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 (Fig. 2).12,13 Several variations of the same technology were cre-
This paper describes a material derived from natural sources that ated to overcome the toxicity issues associated with formaldehyde
can be used to crosslink a variety of acrylamide-based polymers and phenol. These processes generally involve replacing formal-
over a broad temperature range to produce gels for confor- dehyde and phenol with less toxic derivatives that generate phenol
mance applications. and formaldehyde in situ, or are themselves active components of
Delayed crosslinked polymer systems have been used for many the crosslinking system. For example, formaldehyde can be re-
years in conformance applications. For the past decade, the most placed with hexamethylene tetramine (HMTA), glyoxal, or 1, 3,
widely used system has been based on chromium (3+) crosslinked 5-trioxane. Substitutions for phenol included phenyl acetate, phe-
polyacrylamide. Organic crosslinkers, such as phenol/formaldehyde nyl salicylate, or hydroquinone, among others.12,13 Extensive pat-
and polyethyleneimine (PEI) have also been used with a variety of ent literature for this technology exists.1422
polymers. However, these systems are being scrutinized by gov- Recently, a less toxic crosslinker was tested extensively in field
ernmental agencies and have been scheduled for phaseout in some trials worldwide and enjoyed a very high success rate.2327 This
countries. Because of these issues, a single, environmentally system is based on PEI crosslinker and a copolymer of acrylamide
friendly crosslinker that could be used with a variety of polymers and t-butyl acrylate (PA-t-BA). PEI is a low-toxicity material that
over a broad temperature range was the focus of this study. is approved in the United States for food contact.2831 PA-t-BA is
This paper details the laboratory development of an environ- a relatively low molecular-weight polymer. The low molecular
mentally friendly, natural polyamine crosslinker system. This weight is expected to provide rigid ringing gels. The crosslink-
crosslinker can be used with a variety of polymers, such as poly- ing is believed to take place in situ by amidation of the pendant
acrylamide, AMPS/acrylamide, or alkylacrylate polymers. Gels ester groups on the base polymer (Fig. 3). Recent test results
ranging from stiff and ringing type to lipping gels have been indicate that a variety of polymers containing acrylamide pendant
obtained. The data illustrate a simple, commercially available sys- groups react with PEI nitrogens through a transamidation reaction
tem that can be applied to field operations. Potential crosslinking pathway to provide gels (Fig. 4).32
mechanism(s) of the system will be discussed. 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
Introduction containing amino groups suggested that chitosan (Fig. 5) may react
Water production in oil-producing wells becomes a more serious with acrylamide-based polymers in a manner similar to PEI. Chi-
problem as the wells mature. Remediation techniques for conform- tosan is a polysaccharide obtained by de-acetylating chitin, a ho-
ance control are selected on the basis of the water source and the mopolymer containing -(1-4)-2-acetamido-2-deoxy-D-glucose
method of entry into the wellbore. Treatment options include seal- (Fig. 6) that occurs in the shell or skin of anthropods or crusta-
ant treatments and relative permeability modifiers (also referred to ceous water animals. Chitosan is also present in the environment,
as disproportionate permeability modifiers). This paper primarily although in lesser amounts than the chitin. The degree of de-
discusses water control with water-based gels for applications in acetylation in the commercially-available chitosan materials is
wells in which the oil- and water-producing zones are clearly usually in the 70 to 78% range. The chitosan solubility in acidified
separated and can be mechanically isolated. water, for example in acetic or hydrochloric acid, is in the 1 to 2%
Chromium(III) crosslinked polyacrylamide gels can be choice range. The viscosity of the solutions depends on the molecular
materials for matrix-fluid shut-off systems.14 The crosslinking reac- weight of the polymer. If the pH of the solution is increased above
tions in these gel systems take place by the complexation of Cr(III) 6.0, polymer precipitation occurs.
oligomers with carboxylate groups on the polymer chains (Fig. 1). This paper presents results using chitosan as an environmen-
Because of the nature of the chemical bond between Cr(III) and tally preferable crosslinker for use in combination with acryla-
the pendant carboxylate groups, formation of insoluble chromium mide-based polymers. Gel treatments using this material should
species can occur at high pH levels. Other problems with these contain a biocide. The advantage here is that if inadvertently dis-
systems include thermal instability, unpredictable gel times, and charged, the chitosan will biodegrade.
gel instability in the presence of chemical species that are potential
ligands. The gel times are controlled by the addition of materials Experimental Methods
that chelate with chromium in competition with the polymer- Preparation of Chitosan Solutions. Commercial solid chitosan
bound carboxylate groups.5,6 samples were dissolved in fresh water solutions containing 1%
Another popular water-based gel system for water-control ap- acetic acid to make 1.0 to 1.5% polymer solutions. Chitosan lactate
plications is based on a phenol/formaldehyde crosslinker system salt, which is also commercially available, can be dissolved di-
for homo-, co-, and ter- polymer systems containing acrylamide.711 rectly in fresh water to prepare solutions with similar polymer
Depending on the polymer composition, these gels are thermally concentration. The viscosities and clarity of the solutions depended
stable, and the gel times are controllable over a wide temperature on the polymer molecular weight and the degree of de-acetylation.
range. The crosslinking mechanism involves hydroxymethylation Aqueous solutions of chitosan salts are also available commer-
of the amide nitrogen, with the subsequent propagation cially, which can be used directly for crosslinking base polymers. The
of crosslinking by multiple alkylation on the phenolic ring 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,
Copyright 2003 Society of Petroleum Engineers
PHPA, contained acrylate groups (11 mole %) introduced by par-
This paper (SPE 84937) was revised for publication from paper SPE 75163, first presented tial hydrolysis. The molecular weight of this polymer is approxi-
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.
mately 6 million. The second polymer, PA-t-BA, contained about
Manuscript peer approved 10 March 2003. 5 mole % of tert-butyl acrylate as the comonomer, and hydrolysis

June 2003 SPE Journal 99

 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.
Fig. 1Crosslinking reactions take place by the complexation The time needed to reach a gelation of 94% or higher is the gel time.
of carboxylate groups on the polymer chains by chromium spe- If gel syneresis occurred after the gel was formed, the syneresis
cies (Mn+=Cr3+ and/or oligomers).35 was measured as described in Eq. 1, except that h equaled the
gel-column height before the gel was aged at a given temperature.

was less than 0.5% with a molecular weight of 500,000. The third Thermal Stability Measurements. The gels were stored in sealed
polymer, AMPS/AA, contained about 30 mole % of 2-acrylamido- tubes in thermostat-controlled ovens kept at 225 and 250F. Peri-
2-methylpropane sulfonic acid. The molecular weight of this poly- odically, the test tubes were visually inspected at temperature
mer was about 5 to 6 million, and the hydrolysis was less than 1%. (without cooling) for gel syneresis and/or degradation.
The viscosities of a solution containing 7% PA-t-BA and 0.5%
chitosan lactate in 85% fresh water and 15% synthetic seawater Single-Core Flow Testing With a Multitap Flow Cell. The fol-
were measured using a Fann 35 Rheometer and a Brookfield LVT lowing is a procedure for measuring permeability reduction to water
viscometer. The results are shown in Table 1. The viscosity values using the chitosan/PA-t-BA polymer gel system. A more detailed
observed are in the range typical for polymer solutions used in description of the experimental setup was presented earlier.33
conformance applications. 1. Record the test-core dimensions and place the core in a suit-
In the case of PHPA and AMPS/AA, because of the very high able holder, such as a Hassler sleeve apparatus. Place sufficient
polymer molecular weights, the concentrations of base polymers overburden pressure on the test core to ensure that no fluid by-
in aqueous solutions were kept near 0.7% so that the viscosities passes the core. (Generally, an overburden pressure of 450 to 500
of the base polymer solutions were within useful range for prac- psi over the treatment pressure is used for this purpose.)
tical applications. 2. Determine water viscosity at the temperature that will be
used in the flow tests. All flow series were performed at the desired
Gel Time Measurements. Two methods were used to measure test temperature of 175F.
gel times: 3. Stabilize water flow through the core in the normal produc-
Method ABrookfield Viscosity Method. Approximately 300 tion direction.
mL of the polymer composition for testing was placed in a 400-mL 4. Pump the treatment through the core in the reverse-flow direction.
beaker. The beaker was then inserted into a preheated, thermostat- 5. Repeat Step 3.
controlled Brookfield viscometer with a No. 2 spindle. The poly- 6. Determine the cores residual resistance factor (RRF) for
mer solution was stirred at 10 rev/min, and the viscosity changes water by dividing the cores pretreatment permeability-to-water to
were monitored as a function of time. A plot of viscosity vs. time its post-treatment permeability-to-water (RRFpretreatment per-
can be generated for estimating gel time, which is defined as the meability-to-water post-treatment permeability-to-water).

Fig. 2Crosslinking mechanism involving hydroxymethylation of the amide nitrogen, with subsequent propagation of crosslinking
by multiple alkylation on the phenolic ring.

100 June 2003 SPE Journal

Fig. 3Less-toxic crosslinker based on polyethyleneimine Fig. 4Polymers containing acrylamide pendant groups react
(PEI) crosslinker and a copolymer of acrylamide and t-butyl- with PEI nitrogens through a transamidation reaction pathway
acrylate (PA-t-BA). to provide gels.

very low (<150F) temperatures, the gel times were either too
Environmental Testing. Inhouse BOD (Biochemical-Oxygen- short or too long at this ratio. The trends observed with PA-t-BA
Demand) tests were done according to HACH Method 10099, were confirmed with PHPA copolymer. Based on the gel times
and Chemical-Oxygen-Demand (COD) tests were conducted ac- shown in Tables 2 and 3, it appears that PHPA may be a suitable
cording to HACH Method 8000 described in the HACH Water base polymer for low temperatures, whereas AMPS/AA may be
Analysis Handbook.34 suitable for high-temperature conformance applications.
Results and Discussion pH Effects. The results in Table 4 show that as the pH is de-
All the variables tested that can potentially impact gelling of poly- creased, the gel times are increased. At the lower temperatures, this
mers with chitosan are: observation is in accordance with expectations for amine-type
Base polymer. crosslinkers. In acidic media, the lone pair of electrons on the
Crosslinker concentration. amine nitrogens are expected to be protonated, thus making them
pH. unavailable to initiate a nucleophilic attack on an amide carbonyl
Mix water. group of the base polymer (Fig. 4). By controlling the pH, the gel
Temperature. 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
Base Polymer. The results in Table 2 indicate that polyacryl- of the chitosan solutions. For example, when the pH of the chito-
amide, PHPA, crosslinked fastest followed by PA-t-BA and san solution was lowered, with either acetic or lactic acid, similar
AMPS/AA. The order of the ease of crosslinking reactivity sug- gel times were obtained. This effect is less obvious in the higher
gests steric resistance to the approach of the amino group at the temperature experiments because of the short gel time and inherent
amide carbonyl group in PA-t-BA and AMPS/AA copolymers experimental limits on gel-time measurement.
because of the adjacent bulky groups. A similar order of reactivity
was noted for crosslinking of the above polymers with PEI, sug- Mix Water. The mix water effects on the crosslinking reaction of
gesting similar operating mechanisms. In the case of AMPS/AA, PA-t-BA with chitosan salts were also tested. The results are pre-
presence of a smaller amount of acrylamide may also be a con- sented in Table 5.
tributing factor. Test results show that the reactions proceed significantly faster
An advantage of a low-molecular-weight polymer such as the in fresh water compared to seawater even though the amount of
PA-t-BA is that higher concentrations can be used, as compared to seawater, or 2% KCl solution in the total composition, is only 15
other higher-molecular-weight polymers, without increasing the to 18%. Similar results were observed in the crosslinking reactions
viscosity of the base solution. Further, the gels obtained with the of PA-t-BA with PEI.
higher concentration of the base polymer result in rigid, ringing
gels, as seen in Tables 2 through 4. Temperature. The temperature effects observed are presented in
Fig. 8 and are as expected. As mentioned earlier, partially hydro-
Crosslinker Concentration. Typically, the gel times depend on lyzed polyacrylamide provides faster crosslinking rates than the
the weight ratio of base polymer to crosslinker. In this study, the acylamide copolymers containing t-butylacrylate or AMPS as the
ratio effects were studied by using PA-t-BA as the representative comonomers. Greater steric hindrance to the approach of an amino
base polymer. The results presented in Table 3 show that a ratio of group at the acrylamide carbonyl group flanked by bulky groups
base polymer to chitosan of 14 was adequate to provide gel times may explain the differences in the observed differences in the
useful for commercial applications. At very high (>250F) and crosslinking reaction rates.

Fig. 5Chitosan.

June 2003 SPE Journal 101

 Fig. 6Chitin.

Gel Thermal Stability. The gels turned light brown within a few Environmental Issues
days at the oven temperatures. However, no syneresis was ob-
Chitosan occurs in nature in small amounts. Chitosan-degrading
served over a 6-week period in the 200 to 250F range.
enzymes, namely chitinases, chitosanases, and lysozymes that de-
grade chitin-derived materials, occur in bacteria, fungi, algae
Multipressure Tap Core Flow Tests. The core flow study results
mammals, birds, fish, and so on.
are shown in Fig. 9 and Table 6. A Berea sandstone core was used
Chitosan and the constituent monomer, glucosamine, are ap-
as the test medium, the evaluation temperature was 190F, and 7%
proved for human consumption as dietary supplements. It is cur-
KCl was used as the evaluation brine. After stabilizing the flow of
rently used in the U.S. as an ingredient in animal feed on an
the brine through the core, a 100-mL treatment (composed of 7%
experimental basis, and as a filter medium for potable water.
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 Toxicity. An LD50 value of 16 grams per kilogram body weight in
viscosity of the polymer/crosslinker solution within the rock dur- mice when administered orally was reported by Arai et al.34 Ac-
ing treatment was calculated using the initial permeability as a cording to this group, the LD50 values are of the same order of
constant and solving for viscosity using Darcys linear flow equa- magnitude as lethal doses of sugar (sucrose) or salt.
tion (Eq. 2): The aquatic toxicity values (obtained by a supplier) for the
glycolate salt of chitosan are:
AKP Acute fish toxicity: LC 50>100 mg product/liter.
= . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (2)
QL Acute bacteria toxicity: EC 0>100 mg product/liter.

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- Biodegradability and Persistence. According to the supplier, chi-
ment stage, indicating that the fluid was moving evenly throughout tosan is readily and rapidly biodegradable: all individual organic
the core and no face plugging of the core was occurring. The end substances contained in the product achieve values in tests for
segments of the core typically show lower permeability than the ready biodegradability (e.g., OECD 301 A-F) of at least 60%
center two segments. This result is normal and is caused by end BOD/COD or 70% DOC reduction (tolerance value for classifica-
effects (short segment length, contamination of the core ends via tion as readily biodegradable: >70% DOC reduction or
the fluid used to drill the cores, etc.). This data is used only to help >60% BOD/COD in 28 days).
determine the occurrence of face plugging in fluid treatments. A 5-day inhouse environmental test of chitosan showed a BOC/
Following the overnight shut-in period, the flow of 7% KCl COD of 54% compared to 32% for hydroxyethyl cellulose (HEC).
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 Conclusions
Berea sandstone core, resulting in a RRF of 3310. No wash-off or 1. Chitosan is an effective crosslinker for acrylamide-based water-
removal of the gel treatment was observed during an overnight soluble base polymers, and provides lipping to rigid ringing
flow study. 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.

102 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

 Fig. 8Temperature vs. gel time.
Nomenclature
A area, cm2
h height of the initial fluid column when the tube is in 7. Bryant, S.L. et al.: Polymer Gelants for High-Temperature Water
the vertical position Shutoff Applications, paper SPE 36911 presented at the 1996 SPE
European Petroleum Conference, Milan, Italy, 2224 October.
K permeability, darcies
8. Albonico, P. et al.: Studies on Phenol-Formaldehyde Crosslinked
l length of the tube
Polymer Gels in Bulk and Porous Media, paper SPE 28983 presented
L length of the core, cm
at the 1995 SPE International Symposium on Oilfield Chemistry, San
Q flow rate, cm3/sec Antonio, Texas, 1417 February.
t length of the liquid/gel level when the tube is in the 9. Hutchins, R.D. and Dovan, H.T.: Composition for Selectively Reduc-
horizontal position ing Subterranean Formation Permeability, U.S. Patent No. 5,418,217
P differential pressure in atmosphere (1995).
viscosity, cp 10. Bryant, S.L. et al.: Experimental Investigation of the Injectivity of
Phenol-Formaldehyde/Polymer Gelants, paper SPE 37244 presented
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2. Southwell, G.P. and Posey, S.M.: Applications and Results of Acry- vanced Technical Series (April 1993) 140.
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27779 presented at the 1994 SPE/DOE Symposium on Improved Oil tems in Production of Thermally Stable Gels, paper SPE 27826 pre-
Recovery, Tulsa, 1720 April. sented at the 1994 SPE/DOE Symposium on Improved Oil Recovery,
3. Fulleylove, R.J. et al.: Water Shutoff in Oil Production Wells Tulsa, 1720 April.
Lessons from 12 Treatments, paper SPE 36211 presented at the 1996 13. Krilove, Z. et al.: Water Shutoff in Extremely Hostile Environments:
SPE Abu Dhabi International Petroleum Exhibition and Conference, An Experimental Approach in Geologically Complex, Gas Condensate
Abu Dhabi, UAE, 1316 October. Reservoirs Using Crosslinked Gels, U.S. Patent No. 4,776,398 (1998).
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Fig. 9Multipressure tap flow cell schematic.

104 June 2003 SPE Journal

20. Compositions and Processes for Treating Hydrocarbon-Bearing For- International Oilfield Chemicals Symposium, Fagernes, Norway, 19
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50738 presented at the 1999 SPE International Symposium on Oilfield B.R. Reddy is a research and product development chemist
Chemistry, Houston, 1619 February. working in the areas of cementing and conformance control
27. Lamination or sealing of food packaging application, FDA 175.105. for Halliburton. e-mail: raghava.reddy@halliburton.com. He
28. Component of paper and paperboard in contact with aqueous and fatty did postdoctoral teaching and research work at the U. of
food, FDA 176.170. Texas, U. of Oklahoma, U. of Louisville, and Trinity U. Reddy
29. Component of paper and paperboard in contact with dry food, FDA worked for Fina Oil and Chemical Co. as a research scientist
176.180. during 19901997 prior to joining Halliburton Technology Cen-
ter in Duncan, Oklahoma. Reddy holds BS and MS degrees
30. Prime coat for cellophane used for packaging food impregnate in from Osmania U., India, and a PhD degree from Oklahoma
regenerated cellulose sheet, FDA 177.1200. State U. Larry Eoff is a Principal Scientist in the Conformance
31. Reddy, B.R. et al.: Environmentally Friendly Cross-Linker System for Group at the Halliburton Technology Center in Duncan, Okla-
Conformance Polymer Systems, paper No. 3 presented at the 2000 homa. e-mail: larry.eoff@halliburton.com. He has been with

Fig. 10Permeability reduction in a core owing to chitosan PA-t-BA gel at 190oF. Berea sandstone: core length = 14.3 cm, core
diameter = 2.51 cm, porosity = 20%.

June 2003 SPE Journal 105

Halliburton for 11 years in both conformance and cement State U. (satellite of Oklahoma State U.). David Brown has been
product development. Eoff holds a BS degree in chemistry with Halliburton nearly 24 years and holds the title of Technolo-
from the U. of Central Arkansas and a PhD degree in organic gist. e-mail: david.brown@halliburton.com. While employed
chemistry from the U. of Arkansas. E. Dwyann Dalrymple is a with Halliburton, he has been responsible for the development
scientific adviser for Halliburton in Conformance Technology. of chemicals and chemical processes used in the water and
e-mail: dwyann.dalrymple@halliburton.com. For the past 28 sand control field of the oil industry. He holds a number of U.S.
years, Dalrymple has been primarily involved in all phases of and foreign patents for chemicals and chemical processes
water control: well preparation, conformance control, clay used in water and sand control. He has been responsible for
control, and improved oil recovery methods; assisting with field designing models, equipment, test training aids, and training
implementation, and consultation on procedures and job rec- manuals for Conformance and Sand Control units within Halli-
ommendations. He holds 14 U.S. patents relating to the oilfield. burton. Brown holds a BS degree from Cameron U. Marcel
Dalrymple holds a BS degree in chemistry from Cameron U. Rietjens currently works with Cimcool in Vlaardingen, The Neth-
Kathy D. Black, Principal Technician, has worked in a variety of erlands. e-mail: marcel.rietjens@halliburton.com. Previously, Ri-
areas in her 25 years with Halliburton. e-mail: kathy.black@ etjens worked as a Principal Chemist for Halliburton in Leider-
halliburton.com. She has spent the past 20 years in the Ana- dorp, The Netherlands, until the closure of the European Re-
lytical section as manager and operator of the Environmental search Centre in 2002. While at Halliburton, he was involved in
Scanning Electron Microscope. She also has other areas of research and product development for acidizing, fracturing,
responsibility, including X-ray diffraction, petrographic analysis, and water control, with special interest in asphaltenes, sludge,
NMR, and the Bioassay area of the Organic Dept. Recently, surfactants, and polymers. Rietjens holds a BSc degree in ana-
she moved out of the laboratory into Technology Project Con- lytical chemistry and an MSc degree in organic chemistry from
trols. Black holds an Associate Science degree from Connors the U. of Groningen, The Netherlands.

106 June 2003 SPE Journal