
10 No. 9, hydrogenated — 48 52 1.017 1.171 1.290
No. 8 25 0.685 0.891
11 Sumatra: tin 7, fraction 11 12 15 73 0.961 1.067
40 0.518 0.704 0.822
12 Venezuela: tin 8, fraction 1 12 47 41 0.692 0.786
65 0.299 0.470 0.567
13 Iran: tin 9, fraction 3 12 26 62 0.485 0.573
90 0.129 0.283 0.378
14 Iran: tin 9, fraction 6 16 23 61 1.733 1.891
No. 9 25 1.099 1.358 1.523
15 Iran: tin 9, fraction 7 17 21 62 1.427 1.569
40 0.854 1.100 1.249
16 Iran: tin 9, fraction 8 18 21 61 1.049 1.165
65 0.572 0.772 0.898
17 Texas: tin 11, fraction 7 16 24 60 0.776 0.876
90 0.355 0.535 0.646
18 No. 17, hydrogenated — 40 60 1.673 1.841
Rijswijk: fraction 10 No. 10 25 1.037 1.295 1.465
19 12 24 64 1.390 1.527
20 Rijswijk: fraction 12 11 22 67 40 0.813 1.051 1.210
65 0.536 0.742 0.872 1.144
1.025
90 0.325 0.863
0.513 0.626 0.760
No. 11 40 0.818 1.023 1.148
The present mineral oils have been the subject of extensive in- 65 0.550 0.738 0.842 0.977 1 !O77
vestigations, of various kinds, carried out at the Laboratory for 90 0.345 0.518 0.619 0.736 0.826
No. 12 25 0.313 0.489 0.599 0.735 0.838
Chemical Technology of the Technological University of Delft
40 0.192 0.357 0.457 0.580 0.672
[10-12], As regards their origin and chemical composition they 0.269
65 0.018 0.179 0.373 0.456
may be considered as representative of the full range of natural 90 0.123 0.291
-0.114 0.037 0.219
mineral oils known so far. In addition, fully hydrogenated No. 13 25 0.355 0.527 0.633 0.762 0.860
samples—of course having a vanishing percentage CA—of four 40 0.226 0.386 0.486 0.604 0.696
65 0.050 0.206 0.294 0.400 0.480
of the natural fractions have been included.
90 -0.089 0.055 0.149 0.240 0.317
In Table 2 are listed the viscosity data, as a function of tem- 1.197 1.491
No. 14 25 0.840 1.059 1.363
perature and pressure, obtained in the present experiments. 40 0.651 0.978 1.126 1.244
0.848
65 0.408 0.583 0.692 0.819 0.920
90 0.216 0.380 0.478 0.595 0.685
1.435
Ill The Isobaric Viscosity-Temperature Relationship for a No. 15 25 1.044 1.284 1.621
40 1.176 1.344
0.825 1.043 1 '470
Given Liquid 0.851 0.994 1.099
65 0.545 0.736
0.612 0.738 0.830
Mathematical Description of the Isobars. A f e w 3'ears a g o , Cor- 90 0.334 0.506
nelissen and Waterman [13] introduced the following formula 4 No. 16 25 1.317 1.583
40 1.062 1.299 1 '450 L630
to describe the relationship, at atmospheric pressure, between 65 0.735 1.219 1.332
0.938 1.068
dynamic 5 viscosity 770 of liquids and absolute temperature T: 90 0.486 0.673 0.788 0.923 1.027
No. 17 25 1.132 1.382 1.556
40 0.896 1.130 1.270 1.438 L574
log Vo = + Bo, (1) 1.184
65 0.606 0.803 0.929 1.074
90 0.386 0.567 0.676 0.802 0.898
where Ao, Bo, and x denote constants characteristic of the liquid No. 18 25 1.053 1.304 1.460
40 0.832 1.066 1.208 L372 Loi4
concerned, the subscript " z e r o " referring to atmospheric pressure.
65 0.553 0.752 0.881 1.026 1.139
Equation (1) has been shown to possess a very wide applicability; 90 0.347 0.525 0.638 0.761 0.869
for widely varying liquids, at temperatures from about 20 to 150 No. 19 25 0.506 0.696 0.810 0.958 1.068
40 0.363 0.537 0.646 0.773 0.871
3 As defined in the Nomenclature, 1 atm = 1.0332 kgf/cm 2 = 65 0.165 0.330 0.422 0.537 0.622
14.696 psi. 90 0.011 0.166 0.256 0.358 0.438
' As stated in the Nomenclature, throughout this paper " l o g " de- No. 20 25 0.703 0.903 1.033 1.188 1.306
notes the common or Briggsian logarithm, logio. 40 0.522 0.711 0.835 0.974 1.080
6 In their original formula Cornelissen and Waterman used kine- 65 0.298 0.471 0.569 0.692 0.793
matic instead of dynamic viscosity. 90 0.125 0.285 0.380 0.498 0.576

602 / DECEMBER 1963 Transactions of the ASME

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 deg C, the deviations from the latter formula are mostly within
± 2 percent [10, 13]. It should be regarded as one of the most
valuable viscosity-temperature formulas proposed hitherto.
The exponent x usually has values between 1 and 5, the tem-
perature T being expressed in deg K. As within certain classes of
liquids the x-values do not vary so very much from one member to
another in such a class, it has been found permissible to use some
suitably chosen mean value for all members of a given class. For
instance, for mineral lubricating-oil fractions the x-values range
from about 3 to 4, but one may suitably take one common value,
x — 3.5. Consequently, their atmospheric viscosity-temperature
isobars are represented by straight lines, in one and the same log
77 — T~* diagram, by taking x = 3.5 throughout.
The present authors have found that the applicability of equa-
tion (1) is not at all restricted to atmospheric pressure. In fact,
it appears to hold almost equally well at higher pressures, gen-
erally up to at least 3000 atmospheres. Since it has, moreover,
been found that the exponent x may be taken to be independent
of pressure, at elevated pressure we arrive at:
log v = Y* + b>
where, unlike x, the constants A and B do depend on pressure,
however. This formula may be rewritten as:
V A
log - = Jz,
where log — B, the viscosity fj„, representing the viscosity at
T~1 = 0, that is, at T = ».
Equation (2a) has been checked by both the present measure-
ments on twenty mineral-oil fractions and reliable data from
literature, the latter chiefly referring to mineral oils and pure
hydrocarbons, but also including some silicones, fatty oils, and
alcohols [1, 8, and 14-19]. Many literature data cover ranges of
viscosity, temperature, and pressure that are more extensive than
those of the authors. For all these liquids equation (2a) proved
valid in a wide range of temperature and pressure. Usually, it
may be applied satisfactorily from about 20 to 150 deg C and up
to pressures of at least 3000 atm.
The Relationship Between the Family of Isobars Characterizing a Given
Liquid; a Complete Viscosity-Temperature Formula. All the isobars
of a given liquid conforming to equation (2a) are depicted by
straight lines in one single log rj — T~ x diagram. Now, an im-
portant feature emerged from this diagram in that all the isobars
proved to converge toward a common point, so that the family of
isobars characterizing a given liquid is a fan; in Fig. 1 this con-
vergence of isobars has been illustrated for oil no. 9. The point
of convergence, which is mathematically convenient, that is, for
casting relationships into an analytical form, is termed the
"viscosity-temperature pole," denoted by PT. It has a tem-
TEMPERATURE *C
Fig. 1 Convergence of isobars (oil no. 9 )
Journal of Basic Engineering
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perature coordinate —T P that is strongly negative, even below
zero absolute, and therefore physically insignificant. The vis-
cosity coordinate 77^ is roughly of the order of magnitude of 0.1
cP.
Accounting for this convergence, the following viscosity-tem-
perature formula can be derived that may be termed "complete"
in that it implicitly indicates the effect of pressure on the tem-
perature variation of viscosity by means of one pressure-de-
pendent constant,
Equation (3), in contrast to the basic equation (2a), does describe
the pressure effect implicitly by only one quantity, that is, i)„.
According to equation (3) the viscosity-temperature dependence
at any given value of T}„, and thus at any given pressure, is com-
pletely characterized by the three parameters, Tp, r/r, and x.
IV The Isothermal Viscosity-Pressure Relationship
(2a) for a Given Liquid
Mathematical Description of the Isotherms. A s long a g o as 1893,
Barus [20] proposed the following formula for describing the
isothermal viscosity-pressure dependence of liquids:
log — = ap, (4)
(26)
Vo
where 77 denotes dynamic viscosity at gauge pressure p, i]0 dynamic
viscosity at atmospheric pressure and at the same temperature.
The parameter a characterizes the liquid considered, and would
depend only on temperature, not on pressure.
Although formula (4) is extensively used, it is not generally
applicable and is valid to a reasonable approximation only in a
moderate pressure range. In fact, although according to formula
(4) log r] — p isotherms should be straight lines, generally they
are perceptibly curved. As a rule, these isotherms are more or
less concave toward the pressure axis. Only in comparatively few
cases have they been found to be slightly convex in that direction.
Further, at very high pressures, say, 5000 to 20,000 atm, log
17 — p isotherms that are initially either concave or straight
often show a point of inflection, such that they change into con-
vex ones [14, 21-23],
Because of the shortcomings of formula (4) several other iso-
thermal viscosity-pressure formulas have been proposed, which
usually contain two or more parameters, instead of Barus's
single one [1, 24]. However, it is evident that there is still a
great need for a simple viscosity-pressure formula of an even more
general validity.
Now, it is proposed to fill this gap by introducing the following
formula for describing the isothermal viscosity-pressure de-
pendence:
V
log - = ap", (5a)
where a and y denote parameters characteristic of the liquid con-
cerned. This formula permits describing not only concave and
straight, but also convex log rj — p isotherms; of course, it can-
not hold at pressures so high as to give rise to a point of inflec-
tion. Generally, it applies satisfactorily to all liquids under con-
sideration in the same range of temperature and pressure where
the somewhat analogous viscosity-temperature equation (2a), or
rather (26), is applicable, that is, from about 20 to 150 deg C
and up to pressures of at least 3000 atm. The correlational ac-
curacy reached with equation (5a) is also about equal to that of
equation (2a), which means that the deviations are mostly within
± 2 percent.
It has proved that for numerical evaluation there is not much
sense in retaining more than two decimal places in the values
used for the exponent y. For the various liquids tested these
DECEMBER 1963 / 6 0 3

Fig. 2 Convergence of isotherms (o : l no. 9 )
values ranged from about 0.75 to 1.10, most of them being be-
tween 0.90 and 1.00. Since, fortunately, the exponent y, in con-
trast to a, appears to be almost independent of temperature, all
the isotherms of a given liquid, just as the aforementioned isobars
(see Section III), can be represented by straight lines in one single
log 7] — p" diagram.
Formula (5a) can be rewritten as:
log log - = y log p + log a.
Thus, the isotherms of all liquids conforming to equation (5a) are
•n
stretched to straight lines in one single log log log p diagram.
VO
For any given liquid these lines will be parallel, in contrast to the
isotherms in a log i) — p" diagram where they will be shown to
form a fan.
The Relationship Between the Family of Isotherms Characterizing a
Given Liquid; a Complete Viscosity-Pressure Formula. Just
aforementioned isobars (see Section III), the isotherms of a given
liquid, as represented by straight lines in one single log 77 — p"
diagram with the y-value characteristic of that liquid, converge
toward a common point. Accordingly, this family of isotherms
also constitutes a fan; in Fig. 2 this convergence of isotherms has
been illustrated for oil no. 9. The point of convergence is termed
the "viscosity-pressure pole," denoted by Pp. It has a pressure
coordinate — pP that is strongly negative, like the former pole
temperature — TP, and a viscosity coordinate r)P. Remarkably
enough, this pressure pole viscosity 1iP shows the same value as
the temperature pole viscosity, the viscosity coordinate of the
viscosity-temperature pole.
From the convergence of isotherms the following viscosity-
pressure formula can be deduced that may be termed "complete"
in that it implicitly indicates the effect of temperature on the
pressure variation of viscosity, by means of one temperature-
dependent quantity,
log 1 = ( j l \ log — .
V» \PPJ VP
Equation (6a), in contrast to the basic equation (5a), does describe
the temperature effect implicitly by only one quantity, that is,
the atmospheric viscosity rjo. Thus, as long as equation (6a) holds,
the viscosity-pressure dependence at any given value of rjo, and
thus at any given temperature, is completely characterized by
the three parameters, pp, t)p, and y. But the latter equation is
not yet complete as a viscosity-temperature-pressure relation-
ship, which is now to be derived.
V The Complete Viscosity-Temperature-Pressure
Relationship for a Given Liquid
A strikingly close connection appears to exist between the con-
vergences of isobars and isotherms, as described in Sections III
604 / DECEMBER 1963
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and IV, respectively. In fact, it can be shown mathematically
that the convergence of the isobars of a given liquid involves the
convergence of its isotherms, and vice versa. More particularly,
the remarkable fact, already mentioned, that the viscosities of the
two viscosity poles possess the same value, is found to be also a
mathematical consequence of either convergence.
Owing to the occurrence of both convergences, the following
formula for the complete viscosity-temperature-pressure relation-
ship for any of the liquids under consideration, which expresses
the dynamic viscosity r/, explicitly in terms of temperature T, and
pressure p, can readily be derived:
log V = f x + CP~ + Dpy + B0, (7a)
where the constants C and D are defined in terms solely of A0, Bo,
pP, r)P, and y, as follows:
A0
C = (8)
PP"
and
Bp — log 7ip
D = (9)
PP"
According to equation (7a) six parameters, .lo, Bo, C, D, x, and y,
are needed for describing viscosity 17, as a function of temperature
(56)
T, and pressure p.
For the sake of simplicity, formula (7a) is rewritten in the
form:
Z = AoX + CXY + DY + Bo, (76)
where by definition:
Z = log TI, X = —, and Y = p».
as t h e
So, according to equation (76) four parameters, <4o, B 0 , C, and D,
suffice for defining Z as a function of X and Y, which contain the
remaining two parameters, x and y, respectively. If Z, X, and Y
are used as rectangular coordinate axes, the viscosity-temperature-
pressure relationship is represented by a curved surface, that is,
a hyperbolic paraboloid having two sets of straight generatrices.
Fig. 3 offers a schematic picture of that surface, as described
analytically by the viscosity-temperature-pressure relationship
(76).
For Y = constant, Z is linear in X. This means that the iso-
bars are straight, so that these must form one of the two sets of
straight generatrices. In fact, in the space model of Fig. 3, the
isobars are represented by the secants of the viscosity-tempera-
ture-pressure surface with planes parallel to the Z, X-plane. If
projected on the Z, A'-plane, as in Fig. 1, the isobars possess a
viscosity-temperature pole having —Z P and — X P as its coordi-
nates. Therefore, all the isobars intersect a particular straight
line which is parallel to the F-axis. This line (Z = —ZP, X =
— XP) is termed the "viscosity-temperature pole line."
(6 a)
For X = constant, Z is linear in Y, which means that the iso-
therms are also straight. Spatially, the isotherms, which consti-
tute the other set of straight generatrices, are represented by the
secants of the viscosity-temperature-pressure surface with planes
parallel to the Z, F-plane. Like the isobars,all the isotherms in-
tersect a certain straight line, which is parallel to the X-axis.
This line (Z = —ZP, Y = — YP) is termed the "viscosity-pressure
pole line."
Since the two pole lines intersect—in the "viscosity pole"
P(Z — —ZP, X = —XP, Y = — YP)—they are situated in the
same plane, the "viscosity pole plane" (Z = —ZP), which is
parallel to the X, F-plane.
Of either set of straight generatrices, that is, the isobars and the
isotherms, three are shown in Fig. 3. The isobars correspond to
the following F-values: Y = —YP, giving the viscosity-pressure
Transactions of the A S M E

" S C O S l 1*-PRESSURE ROLE
Fig. 3 Spatial representation of the viscosity-temperature-pressure relationship (7b)
pole line itself; Y = 0, giving the atmospheric isobar, with the
value Z = Z0\ and an arbitrary value Y = YI.
For Z = constant, a hyperbolic relationship between X and Y
results. The hyperbolic curves for X as a function of Y, using Z
as a parameter, are termed "isoviscids." In the above space
model these isoviscids are represented b y the secants of the
viscosity-temperature-pressure surface with planes parallel to
the X, F-plane. The three isoviscids depicted in Fig. 3 cor-
respond to the following ^-values: Z = —ZP, where the isoviscid
has degenerated into a pair of straight lines, that is, the two vis-
cosity pole lines; Z = 0; and Z = So, where the isoviscid inter-
sects the Z-axis ( X = 0, Y = 0).
It should be noted that there must be two limiting curves on
the viscosity-temperature-pressure surface, namely, one for
solidification (or, where the liquid ceases to be Newtonian) and
the other where the liquid starts to volatilize or decompose.
VI Correlation Between the Viscosity-Temperature-
Pressure Relationship of Lubricating Oils and Their
Chemical Constitution
Introduction
Studies have been made by various investigators to establish
correlations for predicting the viscosity-temperature-pressure
relationship of lubricating oils, especially mineral oils, either
through the sole use of quantities that are easily assessable at
atmospheric pressure, or directly from their chemical con-
stitution. 6
However, most of the many existing correlation methods based
on atmospheric quantities do not yield sufficiently accurate pre-
dictions. It seems that only two such prediction methods give
fairly good results throughout, namely, the method by Hartung
[26] which holds for various types of lubricating oils and, par-
ticularly, the method recently developed b y Kuss [7] for applica-
tion to mineral oils. Unfortunately, in both methods a com-
paratively great number of atmospheric quantities is needed and,
partly for this reason, both methods are rather cumbersome.
It would be even more desirable to have available some corre-
lation based on chemical constitution, since this may be deemed
more basic and more informative than the aforementioned quan-
tities. Of course, for correlating purposes "chemical constitution"
must be sufficiently characterized in convenient terms. Restrict-
ing ourselves to mineral oils, this can suitably be done in terms of
the statistical distribution of carbon atoms among aromatic ring,
naphthenic ring, and paraffinic chain molecules, that is, by the
carbon percentages, CA, CN, and Cp, respectively (see also Section
II). Extensive investigations, notably by D o w [25, 27] and
Kuss [7], have been carried out to develop such a correlation.
In practically all of these attempts "the viscosity-pressure co-
• Extensive reviews of correlation methods have been given by
Blok [24], Hersey and Hopkins [1], and Dow [25].
Journal of Basic Engineering
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V1SCCS1TY-TEVPERATURE KA£
efficient" a , in the isothermal relationship (4), has been em-
ployed for defining the viscosity-pressure dependence of a given
mineral oil at some standard reference temperature. Recently,
however, Kuss [7] has clearly demonstrated that no such correla-
tion with a can be achieved that is generally applicable to all
mineral oils. Moreover, from this fact he drew the rather sweep-
ing conclusion that characterization of the oil composition by
means of Waterman's method is not sufficient for determining the
viscosity-pressure behavior. Indeed, as will be elucidated by
what follows, the latter conclusion is overgeneralized and cannot
be upheld.
A Quantitative Correlation for Mineral Oils. F r o m the complete
viscosity-temperature formula or, preferably, the complete vis-
cosity-pressure formula, that is, formulas ( 3 ) and (6a), respec-
tively, simple diagrams can be derived which have proved par-
ticularly suitable for a systematic study of the correlation be-
tween, on the one hand, the temperature and pressure variation
of viscosity of the liquids concerned and, on the other hand, their
chemical constitution. This will be illustrated below by the re-
sults obtained along these lines with mineral oils.'
Once the three characteristic parameters, pP, t]P, and y, in the
formula:
log* = ( ^ Y l o g ^ (6a)
111 \PPJ VP
are known, the complete viscosity-temperature-pressure relation-
ship can be predicted solely from the atmospheric viscosity-
temperature relationship, that is, b y substituting atmospheric
viscosity 7j0, at the temperature to be considered for the given
mineral oil, into this formula. Now, each of these characteristic
parameters has been related to the carbon percentages 8 CA and
CN, in fact to (CA + 1.5C V ), the final equations reading:
500 \i/i/
pP = 500 (10)
fiA + 1.5 C„ + 27: 5 J '
114
log VP = ~ (11)
C A + 1.5 ClV + 27.5'
and
log (y - 0.890) = 0.00855 (CA + 1 . 5 C x ) - 1.930. (12)
For practical purposes, however, the numerical value of each of
' For reasons of space the relevant correlation method cannot be
given in this paper. For an outline of this method reference is made
to the Symposium paper (footnote 1), available from ASME Head-
quarters until April 1, 1963; furthermore, a more elaborate treatment
is to be presented elsewhere in due course.
8 Since the carbon percentages CA, CN, and Cp are mutually re-
lated—their sum being of necessity 100—only two of them need be
taken into consideration. The authors prefer to use the percentages
CA and CN, their sum, CR, representing the total percentage of carbon
atoms in ring structure.
DECEMBER 1963 / 6 0 5
 the three constants need not be calculated individually, as will Considering the width of the range covered by the twenty
now be shown. By substituting pP and i)P according to formulas mineral oils, also with regard to the wide differences in their
(10; and (11), respectively, into equation (6a), it is found that: chemical constitution, it may be expected that, in the above-
specified ranges of atmospheric viscosity, temperature, and pres-
sure, the present correlation may be applied satisfactorily also to
1 0 S l r ( i o ) V K0.002C, + 0.003C* reliable data given by previous investigators. It is noteworthy
that many of these data have been obtained on oils that are far
+ 0.055) log t]o + 0.228], (6b)
from being "natural," their character having been radically
Thus, only the exponent 9 y need be computed, by means of equa- modified, either by the use of additives, or by applying "rough"
chemical or physical treatments to the original base oils.
Table 3 Corresponding values of (CA + }.SCN) and y, according Unfortunately, only in a few investigations by others has
to e q u a t i o n ( 1 2 ) chemical constitution been specified sufficiently for verifying the
(Cx + 1.5C,v) (0.002C.1 + 0.003C,v + 0.055) y present correlation. But the data on the ten oils coded 31-G
0.0 0.055 0.90j through 40-G in the well-known A S M E Project [14] may be used
27.0 0.109 0.91 for additional evidence. Indeed, in the ranges of atmospheric
47.6 0.150 0.92 viscosity, temperature, and pressure for which this correlation
62.2 0.179 0.93 has been derived, it reproduced the latter data equally well as
73.5 0.202 0.94
0.221 those of the authors. In addition, in the few cases where it was
82.8 0.95
90.6 0.236 0.96 tried beyond these ranges, it still gave satisfactory results. It is
97.5 0.250 0.97 true that the relative errors increased, but at the same time the
103.3 0.262 0.98 viscosity variations involved were considerably greater.
108.8 0.273 0.99
113.7 0.282 1.00 B y means of further data on mineral oils of well-defined chemi-
118.0 0.291 1.01 cal constitution, that cover wider ranges of atmospheric viscosity,
122.2 0.299 1.02 temperature, and pressure than those of the authors, the ap-
plicability of the present correlation may perhaps be extended by
tion (12). For convenience, in Table 3 are listed, according to refining it further.
equation (12), the values of y from 0.90 up to 1.02, together with Summarizing, it is concluded that, in a range of temperatures
the corresponding values of ( C A + 1.5 CN), and also those of the and pressures that is representative of many lubrication problems,
quantity (0.002C A + 0.003C,V + 0.055). For a given (CA + the complete viscosity-temperature-pressure relationship of all
1.5 C A 0, the values of y and the quantity (0.002C A + 0.003CV the various kinds of both natural and hydrogenated mineral oils
+ 0.055) corresponding to the nearest ( C A + 1.5 C N ) value listed considered can be predicted to a good accuracy, if only their at-
in Table 3 should be employed. T o give an example, for oil no. 1, mospheric viscosity-temperature relationship and their chemical
with (C'A + 1.5 CN) = 44.5, it follows from this table that the constitution, as defined by CA and CN, be known.
values y = 0.92 and (0.002C A + 0.003C W + 0.055) = 0.150
should be used. Accordingly, for this particular mineral oil,
equation (66) takes the form: Acknowledgments
17 ( p \0 92 The authors are much indebted to the Management of the
Koninklijke/Shell-Laboratorium, Amsterdam, and to Mr. J. W .
M . Boelhouwer of that laboratory, for generous support in con-
B y means of equation (66) and Table 3 viscosities have been structing the falling-needle viscometer and for lending the timing
calculated for each of the twenty mineral-oil fractions tested, at device employed.
all temperatures and elevated pressures where experimental They also wish to express their sincere gratitude to Prof. H.
values were determined. The mean relative deviations between Blok, Professor of Mechanical Engineering, at the Technological
calculated (?}c»ic) and experimental ( 7 ; c s p ) viscosities, 100 (7/ c a i c — University of Delft, for his highly valuable aid in preparing the
»7exp)/7?e*i>, are as follows: manuscript of the present paper, and to Prof. G. A. M . Diepen,
Professor of General and Inorganic Chemistry, at the same Uni-
Gauge pressure in atm versity, for the use of his high-pressure equipment.
°C 300 500 750 950
25 1.4 2.2 3.5 4.9 References
40 1.2 1.4 2.1 3.1
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just as accurate as the values determined experimentally. 6 E. Kuss, "Physik der hochsten Drucke" (Physics of the High-
est Pressures), Chemie-Ingenieur-Technik, vol. 28, 1956, pp. 141-152.
The above correlation has been deduced by means of the
7 E. Kuss," Uber das Viskositats-Druckverhalten von Mineralo-
present data on twenty mineral oils, for values of log rj0 ranging len" (On the Viscosity-Pressure Behavior of Mineral Oils), Malerial-
from about —0.1 to 1.5, for temperatures from 25 to 90 deg C, priifung, vol. 2, I960, pp. 189-197.
and for pressures up to 1000 atm. 8 J. W. M. Boelhouwer and Miss L. H. Toneman, " T h e Vis-
cosity-Pressure Dependence of Some Organic Liquids," Proceedings
• As stated in Section IV, the values to be used for this exponent y of the Conference on Lubrication and Wear, London, England, 1957,
should be rounded off to two decimal places. pp. 214-218.

606 / DECEMBER 1963 Transactions of the A S M E

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10 H . I. Waterman, "Correlation Between Physical Constants
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