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0 1996
17 (1996)
1627-1630
ELSEVIER
0142-9612(95)00330-4
Elsevier Science Limited Printed in Great Britain. All rights reserved 0142-9612/96/$X.00
of Basic Dental Science, **Department of Restorative Dentistry, University of Wales College of Dental School, Heath Park, Cardiff CF4 4XY, UK; Department of Removable Prosthetics, Faculty of
The purpose denture to sinusoidal temperature materials methods. for each formulation mechanical plasticization Elsevier Keywords: properties
Received
properties analysis.
of a range Specimens
soft lining
materials of 30-70C.
deformation
of 64 microns results
and rate of deformation than previously G/G loss tangent materials over (Molloplast
experience modulus
clinically, G, dissipative
temperature generally
decreased,
ing an increased
deformation.
B) and alternative the range chosen. 0 The suggesting of testing. that the 1996
(Novus) process
Science Dental
materials,
denture
liners,
dynamic
mechanical
thermal
analysis,
deformation
16 July
1995; accepted
3 November
1995
Of the physical properties of soft lining materials, the resilience and the capacity of a material to absorb energy are of particular importance. Methods previously used to determine deformation characteristics have been static compression set, torsional pendulum and mechanical impedance tests. Compression set measurements invoke measuring the rate of recovery of the material after the application of a given stress. However, this is a static load application technique and does not predict in viva behaviour. Braden and Clarke realized the importance of measuring deformation at rates appropriate to those the experienced in viva. Hence they measured response of the materials to cyclic (sinusoidal) forces using a torsional pendulum, previously described by Braden and Stafford3. However, the technique is insufficient to maintain a constant amplitude over a set temperature range. Mechanical impedance testing4 has limitations in precision of measurement owing to specimen size requirements. Many of the limitations of the above techniques are overcome by the use of the recently developed dynamic mechanical thermal analysis (DMTA). The technique involves the application of a sinusoidally oscillating stress to a material which enables measurement of the strain at a fixed frequency or range of frequencies over a specific temperature range and also isothermally as a function of time5. Correspondence to Mr M.G.J. Waters.
1627
DMTA has been used to evaluate denture-base polymers6, but investigation of resilient liners using this technique has not been reported. The purpose of this investigation was to compare the moduli of selected resilient lining materials using DMTA.
THEORETICAL CONSIDERATIONS When a sinusoidal stress is applied to a perfectly elastic solid the deformation (and hence the strain) occurs exactly in phase with the applied stress, hence the modulus is not time dependent. A completely viscous material will respond with the deformation lagging behind the applied stress (Figure I). When a sinusoidal stress is applied to a viscoelastic material it will behave neither as a perfectly elastic nor as a perfectly viscous body and the resultant strain will lag behind the stress by some angle(s) where 0 = 90 (Figure z). The magnitude of the loss angle is dependent upon the amount of internal motion occurring in the same frequency range as the imposed stress. For a perfectly elastic material deforming in shear, it is possible to write:
y(f) =
Where y(t) is the shear strain, o(t) is the shear stress and
Biomaterials 1996, Vol. 17 No. 16
1628
DMTA of denture
soft liners:
M. Waters
et al.
The stress and strain are therefore 90 out of phase for a sample whose properties are defined by Equation 4. For a viscoelastic material, the strain will lag behind the stress by an amount normally called the loss angle (6). It is normally convenient to separate the viscoelastic response into in phase and out phase components. The in phase stress and strain result in which is completely energy elastically stored recoverable, while the out of phase stress and strain result in the dissipation of energy. The in phase and the out phase shear moduli G and G are: G, = 4 = Amplitude of in phase stress component
Elastic mawrial t T Viscous mawid
i G,,= c
the response materials to of an
G is the shear modulus and the time dependence oscillation (0). The stress is given by: a(t) = 60 cos wt and the strain as: y(t) = 2 cos wt
of (2)
J=;
and J tan&Cr=_=_=G
(T
Y
y
(3)
The storage modulus is the elastic response and corresponds to completely recoverable energy, whereas the loss modulus is the viscous response corresponding to energy lost through internal motion. The tangent of this loss angle, tan 6, is dimensionless and is equal to the ratio of energy lost (dissipated as heat) to energy stored per cycle: tan6 = Loss modulus G Storage modulus = ??
The strain rate, d/dt responds linearly to stress for a viscous body with a proportionately constant 7, the viscosity. The rate of strain is a maximum when the stress is a maximum and a minimum when the stress is a minimum. Integrating Equation 4 yields:
S1ress t
b
Figure 2 a, Schematic representation of the response of a viscoelastic material to an applied sinusoidal stress. b, Schematic representation of the resolution of the in-andout-of phase stress components.
Biomaterials 1996,
Vol. 17 No. 16
DMTA
of denture
soft liners: M. Waters et al. of materials Type Plasticized acrylic Plasticized acrylic Silicone elastomer Silicone elastomer Copolymer resilient liner Polyphosphazene fluoroelastomer used Manufacturer Coe Laboratories Inc., Chicago, Illinois, USA Dentimex EIV., Zeist, Holland Regneri G-MBH & KG, Karlsruhe, Germany Flexico Developments Ltd., London, UK Weil-Dental G-MBH, Rosbach, Germany Hyginic Corporation, Akron, Ohio, USA
1629
Table 1 Material
Coe Super Soft Vetrex Soft Malloplast B Flexibase RTV Flexor Novus
Table 2 Material
Shear parameters N = 5
measured
at 37C G (MPa) SD 0.055 0.104 0.094 0.117 0.115 0.058 cv 17.6 15.9 21.4 20.0 15.1 16.5 Mean 0.331 0.536 0.029 0.030 0.070 0.041 SD 0.079 0.088 0.008 0.014 0.008 0.003 cv 23.9 16.5 28.9 17.4 11.7 7.7 Tan 6 (G/G) Mean 1.078 0.826 0.066 0.158 0.092 0.117 SD 0.126 0.044 0.015 0.012 0.010 0.014 cv 11.7 5.4 22.7 7.4 11.1 12.3
G (MPa) Mean
1.078.
0 = 47.
and coefficients of Means, standard deviations variation were calculated for all parameters. Means were tested by Students t-test. Results were tested by one-way ANOVA and multiple comparisons of means, together with p-value calculations.
RESULTS
Table 2 gives the mean, standard deviation, and coefficient of variance at 37C for G, G, and tan 6. The shear storage modulus G plotted against temperature is shown in Figure 3. The acrylic materials Vertex Soft and Coe Super Soft are particularly temperature dependent in this temperature range, while the remaining materials indicate G values which are virtually insensitive to temperature. At 37C, Flexor exhibits the highest modulus value and would be expected to develop the highest energy absorbing capacity, with Coe Super Soft the poorest in this respect. Vertex Soft is within the max-min range of moduli at 37C but falls below the non-acrylic materials above
1 .o
50C, while Coe Super Soft exhibits the lowest G value above 35C. Since all materials where cycled over a strain range of 64 microns this figure would also be expected to indicate the resilience of the respective materials, i.e., Flexor the best and Coe Super Soft the poorest at 37C. A plot of the dissipative modulus G against temperature is shown in Figure 4. The nonacrylic materials show a virtually zero modulus change which is indicative of highly elastic and resilient materials in the temperature and strain amplitude range chosen. Both acrylic G values are particularly temperature dependent and since they fall continuously, suggest a Tg value below 30C. The mechanical loss tangent plotted against temperature (Figure 5) merely confirms the elastic behaviour of the non-acrylic materials.
DISCUSSION A necessary requirement of soft lining materials is their ability to elastically recover following deformation
0.8
r+
-\
n
0 Flexibasc +\ X Flexor
Coe
super-soft
n
25 30 35 40 45 C SO 55 60 65 70
25
30
35
40
45
SO
55
60
65
70
C modulus measured over temperaFigure 4 Dissipative range 30-70C. modulus measured over temperature
1630
DMTA of denture
soft liners:
M. Waters
et al.
I.2 r
l y_
+
n
Coe
super-soft
m 6 -) 0.40.2 *-0 25 30 35 I 40 I 45 OC Figure 5 Mechanical ture range 30-70C. loss tangent measured over temperar 50 I 55 I 60 I 65 r 70
during mastication over reasonably long time periods. This elastic recovery response is normally quoted as resilience, i.e. the materials ability to consistently and immediately return to its original shape following deformation. Unfortunately, polymeric materials tend to exhibit time-dependent behaviour during and following deformations 3 7. Thus it would be expected that materials deforming at temperatures near and above their Tg would demonstrate time-dependent properties which may include viscoelastic behaviour. The greater the degree of elastic response elicited during a deformation event, the greater the chance of success as a soft lining material. Another important property requirement is the elastic modulus, since the lower this value the greater the energy absorbed at a given load during the deforming cycle. This behaviour will help in allowing the point applied loads to be spread over a larger area of the material with lower loads transferred to the underlying tissue. These important parameters can be measured in a number of ways as already outlinedy277. However, an important requirement for time-dependent materials is to simulate masticatory deformation by cycling the materials through a given stress-strain regime at a frequency close to that of chewing. Past methods have generally failed to simulate masticatory deformation with periods of cycling as long as 5 mini. In this work, elastic properties have been measured using a dedicated DMTA testing machine which allows measurement of both the elastic and viscous response of materials at specific testing rates over a series of temperatures. The storage modulus measures the perfectly elastic response of the materials. Thus if resilience is the prime requirement of a soft lining material, then at 37C Flexor would be expected to show ideal properties, with Novus the poorest of the non-acrylic materials at 37C. Since the materials were deformed to a specific strain, this behaviour does not represent the energy-absorbing capacities of these soft liners for a given load. If the capacity to absorb energy is a more realistic requirement particularly in terms of patient comfort, then the ranking of materials shown may not represent the in vivo requirement. Evidently, the behaviour of the acrylic materials is highly temperature sensitive, showing good elastic response at 37C in line with the other candidate
Biomaterials 1996. Vol. 17 No. 16
materials but falling away rapidly with temperature. Since both acrylics demonstrate an element of viscous behaviour as evidenced by the dissipative modulus (G) (Figure 4) and tan 6 (Figure 5) plots, this viscous proportion to the total deformation decreases with temperature. The acrylic materials therefore demonstrate improved elastic cycling response with increasing temperature. The clinical consequences of these temperaturedependent changes are difficult to interpret from one type of test. Certainly, an increased proportion of elastic response is desirable compared with time-dependent recovery events (i.e., viscoelastic and viscous). However, at higher temperatures, the modulus of the acrylics may be too low to sustain a given loading in thicknesses normally applicable to soft lining materials. Thus the deforming force may simply move the material allowing direct loading onto the underlying tissues. The DMTA apparatus did prove to be a rapid and convenient method for determination of the deformation properties of soft lining materials under clinically relevant loading and cycling. Further work will look at methods to determine the exact time/ deformation event which is necessary to further classify viscoelastic and viscous materials at or near body temperature. CONCLUSIONS
with all values decreasing with increasing temperature, whilst the other materials indicated moduli which were relatively constant over the temperature range. Flexor was the stiffest material at 37C, i.e. highest modulus. Molloplast was the most resilient material. Dynamic mechanical thermal analysis (DMTA) proved to be a rapid, reliable and convenient method for the determination of viscoelastic properties of resilient liners.
REFERENCES
HR. Soft lining materials: Some relevant properties and their determination. 1 Pro&et Dent1969;21:244-250. Braden M, Clarke RL. Visco-elastic properties of soft lining materials. I Dent Res 1972; 51: 1525-1528. Braden M, Stafford GD. Viscoelastic properties of some denture base materials. 1 Dent Res 1968; 47: 519-523. Clarke RL, Braden M. Determination of visco-elastic properties of dental polymers by mechanical impedance measurements. JDent Res 1982; 61: 1245-1249. Wetton RE, Marsh RDL, Wan-De-Velde TG. Theory and application of dynamic mechanical thermal analysis.
Thermochim
Clarke RL. Dynamic mechanical thermal analysis of dental polymers. 1.Heat-cured poly(methy1 methacrylate)-based materials. Biomaterials 1989; 10: 494-498. Wright PS. Soft lining materials: their status and prospects. J Dent 1976; 4: 247-256.