Thixotropy
Thixotropy
16, 2008
and an equation of state relating shear stress Incorporating the effect of structure on
to shear rate and structure parameter λ: yield stress and viscosity in Eq. 7 gives a
modified version of the Moore-Cheng
τ = τ (γ&, λ ) (2) equation (Eq. 5):
structure breakdown. 20
0
120 0 300 600 900 1200 1500
Shear Rate = 1460 Shear Rate = 1160 -1
100 Shear Rate (s )
Shear Rate = 461 Shear Rate = 146.1
Shear Stress (Pa)
80 Shear Rate = 91.9 Shear Rate = 23.2 Figure 4. Equilibrium flow curves.
60
120
40 Shear Rate = 461 Shear Rate = 91.9
100
20 Shear Rate = 461 Shear Rate = 91.9
30
function does not describe the data
satisfactorily at early times in the 20
experiments. This might suggest that in the
stress-relaxation experiments, where the 10
material is sheared from rest, i.e. a state of
relatively high structure, there is a fast 0
viscous drag-driven structure breakdown (to 0 300 600 900 1200 1500
1.5
N
1
χ =
2
∑ [τ (t ) − τ (ti ) calc. ] 2
-1
1.0
2 i meas .
( N − M )τ e i =1
0.5
(15) 0.0
0 300 600 900 1200 1500
in which N is the number of data points and -1
Shear Rate (s )
M is the number of parameters in the
function to be fitted. For the stress Figure 7. Inverse relaxation time vs. shear
relaxation data, χ2 ranged from 2.5 × 10-5 at rate for stress-relaxation experiments.
Time-Dependence of Shear Stress Table 1. Relaxation times of structure
According to the single-structure rate breakdown and buildup processes.
theory, the relaxation time decreases with Shear rate
To
increasing shear rate (Eq. 11); a plot of T-1 (s-1)
vs. γ& is a straight line with slope b, and From 91.9 146.1 461.0 1460.0
intercept a on the T-1 axis. However, it 91.9 - - 608 143
seems from Fig. 7 that at lower shear rates,
up to about 100 s-1, the relaxation time 146.1 - - 661 331
decreases sharply with increasing γ& and
461.0 1550 1060 - 671
then follows a slower rate of decrease as
shear rate increases. 1460.0 1060 1230 910 -
A method advocated by many for
determining the time dependence of shear The results suggest that the buildup of
stress is the high-low shear rate step-change structure is a slower process than the
procedure illustrated in Fig. 5. Assuming breakdown. In one case (91.9 and 146.1 s-1)
single-exponential time dependence, a least- the close proximity of the two shear rates
squares regression of data at two shear rates made calculation of their relaxation times
gives the time constants for structure subject to large errors.
breakdown and buildup, T1 and T2, For each pair of relaxation times, Eqs. 16
respectively: and 17 were solved simultaneously to find
the constants a and b. These are given in
1 Table 2 for five pairs of the shear rates used.
= a + b γ&1 (16)
T1 Due to the wide variation in the b/a ratio, it
is unlikely that the time dependence of the
1 WBM can be adequately described by a
= a + b γ&2 (17) single relationship over the entire range of
T2 shear rates. A better approximation may be
obtained by fitting two straight lines to the
from which the constants a and b are T-1 vs. γ& data:
calculated. The range of shear rates used in
the step-change experiments was 100–1500 For shear rates in the range 0 – 100 s-1,
s-1. The results of these experiments are
presented in Table 1 as the relaxation times 1
= 1.5 ×10 −5 + 4.8 ×10 −6 γ& (18)
of the breakdown (low-to-high shear rate) T
and buildup (high-to-low shear rate)
processes. The average value of χ2 for these and for 100 – 1500 s-1,
calculations was 7.0 × 10-5, and the error in
the reported relaxation times was less than 1
= 1.5 ×10 − 4 + 7.0 ×10 −7 γ& (19)
1%. The relaxation times to the left of the T
diagonal belong to net buildup of structure,
while those to the right of the diagonal The straight lines in Fig. 7 show a
represent net breakdown. graphical representation of the above
relationships.
Table 2. Rate constants for structure
breakdown and buildup processes. Differentiating Eq. 10 in a similar manner
Shear Rates a b/a gives:
b
(s-1) (s-1) (s)
dλ (t ) λ0 − λe −( Tt )
91.9 ↔ 461.0 4.0×10 -4
2.7×10 -6
0.0068 = e (23)
dt T
91.9 ↔ 1460.0 6.5×10-4 4.3×10-6 0.0066
9.2×10-4 0.4×10-6 τ1
461.0 ↔ 1460.0 0.0004 λ0 − λe = (24)
τ y + c γ& m
In the absence of a single description for
time dependence in the range of shear rates The τ1 vs. γ& data presented in Fig. 6 are
used here, the value of the b/a ratio will adequately described by a simple empirical
have to be determined by means of curve equation of the type:
fitting to the equilibrium stress data.
k1 γ&
Shear-History Dependence of Shear Stress τ1 = (25)
To describe structure as a function of 1 + k 2 γ&
time, it is necessary to find an expression for
λ0. The initial structure λ0 depends on the Combining Eqs. 24 and 25 yields,
previous shear rate(s) to which the material
may have been subjected. Therefore, λ0 is k1 γ&
λ0 − λe = (26)
the parameter that describes the shear- (1 + k 2 γ& ) (τ y + c γ& m )
history dependence of the rheological
properties. λ0 cannot be measured directly Parameters in Equilibrium Flow Curve
but it may be determined in terms of τ1, the The parameters τy, b/a, η∞, c and m in
pre-exponential coefficient in the time Eq. 9 have now to be determined by a
description of stress-relaxation curves, as combination of curve fitting (of the
described below. measured τe data to the modified Moore-
Differentiation of Eqs. 8 and 12 with Cheng model) and independent
respect to time, and at constant shear rate, measurements. The independent measure-
gives: ments are needed to reduce the number of
parameters determined by curve fitting so
dτ (t ) dλ (t ) that a unique “best fit” can be determined.
= (τ y + c γ& m ) (20)
dt dt
dτ (t ) τ −( t )
=− 1e T (21)
dt T
15
40
10
20
5
0 0
0 300 600 900 1200 1500 0 10 20 30 40
-1 -1
Shear Rate (s ) Shear Rate (s )
η ∞ = 0.02 (35) 80
Shear Stress (Pa)
c = 0.20 (36) 60
m = 0.81 (37) 40
b
= 5.44 ×10 − 4 (38) 20
a
0
k1 = 0.145 (39) 0 300 600 900 1200 1500
k 2 = 0.00516 (42) -1
Shear rate (s )
and the time dependence is further defined Figure 10. Hysteresis loops produced by
by the following relationships: ramping the shear rate in the range 14.6-
1460 s-1.
For shear rates in the range 0 – 100 s-1:
The solid lines in Fig. 10 show the
1 calculated hysteresis loops. The model fails
= 1.5 ×10 −5 + 4.8 ×10 −6 γ& (43)
T to predict the first cycle satisfactorily. This
is expected because, as discussed earlier, the
and for 100 – 1500 s-1: single-exponential time dependence does
not fit the stress relaxation data well at early
1 times. However, as time progresses, i.e. as
= 1.5 ×10 − 4 + 7.0 ×10 −7 γ& (44) the cycle is repeated, the agreement between
T
the experimental and predicted values
Prediction of Hysteresis Loops improves. The fourth and fifth cycles
The validity of the model and the practically superpose, indicating that the
accuracy of the final curve fitting can now equilibrium loop (to be distinguished from
be tested by predicting the hysteresis loops the equilibrium flow curve) is obtained after
produced when the shear rate is ramped. If a few cycles. The maximum difference
between the measured stress values and breakdown and buildup are assumed to be
those predicted by the model for the final governed by two rate processes with
loop is about 7%. This value decreases as distinctly different relaxation times. In this
the ramp time is increased. For example, a scheme the first process may be a fast,
total ramp time of 90 min gave a maximum viscous drag-driven breakdown, which
difference of 5% in the last loop, while a breaks the intact (house-of-cards) structure
shorter time of 32 min increased the error to into flocs and aggregates. The second
9%. process has a slower but longer-term effect;
The slopes of the “up” and “down” it causes further breakdown by promoting
curves are determined to a large extent by collision between the mobile flocs and
the value of parameter m. It appears that the aggregates and modifies the orientation of
assumed average value of m = 0.81 produces the particles thus formed in order to fully
good agreement with the experimental data. accommodate the applied shear stress.
For the model to give a good prediction Within the remaining intact structure the
of thixotropic behaviour, one of the rate of collision and particle orientation is
following initial conditions must be negligible due to low mobility of the flocs
satisfied: and aggregates. Therefore, the two structural
1) Material initially sheared at a very high processes may be assumed to be of the
rate so that λ0 ~ 0. This corresponds to consecutive or series type.
the condition of the drilling fluid as it The observations made earlier with
issues at the drill bit, where it is regard to relaxation time-shear rate
subjected to shear rates on the order of relationship for the WBM of this study,
105 s-1. favour a two-structure model. In such a
2) Fluid at equilibrium at a finite shear rate model, the time dependence of structure at
constant shear rate may be described by a
such that λ0 = λe . This condition may
double-exponential function of the type:
correspond to the state of the fluid in the
circulation system at the surface. t t
3) Material initially at rest, as in the case −( ) −( )