Alterations of surface hardness with gypsum die hardeners

Paul E. Harris, DDS,a Scott Hoyer, DDS,b Terry J. Lindquist, DDS, MS,c and
Clark M. Stanford, DDS, PhDd
University of Iowa, College of Dentistry, Iowa City, Iowa
Statement of problem. Die stones require abrasion resistance, dimensional stability with time, and high
surface wettability material properties.

Purpose. The purpose of this study was to compare the surface microhardness (Knoop) of 4 contemporary
gypsum materials with and without surface die hardener.

Material and methods. Materials used were a Type III stone (Microstone) and 3 die stones (Die-Keen, SilkyRock, and ResinRock). Die hardener was cyanoacrylate (Permabond 910) or Clear Coat. Specimens of stone
were hand mixed with distilled room temperature water and vacuum spatulated according to manufacturers
directions. Five cylinders (15 3 15 mm) per group were poured, using vibration, into phenolic ring molds
positioned on top of a glass slide. The face of each specimen was polished with 2400-grit Al2O sandpaper. One
face of each of 5 specimens/material was coated with cyanoacrylate; 5 specimens/material were coated with
Clear Coat, air thinned and dried; and 5 specimens/material had no treatment (control). Knoop hardness (kg/
mm2) readings were made on each face (5 readings/time point) 3, 12, and 24 hours after pouring. An ANOVA
procedure with post hoc Tukey tests were performed (a=.05).
Results. Microhardness did not vary between 3 and 24 hours for any material (P[.05). Microstone had
significantly lower surface hardness (P\.0001) than the die stones. Specimens coated with die hardener had
lower hardness values (P\.001 in all cases)
Conclusions. The 3 types of die stones evaluated in this study did not differ significantly in surface
microhardness. Under these conditions, die hardener coatings reduced the surface hardness of the gypsum
material. (J Prosthet Dent 2004;92:35-8.)

CLINICAL IMPLICATIONS
The die hardeners evaluated did not increase the surface hardness of the gypsum materials but
may have played a role in preventing brittle fracture of the die margin.

ental stones occupy an important role in the

fabrication of indirect dental prostheses. Casts poured in
dental stones should be accurate in every respect,
dimensionally stable over time, hard enough to withstand the fabrication process, resistant to the inadvertent
abrasions caused by fabrication, and have a surface
wettability compatible with the waxing process.
Laboratory technicians and dentists depend on these
characteristics to predictably fabricate accurate, precise
prostheses. ANSI/ADA Specification No. 251 provides
guidelines governing characteristics that group dental
stones into 4 classes of quality based on use and a range
of physical properties. Types I-IV are defined, re-

Private Practice, Logan, Utah.

Oral Surgery Resident.
c
Associate Professor, Prosthodontic Department.
d
Centennial Fund Professor, Director of Clinical Research, Dental
Clinical Research Center (Dows Institute for Dental Research) and
Department of Prosthodontics, University of Iowa.
b

JULY 2004

spectively, as impression plaster, plaster, dental stone,

and high-strength dental stone.2 Each type is equal in its
chemical composition, but differences exist in the
processing of each type to affect setting expansion,
compressive strength, and reproduction of detail.
Dies used to fabricate dental prostheses are often cast
in Type IV or high-expansion Type V gypsum materials
to produce a hard, accurate surface on which to make the
wax pattern for the prosthesis. These materials are often
thought to differ significantly in their hardness and other
characteristics. To increase surface hardness, surface
coatings or various treatments have been recommended
to improve the stones hardness or abrasion resistance.3
Contemporary methods for hardening dies have
changed over the years, from soaking or boiling dies in
different materials4-7 to coating them with various
agents, coupled with different methods for thinning
such agents. These methods include air thinning, brush
thinning, or shaking.8 For the most part, these coatings
have not been shown to alter the dimensions of the
THE JOURNAL OF PROSTHETIC DENTISTRY 35

THE JOURNAL OF PROSTHETIC DENTISTRY

finished die appreciably.8 Some materials, such as

cyanoacrylate, die sealants, and resins, have been found
to increase surface hardness.5,6,8 Each of these studies
used similar testing methods. The results showed
increased strength was dependent on specimen thickness5,6 and film thickness of the applied surface
hardener.8 Polystyrene applied to the surface and surface
hardeners mixed with the stone have not been found to
improve hardness.9,10 Epoxy resin has been shown to
soften gypsum surfaces.9
It is commonly thought that these coatings or
treatments are important to reduce surface abrasion
and surface fracture, especially at critical margin areas of
the dies. In a recent study, the impact of surface coating
materials on improving surface abrasion and preventing
water sorption was shown.11 The purpose of this study
was to determine the effect on surface microhardness of
4 contemporary stone materials with and without die
coating (cyanoacrylate or a ketone-based resin). The use
of surface coatings or hardeners may provide resistance
to surface abrasion and, therefore, provide a more sealed
gypsum surface for use in the dental laboratory setting.

MATERIAL AND METHODS

Four stone materials were included in this study:
a high-expansion Type V die stone material (Die-Keen;
Heraeus Kulzer, Armonk, NY), a Type III stone material
(Microstone; Whip Mix Corp, Louisville, Ky), and 2
Type IV die stone materials (Silky-Rock and ResinRock;
Whip Mix Corp). The stone used was provided in
prepackaged envelopes (Die-Keen, 120 g/25 mL water,
Microstone, 140 g/40 mL water, Silky-Rock, 140 g/32
mL water, and ResinRock, 70 g/14 mL water). Volume
and weight were verified to ensure that stones were
mixed according to manufacturers directions. Volume
of stone for a given weight may differ depending on
temperature, settling of the powder in its container, and
humidity of ambient air.2,13
Two die coatings or hardeners were evaluated:
a cyanoacrylate (Permabond 910; Permabond
International, Bridgewater, NJ) and a blend of ketonebased resins (Clear Coat; American Dental Supply,
Easton, Pa). Both agents utilize an acetone solvent that
evaporates when left exposed to air; new bottles of each
surface hardener were therefore used to minimize the
effect of viscosity due to desiccation.
The stone was hand mixed with distilled, room
temperature water until each material was wetted, then
vacuum spatulated in a 500-mL bowl at 400 rpm for the
specified amount of time, according to manufacturers
recommendations. Mixed specimens were poured immediately under vibration into 15 3 15-mm phenolic
cylinders on top of a glass specimen slide and set aside to
harden (258C, ambient humidity). Fifteen cylinders
were made for each gypsum material group. Five
36

HARRIS ET AL

gypsum specimens were evaluated with no die hardener

(control), 5 were coated with Permabond 910, and 5
were coated with Clear Coat.
Specimens were allowed to polymerize for 45
minutes before being removed from the phenolic
cylinder forms. The flat faces were then dry polished
with 2400-grit aluminum oxide sandpaper. Although
this step removed the surface layer of stone, it facilitated
the subsequent measurement of the Knoop diagonal
(microhardness measurements necessitate a smooth,
highly polished surface for accurate stylus indentation
and visual measurement). After polishing, 5 specimens
of each stone were coated with Permabond 910, and 5
were coated with Clear Coat, which was air thinned and
allowed to dry.
Trials for each stone were conducted by measuring
Knoop microhardness (Micromet II; Buehler, Ltd, Lake
Bluff, Ill, expressed as kg/mm2 or HK) of each specimen
face at 3, 12, and 24 hours after initial pour. Hardness
was determined by loading each specimen face 5 times,
in areas 600 to 1400 mm apart, for 15 seconds with
a force of 25, 50, or 100 g. The determinant of the
amount of force used was defined by the length of the
long diagonal of the Knoop indenter. Since the largest
width of the indentation is 250 mm, the load was
customized to provide indentations of 60 to 250 mm
(the limits of measurement). Knoop microhardness was
calculated with the following formula:
HK

14230 3 F
d2

where HK is Knoop Hardness, F is the force used to load

the instrument in grams, and d is the length of the
imprinted diagonal in micrometers.
Five indentations were recorded for each face, with
the same operator making all measurements. Each
specimen group was analyzed by group measurements
made for each stone, each die coating, and each time of
measurement. One-way ANOVA, 2-way ANOVA, and
3-way ANOVA and post hoc Tukey tests constituted the
statistical analysis. In addition, individual stones were
analyzed for the difference between die coatings and
bare stone by the Bonferroni (Dunn) t test. Significance
was assumed at a Type I error rate of .05 or a=.05.

RESULTS
Data are presented in Figures 1 through 4. ANOVA
statistical tests were employed comparing the Knoop
Hardness associated with each of the following variables:
product (type of stone specimen used), coating
(with without die coating), and time (amount of time
elapsed from initial pour3, 12, or 24 hours).
No significant interaction was observed between the
length of time elapsed from the initial pour and the type
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HARRIS ET AL

Fig. 1. Microhardness of resin-reinforced ResinRock die

material. Gypsum coated with Permabond Cyanoacrylate
resin or Clear Coat. Specimens (n=5/group) evaluated at 3,
12, and 24 hours.

Fig. 3. Microhardness of Silky-Rock die materials. Gypsum

coated with Permabond Cyanoacrylate resin or Clear Coat.
Specimens (n=5/group) evaluated at 3, 12, and 24 hours.

of die coating (P=.6988, F=0.55, df=4). The 3-way

ANOVA between product, time, and coating did not
show significant interaction (P=.0992, F=1.59, df=12).
At 3 hours, microhardness did not vary between
stones. Two-way ANOVA showed that the type of stone
did not have an effect on hardness (P=.0765, F=2.43,
Dfn=3, Dfd=48), while die coating did have a significant
effect on hardness (P\.0001, F=32.56, Dfn=3,
Dfd=48). At 3 hours, there was no significant difference
between the hardness of any of the stones given each type
of coating, while between coating groups, there were
significant differences in hardness. Figures 1 through 4
show that die-coated specimens had significantly lower
Knoop Hardness scores than their noncoated counterparts. All of the noncoated stone specimens were
statistically similar in hardness at 3 hours, as were all of
the specimens coated with Permabond and all of the
specimens coated with Clear Coat.
At 12 hours, there was a significant interaction
between the type of stone and type of coating used
(P=.01, F=3.2, Dfn=6, Dfd=48). The type of stone had
an effect on hardness (P=.0067, F=4.58, Dfn=3,
JULY 2004

THE JOURNAL OF PROSTHETIC DENTISTRY

Fig. 2. Microhardness of Die-Keen die materials. Gypsum

coated with Permabond Cyanoacrylate resin or Clear Coat.
Specimens (n=5/group) evaluated at 3, 12, and 24 hours.

Fig. 4. Microhardness of Microstone Type III Gypsum

materials. Gypsum coated with Permabond Cyanoacrylate
resin or Clear Coat. Specimens (n=5/group) evaluated at 3,
12, and 24 hours. Both coating materials reduced surface
microhardness.

Dfd=48), and die coating also had a significant effect

on hardness (P=.0002, F=10.46, Dfn=2, Dfd=48). By
12 hours, uncoated gypsum materials differed significantly from each other in hardness. The same is true for
stones coated with either Permabond or Clear Coat.
At 24 hours after initial pour, the same trend was
observed as at 12 hours. There was a significant interaction between type of stone and coating used
(P=.0241, F=2.71, Dfn=6, Dfd=48). The type of stone
significantly influenced hardness (P =.0002, F=7.84,
Dfn=3, Dfd=48), and the type of coating significantly
influenced hardness (P =.0014, F=7.6, Dfn=2, Dfd=48).
Between 3 and 12 hours, the initial polymerization of
the stones resulted in significant differences in hardness.
Stones coated with a die coating produced consistently
lower Knoop hardness values at each time period
through 24 hours, and for every type of stone except
for ResinRock.
A comparison of the stones coated with either
Permabond or Clear Coat showed stone-specific differences in surface hardness. For Silky-Rock, Die-Keen,
37

THE JOURNAL OF PROSTHETIC DENTISTRY

and Microstone, specimens with no die coating were

significantly harder than specimens with either die
coating (P=.0013, F=7.84, df=2), (P\.0001,
F=21.77, df=2) and (P=.0052, F=5.96, df=2) respectively. For ResinRock, the die coating did not make
a significant difference in hardness (P=.5447, F=0.62,
df=2).

DISCUSSION
Knoop hardness has been used to evaluate very hard,
brittle materials with a low modulus of elasticity
including enamel, amalgam, gypsum, and porcelain.14
Other hardness scales, such as the Brinnell and Vickers,
are more commonly used in evaluating viscoelastic
materials with a high modulus of elasticity, such as metal
alloys.
In a previous study, low variances were associated
with measures of surface microhardness.15 In the
present study, within the same specimen face, Knoop
hardness differed across the surface of the specimen.
This may be attributed to subsurface porosities in one
site versus another, or to specific sites in the crystalline
matrix that are weaker than others and tend to break
down more quickly, resulting in a lower hardness value.
For example, the nucleus of crystallization may be
harder than the outer fringes where one crystal meets
another. Other limitations of the present study were the
small sample size and the necessity of polishing the
surface layer to facilitate the measurement of the Knoop
diagonal.
Previous studies have differed as to the effect of die
coatings on the surface hardness of dental stones. After
the treatment or application of surface hardeners, some
materials have shown an increase in hardness,5,6,8 while
others have demonstrated no effect,9,10 and still others
have shown a reduction in hardness.9 This may be due,
in part, to differences in measurement technique since
hardness is an operationally defined physical property of
materials. The impact of surface coatings is potentially
more important as a means to reduce surface abrasion
and surface water absorption of die material, as shown by
Lindquist et al.11 Abrasion resistance can be improved
by the impregnation of a supportive resin that acts to
bind the gypsum matrix, filling subsurface voids and
sealing the gypsum surface. Impact fracture and loss of
surface material is thereby reduced by having reinforcement, both at the surface and within the material, due to
surface penetration of the resin. The resin film thickness,
measured by conventional microhardness (Knoop
measurements) as in the present study, may therefore
be lower due to the nature of the surface hardness
measurement of the coating film itself, and not the film/
gypsum matrix.

38

HARRIS ET AL

CONCLUSION
Based on the results of this study, the following
conclusions are made:
The use of air-thinned cyanoacrylate (Permabond
910) and Clear Coat die coatings on Silky-Rock, DieKeen, and Microstone decreased the surface hardness
(P=.0013). At 24 hours, Microstone, a Type III dental
stone, did not differ in hardness from the other Type IV
dental stones evaluated (P=.0002).

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Reprint requests to:
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UNIVERSITY OF IOWA/COLLEGE OF DENTISTRY
N447 DENTAL SCIENCE BUILDING
IOWA CITY, IA 52242
FAX: (319) 335-8895
E-MAIL: Clark-Stanford@uiowa.edu
0022-3913/$30.00
Copyright 2004 by The Editorial Council of The Journal of Prosthetic
Dentistry

doi:10.1016/j.prosdent.2004.04.002

VOLUME 92 NUMBER 1