Polymer characterization is the analytical branch of
polymer science
Polymer science or macromolecular science is a subfield of materials science concerned with polymers, primarily synthetic polymers such as plastics and elastomers. The field of polymer science includes researchers in multiple disciplines includ ...
.
The discipline is concerned with the characterization of polymeric materials on a variety of levels. The characterization typically has as a goal to improve the performance of the material. As such, many characterization techniques should ideally be linked to the desirable properties of the material such as strength, impermeability, thermal stability, and optical properties.
Characterization techniques are typically used to determine
molecular mass
The molecular mass (''m'') is the mass of a given molecule: it is measured in daltons (Da or u). Different molecules of the same compound may have different molecular masses because they contain different isotopes of an element. The related quanti ...
, molecular structure,
morphology
Morphology, from the Greek and meaning "study of shape", may refer to:
Disciplines
* Morphology (archaeology), study of the shapes or forms of artifacts
* Morphology (astronomy), study of the shape of astronomical objects such as nebulae, galaxies ...
, thermal properties, and mechanical properties.
Molecular mass
The molecular mass of a polymer differs from typical molecules, in that polymerization reactions produce a distribution of molecular weights and shapes. The distribution of molecular masses can be summarized by the number average molecular weight, weight average molecular weight, and
polydispersity
In chemistry, the dispersity is a measure of the heterogeneity of sizes of molecules or particles in a mixture. A collection of objects is called uniform if the objects have the same size, shape, or mass. A sample of objects that have an incons ...
. Some of the most common methods for determining these parameters are
colligative property
In chemistry, colligative properties are those properties of Solution (chemistry), solutions that depend on the ratio of the number of solute particles to the number of solvent Particle, particles in a solution, and not on the nature of the chemic ...
measurements,
static light scattering
Static light scattering is a technique in physical chemistry that measures the intensity of the scattered light to obtain the average molecular weight ''Mw'' of a macromolecule like a polymer or a protein in solution. Measurement of the scattering ...
techniques,
viscometry
A viscometer (also called viscosimeter) is an instrument used to measure the viscosity of a fluid. For liquids with viscosities which vary with flow conditions, an instrument called a rheometer is used. Thus, a rheometer can be considered as a spec ...
, and
size exclusion chromatography
Size-exclusion chromatography (SEC), also known as molecular sieve chromatography, is a chromatographic method in which molecules in solution are separated by their size, and in some cases molecular weight. It is usually applied to large molecules ...
.
Gel permeation chromatography Gel permeation chromatography (GPC) is a type of size-exclusion chromatography (SEC), that separates analytes on the basis of size, typically in organic solvents. The technique is often used for the analysis of polymers. As a technique, SEC was firs ...
, a type of size exclusion chromatography, is an especially useful technique used to directly determine the molecular weight distribution parameters based on the polymer's
hydrodynamic volume
The Stokes radius or Stokes–Einstein radius of a solute is the radius of a hard sphere that diffuses at the same rate as that solute. Named after George Gabriel Stokes, it is closely related to solute mobility, factoring in not only size but also ...
. Gel permeation chromatography is often used in combination with
multi-angle light scattering
Multiangle light scattering (MALS) describes a technique for measuring the light scattering, scattered by a sample into a plurality of angles. It is used for determining both the absolute molar mass and the average size of molecules in Solution (c ...
(MALS),
Low-angle laser light scattering Low-angle laser light scattering or LALLS is an application of light scattering that is particularly useful in conjunction with the technique of Size exclusion chromatography, one of the most powerful and widely used techniques to study the molecul ...
(LALLS) and/or
viscometry
A viscometer (also called viscosimeter) is an instrument used to measure the viscosity of a fluid. For liquids with viscosities which vary with flow conditions, an instrument called a rheometer is used. Thus, a rheometer can be considered as a spec ...
for an absolute determination (i.e., independent of the chromatographic separation details) of the molecular weight distribution as well as the branching ratio and degree of long chain branching of a polymer, provided a suitable solvent can be found.
Molar mass determination of
copolymers
In polymer chemistry, a copolymer is a polymer derived from more than one species of monomer. The polymerization of monomers into copolymers is called copolymerization. Copolymers obtained from the copolymerization of two monomer species are some ...
is a much more complicated procedure. The complications arise from the effect of solvent on the
homopolymer
A polymer (; Greek '' poly-'', "many" + '' -mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
s and how this can affect the copolymer morphology. Analysis of copolymers typically requires multiple characterization methods. For instance, copolymers with short chain branching such as
linear low-density polyethylene
Linear low-density polyethylene (LLDPE) is a substantially linear polymer (polyethylene), with significant numbers of short branches, commonly made by copolymerization of ethylene with longer-chain olefins. Linear low-density polyethylene differs ...
(a copolymer of ethylene and a higher alkene such as hexene or octene) require the use of Analytical Temperature Rising Elution Fractionation (ATREF) techniques. These techniques can reveal how the short chain branches are distributed over the various molecular weights. A more efficient analysis of copolymer molecular mass and composition is possible using GPC combined with a triple-detection system comprising
multi-angle light scattering
Multiangle light scattering (MALS) describes a technique for measuring the light scattering, scattered by a sample into a plurality of angles. It is used for determining both the absolute molar mass and the average size of molecules in Solution (c ...
, UV absorption and differential refractometry, if the copolymer is composed of two base polymers that provide different responses to UV and/or refractive index.
Molecular structure
Many of the analytical techniques used to determine the molecular structure of unknown organic compounds are also used in polymer characterization. Spectroscopic techniques such as
ultraviolet-visible spectroscopy,
infrared spectroscopy
Infrared spectroscopy (IR spectroscopy or vibrational spectroscopy) is the measurement of the interaction of infrared radiation with matter by absorption, emission, or reflection. It is used to study and identify chemical substances or function ...
,
Raman spectroscopy
Raman spectroscopy () (named after Indian physicist C. V. Raman) is a spectroscopic technique typically used to determine vibrational modes of molecules, although rotational and other low-frequency modes of systems may also be observed. Raman sp ...
,
nuclear magnetic resonance spectroscopy
Nuclear magnetic resonance spectroscopy, most commonly known as NMR spectroscopy or magnetic resonance spectroscopy (MRS), is a spectroscopic technique to observe local magnetic fields around atomic nuclei. The sample is placed in a magnetic fiel ...
,
electron spin resonance spectroscopy
Electron paramagnetic resonance (EPR) or electron spin resonance (ESR) spectroscopy is a method for studying materials that have unpaired electrons. The basic concepts of EPR are analogous to those of nuclear magnetic resonance (NMR), but the spi ...
,
X-ray diffraction
X-ray crystallography is the experimental science determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to diffract into many specific directions. By measuring the angles ...
, and
mass spectrometry
Mass spectrometry (MS) is an analytical technique that is used to measure the mass-to-charge ratio of ions. The results are presented as a ''mass spectrum'', a plot of intensity as a function of the mass-to-charge ratio. Mass spectrometry is use ...
are used to identify common functional groups.
Morphology
Polymer morphology is a microscale property that is largely dictated by the amorphous or crystalline portions of the polymer chains and their influence on each other. Microscopy techniques are especially useful in determining these microscale properties, as the domains created by the polymer morphology are large enough to be viewed using modern microscopy instruments. Some of the most common microscopy techniques used are
X-ray diffraction
X-ray crystallography is the experimental science determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to diffract into many specific directions. By measuring the angles ...
,
Transmission Electron Microscopy
Transmission electron microscopy (TEM) is a microscopy technique in which a beam of electrons is transmitted through a specimen to form an image. The specimen is most often an ultrathin section less than 100 nm thick or a suspension on a g ...
,
Scanning Transmission Electron Microscopy
A scanning transmission electron microscope (STEM) is a type of transmission electron microscope (TEM). Pronunciation is tÉ›mor ›sti:i:É›m As with a conventional transmission electron microscope (CTEM), images are formed by electrons passing ...
,
Scanning Electron Microscopy, and
Atomic Force Microscopy
Atomic force microscopy (AFM) or scanning force microscopy (SFM) is a very-high-resolution type of scanning probe microscopy (SPM), with demonstrated resolution on the order of fractions of a nanometer, more than 1000 times better than the op ...
.
Polymer morphology on a mesoscale (nanometers to micrometers) is particularly important for the mechanical properties of many materials.
Transmission Electron Microscopy
Transmission electron microscopy (TEM) is a microscopy technique in which a beam of electrons is transmitted through a specimen to form an image. The specimen is most often an ultrathin section less than 100 nm thick or a suspension on a g ...
in combination with
staining
Staining is a technique used to enhance contrast in samples, generally at the microscopic level. Stains and dyes are frequently used in histology (microscopic study of biological tissues), in cytology (microscopic study of cells), and in the ...
techniques, but also
Scanning Electron Microscopy,
Scanning probe microscopy
Scan may refer to:
Acronyms
* Schedules for Clinical Assessment in Neuropsychiatry (SCAN), a psychiatric diagnostic tool developed by WHO
* Shared Check Authorization Network (SCAN), a database of bad check writers and collection agency for bad ...
are important tools to optimize the morphology of materials like
polybutadiene
Polybutadiene utadiene rubber BRis a synthetic rubber. Polybutadiene rubber is a polymer formed from the polymerization of the monomer 1,3-butadiene. Polybutadiene has a high resistance to wear and is used especially in the manufacture of tir ...
-
polystyrene
Polystyrene (PS) is a synthetic polymer made from monomers of the aromatic hydrocarbon styrene. Polystyrene can be solid or foamed. General-purpose polystyrene is clear, hard, and brittle. It is an inexpensive resin per unit weight. It is a ...
polymers and many polymer blends.
X-ray diffraction
X-ray crystallography is the experimental science determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to diffract into many specific directions. By measuring the angles ...
is generally not as powerful for this class of materials as they are either amorphous or poorly crystallized. The
Small-angle scattering Small-angle scattering (SAS) is a scattering technique based on deflection of collimated radiation away from the straight trajectory after it interacts with structures that are much larger than the wavelength of the radiation. The deflection is sma ...
like
Small-angle X-ray scattering
Small-angle X-ray scattering (SAXS) is a small-angle scattering technique by which nanoscale density differences in a sample can be quantified. This means that it can determine nanoparticle size distributions, resolve the size and shape of (monodis ...
(SAXS) can be used to measure the long periods of semicrystalline polymers.
Thermal properties
A true workhorse for polymer characterization is
thermal analysis
Thermal analysis is a branch of materials science where the properties of materials are studied as they change with temperature. Several methods are commonly used – these are distinguished from one another by the property which is measured:
* D ...
, particularly
Differential scanning calorimetry
Differential scanning calorimetry (DSC) is a thermoanalytical technique in which the difference in the amount of heat required to increase the temperature of a sample and reference is measured as a function of temperature. Both the sample and ref ...
. Changes in the compositional and structural parameters of the material usually affect its melting transitions or glass transitions and these in turn can be linked to many performance parameters. For semicrystalline polymers it is an important method to measure crystallinity.
Thermogravimetric analysis
Thermogravimetric analysis or thermal gravimetric analysis (TGA) is a method of thermal analysis in which the mass of a sample is measured over time as the temperature changes. This measurement provides information about physical phenomena, such ...
can also give an indication of polymer thermal stability and the effects of additives such as flame retardants.
Other thermal analysis techniques are typically combinations of the basic techniques and include
differential thermal analysis
Differential thermal analysis (DTA) is a thermoanalytic technique that is similar to differential scanning calorimetry. In DTA, the material under study and an inert reference are made to undergo identical thermal cycles, (i.e., same cooling or ...
,
thermomechanical analysis
Thermomechanical analysis (TMA) is a technique used in thermal analysis, a branch of materials science which studies the properties of materials as they change with temperature.
Thermomechanical analysis is a subdiscipline of the thermomechanome ...
, dynamic mechanical thermal analysis, and
dielectric thermal analysis Dielectric thermal analysis (DETA), or dielectric analysis (DEA), is a materials science technique similar to dynamic mechanical analysis except that an oscillating electrical field is used instead of a mechanical force. For investigation of the c ...
.
Dynamic mechanical spectroscopy
Dynamic mechanical analysis (abbreviated DMA) is a technique used to study and characterize materials. It is most useful for studying the viscoelastic behavior of polymer, polymers. A sinusoidal stress is applied and the strain in the material is ...
and
dielectric spectroscopy
Dielectric spectroscopy (which falls in a subcategory of impedance spectroscopy) measures the dielectric properties of a medium as a function of frequency.Kremer F., Schonhals A., Luck W. Broadband Dielectric Spectroscopy. – Springer-Verlag, 200 ...
are essentially extensions of thermal analysis that can reveal more subtle transitions with temperature as they affect the complex modulus or the dielectric function of the material.
Mechanical properties
The characterization of mechanical properties in polymers typically refers to a measure of the strength, elasticity,
viscoelasticity
In materials science and continuum mechanics, viscoelasticity is the property of materials that exhibit both viscous and elastic characteristics when undergoing deformation. Viscous materials, like water, resist shear flow and strain linearly wi ...
, and anisotropy of a polymeric material. The mechanical properties of a polymer are strongly dependent upon the
Van der Waals interactions of the polymer chains, and the ability of the chains to elongate and align in the direction of the applied force. Other phenomena, such as the propensity of polymers to form crazes can impact the mechanical properties. Typically, polymeric materials are characterized as elastomers, plastics, or rigid polymers depending on their mechanical properties.
The
tensile strength
Ultimate tensile strength (UTS), often shortened to tensile strength (TS), ultimate strength, or F_\text within equations, is the maximum stress that a material can withstand while being stretched or pulled before breaking. In brittle materials t ...
,
yield strength
In materials science and engineering, the yield point is the point on a stress-strain curve that indicates the limit of elastic behavior and the beginning of plastic behavior. Below the yield point, a material will deform elastically and wi ...
, and
Young's modulus
Young's modulus E, the Young modulus, or the modulus of elasticity in tension or compression (i.e., negative tension), is a mechanical property that measures the tensile or compressive stiffness of a solid material when the force is applied leng ...
are measures of strength and elasticity, and are of particular interest for describing the stress-strain properties of polymeric materials. These properties can be measured through tensile testing. For
crystalline
A crystal or crystalline solid is a solid material whose constituents (such as atoms, molecules, or ions) are arranged in a highly ordered microscopic structure, forming a crystal lattice that extends in all directions. In addition, macrosc ...
or
semicrystalline
Crystallinity refers to the degree of structural order in a solid. In a crystal, the atoms or molecules are arranged in a regular, periodic manner. The degree of crystallinity has a big influence on hardness, density, transparency and diffusion ...
polymers, anisotropy plays a large role in the mechanical properties of the polymer. The crystallinity of the polymer can be measured through
differential scanning calorimetry
Differential scanning calorimetry (DSC) is a thermoanalytical technique in which the difference in the amount of heat required to increase the temperature of a sample and reference is measured as a function of temperature. Both the sample and ref ...
. For amorphous and semicrystalline polymers, as stress is applied, the polymer chains are able to disentangle and align. If the stress is applied in the direction of chain alignment, the polymer chains will exhibit a higher yield stress and strength, as the covalent bonds connecting the backbone of the polymer absorb the stress. However, if the stress is applied normal to the direction of chain alignment, the Van der Waals interactions between chains will primarily be responsible for the mechanical properties and thus, the yield stress will decrease. This would be observable in a stress strain graph found through tensile testing. Sample preparation, including chain orientation within the sample, for tensile tests therefore can play a large role in the observed mechanical properties.
The fracture properties of crystalline and semicrystalline polymers can be evaluated with
Charpy impact test
In materials science, the Charpy impact test, also known as the Charpy V-notch test, is a standardized high strain rate test which determines the amount of energy absorbed by a material during fracture. Absorbed energy is a measure of the mate ...
ing. Charpy tests, which can also be used with alloy systems, are performed by creating a notch in the sample, and then using a pendulum to fracture the sample at the notch. The pendulum’s motion can be used to extrapolate the energy absorbed by the sample to fracture it. Charpy tests can also be used to evaluate the strain rate on the fracture, as measured with changes in the pendulum mass. Typically, only brittle and somewhat ductile polymers are evaluated with Charpy tests. In addition to the fracture energy, the type of break can be visually evaluated, as in whether the break was a total fracture of the sample or whether the sample experienced fracture in only part of the sample, and severely deformed section are still connected. Elastomers are typically not evaluated with Charpy tests due to their high yield strain inhibiting the Charpy test results.
There are many properties of polymeric materials that influence their mechanical properties. As the degree of polymerization goes up, so does the polymer’s strength, as a longer chains have high Van der Waals interactions and chain entanglement. Long polymers can entangle, which leads to a subsequent increase in bulk modulus. Crazes are small cracks that form in a polymer matrix, but which are stopped by small defects in the polymer matrix. These defects are typically made up of a second, low modulus polymer that is dispersed throughout the primary phase. The crazes can increase the strength and decrease the brittleness of a polymer by allowing the small cracks to absorb higher stress and strain without leading to fracture. If crazes are allowed to propagate or coalesce, they can lead to cavitation and fracture in the sample. Crazes can be seen with transmission electron microscopy and scanning electron microscopy, and are typically engineered into a polymeric material during synthesis. Crosslinking, typically seen in thermoset polymers, can also increase the modulus, yield stress, and yield strength of a polymer.
Dynamic mechanical analysis
Dynamic mechanical analysis (abbreviated DMA) is a technique used to study and characterize materials. It is most useful for studying the viscoelastic behavior of polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a subst ...
is the most common technique used to characterize viscoelastic behavior common in many polymeric systems. DMA is also another important tool to understand the temperature dependence of polymers’ mechanical behavior. Dynamic mechanical analysis is a characterization technique used to measure storage modulus and glass transition temperature, confirm crosslinking, determine switching temperatures in shape-memory polymers, monitor cures in thermosets, and determine molecular weight. An oscillating force is applied to a polymer sample and the sample’s response is recorded. DMA documents the lag between force applied and deformation recovery in the sample. Viscoelastic samples exhibit a sinusoidal modulus called the
dynamic modulus Dynamic modulus (sometimes complex modulusThe Open University (UK), 2000. ''T838 Design and Manufacture with Polymers: Solid properties and design'', page 30. Milton Keynes: The Open University.) is the ratio of stress to strain under ''vibratory c ...
. Both energy recovered and lost are considered during each deformation and described quantitatively by the elastic modulus (E’) and the loss modulus (E’’) respectively. The applied stress and the strain on the sample exhibit a phase difference, ẟ, which is measured over time. A new modulus is calculated each time stress is applied to the material, so DMA is used to study changes in modulus at various temperatures or stress frequencies.
Other techniques include
viscometry
A viscometer (also called viscosimeter) is an instrument used to measure the viscosity of a fluid. For liquids with viscosities which vary with flow conditions, an instrument called a rheometer is used. Thus, a rheometer can be considered as a spec ...
,
rheometry
Rheometry () generically refers to the experimental techniques used to determine the rheological properties of materials, that is the qualitative and quantitative relationships between stresses and strains and their derivatives. The techniques ...
, and pendulum
hardness
In materials science, hardness (antonym: softness) is a measure of the resistance to localized plastic deformation induced by either mechanical indentation or abrasion. In general, different materials differ in their hardness; for example hard ...
.
Other techniques
*
Field flow fractionation
Field-flow fractionation, abbreviated FFF, is a separation technique which does not have a stationary phase. It is similar to liquid chromatography as it works on dilute solutions or suspensions of the solute. Separation is achieved by applying ...
* laser assisted mass analysis
*
ACOMP[US patent 6052184 and US Patent 6653150, other patents pending]
*
MFI
*
Dual polarisation interferometry
Dual-polarization interferometry (DPI) is an analytical technique that probes molecular layers adsorbed to the surface of a waveguide using the evanescent wave of a laser beam. It is used to measure the conformational change in proteins, or othe ...
*
Matrix-assisted laser desorption/ionization
In mass spectrometry, matrix-assisted laser desorption/ionization (MALDI) is an ionization technique that uses a laser energy absorbing matrix to create ions from large molecules with minimal fragmentation. It has been applied to the analysis of ...
References
{{Reflist
Polymers