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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

with initial setting times of approximately 1~ min for Delton and Concise (EB) and 2 min for Profile (BA). 5 min.m) was produced in this manner.05 level using a t-test for each resin (11). .3_+0.9 12.000 10.' ' ~ ' ' ~ ' ~ ' ~ 70 ~:f2 60 / t~r~ 50 Q * Collection of the spectra took approximately 30 sec at each time period. the increase in DC was approximately linear with time through 24 h.9 51.--. These films were peeled from the slides and analyzed on the FTIR in transmission.) using a Knoop diamond indenter.5 55.3 9.1 70.7+_0.7+-0.2[ 10. 4 min.2-+0. + b_>5.4+0.6 71. 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.7 69.4 13.7 . stable background*.~r-=. 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. using standard baseline procedures (2.3 17.8_+0. .0 18.3 66. 60 min.0+_0.1+0.5+1.0 62. . 1.8 8. At least five values were recorded at each time interval from five different specimens for each resin.2_+0..6 18. Hardness (KHN) vs DC during setting Time DC (%)* 5 min 10 min 20 min 30 min 60 min 120 min 6h 24 h 62.5 57.and post-polymerized resins. 6 h and 24 h) at 37~ The DC (%) vs log t 100 90 80 .9-+0. 10 min.4_+0.8_+1. 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. the temperature in the specimen chamber rose from 34~ to 40~ Three runs were made for each resin system.3 72.9" i/ 9 r// / o.5+1. CA) in transmission mode. 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.3 7. Each point represents an average of three values.7 74.6+0.9 58. -z e-.5 77.5-+0. The correlation coefficient was analyzed for significance at the p --< 0. 2 min. DC Concise (EB) KHN 58. No increase in DC was observed for any resin at 48 h.4_+2.9 10. Therefore. The degree of conversion (DC) was analyzed with a Fourier Transform Inrared (FTIR) Spectrometer (FX6250Analect Instruments.2+0. Means connected by bars were not significantly different (p _< 0. Each hardness reading was made at 23~ under a 100 g toad on a Tukon hardness tester (Page-Wilson Corp. Spectra were acquired at time intervals of 1 min. 10 min.6_+1.. Conn.7 68.2_+0.9 19.7_+0.0+0. 120 min.2 11.0 67.4+0.9+_2.7_+0.0-+1.2 62.12 Ferracane resins with differences in degree of conversion (8). .6-+0.9-+0. A thin resin film ( 2 0 4 0 p.9_+0. Three films were tested for each resin at each time period. .05).8 9.7 9. 4). / ~/" ~ ~ -- .5 15.7 70.0_+I.9-+0.6-+0. 3 min.8 14.6 50. DC at 24 Table 1.6 6. 20 min and 30 min under a nitrogen gas purge to insure a clean. Bridgeport.4 12. Regression analysis was performed to determine the correlation between DC and KHN.4 18.05 level (10).4 66.. Results The three self-curing unfilled resins hardened very rapidly.5_+0.2+ 1..6_+0. 1) revealed that initial setting occurred when fewer than 40% of the available carbon double bonds had reacted in these systems.9 I 10.8_+0.&- .4_+2. 20 min.2-+0.1_+0.~ ! ~J / 30 10 ~ // " 40 20 ~ c i " .5 17... log time for three unfilled resins.--. The DC values for the curing periods of 60 rain.8 Delton KHN (kg/mm2)+ 9.. . Irvine. Degree of Conversion (DC) vs.. At least 10 specimens were made for each resin. 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.000 t(min) Fig. After the first 5 to 10 min of curing. // 9- -- Delton Concise -A Profile (EB) (BA) / I 10 0 I 100 I 1.2_+0. Analysis of the DC with respect to time (Fig.standard deviation.3_+0. * b=2.7 13. 30 min.1+0...8 47. During this time period.0 65. 120 rain.6+1. :=~r -=. according to a procedure outlined in detail previously (4).7+1.6+1.7 76.8 Values are mean +.1-+0. 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.0_+0.7-+1. 6 h and 24 h were determined by polymerizing a drop of mixed resin between glass slides at 37~ for the appropriate time period.5 11.5 Profile (BA) DC KHN 43.

i. Correlation between KHN and DC for three individual resins and for all resins combined (solid line). .:?.937) and significant (p -< 0.P% .4% at 5 min with a hardness value of 9. . Concise (EB) achieves 62. but the DC values for the two resins were statistically equivalent at all time periods. Regression analysis revealed a strong (r -> 0. Despite the correlation between hardness and DC during setting.8 KHN.D C : : KHN 10 1 10 I 100 I 1. while less than 55% of the maximum hardness has been attained. However. Comparison of the percent of maximum DC and maximum hardness (KHN) vs.. Each point represents an average of three values for DC and at least 5 values for KHN.. 3.--e Concise (EB) * ..y "7 2. /~. Both properties showed rather linear increases with time from 10 min to 6 h. Fig. the hardness values for Delton and Profile (BA) were statistically equivalent at all time periods.0 // / /9 14. log time for Delton. the greatest increase in hardness occurs during a period in which very subtle changes in DC take place.~ 60 5O 3O 2O For a dental restorative resin. . D C fit K H N % of Max vs log 100 90 80 .0 Z [] / I /~/e' . and the only significant increase in DC after 6 h occurred with Concise (EB).. after 85% of the total conversion has been achieved..961 //__ 0 100 (%) Fig. ..498) when the regression analysis was repeated to include all three resins at all time periods (Fig. Delton achieves a DC of 62. ..o all points r=~498 r=.I" 9 /" .6 KHN./~/ /I/i /~/" . . 50 60 70 DC r = r = r = 9 . 2 reveals that at 5 min.--. .:/ - . There was no significant increase in hardness beyond 6 h.7% conversion at l0 rain. For example. but the slope for hardness was much greater. The curves for Profile (BA) and Concise (EB) were similar to that for Delton.000 10. 3). . In fact. 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)..0 ~/- /2 ~ [] .e.. specific hardness value cannot be correlated to a specific DC when comparing different resin formulations. DC for Delton has reached 70-80% of its maximum value. The hardness of Concise (EB) was significantly lower than that of Delton at 5 and 10 rain and at 30 through 120 rain. Each point represents an average value for the different time periods.--* P r o f i l e (BA) /7 /. with a hardness value of 7.13 Correlation between hardness and conversion in dental resins h will be referred to as maximum DC.. the acquisition of hardness chronologically lags behind the conversion of carbon double bonds.0 ./)/ I 16. 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.944 .::/ 9 // / " I . 4..498 . a KHN vs DC. The mechanical properties of these resins are influenced by the crosslinking and network formation taking place during setting. there appears to be a good correlation between increasing hardness and increasing degree of conversion during the setting reaction. Therefore.05) correlation between DC and hardness with time for all three resins (Fig. 9 Z 9 18.. Despite the differences in DC between the resins.000 t(min) Fig. However. the correlation between hardness and DC was very poor (r = 0.0 / 0/ "/ / " // C Z /~t H Discussion t . However..937 . -~ D e l t o n o-.0 E 1oo / / 9 / */ / / "r" 0.S/ 9 o. The maximum DC for Profile ( B A ) i s polymer chains than are reacted to crosslink existing chains. the acquisition of maximum (24 h) hardness and DC are not synchronized. ~ 8. A much greater percentage of carbon double bonds are reacted to form -- -. even though the DC was always 15 to 20% greater for Delton. 3). there were no significant differences between the hardness values at 24 h. 2. This network formation occurs after an initial stage of polymer chain propagation (12).

2. ASMUSSENE. CICCHETTIDV. 4. This restricts the use of indirect modes for testing degree of conversion. New York: McGraw Hill~ 1975. Calorimetric investigation of polymerization reactions. Scand J Dent Res 1976: 84: 396--400. M. MURAOKA. MITA I. Extension of multiple-range tests to interaction tables in the analysis of variance: a rapid approximate solution. 10. Profile (BA) has a hardness of 18. TIRTHAR. HORIE K. Irvine. FERRACANEJL. At this DC. Acknowledgements . reaction with initiator radicals. however. Illinois: Northwestern University. Acta Odontol Scand 1978: 36: 75-82. 314 pp. SJOVIK IJ. POWERSJM. 7.The author would like to thank Analect Instruments. As stated previously.14 Ferracane 62. However. Dissertation. FERRACANEJ. The correlation between the physical properties and degree of conversion in unfilled Bis-GMA-based dental resins. Post-irradiation polymerization of visible light-activated composite resins. Factors affecting the quantity of remaining double bonds in restorative resin polymers. 11. J Dent Res (in press). Infrared spectroscopic analysis of the degree of conversion of monomer to polymer in dental resins is a very accurate and reproducible technique. GREENER EH. DENNISON JB. which is not equivalent to conversion in these materials. approximately twice that of Delton and Concise (EB). it is possible that two resins with significantly different degrees of conversion may have identical properties when tested at ambient temperature. 9. Although the higher concentration of BIS-GMA in Profile (BA) contributes to its higher viscosity and to a lower DC (8). crosslinked copolymerization of methylmethacrylate with ethylene dimethacrylate. 3. when one is interested in the effect of residual reactive species on biocompatibility or dimensional change. Fourier transform infrared analysis of degree of polymerization in unfilled resins . Scand J Dent Res 1982: 90: 490-6. the hardness at ambient temperature is not similarly reduced. CA for the use of the FX6250 FTIR spectrophotometer used in this study. J Polym Sci Polym Chem Ed 1975: 13: 445-54. It does appear to be valid. OTAGAWAA. Therefore. Of less importance is the overall conversion of reactive species. References 1. indirect methods for measuring the degree of cure for comparison among resins are limited. However. SPIEGEL MR. 1983. The discrepancy lies in the nature of the two experiments. Psych Bull 1972: 77: 405-8. an absolute hardness value cannot be used to predict an absolute value for degree of conversion in all resins. It would not be correct to indirectly determine the degree of cure in two different resin systems by evaluating their hardness. FAN PL. Therefore. 5. the conversion of a carbon double bond to a single bond during the setting of dimethacrylate resins may occur via several mechanisms. This is due to the fact that the mechanical properties of the resin are very much dependent upon network formation. Schaum Outline Series. JOHNSTON WM. 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. Composition of dental resins and composite materials. as has been shown previously (8) and in this study. In vitro depth of cure of photoactivated composites. 12. A n infrared spectroscopic study of sealants. . V. The two 9 modes for evaluating degree of cure are sensitive to different variables. Acta Odontol Scand 1981: 39: 133-46. Remaining methacrylate groups in composite restorative materials. RUYTER IE. Restorative resins: hardness and strength vs. GYOROSIPP. LEUNG RL. RUYTER ID. SVENDSEN SA. 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. Scand J Dent Res 1982: 90: 484-9. including: chain elongation. J Dent Res 1983: 62: 363-5. 8. RUYTERIE. ASMUSSEN E. Evanston. quantity of remaining double bonds. 6.methods comparison. to use these indirect tests to predict the relative degree of conversion for a specific resin at different time periods or under variable conditions.9. crosslinking. J Dent Res 1982: 61: 1184-7. FAN PL.0%. Probability and Statistics.