Analysis and testing of polymers:

 Chemical analysis of polymers

 Spectroscopic methods
 X-ray diffraction study
 Microscopy
 Thermal analysis
 Hardness
 Abrasion resistance
 Chemical Analysis of Polymers
Chemical testing of polymers and plastics is required to ensure that a material is suitable for its intended application. Polymer
chemical testing is used to identify fundamental structural information including as molecular weight, molecular weight
distribution and information on branching. Chemical analysis and testing for plastic and polymer automotive materials including
identification, chemical composition & determination of trace substances. The properties of polymers is related to their
structures, which in turn, depend upon the chemical composition.

 Spectroscopic methods
 X-ray diffraction study
 Microscopy
 Thermal analysis
 Hardness
 Abrasion resistance
 Spectroscopic methods
Spectroscopic methods are new widely used in the polymer field as an analytical to probe structure and to obtain information
on physico-chemical changes occurring in polymers and polymer additives. Spectroscopy utilizes the interaction of radiation
with matter to provide details of molecular energy levels, energy state lifetimes and transition probabilities for polymers. The
physico – chemical changes induced in polymers following to radiation can be studied by a range of spectroscopic techniques.
The applications of these spectroscopic methods in polymer studies are reviewed with emphasis on their utility in
investigations of radiation effects on macromolecules. molecular spectroscopy is required for an identification of the
interacting species, which allows a better understanding of the composite properties and helps the development of new
polymer composites. This information in turn, may be applied in studying chemical structure, molecular environment, polymer
tacticity, conformation, and to monitor changes in these properties following external perturbations (e.g., mechanical stress,
thermal treatment, radiation exposure).
There are many different types of spectroscopy, but the most common types used for chemical analysis include atomic
spectroscopy, ultraviolet and visible spectroscopy, infrared spectroscopy, Raman spectroscopy and nuclear magnetic
resonance.
The advantages of spectroscopic measurements over other means of polymer characterization that they are a non-destructive and
rapid means of providing information at a molecular level (1). Exposure of polymers to ultraviolet and higher energy radiation
can lead to extensive physical and chemical modification of polymeric materials. These changes in properties may have both
detrimental and beneficial consequences in determining the enduses of the polymer Spectroscopy can provide a detailed insight
into the mechanisms of polymer modification occurring under irradiation thus enabling control of the final material properties.

The various spectroscopic methods can be distinguished by the energy of the transitions investigated and this notation is
employed in the sub-headings discussed below. Surface analysis techniques will not be described in detail in this article
although mention may be made of ESCA (Electron Spectroscopy for Chemical Analysis) as one recent technique which may be
used to analyze surface properties.
UV visible absorption and emission spectra
The UV visible absorption and emission spectra and excited state lifetimes of polymers are sensitive to chemical structure,
polymer conformation and molecular environment and thus information concerning these properties is accessible by electronic
spectroscopy measurements. UV energy absorbed by plastics can excite photons, which then create free radicals. While many
pure plastics cannot absorb UV radiation, the presence of catalyst residues and other impurities will often act as receptors,
causing degradation.
 UV/Vis spectroscopy is routinely used in analytical chemistry for the
quantitative determination of different analytes, such as transition metal
ions, highly conjugated organic compounds, and biological
macromolecules. Spectroscopic analysis is commonly carried out in
solutions but solids and gases may also be studied.

 Growth of metal nanoparticles in polymeric network or growth of polymeric

network around metal nanoparticle core can be studied by using UV/Vis
spectroscopy. This technique can also be used for investigation of various
applications of hybrid materials in catalysis, photonics, and sensing.
 UV absorption spectroscopy can characterize those types of compounds
which absorbs UV radiation thus used in qualitative determination of
compounds.

 In polymer chemistry photo-oxidation (sometimes: oxidative

photodegradation) is the degradation of a polymer surface due to the
combined action of light and oxygen
 FTIR analysis
 Fourier Transform-Infrared Spectroscopy (FTIR) is a reliable and cost-effective analytical tool for identification of
polymers and assessment of the quality of plastic materials. When a plastic material absorbs infrared light, typically in the
mid-infrared region, the resulting spectrum (absorbance or transmittance) gives a distinctive “fingerprint” that can be used
to easily screen and test samples for many different applications. The quality and performance of plastic products depends
on the quality of the polymers materials used during manufacturing, and so confirmation of identity and quality testing of
materials is critical.
 FTIR spectroscopy is a fundamental analytical tool across all phases of the plastic and polymer product development
lifecycle, including quality control, competitive reverse engineering and problem solving. These capabilities arise because
FTIR provides quick and definitive identification of compounded plastics, blends, fillers, paints, rubbers, coatings, resins,
adhesives and contaminants.
FTIR and its many applications in plastic and polymer analysis,
including:
 Material identification and verification
 Copolymer and blend assessment
 Additive identification and quantification
 Contaminant identification—bulk and surface
 Deformulation for failure analysis and reverse engineering.
 Raman spectroscopy
Raman microscopy combines Raman spectroscopy and optical microscopy, and is one of the most efficient and effective ways
to identify polymers. It allows researchers to analyze microscopic pieces of plastics by focusing a laser beam onto a small spot
to obtain Raman spectra. Raman spectroscopy can probe microplastics down to the submicron size range and characterizes
them by probing different vibrational modes in the molecule. Each polymer has a distinct, unique set of vibrational modes that
researchers can use for chemical identification. If a microplastic comprises a mixture of components, Raman spectroscopy can
chemically identify the polymer as well as any additives, including pigments.

A Raman spectrometer produces a Raman spectrum, which has units of relative wave number shift (cm−1) on the X axis and
intensity on the Y axis. Quantized vibrational modes within the molecule have different energies, leading to peaks in the
Raman spectrum that can span anywhere from 0 cm−1 to 4000 cm−1. Raman spectroscopy is also used by researchers to identify
additives like pigments and dyes. The spatial selectivity that Raman microscopy offers allows them to characterize
heterogeneous samples they might otherwise misidentify or mischaracterize using macroscopic techniques. By identifying
vibrational modes, determination of the chemical structure of each molecule can be made. Scientists will also frequently search
polymer databases to help identify micro-plastics. In these cases, researchers compare an unknown spectrum with a reference
spectrum from a database.
 NMR analysis
 Nuclear Magnetic Resonance (NMR) is essential in regard to determination of product integrity and as part of gaining
understanding into expectations of industry specifications. understand the composition and formulation of packaging
materials. Polymer characterisation by Nuclear Magnetic Resonance Spectroscopy (NMR) provides detailed structural
information for product development and quality control considerations (QC).
 NMR can be used to determine molecular conformation in solution as well as studying physical properties at the molecular
level such as conformational exchange, phase changes, solubility, and diffusion.
 These three important features of a proton NMR spectrum—chemical shift, relative peak size, and spin-spin splitting—
provide detailed information about the number and location of hydrogen atoms in a molecule.
 NMR spectra tell us how many C and H atoms are in a molecule and which atoms are attached to which.
 Nuclear magnetic resonance spectroscopy is widely used to determine the structure of organic molecules in solution and
study molecular physics and crystals as well as non-crystalline materials. NMR is also routinely used in advanced medical
imaging techniques, such as in magnetic resonance imaging (MRI).
 NMR allows users to obtain rich structural information from the vibrations of the molecules in their natural environment
while they're still intact. NMR spectrometers simplify and speed up the data acquisition and analysis process.
 X-ray diffraction study
The general principles of diffraction are covered in Cullity, "Elements of X-ray Diffraction". If you are unfamiliar with XRD
you will need to review or read Cullity Chapters 1-7 and the appendices. Alexander's text referenced above is also useful as an
introduction to XRD but is less general and at a slightly more advanced level.
There are a number of differences between x-ray diffraction in polymers and metallurgical (Cullity) or ceramic diffraction.
1) Polymers are not highly absorbing to x-rays. The dominant experiment is a transmission experiment where the x-ray beam
passes through the sample. This greatly simplifies analysis of diffraction spectra for polymers but requires somewhat
specialized diffractometer from those commonly used for metallurgy (usually a reflection experiment).
2) DOC: Polymers are never 100% crystalline. XRD is a primary technique to determine
the degree of crystallinity in polymers.

3) Synthetic polymers almost never occur as single crystals. The diffraction pattern from
polymers is almost always either a "powder" pattern (polycrystalline) or a fiber pattern
(oriented polycrystalline). (Electron diffraction in a TEM is an exception to this rule in
some cases.)

4) Microstructure: Crystallite size in polymers is usually on the nano-scale in the

thickness direction. The size of crystallites can be determined using variants of the
Scherrer equation.
5) Orientation: Polymers, due to their long chain structure, are highly susceptible to orientation. XRD is a primary tool for the
determination of crystalline orientation through the Hermans orientation function.

6) Polymer crystals display a relatively large number of defects in some cases. This leads to diffraction peak broadening (see
Campbell and White or Alexander for details).

7) Polymer crystallites are very small with a large surface to volume ratio which enhances the contribution of interfacial
disorganization on the diffraction pattern.

8) SAXS: Due to the nano-scale size of polymer crystallites, small-angle scattering is intense in semi-crystalline polymers and a
separate field of analysis based on diffraction at angles below 6deg. has developed.
Bragg's Law:
Cullity and Alexander derive Bragg's Law using the mirror analogy (specular analogy). It can also be derived from interference
laws or using "inverse space" (see appendix in Cullity). The features of Bragg's Law is that structural size is inversely
proportional to a reduced scattering angle, so high angle relates to smaller structure and low angle relates to large structure.
Small-angle scattering measures colloidal to nano-scale sizes. There is no large scale limit to diffraction. The small scale limit
(i.e. the smallest measurable size) is [lambda]/2 as is inherent in Bragg's Law:

where, n is the order of reflection, λ is the wavelength of radiation, θ is the angle of diffraction, and ‘d’ is the interlamellar
spacing.
Polymers come in many forms, including highly crystalline, semi-crystalline,
microcrystalline or amorphous, and it is possible that in a single polymer
sample, all three may be observed. The presence and relative quantity of these
forms depend on how the polymer was formulated and processed and this in
turn is known to affect mechanical properties such as compression, tensile
strength, buckling, and creep. X-ray diffraction analysis (XRD) to study
solid-state structural properties such as the degree of crystallinity for semi-
crystalline, amorphous polymeric and composite materials which can be
inferred from the XRD pattern appearance.
XRD analysis can assist in assessment and quantification of the crystalline phases (polymorphism), polytypes and all types of
solid state molecular arrangements. If the polymer is crystalline, then the XRD diffraction pattern is a result of a crystal
structure (as related by Bragg’s law); the pattern can be indexed and represented by a stick pattern of positions and intensities.
Polymers can be processed into fibres and films and can be molded and extruded. Each of these processes can orient the
molecules and the diffraction can be used to measure the orientation – in both crystalline and non-crystalline materials. Our
experts use XRD patterns as the primary tool for the determination of crystalline orientation through the Hermans orientation
function.
 Microscopy
Microscopy analysis of polymers provides a means to study and characterize the micro and nano-structural features of
polymers, composites and products. The magnification offered by optical or electron microscopy can be used to obtain
chemical and physical information about a polymer’s structural features. This is essential as it provides insight which can be
related to the performance of the material. A range of advanced techniques which include optical microscopy, scanning electron
microscopy (SEM), transmission electron microscopy (TEM) are required to characterize the surface morphology of polymer.
These techniques are particularly powerful during polymer failure investigations where study of surfaces and cross sections of a
failed component can assist in determination of the root cause of failure.
The simplest technique, is optical microscopy which observes optical scale structure, birefringence. It is common to observe
colloidal scale structure using SEM after gold coating polymer samples, especially for semi-crystalline or filled polymers. TEM
for polymers is a fairly difficult experiment and is usually only performed by experts. Recently, with the advent of atomic force
microscopy, AFM, a much less expensive, simpler and potentially more powerful microscopic technique has replaced many of
these now conventional direct imaging approaches. AFM can be used across the size ranges covered by OM, SEM, and TEM
under proper conditions. Types of microscopic analysis

 Optical microscope (OM)  Transmission electron microscopy (TEM)

 Scanning electron microscope (SEM & FE-SEM)  Atomic force microscope (AFM)
 Optical microscope (OM)
Microscopy analysis of polymers provides a means to study and characterize the micro and nano-structural features of polymers,
composites and products. The magnification offered by optical or electron microscopy can be used to obtain chemical and
physical information about a polymer's structural features. Optical Microscopy (OM) is often the first technique used to examine
or compare products or prepare small samples before further analysis is performed. It is often used to document sampling sites
or phenomenon encountered during other tests. With magnifications from 10x to a bit over 100x, many details and features of
samples are revealed.

A microscope is an instrument that makes an enlarged image of a small object, thus revealing details too small to be seen by the
unaided eye. The most familiar kind of microscope is the optical microscope, which uses visible light focused through lenses.

The optical microscope, also referred to as a light microscope, is a type of

microscope that commonly uses visible light and a system of lenses to generate
magnified images of small objects. Optical microscopes are the oldest design of
microscope and were possibly invented in their present compound form in the 17th
century. Basic optical microscopes can be very simple, although many complex
designs aim to improve resolution and sample contrast.
 The object is placed on a stage and may be directly viewed through one or two eyepieces on the microscope. In high-power
microscopes, both eyepieces typically show the same image, but with a stereo microscope, slightly different images are used
to create a 3-D effect. A camera is typically used to capture the image (micrograph).
 The sample can be lit in a variety of ways. Transparent objects can be lit from below and solid objects can be lit with light
coming through (bright field) or around (dark field) the objective lens. Polarised light may be used to determine crystal
orientation of metallic objects. Phase-contrast imaging can be used to increase image contrast by highlighting small details of
differing refractive index.
 A range of objective lenses with different magnification are usually provided mounted on a turret, allowing them to be
rotated into place and providing an ability to zoom-in. The maximum magnification power of optical microscopes is
typically limited to around 1000x because of the limited resolving power of visible light. The magnification of a compound
optical microscope is the product of the magnification of the eyepiece (say 10x) and the objective lens (say 100x), to give a
total magnification of 1,000×. Modified environments such as the use of oil or ultraviolet light can increase the
magnification.
A compound microscope uses a lens close to the object being viewed to collect light (called the objective lens) which focuses a
real image of the object inside the microscope. That image is then magnified by a second lens or group of lenses (called the
eyepiece) that gives the viewer an enlarged inverted virtual image of the object. The use of a compound objective/eyepiece
combination allows for much higher magnification. Common compound microscopes often feature exchangeable objective
lenses, allowing the user to quickly adjust the magnification. A compound microscope also enables more advanced
illumination setups, such as phase contrast.

 A colored polymer surface can be viewed and images can be photographed

 Polymer, fiber surface analysis can be viewed after any alkali, acid or polymeric treatment
 Surface are can be calculated
 Interaction of polymers in a blend/composite can be characterized
 Optical images are more clear and have high resolution
 These images can be useful for different treatment on fiber
 Scanning electron microscope (SEM & FE-SEM)
The scanning electron microscope (SEM) is a very useful imaging
technique that utilized a beam of electrons to acquire high magnification
images of specimens. Very similar to the transmission electron
microscope (TEM), the SEM maps the reflected electrons and allows
imaging of thick (~mm) samples, whereas the TEM requires extremely
thin specimens for imaging; however, the SEM has lower magnifications.
Although both SEM and TEM use an electron beam, the image is formed
very differently.

The scanning electron microscope (SEM) is a highly versatile tool for the morphological characterisation of polymers, bridging
the gap between light microscopy, where large dimensions are measured at a low resolution, and high-resolution. SEM analysis,
provides high-resolution imaging useful for evaluating various materials for surface fractures, flaws, contaminants or corrosion.
Scanning electron microscopes (SEMs) use an electron beam to image samples with a resolution down to the nanometer scale.
The electrons are emitted from a filament and collimated into a beam in the electron source. The beam is then focused on the
sample surface by a set of lenses in the electron column.
 The electron column consists of the electron source, where the electrons are
emitted, and a set of lenses. The electrons are condensed into a beam by the
condenser lenses and then focused onto the sample surface by the final lens,
also called the objective lens, as shown. The source tilt and the scanning of the
beam at the sample is done by coils at the source and right above the final lens.
All SEMs — whether we’re talking desktop or floor models — have an
electron column with electrostatic lenses and magnetic lenses.
SEM’s operate in a vacuum. Samples can be seriously affected by a vacuum. For
example, loose particles can detach from any surface, all liquids will evaporate
immediately, and delicate materials will outgas. This is the reason why a fly can
be easily imaged.
The resolution of a SEM is basically given by the minimal spot size which can be formed. This probe is formed by
demagnifying the image of your gun. A field emission gun emits the electrons from a much smaller area then a therionic gun.
Therefore the probe will principally be smaller for a FEG-instrument compared to a W- or a LaB6 instrument. Additionally the
coherency is much higher, the energy spread smaller. This again allows to more perfectly focus the beam.
 Applications of SEM
SEMs can be used in a variety of industrial, commercial, and research applications.
MATERIALS SCIENCE
SEMs are used in materials science for research, quality control and failure analysis.
 In modern materials science, investigations into nanotubes and nanofibres, high temperature superconductors, mesoporous
architectures and alloy strength, all rely heavily on the use of SEMs for research and investigation.
 In fact, just about any material science industry, from aerospace and chemistry to electronics and energy usage, have only
been made possible with the help of SEMs.
NANOWIRES FOR GAS SENSING
Researchers are exploring new ways nanowires can be used as gas sensors by improving existing fabrication methods and
developing new ones. Electron microscopy is vitally important in helping characterise nanowires and understanding their gas
sensing behaviour.

SEMICONDUCTOR INSPECTION
Reliable performance of semiconductors requires accurate topographical information. The high resolution three dimensional
images produced by SEMs offers a speedy, accurate measurement of the composition of the semiconductor.
In fact, in just about all wafer manufacturing processes, SEMs are one of three essential quality control tools used. In the case of
repetitive daily quality control tests, larger monitors (19 inches) have been shown to reduce visual fatigue for inspectors.

MICROCHIP ASSEMBLY
Microchip production is increasingly relying on SEMs to help gain insight into the effectiveness of new production and
fabrication methods. With smaller and smaller scales and materials, as well as the potential of complex self assembling polymers,
the high resolution, three-dimensional capacity of SEMs is invaluable to microchip design and production.
FORENSIC INVESTIGATIONS
Criminal and other forensic investigations utilise SEMs to uncover evidence and gain further forensic insight. Uses include:
 analysis of gunshot residue
 jewellery examination
 bullet marking comparison
 handwriting and print analysis
 examination of banknote authenticity.
 paint particle and fibre analysis
 filament bulb analysis in traffic incidents
Since SEMs offer the ability to examine a wide range of materials at high and low magnification without sacrificing depth of
focus, their use in forensic sciences makes it possible to draw conclusions, identify material origins and contribute to a body of
evidence in criminal and legal matters.
BIOLOGICAL SCIENCES
In biological sciences, SEMs can be used on anything from insects and animal tissue to
bacteria and viruses. Uses include:
measuring the effect of climate change of species.
identifying new bacteria and virulent strains
vaccination testing
uncovering new species
work within the field of genetics
SOIL AND ROCK SAMPLING
MEDICAL SCIENCE
 Advantages and Disadvantages of SEM
Advantages
1. Resolution.
This test provides digital image resolution as low as 15 nanometers, providing instructive data for characterizing
microstructures such as fracture, corrosion, grains, and grain boundaries.
2. Traceable standard for magnification.
Because all imaging is calibrated to a traceable standard, it’s easy to apply analysis—such coating thicknesses, grain size
determinations, and particle sizing—to saved images.
3. Chemical analysis.
SEM with EDS provides qualitative elemental analysis, standardless quantitative analysis, x-ray line scans, and mapping.
This data can be used to examine product defects, identify the elemental composition of foreign materials, assess the
thickness of coatings, and determine grain and particle size.
Disadvantages
1. Vacuum environment.
In most cases, SEM samples must be solid and vacuum-compatible. However, higher pressures can be used for imaging of
vacuum-sensitive samples that are nonconductive and volatile. For more information, read our comparison of conventional
SEM, variable pressure SEM (VPSEM), and field emission SEM (FESEM).
2. Artifacts are possible.
Samples that are strong insulators must be coated—usually with gold or carbon—before testing. However, this process can
result in artifacts. That said, preparation and analysis by a knowledgeable SEM testing lab ensures that these artifacts have
minimal impact on testing results.
 Transmission electron microscopy (TEM)
Transmission electron microscopy (TEM) is a microscopy technique in which a beam of electrons is transmitted through an
ultra-thin specimen, and these electrons interact with the specimen as they pass through. Thus, an image is formed from the
interaction of the electrons transmitted through the specimen.
Transmission Electron Microscopy
Analysis includes:
 Phase morphology
 Dispersion of polymer blends
 Failure analysis
 Cellular structure of dispersed
phases
 Nanoscale particle incorporation
 Metalized layer coherence and
thickness analysis in laminated
films
Sample preparation

 The cryocut polymer specimens can be carried out using an ultra-microtome (Leica, Ultracut UCT) and placed on 300
mesh Cu grids (35 mm diameter) for the TEM analysis. After ultra-microtome cutting the sample thickness is around 30 to
130 nm.
 Preparation of TEM samples for solid materials are quite easy but in the polymer/thin membrane layer case it’s too difficult
to prepare the sample for TEM analysis. If you have membrane samples then it is too soft to withstand sectioning at room
temperature without distorting, even if supported by a surrounding layer of epoxy resin. For this reason polymers need to
be hardened by cooling to sub-zero temperatures (anywhere between -40 to -150°C) and cryo-sectioned at that temperature.
Sections are placed on regular TEM Cu grids for support during viewing.
 Powder samples of composite samples can be dispersed in appropriate solvent and a drop of solution will be taken on
carbon coated copper foil for TEM analysis.
 TEM analyses for bulk morphology study of nano-biocomposites can be investigated using a HRTEM (JEM-2100, JEOL,
Japan) instrument with an acceleration voltage of 100 kV and high vacuum.
 TEM specimens are typically very thin, approximately 0.1 microns in thickness. Specimens are acquired from regions of
the sample based on the goal you hope to achieve through TEM testing.
 Application of TEM
 TEM can be used to study the growth of layers, their composition and defects in semiconductors. High resolution can be used
to analyze the quality, shape, size and density of quantum wells, wires and dots. The TEM operates on the same basic
principles as the light microscope but uses electrons instead of light.
 Transmission Electron Microscopy (TEM) provides powerful techniques for understanding various information of materials
at very high spatial resolution, including morphology, size distribution, crystal structure, strain, defects, chemical information
down to atomic level and so on.
 Transmission electron microscopy (TEM) is a technique used to observe the features of very small specimens. The
technology uses an accelerated beam of electrons, which passes through a very thin specimen to enable a scientist the observe
features such as structure and morphology.
 Principle:- The mechanism of a light microscope is that an increase in resolution power decreases the wavelength of the
light, but in the TEM, when the electron illuminates the specimen, the resolution power increases increasing the wavelength
of the electron transmission.
 It is a technique that uses an electron beam to image a nanoparticle sample, providing much higher resolution than is possible
with light-based imaging techniques. TEM is the preferred method to directly measure nanoparticle size, grain size, size
distribution, and morphology.
 Advantages and disadvantages of TEM
In general, Transmission Electron Microscopy (TEM) techniques are very powerful in material analysis with various
Advantages:
i) High-quality images can be obtained with TEMs.
ii) TEMs have various applications at high spatial resolutions in different fields such as scientific, educational and
industrial fields.
iii) TEMs in combination with EDS and EELS provide elemental and atomic-bonding information.
iv) TEMs provide the highest magnification in microscope field.
v) TEMs can provide information about surface features, shape, size and structure.
Disadvantages:
i) The instruments are very large and expensive.
ii) TEMs require special housing and maintenance because they are sensitive to mechanical vibration, fluctuation of
electromagnetic fields, and variation of cooling water.
iii) Sample preparations from bulk materials are normally very time-consuming.
iv) Potential artifacts can be generated by sample preparation.
v) Special training is needed for tool operation and data analysis.
vi) TEM samples are limited to those that tolerate the vacuum chamber and are small enough to fit in the chamber.
 Atomic force microscope (AFM)
Atomic force microscopy is a powerful characterization tool for polymer
science, capable of revealing surface structures with superior spatial
resolution. The universal character of repulsive forces between the tip and
the sample, which are employed for surface analysis in AFM, enables
examination of even single polymer molecules without disturbance of
their integrity. Being initially developed as the analogue of scanning
tunneling microscopy (STM) for the high-resolution profiling of non-
conducting surfaces, AFM has developed into a multifunctional technique
suitable for characterization of topography, adhesion, mechanical, and
other properties on scales from tens of microns to nanometers

Atomic force microscopy (AFM) is uniquely suited to characterize polymer materials on the nanoscale revealing structures and
morphology without the need for extensive sample prep or vacuum environment. Unlike its electron microscopy counterparts,
the interaction between probe and sample in AFM is mechanical-based making it especially suited to provide contrast on
polymeric type samples.
A schematic representation of the basic AFM setup is shown in Figure 1. Using
atomic force microscopy (AFM), a tip attached to a flexible cantilever will move
across the sample surface to measure the surface morphology on the atomic scale. The
forces between the tip and the sample are measured during scanning, by monitoring
the deflection of the cantilever [1]. This force is a function of tip sample separation
and the material properties of the tip and the sample. Further interactions arising
between the tip and the sample can be used to investigate other characteristics of the
sample, the tip, or the medium in-between [4].
Without proper experiment design, quantitative measurements using AFM are not
possible. In this light several preparation steps have to be included in the planning phase
of an experiment

Mapping chemical functional groups and examining their interactions with different materials is of significant importance for
problems ranging from lubrication and adhesion, to the recognition of biological systems and pharmacy [22]. Changing
environmental conditions during the measurement has also been extensively used to monitor changes in the interactions between
different functional groups and surfaces to simulate the material behavior upon exposure to a real environment
AFM is unique in that provides true measurement of z, or height. This enables any measurements that requires the sample
height such as thickness or roughness to be measured accurately and with very high resolution. The AFM can provide a true
three-dimensional map of the surface like the one shown here which is very useful for certain applications.
The morphology is also a very useful measurement. Morphology refers to features like particle and domain size and
distribution, geometry and size of features, and other size-based descriptions of the surface. AFM is uniquely suited to provide
morphology on polymer samples, since the mechanism for contrast is mechanical—based on a mechanical interaction
between the tip and sample. This is very different than the contrast mechanism between electrons and the sample in SEM or
TEM. The kind of contrast required for SEM and TEM can be hard to obtain for polymer samples, since there might not be
much chemical differentiation between the materials. Very often, in those cases, the AFM mechanism of contrast is superior
and very easy to obtain.
There are a number of different AFM modes that can be operated to obtain images based on mechanical contrast, with the
most common mode called phase imaging. Here is an AFM image showing the topography and phase of alternating sets of
high and low density polyethylene. The topography image on the left shows little contrast, but the material-based contrast of
the phase image on the right shows unambiguous contrast between the two components.
 AFM can be used to make semiquantitative, or, in some cases, even quantitative, measurements of mechanical properties of a
material, including stiffness or modulus, adhesion, and viscoelasticity. And all of these measurements can be made with
impressive nanometer lateral resolution and sub-nanometer vertical resolution. I’m not going to be showing applications of
these quantitative mechanical measurement even though they are quite polymer for polymer applications and that is because
they are more complicated than the imaging methods I have time to describe today.
 The interaction between the very sharp probe and the sample. There are a number of ways the probe can interact with the
sample, including methods that are both static, or non-resonant, and those that are dynamic, or resonant. These resonant
methods take advantage of oscillating the cantilever at resonance through this shake piezo, shown here, in order to interact
with the surface.

 One of the strengths of AFM is that it is capable of a wide variety of in situ measurements because of the flexibility of the
platform. One such measurement is shown here, where the impact copolymer is being stretched under tensile stress, and the
AFM is imaging it in situ while it is being stretched.

 Another theme of in situ measurements is the AFM as a powerful tool for studying polymer crystallization.
 Thermal Analysis

Thermal analysis is a general term defining a technique used to analyze the time and temperature at which physical changes
occur when a substance is heated or cooled. Each technique is defined according to the types of physical changes being analyzed.
Thermal analysis is a branch of materials science where the properties of materials are studied as they change with temperature.
 Hardness testing of polymers
 Hardness testing is to evaluate the strength, ductility and wear resistance of a material, which can determine whether a
material is suitable for the purpose of requirement. The hardness of a metallic material can be defined as its resistance to
plastic deformation caused by a force applied through an indenter.
 The principal purpose of the hardness test is to determine the suitability of a material for a given application, or the
particular treatment to which the material has been subjected.
 Hardness 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 metals such as titanium and beryllium are
harder than soft metals such as sodium and metallic tin, or wood and common plastics. Macroscopic hardness is generally
characterized by strong intermolecular bonds, but the behavior of solid materials under force is complex; therefore, there are
different measurements of hardness: scratch hardness, indentation hardness, and rebound hardness.
 Hardness is dependent on ductility, elastic stiffness, plasticity, strain, strength, toughness, viscoelasticity, and viscosity.
 Common examples of hard matter are ceramics, concrete, certain metals, and superhard materials, which can be contrasted
with soft matter.
 Plastic hardness qualifies the resistance to penetration of a plastic by a harder body. The harder material wears or scratches
the softer material. It's a key engineering parameter for constructing devices, consumer products or industrial parts.
 Types of Hardness Testing
ASTM Hardness Standards Reference Guide

ASTM Description
Standard
D2240 Standard Test Method for Rubber Property-Durometer Hardness
Standard Test Method for Indentation Hardness of Rigid Plastic by
D2583
Means of a Barcol Impressor
E10 Standard Test Method for Brinell Hardness of Metallic Materials

Measuring hardness
There are three main types of hardness measurements: scratch, indentation, and rebound. Within each of these classes of
measurement there are individual measurement scales. For practical reasons conversion tables are used to convert between one
scale and another.
Scratch hardness

Scratch hardness is the measure of how resistant a sample is to fracture or permanent plastic deformation due to friction from a
sharp object. The principle is that an object made of a harder material will scratch an object made of a softer material. When
testing coatings, scratch hardness refers to the force necessary to cut through the film to the substrate. The most common test is
Mohs scale, which is used in mineralogy. One tool to make this measurement is the sclerometer.
Another tool used to make these tests is the pocket hardness tester. This tool consists of a scale arm with graduated markings
attached to a four-wheeled carriage. A scratch tool with a sharp rim is mounted at a predetermined angle to the testing surface.
In order to use it a weight of known mass is added to the scale arm at one of the graduated markings, the tool is then drawn
across the test surface. The use of the weight and markings allows a known pressure to be applied without the need for
complicated machinery
Indentation hardness

Indentation hardness measures the resistance of a sample to material deformation due to a constant compression load from a
sharp object. Tests for indentation hardness are primarily used in engineering and metallurgy fields. The tests work on the basic
premise of measuring the critical dimensions of an indentation left by a specifically dimensioned and loaded indenter.
Common indentation hardness scales are Rockwell, Vickers, Shore, and Brinell, amongst others.
Rebound hardness
Rebound hardness, also known as dynamic hardness, measures the height of the "bounce" of a diamond-tipped hammer dropped
from a fixed height onto a material. This type of hardness is related to elasticity. The device used to take this measurement is
known as a scleroscope.
Two scales that measures rebound hardness are the Leeb rebound hardness test and Bennett hardness scale.
Ultrasonic Contact Impedance (UCI) method determines hardness by measuring the frequency of an oscillating rod. The rod
consists of a metal shaft with vibrating element and a pyramid-shaped diamond mounted on one end.
Vicker’s Hardness Test
It was decided that the indenter shape should be capable of producing geometrically similar
impressions, irrespective of size; the impression should have well-defined points of measurement;
and the indenter should have high resistance to self-deformation. A diamond in the form of a
square-based pyramid satisfied these conditions. It had been established that the ideal size of a
Brinell impression was 3⁄8 of the ball diameter. As two tangents to the circle at the ends of a chord
3d/8 long intersect at 136°, it was decided to use this as the included angle between plane faces of
the indenter tip. This gives an angle from each face normal to the horizontal plane normal of 22° on
each side. The angle was varied experimentally and it was found that the hardness value obtained
on a homogeneous piece of material remained constant, irrespective of load.[2] Accordingly, loads
of various magnitudes are applied to a flat surface, depending on the hardness of the material to be
measured. The HV number is then determined by the ratio F/A, where F is the force applied to the
diamond in kilograms-force and A is the surface area of the resulting indentation in square
millimeters. A can be determined by the formula.
A Vickers hardness tester
Rockwell Hardness Test
The rockwell hardness test is used to measure the ‘hardness’ of a plastic, it’s ability to
resist permanent indentation, this information can be ascertained through the use of a
loaded ball indenter. In layman’s terms a loaded ball indenter is a weighted steel ball.
The ball diameter will change depending on the test method used. This is in agreement
with standard ISO 2039-2, but standard ISO 2039-1 may be used.
The measured indentation depth is used to calculate the surface area of the indent and
therefore the ‘hardness’. There are several different Rockwell Hardness test scales, each
employ different sized steel balls and different loads. These scales are listed
alphabetically and the most common scales for soft materials like plastics and rubbers.
Test Procedure
The Rockwell Hardness test method is performed in two key stages. By performing the test in these two stages it removes the
potential for errors caused by and material surface irregularity and incorrect measuring due to backlash from the created
indentation depth.
The steel ball (indenter) is pressed into the plastic material at a specified force (normally 9.8N) and this is often referred to as the
preload. The indenter is pressed to a specified indentation depth. This is known as the reference level for the test and all
subsequent loads will be measured against this indentation depth.
The indenter is allowed time to dwell, the timeframe will be in accordance with the relevant standard and then the indentation
depth is again measured. The test force has preselected values 49N, 132N, 358N and 961N. Which value of force is chosen is
dependant on the created depth in the material. The value must be between 0.15 and 0.35mm. If the indentation depth is out with
these measurements then the force used must be adapted to suit the material.
Once completed, the indentation depth can then be determined. The depth is then used to calculate the surface area of the indent,
and then the ball indentation hardness using a formula referenced in the standard.
 Abrasion Resistance
 Abrasion resistance refers to the ability of materials and structures to withstand abrasion. It is a method of wearing down or
rubbing away by means of friction. This ability helps to keep the material's original structure and look. Abrasion resistance
resists mechanical wear. Abrasion-resistant materials are useful for both moving and fixed parts in settings where wearing is
an issue.
 Abrasion resistance has close proximity to the compressive strength of concrete. Strong concrete is more abrasion-resistant
than weak concrete. The abrasion resistance of materials and structures can be evaluated by a variety of test methods.

 Abrasion resistance is the ability of materials to withstand the effects of abrasion, for example: repeated wearing, rubbing,
scrapping, etc.
 Abrasion-resistant materials are handy in inhibiting mechanical wearing and damage. They can be used in the construction of
space shuttle components. The abrasion resistance of high-performance concrete is high.
 Abrasion resistance is a property that allows a material to resist wear. The abrasion resistance of a material helps to withstand
mechanical action and tends to protect the removal of materials from its surface. This allows the material to retain its integrity
and hold its form. This can be important when the form of a material is critical to its function, as seen when moving parts are
carefully machined for maximum efficiency. Abrasion resistance can be measured by using the abrasion scrub tester.
 Abrasion testing can be used to measure and predict overall durability of the material as it may perform in real world
applications. This test method measures the volume loss due to the abrasive action of rubbing a test piece over a specified
grade of abrasive sheet.

 The degree of abrasion can be determined by loss of weight for severe damage , but is more usually measured by evidence
of surface marring , such as loss of gloss or development of haze in transparent specimens.

Abrasion resistance can be controlled through:

 Using proper lubricants
 Covering items with an abrasion-resistant material
 Controlling the cause of abrasion
 Utilizing abrasion-resistant coating
In rubber, there are two types of abrasion:
 Sliding – the passing of an adjacent surface across the rubber surface.
 Impingement – wearing of the rubber exemplified by sand particles hitting the surface.
When the rubber cannot withstand localized friction forces, abrasion and wear takes place.
 Many rubber or plastic materials make repeated contact with various surfaces in their service environment, so it’s crucial to
assess wear and abrasion characteristics in the product development stage. Abrasion testing can be used to measure and
predict overall durability of the material as it may perform in real world applications.

 Abrasion resistance is a performance factor of paramount importance for many rubber products, such as tires, conveyor belts,
power transmission belts, hoses, footwear, and floor covering. A test capable of measuring resistance to abrasion of rubber,
including uniformity of wear behavior under abrasive/frictional service conditions is therefore highly desirable.

Common Standards
•ASTM D1630 – Standard Test Method for Rubber Property—Abrasion Resistance (Footwear Abrader)
•​ASTM D2228 – Standard Test Method for Rubber Property—Relative Abrasion Resistance by Pico Abrader Method
•ASTM D3389 – Standard Test Method for Coated Fabrics Abrasion Resistance (Rotary Platform Abrader)
•ASTM D4157 – Standard Test Method for Abrasion Resistance of Textile Fabrics (Oscillatory Cylinder Method)
•ASTM D5963 – Standard Test Method for Rubber Property—Abrasion Resistance (Rotary Drum Abrader)
•BS EN ISO 5470 – Rubber- or plastics-coated fabrics -- Determination of abrasion resistance -- Part 2: Martindale abrader
•BSO ISO 4649 – Rubber, vulcanized, or thermoplastic -- Determination of abrasion resistance using a rotating cylindrical drum
device
 Types of Abrasion testing
 Rotary Drum Abrasion (DIN Abrasion)
This test method measures the volume loss due to the abrasive action of rubbing a test piece over a specified grade of
abrasive sheet. The result can be reported as a relative volume loss or an abrasion resistance index.
 Taber Abrasion
This test method is used to determine the resistance to abrasive wear of plastics or rubber under the action of abrasive
wheels. We can offer a wide range of abrasive wheels, speeds and test loadings.
 NBS Abrasion
This test method is used to determine resistance of rubber by applying a downward force. This method is most commonly
used for evaluating abrasion resistance in footwear, such as rubber soles and heels.
 Pico Abrasion
In this test method, rubber or plastic samples are pressed against two metal blades and rotated at a specified speed to help
determine resistance to abrasion.
 Rotary drum abrasion
 Dimensions of the specimen mm : 16mm diameter with minimum height of 6
testing
 Dimensions of rotating drum : 150 mm diameter with x about 460 mm long
 Speed of rotation of drum : 40 rpm
 Lateral movement of test specimen holder : 4.2 mm per revolution of drum
 Rotation of test specimen : 1 revolution per 50 revolutions of drum
 Load on test specimen : 5/10N
 Total length of abrasion run : 40 meters (about 84 revolutions)
The ASIAN Din Abrasion Tester is designed to determine abrasion resistance index of natural and synthetic rubber in accordance
with the above principle. It consists of test specimen holder with a cylindrical opening adjustable between 15.5 to 16.3 mm to
clamp the test specimen with an arrangement to adjust the length of test specimen protruding out. The holder is mounted by a
screw mechanism along a length of a rotating drum on which the abrasive cloth is fixed. The movement to the screw mechanism
and drum is given by an electric motor, gearbox and chain mechanism to give the specified speed of rotation to the drum and the
specified lateral movement to the test specimen holder. The swivel arm and test specimen holder are so disposed that the test
specimen is pressed against the drum under the specified load with its center axis at an inclination of 3 degree to the perpendicular
in the direction of rotation and placed above the longitudinal axis of drum. A rack and pinion arrangement to rotate the test
specimen about its axis during the test.