Viscosity of monophase addition silicones as a function of

shear rate
Kyoung-Nam Kim, DDS,a Robert G. Craig, PhD,b and
Andrew Koran III, DDS, MSc
Yonsei University College of Dentistry, Seoul, Korea, and University of Michigan, School of
Dentistry, Ann Arbor, Mich.

The viscosity of monophase addition silicone impression materials was measured

as a function of shear rate. The setting of mixed catalyst and base was prevented
by addition of a small amount of phenyl propiolic acid. All products showed a B- to
lo-fold decrease in viscosity with an increasing shear rate (shear thinning). The
addition of phenyl propiolic acid had little or no effect on the viscosity of three
materials. However, when added to the catalyst or base only of two products, it
increased their viscosity and exaggerated the shear thinning effect. (J PROSTHET
DENT 1992;67:794-8.)

A ddition silicone impression materials have high

accuracy, little dimensional change after setting, moder-
ately short working and. setting time, and excellent recov-
ery from deformation on removal. Although they are
expensive, some are more rigid than condensation silicones
and thus are more difficult to remove from undercuts.1-5
Addition silicones have been traditionally available in
four consistencies (viscosities), low, medium, heavy, and
putty, which are used in various impression techniques.
The low and medium types have been used as syringe ma-
terials and the medium, heavy, and putty types as tray
materials.
Recent advances in addition silicones have involved the
elimination of hydrogen evolution after setting and the de-
velopment of automatic mixers and hydrophilic types. The
automatic systems simplified mixing and reduced the Fig. 1. Sketch of water chamber and material container
number of voids in mixes.6 Incorporation of surfactants in- with T-bar: A, viscometer; B, T-bar; C, container; D, water
creased the wettability of the impression by mixes of gyp- chamber; E, supporting rod and plate.
sum and made them hydrophilic.7 Purification of the reac-
tants or addition of finely divided palladium or platinum
eliminated the evolution of hydrogen and allowed the im- high shear, and another portion used in the tray, where the
pression to be poured immediately. viscosity is high because the shear rate is low.
The introduction of single viscosity or monophase addi- Koran et a1.8using a Brookfield viscometer (Brookfield
tion silicones, which can be used both in the syringe and the Corp., Brookfield, Mass.), found that some rubber base
tray, allows the number of consistencies to be reduced. This impression materials were newtonian materials, but several
change is possible because the materials possess the qual- others were nonnewtonian. McCabe and Bowman9 mea-
ity of shear thinning, where the viscosity decreases as the sured the viscosity of rubber base impression materials us-
shear rate is increased. Thus, a portion of the mix can be ing an extrusion rheometer and observed that all materials
used in the syringe, where the viscosity is low because of were pseudoplastic, with the viscosity decreasing with in-
creasing shear rates. CooklO studied the polymerization of
elastomeric impression materials using viscosity as a mea-
aAssistant Professor, Department of Dental Materials, Yonsei sure of the reaction.
University. One difficulty with these studies was that the impression
bProfessor, Department of Biologic and Materials Sciences, School
materials were setting when tte viscosity was being mea-
of Dentistry, University of Michigan.
cProfessor, Department of Prosthodontics, School of Dentistry, sured and the effect of shear rate was being determined.
University of Michigan. Thus, one was forced to measure the viscosity of the cat-
10/l/36684 alyst and base separately or measure the viscosity of mixes

794 JUNE1992 VOLUME67 NUMBER6

VISCOSITY OF MONOPHASE SILICONES

Table I. Addition silicone products and their code, type, viscosity, mixing method, batch number, and manufacturer
Mixing Batch
Products Code Type Viscosity method no. Manufacturer

Baysilex Ba Type 1 High Hand 77171 Cutter Dental

Green-Mousse Gr * * Auto 934935 Parke11
Hydrosil HY ‘be 1 Medium Hand 1018892 L.D. Caulk
Imprint Im Type 1 Medium Auto P890926 3M Dental
Omnisil Om ‘Ihe 1 Medium Hand 091389A Coe Lab. Inc.
*No marks on products.

at a fixed time. Stannard and Craigll studied the retarda-
tion of the setting of addition silicones by measuring the
viscosity of mixes containing various concentrations
phenyl propiolic acid (PPA). It was found that the setting
could be essentially stopped with small amounts of added
PPA.
This investigation examined the shear thinning of
monophase addition silicones of the two paste type and the
automatic mixing type by measuring the viscosity as a
function of shear rate with and without this retarder to stop
the setting reaction.
MATERIALS AND METHODS
Five addition silicones developed as monophase systems
were evaluated for their viscosity. Codes, types, mixing
methods, batch numbers, and manufacturers of the prod-
ucts are listed in Table I. Only monophase addition
silicones were used in this study.
A rotational viscometer (Rheolog model ‘/ RVT-RL-199,
Brookfield Corp.) fixed with special T bar-type spindle
(spindle cross-bar length of 5 mm) was used to evaluate
the viscosity of the impression materials. Values of viscos-
ity recorded by the pneumatic recorder (Model 5400, Fox-
boro Corp., Foxboro, Mass.) were calibrated in centipoise
(cp) by using a conversion equation obtained from cali-
brating solutions (N3500, S-8000, and N190000 Certified
Viscosity Standard, Cannon Instrument Co., State College,
pa .) .s,ll, 12
Cups, 3 cm in diameter and 2 cm deep, were completely
filled with the experimental materials and were placed in
a water chamber connected to a constant temperature bath
(Model NB-Reservoir and Circulating, Brookfield Engi-
neering Lab., Inc., Stoughton, Mass.) that circulated water
of 37” C (Fig. 1). The viscosities of the base and the cata-
lyst paste of each impression material were measured at 2.5
rpm spindle speed and the reading was recorded 10 minutes
after the viscometer was started. The viscosity of the mixed
materials without retarder was measured as a function of
time at 0.5 and 2.5 rpm of rotational speed at 1 minute and
1.5 minutes after the e.nd of mixing. All materials were
mixed at the same weight ratio of the base and catalyst
paste for hand-mixed types and extruded from the auto-
matic mixer type according to the manufacturer’s instruc-
tion for the automix types. The mixes filled the cup with
a volume that weighed :!O to 21 gm.
The viscosity of mixed materials with retarder as a func-
tion of rotational speed was measured at five rotational
of speeds (0.5, 1, 2.5, 5, and 10 rpm) and readings were
recorded 10 minutes after the viscometer was started. PPA
(Aldrich Chemical Co., Milwaukee, Wis.) was used to
maintain the mixed materials in the unpolymerized state.
PPA has a retarding (poisoning) effect on the chloropla-
tinic acid catalyst present in the addition silicones. Since
very small quantities of PPA were needed to inhibit the
reaction, 1 gm of PPA was dissolved in 10 ml of dibutyl ph-
thalate (DBP) (Fisher Scientific Co., Fair Lawn, N.J.). This
solution was used in the following ratios to the impression
materials: Ba, 20 gm/0.4 ml solution; Gr, 21 gm/0.5 ml; Hy,
20 gm/0.5 ml; Im, 21 gm/0.5 ml; and Om, 20 gm/0.5 ml. At
these ratios the setting reaction was retarded for more than
6 hours. In the hand-mixing type, the base paste and the
catalyst paste were mixed together for 30 seconds after the
solution was mixed with the catalyst paste for 30 seconds.
In automatic mixing types the solution was mixed with the
extruded materials for 30 seconds.
To compare the effects of the PPA on the tested mate-
rials, the same volume of the base and the catalyst paste
were mixed$ibh the same amount of PPA as the mixed
materials for 30 seconds and the viscosity of each paste was
measured at a rotational speed 2.5 rpm 10 minutes after the
viscometer was started.
All impression materials were mixed at room tempera-
ture (23 + lo C) and the viscosity measured at 37 + 0.5’
C. All experiments were replicated five times and the
means and standard deviations were calculated.
RESULTS
The viscosities of the base and catalyst pastes at a rota-
tional speed of 2.5 rpm, 10 minutes after the start of the
viscometer, are shown in Table II. The viscosities of the
base and the catalyst pastes of individual materials were
similar, except for Om. The viscosity of the catalyst paste
of Om was approximately 65 % higher than the base paste.
The lowest viscosity was observed for Hy and the highest
for Ba.
The viscosities of the mixed materials with added PPA
to retard polymerization are shown in Fig. 2. The viscosity
of all materials decreased as the rotational speed increased.
When the rotational speed was increased from 0.5 to 10 rpm
the viscosities of Ba and Hy were decreased approximately

THE JOURNAL OF PROSTHETIC DENTISTRY 795

 KIM, CRAIG, AND KORAN

e
. 200
E
*

t
a
0
ii
T

100

0
0.0 2.0 4.0 6.0 8.0 10.0

ROTATIONAL SPEED, rpm

Fig. 2. Viscosity of mixed materials retarded with PPA as function of rotational speed.

Table II. Viscosity of base and catalyst pastes 10 nificantly higher (Fig. 2) than the averages of the viscosi-
minutes after the viscometer was started at 2.5 rpm and ties of the base and catalyst (Table II).
37O c (x104 cp) Table III presents the viscosities of mixed materials
Base Catalyst without retarder at 1.0 and 1.5 minutes and at 0.5 and 2.5
Material code (SD) (SD) rpm. At 0.5 rpm the viscosities of Ba and Gr increased ap-
proximately 80% between 1 and 1.5 minute; however, the
Ba 65.5 (0.6) 70.6 (1.0)
viscosities of Hy, Im, and Om increased more than 100%.
Gr 29.8 (1.3) 25.0 (1.5)
At 2.5 rpm the viscosity of Hy increased only 18% from 1
HY 16.1 (0.9) 19.1 (0.8)
Im 42.3 (1.1) 50.0 (0.6)
to 1.5 minutes, whereas Gr and Om increased 37 % and 50 %
Om 35.2 (0.9) 58.5 (2.0) and Ba and Im increased 83 % and 116 % , respectively. At
comparable times the viscosities of all materials were lower
SD, Standard deviation.
at 2.5 than at 0.5 rpm. Decreases at 1 minute ranged from
25 % to 57 % , whereas decreases at 1.5 minute ranged from
10 times, and those of Gr, Im, and Om decreased approx- 29 % t.o 69 % . Gr had the largest decrease at both times. In
imately sixfold. All tested materials demonstrated pseudo- a comparison of the values in Tables II and III at 2.5 rpm,
plastic behavior (or shear thinning) and therefore a de- the viscosity of Ba was unchanged between 0 and 1 minute,
crease in viscosity with an increase in rotational speed whereas those of Gr, Im, and Om increased by 2 times and
(shear rate). Hy by 7 times.
In a comparison of the average viscosities of the base and
catalyst for individual products from Table II with the DISCUSSION
values of the same products mixed with PPA (Fig. 2) at 2.5 The recent trend in making clinical impresgions is to
rpm, the viscosities were comparable for Gr, Im, and Om, make more accurate impressions with simpler techniques.13
but the viscosities of Ba and Hy mixes with PPA were sig- To make an accurate impression, it is necessary to recog-

796 JUNE 1992 VOLUME 67 NUMBER 6

VISCOSITY OF MONOPHASE SILICONES

HBase q Ba+PPA

n Catalyst q Ca+PPA

0 Ba+Ca+PPA

Eaysilex Green-Mousse, Hydrosil Imprint

Fig. 3. Viscosity of base and catalyst with or without F’PA and mixed material retarded
with PPA at 2.5 rpm and 37” C.
Omnisil
I
nize that the viscosity of impression materials is related to Table XII. Viscosity of mixed materials as function of
its ability to record detail, because the lower the viscosity time after mixing at 0.5 and 2.5 rpm and 37’ C (~10~
the greater the flow into spaces of fine detail. cp)
The viscosity may vary with the material, temperature, Material Viscosity Viscosity
time after mixing, and mixing method or speed. The addi- code rPm at 1 min at 1.5 min

tion silicones tested were pseudoplastic (shear thinning)

Ba 0.5 122.1 (2.8) 211.2 (14.7)
materials, where the viscosity was higher under low shear 2.5 68.9 (2.5) 148.8 ( 1.2)
stress but lower under high shear stress. This characteris- GI 0.5 133.7 (8.9) 247.9 (14.9)
tic is important in the s,ingle-mix technique. When sub- 2.5 56.7 (2.9) 78.0 ( 2.8)
jected to low shear stress, as when mixed .material is in a HY 0.5 194.2 (8.5) 398.07 (7.8)
tray, these impression materials have viscosities and do not 2.5 129.4 (4.1) 153.5*
flow out of the tray. If these materials are used in a syringe, Im 0.5 106.5 (12.2) 245.1 (8.9)
higher shear rates are encountered during extrusion from 2.5 79.7 ( 2.2) 146.2 (5.9)
the syringe tip, the viscosity decreases, and they flow OItl 0.5 156.6 (11.8) 347.1 (5.2)
2.5 102.5 ( 1.9) 153.5?
readily into the detailed areas.14 This quality of shear
thinning varies among materials. SD, Standard deviation.
The viscosity of the base and the catalyst paste should *Value at. 75 seconds after mixing.
TValue at. 77 seconds after mixing.
be similar to improve the ease of mixing of the hand-spat-
ulated type as well as improve the mixing of the two pastes
in the static mixing tip of the automatic mixing system. The
base and the catalyst of the individual products tested, ex- of Gr, Im, and Om decreased six times. At high shear rates
cept Om, had similar viscosities. Although all materials had all materials had similar viscosities within 200,000 cp,
pseudoplastic characteristics, the decrease in viscosity with whereas large differences in viscosities occurred at low
increasing shear rate was not the same for all materials. shear rates (as high as 2,500,OOOcp). This shear thinning
When the rotational speed increased from 0.5 to 10 rpm the charact,eristic was also shown in Table III when the rota-
viscosities of Ba and Hy decreased 10 times, whereas those tional speed was changed from 0.5 to 2.5 rpm. Between 1

THE JOURNAL OF PROSTHETIC DENTISTRY

 KIM, CRAIG, AND KORAN

and 1.5 minutes the viscosity of Ba and Im increased ap- uated. The viscosity of the base paste and catalyst pastes
proximately two times at both 0.5 and 2.5 rpm, but the vis- were determined separately. The changes in viscosity after
cosity of Gr, Hy, and Cm increased approximately two base and catalyst were mixed as a function of time at 0.5
times at 0.5 rpm and approximately one-half at 2.5 rpm. and 2.5 rpm were also determined. Finally, changes in vis-
It was presumed that the viscosity of unpolymerized cosity of base and catalyst mix with a retarder were mea-
mixed materials would ‘be similar to the average viscosity sured as a function of rotational speed at 37” C. The base
of the base and the catalyst paste at the same shear rate. and the catalyst paste of each material except Om had
In comparing the viscosities in Table II and Fig. 2, Gr, Im, similar viscosities. The viscosity of mixes of base and cat-
and Om mixed with PPA had the same viscosities as the alyst decreased as a function of shear rate and increased as
average viscosities of the base and the catalyst pastes. a function of time. When the mixes of base and catalyst
However, this was not true for Ba and Hy. Thus, the true were retarded with PPA, the viscosity of Ba and Hy were
shear thinning effect as a function of shear rate for Ba and decreased 10 times, and those of Gr, Im, and Om were de-
Hy (shown in Fig. 2) is somewhat exaggerated by the pres- creased six times when the rotational speed increased from
ence of PPA. This effect is further illustrated in Fig. 3, in 0.5 to 10 rpm.
which the viscosities of (1) the base only, (2) the base plus
PPA, (3) the catalyst only, (4) the catalyst plus PPA, and REFERENCES
(5) the base plus catalyst plus PPA are plotted for the var- 1. Council on Dental Materials, Instruments, and Equipment. Revised
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__ . concentrations retarded the 14. Craig RG. Restorative dental materials. 8th ed. St Louis: CV Mosby,
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cial dental addition silicones are applied with retarders
that increase the working and setting times.16 These mate- Reprintrequeststo:
DR. ROBERT G. CRAIG
rials are low molecular weight silicone polymers that have
DEPARTMENT OF BIOLOGIC AND MATERIALS SCIENCE
the same general composition as the impression materials SCHOOL OF DENTISTRY
and react during setting.14 UNIVEILSITY OF MICHIGAN
ANN ARBOR, MI 48109-1078
SUMMARY
The viscosities of five commercial monophase (single-
viscosity) addition silicone impression materials were eval-

798 JUNE 1992 VOLUME 67 NUMBER 6