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Polymer Structure and Its Relationship to the

Dilute Solution Properties of High
Molecular Weight Polyacryl amide
By

James k,Herr and Willis G. Routson, Member SPE-AIME, Dow Chemical Co., U.S.A.

@Copyright 1974
American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc.

This paper was prepared for the hgth Annual Fall Meeting of the Society of Petroleum
Engineers of AI14E,to be held illHouston, Texas, Oct. 6-9, 1974. Permission to COpy is
restricted to an abstract of n~t more than 300 words. Illustrations may nat be c~pied.
The abstract should c~ntain conspicuous acknowledgment ofwhere and by vihomthe paper is
presented. Publication elsewhere after publication in the JOU?/NALOF PETROLEUM TECHNOLOGY
or the SOCIETY OF PETROLEUM ENGINEERS JOURNAL is usually granted upon request to the Editor
of the appropriate journal provided agreement to give proper credit is made.

Discussion of this paper is invited. Three copies ofany discussion should be sent tc
the Society of Petroleum Engineers ~ffice. Such discussions may be >resented at the above
meeting and, with the paper, may be considered for publication in one of the two SPE magazines.

ABSTRACT

The anomalous viscosity behavior of high soluble polymer of interest in secondary oil
molecular weight polyscrylamide (PAA) has been recovery operations. A unique property of dilutt
studied on the basis of macromolecular structure solutions of PAA of molecular weight ~ 1 x 106
and referenced to more classical theological is the anomalous viscosity observed when these
studies. Specialized electron microscope dilute Folymer solutions pass through porous
techniques were devel.;ed to study the super- media. Pye and co-workers have reported that
molecular structure of PAA and allow the direct viscosities calculated from Darcys equation for
measurement of its molecular weight (MW) and flow through porous media gave viscosities for
MW distribution. PAA solutions 5 to 20 times greater than those
determined for the same concentration of polymer
Supermolecular structures that are NW solution using classical theological procedures
dependent characterized the morphology of PAA (1), This anomclous viscosity effect has become
in dilute aqueous solutions. Variations in the known.as the resistance factor. Subsequent
properties of dilute PM solutions following studies have confirmed much of this early work
controlled degradation were found to be reflected and established the anomalous viscosity behavior
in the gross alteration of the observed super- of PAA as a distinctly unique property of the
molecular structure. polymer in dilute aqueous solution.

The ability to relate the dilute solution
properties of PAA to a physical base has been
helpful in advancing our understanding of the
unusual properties of this polymer as well as
allowing us to more effectively utilize this
unique material in secondary oil recovery
processes.
INTRODUCTION
The unusually high solution viscosity
obse~ed for very dilute solutions of poly-
acrylamide (PAA) has made this synthetic water
Although classical studies of polymer rheology
and characterizationhave been useful in the
practical exploitation of the resistance phe-
nomenon, a clear understanding at the fundamental
level has not been satisfactorily achieved. In
the final analysis it is the size, shape, and
chemical functionality of the polymer molecules
ir,solution and their interaction with the sol-
vent and one another that is responsible for the
cumulative properties of a dilute polymer solu-
tion.
References and illustrations at end of paper


POLYMER STRUCTURE AND ITS RELATIONSHIP TO THE

7 DILUTE SOLUTION PROPERTIES OF HIGH MOLECULAR WEIGHT POLYACRYLAMIDE SPE 5098

Our goal has been to characterize the PA4 PAA molecules in practical solutions. Conse-
nolecules in solution by direct observation quently we adopted the techniques of molecular
techniques and to attempt to relate measurable biology used to study DNA and similar macro-
physical properties to solution polymer morpho- molecules for our early work with PAA. The
logy. method utilized a spreading technique o~ t?je
aqueous interface of a Langmuir trough ( 7 .
XARACTERIZATION OF PAA MOLECULES Subsequently, a faster and less complicated
technique evolved that utilized the direct ab-
Recent advances in high resolution electron- sorption of PAA from solution onto a controlled
microscopy combined with the rapidly advancing substrate (8s9). The substrate film, 200-500 ~
techniques of molecular biology have overcome thick, is supported on a 200 mesh electron micro-
the many problems associated with early studies scope grid and floated, film side down, on the
>f macromolecular structure. The techniques and surface of the polymer solution of interest.
instrumentationhave reached the point of After five minutes the griclis removed from the
developmentwhere macromolecular studies may be liquid surface and the excess drop of adherent
carried out in almost any well equipped electron- polymer removed by touching one edge of the grid
Microscopy laboratory. Some work on the molec- with a moistened piece of filter paper. The
ular configuration of PAA by electronmicroscopy grid is then floated on ethyl alcohol,re-blotted
has appeared in the literature (2$3)4). These transferred to a vacuum metalizer and shadowed
studies reveal what appear to be supermolecular with uranium at an angle of tan 1 1/4. The
structures composed of macro-fibrils believed resulting specimen may be studied in the trans-
to be built up of numerous single molecules mission electron microscope.
that are aggregated or entangled much like the
strands of a fiber. Molecular Weight Determination

Basic calculations can be made that will
give the range of size that might be expected
for a molecule of PAA based upon its chemical
composition and approximate molecular weight.
A general calculation is presented in Figure 1
for a 30% hydrolyzed PAA polymer of 4 x 106
molecular weight. It can be seen that a fully
extended molecule of Pluiin a good solvent could
exist as a fibril 7-25 ~ in diameter and exceed
10 microns in length. Other estimates based on
various .?pproximationsused in light scattering
and rheology give size estimates ranging from
several hundred angstroms to seberal thousand
angstroms. These approximations are based upon
more classical polymer systems and become
questionablewhen translated to high molecular
aeight functional polyelectrolytes.
Electron Microscope Procedure
Early studies, in our laboratory, of high
molecular weight partially hydrolyzed PAA de-
posited from distilled water solution and 0.5 M
NaCl revealed unusually gross structures,
Figure 2. The structures observed were not un-
like those reported by Farrer and Larreal (5).
These dendritic-like structures appeared suf-
ficiently similar to salt crystallization
patterns and snowflake-like structures to raise
suspicion of their orgin. Selected area electron
diffraction patterns were obtained from t~.ese
structures which identified the material as
NaCl and Na2S04. This confirmed our suspicion
that these extremely gross structures were not
PU micro-gels but rather preparation artifacts
due to the presence of inorganic salts.
It was obvious that a more sophisticated
technique would be necessary to characterize
It has been shown that the molecular weight
distribution of polymers with molecular weight
in the range of 1 x 106 or greater can be
determined directly using the electron micro-
scope (10J11$12). The method entails the
atomization of a dilute ternary solution of PAA,
water, and miscible non-solvent onto a dimen-
sionally stable substrate. The solvent-non-sol-
vent mixture was chosen so that the good
solvent was more volatile than the non-solvent
and solvent rich azeotropes were not possible.
Reaching the substrate the spray droplets were
spread by surface tension and evaporation ensued
The molecules of FAAcontracted into a tight
spherical configuration (coil) and precipitated
on the substrate as the solvent became poorer
due to the loss of the more volatile good
solvent. The resulting spherical particles
(molecules)were lightly shadowed with a heavy
metal at a known angle which permited the mole-
cular diameter to be measured in the electron
microscope from the length of the shadows cast.
In our work the non-solvent was 2-ethoxy
ethanol at the initial solvent-non-solventratio
of 30170. Aside from the choice of non-solvent
the procedure outlined by ;; le in the litera-
ture was closely followed ?7 . Solutions of 10J
and high molecular weight PAA were prepared in
3X distilled and ultrafiltered water at 500 ppm
and volumetrically diluted to give 10, 5 and
1 ppm polymer concentrations in the ternary
solution. Electron micrographs revealed spheri-
cal particles (molecules) of PAA deposited from
each solution in agreement with Quayles report.
Sufficient micrographs were obtained at each
concentration to yield statistically reliable
data (600-2000particle measurements).
SPE 5098 JAMES W. HERR
Cumulative molecular weight distributions
for the two polymers studied were prepared and
are shown in Figures 3 and 4. It can be seen
that the molecular weight distribution fluctu-
ates with concentration and appears to approach
a limiting value at concentrations in the range
of 1 ppm. Similar molecular weight-concentra-
tion effects have been observed in studies of
polystyrene and polyacrylates. It was con-
eluded from the literature reports that at
concentrations in the range of 5 to 1 ppm the
size frequency distribution remained essentially
unchanged, indicating the approach to the true
molecular weight distribution. We examined the
efficacy of this assumption by plotting the
average molecular weight, determined from the
electron microscope procedure, as a functicn
of concentration. The 30% hydrolyzed high
molecular weight PAA sample behaved as expected
and the MW decreased with concentration. Extra-
polation of the molecular weight vs. concentra-
tion curve to zero polymer concentration gave
a limiting molecular weight value of 1.6 x 106
NW. This extrapolation showed no significant
discontinuity in the slope of the curve.
A similar treatment of the molecular weight
data was carried out on the unhydrolyzed low
molecular weight polymer studied. These data
showed considerable discontinuity in the slope
of the average NW vs. concentration curve.
The effect observed is believed to be associated
with the increased uncertainty in the measure-
ment of the smaller molecules (< 100 ~ diameter).
It is for this reason that the lower threshold
for the technique has been placed at ~ 5 x 105
Mw. The agreement between the molecular weight
derived from electronmicroscopyand that obtained
from intrinsic viscosity using the following
correlation is presented in Table 1 (14).
n=
[1 3.73 x 10-4 @v) O*66
The size frequency distribution of the high
molecular weight PAA polyme. at 1 ppm concentra-
tion is shown in Figure 5.
STRUCTURE - PROPERTY RELATIONSHIP
Influence of Molecular Weight
The structure of the high and low molecular
weight samples of PAA characterized in the
molecular weight study was examined in distilled
water by the adsorption technique described.
Typical structures are presented in Figures 6
and 7. Differences in molecular weight and the
degree of hydrolysis are reflected in the size
and extent of the supermolecular aggregates.
The structures observed are similar to those
reported in the literature and emphasize the
unusual macro-fibrous nature of the super-
molecular aggregates.
3
Solvent Effects
One important observation based on labora-
tory and field testing has been the influence
of inorganic salts upon the anomalous viscosity
of PAA. Data presented in Figure 8 show the
reduction in the anomalous viscosity (resistance
fctor) of PAA in 0.5 M NaCl compared with the
same polymer in distilled water. It was of
interest to examine the macromolecular structure
of the polymer to determine if any change in the
structure of the polymer could be detected. An
electron micrograph of the polymer structure in
0.5 M NaCl is shown in Figure 9, which may be
compared with the same polymer in distilled
water, Figure 7.
It can be seen that hhe polymer in a good
solvent (distilledwater) is composed of ex-
tended macro-fibrils displaying considerable
polymer-polymer entanglements and/or associa-
tions characterized by the complex branched
appearance of the supermolecular structure.
The change in solution polymer structure
effected by altering the solvent power of water
with an inorganic salt (NaCl) is clearly evi-
dent. The polymer appears to have become more
rigid (fibrous) and less gel-like with signifi-
cantly reduced entanglements or polymer-polymer
interaction. This is especially seen in the
reduction of the branching phenomenon and the
appearance of smaller discrete macro-fibrils.
Mechanical Degradation
Solutions of high molecular weight PM
exhibit a variable attrition in properties when
exposed to conditions of high shear. The
influence of shear on the supermolecular struc-
ture of a laboratory prepared high molecular
weight PAA in 0.5 M NaCl was determined.
A portionof the solution was placed in a
Virtis homogenizer and degraded under conditions
of very high shear. The measured physical
properties of the control and degraded polymer
at 500 ppm concentrations are given in Table 2.
Electron micrographs of the control and
shear degraded polymer are presented in Figures
10 and 11. The disruption of the extensive
supermolecular structure of the control polymer
is clearly evident. The destruction of the
macro-fibrillar structure of PAA appears to
coincide with the loss of dilute solution rheo-
logical properties.
Attempts were made to determine if struc-
turally degraded polymer solutions could be
reconstituted. Samples of the shear degraded
PAA solutions were solution annealed with gentle
agitation ( 2 RPM) at 10C and 35C respectively,
 POLYMER STRUCTURE AND ITS RELATIONSHIP TO THE
4 DILUTE SOLUTION PROPERTIES OF HIGH MOLECULAR WEIGHT POLYACRYLAMIDE SPE 5098

Samples examined after 36 and 72 hours
showed no evidence of reformation of the super-
molecular structure. The dilute solution
rhenlogical properties remained unchanged,
indicating the irreversible nature of the
mechanism of polymer degradation.
Table 3. Although these data are far from
sufficient to establish a statistically reliable
trend they seem to follow the qualitative
inferences gleaned from the electron micrographs
and are consistent with the theological measure-
ments.

Thermal-OxidativeDegradation NATURE OF SUPERMOLECULAR STRUCTURE

Exposure of dilute solutions of high The presence of supermolecular structure in

molecular weight PPA to temperatures in the dilute solutions of both synthetic and biological
range of 90C in the presence of air lead to polymers is well documented (16s17s18). The
attrition of the dilute solution theological often unusual behavior of dilute solutions of
properties (15). these materials is ascribed to solute-solvent
interaction through hydrogen bonding or variable
The effect of thermal-oxidativedegradation volubility due to heterogeneity in the chemical
on the supermolecular structure of PAA was cross link density of the solute.
examined in the laboratory by exposing an
agitated solution of PAA at 500 ppm in 0.5 M In the case of PAA, neither of the usual
NaCl to temperatures in the range of 85C-95C explanations most often advanced fits the
for 15 minutes. Electron micrographs were pre- experimental observations.
pared of the supermolecular structure showing
the effect of thermal-oxidativedegradation, Early work has pointed our that PAA is not
Figure 12. strongly hydrogen bonded (19). Lynch and
MacWilliams have reported that studies of chemi-
Millipore Filtration cal cross linking o: FAA,at very low cross
linking levels, contributed to three dimensional
The change in the anomalous viscosity and network formation and microgels. These gels and
capillary solution viscosity of PAA following networka reportedly changed the flow behavior
successive filtration through a series of milli- characteristics of dilute PM solutions in porou~
pore filters of progressively smaller pore size media (20). No abnormal change in the flow
is shown in Figure 13 for high molecular weight characteristics of the various P}! polymers used
PAA, 500 ppm concentration in 0.5 M NaC1. The in our studies was noted that would lead us to
supermolecular structure was studied in the suspect that variable polymer cross linking was
electron microscope and referenced to a typical significant to the origin of the supermol.ecular
control structure, Figure 9. The effluent structure observed.
passing the 8 and 3 micron filters showed
essentially no change in the supermolecular The experimental observation of the effect
structure observed by electronmicroscopy in of neutral salts such as NaCl on the super-
agreement with the theological data. Polymer molecular structure and corresponding rheologica:
structures passing through the 1.2 micron filter properties of PM suggests a method to probe the
suggested the onset of disaggregation or de- originand stability of these unique structures.
fibrillation of the large supermolecular Typical salts such as urea and potassium thio-
structures. This was evidenced by a reduction cyanate (KSCN) are well known for their effec-
in the size and number of large macro-fibers tiveness in reducing the degree of structure in
coupled with an increase in the population of macromolecular systems stabilized by hydrogen
smaller more filamentary fibrils which we have bonding. The addition of urea and KSCN at
designated as micro-fibrils, Figure 14. The levels up to one molar salt showed little change
reduction in both the anomalous viscosity and in the supermolecular structure or theological
capillary viscosity continued as the pore sizes properties over those observed for NaC1. This
decreased to 0.45 microns. Electron micrographs may be cited as further evidence that hydrogen
of the effluents through these filters showed bonding does not play a significant role in the
that the supermolecular structures were pro- supermolecular structure of PAA.
gressively reduced in both size and number.
Concurrent with this was an increase in the The effect of inorganic salts was further
population density of the smaller more filamen- studied by examining the temperature at which
tary micro-fibrils. A representative micrograph the supermolecular structure of PAA was signifi-
of the effluent passing the 0.45 micron filter cantly degraded. Degradation was measured by
is shown in Figure 15. comparing the supermolecular structure of the
polymer, in the particular level of inorganic
A tabulation of the change in structure salt, at room temperature to the structure
observed in the electron microscope study of the observed following exposure of the solution to
various millipore filtrate fractions based on thermal-oxidativedegradation at various tem-
fiber length measurements is presented in peratures. These results are presented in
Figure 16.
SPE 5098 JAMES W. HERR 5

Inorganic salts such as LiBr and CaC12 were
Eound to reduce the temperature for thermal-
~xidative degradation of the supermolecular
structure of PAA. Other inorganic salts were
;een to have had little effect on stability
~hile others such as Na2S04 seemed to impart
~ stabilizing effect measured by the higher
temperaturesrequired for polymer degradation.
The effect of inorganic salts on the sta-
>ility of the supermolecular structure of high
nolecularweight PAA observed, generally fits
the Hofmeister series which applies to a wide
range of ionic phenomena. The only exception
is that KSCN and urea, unsually ranked as
?owerful structure destabilizers, have little
~ffect upon the structure of Pm. This is most
likely related to the fact that PAA is not
strongly hydrogen bonded.
corresponding increase in the number of small
filamentary micro-fibrils. It is envisioned
that the large supermolecular structures become
preferentially immobilized in the filter media.
As the pressure increases, the supermolecular
structures undergo a shear type degradation
within the pore structure. In this process the
hydrostatic force exerted on the polymer becomes
sufficient to exceed the weak secondary bonding
forces, stabilizing the supermolecularstructure.
At this point the secondary structure of the
polymer begins to break up, giving rise to
smaller and smaller micro-fibrils approaching
the calculated size of extended PAA molecules
in the pore size range of 0.5 microns. Chemical
analysis for total carbon content of the
effluent passing the 0.5 micron filter indicated
that only a 20% drop in polymer concentration
had occurred over the unfiltered control.

DISCUSSION The change in the supermolecular structure

of PAA and its stability in controlled degrada-
Supermolecular structures consisting of ti.onstudies highlights the importance of the
extensive macro-fibrils appear to characterize unique nature of the solvent system. The effect
the dilute solution structure of high molecular of inorganic salts on the structural confirma-
~eight P&!. These structures are undoubtedly tion and stability of Pm in dilute solution is
secondary in nature and are composed of highly likely tied to the manner in which various
solvated and associated PAA molecules, stabilized ionic species interact with the aqueous solvent.
by relatively weak bonding forces. The length This alters the solvent power of the aqueous
~nd diameter of these structures are far too diluent which in turn modifies polymer-solvent
extensive to be ccnstrued as single PAA interaction.
molecules. Similar types of supermolecular
structures have been observed in dilute solutions We have used the electron microscope to
Df functional biological macromolecules. The characterize the supermolecular structure of
precise mechanism responsible for the formation PA which appears to be in general agrecinent
of supermolecular structure is not well under- with most of the literature reports. The
stood. Enough evidence is available from structures observed with the electron microscope
studies of these unusual systems to suggest that correlated well with other physical data.
unique solvent-macromolecularinteraction appears
to play an important role. The highly branched appearance of the
secondary structure of high MW polymer in
The molecular weight distribution of the two distilled water is thought to arise in part from
PAA samples investigated points out the broad the preparation technique. This comes as either
range of molecular weight that may exist in PAA the monolayer or adsorbed species is attached
polymers. The unusual drift in the average to the active sites on the substrate and the
molecular weight of the unhydrolyzed polymer is remaining polymer solution is withdrawn. In
believed to result from our attempt to extend this process the actual physical entanglement
the method into the lower molecular weight range, with adjacent polymer aggregate neighbors causes
<5 x 105. In this range the error in molecular them to be trapped at the substrate with the
size measurement becomes appreciable and attached species. When the solvent is removed
seriously impairs the reliability of the molecu- in the drying step prior to shadowing, the
lar weight data. polymer entanglements fuse. It must be
emphasized at this point that this entanglement
The variation in the theological properties is physical in or.ginand should not be construed
of high molecular weight PAA following experi- as a first or second order manifestation of
mental degradation is manifest in the super- molecular branching or cross linking.
molecular structure of the polymer as viewed by
the electron microscope method. As the Additional work is needed to more fully
theological properties decline the macro-fibril- explore the adsorption pher,omenonof functional
lar structure of the polymer becomes retrograde. macromolecules from dilute $olution onto an
Subtle changes in polymer structure were observed active substrate such as those used in our work.
in the millipore filtration study. These were It is felt that a better technique is needed as
documented as a reduction in the size and number a reference method that might permit us to more
of the large supermolecular fibrils with a faithfully approach the structilrein dilute
 POLYMER STRUCTURE AND ITS RELATIONSHIP TO THE
6 DILUTE SOLUTION PROPERTIES OF HIGH MOLECULAR WEIGHT POLYACRYLAMIDE
valution. Currently, freeze-etching and critical
jointdrying are being examined in our laboratory
in an effort to approach this goal. A modicum
)f success in this area will provide the
lecessarybase to allow the extension of direct
morphologicalobservation into the solution state
)f macromolecules.
CONCLUSIONS
Supermolecularmacro-fibrillar structures
characterizethe morphology of high molecular
?eightPAA in dilute aqueous solution. The
configurationof the supermoleclar structure is
Iependentupon the molecular weight of the poly-
ner and the solvent power of the aqueous diluent.
;hanges in polymer properties, measured by
:lassicaltheological techniques and in flow
:hroughporous media (resistance factor), were
lsed t.Jmeasure laboratory induced polymer
Degradation. In general, attrition of the
neasuredsolution properties of PAA were re-
Tlected in the electron microscope work as gross 10. Ruscher, C., and Zuchold, H., Electron
Iterations of the observed supermolecular
;tructure. The stability of the supermolecular
ltructurein aqueous solution appears to follow
:he Hofmeister series with the exception that
;trong hydrogen bond Ibreakershave little 11. Richardson, M.J. The Direct Observation of
~ffect upon the supermolecular structure.
ACKNOWLEDGEMENTS
The writers wish to recognize the basic work
>f W.W. Trask of this laboratory who carried out
:he initial electron microscope technique
developmentwork.
D.C. MacWilliams and J.H. Rogers, also of
khis laboratory, supplied the data and samples
Eor the shear degradation and millipore filtra-
tion studies. The assistance of Mrs. H.G. Moore,
Irs. J.L. Cotter and W.W. Trask in the prepara-
tion of the manuscript and illustrations is
;reatly appreciated.
?JZFERENCES
1. Pye, D.J. Improved Secondary Recovery by
Control of Water Mobility (Aug. 1964)
Petroleum Transactions, 911-916.
2. Rochow, T.G. Resinography of High Polymers
(1961) Analytical Chemistry, Vol. 33,
No. 13, 1810-1816.
3. Richardson, M.J. Direct Observation of
Polymer Molecules (April 1963) Nature, 198,
252-253.
4. Quayle, D.V. An Electron Microscopical Study
of Polyacrylamide (1967) Polymer 8, ~
217-224.
SPE 5098
5. Ferrer, G.J. and Larreal, B.J. Microscopic
Observations of Polyacrylamide Structures
(Jan. 1973) J. Pet. Tech, 80-81.
6. Kleinschmidt, A.D., Lang, D. and Zahn, R.K.
Intracellular Structure of Bacterial
Deoxyribonucleic Acid-DNA (1961)
Z. Naturforsch, 16B, 730-739.
7. Solari, A.J., Electron Microscopy of Nativ
DNAin Sea Urchin Cells (1967)
J. Ultrastruct. Res., 17, 421-438.
8. Beer, M., Electron Microscopy of Unbroken
DNA Holecules(l96l)J. Mol. Biol. ~,
263-266.
9. Gordon, C.N. and Kleinschmidt, A.K.,
Electron Microscopic Observation of DNA
Adsorbed on Aluminum-Mica (Sept. 1970)
J, Colloid Interface Sci., 34, (1) 131-141.
Microscopic Investigation of Solutions of
High Polymers (1964) Faserforsch, a.
Textiltechnik~, 626-630.
Polymer Molecules and Determination of
their Molecular Weight (1963) Proc. Roy.
SOC. A, Vol. 279, 50-61.
12. Quayle, D.V.,An Electron Microscopical
Study of Polyacrylamide(Dec.1967) J. Roy
Mic. SOC., 87, 353-359.
13. Quayle, D.V., Molecular Weight Determina-
tions on Polymers by Electron Microscopy
(Jan. 1969) Br. Polym. J. ~, 15-23.
14. American Cyanamide Co. (1950) Pub.
No. MDD-9236-5M.
15. Burcik, E.J. and Walrond, K.W., Microgel
in Polyacrylamide Solutions and Its Role
in Mobility Control (1968) Prod. Monthly
~, No. 9, 12-14.
16. Doty, P., Wagner, H. and Singer, S.,
The Association of Polymer Molecules in
Dilute Solution (1947) J. of Phys.
Colloid Chem. 51, 32-53.
17. Peterlin, A., Quan, C., and Turners D.T.~
Temporary Network Formation in Shearing
Solutions of Poly (Methyl Methacrylate)
in Aroclor (1965) Polymer Letters ~,
517-520.
18. Klenin, V.J., Klenina, O.V., et al.,
Structural Levels of Supermolecular
Organization in Aqueous Solutions of Poly
(Vinyl Alcohol) (1973) J. Polym. Sci..,
~, 931-942.
SPE 5098 JAMES W. HERR 7

19* Eliassaf, J., and Silberberg~ A.,
The Effect of Hydrogen Bonding Addends
on the Dilute Solution Viscosity of Poly-
(acrylamide)and Unionized Poly(acrylic
Acid) and Poly(methacrylic Acid) (1959)
J. Polym. Sci. 41, 33-51.
20 Lynch, E.J. MacWilliams, D.C., Mobility
Control with Partially Hydrolyzed
Polyacrylamide - A reply to Emil Burcik
(Oct. 1969) J. Pet. Tech, 1247-1248.
APPENDIX I
The high molecular weight polyacrylamide
polymer at 30% hydrolysis was taken from a
commercially produced lot of Pusher@500. Unless
otherwise specifically indicated, this is the
high MW material used in the reported research.
The low molecular weight polymer was a
laboratory prepared material in the unhydrolyzed
state.
The experimental high molecular weight
polymer used in the mechanical degradation study
was a laboratory prepared material at the 25%
hydrolysis level.
@ Pusher is a registered trademark of
the Dow Chemical Company, Midland, Michigan.

TABLE I

VISCOSITY AVERAGE ELECTRON MICROSCOPE AVERAGE

POLYMER MOLECULAR WEIGHT MOLECULAR WEIGHT

HIGH MW PAA
30A HYDROLYZED 2.8 X 106 2.3x 106

LOW MW PAA
UNHYDROLYZED 2.5x 108 3.5x 105
 TABLE 2

CAPILLARY SOLUTION ANOMALOUS VISCOSITY

SAMPLE VISCOSITY IN POROUS MEDIA

CONTROL 2.61 CPS 31.2 CPS

DEGRADED 1.17 CPS 1.08 CPS

TABLE 3

3p ~ O* o~ *
CONTROL
!2
#MACRO F18RILS 7 8 4 5 4 I o

# MICRO FIBRILS 3 10 6 !6 15 27 28-35

MEAN MACROFIBRIL, 100- 85A loo-B5fi 100-85 L 100-851 85-60; 45 i NONE PRESENT
DIAMETER

MEAN MICRO FIE$RIL, 75-503 75-5oi 75-5oli <75iz?jc); cEQi>25ii <50ii>25& xWi>25i
DIAMETER

tfA:A~FIBRIL, > lop > lop Xop >@ > lop >Iop NONE PRESENT

2-5P 2-5p 2-5p 2-3p 2-3p 2-3P 1.5-2.5p

 p-~),:f,,-~=),j,,o
SUBSTITUENT
POLYMERGROUPS

(70+ 30) 560= 5,6 X 104MER UNITS

LENGTHOF ONEMER UNITCH2-CHCONH2

OR CH2CHCOOH
IS 2,5ANGSTROMS

MOLECULAR LENGTH
X 5,6 X 104MER= 1,4 X 105i
L = 2s5A/MER
EXTENDEDMOLECULE14 MICRONS

MOLECULAR
DIAMETER~ROil
MODELSTUDIES7-25A
Fig. 1 - Calculatedsize of polyacrylamidemolecules
of molecularweight 4 x 10G.

Fig. 2 - Gross structureof high MW polyacrylamide

depositedfrom distilledwater.
 0.11 1 1 I i 1 I 1 1 t 1
ol~ 10 203040 S06070W 90
20s040s0s07000 90
PERCENT PERCENT

Fig. 3 - Cumulative molecular weight distribution Fig. 4 - Cumulative molecular weight distribution
of high MW polyacrylamide. of low MW polyacrylamide.

n
!4 Ill HIGH M.W. POLYMER

1 1 1 1 I I 1 a 1

MOLECULAR WEIGHT x Id
Fig. 5 - Frequency distribution of high MW polyacryla-
mide at 1 ppm concentration.
Fig. 6 - Electronmicr~graphof low MW unhydrolizedpoly-
acrylamidein distilledwater, 500 ppm concentration.

Fig. 7- Electronmicrographof high MW polyacrylamide,

30 percenthydrolysis,in distilledwater, 500 ppm
concentration.
 HIGH M.W. POLYMER
OiS71LLED WATER
\

CAPIUARY VISCOSITY
HIOH M. W. POLYMER
~ 0.6 M NaCl

~
100s00300400500
POLYMER CONCENTRATION, PPM

Fig. 9 - Electronmicrographof high MW polyacrylamide,

500ppm concentrationin 0.5M NaC1.
Fig. 11 - Electronmicrographof mechanicallydegraded
high MW polyacrylamide,25 percenthydrolysis,500 ppm
concentrationin 0.5M NaC1.
 Fig. 12 - EZectron micrograph of high MW polyacrylami.de,
in 0.5 M NaCl thermally degraded 90C for 15 minutes.

A CAPILLARY VISCOSITY
O ANOMALOUS VISCOSITY
(RESISTANCE FACTOR)

1 1 1 I 1 1 1 1 I
I
I I 2
P6iE SIZE: MICROfiS
6 7 8

I
Fig. 13 - Graph of the anomalous viscosity and capillary
solution viscosity of high MW polyacrylamide, 500 ppm
concentration in 0.5M NaCl, as a function of millipore
filter size.
 Fig. 14 - Electronmicrogrephof hign MW polyecryl.amide,
500 ppm in CI.5MNaCl after passing the 1.2 micron
milliporefilter.

Fig* 15 - Electronmicrographof nigh MWpolyacryl.amide

500 ppm in 0.5M NaCl after passing the 0.45 micron
milliporefilter.
 60

1~

SALT CONCENTRATION(iOLES/LITER)

Fig. 16 - The effect of inorganic salts on the temperature

for thermal-oxidative degradation of the supermolecular
structure of high MW polyacrylamide.