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http://www.intl.elsevierhealth.com/journals/dema
Institute of Materials Science and Engineering, National Sun Yat-Sen University, Kaohsiung 80424,
Taiwan, ROC
b
Dental Department, Veterans General Hospital-Kaohsiung, Kaohsiung 813 Taiwan, ROC
Received 7 March 2002; received in revised form 1 January 2003; accepted 12 March 2003
KEYWORDS
Denture; Poly(methyl
methacrylate);
Microwave; Morphology;
Transmission electron
microscopy
Summary Objectives. This study examined the influence of microwave energy levels
on the morphology and properties of an impact resistant denture material poly(methyl
methacrylate) with a thickness of 10 mm.
Methods. A microwave flask containing two resin blocks was processed at 80, 160,
240, and 560 W for 15, 10, 7, and 2 min, separately. Each Flask was then turned over,
and cured for an additional 2 min at 560 W. The process using conventional methods
was carried out at 70 8C for 9 h. The blocks were tested for hardness, porosity, flexural
properties, solubility, and molecular weight. The morphology of the specimens after
staining with osmium tetroxide was examined by transmission electron microscope.
Results. The changes in temperature with time were recorded during microwave
heating at 80, 160, and 240 W, respectively. A significantly large difference in the
curing temperature was observed when comparing these two processing methods.
There was little difference in the mean values of surface hardness and the weight
percents of the insoluble parts. The mean domain size and the volume fraction of the
rubber phase favor of the water-bath method. However, the porosity in the waterbath-cured specimens was much less than that in the microwave-cured specimens.
Thus, the conventionally cured specimens showed better flexural strength and flexural
modulus than the microwave-cured specimens.
Significance. This study has shown that microwave energy can efficiently polymerize
denture base polymer. Highly statistical differences in morphology and flexural
properties favor of the water-bath method. Choice of a suitable microwave power and
polymerization time is important in order to reduce porosity to a minimum level and
increase the domain size and volume of the rubber phase.
Q 2003 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
Introduction
*Corresponding author. Tel.: 886-7-5252000x4062; fax:
886-7-525-4099.
E-mail address: mingchen@mail.nsysu.edu.tw
0109-5641/$ - see front matter Q 2003 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/S0109-5641(03)00084-8
134
135
Hardness
Porosity
The pulse echo C-scans were performed with the
Testech ultrasonic tester (model VI-100). The
polished blocks were inspected at a test frequency
of 10 MHz using a 25.4 mm (1 in.) element transducer with approximately a 38.1 mm (1.5 in.) focal
length in the coupling medium (water), and were
scanned along the top surface at a speed of
0.2 mm/s. The interface delay was measured and
converted into a gray scale value on a C-scan image.
Flexural test
The mechanical test used was the three-pointbending test with a span-to-thickness ratio s=t of
4:1. Six to eight blocks of each condition were
tested at room temperature on a MTS dynamic
tensile testing machine (Model 810) at a crosshead
speed of 1.25 mm/min. The deflection reading as a
function of the applied load was recorded during
the entire test until the applied load dropped
substantially, as a result of internal damage in the
specimens.
Solubility
A sample from the fracture surface was cut into a
piece of about 0.2 g. It was then refluxed with
150 ml of tetrahydrofuran (THF) in a round-bottomed flask at a cycle of about 45 min. This
procedure continued for 25 26 h to ensure that all
soluble PMMA in the cuttings was extracted into
solution. The insoluble part was dried and then
weighed to determine its percentage. Three
136
Results
Figure 1 Specimen temperature versus time for microwave power at 80, 160 and 240 W, respectively.
Statistics
Means and standard deviations were calculated for
each measurement or property. A one-way analysis
of variance (ANOVA) was conducted on the data of
domain size, hardness, and flexural properties
seeking statistically significant difference between
one water-bath and four microwave cured specimens. Means were compared at the 95% level of
Figure 2 TEM micrographs of denture base resins cured in conventional water-bath (a) overall view and definition of
domains, (b) close view.
137
Table 1 Statistical analysis of the domain size of the effective rubber phase.
Number of
domains
Water-bath curing
Microwave power
Overall
80 W
160 W
240 W
560 W
383
2485
685
756
675
369
Mean domain
size (mm)
0.395
0.373
0.379
0.378
0.370
0.354
Std. dev.
(mm)
0.068
0.067
0.060
0.070
0.072
0.062
95% Confidence
interval (mm)
Lower
bound
Upper
bound
P-value
P , 0:05
0.388
0.370
0.375
0.373
0.365
0.347
0.402
0.375
0.384
0.383
0.375
0.360
1.346 1027
8.926 1025
1.101 1024
2.985 1028
1.576 10217
Yes
Yes
Yes
Yes
Yes
Figure 3 TEM micrographs of denture base resins cured by microwave power at (a) 80, (b) 160, (c) 240, and (d) 560 W,
respectively.
138
Insoluble wt%
Porosity
Molecular weights
n
M
w
M
n
w =M
M
p
M
a
Microwave power
80 W
160 W
240 W
560 W
60.6 (2.2)a
0 10%
65.2 (2.8)
60%
60.0 (7.9)
65%
68.0 (1.8)
40%
62.7 (1.8)
80%
64400 (1350)
171500 (1630)
2.75
153,500
68600 (4600)
170300 (4260)
2.48
141,800
59500 (3140)
163000 (7120)
2.74
140,700
65300 (2690)
154900 (6400)
2.37
129,400
66900 (1230)
167200 (8470)
2.50
130,500
139
Water-bath curing
Microwave power
Overall
80 W
160 W
240 W
560 W
150 (10)
184 (32)
46 (8)
46 (8)
46 (8)
46 (8)
Mean
17.62
17.38
17.41
17.20
17.65
17.25
Std. dev.
0.78
0.33
0.28
0.27
0.27
0.32
Discussion
Microwave polymerization is affected by the random availability of benzoyl peroxide, and the
variation in duration and magnitude of exothermic
reaction, etc.10,11 The half-lives of benzoyl peroxide initiator are 7.3, 1.4 h, and 19.8 min at 70,
85, and 100 8C, respectively.12 The higher the
power applied to the system, the more the resin
temperature rises,13 the faster the benzoyl peroxide decomposes, and the more rapid is the
polymerization reaction. In these experiments,
the temperatures rose rapidly in the center of the
resin blocks. Because a microwave oven has almost
no thermal inertia, the response is effective and
almost instantaneous. From the half-lives of benzoyl peroxide, it is clear that the time required for
substantial conversion of monomer to polymer
would be impractically long at temperatures much
below 100 8C.14 To avoid porosity especially in the
thick parts of dentures, polymerization must be
conducted at a relatively low temperature (70 8C)
and slowly (9 h) in a hot-water bath. When
comparing both heating methods, quite a large
difference in the curing temperature was observed.
This study has shown that microwave energy can
efficiently polymerize denture base polymer. Microwave processing has a potential for saving a great
amount of time in processing dentures.
Microwaves acted initially on the MMA monomers
inside the resin blocks, therefore MMA absorbed
much energy in the beginning of polymerization.
After initiation of polymerization and a period of
conversion of MMA monomers, the resulting exotherm raised the heating rate.10 The standard
deviation of the final equilibrium temperature was
Water-bath vs.
microwave
Lower bound
Upper bound
P-value
P , 0:05
17.49
17.33
17.33
17.12
17.57
17.15
17.75
17.43
17.50
17.29
17.73
17.34
1.820 1024
0.0825
5.070 1024
0.815
1.961 1023
Yes
No
Yes
No
Yes
140
Water-bath curing
Microwave power
Mean
strength (MPa)
Std. dev.
(MPa)
Water-bath vs.
micsrowave
Lower bound
Upper bound
P-value
P , 0:05
0.011
Yes
0.861
(Microwave-vs.
microwave-)
No
Overall
80 W
160 W
240 W
6
30
7
8
8
144
130
128
128
132
17
10
9
12
10
126
126
120
118
124
161
134
136
138
140
560 W
131
11
120
142
Water-bath curing
Microwave power
Displacement,
mean (mm)
Std. dev.
(mm)
Lower bound
Upper bound
P-value
P , 0:05
1.576 10217
Yes
0.947
(Microwave-vs.
microwave-)
No
Overall
80 W
160 W
240 W
6
30
7
8
8
0.83
2.36
2.33
2.34
2.35
0.17
0.35
0.22
0.21
0.40
0.65
2.23
2.13
2.16
2.02
1.01
2.49
2.54
2.51
2.69
560 W
2.43
0.54
1.94
2.93
141
Conclusions
A significantly large difference in the curing
temperature was observed upon comparing these
two processing methods. This study has shown that
microwave energy can efficiently polymerize and
cure denture base polymer from the results of
insoluble weight percent and the curing temperature. Highly statistical differences in morphology
and flexural properties were evident in a comparison of processing methods. The size and the volume
fraction of the rubber phase are in favor of the
water-bath method. However, the amount of
porosity increased with an increase in microwave
energy level. Thus, the water-bath cured specimens
showed better flexural strength and flexural modulus than the microwave-cured specimens. There
were no significant differences in the surface
hardness and the domain size distribution of the
effective rubber phase. It has been stated that
choice of a suitable power and polymerization time
is important in order to reduce porosity to a
minimum level. Microwave processing has a potential for saving time in processing dentures.
Acknowledgements
This work was partially supported by grant
VGHNSU88-01 from the Veterans Affairs Commission, Executive Yuan, ROC, and by grant NSC
References
1. Craig RG. Restorative dental materials, 7th ed. St Louis: CV
Mosby Co; 1985. p. 362.
2. Nishii M. Studies on the curing of denture base resins with
microwave irradiation: with particular reference to heatcuring resins. J Osaka Dent Univ 1968;2:2340.
3. Kimura H, Teraoka F, Ohnishi H, Saito T, Yato M. Applications
of microwave for dental technique (Part 1): dough-forming
and curing of acrylic resins. J Osaka Univ Dent Sch 1983;23:
439.
4. Kimura H, Teraoka F, Saito T. Applications of microwave for
dental technique (Part 2): adaptability of cured acrylic
resins. J Osaka Univ Dent Sch 1984;23:439.
5. Reitz PV, Sanders JL, Levin B. The curing of denture acrylic
resins by microwave energy: physical properties. Quint Int
1985;8:54751.
6. Peyton FA. Packing and processing denture base resins. J Am
Dent Assoc 1950;40:5216.
7. Hayden WJ. Flexural strength of microwave-cured denture
baseplates. Gen Dent 1986;34:36771.
8. Shlosberg SR, Goodacre CJ, Munoz CA, Moore BK, Schnell RJ.
Microwave energy polymerization of poly(methyl methacrylate) denture base resin. Int J Prosthodont 1989;2:4538.
9. Smith LT, Powers JM, Ladd D. Mechanical properties of new
denture resins polymerized by visible light, heat, and
microwave energy. Int J Prosthodont 1992;5:31520.
10. De Clerck JP. Microwave polymerization of acrylic resins
used in dental prostheses. J Prosthet Dent 1987;57:6508.
11. Huggett R, Brooks SC, Bates JF. The effect of different curing
cycles on levels of residual monomer in acrylic resin denture
base materials. Quint Dent Technol 1984;8:36571.
12. Odian G. Principles of polymerization, 2nd ed. New York:
Wiley; 1981. p. 196.
13. Chen M, Siochi EJ, Ward TC, McGrath JE. Basic ideas of
microwave processing of polymers. Polym Engng Sci 1993;33:
1092109.
14. Al Doori D, Huggett R, Bates JF, Brooks SC. A comparison of
denture base acrylic resins polymerized by microwave
irradiation and by conventional water bath curing systems.
Dent Mater 1988;4:2532.
15. Chen M, Siochi EJ, Ward TC, McGrath JE. The dielectric
behavior of glassy amorphous polymers at 2.45 GHz. Polym
Engng Sci 1993;33:111021.