80 Narayanamurti, Some Aspeeis of the Rheology
Zeitschrfft
From the Forest Besea~vh Instit~de, Dehra Dun (India)
Some Aspects of t h e R h e o l o g y of A d h e s i v e s
By D. 5r arayarilra#~ lt;'ti
With 14 figures i7~ 27 details and 5 tables
P~heology plays an important role not
only in the application and use of wood but
in m a n y processes employed for improving
the properties of wood and thus help it in
its better utilization. A study of the rheo-
logical properties of wood under a wide
variety of conditions can be expected to
increase our fundamental knowledge in this
subject and indicate the part played by
cellulose, lignin and other constituents of
wood and also help to explain such pheno-
mena like creep, etc. In the kiln drying of
wood a knowledge of these properties will
help in devising the most appropriate
schedules to avoid collapse, etc. Similarly
in the t;ending of wood and other moulded
products, the manufacture of plywood,
compressed wood, compreg, the swelling of
wood under restraint (which has m a n y
practical applications) etc., as also in the
manufacture of wood plasties, and tem-
pering of hard boards rheologie~l pheno-
mena play an important part and help in
the release of stresses and thus assist in
improving the products.
In the field of adhesives, which have help-
ed us to extend the use and applications
of wood, rheological considerations play a
very important role. If the adhesive is too
thick it may be difficult to spread. If thin
it may penetrate and create starved joints.
Thus thixotropic behaviour in an adhesive
-- thin while brushing and viscous after-
w a r d s - may help. Also with correct vis-
cosity, chain segments may approach
quite closely the interface. Thus rheologicM
phenomena are to be taken into account in
the application, development of tack,
setting and behaviour of the hardened
adhesive. I t is therefore easy to realise the
importance of studies on the rheology of
adhesives and wood both from theoretical
as well as practical considerations.
During the past few years the author and
his collaborators have been engaged on
certain aspects of the subject and
this note deals with some of the results
obtained. These include : (a) The rheologieal
*) Vortrag, angemeldet ffir die 5. Tagung der
Deutschen Rheologisehert Gesellschaft in Frankfurt
a. M. v o m 17. - - 18. 5. 1955.
Kottoid-
and Wood*)
(Eingegangen
an, .30.Juni 1955)
changes taking place in adhesive systems,
including the setting time of adhesives, (b)
properties of adhesive gels and films and
(e) some rheological properties of wood.
1. Rheological changes in adhesive systems
a~d setti.~g time of adhesives.
tn these studies two different types of
viscometers were employed, viz. the
C o u t t e rotating type of viscometer and
the penetro-viseometer [vide B i k e r m a n n
(7)], the adhesives investigated being mainly
casein glue and a commercial variety of
resorcinol-formaldehyde adhesive. The vis-
cosity time curve of casein glue (vide fig. 1)
could be divided into five parts~ viz. a
comparatively flat portion where the vis-
cosity changes only slowly, a steep rising
portion indicating rapid increase in vis-
cosity, a sharp decline followed by a second
comparatively flat, portion and finally a
rising curve Ieading to gel formation. The
shape of the curve suggests that the casein
molecule gets unfolded slowly, to be follow-
ed by greater speed with i~lereased ~ds-
cosily, then breaks into smaller chains
(with consequent reduction in viscosity)
which later combine to a network. In the
early stages the systemis almost Newtonian
but it later becomes non-Newtonian with
a yield value. The influence of various
factors was studied with interesting results.
Soaking the casein was found to increase
Casein Glue Formulo Alkali 13 Pa,-L~.
Temp.:25 ~
- . I4
v) 1; o
10
8
J
Time in minufes
120 150 180 210
Fig. 1. Comparison of the viscosity values obtained
with the C o u e t t e and penetro-~-iscometers
Band 145 ] Narayanamurti, S o m e A s p e c t s of t h e t l h e o l o g y 8[
Heft 2 (1955) j

6s
450(,
4006
"/
-•300C 2 /
b 2ooc
c ./ , ~ P . , ?
u 1506 20 40 60 80./
1006 \ O~ / Blank
k / ~ (Cosein-SodiumHydroxide
50C WoterSystem)

Effect of different concentrotions /.25 250 375 500 575

of Furfurztdehyde in the beginning Time (Mins )
'7

30~

~ 2~ 20 40 60 80 20406080
2g 09 Flow Curve
Const~tencycurve
os o funktion of d / o 20% Furfut ~ldehy~ edded
/~ amount of / / 1,5
350rains flier mixing
~ ? . 2.0% FuN zraldehyde \ /.0._d&
udded125m,. aftermixing \
f , ~5dtFlow Curve
t
I02XC
50 100 200 300 4oo 5oo o 300 425 2oo 0 ~ 50 70 L'O
35O
-- ,'gme ( Nins)
Fig. 2. Effect of a d d i t i o n of f u r f u r a l d e h y d e on t h e rheological propert,ics of casein glue

the rate of unfolding of the sphero-mole-
cules. The ash content of the casein had a
pronounced effect on the viscosity, the
higher the ash content the higher being the
viscosity. B y de-fatting and de-ashing the
difference between different easeina could
almost be e 1minaret_ and the first m a x i m a
in the curve was found to be absent. W i t h
denaturing agents (e.g. urea) the rate of
change of viscosity on the addition of
alkali was found to be high. Agents like
dioxane which inhibit hydrogen bond for-
mation adversely affected the rate of
change of viscosity and yield values. The
t y p e of formula used also influenced the
viscosity ehanges~ the l i m e - fluoride and
lime-phosphate glues differing from the
casein -- sodium hydroxide and casein-lime-
sodium h y d r o x i d e glues in t h a t they
became thin at the end of their working
life (ndde N a r a y a n a m u r t i and S o d h i
(22)). Addition of various chemicals like
formaldehyde, etc. were found to affect the
course of viscosity changes and gel strength.
The influence of fm'furaldehyde can be seen
from figs. 2.
Finally the nature of the solid surface
was found to have a m a r k e d effect on the
changes, (vide fig. 3) being more rapid
with wood. B o t h the density and the natm'e
of the surface of the wood seem to affect
the viscosity changes with time. Diffusion,
adsorption and orientation of adhesive
molecules and chemical action m a y play a
part. In contrast to the casein glues a
commercial sample of resorcinol-formal-
dehyde adhesive was found to be almost
N e w t o n i a n in behaviour with almost no
yield value.
F o r following the course of the setting of
adhesives several methods are possible, the
most common m e t h o d being that of test, lug
joints prepared with the adhesives at
different periods. In this laboratory the
wire resistance strain gauge technique
originally proposed b y L f t t l e and P e p p e r
(13) has been used with good results for
studying the influence of psychrometric
conditions on the, setting time of animal
glue, casein glue, and urea formaldehyde
resin adhesive.
T h e a c t i v e g a u g e wa.s fixed t.o a piece of v e n e e r
(50 • 25 • 0.4 ram) w i t h Durofix ~ n d this w a s allowed
to set in a v a c u u m d e s i c c a t o r for a t least a week before
use. T h i s v e n e e r f o r m e d one o f t h e faces to be g l u e d ,
82 Naravanamurti,. Some Aspects of the Rheology I ZeitschriftK~176

Brass Rod Pinus Longifolia

600 32006

,~ 45O
{,9

300
2400C

16 000
J
150 / 8000
J i

0 120" 240" 360' 480' O" 120" 240"

' 3'60' 480'

Fig. 3. Variation of viscosity of casein glue with time with brass and Pinus longi/olia rods in the penetro-viscometer

the ogher being a piece of resin bonded plywood
250 m m long and 25 m m wide. The veneer piece was
fixed with the glue under investigation to the middle
of the plywood strip. One end of the plywood strip
was cl~mped, the other end being periodically lo~ded
with a 200 gin. weight.
The deflection method was employed for
noticing the change in resistance of the
gauge due to the setting of the glue. Some
of the results obtained are given in figs. 4.
The influence of humidity wus different
for different glues. While with casein ~nd
animal glues the shupe of the curves is
similar to the equilibrium moisture con-
tent curve, it is S-shaped with the urea
glue investigated. The drop in the curve
after the maximum obt,~ined, may pro-
bably be due to stress concentrations at the
ends of the joint and or crazing of the glue.
Temperatm'e as is to be expected accelerat-
ed setting. The heavier the wood is~ the
greater is generally the time tuken for
setting.
The strength and durability of glue
joints will depend on the mechanical con-
stunts (elastic moduli) of the adherend
and the adhesive and their changes with
psychrometric conditions [vide D i e t z and
G r i n s f e l d e r (8) a n d D e B r u y n e (14)]. It
will therefore be easily realised that the
investigation of the rheological properties
of adhesives in gel and film form should
yield valuable data.
The rigi4ity modulus of gelatin gels was
investigated by means of ~u apparatus
similar to that of W a r d et al (1954} and
the influence of various factors on the
rigidity modulus of gelatin gels can be seen
from figs. 5a, b~ e.*) In the concentration
range studied~ the rigidity varies as the
square of the co~lcentration. Fig. 6 shows
the infiucnce of concentration of sodium
chloride on rigidity. It is held that highly
purified gelatin may not gel. Work on
*) 5e is for casein.

525

Glue
5O0

45 456

~T35~~
400 406

350 356 CaseinGlue ,00j

I An~real Glue

\29% "~300
\\
.~.250 \ "~E 0 % oCj ~ 300,

~ 20P ~125o::
~ ~5o
t2%
~ 200I'
I00 too~ 150
, ~
50 too,~_
2O 25 30 35 40 45 50 4o ~ sol70 ao 90 30 40 50 6o 70 80 90
Temperature ~ Relative Humidity % Relative Humidity %

Fig. 4. Variation of setting time of casein glue with temperature and relative humidity
Band 145 l N a r a v a n a m u r t i , Some Aspects of the Rheology . 83
Heft 2 11956) J " "

12
II
32 I0
9
68
28
7
•
6
5
24
4
3
2
20
1

10 20 30 40 50 -~ 70 J,'. gO
16 Hours
Fig. 5e. Development of rigidity with time in casein
gels during setting
12

e ~§

o i lb ~ i0 ~5
Hours
Fig, 5a. The variation of the rigidity of gelatin gels
with setting time a t different conditions
I

25 Sod. Chloride %
Fig. 6. Influene3 of concentration o~" sodium ehloride
on rigidity of ~e]atin gels

25
oscillation impulse is t r a n s m i t t e d to the inertia disc a n d
the system set into torsional vibrations. Care is t a k e n
20 to have a very small angle of rotation, so t h a t we are
in the region of small deformation. The period of
G oscillation is given by
15
I/3//[//1 "t~

I0
/ and the rigidity is given by

5
/
0 .60 100 150 200
C2
Fig, 5b- The variation of the rigidity of gelatin gels
with concentration
electrodiMysed and pttrified gelatins is in
progress in this la.boratory.
F o r studying the rheologicM properties
of adhesive films the torsion p e n d u l u m
(vide N a r a y a n a m u r t i and G u p t a (15),
S c h m i e d e r and W o l f (25)) was employed.
A bund of adhesive fihn a b o u t 109 mm long, 12.5 mill
wide and 0.075 m m thick is clamped at, t.he top end
of the apparatus. The lower end of the b a n d carries
the inertia disc. Through slight rotation of the top clamp
250 Films of casein, gelatin and prolamin
have been investigated. The value of the
torsional modulus was found to increase
and the logarithmic decrement decreases
with the mass of the inertial disc. This is
possibly to be ascribed to the i m p r o v e d
orientation of the mieelles with loa.d. The
variation of the modulus of rigidity of the
fihn with t e m p e r a t u r e is shown b y fig. 7.
The extrapolated values of the torsion
modulus and logarithmic decrement to zero
load are shown in fig. 7. W i t h gelatin there
is a m a r k e d decrease in the torsionM modu-
lus from 18: to 90 ~ C and then a very slight
increase. The logarithmic decrement shows

2*
84 Narayanamurti, Some Aspects of the Rheology [ ZeitschriftK~176

35 O28
7C
Casein+ 20 % Glycerin
p
~E 30 ; 024 66
25 ' i }20
55

4C
-~" 15 ~.-_ / ..=, / 012 '~
AG
36

s ~"-'-"'~,..j'~'k~"~ " 004 26

~. 0 2b 4b 6o do fOo ~ iio 16o 10

Fig. 7. Influence of temperature on the modulus of
rigidity and logarithmic decrement in torsion. O e~sein
film, / ~ prolamin film, [] gelatin film, -- rigidity,
- - - Log. decrement
an oscillating character. The film contracted
b y a b o u t r % up to 90 ~ and then remained
constant. I t can be seen t h a t the rigidity
modulus of the d r y film is several times
t h a t of the gel.
W i t h casein the torsionM modulus gradu-
ally increases up to 100 ~ C mad then again
falls, the value at 150 ~ C being slightly less
than t h a t at 18 o C. H e r e also a slight con-
traction of the f i l m was obtained. It is
interesting to record t h a t S u l z b e r g e r (27)
noticed a slight increase in the shear
strength of casein g l u e d joints with tem-
perature. The influence of load with time
is shown in fig. 8.
Time in Hours
Fig. 8. Percentage increase in the value of the
modulus of rigidity with time on loading-casein
Prolamin film on the other h a n d showed
practically no change up to 60 ~C after which
it showed a rapid flow. There was ~ slight
increase in length after 80 ~ C. While the
modulus of rigidity of gelatin gels was im-
p r o v e d b y the addition of glycerine i t
lowered the torsional modulus of films
which are dry. Gelatin films had a higher
rigidity and lower damping capacity than
timbers; the other two films h~d similar
rigidity b u t higher damping capacity.
The tensile modulus and creep b e h a v i o u r
of these films have also been studied with

Fig. 9. Cope and Cope constant stress rheometer

Band 145 ] N a r a y a n a m u r t i , Some Aspeeis of the R h e o l o g v 85
Heft 2 [1956) J

~ y J
31r I .~ !:I /

o Y. ,

Load b

1 2 3 4 5 6' 7 O 9 10
Time in rain.
Time in rain.

.~
I
1,1" ~ . ,

0.5 b is io d
~ Load O

"~ o 0.25 o5 (175 N

Load
Time it,mir,.
Fig. 10. Creep-recovery era'yes for adhesive fihns with Ioad. (a) Casein fihn-insert stress:strain curve, ( b ea-
sein-20~ film-insert stress/strain curve, (e) casein-20~ urea fihn-insert stress:strain curve a n d
(d) stress:strain curve for gelatin fihu (top) a n d prolamin film (bottom)

interesting results. These st adies were done
with a C o p e a n d C o p e c o n s t a n t stress
rheometer (fig. 9) and the result, s are given
in Table t a n d fig. 10.
Table I
Film
Gelatfil (dried over P205) 13406
Gelatin at 20?o R.H. 13123
Prolamin prepared
at 25~C. (P20~) 5503
Prolamin prepared at. 20~ R.H. 3052
Prolamin prepared at 500~ P,.H. 3578
Casein, ordinary variety (P~O.~) 2958
Casein, high grade, 40~ R.H. 7338
Casein + 20~ glycerine --
Casein -}- 20~o urea
These studies are being continued.
2. Rheological properties of wood
Coming now to the theological properties
of wood the main properties studied were
modulus of elasticity and logarithmic decre-
m e n t in bending, torsional modnlus and
logarithmic decrement in torsion a n d the
influence of moisture content: extraetives~
impregnants, corrosive chemicals, tempera-
tur% etc. on these properties. For measuring
the modulus of elasticity and logarithmic
decrement in flexure the m e t h o d of free
vibrations similar to t.hose of K r u e g e r a n d
R o h l o f f (12), R o h l o f f a n d L a w r y n o -
w i e z (2~) and G r e e n h i l t (9) with slight
Tensile Tensile modification was employed [vide N a r a -
strength modulus y a n a m u r t i and J a i n (17)]. The vibrating
lbs./sq.in, lbs./sq.in. strip is rigidly fixed at an end. At the free
2.12.105
end a mirror is a t t a c h e d a n d an optical
2.12 - 10 ~ system is employed. The beana of l i g h t
from the mirror is condensed to a point by
the second lens on the photographic paper
a t t a c h e d to the recording drum which is
1.17.10 a
driven b y an electric motor at a c o n s t a n t
1.75.105 speed. For torsional properties an equip-
1.2~. 10 ~ merit similar to t h a t used for the adhesive
- - 1.48-16 ~
films as also the Cambridge torsional dam-
ping recorder: also vide N a r a , y a n g -
m u r t i a n d P r a s a . d (21); were employed.
Figs. !1 show some of the curves obtained 9
in flexurM vibrations. The t r e n d of the
vMues for elasticity in bending can be seen
from figs. 12. The logarithmic decrement
values were lower t h a n those reported by
B a r d u e c i a n d P a s q n M i n i (5), K r u e g e r
and R o h t o f f (12): etc. B u t the moisture
content of the pieces were also lower. The
86 Narayanamurti, Some Aspects of the Rheologv [ Kolioid-
~ [ Zeitschrift

ratio of the logarithmic decrement across

the grain of the wood to that along the
grain varied from 2 to 4. The value CO
, (logarithmic decrement x velocity of sound)
ir o oc
i ~ !~AA~ttA~.~,,^~^., ................. t i r e of species and direction of grain.
Similar results were f o u n d in torsion. The
ilVitI '"" logarithmic decrement in torsion was
a b o u t 1.5 to 4.5 times t h a t in flexure.
Moisture c o n t e n t and temperatm'e as is to
be expected lowered the moduli b u t in-
creased the value of the logarithmic decre-
Fig. 11. Damping of wood (Quercus sp) strip (along ment.
the grain)
Table II
240 X

220 Ed* Gd
Species. Ew G~
200
180 " Adina cordifolia 1.22 1.61
160 Mitragyna parvifolia 1.10 1.51
140 ' Pinus longifolia 1.48 1.95
120 " ~" Bombax malabaricum 1.21 1.26
100 *d:dry, w=wet.
80
60 V a r i o u s i m p r e g n a n t s w e r e also f o u n d t o
40 x
a f f e c t t h e s e p r o p e r t i e s . T h e i n f l u e n c e of
20. extractives was quite interesting. Tables
oI 02 o3 o~ 05 o$ o:7 0~ o9 ~o 7.1 z2 z3 ~ o s I I I , I V , V give s o m e r e s u l t s .
Sp.Gr
Table III
40 Effect of extraetives on modulus of rigidity,
35 in 109 dynes/ore~
30.
Wet We~ ether Difference
25, Species. control extracted ~o
E 20, X

15 x Adina cordifolia
(Haldu). 4.71 4.00 --15.00
5 ~,
Mitragyna parvifolia
o o) d2d30.4osasO2~d.91D U (Kaim). 2.67 1.89 - 29.21
Sp.Gr Pinus longifolia
(Chir). 4.96 4.09 -- 17.50
Fig. 12. Variation of modulus of elasticity of wood with Bombax malabaricum
specific gravity (Semul). -- --

0.8 ,o
0.7
O
Ao ?.7
[6
x

o2O, f'
6 O5
o,t'f i"< 7.4 xo
'13
01'~ 12
01 [1.15 0.7 U

o i2 3 4 0 i 2 3 4
Weeks Weeks
Fig. 13. Change of rigidity and logarithmic decrement of wood with time of soaking in acid and alkali
(spruce and teak)
Band2145
Heft (1956) l Narayanamurti, Some Aspects of the Rheology 87

the wood. Fig. 13 shows the effect of alkali

soaking on these properties with time.
I t will thus be seen t h a t this gives a simple
m e t h o d for following i m p r o v e m e n t or de-
grade in wood. The influence of loading on
/.3 the plastic flow of wood and resulting
changes in strength was studied with inter-
._~
0o /.2 esting results. B a r k a s (2) observed a 1 0 %
increase in the bending modulus. In some
tests done here strips of w e t Terminalia

I.I~/ bialata were loaded with a 1250 gin. weight

and the torsional modulus followed with
time. As can be seen from Fig. 14 the modu-
lus increases to as high a value as 50~
The same, when repeated with another
~.o ~ .2 .j ,~ species, showed an increase followed b y a
Days lowering after a few days. This is due to the
Fig. 14. Plastic flow in wood. Increase of torsional
leaching of the extractive in the wood.
modulus with time of loading A t t e m p t s have been m a d e to explain the
theological behaviour of wood on M a x w e l l
or other models. Cellulose has b o t h cry-
T a b l e IV
stalline and amorphous regions. I t can
Effect of extractives on modulus of rigidity therefore be considered as the equivalent
in 10~ dynes/era 2
of a spring and dash-pot in series. B a r k a s
~Vet Wet, Difference (2) considered in addition to springs and
Species control alcohol- ~o dash-pot a frictional element also necessary
benzene to explain the plasticity of wood. W o r k on
extracted the plasticisation of wood in the high
Adina cordifolia frequency field ( K o l l m a n n and N a r a -
(Haldu). 4.68 4.31 -- 8.0 yanamurti (19)) and the swelling and
Mitragyna parvifolia shrinkage of wood under restraint [N a r a-
(Kaim). 2.45 2.39 2.5 yanamurti and M a h a j a n (23)] have
Pinus longifolia
(Chir). 4.91 4.41 --10.0 been carried out. These and other work
Bombax malabaricum will form the subject of a future communi-
(Senml). -- - -- cation.

Table V Su, m m a r y
Effect of extractives on damping capacity in torsion After briefly mentioning the important role played
by rheology in the study and use of wood and adhesives,
Wet Wet ether Increase work done on the subject in the author's laboratory is
Species control extracted % briefly described.
From a study of the rheological changes taking place
Adina cordifolia
in casein glues with the help of a C o u e t t e viscometer
(Italdu). 0.0387 0.0416 7.50 a possible mechanism of gel formation is presented.
Mitrag)ma parvifolia The influence of various factors on gel formation were
(Kaim). 0.0517 0.0610 17.99 also studied with interesting results. ~'or following the
Pinus longifolia course of setting of adhesives the method using tile
(Chir). 0.0437 0.0741 69.51 wire resistance strain gauge was employed and the
influence of temperature and humidity on the setting
The vibrational m e t h o d s have also been time investigated.
v e r y useful in following changes in wood The rigidity modulus of gelatin gels measured with
caused b y decay, action of corrosive chemi- a S a u n d e r s and W a r d apparatus was found to
vary as the square of the concentration. Sodium
cals, etc. F u n g a l decay was found to lower chloride increased the rigidity.
the elastic modulus and increase the loga- t~heological properties of adhesive films of gelatin,
rithmic decrement and this could be detec- casein and prolamin were studied under a wide variety
t e d in a short period ( N a r a y a n a m u r t i of conditions with the torsion pendulum and the
and J a i n (4, 18)). B u t it was noticed t h a t interesting results reported.
in the v e r y early stages there is a slight Interesting results were also obtained on the rheo-
logical properties of wood and the influence of extrae-
increase in the modulus. If this is confirmed tires, acids, alkali, etc. on such properties. Finally
it m a y be due to the release of stresses in plastic flow in wood with loading was investigated.
88 Boyer, Viscosities of Extremely Dilute Polystyrene.
Zusammen]assung
Nach kurzer Skizzierung der wiehtigen Rolle, die
die Rheologie im Studium und Gebrauch yon Holz
und Leim spielt, folgt eine kurze zusammenfassende
Wiedergabe yon Arbeiten aus dem Laboratorium des
Autors.
Aus Untersuchungen fiber die Anderungen im rheo-
logisehen VerhMten yon Kasein-Leimen mit Hilfe eines
Couette-Viskosimeters wird ein Meehanismus der
Gel-Bildung vorgeschlagen. Der Einflug verschie-
denster Faktoren auf diese Gel-Bildung wurde ebenso
mit interessanten Ergebnissen studiert. Zum Verfolgen
des Erstarrens der Klebstoffe wurde eine Widerstands-
dr~htwaage gebraucht und hiermit der EinfluB yon
Temperatur und Feuehtigkeit auf die Erstarrungszeit
gemessen.
Der Festigkeitsmodul yon Gelatine-Gelen, unter-
sucht mit einer Saunders- und Ward-Apparatur,
variiert mit dem Quadrat der Konzentration, NaCt
erhSht die Festigkeit.
Rheologische Eigenschaff.en yon Klebstoff-Filmen
aus Gelatine-K_asein und Prola.min wurden bei weft
wriierten Bedingungen mit Hilfe des Torsionspendels
untersueht und dabei interessante Ergebnisse gefunden.
Interessante Resultate ergaben sich ferner fftr die
rheologischen Eigensehaften yon Holz und den Einflul]
yon Quelhnitteln, Sgm'en und Alkali u.a. auf diese.
SehlieBlich wurde das plastisehe Fliel]eu yon Holz
bei Belastung gemessen.
Re/erences
l) A r o r a , Unpublished experiments.
2) B a r k a s , W. W., F. P. R. L. Reports 194~, 1947.
3) Ibid, In ,,Mechanical properties of wood and
paper". (Amsterdam 1953).
4) Ibid, In ,,Some recent developments in Rheology"
(New York 1950).
5) B a r d u c c i , I and P a s q u a l i n i , Nuovo Chim.
5, 416 (1948).
From the Dow Chemical Company, Midland, Michigan, USA.
Viscosities of Extremely Dilute Polystyrene Solutions*)
By R.F. Boyer
With 3/igure,s
I t was f o u n d (1) as shown in Fig. 1 ~hat
a plot of ~]~p/efor a polystyrene fraction
(i~:/~ = 250,000) in toluene decreases ap-
p r o x i m a t e l y linearly as the concentration
is lowered from 1.0 to 0.1 g./100 ml. and
t h e n increases to a m a x i m u m at 0.001 g./
100 ml. as the concentration is lowered still
further. This increase in ~]~p~,'cwith dilution
was first ascribed to the expansion of poly-
mer coils as well as to the disentangling of
entire p o l y m e r molecules once the con-
*) Referat des Vortrages, gehalten auf der 5. Ta-
gung der Deutschen Rheologischen Gesellschaft in
Frankfurt a. M. vom 17. -- 18. 5. 1955.
. Solutions [ ZeitschriftK~176
6) C h o p r a , J. L., M. Se. thesis (Punjab University).
7) B i k e r m a n n , J. J., J. Coll. Sei.
8) I ) i e t z , A. G. H., H. G r i n s f e l d e r and E . R e i s s -
n e t , Trans. Amer. Soc. Mech. Eng. 68, 329 (1946).
9) G r e e n h i l l , W.L., J. Coun-C-Sci. Ind. Res.
Austr..5, 146 (1942).
10) G u p t a , l:t. C., unpublished work.
11) H e a r m o n , R. F. S., In ,,Mechanical properties
of wood and paper" (Amsterdam 19,53).
12 K r u e g e r , F. ~nd ~. R o h l o f f , Z. Phys. 110,
58 (1938).
13 L i t t l e , G. E. and K. W. P e p p e r , (Jhem.Res.
Lab. Rep. 19~3.
14 M y l o n a s , C. and N. A. De B r n y n e , ,,Adhesion
and Adhesives", p. 91 (Amsterdam 1951).
15 N a r a y a n a m u r t i , D. andR. C. Gupta,Comp.
Wood l, 133 (1954); Ind. For. Leakel. No. ll4.
16 N a r a y a n a m u r t i , D. and B. K. H a n d a , Kol-
loid-Z. 135, 140 (1954).
17 N a r a y a n a m u r t i , D. mid N. C. J a i n , J. Aero.
Soc. Ind. 3, 79 (1951).
18) Ibid, Comp. Wood. 1 (1954).
19) N a r a y a n a m u r t i , D. and F. K o l l m a n n ,
Holz als Roh- und Werkstoff, 1955, (in the press).
20) N a r a y , ~ n a m u r t i , D. and R. P. M a t h u r , 3.
Appl. Sei. Res. 195,5, (in the press).
21) N a r a y a n a m u r t i , D. and B.N. P r a s a d , J.
Aero. Soc. Ind. 1 (3) 30 (194:9).
22) N a r a y a n a m u r t i , D. and J. S. Sodhi, Kol-
loid-Z. 138, 68 (1954).
23) N a r a y ~ n a m u r t i , D. and P. C. M a h a j a n , (in
the press.).
24) R o h l o f f , M. and N. L a w r y n o w i e z , Z. Tech.
Phys. 32, l l 0 (1941).
25) S e h m i e d e r and K. Wolf, Kolloid-Z. 127, 65
(1952).
26) S a u n d e r s , P. R. and A. G. W a r d , Proe. 2rot
Inc. Cong. Rheol. (expend 1954).
27) S u l z b e r g e r , P. H., Aero.Res. Corn. Repr. Ane.
1953, AeA 46).
28) V e n k a t e s h , N a r a y a n a m u r t i , unpublished
work.
(Eingegangenam 14. Oktober 1955)
centration is lowered to where there is
ample room in the solution for each po-
lymer molecule. The new techniques employ
a viscometer with a flow time of 3893
seconds for toluene, special filtering of the
sohltions, a n d prolonged agitation of the
solutions after each dilution. ~7~p/cis time
dependent at concentrations below 0.1 g./
100 ml. (see Fig. 2), the time effects being
greater in a poor solvent such as m e t h y l
ethyl ketone t h a n in a good solvent, such
as toluene.
Similar dilute solution viscosity anomalies
have also been f o u n d by others on a v a r i e t y
of polymers (2, 3, 4, 5).