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E&P
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Construction and Application of

Clay-Swelling Diagrams by
Use of XRD Methods
Zhihong Zhou, SPE, Alberta Research Council

Slay swelling is one of the major causes of formation damage in
hydrocarbon reservoirs and also can cause many drilling opera-
tions problems in shaly formations.’ Clay swelling is controlled
?rimarily by the compositions of aqueous solutions with which
:he clay comes into contact. In this paper, we introduce a method
to construct clay-swelling diagrams that can be used to determine
the compatibility between swelling clays and aqueous fluids.
Smectite minerals can swell in two very different ways. In con-
centrated brine or in a solution dominated by divalent or multival-
mt cations, smectites experience only a small volume increase or
swelling. In these solutions, water molecules are structured in lay-
trs on the clay surface; this type is called crystalline swelling.2 In
$;!~~e-“. . ----. -N~+ ~St~.e &MIIinaSSt cation, smectites expe-
-.. ... where
cnl,lfionc
rience a large volume increase or swelling. In these solutions, an
electric double layer will develop on the clay surface and cause a
strong repulsion between the clay platelets; this is called osmotic
swelling.2 Osmotic swelling is much more damaging to hydrocar-
bon reservoirs than crystalline swelling. If the solution composi-
tions leading to osmotic swelling conditions can be well defined,
formation damage caused by clay swelling maybe avoided.
Swelling characteristics of clay minerals can be quantified by
the X-ray diffraction (XRD) method.3 To many petroleum geolo-
gists and engineers, XRD is a method useful only for mineral iden-
tification. However, with a proper sample holder, the method can
also be very useful for clay-swelling studies4 because clay swell-
ing is a result of the increase in interlayer spacing in clay particles;
damage, fluid composition falling in the osmotic-swelling field
should be avoided as much as possible.
It is important to note that the ability of Ca2+to inhibit montmo-
rillonite swelling depends on Na concentration in solution. At low
Na concentrations, a small amount of Ca in solution would effec-
tively limit the montmorillonite swelling. At higher Na concentra-
tion, a much larger Ca concentration is needed to control montmo-
rillonite swelling. This is because Ca2+ is preferred on clay surface
in Iow-ionic-strength solutions and it is the surface Ca2+ coverage
that controls the smectite swelling in reservoirs.
Fig. 1 is applicable for the systems in which major cations are
Na+ and Ca2+. However, a similar approach can be used for other
systems. For example, swelling diagrams can be constructed for
montmorillonite in-NaCl/KC1 solutions4 or in NaC1/NHqCl soht-
tions. These swelling diagrams are similar to that of Fig. 1and can
be used the same way, Other swelling clays may behave differ-
ently from montmorillonite, and the crystalline-/osmotic-swell-
ing boundary may shift as a result. If a reservoir clay is expected
to behave very differently from montmorillonite, the reservoir
clay can be used directly for swelling tests with XRD.
References
1. Krueger,R.F.: “An Overview of Formation Damage and Well Produc-
tivity in Oilfield Operation.” JPT (1986) 131: Tram.. AIME, 281.
2. Norrish, K.: “The Swelling of Montmorillonite” Discussions Faraday
.%C. ( [954) 18, 120.

this increase in interlayer spacing [called (001) d spacing] can be 3. Vhmi,B.E., Low,P.F.,and Roth. C.B.: “Dkct Measurementof the Rela-
quantified by an XRD method. tion BetweenhrterlayerForce and InterlayerDkarrce in the Swelling of
As a demonstration, we used the montmorillonite/NaCl/CaC12 Montmorillonite,”J. Co//oid & lnre~ace Sci. ( 1983)%, 229.
..,.+-- Cn,-hlm .mwl mbh,m iorm are t~e Aminant eatinns in most 4. Zhou, Z. er al.: “The Effect of Clay Swelling on Reservoir Quality,”
Z.y>.ha,,. --,”... CA..”
*W.-. ”... . . ..Z . ..- . . - -v . . . . -------------- . . . . ----- --------
paper UM 94-34 presented at the i!+t ?eiiokm %xiety of C!~f
reservoir and injection fluids. Anions have little effect on clay Annual Technical Meeting, Calgary, Aka., June 12-15.
swelling. Therefore, the system chosen here has broad applica-
tion. W.en W.QntrnQri!!Qnite is fu!!y sanrmted and experiences AXI.W E-01 =nm

crystalline swelling in NaCi/CaC12 solutions, its (001) dhYraction .Converaion factor IS exact.
peak is sharp and very well defined, and its d spacing is =19 ~.
(SPE 29224)
When montmorillonite experiences osmotic swelling in the sohr-
tion, its (001) diffraction peak becomes very broad and its d spac-
ing is usurdly >20 ~. For example, the (001) d spacing of mont-
nmri!lonite is 19.2 ~ in 0.14 N NaCi/O.06 N CaC12 solution, but f
I
“ ““’’’” “ ‘“’’” ‘ “’”-’l
●
t).
51 ~ in 0.19 N NaC1/O.01N CaC12 solution. Therefore, use of
Crystalline Swelling ●
XRD method to quantify the effect of solution composition on the
swelling behavior of montmorillonite is very convenient. On the
basis of this type of data, a swelling diagram like that in Fig. 1 can
be constructed. The position of each point in NaCi/CaC12 com-
position space defines the solution composition of this run. The
solid dots indicate that crystalline swelling is observed under the 0.001
solution composition; open circles indicate that osmotic swelling
is observed under the solution composition. The solid line is a ?ormation DusIaLe
visual-fit boundary between crystalline and osmotic swelling. As
pointed out earlier, formation damage is most likely to occur when
clay mineraIs experience osmotic swelling. Because it delineates 0.001 0.01 0.1 i
a composition field in which osmotic swelling would take place,
Fig. 1 can be used as a simple tool to determine the compatibility NaCl(N)
between a montmorillonite-rich formation and foreign (drilling Fig. l-Swelling diagram of montmorilionite in NaC1/CaCl:
and injection) fluids. To minimize swelling-related formation aolutiorm
-J

306 April 1995*JPT