Compatibility of Resin-Coated
Proppants With Crosslinked
Fracturing Fluids
K.H. Nlmerlck, SPE, S.B. McConnell, SPE, and M.L. Samuelson, SPE, Dowell Schlumberger
Summa..,. This paper describes the additive interaction and/or compatibility of various resin-coated proppants (RCP's) with low-,
neutral-, and high-pH water-based fracturing fluids. Solutions are provided for those fluids exhibiting compatibility problems with RCP's.
Introduction
Proppant flowback following fracture stimulation treatments is a
major concern. This flowback can occur several months after the
stimulation treatment. Various mechanical and chemical methods
are used to prevent or to reduce proppant flowback. 1 To reduce
proppant flowback while maintaining a high concentration of sand
in the fracture, a tail-in of curable RCP's in a crosslinked fractur-
ing fluid is used in the fracture stimulation treatment. Since the late
1970's, curable RCP's have been used to control proppant
flowback. 2-4
Curable RCP's are manufactured by placing a layer of a partial-
ly cured phenolic resin on commercially available proppants. When
temperatures exceeding 130°F and closure pressure are applied,
the curable RCP chemically bonds to form a consolidated, highly
conductive, permeable barrier against proppant flowback. 5 ,6 The
curable RCP must be placed across the entire producing interval
to reduce proppant flowback effectively. The RCP is often pumped
downhole with water-based, crosslinked fracturing fluids. These
fracturing fluids are made with either synthetic or natural polymers
complexed with a borate or a transition-metal ion. Transition-metal
crosslinkers are generally used for fracturing high-temperature
wells. These crosslinkers are used frequently because of the reac-
tion between the polymer's oxygen functionalities (cis-OH's) and
stable +4 oxidation states. The transition-metal crosslinkers are
used in low-, neutral-, and high-pH polymer solutions. The
transition-metal crosslinked fracturing fluid is thermally stable and
reduces friction pressure by controlled, delayed crosslinking. Fluid
temperature, pH, shear conditions, crosslinker type, and compet-
ing complexation ligands affect the crosslinking rate. 7 Many
different organic molecules (ligands) are capable of reacting with
the metal ion, either delaying or inhibiting the metal/polymer cross-
linking mechanism. Therefore, any organic additives and/or reac-
tion products within the treatment fluid could affect the performance
of the crosslinked fracturing fluid.
Exposure of curable RCP to very basic fluids has been found to
weaken the resin coating and bond strength.3 Previous work 1
showed that fracturing-fluid crosslink time may tncrease by as much
as 100% from the addition of curable RCP. This change can ad-
versely affect the performance of the fracture stimulation by reduc-
ing gel stability. 1 Successful fracturing treatments depend on
complex slurry designs that demand maximum performance from
all additives. The interaction between curable RCP and crosslinked
fracturing gels can affect fluid rheology and, in some instances,
cause the fracturing treatment to end prematurely.
Laborato.., DevelopmentlTestlng
A number of tests were performed to better our understanding of
the interactions and/or compatibility of various fracturing fluids with
RCP's. These tests were designed to elucidate pH effects, extract-
ability of RCP's in aqueous solutions, RCP bond strength, cross-
linker distribution, fluid rheology, and characterization of
water-solubilized RCP organic compounds.
Fracturing-Fluid Mixing Procedure. The gel containing the ap-
propriate additives was mixed and hydrated in a blender. RCP was
Copyright 1992 Society 01 Petroleum Engineers
SPE Production Engineering, February 1992
slurried into the gel at a concentration of 8 Ibm/gal. The crosslinker
was added, and stirring continued for 30 seconds. The slurry was
then poured into glass containers and placed in a 185°F bath to
activate the crosslink. The gel was shaken frequently to keep the
RCP suspended until crosslinking was complete. After 1 hour at
185°F, slurry was removed from the bath, and the distribution of
crosslinker between the gel and RCP was determined.
Transition-Metal Crosslinker Evaluation. The transition-metal
crosslinked fracturing fluid was separated from the RCP with a high-
speed centrifuge. The RCP was washed with deionized water to
remove any residual fracturing fluid. The concentration of the tran-
sition metal in the fracturing gel was determined by energy-
dispersive X-ray spectroscopy (EDX) against the transition-metal
crosslinker in gel laboratory standards. The RCP was scanned with
EDX to determine the presence of the transition-metal crosslinker
on the surface.
RCP Extraction. Samples were prepared for ultraviolet/visible
spectroscopy by extracting the RCP in water, pH adjusted to '" 10
with sodium carbonate, for about 30 minutes. The resulting extract
was filtered and then diluted with deionized water. Total organic
carbon analysis was performed on extracts of two RCP's prepared
at various pH values. Fourier-transform infrared spectroscopy re-
quires a much larger sample than either ultraviolet/visible spec-
troscopy or total organic carbon analysis (milligram vs. microgram
quantities). Consequently, the RCP extract had to be significantly
concentrated to obtain a spectrum. An aqueous extract, obtained
for ultraviolet/visible spectroscopy and total organic carbon anal-
ysis, was placed in a steam bath to concentrate the extracted resin.
Once dried, the nonvolatile residue was used to prepare a KBr pellet
for Fourier-transform infrared spectroscopy analysis.
Fluid Rheology/Stabllity and Effects on Compressive Strength
of RCP. A gel containing 50-Ibm hydroxypropylguar (HPG)/I,OOO
gal was prepared with appropriate additives and pH in a blender.
While the gel was stirred, the RCP was slurried into it at a concen-
tration of 8 Ibm/gal. An aliquot of the slurry was transferred to
a specially equipped Baroid™ cell. A sufficient amount of the gel
was squeezed out of the slurry for a Fann 50™ rheology test. The
temperature of the Baroid cell was raised to 200°F. After I hour,
all the free gel was squeezed from the RCP slurry by nitrogen to
drive the compression piston. Nitrogen pressure was increased to
300 psi on the compression piston. The lower stem of the Baroid
cell was closed, and the temperature was increased to 275°F. Af-
ter the RCP was cured for 24 hours at 300 psi and 275°F, the Baroid
cell was cooled to room temperature. The "'2-in.-Iongx2-in.-
diameter RCP wafer was removed from the Baroid cell. A hydrau-
lic press was used to determine the compressive strength of the RCP.
Results and Discussion
RCP Aqueous Extract Characterization. The high-pH extracts
of the curable RCP show a major ultraviolet absorbance in the 280-
nm region that can be attributed to phenolic materials (Fig. 1). The
peak at 280 nm increases in intensity as the extract is concentrat-
ed. This indicates that an ultraviolet trace could possibly be used
29
 TABLE 1-REDUCTION IN ZIRCONIUM CROSSLINKER
BY RCP (50 Ibm HPG fluldj pH = 9.0)

Metal Crosslinker Metal

Concentration Crosslinker Loss
Test' (ppm) (0/0)
Ambient control 32
Bath control 33
CR Sand S1 23 30
CR Sand 52 24 27
CR Sand A1 24 27
CR Sand A2 24 27
PR Sand A1 29 12
PR Sand A2 28 15
'CR-curable resin. PR-precured resin.

various pH values show that the concentration of organic extracted

280nm
from the curable RCP increases with pH, with a significant increase
occurring between pH values of 7 and 11 (Fig. 2). This indicates
that the resin coating is affected. In addition, the total organic car-
bon in solution may represent a complexor or ligand that could in-
terfere with the crosslinking mechanism. The precured RCP was
affected only slightly by the pH changes.
Spectral analysis by Fourier-transform infrared spectroscopy
shows more specific functionality not seen by ultraviolet spectrosco-
py. The Fourier-transform infrared spectroscopy spectrum shows
PnlCUF8d RCS
(10 fold clludon) peaks characteristic of the -OH and q,-O stretches in phenolic
compounds (Fig. 3). Other stretches indicate the presence of the
curing agent, hexamethylene tetramine (or methenamine), and some
carbonyl functionality. This analysis confirms that the organic ma-
terial extracted is a combination of curing agent and a material with
some carbonyl functionality. It also shows that the extracted resin
material can be monitored with this technique.
400nm Metal Crosslinker Concentration/Distribution. The loss of the
Fig. 1-Ultravlolet spectral comparison of aqueous RCP zirconium metal crosslinker from the fracturing fluid containing
extracts. 8 Ibm RCP/gal varies from 12% to 30% (Tables 1 and 2). EDX
analysis of the RCP separated from the fracturing fluid shows metal
crosslinker on the surface (Fig. 4). The most obvious factor affecting
to detennine the organic concentrations extracted from the curable the fracturing-fluid performance is the loss of the "active" metal
RCP. The precured RCP extract shows no ultraviolet-active mate- crosslinker. The metal complexed by the RCP surface is not avail-
rial in the same region (Fig. 1). Total organic carbon analyses at able for crosslinking the polymer. The gel neither crosslinks ef-

-a 1000

900 t-----ii-----t-'-----i ~ CURABLE

I ~. PRECURED I
-
~
~ 800 /
Z
0 700 /
/
!XI /-)
~ 600
t,)
t,)
500 ./
~
~
400; ;

300
0

~
200

100 ------< r------~

0 L~--­
E-4 ___ fr'- ----..(~-----~
0
5 6 7 8 9 10 11
pH

Fig. 2-Effect of pH on r8aln-temperature=75°Fj 1·hour extract.

30 SPE Production Engineering, February 1992

 .
i
•• OH

•• 0

4, 000 1,aoo 1,Il00 1,400 1,2110 1,000 IlOO eoo _

WAVENUMBER~cm-1)

Fig. 3-Fourler-transform Infrared spectrum of curable Rep extract.

RESIN-COATED PROPPANT 2110

PR-150S 150sec OINT I ~·CURABLE
V-256 H-20KEV 1:10 AO-20KEV 10 -a
22II I .A.
-e- PRECURED
CONTROL
.,!:!. 200
.... .....
I f.....,. .....
~ 17
fIl ----~.
....... -
~ 1110
.... ----::::j
~' ..
~ 12II
--~ ..
~ 100
~
;~
METAL CROSSLINKER
6 ~

2II 0 2
TDIE (hr)

Fig. 5-Effect of Rep on titanium crosslinked HPG--pH = 4.5j

temperature = 200° F.
<13.60KEV XES 18.72KEV>

Fig. 4-X-ray spectrum of Rep surface showing crossllnker. 176

I...-e--PRECURED
CURABLE I I

fectively nor suspends the RCP. Crosslinker concentration is re-

duced when the curable RCP is used in conjunction with other metal
crosslinked fracturing fluids (Table 2).
j1110
....
I 121i1
: .....
.A·CONTROL I

~'"
~ '. " .

Fluid Rheology/Stability. Rheological data were generated for ~ 100

titanium and zirconium crosslinked gels containing curable and pre-
....
'>~"""""
cured RCP. The titanium gel was evaluated at pH values of 4.5
-..._-- .........._---
_- _- ~D
and 9.0. The zirconium gel was evaluated at a pH of9.0. The high
viscosity and thermal stability provided by zirconium crosslinked -- ...... ... ......
gels make them preferable for extensive compatibility testing with -----------
curable RCP.
The titanium gel at a pH of 4.5 shows only a slight loss in early
viscosity resulting from the presence of curable and precured RCP '!J.o 0.1i 1.0 1.6 2.0
at 200°F (Fig. 5). The minimal effect from a 25% loss of titanium TDIE (hr)
indicates that there is an excess of titanium present in the gel (Ta-
ble 2). Fig. 6-Effect of Rep on titanium crosslinked HPG--pH = 9.0j
At a pH of 9.0, the curable RCP's were more detrimental to titani- temperature =275°F.
um and zirconium crosslinked gels. A 16% and 30% loss of titanium
SPE Production Engineering, February 1992 31
 TABLE 2-CROSSLINKER REDUCTION BY CURABLE RCP

Crosslinker Crosslinker
Concentration Concentration Crosslinker
50-Ibm HPG-Based Before Addition of RCP After Addition of RCP Loss
Fracturing Fluid (ppm) (ppm) (%)
Low-pH (4.5) Ti 160 120 25
Neutral-pH (7.0) Ti 62 49 21
High-pH (9.0) Ti 51 43 16

200 ....

75
....... , • .t.. CONTROL - 70% OF std Zr
_
~-
RESIN REMOVED BEFORE Zr
RES1N PRESENT WITH Zr
l
~260~----~~~---+~~~~~~--+-----~ ....................
i 226k~------I__--------'l~"--------+-------+-------i
50 ~ ..
.......
~200~--~~-------+------~=-----+_----~ 25" ....
CIJ
~m
~ 160~----_4-------+--~~~------+_----~
r------.
-------------:-'
.......,

<
~ 121>
75 t:-----
---"'-- _-
~
...
__~_-
~1001~ __-__-_-
__4-------I-------+------+-~~~
50 ........ _-
~ 76
21)
60~-----4------_+~~=-~------+-----~

260~----~-------+------~------~----~ 0
o 2 3
TIME (hr)

Fig. 7-Effect of RCP on zirconium crosslinked HPG- Fig. 8-Effect of curable resin leachate on zirconium cross-
pH = 9.0; temperature = 275°F. linked gel-pH = 9.0; temperature = 275°F.

300r------r------~~~~~==~r_----1
2761---""-,.,:---+--------+-11
~260~----~~~...-... --+~==~~=====d~----~
±:t~~~;O~;std lH--------I
Zr
~
~r-----~------~~~~~~~----_r~
276
.!'l pH 9.0 + 30% Zr
.....

,It 260 t------'l'-"-..",----t--i

...
-1'- pH 10 w/Add.3 +30% Zr ~
~·.pH 9.6 w/Add.l +30% Zr
- pH 10 w/Add.l +30% Zr I - -
,It .. ..t.. pH 9.0; std Zr; CONTROL
i
-I 2261-------11-------+'-0-,-----+-------+-------1

~
......... .
~
2261':-----,·
200 --- _= t'--- .............. .
~
200
176'.",..______
...... .
",-----+-------+-------1-------""f~------I ~ 17~·-::~··=~~: ------- t:::----... ..............

-~ ---""1"- ___
.... ~ 150 ................ . .~~~,.. ...~~-------- -------'k . . . .
<
i>"
1601-----~~-=_--+_------1__----_+----~~

126 -"'i"-- ____ ~ 121)JI!~

--------- ---.,
~101~~--+-----~---
o
~+~~~_r------I
---------- ----, r----
~ : ~----_4------------_+~-.-~--~=_~------+_--------.,~
~
?.~
1: .....-.. --t(D-~~--':::=.::~_'.~.".'""'.1
.---+----t----+--··-
60~----_1-------+------1-------+-----~
----I>
2I)0~----~------~2------~3~----~.------~5 260~----~------~2------~S~-----+.------~5
TDIE (hr) TDIE (hr)

Fig. 9-Effect of curable resin on zirconium crosslinked gel-
=
pH 9.0; temperature 275°F. = linked gel-temperature 275°F.
and zirconium, respectively, to the curable Rep accounted for a
significant loss of viscosity at 275°F (Figs. 6 and 7). The precured
Rep reduces the viscosity of titanium and zirconium gels by about
15% at 275°F (Figs. 6 and 7). The zirconium crosslinked gels still
provide higher viscosities and better stability in the presence of cura-
ble and precured Rep compared with titanium crosslinked gels.
Rheology tests were conducted to determine the effects of ex-
posing the curable Rep to a gel with a pH of 9.0, separating the
gel, and crosslinking it with a zirconium crosslinker. It was found
that the loss of viscosity caused by adding curable Rep to the gel
is related to more than just loss of zirconium to the resin. The vis-
cosity is significantly reduced by the organic leachate removed from
the Rep as indicated by a comparison with the viscosity achieved
with 70 % of the normal amount of zirconium crosslinker (Fig. 8).
The Fourier-transform infrared spectral analysis showed that the
organic leachate contained a phenolic-type material with carbonyl
functionality (Fig. 3). Increasing the zirconium by the amount lost
32
Fig. 10-Effect of curable resin on buffered zirconium cross-
=
to the resin significantly helps increase viscosity. This crosslinker
adjustment did not lead to total viscosity recovery (Fig. 9).
It was found that the interference caused by curable Rep can
be minimized by elevating and buffering the pH with special addi-
tives. Additional crosslinker is added to compensate for the amount
lost to the resin. The pH is elevated to between 9.6 and 10.0. Fig.
10 shows the effects of different pH-elevating additives. Excellent
results were obtained with Additive 1 at pH values of9.6 and 10.0.
The performance of Additive 3 shows that not all pH-elevating ad-
ditives were effective.
It was also found that a curable resin may give inconsistent
responses. Results from a curable Rep obtained from sand storage
on location indicate that elevating the crosslinker concentration will
not sufficiently increase the viscosity to transport proppant (Fig.
11). The use of Additive 1 to elevate the pH significantly improves
fluid stability. Tests should be conducted on location to determine
what fluid changes are required.
SPE Production Engineering, February 1992
 300 Authors
+ 3070 Zr
.E'l pH 9.0
2 75 .... -+. pH 10 w/Add.1 +3070 Zr r--
..- pH 9.6 w/Add.1 +3070 Zr
~250 ,
............ ..
~ pH 10 w/Add.3 +3070 Zr r--
.1:.. pH 9.0; sid Zr; CONTROL
i 225 •.................... ............
~ 2
---------- - -'-'" .....
.....
.... -.
... 50' 1'--.
~ 175
------.. "'--- ........, .......... .... .....,..
....

---..., !'---- ... _-- ....................

25 ------ -
00
-" r---- -- ..._--- ..-
7& r--- McConne" Nlmerlck Samuelson
50 I
r:p Kenneth H. Nlmerlck Is a senior development engineer at
25
o 2 3 5 Dowell Schlumberger In Tulsa. He has worked In both 011 and
TIME (hr) gas, as well as In minerai handling and processing rasearch.
Nlmerlck holds a BS degree In chemistry from Central State
Fig. 11-Effect of curable realn (field sample) on bufferad zir- U. In Edmond, OK. at.nley B. McConnell Is a senior devel-
conium crosslinked gel-temperature 275°F. = opment engineer at Dowell Schlumberger's Western Dlv.
Technology Center In Englewood, CO. He specializes In In-
dustrial waste treatment and o"we" fracturing fluids. He holds
Compressive-strength data were obtained on 2-in.-diameterx2- a as degree In chemistry from Southwestern Oklahoma State
in.-Iong plugs cured at 275°F and 300 psi for 24 hours (Table 3). U. In Weatherford, OK. Mlch.el L a.muelson Is a senior
Compressive strengths were used to evaluate the effect of the pro- development engineer with Dowell Schlumberger In Tulsa.
He began his career with Dowell Schlumberger In 1979 as an
posed buffering additive and increased crosslinker levels on the RCP analytical chemist and has since held various positions In
(Table 3). The compressive strengths, although lower, should be product development and field support. Samuelson's tech-
sufficient to prevent proppant flowback. nlcallnterast Includes chemical analysis of o"fleld products.
He holds a BS degrae In chemistry from Oral Roberts U. In
Conclusions Tulsa.
1. Use of pH buffering additives with appropriate adjustments
of crosslinker concentration produces stable crosslinked gels in the
presence of curable RCP. TABLE 3-EFFECTS OF ELEVATED pH ON COMPRESSIVE
2. The addition of the RCP to organo-metallic crosslinked frac- STRENGTH OF CURABLE RCP
turing fluids can interfere with the crosslinking mechanism, there-
Compressive
by adversely affecting stability. Fluid Strength % of
3. Rheological tests show that the curable RCP causes a substan- (lbm/1,000 gal) pH Additive (psi) Standard
tial reduction of gel stability when used with high-pH organo- 50 HPG-ZRxL· 9.0 None 1,456
metallic crosslinked fracturing gels. 50 HPG-ZRxL 9.6 Additive 1 472 32.4
4. Loss of the metal crosslinker to the RCP surface varied from 50 HPG-ZRxL 10.0 Additive 1 334 22.9
12% to 30%. 50 HPG-ZRxL 10.0 Additive 2 597 41.0
5. Ultraviolet and Fourier-transform infrared spectroscopy tech- 50 HPG-ZRxL 10.0 Additive 3 528 36.3
niques can be useful for predicting the compatibility of RCP and ·Zlrconlum crosslinked.
fracturing fluids. Samples cured for 24 hours at 275°F and 300 pSi.

Acknowledgment
5. "AcFrac™ CR Curable Resin-Coated Sand Proppant Technical Data,"
We express our appreciation to Dowell Schlumberger for permis- Acme Resin Corp., Forrest Park, IL (Sept. 1986).
sion to publish this study. 6. "Super Sand™ Technical Data," Santrol Products Inc., Houston (Sept.
1983).
References 7. Reservoir Stimulation, M.I. Economides and K.G. Nolte (eds.), Schlum-
berger Educational Services, Houston (1987) 4-4-4-6.
1. Pope, C.D., Wiles, T.I., and Pierce, B.R.: "Curable Resin-Coated Sand
Controls Proppant Flowback, " paper SPE 16209 presented at the 1987 81 Metric Conversion Factors
SPE Production Operations Symposium, Oklahoma City, March 8-10.
2. Graham, I.W., Muecke, T.W., and Cook, C.E.: "Method for Treating
OF (OP-32)/1.8 °C
Subterranean Formation," U.S. Patent No.3,929,191 (Dec. 1975). in. x 2.54* E+OO cm
3. Sinclair, A.R.: "'An Effective Method of Sand Control," paper SPE 7004 Ibm/gal x 1.198264 E+02 = kg/m 3
presented'at the 1978 SPE Symposium on Formation Damage Control, psi x 6.894 757 E+OO kPa
Lafayette, Feb. 15-16.
4. Sinclair, A.R., Graham, I.W., and Sinclair, C.P.: "Improved Well
·Conversion factor is exact. SPEPE
Stimulation With Resin-Coated Proppants," paper SPE 11579 present- Original SPE manuscript received for review Sept. 23. 1990. Revised manuscript received
July 15. 1991. Paper accepted for publication July 29. 1991. Paper (SPE 2(639) first pr.enl-
ed at the 1983 SPE Production Operations Symposium, Oklahoma City, ed at the 1990 SPE Annual Technical Conference and Exhlbhlon held In New Orleans.
Feb. 27-March 1. Sept. 23-26.

SPE Production Engineering, February 1992 33