Dynamic mechanical analysis techniques

Basically, three methods are available for determining dynamic properties free oscillation, forced oscillation, and steady-state rotation. Experimental and analytical details for the first two are reviewed extensively by Ferry [7]. 

Expressions for other specimen geometries and higher damping are reviewed by Nielson [9]. Solid or rubbery samples are twisted as illustrated in the form of rods, tubes, strips, etc. Liquids or soft solids may be contained in one of the geometries described for rotational viscometry earher (Couette, cone-and-plate, etc.). 

Although the frequency can be varied somewhat by changing the moment of inertia of the oscillating portion of the mechanism, torsion pendulums are usually intended to study only the temperature dependence of dynamic properties at a constant, relatively low frequency ( 1 cycle/s). On the other hand, they are inexpensive and rather simple to constmct. 

1 Dynamic Mechanical Analyzers DMAs are forced-oscdlation devices ( jiggle machines ) that apply a sinusoidal stress or strain of known amplitude and frequency and measure the resulting strain or stress. The dynamic properties are calculated from the relation between the two. Solid materials are clamped into a DMA 

FIGURE 16.8 Dynamic mechanical analysis testing clamps (used with permission from TA Instruments, New Castle, DE). Different clamp setups can he used for tension, compression, three-point bending, and shear tests. The application of stress (or strain) is sinusoidal. 

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Dynamic mechanical analysis techniques permit measurement of the ability of materials to store and dissipate mechanical energy during deformation. DMA is used to determine the modulus, glass transition, mechanical damping and impact resistance, etc., of thermoplastics, thermosets, elastomers and other polymer materials. Information regarding the phase separation of polymers is also available by DMA [2]. In DMA, viscoelastic materials are deformed in a sinusoidal, low strain displacement and their responses are measured. Elastic modulus and energy dissipation are the measured properties. 

Dynamic mechanical analysis techniques permit measurement of the ability of materials to store and dissipate mechanical energy during deformation. Dynamic mechanical analysis is used to determine the modulus, glass transition, mechanical damping and impact resistance, and so forth, of thermoplastics, thermosets. 

Thermal methods include differential scaiming calorimetry, thermomechanical analysis, hot stage microscopy, and a new technique referred to as "photo DSC." Two dynamic mechanical analysis techniques have been developed, the first employing a perforated shim stock support, and the second utilizing polymer blend encapsulation. 

Photo DSC refers to a new technique applied to the observation of macroscopic changes in sample physical dimensions, meanwhile recording a DSC scan of the material. Two dynamic mechanical analysis techniques have been developed to study liquid state relaxations. The first employs a perforated shim stock support upon which the sample to be studied is coated. An alternative support mechanism involves polymer blend encapsulatioiL Here, the polymer of interest is incorporated into a high-7, continuous-phase polymer matrix. Both techniques have been employed to examine the polymer liquid state to well over 100 C above Tg, and requite very small amounts of the polymer sample of interest... 

Thermomechanical analysis (TMA) predates the use of dynamic mechanical analysis techniques. TMA is used for 7 determination, but is significantly less sensitive than DMA and cannot be used for studying the weaker p relaxations, as seen in many polymers. In many respects TMA is the simplest form of thermal analysis equipment. A small sample is mounted in the instrument, which is surrounded by a furnace and the variation of sample length is recorded as a function of time or temperature. 

The principal techniques for determining the microstmcture of phenoHc resins include mass spectroscopy, proton, and C-nmr spectroscopy, as well as gc, Ic, and gpc. The softening and curing processes of phenoHc resins are effectively studied by using thermal and mechanical techniques, such as tga, dsc, and dynamic mechanical analysis (dma). Infrared (ir) and electron spectroscopy are also employed. 

Dynamic mechanical analysis provides a useful technique to study the cure kinetics and high temperature mechanical properties of phenoHc resins. The volatile components of the resin do not affect the scan or limit the temperature range of the experiment. However, uncured samples must be... 

Thermal analysis iavolves techniques ia which a physical property of a material is measured agaiast temperature at the same time the material is exposed to a coatroUed temperature program. A wide range of thermal analysis techniques have been developed siace the commercial development of automated thermal equipment as Hsted ia Table 1. Of these the best known and most often used for polymers are thermogravimetry (tg), differential thermal analysis (dta), differential scanning calorimetry (dsc), and dynamic mechanical analysis (dma). 

Changes in heat capacity and measurement of T for blends have been used to determine components of copolymers and blends (126—129), although dynamic mechanical analysis has been found to give better resolution. Equations relating T of miscible blends and ratios of components have been developed from dsc techniques, eg, the Fox equation (eq. 1), where f the blend, or is the weight fraction of component 1 or 2,... 

In a similar fashion. Thermally Stimulated Current spectrometry (TSC) makes use of an appHed d-c potential that acts as the stress to orient dipoles. The temperature is then lowered to trap these dipoles, and small electrical currents are measured during heating as the dipoles relax. The resulting relaxation maps have been related to G and G" curves obtained by dynamic mechanical analysis (244—246). This technique, long carried out only in laboratory-built instmments, is available as a commercial TSC spectrometer from Thermold Partners L.P., formerly Solomat Instmments (247). 

The thermal glass-transition temperatures of poly(vinyl acetal)s can be determined by dynamic mechanical analysis, differential scanning calorimetry, and nmr techniques (31). The thermal glass-transition temperature of poly(vinyl acetal) resins prepared from aliphatic aldehydes can be estimated from empirical relationships such as equation 1 where OH and OAc are the weight percent of vinyl alcohol and vinyl acetate units and C is the number of carbons in the chain derived from the aldehyde. The symbols with subscripts are the corresponding values for a standard (s) resin with known parameters (32). The formula accurately predicts that resin T increases as vinyl alcohol content increases, and decreases as vinyl acetate content and aldehyde carbon chain length increases. 

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... 

A number of analytical techniques such as FTIR spectroscopy,65-66 13C NMR,67,68 solid-state 13 C NMR,69 GPC or size exclusion chromatography (SEC),67-72 HPLC,73 mass spectrometric analysis,74 differential scanning calorimetry (DSC),67 75 76 and dynamic mechanical analysis (DMA)77 78 have been utilized to characterize resole syntheses and crosslinking reactions. Packed-column supercritical fluid chromatography with a negative-ion atmospheric pressure chemical ionization mass spectrometric detector has also been used to separate and characterize resoles resins.79 This section provides some examples of how these techniques are used in practical applications. 

In an NMR analysis of the effects of /-irradiation induced degradation on a specific polyurethane (PU) elastomer system, Maxwell and co-workers [87] used a combination of both H and 13C NMR techniques, and correlated these with mechanical properties derived from dynamic mechanical analysis (DMA). 1H NMR was used to determine spin-echo decay curves for three samples, which consisted of a control and two samples exposed to different levels of /-irradiation in air. These results were deconvoluted into three T2 components that represented T2 values which could be attributed to an interfacial domain between hard and soft segments of the PU, the PU soft segment, and the sol... 

Crosslinked polymer networks formed from multifunctional acrylates are completely insoluble. Consequently, solid-state nuclear magnetic resonance (NMR) spectroscopy becomes an attractive method to determine the degree of crosslinking of such polymers (1-4). Solid-state NMR spectroscopy has been used to study the homopolymerization kinetics of various diacrylates and to distinguish between constrained and unconstrained, or unreacted double bonds in polymers (5,6). Solid-state NMR techniques can also be used to determine the domain sizes of different polymer phases and to determine the presence of microgels within a poly multiacrylate sample (7). The results of solid-state NMR experiments have also been correlated to dynamic mechanical analysis measurements of the glass transition (1,8,9) of various polydiacrylates. 

An associated technique which links thermal properties with mechanical ones is dynamic mechanical analysis (DMA). In this, a bar of the sample is typically fixed into a frame by clamping at both ends. It is then oscillated by means of a ceramic shaft applied at the centre. The resonant frequency and the mechanical damping exhibited by the sample are sensitive measurements of the mechanical properties of a polymer which can be made over a wide range of temperatures. The effects of compositional changes and methods of preparation can be directly assessed. DMA is assuming a position of major importance in the study of the physico-chemical properties of polymers and composites. 

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 investigation of pure PET and PET/additive blends by combining dynamic mechanical analysis, dielectric relaxation and solid-state NMR techniques, leads to a clear attribution of the molecular processes involved in the ft relaxation of PET, as well as an understanding of the effect of an antiplasticiser additive ... 

Various experimental techniques (dielectric relaxation, dynamic mechanical analysis, 1H, 2H and 13C solid-state NMR) have been used for investigating the secondary transitions of BPA-PC, and the block copolymers of BPA and TMBPA carbonates as well as compatible blends of BPA-PC and TMBPA-PC. They have provided lots of information on the motions of methyl, phenyl ring and carbonate units in bulk BPA-PC. The effect of intermolecular packing has also been clearly evidenced. 

It is worth noticing that a molecular modelling approach is used to complement the experimental techniques of dynamic mechanical analysis, dielectric relaxation, solid-state 13C and 2H NMR. 

The approach developed in this paper, combining on the one side experimental techniques (dynamic mechanical analysis, dielectric relaxation, solid-state 1H, 2H and 13C NMR on nuclei at natural abundance or through specific labelling), and on the other side atomistic modelling, allows one to reach quite a detailed description of the motions involved in the solid-state transitions of amorphous polymers. Bisphenol A polycarbonate, poly(methyl methacrylate) and its maleimide and glutarimide copolymers give perfect illustrations of the level of detail that can be achieved. 

The estimation was made by putting different data together, which included thermal transition data obtained by dynamic mechanical analysis and spectroscopic data quantified mainly by solid-state NMR techniques [43-48], The binary compositions situated in an enclosed area, denoted by connection of dotted lines in the scale list, can be assumed to be a highly compatible state of mixing. a Obtained by hydrolysis treatment of MC/P4VPy... 

Thermal analysis is a group of techniques in which a physical property of a substance is measured as a function of temperature when the sample is subjected to a controlled temperature program. Single techniques, such as thermogravimetry (TG), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), dielectric thermal analysis, etc., provide important information on the thermal behaviour of materials. However, for polymer characterisation, for instance in case of degradation, further analysis is required, particularly because all of the techniques listed above mainly describe materials only from a physical point of view. A hyphenated thermal analyser is a powerful tool to yield the much-needed additional chemical information. In this paper we will concentrate on simultaneous thermogravimetric techniques. 

In addition, Seferis and Wedgewood have pointed out the many pitfalls that should be avoided when using dynamic mechanical analysis (DMA) to determine thermal properties in epoxy systems [134]. However, Sanz, et al. have investigated Tg of epoxy systems via DMA for a myriad of epoxy compositions and compiled large amounts of reasonable data using this technique [ 135]. Zukas has done the same using torsional braid analysis (TBA) on many epoxy systems and produced similar conclusions to Sanz [129]. 

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