Correlation between hardness

and degree of conversion

during the setting reaction of
unfilled dental restorative
resins

Jack L. Ferracane
Dental Materials Science Program, Baylor
College of Dentistry, Dallas, Texas, USA.

Ferracane JL. Correlation between hardness and degree of conversion during

the setting reaction of unfilled dental restorative resins. Dental Materials 1985;
1: 11-14.
Abstract. - Knoop hardness was correlated to degree of conversion (DC) of
carbon double bonds, determined by IR, during the setting reaction of three
unfilled dental resins. For a specific resin, increase in hardness correlates well
with increases in DC during setting. However, an absolute hardness number
cannot be used to predict a DC when comparing different resins. The two
techniques for determining extent of cure in dental resins cannot always be used
interchangeably, since each is sensitive to different variables.

It is desirable for a dental restorative

resin to convert all of its monomer to
polymer during the polymerization reaction. However, with Bis-GMA-based
resins there is always a significant concentration of unreacted carbon double
bonds remaining in the resin when it is
cured at or near the oral temperature.
This is believed to be due mainly to
limitations on the mobility of reactive
species imposed by the rapid formation
of a cross-linked polymeric network.
Since the extent of cure may exert an
effect on nearly every physical property
of the resin system (including: mechanical properties, solubility, dimensional stability, color change and biocompatibility), degree of conversion
may play an important role in determining the ultimate success of the restorative.
The degree of conversion in BisGMA-based restorative resins has been
analyzed with infrared spectroscopy by
several researchers and has been shown
to be in the range of 50 to 80% ( 1 4 ) .
However, it is common practice to
measure mechanical properties as a
means of indirectly evaluating degree
of cure.
In 1982, Tirtha et al. (5) evaluated
the Barcol hardness and transverse

strength of a series of light-cured dental

composite resins to determine depth of
cure. Barcol hardness was also used by
Leung et al. (6) to determine depth of
cure in visible light-cured composites as
a function of curing and illumination
time. Although there are several more
reports in the literature in which degree
of cure has been evaluated indirectly by
measuring mechanical properties, there
are only a few studies which have compared these indirect modes to IR techniques.
Asmussen (7) reported a good correlation between Wallace hardness, diametral tensile strength and degree of
conversion by IR for experimental
composite formulations in 1982. More
recently, Ferracane (8) measured the
degree of conversion in unfilled resins
by IR and correlated the results with
those obtained from tests of several
mechanical properties. He found a
good correlation between the degree of
conversion and the storage modulus
and glass transition temperature results
obtained by performing dynamic mechanical testing over a broad temperature range. The correlation between
degree of conversion and ambient temperature properties was not as strong,
however.

Key words: hardness, degree of conversion,

resins, composites, extent of cure.
Dr. Jack L. Ferracane, Dental Materials Science
Program, Baylor College of Dentistry, 3302
Gaston Avenue, Dallas, TX 75246, USA.

Accepted for publication21 August 1984.

Objectives

The objective of this study was to determine the nature of the correlation
between the Knoop hardness and the
degree of conversion of carbon double
bonds, as determined by IR analysis,
for unfilled dental restorative resins.
An attempt was also made to compare
the time frames at which maximum
hardness and degree of conversion are
acquired in these quick-setting resins.
Methods

Three commercially available, chemically-cured Bis-GMA-based resins

were used in this study. They were:
Delton Pit and Fissure Sealant
(Johnson & Johnson, East Windsor,
N J), Profile bonding agent (S. S. White
Dental Products International, Philadelphia, PA) and Concise Enamel
Bond (Dental Products/3M, St. Paul,
MN). The Profile bonding agent
(Profile BA) and the Concise Enamel
Bond (Concise EB) were supplied with
their respective composite resin restoratives. These unfilled resins were
chosen on the basis of differences in
monomer compositions (9) and viscosities, which were expected to produce

12

Ferracane

resins with differences in degree of conversion (8).

The degree of conversion (DC) was
analyzed with a Fourier Transform Inrared (FTIR) Spectrometer (FX6250Analect Instruments, Irvine, CA) in
transmission mode. The conversion
during the first 30 rain of the reaction
was followed by polymerizing the resin
between AgC1 windows in the path of
the IR. Spectra were acquired at time
intervals of 1 min, 2 min, 3 min, 4 min,
5 min, 10 min, 20 min and 30 min under
a nitrogen gas purge to insure a clean,
stable background*. During this time
period, the temperature in the
specimen chamber rose from 34~ to
40~ Three runs were made for each
resin system.
The DC values for the curing periods
of 60 rain, 120 min, 6 h and 24 h were
determined by polymerizing a drop of
mixed resin between glass slides at
37~ for the appropriate time period.
A thin resin film ( 2 0 4 0 p,m) was
produced in this manner. These films
were peeled from the slides and analyzed on the FTIR in transmission, according to a procedure outlined in
detail previously (4). Three films were
tested for each resin at each time
period.
The DC was calculated by comparing
the absorbance ratio of the C = C peak
at 1640 cm 1 to the unchanging aromatic ring peak at 1610 cm -a for the
pre- and post-polymerized resins, using
standard baseline procedures (2, 4).
Specimens were made for Knoop
hardness (KHN) testing by curing the
resins in a 6 mm x 3 mm steel disk
mold for the appropriate time periods
(5 min, 10 min, 20 min, 30 min, 60 min,
120 rain, 6 h and 24 h) at 37~ The

DC (%) vs log t
100
90
80

.....

:=~r -=.~r-=- - . - - ' ' ~ ' ' ~ ' ~ ' ~

70

~:f2

60

/ t~r~

50

* Collection of the spectra took approximately 30 sec at each time period.

/ ~/"

--

.&-

..~ !

~J

30

10

// "

40

20

c i " .9"

i/
9

r//

o- . . . . . .

-z

e-.--.--.

//

9-

--

Delton
Concise

-A

Profile

(EB)
(BA)

/
I
10

I
100

I
1,000

10,000

t(min)
Fig. 1. Degree of Conversion (DC) vs. log time for three unfilled resins. Each point represents an average of three values.
specimens were sanded fiat with 320
emery paper before the initial test to
insure that any air-inhibited surface
layer of resin had been removed. At
least 10 specimens were made for each
resin. An individual specimen was
tested at alternate time periods to
insure that it had been allowed to cure
at 37~ for the entire specified time
before testing. Each hardness reading
was made at 23~ under a 100 g toad on
a Tukon hardness tester (Page-Wilson
Corp., Bridgeport, Conn.) using a
Knoop diamond indenter. At least five
values were recorded at each time interval from five different specimens for
each resin.
The DC and hardness results were
analyzed by analysis of variance and
Scheffes test for making multiple comparisons between unconfounded means
at the p -< 0.05 level (10). Regression

analysis was performed to determine

the correlation between DC and KHN.
The correlation coefficient was analyzed for significance at the p --< 0.05
level using a t-test for each resin (11).
Results

The three self-curing unfilled resins

hardened very rapidly, with initial
setting times of approximately 1~ min
for Delton and Concise (EB) and 2 min
for Profile (BA). Analysis of the DC
with respect to time (Fig. 1) revealed
that initial setting occurred when fewer
than 40% of the available carbon
double bonds had reacted in these systems. After the first 5 to 10 min of curing, the increase in DC was approximately linear with time through 24 h.
No increase in DC was observed for
any resin at 48 h. Therefore, DC at 24

Table 1. Hardness (KHN) vs DC during setting

Time

DC (%)*

5 min
10 min
20 min
30 min
60 min
120 min
6h
24 h

62.4_+2.0
65.8_+0.7
68.2_+0.7
69.4_+0.7
70.5_+0.6
71.2_+0.7
74.7_+0.5
77.6+1.8

Delton
KHN (kg/mm2)+
9.8_+0.2[
10.0+0.9
10.9-+0.9
12.0_+0.7
13.3_+0.8
14.9_+0.9
19.0_+I.0
18.6_+1.5

Profile (BA)
DC

KHN

43.4_+2.8
47.5+1.6
50.6+1.9
51.8_+1.5
55.7+-0.5
57.2+0.9
58.6_+0.2
62.0+_0.8

8.1-+0.8
9.4+0.9 I
10.6-+0.5
11.2-+0.4
13.1+0.5
15.3_+0.6
18.2+ 1.4
18.9-+0.8

Values are mean +- standard deviation.

Means connected by bars were not significantly different (p _< 0.05).
*

b=2.

+ b_>5.

DC

Concise (EB)
KHN

58.5+1.0
62.7+1.3
66.0-+1.4
66.9+_2.0
67.7-+1.1
70.1+0.3
72.2-+0.7
76.9-+0.6

6.4+0.3
7.6+0.3
9.1_+0.7
9.7_+0.2
11.2_+0.4
12.7+_0.5
17.5-+0.3
17.6-+0.7

13

Correlation between hardness and conversion in dental resins

h will be referred to as maximum DC.
The DC values at 24 h were equivalent for Delton and Concise (EB) and
were approximately 15% greater than
that of Profile (BA) (Table 1). Despite
the differences in DC between the resins, there were no significant differences between the hardness values at
24 h. In fact, the hardness values for
Delton and Profile (BA) were statistically equivalent at all time periods,
even though the DC was always 15 to
20% greater for Delton. The hardness
of Concise (EB) was significantly lower
than that of Delton at 5 and 10 rain and
at 30 through 120 rain, but the DC
values for the two resins were statistically equivalent at all time periods.
It is apparent from the results in
Table 1 that both the hardness and DC
continue to increase with time after
setting for these resins. However, the
acquisition of maximum (24 h)
hardness and DC are not synchronized.
Fig. 2 reveals that at 5 min, DC for
Delton has reached 70-80% of its
maximum value, while less than 55% of
the maximum hardness has been attained. Both properties showed rather
linear increases with time from 10 min
to 6 h, but the slope for hardness was
much greater. The curves for Profile
(BA) and Concise (EB) were similar to
that for Delton. There was no significant increase in hardness beyond 6 h,
and the only significant increase in DC
after 6 h occurred with Concise (EB).
Regression analysis revealed a strong
(r -> 0.937) and significant (p -< 0.05)
correlation between DC and hardness
with time for all three resins (Fig. 3).
However, the correlation between
hardness and DC was very poor (r =
0.498) when the regression analysis was
repeated to include all three resins at
all time periods (Fig. 3).

D C fit K H N
% of Max vs log
100

90
80

,~

60
5O

3O
2O

For a dental restorative resin, there appears to be a good correlation between

increasing hardness and increasing
degree of conversion during the setting
reaction. However, the acquisition of
hardness chronologically lags behind
the conversion of carbon double bonds.
The mechanical properties of these
resins are influenced by the crosslinking and network formation taking
place during setting. This network formation occurs after an initial stage of
polymer chain propagation (12). A
much greater percentage of carbon
double bonds are reacted to form

--

-- D C

: KHN

10
1
10

I
100

I
1,000

10,000

t(min)
Fig. 2. Comparison of the percent of maximum DC and maximum hardness (KHN) vs. log
time for Delton. Each point represents an average of three values for DC and at least 5
values for KHN.
specific hardness value cannot be correlated to a specific DC when comparing different resin formulations. For
example, Delton achieves a DC of
62.4% at 5 min with a hardness value of
9.8 KHN. Concise (EB) achieves
62.7% conversion at l0 rain, with a
hardness value of 7.6 KHN. The
maximum DC for Profile ( B A ) i s

polymer chains than are reacted to

crosslink existing chains. Therefore,
the greatest increase in hardness occurs
during a period in which very subtle
changes in DC take place, i.e. after
85% of the total conversion has been
achieved.
Despite the correlation between
hardness and DC during setting, a

KHN

vs DC.
9 Z

18.0

[]

/~/e'
,;I"

/"

,/)/

16.0

//

/ /9
14.0

E 1oo

/ 9
/ */

"r"

0.o

all points
r=~498
r=.498

,,;P%
,,;:/ -

,,::/ 9

//
/

"

/~,.

4.0

,/~/

/I/i

/~/"
,S/
9

o- . . . . . . -~ D e l t o n
o-.--.--e Concise
(EB)
* - - - - --* P r o f i l e
(BA)

/7
/,y
"7

2.0

~/-

/2 ~

[] .,,:?.

~
8.0

0/ "/ / "

//

/~t

Discussion

50

60

70

DC

r =
r =
r =

.937
.944
.961

//__
0

100

(%)

Fig. 3. Correlation between KHN and DC for three individual resins and for all resins combined (solid line). Each point represents an average value for the different time periods.

14

Ferracane

62.0%. At this DC, Profile (BA) has a

hardness of 18.9, approximately twice
that of Delton and Concise (EB). Although the higher concentration of
BIS-GMA in Profile (BA) contributes
to its higher viscosity and to a lower
DC (8), the hardness at ambient temperature is not similarly reduced. The
discrepancy lies in the nature of the two
experiments.
Infrared spectroscopic analysis of the
degree of conversion of monomer to
polymer in dental resins is a very accurate and reproducible technique.
However, the conversion of a carbon
double bond to a single bond during
the setting of dimethacrylate resins
may occur via several mechanisms, including: chain elongation, crosslinking, reaction with initiator radicals.
As stated previously, the mechanical
properties of a resin system are very
much dependent upon the cross-linking
density and the quality of the network
which forms during polymerization. Of
less importance is the overall conversion of reactive species. The two
9 modes for evaluating degree of cure are
sensitive to different variables. Therefore, it is possible that two resins with
significantly different degrees of conversion may have identical properties
when tested at ambient temperature, as
has been shown previously (8) and in
this study. This restricts the use of indirect modes for testing degree of conversion. It would not be correct to indirectly determine the degree of cure in
two different resin systems by evaluating their hardness, when one is interested in the effect of residual reactive
species on biocompatibility or dimensional change.
Conclusions
The acquisition of hardness during the
setting of unfillled dental restorative
resins correlates well with the increase
in degree of conversion for a specific
resin. However, an absolute hardness
value cannot be used to predict an absolute value for degree of conversion in
all resins. This is due to the fact that the
mechanical properties of the resin are
very much dependent upon network
formation, which is not equivalent to
conversion in these materials. Therefore, indirect methods for measuring
the degree of cure for comparison
among resins are limited. It does
appear to be valid, however, to use
these indirect tests to predict the relative degree of conversion for a

specific resin at different time periods

or under variable conditions.

Acknowledgements - The author would like

to thank Analect Instruments, Irvine, CA
for the use of the FX6250 FTIR spectrophotometer used in this study.

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