A Natural Polymer-Based Cross-Linker
System for Conformance Gel Systems
B.R. Reddy, Larry Eoff, E. Dwyann Dalrymple, SPE, Kathy Black, David Brown, and Marcel Rietjens, Halliburton
Summary
This paper describes a material derived from natural sources that
can be used to crosslink a variety of acrylamide-based polymers
over a broad temperature range to produce gels for confor-
mance applications.
Delayed crosslinked polymer systems have been used for many
years in conformance applications. For the past decade, the most
widely used system has been based on chromium (3+) crosslinked
polyacrylamide. Organic crosslinkers, such as phenol/formaldehyde
and polyethyleneimine (PEI) have also been used with a variety of
polymers. However, these systems are being scrutinized by gov-
ernmental agencies and have been scheduled for phaseout in some
countries. Because of these issues, a single, environmentally
friendly crosslinker that could be used with a variety of polymers
over a broad temperature range was the focus of this study.
This paper details the laboratory development of an environ-
mentally friendly, natural polyamine crosslinker system. This
crosslinker can be used with a variety of polymers, such as poly-
acrylamide, AMPS/acrylamide, or alkylacrylate polymers. Gels
ranging from stiff and ringing type to lipping gels have been
obtained. The data illustrate a simple, commercially available sys-
tem that can be applied to field operations. Potential crosslinking
mechanism(s) of the system will be discussed.
Introduction
Water production in oil-producing wells becomes a more serious
problem as the wells mature. Remediation techniques for conform-
ance control are selected on the basis of the water source and the
method of entry into the wellbore. Treatment options include seal-
ant treatments and relative permeability modifiers (also referred to
as disproportionate permeability modifiers). This paper primarily
discusses water control with water-based gels for applications in
wells in which the oil- and water-producing zones are clearly
separated and can be mechanically isolated.
Chromium(III) crosslinked polyacrylamide gels can be choice
materials for matrix-fluid shut-off systems.14 The crosslinking reac-
tions in these gel systems take place by the complexation of Cr(III)
oligomers with carboxylate groups on the polymer chains (Fig. 1).
Because of the nature of the chemical bond between Cr(III) and
the pendant carboxylate groups, formation of insoluble chromium
species can occur at high pH levels. Other problems with these
systems include thermal instability, unpredictable gel times, and
gel instability in the presence of chemical species that are potential
ligands. The gel times are controlled by the addition of materials
that chelate with chromium in competition with the polymer-
bound carboxylate groups.5,6
Another popular water-based gel system for water-control ap-
plications is based on a phenol/formaldehyde crosslinker system
for homo-, co-, and ter- polymer systems containing acrylamide.711
Depending on the polymer composition, these gels are thermally
stable, and the gel times are controllable over a wide temperature
range. The crosslinking mechanism involves hydroxymethylation
of the amide nitrogen, with the subsequent propagation
of crosslinking by multiple alkylation on the phenolic ring
Copyright 2003 Society of Petroleum Engineers
This paper (SPE 84937) was revised for publication from paper SPE 75163, first presented
at the 2002 SPE/DOE Improved Oil Recovery Symposium, Tulsa, 1317 April. Original
manuscript received for review 29 May 2002. Revised manuscript received 3 March 2003.
Manuscript peer approved 10 March 2003.
June 2003 SPE Journal
(Fig. 2).12,13 Several variations of the same technology were cre-
ated to overcome the toxicity issues associated with formaldehyde
and phenol. These processes generally involve replacing formal-
dehyde and phenol with less toxic derivatives that generate phenol
and formaldehyde in situ, or are themselves active components of
the crosslinking system. For example, formaldehyde can be re-
placed with hexamethylene tetramine (HMTA), glyoxal, or 1, 3,
5-trioxane. Substitutions for phenol included phenyl acetate, phe-
nyl salicylate, or hydroquinone, among others.12,13 Extensive pat-
ent literature for this technology exists.1422
Recently, a less toxic crosslinker was tested extensively in field
trials worldwide and enjoyed a very high success rate.2327 This
system is based on PEI crosslinker and a copolymer of acrylamide
and t-butyl acrylate (PA-t-BA). PEI is a low-toxicity material that
is approved in the United States for food contact.2831 PA-t-BA is
a relatively low molecular-weight polymer. The low molecular
weight is expected to provide rigid ringing gels. The crosslink-
ing is believed to take place in situ by amidation of the pendant
ester groups on the base polymer (Fig. 3). Recent test results
indicate that a variety of polymers containing acrylamide pendant
groups react with PEI nitrogens through a transamidation reaction
pathway to provide gels (Fig. 4).32
Because of recent changes in European environmental regula-
tions, PEI is targeted for phase-out from the Norwegian section of
the North Sea within the next few years. A search for biopolymers
containing amino groups suggested that chitosan (Fig. 5) may react
with acrylamide-based polymers in a manner similar to PEI. Chi-
tosan is a polysaccharide obtained by de-acetylating chitin, a ho-
mopolymer containing -(1-4)-2-acetamido-2-deoxy-D-glucose
(Fig. 6) that occurs in the shell or skin of anthropods or crusta-
ceous water animals. Chitosan is also present in the environment,
although in lesser amounts than the chitin. The degree of de-
acetylation in the commercially-available chitosan materials is
usually in the 70 to 78% range. The chitosan solubility in acidified
water, for example in acetic or hydrochloric acid, is in the 1 to 2%
range. The viscosity of the solutions depends on the molecular
weight of the polymer. If the pH of the solution is increased above
6.0, polymer precipitation occurs.
This paper presents results using chitosan as an environmen-
tally preferable crosslinker for use in combination with acryla-
mide-based polymers. Gel treatments using this material should
contain a biocide. The advantage here is that if inadvertently dis-
charged, the chitosan will biodegrade.
Experimental Methods
Preparation of Chitosan Solutions. Commercial solid chitosan
samples were dissolved in fresh water solutions containing 1%
acetic acid to make 1.0 to 1.5% polymer solutions. Chitosan lactate
salt, which is also commercially available, can be dissolved di-
rectly in fresh water to prepare solutions with similar polymer
concentration. The viscosities and clarity of the solutions depended
on the polymer molecular weight and the degree of de-acetylation.
Aqueous solutions of chitosan salts are also available commer-
cially, which can be used directly for crosslinking base polymers. The
preformed chitosan salts are insoluble in salt water or seawater.
Viscosities of Base Polymer and Crosslinker Mixtures. All the
base polymers contained acrylamide. Additionally, one polymer,
PHPA, contained acrylate groups (11 mole %) introduced by par-
tial hydrolysis. The molecular weight of this polymer is approxi-
mately 6 million. The second polymer, PA-t-BA, contained about
5 mole % of tert-butyl acrylate as the comonomer, and hydrolysis
99

Fig. 1Crosslinking reactions take place by the complexation
of carboxylate groups on the polymer chains by chromium spe-
cies (Mn+=Cr3+ and/or oligomers).35
was less than 0.5% with a molecular weight of 500,000. The third
polymer, AMPS/AA, contained about 30 mole % of 2-acrylamido-
2-methylpropane sulfonic acid. The molecular weight of this poly-
mer was about 5 to 6 million, and the hydrolysis was less than 1%.
The viscosities of a solution containing 7% PA-t-BA and 0.5%
chitosan lactate in 85% fresh water and 15% synthetic seawater
were measured using a Fann 35 Rheometer and a Brookfield LVT
viscometer. The results are shown in Table 1. The viscosity values
observed are in the range typical for polymer solutions used in
conformance applications.
In the case of PHPA and AMPS/AA, because of the very high
polymer molecular weights, the concentrations of base polymers
in aqueous solutions were kept near 0.7% so that the viscosities
of the base polymer solutions were within useful range for prac-
tical applications.
Gel Time Measurements. Two methods were used to measure
gel times:
Method ABrookfield Viscosity Method. Approximately 300
mL of the polymer composition for testing was placed in a 400-mL
beaker. The beaker was then inserted into a preheated, thermostat-
controlled Brookfield viscometer with a No. 2 spindle. The poly-
mer solution was stirred at 10 rev/min, and the viscosity changes
were monitored as a function of time. A plot of viscosity vs. time
can be generated for estimating gel time, which is defined as the
Fig. 2Crosslinking mechanism involving hydroxymethylation of the amide nitrogen, with subsequent propagation of crosslinking
by multiple alkylation on the phenolic ring.
100
inflection point of the plot (Fig. 7). With this method, gel times are
rarely a function of the viscometer.
A typical viscosity vs. time curve obtained using this method for
chitosan lactate and PA-t-BA mixture at 150F is shown in Fig. 7.
Method BSealed-Tube Method. Either a 16150-mm boro-
silicate glass tube with a screw cap or a 10.2-cm pressure tube with
a screw cap was filled with the polymer composition to approxi-
mately one-half its capacity. The tube was purged with nitrogen
and the screw cap was sealed with a high-temperature silicone
sealant. In addition, a TEFLON plug was used inside the cap. The
tube was placed inside a steel bomb (container), and the bomb was
placed in a preheated oven set at the test temperature. The steel bomb
was taken out periodically, cooled to below 150F, and the tube was
removed. The tube was laid on its side, and the liquid level was
measured. Using Eq. 1, the degree of gelation was measured.
Percentage of gelation = 100 l t l h, . . . . . . . . . . (1)
wherein tlength of the liquid/gel level when the tube is in the
horizontal position, llength of the tube, and hheight of the
initial fluid column when the tube is in the vertical position.
The time needed to reach a gelation of 94% or higher is the gel time.
If gel syneresis occurred after the gel was formed, the syneresis
was measured as described in Eq. 1, except that h equaled the
gel-column height before the gel was aged at a given temperature.
Thermal Stability Measurements. The gels were stored in sealed
tubes in thermostat-controlled ovens kept at 225 and 250F. Peri-
odically, the test tubes were visually inspected at temperature
(without cooling) for gel syneresis and/or degradation.
Single-Core Flow Testing With a Multitap Flow Cell. The fol-
lowing is a procedure for measuring permeability reduction to water
using the chitosan/PA-t-BA polymer gel system. A more detailed
description of the experimental setup was presented earlier.33
1. Record the test-core dimensions and place the core in a suit-
able holder, such as a Hassler sleeve apparatus. Place sufficient
overburden pressure on the test core to ensure that no fluid by-
passes the core. (Generally, an overburden pressure of 450 to 500
psi over the treatment pressure is used for this purpose.)
2. Determine water viscosity at the temperature that will be
used in the flow tests. All flow series were performed at the desired
test temperature of 175F.
3. Stabilize water flow through the core in the normal produc-
tion direction.
4. Pump the treatment through the core in the reverse-flow direction.
5. Repeat Step 3.
6. Determine the cores residual resistance factor (RRF) for
water by dividing the cores pretreatment permeability-to-water to
its post-treatment permeability-to-water (RRFpretreatment per-
meability-to-water post-treatment permeability-to-water).
June 2003 SPE Journal
Fig. 3Less-toxic crosslinker based on polyethyleneimine
(PEI) crosslinker and a copolymer of acrylamide and t-butyl-
acrylate (PA-t-BA).
Environmental Testing. Inhouse BOD (Biochemical-Oxygen-
Demand) tests were done according to HACH Method 10099,
and Chemical-Oxygen-Demand (COD) tests were conducted ac-
cording to HACH Method 8000 described in the HACH Water
Analysis Handbook.34
Results and Discussion
All the variables tested that can potentially impact gelling of poly-
mers with chitosan are:
Base polymer.
Crosslinker concentration.
pH.
Mix water.
Temperature.
Base Polymer. The results in Table 2 indicate that polyacryl-
amide, PHPA, crosslinked fastest followed by PA-t-BA and
AMPS/AA. The order of the ease of crosslinking reactivity sug-
gests steric resistance to the approach of the amino group at the
amide carbonyl group in PA-t-BA and AMPS/AA copolymers
because of the adjacent bulky groups. A similar order of reactivity
was noted for crosslinking of the above polymers with PEI, sug-
gesting similar operating mechanisms. In the case of AMPS/AA,
presence of a smaller amount of acrylamide may also be a con-
tributing factor.
An advantage of a low-molecular-weight polymer such as the
PA-t-BA is that higher concentrations can be used, as compared to
other higher-molecular-weight polymers, without increasing the
viscosity of the base solution. Further, the gels obtained with the
higher concentration of the base polymer result in rigid, ringing
gels, as seen in Tables 2 through 4.
Crosslinker Concentration. Typically, the gel times depend on
the weight ratio of base polymer to crosslinker. In this study, the
ratio effects were studied by using PA-t-BA as the representative
base polymer. The results presented in Table 3 show that a ratio of
base polymer to chitosan of 14 was adequate to provide gel times
useful for commercial applications. At very high (>250F) and
Fig. 5Chitosan.
June 2003 SPE Journal
Fig. 4Polymers containing acrylamide pendant groups react
with PEI nitrogens through a transamidation reaction pathway
to provide gels.
very low (<150F) temperatures, the gel times were either too
short or too long at this ratio. The trends observed with PA-t-BA
were confirmed with PHPA copolymer. Based on the gel times
shown in Tables 2 and 3, it appears that PHPA may be a suitable
base polymer for low temperatures, whereas AMPS/AA may be
suitable for high-temperature conformance applications.
pH Effects. The results in Table 4 show that as the pH is de-
creased, the gel times are increased. At the lower temperatures, this
observation is in accordance with expectations for amine-type
crosslinkers. In acidic media, the lone pair of electrons on the
amine nitrogens are expected to be protonated, thus making them
unavailable to initiate a nucleophilic attack on an amide carbonyl
group of the base polymer (Fig. 4). By controlling the pH, the gel
times could be adjusted to fit the need. The gel-time decrease
appears to be independent of the organic acid used to lower the pH
of the chitosan solutions. For example, when the pH of the chito-
san solution was lowered, with either acetic or lactic acid, similar
gel times were obtained. This effect is less obvious in the higher
temperature experiments because of the short gel time and inherent
experimental limits on gel-time measurement.
Mix Water. The mix water effects on the crosslinking reaction of
PA-t-BA with chitosan salts were also tested. The results are pre-
sented in Table 5.
Test results show that the reactions proceed significantly faster
in fresh water compared to seawater even though the amount of
seawater, or 2% KCl solution in the total composition, is only 15
to 18%. Similar results were observed in the crosslinking reactions
of PA-t-BA with PEI.
Temperature. The temperature effects observed are presented in
Fig. 8 and are as expected. As mentioned earlier, partially hydro-
lyzed polyacrylamide provides faster crosslinking rates than the
acylamide copolymers containing t-butylacrylate or AMPS as the
comonomers. Greater steric hindrance to the approach of an amino
group at the acrylamide carbonyl group flanked by bulky groups
may explain the differences in the observed differences in the
crosslinking reaction rates.
101
 Fig. 6Chitin.
Gel Thermal Stability. The gels turned light brown within a few
days at the oven temperatures. However, no syneresis was ob-
served over a 6-week period in the 200 to 250F range.
Multipressure Tap Core Flow Tests. The core flow study results
are shown in Fig. 9 and Table 6. A Berea sandstone core was used
as the test medium, the evaluation temperature was 190F, and 7%
KCl was used as the evaluation brine. After stabilizing the flow of
the brine through the core, a 100-mL treatment (composed of 7%
polymer, 0.5% chitosan crosslinker, a pH of 5.7, using seawater as
the makeup water) was injected through the core in the reverse-
flow direction. The core was then shut in overnight. The effective
viscosity of the polymer/crosslinker solution within the rock dur-
ing treatment was calculated using the initial permeability as a
constant and solving for viscosity using Darcys linear flow equa-
tion (Eq. 2):
AKP
= . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (2)
QL
The value was determined to be 13.9 cp at 190oF. As seen in Fig.
10, the permeability values were fairly constant during the treat-
ment stage, indicating that the fluid was moving evenly throughout
the core and no face plugging of the core was occurring. The end
segments of the core typically show lower permeability than the
center two segments. This result is normal and is caused by end
effects (short segment length, contamination of the core ends via
the fluid used to drill the cores, etc.). This data is used only to help
determine the occurrence of face plugging in fluid treatments.
Following the overnight shut-in period, the flow of 7% KCl
was resumed to determine the effective permeability of the core
after treatment. As illustrated in Fig. 9 and Table 6, the chitosan
crosslinked polymer formed a very effective porosity seal of the
Berea sandstone core, resulting in a RRF of 3310. No wash-off or
removal of the gel treatment was observed during an overnight
flow study.
102
Environmental Issues
Chitosan occurs in nature in small amounts. Chitosan-degrading
enzymes, namely chitinases, chitosanases, and lysozymes that de-
grade chitin-derived materials, occur in bacteria, fungi, algae
mammals, birds, fish, and so on.
Chitosan and the constituent monomer, glucosamine, are ap-
proved for human consumption as dietary supplements. It is cur-
rently used in the U.S. as an ingredient in animal feed on an
experimental basis, and as a filter medium for potable water.
Toxicity. An LD50 value of 16 grams per kilogram body weight in
mice when administered orally was reported by Arai et al.34 Ac-
cording to this group, the LD50 values are of the same order of
magnitude as lethal doses of sugar (sucrose) or salt.
The aquatic toxicity values (obtained by a supplier) for the
glycolate salt of chitosan are:
Acute fish toxicity: LC 50>100 mg product/liter.
Acute bacteria toxicity: EC 0>100 mg product/liter.
Biodegradability and Persistence. According to the supplier, chi-
tosan is readily and rapidly biodegradable: all individual organic
substances contained in the product achieve values in tests for
ready biodegradability (e.g., OECD 301 A-F) of at least 60%
BOD/COD or 70% DOC reduction (tolerance value for classifica-
tion as readily biodegradable: >70% DOC reduction or
>60% BOD/COD in 28 days).
A 5-day inhouse environmental test of chitosan showed a BOC/
COD of 54% compared to 32% for hydroxyethyl cellulose (HEC).
Conclusions
1. Chitosan is an effective crosslinker for acrylamide-based water-
soluble base polymers, and provides lipping to rigid ringing
gels suitable for conformance applications for a temperature
range of 150 to 250oF.
2. The reactivity of the base polymers is highest with partially
hydrolyzed polyacrylamides, followed by acrylamide polymers
with bulky comonomers such as t-butylacrylate or AMPS. The
reactivity differences among the base polymers allows the se-
lection of suitable polymers for a wide range of formation tem-
peratures in conformance applications.
3. The mix water composition also offers a means to design com-
position to suit a particular application. Fresh water solutions
provide the fastest crosslinking times. Addition of salts de-
creases reaction rates.
4. Core flow tests clearly show that the chitosan/acrylamide-based
polymer gels are effective plugging agents.
5. The gels are thermally stable up to 250oF.
6. Chitosan is a nontoxic, biodegradable crosslinker that reacts
with acrylamide-based polymers in a manner similar to PEI.
June 2003 SPE Journal
 Fig. 7Typical gel time experiment using Brookfield viscometer method for chitosan lactate and PA-t-BA mixture at 150F.

June 2003 SPE Journal 103


Nomenclature
A area, cm2
h height of the initial fluid column when the tube is in
the vertical position
K permeability, darcies
l length of the tube
L length of the core, cm
Q flow rate, cm3/sec
t length of the liquid/gel level when the tube is in the
horizontal position
P differential pressure in atmosphere
viscosity, cp
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diameter = 2.51 cm, porosity = 20%.
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SI Metric Conversion Factors
F (F 32)/1.8 C
mL 1.0* E + 00 cm3
*Conversion factor is exact.
B.R. Reddy is a research and product development chemist
working in the areas of cementing and conformance control
for Halliburton. e-mail: raghava.reddy@halliburton.com. He
did postdoctoral teaching and research work at the U. of
Texas, U. of Oklahoma, U. of Louisville, and Trinity U. Reddy
worked for Fina Oil and Chemical Co. as a research scientist
during 19901997 prior to joining Halliburton Technology Cen-
ter in Duncan, Oklahoma. Reddy holds BS and MS degrees
from Osmania U., India, and a PhD degree from Oklahoma
State U. Larry Eoff is a Principal Scientist in the Conformance
Group at the Halliburton Technology Center in Duncan, Okla-
homa. e-mail: larry.eoff@halliburton.com. He has been with
105
Halliburton for 11 years in both conformance and cement
product development. Eoff holds a BS degree in chemistry
from the U. of Central Arkansas and a PhD degree in organic
chemistry from the U. of Arkansas. E. Dwyann Dalrymple is a
scientific adviser for Halliburton in Conformance Technology.
e-mail: dwyann.dalrymple@halliburton.com. For the past 28
years, Dalrymple has been primarily involved in all phases of
water control: well preparation, conformance control, clay
control, and improved oil recovery methods; assisting with field
implementation, and consultation on procedures and job rec-
ommendations. He holds 14 U.S. patents relating to the oilfield.
Dalrymple holds a BS degree in chemistry from Cameron U.
Kathy D. Black, Principal Technician, has worked in a variety of
areas in her 25 years with Halliburton. e-mail: kathy.black@
halliburton.com. She has spent the past 20 years in the Ana-
lytical section as manager and operator of the Environmental
Scanning Electron Microscope. She also has other areas of
responsibility, including X-ray diffraction, petrographic analysis,
NMR, and the Bioassay area of the Organic Dept. Recently,
she moved out of the laboratory into Technology Project Con-
trols. Black holds an Associate Science degree from Connors
106
State U. (satellite of Oklahoma State U.). David Brown has been
with Halliburton nearly 24 years and holds the title of Technolo-
gist. e-mail: david.brown@halliburton.com. While employed
with Halliburton, he has been responsible for the development
of chemicals and chemical processes used in the water and
sand control field of the oil industry. He holds a number of U.S.
and foreign patents for chemicals and chemical processes
used in water and sand control. He has been responsible for
designing models, equipment, test training aids, and training
manuals for Conformance and Sand Control units within Halli-
burton. Brown holds a BS degree from Cameron U. Marcel
Rietjens currently works with Cimcool in Vlaardingen, The Neth-
erlands. e-mail: marcel.rietjens@halliburton.com. Previously, Ri-
etjens worked as a Principal Chemist for Halliburton in Leider-
dorp, The Netherlands, until the closure of the European Re-
search Centre in 2002. While at Halliburton, he was involved in
research and product development for acidizing, fracturing,
and water control, with special interest in asphaltenes, sludge,
surfactants, and polymers. Rietjens holds a BSc degree in ana-
lytical chemistry and an MSc degree in organic chemistry from
the U. of Groningen, The Netherlands.
June 2003 SPE Journal