Chemical Thickening-Time Test

for Cement Blends

Paul M. McElfresh, BJ-Hughes Services
Jo Ann Cobb, BJ-Hughes Services

Summary
Considerable time is lost during field operations waiting
for cement-thickening times to be determined. Our
method to minimize the amount of waiting time is a colorimetric procedure based on Basic Blue 9 dye for determining a relative measure of the thickening time for a cement blend. This test is applicable to any field blend
regardless of the additives used, and can be run in a matter of minutes rather than hours.

Introduction
Consistometer thickening-time tests always have been
used to establish whether a particular field blend will
perform as expected downhole. These tests involve use
of expensive equipment and one test sometimes requires
an entire working day or more to complete. The consistometer thickening times are costly because of the
equipment involved, the manpower costs associated in
running the tests, and the time lost in the field. The
chemical method presented here was developed to
minimize the number of samples run on the consistometer and thus to reduce the time and cost factors
involved.
The primary application of the chemical thickeningtime test is to verify the blended composition of field
mixtures relative to a laboratory-prepared pilot mixture.
Specifically, it is designed to monitor the uniformity of
the blending process when blending large jobs. Each
100- to 200-sack portion of the total amount to be blended-a "drop"-is tested and compared to the pilot blend
to ensure that the entire slurry will be uniform downhole.
This test can be a substitute for rerunning consistometer
0149-2136/63/0021-0220$00.25
Copyright 1963 Society of Petroleum Engineers of AIME

FEBRUARY 1983

thickening-time tests when time does not permit additional testing. The method also can be used to provide
quality-control analyses for additives that normally require consistometer thickening-times. Data presented
support the use of colorimetric determination to monitor
thickening time, provided that a pilot blend that has had
its thickening time measured on a consistometer is used
as a standard. This approach also can be used to design
slurries without repeated thickening-time determinations. This is accomplished by preparing two standards
that bracket the desired thickening time.

Theory
The chemical thickening-time test is based on a colorimetric procedure that measures the amount of ionic
dye in cement filtrate. Young 1 proposes that cement particles have active sites onto which various additives are
adsorbed. When cement is blended and hydrated, the additives are exposed thoroughly to these active sites and
are adsorbed onto the cement particles. This adsorption
determines the performance of the cement with regard to
such properties as thickening time and fluid loss_ The
ionic nature of the dye added after the cement has been
hydrated allows it to be adsorbed onto the remaining active sites of the cement. It is the number of these vacant
active sites that determines the concentration of dye left
in the cement filtrate, and, therefore, becomes an indirect measure of the total additive concentration.
Some of the additives that are used for extenders and
for weighting materials are not adsorbed onto the cement, but these additives have active sites that are very
similar to those on cement. The ionic dye also is adsorbed by these additives and by the cement, giving the
321

10
1
10
70

"T

"T
10

.0

10

.0
0

.~

.1
Weight Percent

Fig. 1-Test response with retarder.

capability of detennining the amount of inert as well as

active additives.
Because the colorimetric procedure used measures the
amount of unadsorbed ionic dye left in the cement
filtrate, the percent transmittance measured can be correlated to thickening time detennined on a pilot blend.
The percent transmittance also can be used for qualitycontrol purposes by running a standard and comparing its
transmittance with that of the sample tested.

Apparatus and Procedure

The procedure for mixing the slurry is the same as the
present API method 2 for consistometer thickening
times. After the slurry properties for the blend are determined, calculate the weight of additives needed for a
600-cm 3 (600-mL) laboratory blend. The volume of dye
to be used then is calculated from the amount of mixing
water. The cement and water are combined by blending
at high speed for 35 seconds in a blender. Then the dye is
added and blended an additional 35 seconds. The cement
slurry then is transferred to a Fann filter press cup and a
1O-cm 3 (lO-mL) sample of the filtrate is collected, using
just enough pressure to initiate flow. The filtrate should
be stored in sample bottles with screw-top lids to prevent
scaling caused by the fonnation of calcium carbonate
(CaC0 3 ). Next, the percent transmittances for each
sample are detennined on a colorimeter. If dilutions are
necessary, the same dilution should be used for all
samples in the same set. Compare the percent transmittance reading for the pilot blend with the readings for the
field blends. If readings for the field blends are within
8 transmittance units of the reading for the pilot blend,
then the perfonnance and, hence, the thickening times of
the field blends are assumed similar.

Results and Discussion

The response of this method was detennined by using
three concentrations of a retarder in Class H cement. The
results, shown in Fig. 1, indicate that plotting transmittance vs. percentage of retarder on semilog paper results
in a linear response. Likewise, the experiment was
repeated using CaC1 2 accelerator in the same Class H cement. The result, shown in Fig. 2, also was linear, but
the slopes were opposite in sign. Therefore, in the one
additive case, relative retardation or acceleration could
322

.Oo~-----+----~-----+.-----;-----;----~
Weight P.roent

Fig. 2-Test response with accelerator.

be detected. To detennine the range of applicability of

this method, a pilot blend of Class H cement plus 3 %
salt plus 0.3% retarder plus 0.5% dispersant was used
initially to test the method. The type of salt and type of
retarder then were varied to detennine whether such
changes in thickening time would be predictable from
the chemical thickening-time method. Table I shows the
blends used and the resultant transmittances. From these
data it can be seen that changing from one salt to another
or from one retarder to another changes the percent
transmittance values for the blends. By comparing
thickening times with percent transmittance, a general
trend is observed. The higher the percent transmittance,
the shorter the thickening time. Note that the thickening
times and percent transmittance values are comparable
only for blends made up of the same additives.
The difference between Class H and Class A cements
also can be distinguished as shown by the results in
Table 1. The Class H cement with KCI, retarder, and
dispersant produced a 23.0% transmittance with a
thickening time of 4 hours and 20 minutes. The Class A
cement with identical additives of identical concentration
resulted in a 66.4 % transmittance, with a thickening
time of 3 hours and 16 minutes. A test of neat cements
gave differing results for several classes and manufacturers (Table 2). These differences are attributed to particle size differences and C 3 A content. The data indicate a
rapid screening procedure could be devised to aid in the
detection of contaminated cement or even the differences
in mill runs of cement.
Blending studies have been perfonned using the colorimetric test to help improve the blending process.
Samples were collected from each 20,OOO-lbm (9070-kg)
drop during transfer to bulk storage. Thickening times
were run along with the chemical thickening-time tests.
Results of the chemical analyses (Table 3) show that the
composition of the blend varied significantly for the
seventh drop. The values shown in Table 3 also
demonstrate how the difference in composition of the
blends can be detected by the chemical thickening-tiJl!e
test. The data often yield a linear correlation between
percent transmittance and thickening time for a unified
set of samples such as those in this study. With these
data, it can be seen how this test could be used to save
time as well as to detennine which blending techniques
JOURNAL OF PETROLEUM TECHNOLOGY

TABLE 1-RELATIVE DIFFERENCES IN PERCENT TRANSMITTANCE

FOR VARIOUS BLENDS

Cement Blend"

Trans
mittance
(%)

Thickening
Time""
(hours:minutes)

Class
Class
Class
Class
Class
Class

H
H
H
H
H
H

+3%
+ 3%
+ 3%
+ 3%
+ 3%
+ 3%

CaCI 2 +0.3% R1 +0.5% D

KCI + 0.3% R-1 + 0.5% FL
KCI + 0.3% R-1 + 0.5% D
KCI + 0.3% R-3 + 0.5% D
NaCI + 0.3% R-1 + 0.5% D
KCI + 0.3% R-2 + 0.5% D

62.8
61.2
23.0
17.3
18.1
14.7

1 :02
3:08
4:20
5:12
5:42
9:29

Class
Class
Class
Class
Class
Class

A
A
A
A
A
A

+ 3%
+ 3%
+ 3%
+ 3%
+ 3%
+ 3%

CaCI 2 + 0.3% R1 + 0.5% D

NaCI + 0.3% R1 + 0.5% D
KCI + 0.3% R-1 + 0.5% FL
KCI + 0.3% R-3 + 0.5% D
KCI + 0.3% R1 + 0.5% D
KCI + 0.3% R2 + 0.5% D

89.1
59.4
74.0
51.4
66.4
25.3

0:47
1:49
2:23
2:45
3:16
3:38

'R-l, R-2, and R-3 are relarders, D=dispersant, and FL=fluid loss agent .
.. API Schedule 6, 30S0-m (10,000-11) casing-cementing well-simulation test, temperature
gradient 01 2.7C/l00 m (1.soF/100 11).

are best suited for different types of cement blends.

In addition to blending studies, the chemical
thickening-time test has been used for quality control of
cement additives that use a thickening-time screening
test. A laboratory standard of known composition is run
using both tests, and the samples subsequently are compared to the colorimetric standard. Questionable samples
then are tested by consistometer. Typical data for
retarder quality control are shown in Table 4. Samples 4,
6, 7, and 8 were detected as unacceptable from the
chemical thickening-time test because they were not
within 8 transmittance units of the reading for the standard. One of the active ingredients in Samples 4 and 6
was determined by separate analysis to be low in concentration, and, in Samples 7 and 8, the level of the active
ingredients was determined to be high in concentration.
By examining the thickening times and chemical
analyses, it can be seen that the colorimetric test offers
an accurate alternative method that requires less time and
effort than a consistometer test. The results of the
chemical thickening-time test and the consistometer are
in good agreement. Data compiled on 178 quality control
tests using these methods showed that they agreed in acceptance and in rejection 98 % of the time. The remaining 2 % proved to be those samples borderline in acceptance or rejection.
Samples also were collected from actual job blends. A
sample from each drop was taken, and the thickening
times were determined along with the percent transmittance values from the chemical thickening-time test.
Data in Table 5 exemplify the type of results obtained. In
this example, the first four drops were fairly uniform.
The fifth drop gave a very high percent transmittance and
a short thickening time. Being able to spot such potential
problems before they reach the job site will save time
and money.
The chemical thickening-time method also has been
used in slurry design. When ajob design is proposed, the
slurry designs have to be tested to ensure the proper
thickening time. The process of finding the appropriate
additive concentrations is often a trial-and-error process,
and much consistometer time may be required to achieve
the desired thickening time. Fig. 3 shows how the colFEBRUARY 1983

TABLE 2-RELATIVE DIFFERENCES IN PERCENT

TRANSMITTANCE VALUES OF NEAT CEMENTS
Lone Star A
Trinity A
Incor C
Victor G
Kaiser G
Trinity H
Centex H
Lone Star H

36.5
35.0
27.7
52.5
95.4
26.1
34.3
37.4

TABLE 3-COMPARISON OF PERCENT TRANSMITTANCE

VALUES WITH THICKENING TIMES FOR BLENDING
STUDY

Drop
Number"

Transmittance
(%)

Thickening
Time""
(hours:minutes)

85.5
84.4
83.2
43.0
70.5

0:59
1:00
0:59
2:20
1:26

---

1
3
5
7
pilot

'Blend composition: Class H plus 19.37%

weighting material plus 2.77% sand plus 1.66%
KCI plus 1.11 % retarder plus 0.S3% antiloamer.
.. API Schedule 19, 4270-m (14,000-lt) squeezecementing well~simulation test.

TABLE 4-QUALITY CONTROL SAMPLES

Sample
laboratory standard
1

2
3
4
5
6
7

8
9
10

Transmittance
(%)

Thickening
Time"
(hours:minutes)

21.3
20.7
21.9
19.6
8.4
18.8
7.5
65.7
71.8
19.7
20.3

2:30
2:40
2:20
2:23
2:12
2:39
2:11
2:46
2:49
2:36
2:24

'API Schedule 8, 4270-m (14,000-tt) casing-cementing wellsimulation test, temperature gradient 2.7C/100 m (1.soF/100
tt).

323

10

TABLE 5-COMPARISON OF PERCENT TRANSMITTANCE

VALUES WITH THICKENING TIMES

,.

40

Drop'
1
2
3
4

Transmittance
(%)
37.5
35.7
37.6
27.8
79.1

Thickening
Time"
(hours:minutes)
3:58
3:29
3:02
3:12
2:40

"Blend composition: Class H plus 1.4% fluidloss agent plus 3% KCI plus 0.2%
antifoamer.
" "API Schedule 5, 2440m (8,0001t) casingcementing well-simulation test, temperature
gradient 2.7C/l00 m (1.5F/l00 It).

"'l

10

I
~

flT

c
C

.
i

10

':L.----~,~.O~--~,~.~--.~.O.---~.I.---~A.---~
.".tard.,

Fig. 3-Plot for slurry design.

orimetric method can be used to predict the proper concentration of retarder to obtain the desired thickening
time of 4 to 4 V2 hours. The basic slurry design in this example was Class H cement plus 35% sand plus 15.1 %
weighting material plus 3 % KCl plus 1.4 % fluid loss additive plus 0.4 % antifoamer plus? % retarder plus? % intensifier. The retarder and retarder-intensifier concentrations used for Point 1 were 1.6% and 2.5%, respectively. The result was 44.0% transmittance with a thickening
time of 3 hours and 46 minutes. This point is used as a
known low or short thickening-time point. The third
point has a retarder concentration of 3 % and retarder intensifier concentration of 4.5 %. These concentrations
resulted in 12.7% transmittance and a thickening time of
5 hours and 32 minutes. This point then is used as a
known high or long thickening-time point. Concentrations for Point 2 were 2 % retarder and 3 % retarder intensifier, with 39.3% transmittance as a result. Assuming a
linear response between Points 1 and 3, the 39.3%
transmittance should yield a thickening time of 4 hours
and 23 minutes. This particular blend then was run on
the consistometer for confirmation with a resultant time
of 4 hours and 21 minutes. These thickening times were
run on a modified API schedule from 2rC (80F) up to
197C (388F) with pressure from 17200 to 179300
kPa (2,500 to 26,000 psi). From these data, it can be
seen how helpful this method could be for designing
slurries with long thickening times.

324

Conclusions
Data have been presented for a new method of screening
cement-thickening times without the use of a consistometer. As long as each sample contains the same cement and additives as the pilot blend, the new method is
capable of pointing out unacceptable, as well as acceptable, blends of cement, and depends on a consistometer
thickening time only for calibration and final approval of
that thickening time. The method is sensitive to the factors that affect cement thickening time from a chemical
standpoint. Several applications of this test, including
field performance, blending studies, quality control, and
slurry design, demonstrate the usefulness and potential
of the method.

References
I. Young, J. F.: "A Review of the Mechanisms of Set Retardation in
Portland Cement Pastes Containing Organic Admixtures," Cement and Concrete Res. (1972) 415-33.
2. API Recommended Practice for Testing Oil-Well Cements and Cement Additives, API, Dallas (1979).

JPT

Original manuscript received in Society of Petroleum Engineers office July 20, 1981.
Paper accepted for publication Sept. 14, 1982. Revised manuscript received Dec. 7,
1982. Paper (SPE 10220) first presented at the 1981 SPE Annual Technical Con
ference and Exhibition held in San Antonio Oct. 4-7.

JOURNAL OF PETROLEUM TECHNOLOGY