Dynamic Mechanical Analysis, viscoelasticity

Thermal and thermomechanical analyses44 are very important for determining die upper and lower usage temperature of polymeric materials as well as showing how they behave between diose temperature extremes. An especially useful thermal technique for polyurethanes is dynamic mechanical analysis (DMA).45 Uiis is used to study dynamic viscoelastic properties and measures die ability to... 

Dynamic mechanical analysis (DMA) or dynamic mechanical thermal analysis (DMTA) provides a method for determining elastic and loss moduli of polymers as a function of temperature, frequency or time, or both [1-13]. Viscoelasticity describes the time-dependent mechanical properties of polymers, which in limiting cases can behave as either elastic solids or viscous liquids (Fig. 23.2). Knowledge of the viscoelastic behavior of polymers and its relation to molecular structure is essential in the understanding of both processing and end-use properties. 

One of most popular techniques for dynamic mechanical analysis is the torsion pendulum method. In a modification of this method designed to follow curing processes, a torsion bar is manufactured from a braid of fibers impregnated with the composition to be studied this is the so-called torsional braid analysis (TBA) method.61 62,148 The forced harmonic oscillation method has been also used and has proven to be valuable. This method employs various types of rheogoniometers and vibroreometers,1 9,150 which measure the absolute values of the viscoelastic properties of the system under study these properties can be measured at any stage of the process. The use of computers further contributes to improvements in dynamic mechanical analysis methods for rheokinetic measurements. As will be seen below, new possibilities are opened up by applying computer methods to results of dynamic measurements. 

The physical properties of barrier dressings were evaluated using the Seiko Model DMS 210 Dynamic Mechanical Analyzer Instrument (see Fig. 2.45). Referring to Fig. 2.46, dynamic mechanical analysis consists of oscillating (1 Hz) tensile force of a material in an environmentally (37°C) controlled chamber (see Fig. 2.47) to measure loss modulus (E") and stored modulus (E ). Many materials including polymers and tissue are viscoelastic, meaning that they deform (stretch or pull) with applied force and return to their original shape with time. The effect is a function of the viscous property (E") within the material that resists deformation and the elastic property (E )... 

Viscoelasticity is studied using dynamic mechanical analysis. When we apply a small oscillatory strain and measure the resulting stress. Purely elastic materials have stress and strain in phase, so that the response of one caused by the other is immediate. In purely viscous material the phase delay between stress and strain reach 90 degree phase lag. 

In this section we are going to examine such viscoelastic properties in some detail and we will start by examining in turn three important mechanical methods of measurement creep, stress relaxation, and dynamic mechanical analysis. This will lead us to interesting things like time-temperature equivalence and a discussion of the molecular basis of what we have referred to as relaxation behavior. 

Finally, one of the most useful ways of measuring viscoelastic properties is dynamic mechanical analysis, or DMA. In this type of experiment, an oscillating stress is applied to the sample and the response is measured as a function of the frequency of the oscillation. By using different instruments this frequency can be varied over an enormous range. Actually, the sample is usually stretched a little bit and oscillated about this strain also, the stress necessary to produce an oscillatory strain of a given magnitude is the quantity usually measured. If the sample being oscillated happens to be perfectly elastic, so that its response is instantaneous, then the stress and strain would be completely in-phase. If a sinusoidal shear strain is imposed on the sample we have (Equation 13-72) ... 

Dynamic mechanical analysis (DMA). This technique is mainly used for determining the viscoelastic properties of a sample. The sample is subjected to an oscillating deformation and the amount of energy stored or lost is measured. In a purely elastic material, Hooke s law will be obeyed and the stress and strain will be in-phase. In a viscoelastic material, the ratio of the viscous (or dissipating) energy to elastic (or storage) energy is obtained as tan 8. 

Dynamic mechanical analysis involves the determination of the dynamic properties of polymers and their mixtures, usually by applying a mechanical sinusoidal stress For linear viscoelastic behaviour the strain will alternate sinusoidally but will be out of phase with the stress. The phase lag results from the time necessary for molecular rearrangements and this is associated with the relaxation phenomena. The energy loss per cycle, or damping in the system, can be measured from the loss tangent defined as ... 

The mechanical behavior of the hydrogels can be described by the theories of rubber elasticity and viscoelasticity, which are based on time-independent and time-dependent recovery of the chain orientation and structure, respectively. Mechanical properties due to rubber elastic behavior of hydrogels can be determined by tensile measurements, while the viscoelastic behavior can be determined through dynamic mechanical analysis. 

The ability of a polymer to effectively dissipate energy as part of a structure can be related to its linear viscoelastic properties. These are measured by dynamic mechanical analysis. 

Pellicle and tea-immersed pellicle were analyzed using nanoDMA (dynamic mechanical analysis) to see if the tannins had an effect on the viscoelasticity of the pellicle. NanoDMA is a technique used to study and characterize mechanical properties in viscoelastic materials. The method is an extension of nanoindentation testing [58, 59], An analysis of the nanoindentation load-depth curve gives the hardness (H) and reduced elastic modulus (E ), provided the area of contact, A, between the indenter tip and the sample is known [ 13]. By... 

The dynamic mechanical analysis gives detailed information about the viscoelastic properties of a sample when heated, cooled, or held under isothermal conditions. The three a, (3, and y peaks displayed by the material before melting can be used to evaluate the effects on the PE molecular structure of additives... 

For viscoelastic materials such as polymers and many biomaterials, recently developed nanoindentation dynamic mechanical analysis (DMA) techniques enable the study of dynamic response as a function of load amplitude and frequency. The DMA stiffness mapping technique offers the unique capability of mapping storage and loss moduli of the sample... 

Tensile properties were measured by using Shimadzu mechanical tester DSS5000. The cross head speed was 2 mm/min. Viscoelastic properties(tensile storage modulus and tan S) were measured by a tensile type dynamic mechanical analysis(SEIKO Instrument DMS 200). The... 

Whereas there have been several applications of dynamic mechanical analysis for the characterization of the viscoelastic and mechanical properties of biomedical polymers, the characterization of pharmaceutical polymers has not received similar attention. One possible reason for this disparity has been the relative unavailability of appropriate sample geometries for pharmaceutical systems. However, the availability of newer geometries should address this problem. In spite of these difficulties, several studies have successfully employed dynamic mechanical analysis for the characterization of pharmaceutical systems and some of these are described in the following paragraph. 

Dynamic-mechanical analysis (DMA) is a versatile method for measuring viscoelastic values over a wide frequency range commonly the modulus of elasticity and the damping values are determined. Moreover the testing method is used to investigate material behaviour as a function of temperature (e.g. for determine the glass transition temperature). 

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