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The Non-Newtonian Characteristics of Lubricating

Oils
a
T. W. Selby
a
General Motors Technical Center , 30800 Mound Rd., Warren, Michigan
Published online: 08 Feb 2011.

To cite this article: T. W. Selby (1958) The Non-Newtonian Characteristics of Lubricating Oils, A S L E Transactions,
1:1, 68-81, DOI: 10.1080/05698195808972315

To link to this article: http://dx.doi.org/10.1080/05698195808972315

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 By T . W. SELBYl

Interest is growing concerning the influence of polymeric additives upon the viscosity of
mineral oils at extremes of temperature, pressure, and shear. In this paper the author discusses
the viscometry of mineral oils and mineral oil-polymer blends at moderate temperatures and
high shear and at low temperatures and low shear.
The non-Newtonian influences of two common polymeric additives, polyalkylmethacrylate
and polyisobutylene, are shown to vary considerably at low temperatures in their effects on a
common base oil. Shear dependence of polymer-containing oils at high shear rates is experi-
mentally indicated to reduce the viscosity of the blend to approximately that of the base oil.
Conclusions of practical interest are drawn from the experimental results.

Introduction At their cloud temperatures and below, mineral oils

FEW people outside of the petroleum industry fully frequently exhibit the non-Newtonian characteristics of
realize the volume of lubricant usage in America. In 1956, thixotropy. In contrast to Newtonian behavior, as shown in
automotive engines alone used almost 600 million gallons of Figs. 1band 1c, the viscosity is no longer constant under
engine oils. This volume included at least 150 million increasing shear .
gallons containing more than one hundred million pounds
of polymeric additives (1) which were added primarily
(0) (b)
to yield products having better viscosity-temperature REVERSIBLE
NEWTONIAN
characteristics, especially at low temperatures. It is sur- FLOW THIXOTROPY
prising, then, to find where such huge quantities of
lubricating oils are sold primarily on their viscometric
properties, that confusion seems to exist in both the applica-
Downloaded by [Virginia Tech Libraries] at 01:13 14 March 2015

tion and terminology of lubricating oil viscometry. This

>-
is well exemplified by the common practice today of de- l-
v;
termining the low-temperature viscosities of engine oils by §I-----(c~)----+---~~-------1 A
(d)
extrapolation of the 100° and 210°F viscosities using the

empirical Walther Equation (2). The errors in viscosity
and judgement that this practice has encouraged was dis-
cussed in a previous paper (3).
Moreover, the exact meaning of "temporary viscosity
loss", "permanent viscosity loss", "viscosity index", etc.,
as applied to lubricating oils at higher temperatures is
obscured by the complex viscometry these same lubricating
oils possess at low temperatures. Generally similar viscous
effects are too readily interpreted as having similar causes,
It is the author's purpose in writing this paper to
(a) define the various viscometric phenomena of lubricat-
ing oils at high and low temperatures,
(b) present the results of an investigation into the visco-
metric effects of polymeric additives on a mineral oil
at low temperatures and,
(c) discuss the significance of these observations in re-
gard to present usage of lubricating oils.
THE VISCOMETRY OF PURE MINERAL OILS
At temperatures above the cloud point most pure mineral
oils are Newtonian. That is, their viscosities remain constant
under increasing shear as shown in Fig. la.
Contributed by the ASLE Technical Committee on Lubrication
Fundamentals an d presented at the Annual M eeting of the
American Society of Lubrication Engineers held in Detroit,
Mich., April, 1957.
1 Senior Research E ngin eer, General Motors Technical Center,
30800 Mound Rd ., Warren, Michigan.
68
;;:'
> IRREVERSIBLE POLYMER
ORIE NTATION
B
"a
" "
C
B c
SHEAR RATE OR SHEAR STRESS
FIG. 1. Shear dependen ce of lubricating oils.
Reversible and irreversible thixotropy
Thixotropy is theoretically explained (4) by the progres-
sive breakdown or mastication of a flow-restrainingstruc-
ture which has formed in the liquid being analysed . The
higher the shear, the more extensive the structural break-
down and the lower the viscosity since the smaller structural
elements flow more readily than the larger elements.
If, at the temperature of analysis, the structure tends to
repair itself more quickly than the shear rate or shear stress
can be changed, then the curve shown in Fig. 1b results, in
which the decreasing shear curve falls upon the increasing
shear curve. However if, at the temperature of analysis, the
structure does not repair itself or is slow in rebuilding itself,
then the curves shown in 1c result . In this Figure the curve
A represents results obtained under increasing shear , B
is an arbitrary point at which the shear is reversed and,
under decreasing shear, the curve C represents a fluid in
 and, more specifically, fo llow t he pattern A --+ B --+ C .
Although the m ast icat ed st ructure of a pure miner al
oil does not usu ally g ive ev ide nce of re -forming while the
fluid is held at the temperature of ana lysis, if the oil is
heated to sufficiently high temperatures and then again
cooledto the temperature of original an alysis, the structure
will return. Generally, the degree of structure formation is
temperature and time dependent. D ecreasing temperature
or increasing time interval before viscom et ric analysis at a
given temperature favors the de velopment and strength, or
shear resistan ce, of the structure.
Polymers as pour-point depressants
One of th e firs t uses of polymeric additives was to in -
hibit the intern al structural formation or gelation of mineral
oils and thus lower the temperature at which the oil would
become rigid. These polymers ar e the so -c alled " pou r-
point depressants" .
THE VISCOMETRY OF OIL-POLYMER BLENDS
The viscous nature of a mineral oi l becomes q u ite co m -
plicated as might be expecte d , wh en polym eri c m at er ials
are blended with it . On e of the major reasons today for
using polymeric addit ives is to obtain a product wh ich has
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better viscosity-t emperature characterist ics (i. e. less change
of viscosity with t emperature) than a com para b le pure
mineral oil. Su ch polym eri c additi ves are called viscosity
index improvers from their effect on miner al oils classified
in the Dean and D avis (5) viscos ity index system.
Ablend of a viscosit y index im prover and a ba se mineral
oil, however , does not n ecessarily p rod u ce viscosity-
temperature charac teristics w h ich are p ro po rtio na te ly
better than th ose of the b ase oil. T o ex plain this apparent
contradiction in terms it will be pertinent to co ns ide r the
physico-chemi cal m echanism b y which visco sity index
improvers influence the visco us behavior of the base oil.
Mechanism of action of V.1. improvers
Viscosity or inte rnal flu id fri cti on may simply be attri-
buted to the d ifficu lty the m olecul es ex pe rience in ge tt ing
past one another during flow of t he fluid mass ; the greater
the difficulty, the h ighe r the viscosity. If now, in t his flow-
ing mass of sm aller m olecules, so me larger m ol e cules are
placed, the larger particles , which m ove less readily, will
restrain the progr ess of the smaller an d this restraint will
be manifested as an in crease in viscos ity. Moreov er, the
larger or more numer ou s the over sized m olecul es, the
greater their collecti ve imped ance and the hi gher the so lu -
tion viscosity.
The ability of a viscosity index im prover to alter the
riscosity-temper ature relati onship of t he base m in eral oil
resides in th e inherent prop erty of the polymer m olecul e in
solution to expan d with in cr easing temperature and thus to
proportionately exe rc ise m ore influence as the so lven t
vs cosity decreases (due to increasing temper ature). This
Goo d polym er so lvents are us ually composed of mole-
cu les si m ilar in prope rt ies to t he mo no mer lin ks wh ich form
the po lymer chain . S ince simi lar molec ules usu ally associ-
at e freely, the po lymer lin ks m igrate (u nde r the restraint of
their connected brother lin ks) into the solvent and as a
result the po lymer molecul e expands as in Fig. 2f. The
opposite behavior of the links occurs when the polymer is
dissolved in a relati vely po or solvent. That is, the macro-
m olecule contracts as in Figs 2a or 2b.
H YDRODYNAM IC VOLUME
~~
(d)
(f)
POOR _.~-------------- GOOD
SOLVENT
LOW - - - - - -TEMPERATURE
- ---=----=---=,..------- H IGH
F IG. 2. E xpansi on a n d contraction of a m acromolecule.
From a more fundamenta l standpoint, one may co ns id er
this ch ange of polymer shape in so lut ion a result of the par-
tition solu b ility of th e m acromolecule's links between
themsel ves and the true so lven t.
Now if the macro m olecular sha pe is dependent on the
efficac y of t he solvent, so too- if it is di ssol ved in a fair
so lvent- is the sha pe dep enden t u pon the temper ature of
the sys te m . F or as the temperature in creases, a so lven t
no rm all y b ecomes more effective and , as previou sl y sh own,
in a better so lve nt t he polymer m olecul e ex pa nds . Co nve rse -
. ly, as the temper ature decreases, the effe ct ive nes s of the
solvent decreas es and the macromolecule cont racts even to
the point of leavin g the solut ion as a pre cipitate.
Viscosity-temperature improvers
F ro m what has been sa id previously abo ut t he impedance
of lar ger mo lecu les in a sys tem of smaller m ol ecules it is
now pe rha ps eas ie r to under stand that, if the oi l is a fair
so lve nt, as t he temperature in cr eases, the b ase oil m olecules
tend to flow mo re read ily but, sim u ltaneo us ly , the swelling
m acromolecul es exe rt an in cr easing flow-restraining in -
fluence. The polymer thus rai ses the viscos ity of the
base oil proportionately more at higher tem perat u res than
at lowe r temperatures. The viscosity index im p ro ver
which can produ ce this result the author will term a
viscosity-te m pe ratu re improver.
Thickeners
If, how ever, a polym er is used for which the oil is a good
so lve nt at low temper atu res, then an in cr ease in temperature
has little effect on the physi cal configuration of the po lymer
and the influence of the polymer will be proportionat ely
 Br owni an bombardment of the su rro un di ng solvent mole-
cules tends to drive th e m acr om olecul e's sec tions somewha t
closer t o one anothe r since the in di vidu al links are n ot en -
t irely free to return the bombard m ent. T his results in a
slight con traction of the m olecu les an d a lessen ed visco us
influ en ce.) \ index of th e bl end over tha t of the b ase oil and yet produce
T he fact th at bo th th icken ers an d viscosity-tempera-
t ure improvers are classed as viscosity in dex im provers
is d ue to u se of the D ean an d Davis viscosity index
sys tem which was develop ed for pure m ine ral oils. This
system has ma ny sho rt -co mings when it is ap plied to
p olym er-containing oils, n ot th e least of w hich is an ina-
b ility to in dicate whether t he additive p rop orti on ately im -
p roves the viscosity- tem pe rature characteristics of the base
oil or not .
Differentiation of V-T improvers and thickeners
W hether a polym eri c additi ve is a viscosity- temperat ure
improver or a th ickener is q uite easy to det er mine by
measuring the viscosity cont ribution of the polym er at
100 ° an d 210°F. If the viscosity contribution (or specific
vis cosi ty, fL SP ) of t he additive at 210 °F exceeds its contri-
bution at 100 °F, t he additive is a V-T im prover. Thus ,
for a V- T im p rov er:
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In Table 1 it is quite eviden t th at a signi ficantly higher
viscosity index of a blend does not n ecessari ly m ean a pro-
porti on ately better viscos ity- te m pe ratu re relati on sh ip than
of t he base oil. In fact, as noted fr om the use of brigh t stock
it is possible to obtai n a slight in crease in the viscosity
a blend which is markedly p oorer in its relat ive viscosity-
temper ature propert ies as a lubricant.
It sho uld be noted th at since a give n polym eri c material
m ay have different solu bilities in differ ent solve nts, it is
conc eiva ble that in oils of widely different com pos ition a
viscosity-tem peratu re im prove r may b ecome a th ickener
and vice versa. This m ay also occu r wit h a ch ange in molecu-
lar weight of the polym er. Data presented recently by
H orowit z (6) indicat es that the more or less cons tant mo-
lecul ar weig ht PAM A and P In lub ricant addit ives retain
th eir resp ective viscosi ty-te m pe ratu re improver and
t hicken er cha racteristics whe n blended with a series of
oils covering a fairly wide range of compositio ns . As might
b e ex pec te d fr om the greate r solvent sens itivity of a V-T
improver, the PAMA showed th e g reates t degree of change
with oil composition , whe reas t he PIn as a thickener
showed little influence of oil com pos ition.
Polymer orientation (temporary viscosity loss)

fLSP(210 ) > 1
where fL SP
fL - fLo The presen ce of macromo lecules in solution in mineral
fL SP( lOO) fLo oils gives rise to another form of non- N ewt oni an flow which
in which fL SP is the specific viscosity is shown in F ig. ld. It is believed p roduced by the distor-
fL is t he blen d viscosity tion and subsequent alignment of t he macromolecules
fLo is t he base oil viscosity under high sh ear. T hese polymer mo lecu les, distort ed into
It is obvious that the more specific viscosity ratio exc eeds ellipsoids as in Fig. 3, are thought (7, 8) to be ro tated under
1, the be tter t he V-T improver. high shear with a va riab le angular velocity which is related
I n Table 1 the viscos ity in dex an d the vis cosity- to the rela t ive positio n of the ellipsoid 's major axis in the
tempe rature character istic of three blends were calculate d flowing solvent. The degree of orienta tion at a given shear
and compared . The base oil was t he same in all cases an d is also dep en den t on th e pol yme r's molecular weight and
t he bl ends were adjusted to give the same viscosity at 210 °F. configuration.

TABLE 1
Viscosity I ndex and V iscosity-Temp erature Characteristics of Three Blends.
I
Vi sc osity P.S P V-T

Bl end Vi sc osity
co n tr ib u tio n of ad d it ive

100eF
(p. - p.o) ( p. -
1"0
1"0
)
2 10°F
C hara cte ris t ic
P.S P21 0 V .L
lOO°F 2 10°F 2 10°F 100°F P.S PIOO

Cen ti stokes C en tisto kes

Base o il 3 5. 15 5.41 - - - - - 96

Base oil +
I.I 3 % P AMA 4 5.90 7.4 6 10.7 5 2 .50 0 .30 5 0 .379 1.239 130

Base oi l +
0 .8 4 % PIB 50 .05 7.47 14. 90 2 .06 0 .424 0 .381 0 .900 119

Base oi l + 10 %
b ri ght stoc k 56. 99 7.47 21. 84 2.06 0 .622 0 .38 1 0 .61 3 10 1
 decreases as distorti on an d o rie ntation in crease ; at high
shear (section C) t he viscosity tends to become cons tant
again as maximum distorti on an d orientation is reached. As
indicated, increasing and decreasing sh ear curves are super-
jacent.
STATIONARY SH E ARE D
FIG. 3. Distort ion of a p olym er co il und er sh ea r .
Experimental obse rv at ions by K laus and F en ske (9),
Georgi (10) and others , indicate that orie n tat ion of t he
polymer may account for loss of 80 % or m ore of the pol y-
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the viscosity decreases ex po ne ntially with time, an d re-
mo ving t he high shear conditi on does not res u lt in recovery
of the origina lly higher viscosity .
LOW TEMPERATURE ST UD Y OF POL Y MER-OIL
B LEN DS
Of th e effec t of t he polymeric ad ditives on the low t em -
perature viscosity of mi n er al oils, little see ms to be known
excep t that certain polym ers ma y act as " pou r p oint
depressants" .
T o fill this gap in the viscome t ry of lubri cat ing oils, the
aut ho r, being not su fficiently impressed by the arts of
ext ra po lat ion, h as cond uc te d a b rief stu dy of th e viscome t ric
inte rrelatio ns hips bet ween t wo common polym eri c addi-
ti ves an d a m in er al oil base stoc k at te m peratu res of 0°
and _ 10°F .
T he viscomete r used du ring the low-tem perature ana-
lysis is show n in Figs. 4 and S. It is called t he forced -ba ll
viscometer, and will be fu lly descri bed in a futu re article .
I t is suffi cient to say at this poi nt that viscom et ric det erm in a-
t ions ar e made by tim ing the fall of the ba ll through the
sam p le of liq u id held in the clos ed-end cylinder.

mer's contributed visco sity . De Hart (11 ) has ex pe rime ntally

contrasted a base oil and the base oil plus a polyalk yl-
methacrylate V-T I m p rover. At low shear rates of approxi-
mately 100 sec-lor less, the P A M A in cre ased the ba se oi l { C A BL E RELEASE
viscosity by 70% . H owever, in a journal bea ring at sh ear
rates of5 X 10 4 p.p to 10 7 [sec, the ba se oil and t he blend gav e U PPE R C O NT A CT
WEI GHT
almost identical res u lts viscometrically (as interp reted S WITCH

from friction m easuremen ts ) ; that is, approximate ly 100% PLATFOR M"",c:!':!'~~~~~~ral~

of the polym er 's viscosity contribu tion was lost at high l.-.r.-....--"''--- L ATC H
shear rates. At the conclusio n of the test t he base oil an d
the blend were reanalyse d at low shear rat es and th e vis-
cosities were found t o b e virtua lly t he same as before the
~;;;::T--l--.~'~'- LOW E R CO NTA CT
test, indicatin g that degra d ation of the polym er had not SWITC H
occurred at high shear rates .
Whether or n ot t he loss of bl end viscosity d ue to po lymer
orientation affects the load- carrying capacity of th e lubri-
cant in a jo urnal b eari ng is at present subj ect to debate.
O IL RES ER V O IR ~ _
Dubois et al. (12) h ave suggested that althou gh t he visco-
sity of a polym er-oil b lend depreciated during high sh ear,
the load-carrying ability of the fluid rem ain ed at th e level
that would be ex pe cte d b y its low-sh ear viscosity .
This viscom etric phenomenon of viscosity loss at h igh
shear has received the t erm " te m po ra ry viscosity loss "
since on removing th e high she ar condition s t he original
low-shear viscosity is immediately rec overed . H owever, the
observant read er will n ote the similar it y of the curves in
Figs. 1b and 1d ; a similari ty which st ems from funda-
mentally differ ent causes. Thus it is quite easy to confuse
reversible thixot ropy wi th orie ntation , esp ecially if they c7'-------.~
III II'-'==7i
occur in the sam e fluid, an d more so if th ey occur at the
same temperatu re. FIG . 4. Forced ba ll visco m ete r assembly.
 results of this stu dy.

Low-temperature base-oil analysis

The base oil was viscome trically ana lyse d at 0° and - 10°
an d the results are shown in Fi g. 6 . At O°F the oil is almo
Ne wton ian exce pt for slight ev ide nce of reversible thixo
t rop y at th e lower shea r rates wh e re a slight upturn of
curve throu gh th e points m ay be not ed. At - 10°F the o
shows irreversible thixotropy.

Low-temperature base-oil /diluent-oil blend analys

F IG. 5 . T est ap paratu s.
Method of study
Since th e polym eri c additives wer e com posed of a poly-
mer diss olved in a di lue nt mineral oil, it was n ecessary to
carry out th e study by ana lysing th e visco us contribution
of each compon ent of th e fina l blend-a " b len d reassembly"
techniqu e. Thus th e viscomet ri c ana lysis of th e base oil
was first ma de, followe d by th e ana lysis of th e base oil
plus the exact am ount of di lu ent oil in th e fin ishe d blend,
an d this in t u rn followe d by an ana lysis of th e fin ish ed
base-oi l/polymeric-a dd it ive bl end . Increasing and de -
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The arbit rary select ion of 10 and 20 % conce nt rat ions
eac h of th e polym eri c additives in b ase oil requ ire d a spe
cific conce nt rat ion of eac h diluent oil in th e se cond step
th e stu dy-the diluent-oil/base-oil ana lysis. The perti nen
d at a ar e show n in Table 3.
Viscome tric ana lysis of th e fou r di lu ent-oil/b ase-o
bl ends given in colum n 4 of T abl e ~3, at 0° an d - 10°F ar
shown in Fi gs. 7, 8 , 9 and 10. O nly slight visco metr
influe nce of th e diluent oils may be n oted w hen th e bas
oil curves of F ig. 6 are com pa red to th ese results. Thus th
base oil and the two di lue nt oils see m to be simi lar i
com posi tio n which was also indicate d by th eir viscometr
p rop erties in T abl e 2.

creas ing shear analyses wer e made on each sample to

de te rm ine the presenc e an d extent of gelat ion . Tem pe rat u re
control was 0 .05 °F of th e desired temperature.
Two polymeric add itiv es were used, one containing
polymethacrylat e (PAMA) and the other containing po ly-
isobu tylene (P I B). Som e viscome tric in format ion ob taine d
at 100 ° and 210°F from the base oil, dil uent oi ls, and blends
is gi ven in T ab le 2 .
T hese oil-polyme r b lends were n ot intended as engine
oil s, but were desi gn ed to provide inform at ion conce rning
the re lat ive viscous influence of PAMA and P IB on lub ri-
cating oils at low temperatures. However, as indicated in
Low-temperature base oil/polymeric-additive blend
analysis
In the t hird ste p of the study blends of the bas e oil plu
10 an d 20 % of bo th the po lymeric additives we re analyse
at 0° an d _ 10°F an d th e results shown in Figs. 11, 12, 1
an d 14 were obtained .
Conside ring the PAMA series first, it is apparent that th
po lymer has a definite visco us influe nce . At O°F and at
shear rate of 4000/sec, the polymer inc rease d the diluen
oil/base-oil b lend viscosity by about 50% at the 10% add

TABLE 2

Viscom etric Data on Oils and Blends.

Nomi na l /LS P X 100

Vi scosi ty, ce n t isto kes SAE ( % P ol yme r v is , V -T
O il o r bl end 100 °F 2 10°F OaF cla ss ificat ion co n t rib u t ion) V .1. . characteris tic
(E X T R A P) 100 °F 21 0 °F

Base o il :~ 3 . :~ 5.25 1834 96

PAM A d ilu ent o il

II 32. 5 5.34 108
PIB di luent oil 32.6 5.30 104

Base oil + 5.4 % PAMA ad d it ive 55 .2 9 .48 152G IOW-20 66 81 152 1.225
Base o il + 10 % P AMA ad d it ive 7G.6 13.5 1777 I OW- 40 130 158 146 1.21 5
Base o il + 20 % P AM A additive 164 .8 I 29 .3 30 10 20W-60 395 458 14 2 1.160

Base oi l + 10 % PIB ad d iti ve

I 74 .0 10. 75 3 270 20W-3 0 122 l OS 129 0.859
Base oi l + 20 % PIB additive 142.4 19 .32 56 90 20W-50 328 268 134 0 .81 7
I
 W
level. Although the ir reversible thixotropy of the bl end was u
repressed by the p olymer at the 10% le vel, it again b e- ~
I-
came evident at the 20% level. The d ecr easing viscous Ui
0 -
contribution of the P AMA fro m 0 0 to - 10°F is indi cative u
II)
5000 o 0 0 - 10 · F"
• •• o. o .o . o. o . c. o . o. ~ o 010 010 0
of the coiling o r con t ract ion of the mac ro molecu le w it h s
decreasing temperature m entioned ea rl ie r. It wo u ld see m
that the effect of the polyme r o n the thixotropy of the b ase
oil was to in crease the rate of stru ct u re re-fo rm ation, p os- o 1000 2000 3000 4000
SHEAR RATE,sec- 1
sibly by a su bstitution of p ol ymer coi ls fo r the b as e oi l's
original structural units (i.e ., w ax fibrils, etc.) . It is also
FIG. 8. Low temperature viscomet r ic analysis of base oil + 12. 6 %
PAMA diluent oil.
possible that so m e orien ta t ion of the p ol ymer molecu les
was occurring. 15 OOOr -- -- , -- ---,-- - - , -- - - - - - -----,
w
II)
o INC REA SING SH E A R
T AB L E 3 6o, • DE CRE A SIN G SHE AR
Crmeentration of Diluent Oil and Polymer in B ase Oil at 10 e INCR E A S ING AND DE CR EASI NG SH E AR
;:::
and 20% A dditive L ev el. f5 10 000
u

>--
Arb itr ary Result ant Result ant I-
Polymer V . I. imp rover diluent oil polymer Ui
I
! cone. in cone. in cone. In cone. In
8 5 000 -
0 0 0" 0
- IO' F
~
Polymer : V .I. imp rover base oil base oil base oil >
O' F
o " .. (1 0 " ", ,AI ,.

10 % 6. 3 % :3.7%
PAMA :l7 % 20 % 12.6 % 7.4 % o 10 0 0 20 0 0 3000 4000
SH E A R RATE , sec"!
10 % 8.0 % 2.0 % F IG. 9. Low temp erature viscorne t r ic analysis of base oil + 8%
PIB
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20 % 20 % 16.0 % 4.0 % PIB diluent oil.

15 OOO,---...----,--------,----,----~
T
15000r------.-----.---.,----~-----, oINCR E ASI N G SH E AR
,DE CREA S ING SH EA R
W
III w
(5 II)
n. 6 10 0 00 -
~ 10000 !!,
I-
w Z
o W
U
,;
.... >-- 5 0 0 0 0 0 00 - 10 ' F
iii ....
v; • • •• ::: ~ ~ i .0.0.0.0.0. 0. ~ O. 0
o 5 0 0 0 f- -10 OF
g •o. 0 .
0
•
0
.0.0. .? • i .0.0.0.0.0. o. ~ '- 0
0
u
II)
> s
OL-----,-,~--.l...---..L---..L---
10 0 0
0'"-- - -:-':-.,-----"..,-',-----'-- - - ' - - -- ---'
1000 2 000 3000 4 0 00
SHE AR RATE, s ec - 1 FIG . + 16 %
FIG. 6. Low temperatur e viseometrie analysis of base oil.

150 0 0'r-- - ---.----,,.-- - ..,.--- ---.- - - - 15 0 0 0 r-- - ---.-- ---,-- - .--- ---,--- - -
W • INCRE A SING SH E A R o INCR EASIN G SH EAR
III
• DECRE A SING SH E AR ~
~ 6c..
• DE CRE A SIN G SH E A R
;:::
~ 10 000 ;::: 10000f- -
U z.
W
,:- u
....
iii ~
o
~ ~ 5000 ·~"oooo 20 %
PA M A V. 1. IM PROV E R
s
5000. 0 -10 °F
. 0.° .~ .0 : : : .0 .0. 0. o . o .o. o . ~ '1 ~ 0
8 o O O ·" , . <a. o O C> O O O <:lo «l

O°F 5 Q ~ 0 • 0 ~Oo·/: ~~~~ ~•• I ; I ~~~~~ER 0

-- ---
--'B-A'SE'-OiL-:; -PAMA--6iC.UENf ---
O'--- - =' = - - =' = ----::-.l...---.l...-- -----J
10 0 0 2000 300 0 4000 10 0 0 2 000 3000 4 000
SHE A R RATE, s e c- ' SHEAR RATE, se c- '
Ftc. 7. Low temperature viseometrie analysis of base oil + 6 .3 % FIG. 11. Low temperature viscornet r ic analysis of base oil + 10 and
diluent oil. 20 % PAMA additive at OaF .
 20'/. PAM A V. 1. IM PROVE R
0. o. o. " o. 0. 0 ~ Qt 0 0

40000

35000
o 1000 2000 3000 4000
SHEAR RATE, sec- 1

F IG. 12. L o w te mperature vi scomet ri c a nalys is of b ase o il + 10 a n d

20 % PAMA ad d it ive a t - 10 °F. w 30000
(J)

~
15 0 0 0 , - -- --,- - --,--- - --,- ---,------, >=
z
IN CREASING SH E A R
w
o u
• DECREASI NG SHEAR 25000
>--
l-
v;
o
u
20 '/, PIS V. 1. IM PROV E R !::2 0

,,:-
> 20 000 0 •

.. 20'/. PIS V.I . IMPROVER

l-
v;
o
u
• c. 0

.. ..
~
> 15000 o
~
-""----- -------SA- --SE----O---------
IL PIS DILU ENT o
o
0 0

100 0 200 0
SHEA R R ATE .
3000
s e c"
4 000
10000 ..... .. . . .. .. 10'/. P IS V. J. IM PROV E R
o 0 0

°
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• • 0

F IG. 13 . L ow temperature visco metric a nalysi s of b ase o il + 1 and

20 % PIn ad d it ive a t O°F.
' - , SASE OIL+ P IS DILUENT
5000 ----- - --- ---------._----
The visco us influence of the PIB additive markedl y
exceeds that of the PA M A. At O°F, 10% PIE additive in-
creased t he viscosity of the diluent-oil /base- oil blend by
ab out 150% while 20% ad ditive incr eased the viscosity o 10 0 0 2000 3000 4000
SH EAR RATE, sec- t
b y 325% . At - 10°F , 10% PIE additive increased th e
bl end viscosity by again about 150 %, and, although at an F IG. 14 . L o w temperature vi sc omet r ic a n aly sis o f b ase oi l + 10 a
additive level of 20 % the viscome te r as set up for these 20 % additiv e at - 10 °F.
experiments was not cap ab le of yielding 4000 sec " , at
2300 sec - 1 the 20 % PIB additive increases the bl end vis-
cosity b y 26 0% . It will be n oted from th e abo ve dat a an d The most st riking effect of the PIB, however, is
from Table 2, columns 6 and 7, that the viscous cont rib u- thixotropic cont ribution it makes. At _ 10°F this effe
ti on of the p olymer to the blends is ap p rox imately the same becom es ext re me . The ob vious conclusion is that th e po
at 0° an d _ 10°F as it is at 100° and 210 °F, which in dicates m er itself is resp on sible for m ost of th e structural chara
that the p olymer coil is cont ract ing little, if at all. This in teri sti cs of the bl end at low t emperatures.
turn is ev iden ce that the oil bl end is a goo d solven t for the It might be mention ed that preliminary stu dies indica
polymer, even at low temperatures. that the differen ce in the effects of PAMA and PIB on t
The difference in the visco met ric effect of the PAM A and base oil cannot be attributed to differences in their P O
PIB polymers is even m ore interesting when it is noted in point depressin g ability.
Table 3 that the 20 % PIB add it ive has about the same
polymer concentration as the 10% PAMA additive. Thus,
Low remperature. engine cranking tests
since the ad ditiona l diluent oil effec t is negligible, at - 10°F ,
a 26 % in crease in the diluent-oil /b ase- oil viscosit y due to Con sidering t he marked vis cometric difference betwee
3. 7% PAM A (at 2300 jsec) m ay be contrast ed with the the effects of PAMA and PIB on a base oil, and noting t
260 % in cr ease due to 4.0% PIE (at 2300 jsec). It is quite these bl ends were not dis similar t o com me rcial rnuh
ev ide n t that a much lighter b ase oil wo uld have to be us ed g rade oils, it was of inter est t o see if engine cr anking te
with the PIB additive to make a bl end viscome t rically at low temper atures would qualitatively show the sam
eq u ivalen t to the PAM A additive bl end at an eq u ivalent viscome t ric differen ces. Blends of the base oil plus 2.0%
concentration of polymer. th e PAMA and PIB pol ymers wer e made up and crank
 OaF Cranking Tests on Base Oil Plus 2% PAMA or PIB
Polymer.
2.0 % PAMA 2. 0 % PIB
(5.4 % PAMA A d d it ive) ( 10 % PIE A dditi ve)
6 4.4 rpm 60 .2 rpm
65 .3 59. 5
70 .7 58 .7
62 .6 59.4
6 1.5 57 .0
65 .2 5 4 .7
66 .7 57.6
63 .2 58. 9
64 .8
Avera ge 64.8 Average 58. 2
It is apparent t hat the eng ine response agree s with the
viscometric data just presented. An ave rage differ ence of
6.6 rpm is found at an equ ivalen t pol ymer con cen trat ion
of 2.0% and it m ay be ant icipate d fr om the viscomet ric
data that the average difference in cranking sp eed will be
greater at a 4.0 0/ 0 eq u ivalen t concentration.
If one assumes that most of the viscous drag of the oil in
the cranking engine is found in the cra nksha ft be arings and
on the cylinder walls and further ass u me s clear an ces in these
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areas of 0.001 in ch , th en at 35 rpm the average shear rate
may be calcul at ed (10 ) t o b e ab out 25 00 jsec. Thus the
low-temperature viscome t ric dat a obta ine d fro m the forced-
ball viscometer wo u ld seem to em p hasize the importance
of polymer- con tribu ted viscosity and t hixotropy to engine
oils designed for low temperature se rvi ce.
CONCLUS I ONS
From the st andpoint of effect ive lubri cati on there are
several obser vations w hich should b e m ad e regarding the
non-Newtonian characterist ics of lubri cating oils. These
observations can be cove re d by a di scussion of four visco-
metric properties of a lubric ating oil each of which is
related to, or im portan t b ecause of, the presen ce of poly-
meric materials in the oil.
These four visco me tric p roperties are :
1. The viscosity-temperature relationship of the lubri-
cating oil.
2. The base oil visco sity .
3. The low temperature V IS CO U S con t ribut ion of the
polymer.
4. The shear degradation resistance of the polym er.
The importance of the viscosity-te m pe ra tu re relati on-
ship of the lubricating oil is obvious for oils op erating
through a wid e temper ature ra nge.
As for th e importance of the base oil viscosity ; in hydro-
dynamically lubricat ed bearings the load that m ay be su p -
ported is closely relat ed to the viscosity of t he lubricant.
Base oil viscosity shou ld then be come important when
macromolecular ori entati on m ark edl y reduces t he viscous
that a given p olym er will con tribu te to the load -carryin g
cap acity of the blend under the high shear conditions.
normally found in bearings. There is no question in the
author's mind that further in vestigation of vis cosity loss
an d load-carrying ab ilit y is n eed ed under conditions closely
app ro aching boundary lubrication.
R ega rding the import ance of the po lymer's visc ous contri-
bution at low t emperatures, this prop erty will affect the
manufacturer's cho ice of the base stock viscosity to b e used
with the p olym eric additive to produce a given g rade of oil.
F or example, as previously pointed out, it is evide n t that
P IB contributed much m ore low temperature viscosity to
a common b ase oil than an eq u ivalen t amount of PAMA;
therefore, in order t o prepare fini shed bl ends of equival ent
low temperature vis cosity, it is n ecessary to us e a much
lighter bas e stock with th e PIB. H owever, the use of less
and less viscous base st ock s to m ake, for in stance, engine
oils su itable to a low s hear classification syst em such as that
of th e SAE , must be caut ione d by the po ssibility of
increasing engine wear at high speeds, loads and tempera-
tures. Again, this caut ion points to the n eed of knowledge
concerning the load-carrying ab ilities of pol ymer-containing
oils .
Also the tenden cy of a polym er to produce a structure in
the lubricant at low temperatures must b e con sidere d since
b earing starva tio n may be the ultimat e result of difficulty
in pumping th e st ru ctu re -bo un d lubricant through a
lubricati on n et wo rk at low shear.
The importan ce of polym er degradati on is also quite
evide n t since it is p resumed that if there is suffic ien t re ason
for desiring th e be nefi ts of a p olym er ic ad dit ive, there is
su fficient reason to desire to ret ain these benefits.
S UMMARY
T he no n-Newtonian characteristics of p ure m ine ral oils
are main ly rest ricte d to temperatures b elow th eir cloud
points whe re thixotropy b ecomes evident.
Improvement of the viscosity-te m peratu re relationship
of oil s is obv iously one of the basic reasons for the us e of
polymers as additives. The effective ne ss of different poly-
meric materials varies with their physical and chemical
natures an d with t he solv ency an d other physical properties
of the b ase oil. F or clarit y it has b een found desirab le t o
divide pol ymeri c viscosity index impro ver ad d itives into
t wo g rou ps : the thickeners an d the viscosity- tem peratu re
improvers.
At t em peratures ab ove the cloud point under high and
increasing shear rates an d st res ses , the viscosity of the
polym er-containing oil tends to app roach t he viscosity of
t he base oil. This vis cosi ty loss may be due t o eithe r a dis-
tortion an d orie n tation of the mo lecules, wh ich is temporary,
or to shear degrad at ion, which is perm an ent.
At temperatures above and be low t he clo u d p oint, the
p olymer contributes sign ifican tly t o t he viscosity of the
blend. More im po rta ntly, the polym er may set up structures
 It has been found that different pol ymers may have
q uite di fferent effec ts on b ase oils at low t emperatures.
A n ex pe rimen tal metho d using the forced-ball viscome te r
has been applied which seems capable of separating and
d et erm in ing the viscomet ric prop erties of lubrication oil
com po nen ts at lo w t emperatu res.
One of the primar y purposes of V .I. improvers is t o
increas e the se rv iceab le t emperature range of engine oils
and au to m at ic tran smission fluids. It seems prudent, then,
that the viscom et ric n ature of thes e p ol ymer-containing
o ils an d fluids at low t emperatures sho u ld be in vestigated
ex pe rimen t ally in the compounding of such oils. This is
es pecially true since it has been p ointed out that informa-
ti on gat here d fr om the em pirical ext ra po lat ion of low shear
v iscome t ric data obtain ed in the Newton ian sta te of these
oi ls (su ch as b y the u se of the W alther Equation) is ge nerally
m eaningless w he n the fluid p ass es into the non- N ewtonian
state . This latter state men t ap plies to pure mineral oils as
we ll as p ol ymer- containing mineral oils .
There is littl e doubt that the visco me t ry of p olymer-
co n ta ini ng lubricating oils is co mplica te d b y the su pe r-
p osition of t he pol ym er's an d oil's non- N ewtonian beh avior.
H owever, the visc ometr ic di sse cti on t echnique used in this
stu dy has seem ingly clarified t he roles of the compo ne n ts
and it is felt that it can b e used successfu lly on othe r m ix-
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tu res of even greater complex it y.
Ce rtain ly, it is hoped that t h is stu dy w ill ass ist in se ttling
presen t d ifferences of opinion based on the profus ion an d
confus ion of physi cal facts .
DISCUS SION
H . H . H OROWITZ (Esso R esearch and E ngineering Company
Products R esearch Division, Linden, N ew Je rsey):
In reporting on low temperature viscosities of po lymer
thickened oi ls, lVlr. Selby d eserves t o b e commended fo r
d oin g wo rk in a di fficult fiel d where the re is ce rtainly a
dearth of so u nd data . H e also shou ld b e commended for
recognizing an d emphasizi ng t hat th e subject is complicated
by the existe nce of two d ifferent t yp es of n on- N ewtonian
behavio r-one of an ir reversible nature due to t he crysta l-
lization or ge lat ion of waxy m at erials in the oil and the ot he r
due to the ability of t he p olymer m olecules to align t hem-
selves in the d irection of t he shearing actio n .
H owever, it is usual to stimu late a d iscu ssion like this
one to st ress p oints of d ifference rather than the man y
p oints of ag reeme n t . It is the d ifferences t hat I wo u ld lik e
t o stress. F or on e, 1\1r. Se lby asserts that t he viscosity
co ntrib u te d by t he pol ym er di sappear s under t he she aring
con ditions prevailin g in a be ar in g, leaving the base oil to
carry t he lubri cation load. The implication is that this can
lead t o in ad equ at e lu brication and increased we ar w it h
po lymer oil s lik e t he new 1O\V- 30 multiviscosity gra de
o ils. We are h appy that M r. Se lby indicat ed t hat the true
2. C. W ALTHER; "Evaluating Lubricating Oils", Oel und K ah
vo l. I , 1933 , pp. 71-74 .
3 . G. K . M ALONE a nd T . W . SELBY; " Rela t io nsh ip of Lo
T em p erature C ra n ki ng Res istance to V iscos it y C hara cte r ist
of Multigrad e E ngine O ils", SAE Tran sact ions, vo l. 64 , 195
pp . 602-60 7.
4 . E . K . F ISCHER; Colloidal D isp ersion s, (Joh n Wile y a nd So
In c. , New Y o rk ), 1st ed., 19 50 . , c hap ter V .
5 . E . W . D EAN a n d G . H . B . D AVIS ; " V iscosit y Varia t ions
O ils w it h T emperatures ", C hem . &f M et all. E ng ng ., vo l. 3
19 29 , pp. 6 18- 169.
6 . H . H. H OROWITZ; " P red ict in g the Effects of T emp erature a
S hea r R ate on the Viscos it y of V.1. Improved L u brica nts
present ed at the ACS P et roleum Division Symposiu
"Ad d itives in Lub r icants " , A tla n tic C ity, New Jerse
Sep te m ber, 1956.
7 . F . BUECHE ; " I n flu en ce of R ate o f S hear o n the A p pa re
Vi scosit y o f A - D ilu te P ol ym er Solu t io ns , a n d B-Dul
P ol ym ers " , J . C hern , Phy s. , vo l. 2 2 , 19 54 , pp . 1570-1576.
8 . A. P ETERLIN ; "Effect of the V el ocit y G radient o n th e Intrins
V iscosit y of P ol ym e rs in Solu t io n ", J . P oly m er Sci., vol.
195 2, p. 62 I.
9 . E. E . K LAUS a n d M. R . F ENSKE ; " S o m e Viscosit y-Shea
C haracte ristics of Lubri cants ", Lubrication E ngineerin
vo l. II, 195 5, pp . 101 -1 08 .
10 . C. \ V. GEORGI; "Viscos it y C h a racteris tic s of Moto rs O il
H igh e r R ates of S hear" , P roc. Fo ur th IVorld P et roleu
Co ng ress, Secti on V I, 1955, pp. 2 11-22 I.
1 1. A . O . DE HART ; Gen e ral Motors Research S taff , person
corres p o ndence .'
12 . D UBOIS, O CVIRK a n d W EHE; N ation al A dviso ry Commissio
for A e ronautics, Contract No. NAW-6 197, Progress R epo
No . .9 (Rev ised ), Augu st, 1953 .
situatio n is no t q u ite so clear cu t . M illions of m iles o
au tomotive roa d test d ata have been obtained on the newe
typ e of lub rica nts. P ro perl y fo rm u lated, they are at leas
as good as co nventional m ineral lubricants of t he same vis
cosi ty grade in thei r we ar p roperties, includin g bear in
wea r, cy linder lin er wear, and wear of va lve train parts . I
ad d it ion, they have the ad de d advan tages o f reduce
octane re qu iremen t in crease, lower fu el con su m p ti on, an
also eas ier cold st art ing an d low oil consu m p tion combine
in the same oil.
I n regard to t he s pecific question of the bearing per
fo rmance of non- N ewtonian oils, we would like to em pha
size the importan ce of the wo rk of D uB ois, Ocvirk an
We he (1). This show ed that a bearing opera ted on a non
Newto ni an, pol ymer- thicken ed oil showed reduced fric
t ion as comp ared to a mineral oil of the same viscosity. Bu
the p olymer oil produced n o in creas e in the b earing'
eccen t ricity ratio . Other thin gs being eq ual, the hi g her th
eccen t ricity rat io the hi gher the wear. T hus, in effec t, wit
a po lymer oil it ap pears that yo u can have you r cake an
eat it. The reason for this is n ot clea r , but it m ay be tha
the polymer molecul es align themselves in the di recti on o
mot ion , thus re d uci ng the viscosity in that di rection and th
 Mr. de Hart' s p ri vat e co mmu n icat ion abou t his b earing
experiments, wh ich rep ortedly showe d that the pol ym er
contributes nothing to t he viscosity of t he base oil. Did the L ow T E:\IPEHATUHE PHOPEHTIES
bearings run at the same tem perature wit h t he polymer oil O F IOW- :30 O ILS
and the base oi l ? Sm all t em per ature differences woul d , of
A ll Oi ls C A . II CS at 2 10° F, C A . 70 CS at IOOO F
course, be reflected as differences in the apparen t vis cosi ties. A S T M ext ra po lated vi s./O°F. CA . 2400 CS
Was a control test ru n wi t h a m inera l oil whose viscosity
corresponded to that of the p ol ym er oi l so t ha t one cou ld P AMA PAMA
determine whether this p articul ar bearing was sen siti ve to V . I. I m p rover T yp e P Ill I T yp e I T yp e 2
changes in viscosity , o r whe t her fact o rs lik e dimi nution of Cra n kin g S peed
oil flow rate and in crease in film temperature made it at OO F (r p m) G6 I 57 49
insensitive to viscosity in creases ? It is hard for us to believe,
based on ou r own d at a an d d at a in the lit erature, t hat En gin e vis . at
complete loss in t he visco sity due to the pol ym er cou ld oc cur
O° F (CS ) l 20GO aoao 4 30 0

at only 50,000 reciprocal seco n ds shea r rat e. An d lastl y,

were eccentricit y ratio or m inimum clearan ce measu re -
ments made to d et erm in e w he t he r the d ecr ease in fr iction
was accompani ed b y any cha nges in b earing operation that
might lead to increased we ar? W e beli eve that m u ch more
work will have to be d one b efore the apparent con t ra dic tio ns
in theresults of Dubois an d of d e H art can be exp lained and
the entire situa t ion clar ified.
There is a com m en t to be m ad e regarding lVIr. Se lby's
assertion th at oils m ade with pol yalk ylm ethacrylat es
(PAMA) have better low-temperature p rop ert ies than oils
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1 U s ing engine as a v isco meter.
F IG. 15 . L ow temperature properties of I O\ V- 30 oils.
The PIB oils are, of cou rse , made using lighter base oils
b u t their vis cosi ty prop ert ies d o not suffer at all fro m this
at hi gh temper atures. Figure 16 , using data fr om a p re-
vio us publicat ion (~~) , shows that actual viscosity of a
PIB oil as a functi on of t emperature on an ASTlVI- Walther

chart. The line is not quite st raigh t, as it would be for a

made with polyisobut yl en e (P IB) . It should be pointed out
that this conclu sion is due en t ir ely to the m anner in w hich
Selby formul at ed hi s t est oils . H is bl ends contai ned eq ua l
additive or polym er con cen t rat ions in a sin gle base oil.
He disregard ed the differen t bl ending charac te ristics of the
polymers whi ch are due to t heir d iffering m olecul ar we ights
and the rate of cha nge of t hei r thi cken in g power w it h tem-
perature. His bl ends, ther efore, ra nged wide ly in t heir
viscosities at 100 ° and 2 10°F as well as at O°F an d were no t
comparable on an y reali st ic basis. In h is cold cra n king
tests, for exam ple, he co m pa red an SAE 10\V oil with a
2OWoil. Naturally, t he lO\V oil cran ked fast er.
Experience has s hown that o ils of eq ually good cold
cranking properties can b e m ad e wi th eit he r of the two typ es
of V.I. impr overs. In act ual p ract ice , formulators of lu b ri-
cating oils design thei r oils to meet a given viscosity at 100 °
and 210°F. This proced ure fixes th e q uantity of V. I. im -
prover requi red wh en base oils of va ry ing viscos ity but
equal viscosit y-tem pe ratu re q ua lity are used . The V .I.
improver ma nufacturers have adjusted t he p ro perties of
their additives so th at when t hey are used in thi s way the
optimum balance of polym er conce n t ra tion and shear
stability is ach ieved . (B y "shear sta b ility" we are referring
to the resistance of th e po lym er to perm anent d egradat ion
due to high shea r rates or tu rb ul en ce. )
Blends made in the above man ne r do not sho w t he low
temperature properties of lVI r. Selby's arb itrari ly chosen
combinations. For exa mple, in a 1956 SAE pap er (2), we
showed that lO\V -:10 oils m ad e wit h PI B are at least equ al
and in fact supe r ior to PAlVIA oils of t he same b lend vis -
cosities at 100° and 210°F. Data were ob ta ine d at 0 °, _ 10°,
,:-
>--
iii
o
u 10
'0!2
>
u
~ 5
::< oL------L--~L--___,."L,__-____='
w 50 10 0 150 2 10
z TE M PE RAT URE , OF
52
FIG . 16. V iscos ity tem p erature cha racte rist ics 10 W-30 oil 13 %
P Ill V I S /2 10° F = I U C S , V IS /l OO°F = 7 I CS .
mi neral oil, but cu rves very ge n t ly u p war d. Also shown are
t he viscosit y of t he base oil and the viscosity of the bl end at
500 ,000 d yne sJcm 2 , a high but typi cal engine shear stress .
Abou t 50% of t he viscosity d ue to t he po lymer is lost due
to shear at any tem perat ure. F igu re 17 shows a P A lVIA oil
blended to the same viscosity at 100 ° an d 210°F. The b ase
oil is seen to be much heavier in this case . At O°F t he po ly-
me r d oes very little t hicken ing; at 2 10°F it d oes abo u t two-
t hirds as much as t he pol yb uten e d id . H owever, the PAlVIA
suffers a greate r am ou n t of temporary viscos ity loss than
the P IB - about 80% at 500,000 d ynes /cm ''. This results in
very little temperature viscosity d ecrease at O°F where the
polymer does littl e thickening, but co ns ide ra ble temporary
viscosity loss at 210°F . In F ig. 18 the high shear viscosit ies
 U
~ work on the lubricant to e lim inate the effect of wax almo
t:
Ul
0 immediat ely. Wax in an oil has repeatedly b een shown
U
Ul
s ha ve n o effect on its cold starting properties, though it m
U affect oil pumpability. This is why the SAE has just
~
::;:
5
w 50 10 0
~ 0
'" TEMPER AT URE ,
FIG. 17 . V iscosity temp e ra ture c h a ract e r ist ics 10 W-3 0 o il 5 .5 %
P A MA V IS /2 10 °F = 10 .SC S , V IS / 100 °F = 6S CS .
!:l 5000r:-------,- - ---.--- ,---------,
'" 2 000 ::;"
~ 1000 :--.. ~
;::: 50 0 0- -,
z "- .....
U
W
~
10 0 e-,
>--
12 .9 ' I,P I B:>"",
>- 50
iii
o '"'"
u
Ul
'>
FI G. IS. H ig h Shear vi scosities o f I O\V - :~ o o ils , 500,000 d yn es /cme.
Downloaded by [Virginia Tech Libraries] at 01:13 14 March 2015
of t he two oils are see n to be q ui te comparabl e, with the
PIB sho wing if anyt hing, a slig ht ly lower viscosity at low
temperatures w hile m aintaining a slig ht ly higher viscos ity
at hi gh temperatures.
The above figu res also d emonstrate that contrar y to Mr.
Se lby's fea rs , petroleum re fine rs ar e well aware of the fact
that pol ymer oils d o not ex trapolate as straight lin es on the
A S T M -W alther chart. Co rre lat ions have been d evelop ed
to predict the engine visco sit ies of polymer oils at low tem-
p eratures and the kn owl ed ge thus ob taine d is being used to
fo rm u la te oils of ex cellen t cold st arting p roperties .
O n anot he r point, Mr. Se lby has used waxy base oils and
has pl otted the ap pa ren t viscosities of these waxy oils as
if they we re a fun cti on of the rate of shear. Actually, this
is on ly one of a lar ge number of va riables that control
viscosity. These are ex cellen tly di scussed in several papers
by S . P. J ones and hi s coll eagu es (4) . These au thors show
that the coo ling rat e is important as is the am ount of work
t hat had been d on e on the sample an d the rat e of she ar
under which the wo rk was done. They found it m ost us eful
to pl ot the vis cosity of a waxy oil as functi on of the amo u n t
of wo rk done on the oil. When a certain am ou n t of work
had b een d one, the waxy st ructu re was irreversibly de-
stroyed and the vis cos ity reach ed a minimum. The am ou n t
of work necess ar y was ext re me ly sm all, bein g m easured in
ergs pe r ern". (A n erg is abou t one forty millionth of a small
calorie.) What this m eans, we beli eve, is that if Selby had
alte re d his t est procedure eve n so slig htly as to include m ore
d ata points, hi s results would ha ve been different. If he
mobile engine under cold starting conditions does enoug
fiabl y p referred the A ST M ext ra po lation method f
150 2 10 classifying winter grade mineral oils rather than actual lo
'F temperature v iscosi ty m easurements on waxy oils. (F
polymer oils, of course, the A STM-Walther chart extra
polation is ad equate, as we ha ve explaine d .)
1\1 r . Se lby implies that hi s viscome te r m easurements a
applicable for pred icting the cold st arting chara cteristi
of lubricants because they ac h ieve shear rate s com parable
those encou n te re d during engine cranking. W e believe th
is su bje ct to question for two reasons - firs t of all, we ha
calculate d that the average she ar ra te acting on an oil durin
cold cran king is about 25 ,OOOjs ec rather than 2500jse
as given by M r. Se lby ; secon d ly, the force d ball viscomet
has n o provisi on for centering itself. This m eans that th
bulk of the oil go ing past the ball is probably at a m aximum
rat e of she ar of abo u t one -e ight h the value re port ed by M
Se lby. Se lby 's shear rat e was calcul at ed on the basis of
perfectly cen tered ball. O verall then , we beli eve M
Se lby 's m aximum she ar rate wa s probably about one
fifti eth of that p re vailing du ring cold cranking, to o Iow
shear rat e to show any temporar y viscosity loss due
polym er m olecule align me n t. W e would con clud e that th
forced ball visc ome te r appears to be an excellen t in strumen
for obtaining low she ar, low temperature viscos ities of wax
oils b u t not for predicting cold st arting.
Althou gh we have taken issu e with parts of Mr. Selby'
presentat ion, we wish to commend him for doing pioneerin
work in a difficult field.
R E F ERE N CES
1. D UBOIS, OCVIRK an d WE HE; Natio nal Ad visory Com mitt
for Aeronautics, Con t ract No . N Aw-6 197, P rogr ess Repar
No .9 (Revised) , August, 195 3. .
2. F ISCHL, H OROWITZ and T UTWILER ; SAE T ran sactions, vol. 6
1956, p . 609.
3 . H OROWITZ; ACS Symposium on A ddi tives in Lubricants, vol.
No. 4, p . 32, Septem ber, 1956 , A t la n t ic City.
4. J ONES a n d T YSON ; J. Coll. Sci., vol. 7 , 1952, p. 272 . G AVLIN
SWIRE a n d J ONES ; W right A ir D evelopment Cen ter Te chnu
R eport , No . 53- 11, Ap r il, 195 3 p. 9 4 .
J OSEPH E. F IELDS (M onsant o Chemical Comp any, Dayto
Ohio):
1. Th e rat io of sp. oisc. 210 0 P j l OOOP as an exp ression of ti
effec t of th e p olymer on the viscosity of th e oil blend system
T h is ratio is an important and us eful term. W e have use
this exp ressio n for ye ars in our laboratory and call it th
"efficiency" (E ) of the pol ymer. H orowitz (6) us es it as i
reciprocal and calls it 8 1 0 0 , In a given oil, or sol vent,
exp resses the magnitude of the v iscosity component th
polymer itself will lend to the oil between two temperatures
 although minor va riat ions in these fact ors d o not illustrate
this fact at first glan ce.
For a given solv ent polymers arrange themselves in three
groups: (a) E > 1, percentage vis cosity increase at 2lOoF is
greater than th at at lOO°F, (b) E approx. = I, viscosity in-
creases are perc entagewise approximatel y eq ua l at both
temperatures, and (c) E < 1, visc osit y in cr ease at lOO°F is
greater percentagewise than at 2 10°F.
We should not lose sight of the fact that polymers with
E < I, in a given oil, are still us eful materials. They are
more "efficient" than the use of bright stock to give an oi l
of higher viscosity in that t he b lend from a polymer of
E< I has better viscosity-temperature characteristics than
the bright stock blend. (Data Table 1.)
2. Variation of specific v iscosity with temperature
The author infer s that a polymer in a goo d so lven t might
actually contract upon heating . Much dat a ex ists which
indicate that this is so : K emp and Pet er s; B ell T elephone
Monograph B-1 361. Alfrey, Bartovics, an d Mark, J. Am .
Chem. Soc., vol 64, 1942, p . 1557 ; Fl or y, Principles of
Polymer Chemistry, Co rnell U n ive rs ity Press, 1953.
Alfrey et al. interpret the sol vent-temper ature effect on
specific viscosity ch ange as being due to changes in the
mean molecular sha pe of the polymer m olecul es (int ra-
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molecular agglom eration). A solution of long chain polymer
in an indiffer ent so lven t con tains p olymer molecules in all
different degre es of curling and ex tension but the con-
figuration of intermediate extension predominat es statisti -
cally. The mean value of any molecular property in such an
indifferent solven t is called the "unbiased sta t istical mean" .
IT the solvent is ene rge tically unfavorable (endothermic
process of solut ion- p oor so lvent), then the polymer seg-
ments attra ct eac h other and squeeze o ut the so lvent be -
tween them . T he cu rling forces (p olymer-polymer at-
traction between segments) predomi n ate, an d the properties
of the solution will be shifte d from the unbiased statist ical
mean (in this case to a lower viscosity).
On the oth er hand, if the so lvent is ene rge tically more
favorable th an the indifferent sol vent; then in so lution the
long chain mole cul e will be surrounded by a so lvated hull
which tends to prevent polymer-polym er contacts. In th is
case the un curled con fig urat ions will be favored, and the
mean value of any prop erty will represent a m ore extended
shape than th e unbi ased m ean (high vis cosi ty) .
If the concen t ration is hi gh, then unfavorable solvents
may lead to polymer-polymer contacts b etween different
polymer chains (inte r-m olecu lar agglomeration) and result
in gelation.
Raising th e temper ature of a polym er solution in an in -
different solven t should cause no change in the specific
viscosity. An in crease in t emperature of an unfavorable
(poor) solvent so lu t ion would promote a shift toward the
unbiased mean or an increase in sp ecific viscosity. In a
very good solven t the energetic factors favor the ex tende d
configuration and a temperature increase wo u ld lower the
schematically as follows :
GOoD
u SO(
Vl vF::i\I
s to-. . ..,)
0.: I N DIFF E RE NT SOLVENT(E = l)(U N BIASED
I~
MEAN)
l€. 7 \)
« SO\.." ~
w
a:
,?O~
u
z
'---- - - - - - - - - - - - - -
IN CRE ASING TE MP
F lor y presents a mathematical interpretation of chain
configuration and the thermodynamics of po lymer so lu-
tions in some detail. Neglecting the extensive mat hematical
deri vat ions of these re lationships the deductions are well
borne out by numerous observati ons on the temperature
coefficients of intrinsic viscosities.
F o x an d F LORY; J . A m . C hem, Soc., vo l. 7:l, 1951 , p . 19 09 .
J. Ph ys, C olloid. C hem., vo l, 53 , 194 9, p . 197.
3 . Thixotropy in low temperature viscosity measurements of
polymer-conta ining oils
The thixotropic effects noted by the author in these
particul ar oil blends at the temperatures noted are particu-
larly inter esting . H ow ever, the dat a d o not conclusivel y
sep ar at e the effect of wax an d p olymers at the low tem-
per atures n ot ed. The author n ot es that preliminary studies
indicate the difference in the effects of PAMA and PIB on
the base oil can not be attributed to differences in their
pour-point depressing ability. N o actual data to support
this statem en t is given. Similar data on the same oils de-
wax ed below - 10°F would be most interesting. Si mi la r
data should also be obtained with P IB in the .p resen ce of
po ur depressant . Such data would indica te whe ther t he
irrever sib le t hixotropy no te d with P I B was due m ainly to
the P IB or to wax in the oils . If in the cas e of dewaxed oi ls,
t he effect was still present, the irreversib le thixotropy would
be du e to orientation of P IB under shear stress an d should
be re versible, dependent on time, unless the tempera tures
in volved wer e below a definite transition point for t h is
particular system.
It is quite po ssible that a portion of the high viscosity
n ot ed in P IB -wax containing oils may b e due to a combined
effect of wa x solva te d with highly viscous PIB oil which is
g rea te r than the sum of the tw o alone. Thus the wax
st ru ctu re would be m or e diffi cult to reform after relaxation
of shear (in com parison with a PAMA oil ) because of the
higher visco sity of the PIB oil. It may further be expected
that the irreversible thixotropy would be absent with PAMA
since it d oes have pour depressing properties and since the
PAMA exists in highly coiled compact particles which
would not orient easily to give large viscosity decreases.
U pon shear relaxation the time required to retu rn to its
original state wo u ld be m uch smaller than fo r hi ghly
ori en ted P IB therefore resulting in reversible thixotropy.
 points.
To answer a specific question raised by Dr. F ields :
The statemen t that the high viscosity contributio n of the
PIB at low temperatu res can no t be attrib u te d to its lack of
p our-point depressing abi lity was indicat ed w hen 0.5%
of a P ~MA po~r depressant was adde d t o the 10 and 20 %
PIB- mlOer111 011 bl ends at - lOoF . T he res u lts of this
analysis is shown in Fig. 19 together wi th the previously
p resented ana lysis of the mi xture without the pour de-
pressant.
The curves are almost ide ntical indicating that t he pour
d epressant has n o effect on th e viscous influen ce of the
PIB polymer. This obse rv at ion ma y be easily exte n de d to
50000,- - - - . - - - - - - r - -- , --
• INCREASING SHEAR
• DECREASING SHEAR
45000
40000
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D r. H or owitz in his p rese n ta tio n certainly cannot
considered remiss in raisi ng p oin ts of discussion a
although several of t he poi nts are interest ing I sincere
ho pe t hat he has not m issed th e ma in ones.
T he first major point to be not ed is th at th e low tem
perature study was direct ed toward det ermining th e visc
me t ric influen ce of PAM A and PIB additives at 0° an
- 10°F . The simplest an d most in form ati ve me tho d
doing t his was to make a blen d of equal amounts of eac
additive with a m ineral oi l and th en to eva lua te th e relati
effects of th e polym eri c ad ditives so I selec ted what seeme
to be a commo n m iner al oil from a mid-continent crud
for the base oil. One of th e fac tors influencing my selectio
was th e information that this mineral oil or sim ilar produc
were u sed b y some oil m ark et ers for bl ending lOW·S
--,-----. m ulti -grade engine oils. Thus, it was an d is my op inio n th
r
th e effects of t he po lymeric addi tives 011 this particul ar bas
oil is typi cal of th eir effects on other oils at and be low the
resp ect ive cloud poi n ts .
Ce rtain ly it would see m th at this technique, in whic
one base oil is used to eva lua te th e effect of th e individua
polym ers, is preferable to va ryi ng both the viscosity of th
base stocks and the conce nt ration of the polymers. D
H orowitz, who has followed t he latter p ractice in t he work
he re fers to in his discussion , thus pl aces reliance on

comparison of one b ase-oil-polymer com bination with a

35000 ent irely differ ent com bina tion to in dicate the low tempera
ture superiority of th e PIB polym er. Cons ide ring the almos
infin ite number of base oils of differ ent viscosities and
w
VI
3 0 000 . viscosity indices th at can be used with varying conce ntn
tio ns of polymers, one can show almost any degree o
~ contrast be tween two different polymers in two differen
;::
z base oils.
w
u 25000 W hat D r. H orowitz has rea lly foun d is that 2 .6% PIB
...iii
>-- .. in a ligh t base oil will permit high er cra nking speeds in an
eng ine at O°F th an 2.1 % PAMA in a much heavier base o
0 20 "10 PI S V. I . IM PROV E R
u
+0 .5"10 PAMA POUR DEPRESSANT
and I have found th at 2.0 % PIB in a m od erately light bas
!Q 2 000 0
> oil causes lower cran king speeds at O°F th an 2.0% PAMA
in t he same base oil.
Our data do not conflic t; rat her it is quite obv ious tha
15 0 0 0 - the h ig her cranking speeds he records with PIB is com
pl et ely d ue to his cho ice of base stocks-a fac t which unfor
10 ·'. PIS V. 1. IMPROVER
. + 0 . 5 ·'. PAMA POUR
tunately he cou ld not observe from his data alone . More
10 0 0 0 .. . ..... DEPRESSANT ove r, th e p resent dat a strong ly indicates th at usin g equiva
lent concentratio ns of these po lymers in any given base
oil, the PIB will p roduce higher viscosities an d lowe
cranking speeds than the PAMA at low tem peratu res.
5 000 The fact that eq u ivalen t amoun ts of PAM A an d PIB in
given base oil will not p rod uce t he same viscosities at 100
and 2 10°F is of no conseque nc e in th e present dis cussion
since we are concerne d wit h t he low-temperature properties
1000 2000 3000 4000 of oils and th e effects of po lymers on t hese p rop erti es. It s
SHEAR RATE , sec- I presumed that an engine oil producer would be able to
select refin ed base oils capa b le of being made into multi
FIG . 19 . L ow temperature v iscornetr ic an a lvsi s of b ase oi l
+ 10 % an d 20 % PIE ad d it iv e at ~ l oaF . g rade eng ine oils us ing almost an y po lymeric viscosity
+
0. 5 % P AMA pour-point depressant in dex improver incl uding PAMA and PIE.
 in degree of thixotrop y and in resist ance to mast icat ion .
Without doubt this pol ymer ge lat ion has so me infl ue n ce on
cranking speed but a m ore important effec t mi ght be in its
influence on the low temperature oil su p ply to the bearings
and valve tr ain throu gh the oil ga lle ries w he re low shear
rates may be expecte d .
Having now at some length rediscu ssed the m ai n points
of the paper which I b eli eve sho u ld ans we r m any of Dr.
Horowitz's apparen t p oints of difference, I would lik e to
try briefly to answe r so me of the rest.
Dr. Horowitz questions both the technique an d the calcu-
lations applied to the force d -ball viscomete r.
Considering t he questions on techniq ue firs t, he is con-
cerned with the infl uence of a very d elicate waxy structure
on the viscom etric analysis . He states t hat the amoun t of
work necessar y to break up this structure co m p lete ly and
irreversibly is ve ry small. For the sak e of argument we will
assume that thi s wa xy gelation is important and ignore the
evidence of a m uch greater polymer ge lat ion .
As Dr. Horowitz knows, since his g rou p ha s co ns t ru cte d
a forced-ball visco mete r accord ing to our blueprints, the '
minimum platform load on the b all is abo u t 750 g rams
although we ha ve applied as little as 50 gram s b y using a
counter-balan ce. This b all, carrying a 50 g ra m load, must
fall through a di st ance of abou t 5.1 ern w hile forcin g 6 .5
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em3 of fluid throu gh an annulus with a tot al area of 0.11
em!. The work expen de d to move the 50 gra m b all through
2in. is 38,500 ergs and since eac h vo lu me ele me n t of fluid
must move throu gh the annulus, it is hard to imagine that
awaxy structure as fr agile as the one Dr. H orowitz refers to
would not be com p letely destroyed during the first fal l.
Thus, his suggestion that more data p oints wo u ld change
the analytical results is gro u n d less in the face of h is own
arguments about the de licacy of the wax stru ct u re.
However, if we consider the much m ore evide n t presence
of the PIB polymer gelat ion, his sugge st ion may have some
validity since the structure d efinitel y see ms to be shear
resistant. Certainly if his suggestion is va lid , such shear
resistance would also indicate cran king resistance. U n -
fortunately, in thi s case one cannot have hi s cake and eat it
too.
Considerin g the questions on shear rat e calcu lat ions-
original calcul ati on s for she ar rat e ass u me d that the ball
was centered du ring fall. However, sho rt ly thereaft er it was
experiment ally found that the b all was not cen tere d an d
this informat ion was pass ed on to the d iscusso r's company.
We have since found some experimental ev ide n ce that the
error introdu ced b y the b all 's eccen tricity is m ino r. The
usual ball and ro d assem b ly was rep laced b y a rigid rod an d
floating ball asse m b ly by wh ich according to Duffing's
calculations (1) the b all should seek a concentric position.
Preliminary results from this ass embly we re quite similar
tothose obtaine d from the previous ball and rod assembly.
M y mi nd is open to we ll- found ed p ersuasion, howev e r, and
Dr. Horowitz 's va lue may be a b et ter est im ate .
As to the q uestions on hig h spee d bear in g p erform an ce of
pol ym er-containing oils, I feel there is a need for kn owled ge
of t he wear characterist ics at high s peeds . A recent pap er b y
Savage an d Bowm an (2) wh ich lOW<30 engi ne oi ls have
shown better wear cha rac te rist ics than a 30 g ra de oil has
been reassuring.
A sta te m en t b y Dr. Horowitz that petroleum refiners are
aw ar e of the fact that pol ym er-containing o ils d o not extrapo-
late as straight lin es , should also be reassuring . But, in
view of rec ent knowledge of single, double, and multi-grade
oils from rep u table manufacturers whose respective p ro -
ducts ha ve OaF viscosit ies much in ex cess of SAE lim its
even at m oderately high shear, I am not as confident as Dr.
Horowitz seems to be that the inade q u acy of ext ra po lat ion
methods is gen er al kno wledge. I also feel that the so lution
of the problem is not to ap ply em p irical eq ua t ions of doubt-
ful valid ity at temperatures below the cloud point to correct
the low t emperature erro rs of the em p irica l W alther 's
eq uation . It would seem d efinitel y preferable to simply
m easure the viscos ities of oils at OaF at sufficien tly h igh
shear rates until fundamental rel at ionships are in vestigat ed
an d su ita b le theoretical eq uat ions develop ed .
Not to ignore the q uestio ns of Dr. H orowitz on M r.
d e H art's bearing in vestigations, b ut I fee l that since these
q uestions are m ostly con cerned wi t h t he t echniqu es of
ob tain ing the information rather than with m y applicati on
of the informati on , I can do n o bette r than refer him to Mr.
d e H art w ho has wo rke d in t his area for a number of years .
I sho uld lik e to con clude b y stating t hat I feel the use of
pol ym eri c m at eri als in mineral oi ls as V.l. improver,
d et ergents, etc. , is w ithout a doubt a p rogr essive step in oil
technology. I further feel t ha t su ch us age is one of the first
of m an y steps ye t to be taken to m eet the new and futu re
demands of lubricat ion .
However, somet hin g that is new does n ot m ean usually
something that is perfect, rather, it usuall y m eans something
that is perfectabl e an d I believe the future w ill show us
com b ina tions of mineral oils and m an-mad e molecules much
su pe rio r to an yt h ing we now kn ow if we ha ve ability to
con ti n ue the adv ant ages of ou r p rod uct s and co n cep ts and
th e co u rag e to b e di ssati sfied with t hei r liabilities .
R EFE R E N C E S
I . G . D UFFI:'>G; " M ess u n g d e r Z dhi gk eir d u rch G leichformige
K oac h s ia le 13e weg u n g ei n e r Kuge l in ei nem Kreiszylind er" ,
Z . ang eui, Math, II . Mech. , vol , I :~ , 1833 , p p. 366-373 .
2 . lVI. \ Y. SAVAGE a n d L. O. BOW:\IA:--: ; " R ad ioactive Trace r
Meas urem en ts o f E ngi n e Bea ri ng \V ea r " , Paper No. 869 .
Presented a t the SAE N a t io na l F u el s a nd Lubri cants Meetin g,
Tul sa , Ok la., Novem ber 8-9, 19 56.