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J. C. VLUGTER
Professor of Chemical Technology.
Viscosities of twenty well-defined, representative mineral-oil fractions have been de-
H. I. W A T E R M A N 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.
Late Professor of Chemical Technology,
deceased on February 3 , 1 9 6 1 . 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
Laboratory for Chemical Technology,
some silicones, fatty oils, and alcohols. Many literature data cover ranges of viscosity,
The Technological University of Delft,
Holland 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-
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-
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.
Lubrication Symposium, June 4-6, 1962, Miami Beach, Fla. II Experimental Part
Contributed by the Lubrication Division and presented at the
Winter Annual Meeting, New York, N. Y., November 25-30, 1962, Apart from a few minor technical details, the viscometer used
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 in the present investigations is identical with the falling-needle
received at ASME Headquarters, September 13, 1962. Paper No.
62—WA-178. 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
where, unlike x, the constants A and B do depend on pressure, Barus [20] proposed the following formula for describing the
however. This formula may be rewritten as: isothermal viscosity-pressure dependence of liquids:
where log — B, the viscosity fj„, representing the viscosity at where 77 denotes dynamic viscosity at gauge pressure p, i]0 dynamic
T~1 = 0, that is, at T = ». viscosity at atmospheric pressure and at the same temperature.
Equation (2a) has been checked by both the present measure- The parameter a characterizes the liquid considered, and would
ments on twenty mineral-oil fractions and reliable data from depend only on temperature, not on pressure.
literature, the latter chiefly referring to mineral oils and pure Although formula (4) is extensively used, it is not generally
hydrocarbons, but also including some silicones, fatty oils, and applicable and is valid to a reasonable approximation only in a
alcohols [1, 8, and 14-19]. Many literature data cover ranges of moderate pressure range. In fact, although according to formula
viscosity, temperature, and pressure that are more extensive than (4) log r] — p isotherms should be straight lines, generally they
those of the authors. For all these liquids equation (2a) proved are perceptibly curved. As a rule, these isotherms are more or
valid in a wide range of temperature and pressure. Usually, it less concave toward the pressure axis. Only in comparatively few
may be applied satisfactorily from about 20 to 150 deg C and up cases have they been found to be slightly convex in that direction.
to pressures of at least 3000 atm. Further, at very high pressures, say, 5000 to 20,000 atm, log
17 — p isotherms that are initially either concave or straight
The Relationship Between the Family of Isobars Characterizing a Given
often show a point of inflection, such that they change into con-
Liquid; a Complete Viscosity-Temperature Formula. All the isobars
vex ones [14, 21-23],
of a given liquid conforming to equation (2a) are depicted by
straight lines in one single log rj — T~ x diagram. Now, an im- Because of the shortcomings of formula (4) several other iso-
portant feature emerged from this diagram in that all the isobars thermal viscosity-pressure formulas have been proposed, which
proved to converge toward a common point, so that the family of usually contain two or more parameters, instead of Barus's
isobars characterizing a given liquid is a fan; in Fig. 1 this con- single one [1, 24]. However, it is evident that there is still a
vergence of isobars has been illustrated for oil no. 9. The point great need for a simple viscosity-pressure formula of an even more
of convergence, which is mathematically convenient, that is, for general validity.
casting relationships into an analytical form, is termed the Now, it is proposed to fill this gap by introducing the following
"viscosity-temperature pole," denoted by PT. It has a tem- formula for describing the isothermal viscosity-pressure de-
pendence:
TEMPERATURE *C
V
log - = ap", (5a)
where the constants C and D are defined in terms solely of A0, Bo,
Fig. 2 Convergence of isotherms (o : l no. 9 ) pP, r)P, and y, as follows:
A0
values ranged from about 0.75 to 1.10, most of them being be- C = (8)
PP"
tween 0.90 and 1.00. Since, fortunately, the exponent y, in con-
trast to a, appears to be almost independent of temperature, all and
the isotherms of a given liquid, just as the aforementioned isobars
(see Section III), can be represented by straight lines in one single Bp — log 7ip
D = (9)
log 7] — p" diagram. PP"
Formula (5a) can be rewritten as:
According to equation (7a) six parameters, .lo, Bo, C, D, x, and y,
are needed for describing viscosity 17, as a function of temperature
log log - = y log p + log a. (56)
T, and pressure p.
For the sake of simplicity, formula (7a) is rewritten in the
Thus, the isotherms of all liquids conforming to equation (5a) are
form:
•n
stretched to straight lines in one single log log log p diagram.
VO
Z = AoX + CXY + DY + Bo, (76)
For any given liquid these lines will be parallel, in contrast to the
where by definition:
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
Z = log TI, X = —, and Y = p».
Given Liquid; a Complete Viscosity-Pressure Formula. Just as t h e
aforementioned isobars (see Section III), the isotherms of a given So, according to equation (76) four parameters, <4o, B 0 , C, and D,
liquid, as represented by straight lines in one single log 77 — p" suffice for defining Z as a function of X and Y, which contain the
diagram with the y-value characteristic of that liquid, converge remaining two parameters, x and y, respectively. If Z, X, and Y
toward a common point. Accordingly, this family of isotherms are used as rectangular coordinate axes, the viscosity-temperature-
also constitutes a fan; in Fig. 2 this convergence of isotherms has pressure relationship is represented by a curved surface, that is,
been illustrated for oil no. 9. The point of convergence is termed a hyperbolic paraboloid having two sets of straight generatrices.
the "viscosity-pressure pole," denoted by Pp. It has a pressure Fig. 3 offers a schematic picture of that surface, as described
coordinate — pP that is strongly negative, like the former pole analytically by the viscosity-temperature-pressure relationship
temperature — TP, and a viscosity coordinate r)P. Remarkably (76).
enough, this pressure pole viscosity 1iP shows the same value as For Y = constant, Z is linear in X. This means that the iso-
the temperature pole viscosity, the viscosity coordinate of the bars are straight, so that these must form one of the two sets of
viscosity-temperature pole. straight generatrices. In fact, in the space model of Fig. 3, the
From the convergence of isotherms the following viscosity- isobars are represented by the secants of the viscosity-tempera-
pressure formula can be deduced that may be termed "complete" ture-pressure surface with planes parallel to the Z, X-plane. If
in that it implicitly indicates the effect of temperature on the projected on the Z, A'-plane, as in Fig. 1, the isobars possess a
pressure variation of viscosity, by means of one temperature- viscosity-temperature pole having —Z P and — X P as its coordi-
dependent quantity, 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."
log 1 = ( j l \ log — . (6 a)
V» \PPJ VP For X = constant, Z is linear in Y, which means that the iso-
therms are also straight. Spatially, the isotherms, which consti-
Equation (6a), in contrast to the basic equation (5a), does describe
tute the other set of straight generatrices, are represented by the
the temperature effect implicitly by only one quantity, that is,
secants of the viscosity-temperature-pressure surface with planes
the atmospheric viscosity rjo. Thus, as long as equation (6a) holds,
parallel to the Z, F-plane. Like the isobars,all the isotherms in-
the viscosity-pressure dependence at any given value of rjo, and
tersect a certain straight line, which is parallel to the X-axis.
thus at any given temperature, is completely characterized by
This line (Z = —ZP, Y = — YP) is termed the "viscosity-pressure
the three parameters, pp, t)p, and y. But the latter equation is
pole line."
not yet complete as a viscosity-temperature-pressure relation-
ship, which is now to be derived. 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
V The Complete Viscosity-Temperature-Pressure parallel to the X, F-plane.
Relationship for a Given Liquid Of either set of straight generatrices, that is, the isobars and the
A strikingly close connection appears to exist between the con- isotherms, three are shown in Fig. 3. The isobars correspond to
vergences of isobars and isotherms, as described in Sections III the following F-values: Y = —YP, giving the viscosity-pressure
pole line itself; Y = 0, giving the atmospheric isobar, with the efficient" a , in the isothermal relationship (4), has been em-
value Z = Z0\ and an arbitrary value Y = YI. ployed for defining the viscosity-pressure dependence of a given
For Z = constant, a hyperbolic relationship between X and Y mineral oil at some standard reference temperature. Recently,
results. The hyperbolic curves for X as a function of Y, using Z however, Kuss [7] has clearly demonstrated that no such correla-
as a parameter, are termed "isoviscids." In the above space tion with a can be achieved that is generally applicable to all
model these isoviscids are represented b y the secants of the mineral oils. Moreover, from this fact he drew the rather sweep-
viscosity-temperature-pressure surface with planes parallel to ing conclusion that characterization of the oil composition by
the X, F-plane. The three isoviscids depicted in Fig. 3 cor- means of Waterman's method is not sufficient for determining the
respond to the following ^-values: Z = —ZP, where the isoviscid viscosity-pressure behavior. Indeed, as will be elucidated by
has degenerated into a pair of straight lines, that is, the two vis- what follows, the latter conclusion is overgeneralized and cannot
cosity pole lines; Z = 0; and Z = So, where the isoviscid inter- be upheld.
sects the Z-axis ( X = 0, Y = 0). A Quantitative Correlation for Mineral Oils. F r o m the complete
It should be noted that there must be two limiting curves on viscosity-temperature formula or, preferably, the complete vis-
the viscosity-temperature-pressure surface, namely, one for cosity-pressure formula, that is, formulas ( 3 ) and (6a), respec-
solidification (or, where the liquid ceases to be Newtonian) and tively, simple diagrams can be derived which have proved par-
the other where the liquid starts to volatilize or decompose. 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
VI Correlation Between the Viscosity-Temperature- chemical constitution. This will be illustrated below by the re-
Pressure Relationship of Lubricating Oils and Their sults obtained along these lines with mineral oils.'
Chemical Constitution Once the three characteristic parameters, pP, t]P, and y, in the
Introduction formula:
Studies have been made by various investigators to establish
correlations for predicting the viscosity-temperature-pressure log* = ( ^ Y l o g ^ (6a)
111 \PPJ VP
relationship of lubricating oils, especially mineral oils, either
through the sole use of quantities that are easily assessable at are known, the complete viscosity-temperature-pressure relation-
atmospheric pressure, or directly from their chemical con- ship can be predicted solely from the atmospheric viscosity-
stitution. 6 temperature relationship, that is, b y substituting atmospheric
However, most of the many existing correlation methods based viscosity 7j0, at the temperature to be considered for the given
on atmospheric quantities do not yield sufficiently accurate pre- mineral oil, into this formula. Now, each of these characteristic
dictions. It seems that only two such prediction methods give parameters has been related to the carbon percentages 8 CA and
fairly good results throughout, namely, the method by Hartung CN, in fact to (CA + 1.5C V ), the final equations reading:
[26] which holds for various types of lubricating oils and, par-
500 \i/i/
ticularly, the method recently developed b y Kuss [7] for applica- pP = 500 (10)
tion to mineral oils. Unfortunately, in both methods a com- fiA + 1.5 C„ + 27: 5 J '
paratively great number of atmospheric quantities is needed and,
partly for this reason, both methods are rather cumbersome. 114
log VP = ~ (11)
It would be even more desirable to have available some corre- C A + 1.5 ClV + 27.5'
lation based on chemical constitution, since this may be deemed
and
more basic and more informative than the aforementioned quan-
tities. Of course, for correlating purposes "chemical constitution" log (y - 0.890) = 0.00855 (CA + 1 . 5 C x ) - 1.930. (12)
must be sufficiently characterized in convenient terms. Restrict-
ing ourselves to mineral oils, this can suitably be done in terms of For practical purposes, however, the numerical value of each of
the statistical distribution of carbon atoms among aromatic ring, ' For reasons of space the relevant correlation method cannot be
naphthenic ring, and paraffinic chain molecules, that is, by the given in this paper. For an outline of this method reference is made
carbon percentages, CA, CN, and Cp, respectively (see also Section to the Symposium paper (footnote 1), available from ASME Head-
quarters until April 1, 1963; furthermore, a more elaborate treatment
II). Extensive investigations, notably by D o w [25, 27] and is to be presented elsewhere in due course.
Kuss [7], have been carried out to develop such a correlation. 8 Since the carbon percentages CA, CN, and Cp are mutually re-
In practically all of these attempts "the viscosity-pressure co- lated—their sum being of necessity 100—only two of them need be
taken into consideration. The authors prefer to use the percentages
• Extensive reviews of correlation methods have been given by CA and CN, their sum, CR, representing the total percentage of carbon
Blok [24], Hersey and Hopkins [1], and Dow [25]. atoms in ring structure.